Patent Application
20230119082
The invention relates to particular (aziridinyl hydroxy)-functional organic component. The invention further relates to liquid compositions comprising said (aziridinyl hydroxy)-functional organic component. The invention further relates to coating compositions comprising said (aziridinyl hydroxy)-functional organic component. The invention further relates to liquid coating compositions comprising said (aziridinyl hydroxy)-functional organic component. The invention further relates to a kit-of-parts comprising in one of its parts a liquid composition comprising a particular (aziridinyl hydroxy)-functional organic component. The invention further relates to cured forms of said liquid compositions, coating compositions, and liquid coating compositions. The invention further relates to articles comprising the (aziridinyl hydroxy)-functional organic component and/or the liquid compositions and/or the liquid coating compositions and/or their cured forms. The invention further relates to various uses of the (aziridinyl hydroxy)-functional organic component and/or said liquid compositions, and/or said liquid coating compositions, and/or said kit-of-parts and/or said cured forms.
Several organic compounds bearing aziridine ring(s) (a 3-membered ring system composed of one nitrogen and two carbon atoms) are known in the art. Aziridines—which are three-membered cyclic amines (azacyclopropanes)—are an example of organic compounds bearing the aziridine ring. The ring-strain associated with these molecules makes them extremely reactive compounds and attractive for various industrial applications. However, several organic compounds bearing aziridine ring(s) exhibit an unfavourable genotoxic profile, that is to mean that several organic compounds bearing aziridine ring(s) exhibit positive induced genotoxicity—as this term is defined and determined in the specification-. For example, the trimethylolpropane tris(2-methyl-1-aziridinepropionate (CAS No.: 64265-57-2; available by DSM as ‘Crosslinker CX-100’) and the pentaerythritol tris[3-(1-aziridinyl)propionate (CAS No.: 57116-45-7; available by Ichemco as ‘XAMA®7’), as well as the pentaerythritol tris (3-(1-aziridinyl) propionate (CAS No.: 57116-45-7, available by LLC Aziridines as PZ-33), are polyfunctional aziridine crosslinkers that are used for crosslinking carboxylic acid functional polymers. However, the trimethylolpropane tris(2-methyl-1-aziridinepropionate) has an unfavourable genotoxic profile since it exhibits positive induced genotoxicity. As a result, the use of organic compounds bearing aziridine ring(s) is restricted given the desire and the need—imposed by various national regulatory regimes—for various industries to improve on the safety, health and environmental profile of their products, e.g. adhesives, inks and coatings, and also of the raw materials, e.g. compounds bearing the aziridine ring, used for preparing said products, e.g. adhesives, inks and coatings.
In genetics, genotoxicity describes the property of chemical or physical agents that cause any type of damage to the DNA within a cell, causing mutations that may for example, lead to cancer. The damage to the DNA may not always lead to a transmittable mutation. Genotoxicity must not be confused with mutagenicity; all mutagenic substances are genotoxic while not all genotoxic substances are mutagenic. Mutagenicity refers to the induction of permanent and transmissible DNA changes (as DNA composition or chromosome structure), which are retained in somatic cell division and passed onto progeny in germ cells.
The US 2007/298006 A1 (equivalent to WO 2006/115547 A2) to Dendritic Nanotechnologies, PLLC disclosed dendritic polymers with enhanced amplification and interior functionality. The example 12 of the US 2007/298006 A1 disclosed a compound bearing an aziridine ring. This compound was the only compound bearing an aziridine ring that was disclosed in the US 2007/298006 A1. The compound of Example 12 of the US 2007/298006 A1 was obtained as a clear colourless oil, had a molecular weight of 588 Da, and it was used as a synthesis intermediate (via the aziridine ring-opening reaction) in the preparation of dendritic polymers. The US 2007/298006 A1 did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The US 2007/298006 A1 was silent as to (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would combine no genotoxicity and have good, preferably very good, more preferably excellent, crosslinking efficiency.
The U.S. Pat. No. 3,329,674 to Thiokol Chemical Corporation disclosed low molecular weight aziridinyl compounds. The molecular weight of these aziridinyl compounds was well below 600 Da (see examples 1-7; the molecular weight of these compounds varied from 304 to 526). The U.S. Pat. No. 3,329,674 did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The U.S. Pat. No. 3,329,674 was silent as to (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would combine no genotoxicity and have good, preferably very good, more preferably excellent, crosslinking efficiency.
The EP 1865014 A1 to 3M Innovative Properties Company disclosed compositions comprising a prepolymer as component (A) wherein the prepolymer comprised aziridino groups. On page 8-14 (compounds 1-10), the EP 1865014 A1 disclosed compounds bearing aziridine groups. However, these compounds did not have—at least—a hydroxyl group connected to the 8-carbon atom as to the nitrogen atom of the aziridine group. Moreover, the compounds 1, 2, 3, 4, 9, 10 had an ester group connected to the aforementioned 8-carbon atom while the compounds 5, 6, 7, 8 methyl group connected to the aforementioned 8-carbon atom. Thus, the EP 1865014 A1 disclosed very different compounds bearing aziridine groups. The EP 1865014 A1 did not only disclose very different compounds bearing aziridinyl groups but it also did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The EP 1865014 A1 was silent as to (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would combine no genotoxicity and have good, preferably very good, more preferably excellent, crosslinking efficiency.
The WO 2015/066868 A1 to 3M Innovative Properties Company disclosed a fluoropolymer coating composition comprising an aqueous liquid medium, fluoropolymer particles dispersed in the aqueous liquid medium, and at least one aziridine compound. However, the aziridine compounds did not have—at least—a hydroxyl group connected to the 8-carbon atom as to the nitrogen atom of the aziridine group. Thus, the WO 2015/066868 A1 disclosed very different compounds bearing aziridine groups. Therefore, the WO 2015/066868 A1 did not only disclose very different compounds bearing aziridinyl groups, but it also did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The WO 2015/066868 A1 was silent as to (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would combine no genotoxicity and have good, preferably very good, more preferably excellent, crosslinking efficiency. The EP 0758662 A2 to Rockwell International Corporation disclosed curable resin systems comprising an epoxy resin, a co-reactant selected from N-alkyl and N-aryl substituted aziridines and a catalyst to promote cure at ambient temperature. In its example 3, the EP 0758662 A2 disclosed the reaction of PY 306 epoxy resin with 2-methylaziridine to afford an aziridine-endcapped organic compound as a viscous liquid. According to the EP 0758662 A2, the PY 306 epoxy resin is a bisphenol F epoxy supplied by Ciba Geigy (cf. EP 0758662 A2, from cl. 5, I. 59 to cl. 6, I. 1). This aziridine-endcapped organic compound was obtained as a viscous liquid and had a molecular weight of 426.25 Da (this is worked out from the stoichiometry of the reactants disclosed in the 1st sentence of Example 3 of the EP 0758662 A2), and it was used as a synthesis intermediate. The EP 0758662 A2 did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The EP 0758662 A2 was silent as to (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would combine no genotoxicity and have good, preferably very good, more preferably excellent, crosslinking efficiency.
In order to enable broader use of organic compounds bearing aziridine ring(s) which are generally attractive for a variety of potential industrial applications without compromising on the safety, health and environmental aspects of processes and products where organic compounds bearing aziridine ring(s) are or may be employed, there is the desire to provide for organic compounds bearing aziridine ring(s) that are not genotoxic and have good, preferably very good, more preferably excellent, crosslinking efficiency.
However, the above desire still represents an unmet need since the solution to such a problem is particularly challenging given their rather unfavourable genotoxic profile and the common prejudice against their use in industrial applications because of their known unfavourable genotoxic profile.
Therefore, it is the object of the invention to provide for a solution to the above-mentioned unmet need. In other words, it is the object of the invention to provide for organic compounds bearing aziridine ring(s) that are not genotoxic and have good, preferably very good, more preferably excellent, crosslinking efficiency.
This object was surprisingly achieved by specific (aziridinyl hydroxy)-functional organic compounds [that form the (aziridinyl hydroxy)-functional organic component (abbreviated as ‘AZ-component’)] as described in the claims and as disclosed in the specification.
More particularly, the AZ-component (and a liquid composition comprising the AZ-component) are not genotoxic and have good, preferably very good, more preferably excellent, crosslinking efficiency.
The AZ-component (and a liquid composition comprising the AZ-component) constitutes a significant technological advancement for several industries where the use of highly reactive reagents such as compounds bearing aziridine ring(s), is desired or is on-going. The reason being the AZ-component offers concrete opportunities for the industries not only to pursue new synthetic or application pathways for new and innovative products and processes but also to significantly improve on the safety, health and environmental profile of their operations, products and processes.
Broadly in accordance with the invention, there is provided an AZ-component as described in the claims and as disclosed in the specification.
Broadly in accordance with the invention, there are provided liquid composition as described in the claims and as disclosed in the specification.
Broadly in accordance with the invention, there are provided kits-of-parts as described in the claims and as disclosed in the specification.
Broadly in accordance with the invention, there are provided cured forms as described in the claims and as disclosed in the specification.
Broadly in accordance with the invention, there are provided articles as described in the claims and as disclosed in the specification.
Broadly in accordance with the invention, there is provided a use of any one or any combination of the following:
i) an AZ-component according to any one of A1 to A18 and as disclosed in the entire specification including the claims;
ii) a liquid composition according to any one of A19 to A34 and as disclosed in the entire specification including the claims;
as a crosslinker.
Broadly in accordance with the invention, there is provided a use of any one or any combination of the following:
i) an AZ-component according to any one of A1 to A18 and as disclosed in the entire specification including the claims;
ii) a liquid composition according to any one of A19 to A34 and as disclosed in the entire specification including the claims;
iii) a kit-of-parts according to A35 and as disclosed in the entire specification including the claims;
iv) a cured form according to any of A36 to A37 and as disclosed in the entire specification including the claims;
v) an article according to any one of A38 to A39 and as disclosed in the entire specification, including the claims;
in coatings, paints, inks, varnishes, lubricants, adhesives, additive manufacturing, 3D-printing, textiles, waxes, fuels, photography, plastics, medical compositions, medical devices.
Ala Broadly in accordance with the invention there is provided an (aziridinyl hydroxy)-functional organic component (AZ-component) according to the claim 1.
The following paragraphs A1 to A41 constitute certain explicit preferments of the AZ-component according to Ala, as well as certain further explicit aspects of the invention of the AZ-component according to Ala. More specifically, the preferments of the AZ-component according to Ala include but are not limited to preferments A1 to A18, while the aspects of the invention of the AZ-component according to Ala include but are not limited to aspects A19 to A41. Many other variations, combinations or embodiments of the invention will be apparent to those skilled in the art and such variations, combinations and embodiments are contemplated within the scope of the claimed invention. The antecedent basis for certain terms shown in the preferments and in the aspects can be found in preceding preferments or aspects. Any reference to components includes their preferments and preferred ranges as disclosed in the entire specification, including the claims.
A1 The (aziridinyl hydroxy)-functional organic component (AZ-component) according to Ala or any combination derived from the disclosure in section 1 and the entire specification, wherein the (aziridinyl hydroxy)-functional organic component (AZ-component) is selected from the group consisting of i) to vi): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 having only two aziridine rings (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 having only three aziridine rings (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 having only four aziridine rings (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ4 of Formula A4 having only five aziridine rings (AZ4-compound), v) (aziridinyl hydroxy)-functional organic compound AZ5 of Formula A5 having only six aziridine rings (AZ5-compound), and vi) mixtures thereof, preferably the AZ-component is selected from the group consisting of i) to iv): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 having only two aziridine rings (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 having only three aziridine rings (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 having only four aziridine rings (AZ3-compound), and iv) mixtures thereof,
wherein
X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical, preferably X1 is a bivalent aliphatic organic radical;
X2 is a trivalent aliphatic organic radical or a trivalent aromatic organic radical, preferably X2 is a trivalent aliphatic organic radical;
X3 is a quadrivalent aliphatic organic radical or a quadrivalent aromatic organic radical, preferably X3 is a quadrivalent aliphatic organic radical;
X4 is a pentavalent aliphatic organic radical or a pentavalent aromatic organic radical, preferably X4 is a pentavalent aliphatic organic radical;
X5 is a hexavalent aliphatic organic radical or a hexavalent aromatic organic radical, preferably X5 is a hexavalent aliphatic organic radical;
and wherein each of the X1 to X5 consists of a collection of atoms covalently connected in a configuration that comprises—preferably consists of—linear and/or branched and/or ring structures, which collection of atoms is selected from the group consisting of i) to x):
i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, iv) carbon, hydrogen and sulphur atoms, v) carbon, hydrogen, oxygen and nitrogen atoms, vi) carbon, hydrogen, nitrogen and sulphur atoms, vii) carbon, hydrogen, oxygen and sulphur atoms, viii) carbon, hydrogen, oxygen, nitrogen and sulphur, atoms, ix) carbon, hydrogen and silicon atoms, and x) carbon, hydrogen, oxygen and silicon atoms and xi) any combination of ix) and/or x) with any one or all of the iii) to viii),
and wherein each of the X1 to X5 has carbon atoms and hydrogen atoms,
and wherein each of the X1 to X5 has optionally oxygen atoms and/or nitrogen atoms and/or sulphur atoms and/or silicon atoms,
and wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 may optionally comprise an ionic functional group, preferably the X1, and/or the X2 and/or
the X3 and/or the X4 and/or the X5 does not comprise an ionic functional group, and wherein
Y is a monovalent organic radical selected from the group consisting of: i) monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B1, ii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B2, and iii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B3, preferably Y is a monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B1,
and wherein
R1 is selected from the group consisting of hydrogen and methyl; and
R2 is selected from the group consisting of hydrogen, methyl, and C2-C5 alkyl; and
R3 is selected from the group consisting of methyl, and C2-C4 alkyl; and
R4 is selected from the group consisting of hydrogen, methyl, and C2-C4 alkyl;
and wherein
the Y in each of the compounds A1 to A5 may be the same or different to each other and wherein each of the single covalent bonds between the Y and each one of the X1 to X5 is selected from the group consisting of carbon-carbon single bond, carbon-oxygen single bond and carbon-nitrogen single bond, preferably carbon-oxygen single bond and carbon-nitrogen single bond, more preferably carbon-oxygen single bond,
and wherein
each of the AZ1- to AZ5-compounds has a molecular weight determined via MALDI-TOF MS according to the description, of at least 600 and at most 10000, preferably at least 600 and at most 8000, more preferably at least 600 and at most 7000, even more preferably at least 600 and at most 6000, for example at least 600 and at most 5500, for example at least 600 and at most 5000, for example at least 600 and at most 4000, for example at least 600 and at most 3500, for example at least 600 and at most 3200, for example at least 600 and at most 3000, for example at least 600 and at most 2500, for example at least 600 and at most 2200, for example at least 600 and at most 2000, for example at least 630 and at most 10000, for example at least 630 and at most 8000, for example at least 630 and at most 7000, for example at least 630 and at most 6000, for example at least 630 and at most 5500, for example at least 630 and at most 5000, for example at least 630 and at most 4000, for example at least 630 and at most 3500, for example at least 630 and at most 3200, for example at least 630 and at most 3000, for example at least 630 and at most 2500, for example at least 630 and at most 2200, for example at least 630 and at most 2000, for example at least 640 and at most 10000, for example at least 640 and at most 8000, for example at least 640 and at most 7000, for example at least 640 and at most 6000, for example at least 640 and at most 5500, for example at least 640 and at most 5000, for example at least 640 and at most 4000, for example at least 640 and at most 3500, for example at least 640 and at most 3200, for example at least 640 and at most 3000, for example at least 640 and at most 2500, for example at least 640 and at most 2200, for example at least 640 and at most 2000, for example at least 650 and at most 10000, for example at least 650 and at most 8000, for example at least 650 and at most 7000, for example at least 650 and at most 6000, for example at least 650 and at most 5500, for example at least 650 and at most 5000, for example at least 650 and at most 4000, for example at least 650 and at most 3500, for example at least 650 and at most 3200, for example at least 650 and at most 3000, for example at least 650 and at most 2500, for example at least 650 and at most 2200, for example at least 650 and at most 2000, for example at least 700 and at most 10000, for example at least 700 and at most 8000, for example at least 700 and at most 7000, for example at least 700 and at most 6000, for example at least 700 and at most 5500, for example at least 700 and at most 5000, for example at least 700 and at most 4000, for example at least 700 and at most 3500, for example at least 700 and at most 3200, for example at least 700 and at most 3000, for example at least 700 and at most 2500, for example at least 700 and at most 2200, for example at least 700 and at most 2000, for example at least 750 and at most 10000, for example at least 750 and at most 8000, for example at least 750 and at most 7000, for example at least 750 and at most 6000, for example at least 750 and at most 5500, for example at least 750 and at most 5000, for example at least 750 and at most 4000, for example at least 750 and at most 3500, for example at least 750 and at most 3200, for example at least 750 and at most 3000, for example at least 750 and at most 2500, for example at least 750 and at most 2200, for example at least 750 and at most 2000, for example at least 800 and at most 10000, for example at least 800 and at most 8000, for example at least 800 and at most 7000, for example at least 800 and at most 6000, for example at least 800 and at most 5500, for example at least 800 and at most 5000, for example at least 800 and at most 4000, for example at least 800 and at most 3500, for example at least 800 and at most 3200, for example at least 800 and at most 3000, for example at least 800 and at most 2500, for example at least 800 and at most 2200, for example at least 800 and at most 2000, for example at least 850 and at most 10000, for example at least 850 and at most 8000, for example at least 850 and at most 7000, for example at least 850 and at most 6000, for example at least 850 and at most 5500, for example at least 850 and at most 5000, for example at least 850 and at most 4000, for example at least 850 and at most 3500, for example at least 850 and at most 3200, for example at least 850 and at most 3000, for example at least 850 and at most 2500, for example at least 850 and at most 2200, for example at least 850 and at most 2000, for example at least 900 and at most 10000, for example at least 900 and at most 8000, for example at least 900 and at most 7000, for example at least 900 and at most 6000, for example at least 900 and at most 5500, for example at least 900 and at most 5000, for example at least 900 and at most 4000, for example at least 900 and at most 3500, for example at least 900 and at most 3200, for example at least 900 and at most 3000, for example at least 900 and at most 2500, for example at least 900 and at most 2200, for example at least 900 and at most 2000, for example at least 950 and at most 10000, for example at least 950 and at most 8000, for example at least 950 and at most 7000, for example at least 950 and at most 6000, for example at least 950 and at most 5500, for example at least 950 and at most 5000, for example at least 950 and at most 4000, for example at least 950 and at most 3500, for example at least 950 and at most 3200, for example at least 950 and at most 3000, for example at least 950 and at most 2500, for example at least 950 and at most 2200, for example at least 950 and at most 2000, for example at least 1000 and at most 10000, for example at least 1000 and at most 8000, for example at least 1000 and at most 7000, for example at least 1000 and at most 6000, for example at least 1000 and at most 5500, for example at least 1000 and at most 5000, for example at least 1000 and at most 4000, for example at least 1000 and at most 3500, for example at least 1000 and at most 3200, for example at least 1000 and at most 3000, for example at least 1000 and at most 2500, for example at least 1000 and at most 2200, for example at least 1000 and at most 2000, for example at least 1100 and at most 10000, for example at least 1100 and at most 8000, for example at least 1100 and at most 7000, for example at least 1100 and at most 6000, for example at least 1100 and at most 5500, for example at least 1100 and at most 5000, for example at least 1100 and at most 4000, for example at least 1100 and at most 3500, for example at least 1100 and at most 3200, for example at least 1100 and at most 3000, for example at least 1100 and at most 2500, for example at least 1100 and at most 2200, for example at least 1100 and at most 2000, for example at least 1200 and at most 10000, for example at least 1200 and at most 8000, for example at least 1200 and at most 7000, for example at least 1200 and at most 6000, for example at least 1200 and at most 5500, for example at least 1200 and at most 5000, for example at least 1200 and at most 4000, for example at least 1200 and at most 3500, for example at least 1200 and at most 3200, for example at least 1200 and at most 3000, for example at least 1200 and at most 2500, for example at least 1200 and at most 2200, for example at least 1200 and at most 2000 Da.
A2 The AZ-component according to any one of Ala or A1 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical other than a bivalent radical of bisphenol A.
A3 The AZ-component according to Ala or to any one of A1 to A2 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical other than a bivalent organic radical selected from the group consisting of bivalent radical of bisphenol A, bivalent radical of bisphenol AP, bivalent radical of bisphenol AF, bivalent radical of bisphenol B, bivalent radical of bisphenol BP, bivalent radical of bisphenol C, bivalent radical of bisphenol C2, bivalent radical of bisphenol E, bivalent radical of bisphenol F, bivalent radical of bisphenol G, bivalent radical of bisphenol M, bivalent radical of bisphenol S, bivalent radical of bisphenol P, bivalent radical of bisphenol PH, bivalent radical of bisphenol TMC, bivalent radical of bisphenol Z, bivalent radical of dinitrobisphenol A, bivalent radical of tetrabromobisphenol A, and combinations thereof, preferably X1 is a bivalent aliphatic organic radical.
A4 The AZ-component according to Ala or to any one of A1 to A3 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 comprises at least one structural unit or a combination of structural units selected from the group consisting of unit 1, unit 2, unit 3, unit 4, unit 5, unit 6, unit 7, unit 8, unit 9, unit 10, and unit 11, preferably comprises at least one structural unit or a combination of structural units selected from the group consisting of unit 1, unit 4, unit 9, unit 10 and unit 11, as the units 1 to 11 are depicted below:
wherein
R′ is selected from the group consisting of hydrogen and methyl; and
j is an integer ranging from 1 to 5, preferably from 1 to 3; and
n is an integer ranging from and including 2 up to and including 50, preferably from and including 2 up to and including 40, more preferably from and including 2 up to and including 30, most preferably from and including 2 up to and including 20, for example from and including 2 up to and including 15, for example from and including 2 up to and including 10, for example from and including 2 up to and including 5, for example the n is 2, for example from and including 3 up to and including 50, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15, for example from and including 3 up to and including 10, for example from and including 3 up to and including 5, for example the n is 3, for example from and including 4 up to and including 50, for example from and including 4 up to and including 40, for example from and including 4 up to and including 30, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15, for example from and including 4 up to and including 10, for example from and including 4 up to and including 5, for example the n is 4, for example from and including 5 up to and including 50, for example from and including 5 up to and including 40, for example from and including 5 up to and including 30, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15, for example from and including 5 up to and including 10, for example the n is 5, for example from and including 6 up to and including 50, for example from and including 6 up to and including 40, for example from and including 6 up to and including 30, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15, for example from and including 6 up to and including 10, for example the n is 6, for example from and including 7 up to and including 50, for example from and including 7 up to and including 40, for example from and including 7 up to and including 30, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15, for example from and including 7 up to and including 10, for example the n is 7, for example from and including 8 up to and including 50, for example from and including 8 up to and including 40, for example from and including 8 up to and including 30, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15, for example from and including 8 up to and including 10, for example the n is 8, for example from and including 9 up to and including 50, for example from and including 9 up to and including 40, for example from and including 9 up to and including 30, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15, for example from and including 9 up to and including 10, for example the n is 9, for example from and including 10 up to and including 50, for example from and including 10 up to and including 40, for example from and including 10 up to and including 30, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15, for example the n is 10.
A5 The AZ-component according to Ala or to any one of A1 to A4 or any combination derived from the disclosure in section 1 and the entire specification,
wherein
R1 is selected from the group consisting of hydrogen and methyl; and
R2 is selected from the group consisting of hydrogen, methyl, and ethyl; and
R3 is selected from the group consisting of methyl, and C2-C4 alkyl; and
R4 is selected from the group consisting of hydrogen, methyl, and ethyl.
A6 The AZ-component according to Ala or to any one of A1 to A5 or any combination derived from the disclosure in section 1 and the entire specification, wherein the aggregate number of carbon atoms in R1, and R2 and R3 and R4 is at most 9, preferably at most 4, more preferably at most 2, for example at most 1.
A7 The AZ-component according to Ala or to any one of A1 to A6 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1 and/or the X2 and/or the X3 and/or the X4 and/or the X5 does not contain one or any combination of the following structural units BP1, BP2, BP3, and BS
A8 The AZ-component according to Ala or to any one of A1 to A7 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 comprises at least one unit 11 as a structural unit.
A9 The AZ-component according to Ala or to any one of A1 to A8 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1 is the bivalent aliphatic organic radical of Formula A1a′
wherein
R′ is selected from the group consisting of hydrogen and methyl; and
j is an integer ranging from 1 to 5, preferably from 1 to 3; and
n is an integer ranging from and including 2 up to and including 50, preferably from and including 2 up to and including 40, more preferably from and including 2 up to and including 30, most preferably from and including 2 up to and including 20, for example from and including 2 up to and including 15, for example from and including 2 up to and including 10, for example from and including 2 up to and including 5, for example the n is 2, for example from and including 3 up to and including 50, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15, for example from and including 3 up to and including 10, for example from and including 3 up to and including 5, for example the n is 3, for example from and including 4 up to and including 50, for example from and including 4 up to and including 40, for example from and including 4 up to and including 30, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15, for example from and including 4 up to and including 10, for example from and including 4 up to and including 5, for example the n is 4, for example from and including 5 up to and including 50, for example from and including 5 up to and including 40, for example from and including 5 up to and including 30, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15, for example from and including 5 up to and including 10, for example the n is 5, for example from and including 6 up to and including 50, for example from and including 6 up to and including 40, for example from and including 6 up to and including 30, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15, for example from and including 6 up to and including 10, for example the n is 6, for example from and including 7 up to and including 50, for example from and including 7 up to and including 40, for example from and including 7 up to and including 30, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15, for example from and including 7 up to and including 10, for example the n is 7, for example from and including 8 up to and including 50, for example from and including 8 up to and including 40, for example from and including 8 up to and including 30, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15, for example from and including 8 up to and including 10, for example the n is 8, for example from and including 9 up to and including 50, for example from and including 9 up to and including 40, for example from and including 9 up to and including 30, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15, for example from and including 9 up to and including 10, for example the n is 9, for example from and including 10 up to and including 50, for example from and including 10 up to and including 40, for example from and including 10 up to and including 30, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15, for example the n is 10.
A10 The AZ-component according to A1a or to any one of A1 to A9 or any combination derived from the disclosure in section 1 and the entire specification, wherein each of the X1 to X5 contains only single covalent bonds, or both single and double covalent bonds, and wherein the single covalent bonds are selected from the group consisting of carbon-carbon single bond, carbon-hydrogen single bond, carbon-nitrogen single bond, carbon-sulphur single bond, carbon-silicon single bond, silicon-oxygen single bond, nitrogen-hydrogen single bond, sulphur-oxygen single bond, carbon-oxygen single bond wherein the oxygen is bonded to a hydrogen forming a hydroxyl group, silicon-oxygen-silicon single bonds, and wherein the double covalent bonds are selected from the group consisting of carbon-carbon double bond, carbon-nitrogen double bond, sulphur-oxygen double bond, carbon-oxygen double bond wherein the carbon is a member of a ring structure, and carbon-oxygen double bond wherein the carbon is bonded to another two carbons via carbon-carbon single bonds, carbon-oxygen double bond wherein the carbon is bonded to another oxygen via single bond and to a nitrogen via a single bond, carbon-oxygen double bond wherein the carbon is bonded to two nitrogens via carbon-nitrogen single bonds, carbon-oxygen double bond wherein the carbon is bonded to another two oxygens via single bonds; preferably the double covalent bonds are selected from the group consisting of carbon-carbon double bond, carbon-nitrogen double bond, sulphur-oxygen double bond, carbon-oxygen double bond wherein the carbon is a member of a ring structure, and carbon-oxygen double bond wherein the carbon is bonded to another two carbons via carbon-carbon single bonds, carbon-oxygen double bond wherein the carbon is bonded to another oxygen via single bond and to a nitrogen via a single bond, carbon-oxygen double bond wherein the carbon is bonded to two nitrogens via carbon-nitrogen single bonds.
A11 The AZ-component according to A1a or to any one of A1 to A10 or any combination derived from the disclosure in section 1 and the entire specification, wherein the aggregate number of carbon and hydrogen atoms in X1 and/or X2 and/or X3 and/or X4 and/or X5 is at least 5, preferably at least 10, more preferably at least 15, most preferably at least 20, for example at least 25, for example at least 30, for example at least 35, for example at least 40, for example at least 45, for example at least 50, for example at least 55, for example at least 60, for example at least 65, for example at least 70, for example at least 75, for example at least 80, for example at least 85, for example at least 90, for example at least 95, for example at least 97, for example at least 98, for example at least 99, for example 100% as to the aggregate number of all the atoms present in X1 and/or X2 and/or X3 and/or X4 and/or X5, respectively.
A12 The AZ-component according to Ala or to any one of A1 to A11 or any combination derived from the disclosure in section 1 and the entire specification, wherein the aggregate number of all the atoms present in X1 and/or X2 and/or X3 and/or X4 and/or X5 is at most 600, preferably at most 550, more preferably at most 500, most preferably at most 450, for examples at most 400, for example at most 350, for example at most 300, for example at most 250, for example at most 200.
A13 The AZ-component according to Ala or to any one of A1 to A12 or any combination derived from the disclosure in section 1 and the entire specification, wherein the AZ-component is selected from the group consisting of i) to v): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 (AZ1-compound), 11) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ5 of Formula A5 (AZ5-compound), and vi) mixtures thereof, and
wherein
the AZ1-compound is selected from the group consisting of compounds having the Formula A1a, and compounds having the Formula A1b, as each of these Formulae A1a-A1d is described below
wherein each of the n in Formula A1a is independently selected, and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4; and
wherein the R in Formula A1b is a C3-C10 saturated hydrocarbylene, and wherein each of the n in Formula A1b is independently selected and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4; and
wherein each of the n in Formula A1c is independently selected, and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, and
wherein the R in Formula A1d is a C3-C10 saturated hydrocarbylene, and wherein each of the n in Formula A1d is independently selected and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, and wherein the AZ2-compound is selected from the group consisting of compounds having the Formula A2a, compounds having the Formula A2b, compounds having the Formula A2c, compounds having the Formula A2d, compounds having the Formula A2e, as each of these Formulae A2a-A2e is described below
wherein the n in Formula A2a is an integer ranging from and including 2 up to and including 20, for example from and including 2 up to and including 10, for example from and including 2 up to and including 8, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 8, for example from and including 4 up to and including 20, for example from and including 4 up to and including 10, for example from and including 4 up to and including 8, for example from and including 5 up to and including 20, for example from and including 5 up to and including 10, for example from and including 5 up to and including 8, for example from and including 6 up to and including 20, for example from and including 6 up to and including 10, for example from and including 6 up to and including 8, for example n is equal to 7;
and
wherein each of the n in Formula A2b is independently selected and each of the n in Formula A2b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 12, most preferably from and including 2 up to and including 11, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15 for example from and including 3 up to and including 12 for example from and including 3 up to and including 11, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15 for example from and including 4 up to and including 12 for example from and including 4 up to and including 11, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15 for example from and including 5 up to and including 12 for example from and including 5 up to and including 11, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15 for example from and including 6 up to and including 12 for example from and including 6 up to and including 11, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15 for example from and including 7 up to and including 12 for example from and including 7 up to and including 11, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15 for example from and including 8 up to and including 12 for example from and including 8 up to and including 11, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15 for example from and including 9 up to and including 12 for example from and including 9 up to and including 11, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15 for example from and including 10 up to and including 12 for example from and including 10 up to and including 11, for example n is equal to 11;
and
wherein each of the n in Formula A2c is independently selected and each of the n in Formula A2c is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 12, most preferably from and including 2 up to and including 11, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15 for example from and including 3 up to and including 12 for example from and including 3 up to and including 11, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15 for example from and including 4 up to and including 12 for example from and including 4 up to and including 11, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15 for example from and including 5 up to and including 12 for example from and including 5 up to and including 11, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15 for example from and including 6 up to and including 12 for example from and including 6 up to and including 11, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15 for example from and including 7 up to and including 12 for example from and including 7 up to and including 11, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15 for example from and including 8 up to and including 12 for example from and including 8 up to and including 11, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15 for example from and including 9 up to and including 12 for example from and including 9 up to and including 11, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15 for example from and including 10 up to and including 12 for example from and including 10 up to and including 11, for example n is equal to 11;
and
and
wherein
the AZ3-compound is selected from the group consisting of compounds having the Formula A3a
wherein each of the n in Formula A3a is independently selected, and each of the n in Formula A3a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 10, most preferably from and including 2 up to and including 9, for example from and including 2 up to and including 8, for example from and including 2 up to and including 7, for example from and including 2 up to and including 6, for example from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 2 up to and including 3, for example n is equal to 3, for example n is equal to 2;
and
wherein
the AZ5-compound is selected from the group consisting of compounds having the Formula A5a
wherein each of the n in Formula A5a is independently selected, and each of the n in Formula A5a is an integer ranging from and including 2 up to and including 40, preferably from and including 2 up to and including 30, more preferably from and including 2 up to and including 20, most preferably from and including 2 up to and including 10, for example from and including 2 up to and including 9, for example from and including 2 up to and including 8, for example from and including 2 up to and including 7, for example from and including 2 up to and including 6, for example from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 9, for example from and including 3 up to and including 8, for example from and including 3 up to and including 7, for example from and including 3 up to and including 6, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, for example n is equal to 3.
A14 The AZ-component according to Ala or to any one of A1 to A13 or any combination derived from the disclosure in section 1 and the entire specification, wherein the X1 and/or the X2 and/or the X3 and/or the X4 and/or the X5 does not contain any structural unit of (or equally derived from) phenol formaldehyde resins (also known as phenolic resins); examples of phenol-formaldehyde (PF) resins include novolacs (acid-catalyzed PF resins with a formaldehyde to phenol ratio of equal to or lower than one), and resols (base-catalyzed PF resins with a formaldehyde to phenol ratio of greater than one, usually equal to 1.5).
A15 The AZ-component according to Ala or to any one of A1 to A14 or any combination derived from the disclosure in section 1 and the entire specification, wherein the AZ-component is selected from the group consisting of AZ1-compound and wherein the AZ1-compound is the compound of the following formula
A16 The AZ-component according to Ala or to any one of A1 to A15 or any combination derived from the disclosure in section 1 and the entire specification, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
A17 The AZ-component according to Ala or to any one of A1 to A16 or any combination derived from the disclosure in section 1 and the entire specification, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
A18 The AZ-component according to Ala or to any one of A1 to A17 or any combination derived from the disclosure in section 1 and the entire specification, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
A19 A liquid composition according to any combination derived from the disclosure in sections 1 and 3 and the entire specification, comprising:
i) a liquid medium which is selected from the group consisting of organic solvents, water and a mixture thereof, in an amount of at most 90, preferably at most 85, more preferably at most 80, for example at most 75, for example at most 70, for example at most 65, for example at most 60, for example at most 55, for example at most 50, for example at most 45, for example at most 40, for example at most 35, for example at most 30, for example at most 25, for example at most 20, for example at most 15, for example at most 10 for example at most 5, for example at most 2, for example at most 1 wt % on the total weight of the liquid composition, for example the liquid composition is free of the liquid medium; and
ii) an AZ-component according to Ala or to any one of A1 to A18 or any combination derived from the disclosure in sections 1 and 3 and the entire specification; and wherein the total amount of all the components that make up the liquid composition totals 100 wt %.
A20 The liquid composition according to A19 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition comprises water in an amount of at most 90, preferably at most 85, more preferably at most 80, most preferably at most 75, for example at most 70, for example at most 65, for example at most 60, for example at most 55, for example at most 50, for example at most 45, for example at most 40, for example at most 35, for example at most 30, for example at most 25, for example at most 20, for example at most 15, for example at most 10, for example at most 5, for example at most 2, for example at most 1 wt % on the total weight of the liquid composition, for example the liquid composition is free of water.
A21 The liquid composition according to any one of A14-A20 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition comprises water in an amount of at least 70 and at most 90, preferably at least 75 and at most 85 wt % on the total weight of the liquid composition, and the AZ-compound in an amount of at least 10 and at most 30, preferably at least 15 and at most 25 wt % on the total weight of the liquid composition.
A22 The liquid composition according to any one of A19-A21 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition comprises water in an amount of at least 50 and at most 75, preferably at least 55 and at most 70 wt % on the total weight of the liquid composition, and the AZ-compound in an amount of at least 25 and at most 50, preferably at least 30 and at most 45 wt % on the total weight of the liquid composition.
A23 The liquid composition according to any one of A19-A22 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition comprises water in an amount of at least 40 and at most 70, preferably at least 45 and at most 65 wt % on the total weight of the liquid composition, and the AZ-compound in an amount of at least 30 and at most 60, preferably at least 35 and at most 55 wt % on the total weight of the liquid composition.
A24 The liquid composition according to any one of A19-A23 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the water is present in an amount of at least 30 and at most 95, preferably at least 40 and at most 85, for example at least 45 and at most 85, for example at least 50 and at most 70, for example at least 55 and at most 65 wt % on the total weight of the liquid composition, and wherein the total amount of all the components that make up the liquid composition totals 100 wt %.
A25 The liquid composition according to any one of A19-A24 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, the liquid composition comprises an organic solvent in an amount of at most 40, preferably at most 30, for example at most 25, for example at most 20, for example at most 12, for example at most 10, for example at most 8, for example at most 5, for example at most 4, for example at most 3, for example at most 2, for example at most 1, for example at most 0.5, for example at most 0.2, for example at most 0.1 wt % on the total weight of the liquid composition.
A26 The liquid composition according to any one of A19-A25 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition is free of an organic solvent.
A27 The liquid composition according to any one of A19-A26 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition has a pH determined according to the ISO 976:2013 and according to the description, of at least 7.5 and at most 14.0, preferably at least 8.0 and at most 14.0, for example at least 8.5 and at most 13.5, for example at least 9.0 and at most 13.0, for example at least 9.2 and at most 12.5, for example at least 9.4 and at most 12.0, for example at least 10 and at most 13, for example at least 10.5 and at most 12.0, for example at least 10.5 and at most 11.6, for example at least 10.5 and at most 11.5, with the proviso that the liquid composition comprises water in an amount of at least 20, preferably at least 25, more preferably at least 30, most preferably at least 35 wt % on the total weight of the liquid composition.
A28 The liquid composition according to any one of A19-A27 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition comprises a component T selected from the group consisting of: i) organic compounds having a molecular weight determined via MALDI-TOF MS according to the description, lower than 600 Da and comprising at least one aziridine ring, and ii) mixtures thereof, in an amount, determined via LC-MS according to the description, of at most 5, preferably at most 4, more preferably at most 3, for example at most 2, for example at most 1, for example at most 0.5, for example at most 0.1, for example at most 0.05 wt % on the total weight of the AZ-compound.
A29 The liquid composition according to any one of A19-A28 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition is free of component T.
A30 The liquid composition according to any one of A19-A29 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the amount of chloride determined according to the ASTM D1726-11(2019), is at most 0.3, preferably at most 0.2, more preferably at most 0.1, for example at most 0.05, for example at most 0.03 wt % on the total weight of the liquid composition.
A31 The liquid composition according to any one of A19-A30 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, further comprising:
iii) a polymer which has an acid value determined according to the ASTM D1639-90(1996)e1 of at least 5 and at most 300, preferably at least 8 and at most 200, more preferably at least 10 and at most 150 mg KOH/g and wherein the polymer may optionally comprise ionic functional groups.
A32 The liquid composition according to any one of A19-A31 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the polymer is selected from the group consisting of polyesters, polyamides, polycarbonates, polyimides, alkyds, uralkyds, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, preferably the polymer is selected from the group consisting of polyamides, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, most preferably the polymer is selected from the group consisting of polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof.
A33 The liquid composition according to any one of A19-A32 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the polymer is present in an amount of at least 5 and at most 65, preferably at least 10 and at most 60, more preferably at least 20 and at most 55, for example at least 30 and at most 50 wt % on the total weight of the aqueous composition, and wherein the total amount of all the components that make up the mixture totals 100 wt %.
A34 The liquid composition according to any one of A19-A33 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, wherein the liquid composition is a coating composition, preferably a liquid coating composition.
A35 A kit-of-parts according to any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification, comprising parts A and B which are physically separated from each other, wherein:
i) the part A comprises a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 1 and 3 and the entire specification, and
ii) the part B comprises a polymer which has an acid value determined according to the ASTM D1639-90(1996)e1 in the range from 5 to 300, preferably from 8 to 200, more preferably from 10 to 150 mg KOH/g and wherein the polymer may optionally comprise ionic functional groups, and wherein the polymer is preferably selected from the group consisting of polyesters, polyamides, polycarbonates, polyimides, alkyds, uralkyds, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, more preferably the polymer is selected from the group consisting of polyamides, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, most preferably the polymer is selected from the group consisting of polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, wherein the part A does not comprise the polymer of the part B, and the part B does not comprise the liquid composition of the part A.
A36 A cured form of an AZ-component according to Ala or any one of A1-A18 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification, or of a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification.
A37 The cured form according to A36, wherein the cured form is a film.
A38 An article comprising: i) an AZ-component according to Ala or any one of A1-A13 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification, or ii) a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification, and/or iii) a cured form according to any one of A36-A37 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification.
A39 The article according to A38 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification, wherein the article is selected from the group consisting of textile, glass, metal, composite, plastic, wood, engineered wood, wood-like, leather, artificial leather, paper, fibers.
A40 Use of an AZ-component according to any one of the claims 1-18, or a liquid composition according to any one of claims 19-34, as a crosslinker. A41 Use of any one or any combination of the following:
i) an AZ-component according to Ala or any one of A1-A18 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification;
ii) a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification;
iii) a kit-of-parts according to A35 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification;
iv) a cured form according to any one of A36-A37 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification;
v) an article according to any one of A38-A39 or any combination derived from the disclosure in sections 4, 3 and 1 and the entire specification;
in coatings, paints, inks, varnishes, lubricants, adhesives, additive manufacturing, 3D-printing, textiles, waxes, fuels, photography, plastics, medical compositions, medical devices.
All combinations of minimum and maximum values of the parameters disclosed in the specification may be used to define the parameter ranges for various preferments or embodiments of the invention.
Unless otherwise explicitly stated, any feature, element, component, embodiment, aspect, range and especially any preferred feature, preferred element, preferred embodiment, preferred aspect, preferred range, preferred combination of ranges, preferments, embodiments and aspects in connection with any piece of the disclosure disclosed in any one of A1a or A1 to A41, shown above can be combined with each other and with any other feature, element, component, embodiment, aspect, range and especially any preferred feature, preferred element, preferred embodiment, preferred aspect, preferred range, preferred combination of ranges, preferments, embodiments and aspects of the invention as these are disclosed in the entire specification including the claims.
Unless otherwise explicitly stated, any feature, element, component, embodiment, aspect, range and especially any preferred feature, preferred element, preferred embodiment, preferred aspect, preferred range, preferred combination of ranges, preferments, embodiments and aspects of the invention as these are disclosed in the entire specification including the claims can be combined with each other.
By ‘aziridine ring’ is meant in the specification a 3-membered ring system composed of one nitrogen and two carbon atoms.
By the term ‘saturated hydrocarbylene’ is meant a bivalent organic group formed by removing two hydrogen atoms from a saturated hydrocarbon, the free valences of which are not engaged in a double bond. Exemplary hydrocarbylenes include but are not limited to methylene.
By the term ‘saturated’ is meant that the relevant entity does not contain any unsaturation.
By the term ‘ionic functional group’ is meant herein a functional group that comprises one or both of a cation and an anion and said functional group is covalently bonded to the entity to which it relates to.
By ‘poor chemical resistance’-referring to a cured coating (film)—is meant in the specification that the chemical resistance of a film measured as described in the specification is at most 1 [rating scale 0-5, wherein 5 represents the best performance and 0 represents the worst performance, as the rating scale is disclosed in the specification].
By ‘reasonable chemical resistance’-referring to a cured coating (film)—is meant in the specification that the chemical resistance of a film measured as described in the specification is 2 [rating scale 0-5, wherein 5 represents the best performance and 0 represents the worst performance, as the rating scale is disclosed in the specification].
By ‘good chemical resistance’-referring to a cured coating (film)—is meant in the specification that the chemical resistance of a film measured as described in the specification is 3 [rating scale 0-5, wherein 5 represents the best performance and 0 represents the worst performance, as the rating scale is disclosed in the specification].
By ‘very good chemical resistance’-referring to a cured coating (film)—is meant in the specification that the chemical resistance of a film measured as described in the specification is 4 [rating scale 0-5, wherein 5 represents the best performance and 0 represents the worst performance, as the rating scale is disclosed in the specification].
By ‘excellent chemical resistance’-referring to a cured coating (film)—is meant in the specification that the chemical resistance of a film measured as described in the specification is 5 [rating scale 0-5, wherein 5 represents the best performance and 0 represents the worst performance, as the rating scale is disclosed in the specification].
By ‘poor crosslinking efficiency’-referring to an entity—is meant in the specification that the entity has an end chemical resistance which is poor, or equally that the end chemical resistance of the entity is poor.
By ‘reasonable crosslinking efficiency’-referring to an entity—is meant in the specification that the entity has an end chemical resistance which is reasonable, or equally that the end chemical resistance of the entity is reasonable.
By ‘good crosslinking efficiency’-referring to an entity—is meant in the specification that the entity has an end chemical resistance which is good, or equally that the end chemical resistance of the entity is good.
By ‘very good crosslinking efficiency’-referring to an entity—is meant in the specification that the entity has an end chemical resistance which is very good, or equally that the end chemical resistance of the entity is very good.
By ‘excellent crosslinking efficiency’-referring to an entity—is meant in the specification that the entity has an end chemical resistance which is excellent, or equally that the end chemical resistance of the entity is excellent.
In the context of the specification, the genotoxicity is measured according to the ToxTracker® assay (Toxys, Leiden, the Netherlands) as described in the Examples. In the context of the specification by ‘positive induced genotoxicity’ is meant that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP is equal to or higher than 2-fold in at least one of 10, 25 and 50% cytotoxicity in the absence or presence of the metabolizing system rat S9 liver extract. In the context of the specification by ‘weakly positive induced genotoxicity’ is meant that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP is higher than 1.5-fold and lower than 2-fold in at least one of 10, 25 and 50% cytotoxicity (but lower than 2-fold at 10, 25 and 50% cytotoxicity) in the absence or presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA). In the context of the specification by ‘genotoxicity comparable with the naturally occurring background’ is meant that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP is lower than or equal to 1.5-fold at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA). The induction level of the genotoxicity reporters Bscl2-GFP and Rtkn-GFP is preferably lower than or equal to 1.5-fold at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA). In the context of the specification by ‘non-genotoxic’ (or equally ‘not genotoxic’) is meant that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP is lower than 2-fold—preferably equal to or lower than 1.9-fold, more preferably equal to or lower than 1.8-fold, for example equal to or lower than 1.7-fold, for example equal to or lower than 1.6-fold for example equal to or lower than 1.5-fold at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA).
By ‘room temperature’ is meant herein 23±1° C.
By ‘atmospheric pressure’ is meant in the specification pressure of 1 atm. By ‘standard conditions’ is meant in the specification room temperature and atmospheric pressure, collectively.
By ‘lower than’ is meant in the specification that the relevant maximum boundary value is not included in the range. By ‘higher than’ is meant in the specification that the relevant minimum boundary value is not included in the range.
By ‘rpm’ is meant revolutions per minute.
By ‘polyacrylics’ is meant in the specification any polymer comprising of reacted residues of acrylic acid and/or methacrylic acid and/or an ester of acrylic acid and/or an ester of methacrylic acid, and/or styrene, and/or acrylonitrile, and/or acrylamide, and/or esters of itaconic acid, and/or itaconic acid, and/or divinyl benzene, and/or methacrylonitrile, and/or vinyl esters and/or vinyl halides, and/or esters of fumaric acid, and/or fumaric acid; preferably by ‘polyacrylics’ is meant in the specification any polymer consisting of reacted residues of acrylic acid and/or methacrylic acid and/or an ester of acrylic acid and/or an ester of methacrylic acid, and/or styrene, and/or acrylonitrile, and/or acrylamide, and/or esters of itaconic acid, and/or itaconic acid, and/or divinyl benzene, and/or methacrylonitrile, and/or vinyl esters and/or vinyl halides, and/or esters of fumaric acid, and/or fumaric acid; preferably by ‘vinyl polymer’ is meant in the specification any polymer consisting of reacted residues of acrylic acid and/or methacrylic acid and/or an ester of acrylic acid and/or an ester of methacrylic acid, and/or styrene, and/or acrylonitrile, and/or acrylamide, and/or esters of itaconic acid, and/or itaconic acid, and/or divinyl benzene, and/or methacrylonitrile, and/or vinyl esters and/or vinyl halides, and/or esters of fumaric acid, and/or fumaric acid.
By ‘epoxide protons’ is meant in the specification the two protons of the methylene group (—CH2—) of an oxirane (also known as epoxy) group which group has the following formula
By ‘curing’ or ‘cure’ is meant in the specification the process of becoming ‘set’ that is to form an irreversibly crosslinked network (the so-called ‘cured form’ or ‘cured composition’), a material that can no longer flow, be melted or dissolved. Herein, the terms ‘curing’ ‘cure’ and ‘crosslinking’ are used interchangeably. the curing may take place either at standard conditions (as these are defined in the specification), or by using heat, or by using pressure, or by applying vacuum, or by irradiation, e.g. UV-radiation, or by any combination thereof.
The characterization of the physical state of a chemical entity, e.g. a composition is assessed at and refers to standard conditions. For example, if a composition is characterized as ‘liquid composition’ it means that this composition is liquid at room temperature and at atmospheric pressure.
The (aziridinyl hydroxy)-functional organic component (AZ-component) of the invention is as disclosed in the entire specification (including the claims). The term ‘AZ-component’ as used in the specification includes any and all of its preferments, combinations of its features and ranges as well as combinations of any and all of its preferments with any and all of the combinations of its features and ranges. Thus, any and all of the references to the AZ-component disclosed in this section 1—and its subsections—includes any and all of their preferments, combinations of their features and ranges as well as combinations of any and all of their preferments with any and all of the combinations of their features and ranges, are collectively referred to—in the entire specification—as the AZ-component.
The AZ-component is according to any one of Ala or A1 to A18 or any combination disclosed in the entire specification including the claims. More specifically, the (aziridinyl hydroxy)-functional organic component (AZ-component) is selected from the group consisting of i) to vi): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 having only two aziridine rings (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 having only three aziridine rings (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 having only four aziridine rings (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ4 of Formula A4 having only five aziridine rings (AZ4-compound), v) (aziridinyl hydroxy)-functional organic compound AZ5 of Formula A5 having only six aziridine rings (AZ5-compound), and vi) mixtures thereof, preferably the AZ-component is selected from the group consisting of i) to iv): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 having only two aziridine rings (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 having only three aziridine rings (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 having only four aziridine rings (AZ3-compound), and iv) mixtures thereof,
wherein
X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical, preferably X1 is a bivalent aliphatic organic radical;
X2 is a trivalent aliphatic organic radical or a trivalent aromatic organic radical, preferably X2 is a trivalent aliphatic organic radical;
X3 is a quadrivalent aliphatic organic radical or a quadrivalent aromatic organic radical, preferably X3 is a quadrivalent aliphatic organic radical;
X4 is a pentavalent aliphatic organic radical or a pentavalent aromatic organic radical, preferably X4 is a pentavalent aliphatic organic radical;
X5 is a hexavalent aliphatic organic radical or a hexavalent aromatic organic radical, preferably X5 is a hexavalent aliphatic organic radical;
and wherein each of the X1 to X5 consists of a collection of atoms covalently connected in a configuration that comprises —preferably consists of—linear and/or branched and/or ring structures, which collection of atoms is selected from the group consisting of i) to x): i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, iv) carbon, hydrogen and sulphur atoms, v) carbon, hydrogen, oxygen and nitrogen atoms, vi) carbon, hydrogen, nitrogen and sulphur atoms, vii) carbon, hydrogen, oxygen and sulphur atoms, viii) carbon, hydrogen, oxygen, nitrogen and sulphur, atoms, ix) carbon, hydrogen and silicon atoms, and x) carbon, hydrogen, oxygen and silicon atoms and xi) any combination of ix) and/or x) with any one or all of the iii) to viii),
and wherein each of the X1 to X5 has carbon atoms and hydrogen atoms, and wherein each of the X1 to X5 has optionally oxygen atoms and/or nitrogen atoms and/or sulphur atoms and/or silicon atoms,
and wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 may optionally comprise an ionic functional group, preferably the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 does not comprise an ionic functional group,
and wherein
Y is a monovalent organic radical selected from the group consisting of: i) monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B1, ii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B2, and iii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B3, preferably Y is a monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B1,
and wherein
R1 is selected from the group consisting of hydrogen and methyl; and
R2 is selected from the group consisting of hydrogen, methyl, and C2-C5 alkyl; and
R3 is selected from the group consisting of methyl, and C2-C4 alkyl; and
R4 is selected from the group consisting of hydrogen, methyl, and C2-C4 alkyl;
and wherein
the Y in each of the compounds A1 to A5 may be the same or different to each other and wherein each of the single covalent bonds between the Y and each one of the X1 to X5 is selected from the group consisting of carbon-carbon single bond, carbon-oxygen single bond and carbon-nitrogen single bond, preferably carbon-oxygen single bond and carbon-nitrogen single bond, more preferably carbon-oxygen single bond,
and wherein
each of the AZ1- to AZ5-compounds has a molecular weight determined via MALDI-TOF MS according to the description, of at least 600 and at most 10000, preferably at least 600 and at most 8000, more preferably at least 600 and at most 7000, even more preferably at least 600 and at most 6000, for example at least 600 and at most 5500, for example at least 600 and at most 5000, for example at least 600 and at most 4000, for example at least 600 and at most 3500, for example at least 600 and at most 3200, for example at least 600 and at most 3000, for example at least 600 and at most 2500, for example at least 600 and at most 2200, for example at least 600 and at most 2000, for example at least 630 and at most 10000, for example at least 630 and at most 8000, for example at least 630 and at most 7000, for example at least 630 and at most 6000, for example at least 630 and at most 5500, for example at least 630 and at most 5000, for example at least 630 and at most 4000, for example at least 630 and at most 3500, for example at least 630 and at most 3200, for example at least 630 and at most 3000, for example at least 630 and at most 2500, for example at least 630 and at most 2200, for example at least 630 and at most 2000, for example at least 640 and at most 10000, for example at least 640 and at most 8000, for example at least 640 and at most 7000, for example at least 640 and at most 6000, for example at least 640 and at most 5500, for example at least 640 and at most 5000, for example at least 640 and at most 4000, for example at least 640 and at most 3500, for example at least 640 and at most 3200, for example at least 640 and at most 3000, for example at least 640 and at most 2500, for example at least 640 and at most 2200, for example at least 640 and at most 2000, for example at least 650 and at most 10000, for example at least 650 and at most 8000, for example at least 650 and at most 7000, for example at least 650 and at most 6000, for example at least 650 and at most 5500, for example at least 650 and at most 5000, for example at least 650 and at most 4000, for example at least 650 and at most 3500, for example at least 650 and at most 3200, for example at least 650 and at most 3000, for example at least 650 and at most 2500, for example at least 650 and at most 2200, for example at least 650 and at most 2000, for example at least 700 and at most 10000, for example at least 700 and at most 8000, for example at least 700 and at most 7000, for example at least 700 and at most 6000, for example at least 700 and at most 5500, for example at least 700 and at most 5000, for example at least 700 and at most 4000, for example at least 700 and at most 3500, for example at least 700 and at most 3200, for example at least 700 and at most 3000, for example at least 700 and at most 2500, for example at least 700 and at most 2200, for example at least 700 and at most 2000, for example at least 750 and at most 10000, for example at least 750 and at most 8000, for example at least 750 and at most 7000, for example at least 750 and at most 6000, for example at least 750 and at most 5500, for example at least 750 and at most 5000, for example at least 750 and at most 4000, for example at least 750 and at most 3500, for example at least 750 and at most 3200, for example at least 750 and at most 3000, for example at least 750 and at most 2500, for example at least 750 and at most 2200, for example at least 750 and at most 2000, for example at least 800 and at most 10000, for example at least 800 and at most 8000, for example at least 800 and at most 7000, for example at least 800 and at most 6000, for example at least 800 and at most 5500, for example at least 800 and at most 5000, for example at least 800 and at most 4000, for example at least 800 and at most 3500, for example at least 800 and at most 3200, for example at least 800 and at most 3000, for example at least 800 and at most 2500, for example at least 800 and at most 2200, for example at least 800 and at most 2000, for example at least 850 and at most 10000, for example at least 850 and at most 8000, for example at least 850 and at most 7000, for example at least 850 and at most 6000, for example at least 850 and at most 5500, for example at least 850 and at most 5000, for example at least 850 and at most 4000, for example at least 850 and at most 3500, for example at least 850 and at most 3200, for example at least 850 and at most 3000, for example at least 850 and at most 2500, for example at least 850 and at most 2200, for example at least 850 and at most 2000, for example at least 900 and at most 10000, for example at least 900 and at most 8000, for example at least 900 and at most 7000, for example at least 900 and at most 6000, for example at least 900 and at most 5500, for example at least 900 and at most 5000, for example at least 900 and at most 4000, for example at least 900 and at most 3500, for example at least 900 and at most 3200, for example at least 900 and at most 3000, for example at least 900 and at most 2500, for example at least 900 and at most 2200, for example at least 900 and at most 2000, for example at least 950 and at most 10000, for example at least 950 and at most 8000, for example at least 950 and at most 7000, for example at least 950 and at most 6000, for example at least 950 and at most 5500, for example at least 950 and at most 5000, for example at least 950 and at most 4000, for example at least 950 and at most 3500, for example at least 950 and at most 3200, for example at least 950 and at most 3000, for example at least 950 and at most 2500, for example at least 950 and at most 2200, for example at least 950 and at most 2000, for example at least 1000 and at most 10000, for example at least 1000 and at most 8000, for example at least 1000 and at most 7000, for example at least 1000 and at most 6000, for example at least 1000 and at most 5500, for example at least 1000 and at most 5000, for example at least 1000 and at most 4000, for example at least 1000 and at most 3500, for example at least 1000 and at most 3200, for example at least 1000 and at most 3000, for example at least 1000 and at most 2500, for example at least 1000 and at most 2200, for example at least 1000 and at most 2000, for example at least 1100 and at most 10000, for example at least 1100 and at most 8000, for example at least 1100 and at most 7000, for example at least 1100 and at most 6000, for example at least 1100 and at most 5500, for example at least 1100 and at most 5000, for example at least 1100 and at most 4000, for example at least 1100 and at most 3500, for example at least 1100 and at most 3200, for example at least 1100 and at most 3000, for example at least 1100 and at most 2500, for example at least 1100 and at most 2200, for example at least 1100 and at most 2000, for example at least 1200 and at most 10000, for example at least 1200 and at most 8000, for example at least 1200 and at most 7000, for example at least 1200 and at most 6000, for example at least 1200 and at most 5500, for example at least 1200 and at most 5000, for example at least 1200 and at most 4000, for example at least 1200 and at most 3500, for example at least 1200 and at most 3200, for example at least 1200 and at most 3000, for example at least 1200 and at most 2500, for example at least 1200 and at most 2200, for example at least 1200 and at most 2000 Da.
Preferably the X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical other than a bivalent radical of bisphenol A.
Preferably, the AZ-component according to any one of the preceding claims, wherein the X1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical other than a bivalent organic radical selected from the group consisting of bivalent radical of bisphenol A, bivalent radical of bisphenol AP, bivalent radical of bisphenol AF, bivalent radical of bisphenol B, bivalent radical of bisphenol BP, bivalent radical of bisphenol C, bivalent radical of bisphenol C2, bivalent radical of bisphenol E, bivalent radical of bisphenol F, bivalent radical of bisphenol G, bivalent radical of bisphenol M, bivalent radical of bisphenol S, bivalent radical of bisphenol P, bivalent radical of bisphenol PH, bivalent radical of bisphenol TMC, bivalent radical of bisphenol Z, bivalent radical of dinitrobisphenol A, bivalent radical of tetrabromobisphenol A, and combinations thereof, preferably X1 is a bivalent aliphatic organic radical.
Preferably, the AZ-component according to any one of the preceding claims, wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 comprises at least one structural unit or a combination of structural units selected from the group consisting of unit 1, unit 2, unit 3, unit 4, unit 5, unit 6, unit 7, unit 8, unit 9, unit 10, and unit 11, preferably comprises at least one structural unit or a combination of structural units selected from the group consisting of unit 1, unit 4, unit 9, unit 10 and unit 11, as the units 1 to 11 are depicted below:
wherein
R′ is selected from the group consisting of hydrogen and methyl; and
j is an integer ranging from 1 to 5, preferably from 1 to 3; and
n is an integer ranging from and including 2 up to and including 50, preferably from and including 2 up to and including 40, more preferably from and including 2 up to and including 30, most preferably from and including 2 up to and including 20, for example from and including 2 up to and including 15, for example from and including 2 up to and including 10, for example from and including 2 up to and including 5, for example the n is 2, for example from and including 3 up to and including 50, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15, for example from and including 3 up to and including 10, for example from and including 3 up to and including 5, for example the n is 3, for example from and including 4 up to and including 50, for example from and including 4 up to and including 40, for example from and including 4 up to and including 30, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15, for example from and including 4 up to and including 10, for example from and including 4 up to and including 5, for example the n is 4, for example from and including 5 up to and including 50, for example from and including 5 up to and including 40, for example from and including 5 up to and including 30, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15, for example from and including 5 up to and including 10, for example the n is 5, for example from and including 6 up to and including 50, for example from and including 6 up to and including 40, for example from and including 6 up to and including 30, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15, for example from and including 6 up to and including 10, for example the n is 6, for example from and including 7 up to and including 50, for example from and including 7 up to and including 40, for example from and including 7 up to and including 30, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15, for example from and including 7 up to and including 10, for example the n is 7, for example from and including 8 up to and including 50, for example from and including 8 up to and including 40, for example from and including 8 up to and including 30, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15, for example from and including 8 up to and including 10, for example the n is 8, for example from and including 9 up to and including 50, for example from and including 9 up to and including 40, for example from and including 9 up to and including 30, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15, for example from and including 9 up to and including 10, for example the n is 9, for example from and including 10 up to and including 50, for example from and including 10 up to and including 40, for example from and including 10 up to and including 30, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15, for example the n is 10.
Preferably, the AZ-component according to any one of the preceding claims, wherein
R1 is selected from the group consisting of hydrogen and methyl; and
R2 is selected from the group consisting of hydrogen, methyl, and ethyl; and
R3 is selected from the group consisting of methyl, and C2-C4 alkyl; and
R4 is selected from the group consisting of hydrogen, methyl, and ethyl.
Preferably, the AZ-component according to any one of the preceding claims, wherein the aggregate number of carbon atoms in R1, and R2 and R3 and R4 is at most 9, preferably at most 4, more preferably at most 2, for example at most 1.
Preferably, The AZ-component according to any one of the preceding claims, wherein the X1 and/or the X2 and/or the X3 and/or the X4 and/or the X5 does not contain one or any combination of the following structural units BP1, BP2, BP3, and BS
Preferably, the AZ-component according to any one of the preceding claims, wherein the X1, and/or the X2 and/or the X3 and/or the X4 and/or the X5 comprises at least one unit 11 as a structural unit.
Preferably, the X1 is the bivalent aliphatic organic radical of Formula A1a′
wherein
R′ is selected from the group consisting of hydrogen and methyl; and
j is an integer ranging from 1 to 5, preferably from 1 to 3; and
n is an integer ranging from and including 2 up to and including 50, preferably from and including 2 up to and including 40, more preferably from and including 2 up to and including 30, most preferably from and including 2 up to and including 20, for example from and including 2 up to and including 15, for example from and including 2 up to and including 10, for example from and including 2 up to and including 5, for example the n is 2, for example from and including 3 up to and including 50, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15, for example from and including 3 up to and including 10, for example from and including 3 up to and including 5, for example the n is 3, for example from and including 4 up to and including 50, for example from and including 4 up to and including 40, for example from and including 4 up to and including 30, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15, for example from and including 4 up to and including 10, for example from and including 4 up to and including 5, for example the n is 4, for example from and including 5 up to and including 50, for example from and including 5 up to and including 40, for example from and including 5 up to and including 30, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15, for example from and including 5 up to and including 10, for example the n is 5, for example from and including 6 up to and including 50, for example from and including 6 up to and including 40, for example from and including 6 up to and including 30, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15, for example from and including 6 up to and including 10, for example the n is 6, for example from and including 7 up to and including 50, for example from and including 7 up to and including 40, for example from and including 7 up to and including 30, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15, for example from and including 7 up to and including 10, for example the n is 7, for example from and including 8 up to and including 50, for example from and including 8 up to and including 40, for example from and including 8 up to and including 30, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15, for example from and including 8 up to and including 10, for example the n is 8, for example from and including 9 up to and including 50, for example from and including 9 up to and including 40, for example from and including 9 up to and including 30, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15, for example from and including 9 up to and including 10, for example the n is 9, for example from and including 10 up to and including 50, for example from and including 10 up to and including 40, for example from and including 10 up to and including 30, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15, for example the n is 10.
Preferably, the AZ-component according to any one of the preceding claims, wherein each of the X1 to X5 contains only single covalent bonds, or both single and double covalent bonds, and wherein the single covalent bonds are selected from the group consisting of carbon-carbon single bond, carbon-hydrogen single bond, carbon-nitrogen single bond, carbon-sulphur single bond, carbon-silicon single bond, silicon-oxygen single bond, nitrogen-hydrogen single bond, sulphur-oxygen single bond, carbon-oxygen single bond wherein the oxygen is bonded to a hydrogen forming a hydroxyl group, silicon-oxygen-silicon single bonds, and wherein the double covalent bonds are selected from the group consisting of carbon-carbon double bond, carbon-nitrogen double bond, sulphur-oxygen double bond, carbon-oxygen double bond wherein the carbon is a member of a ring structure, and carbon-oxygen double bond wherein the carbon is bonded to another two carbons via carbon-carbon single bonds, carbon-oxygen double bond wherein the carbon is bonded to another oxygen via single bond and to a nitrogen via a single bond, carbon-oxygen double bond wherein the carbon is bonded to two nitrogens via carbon-nitrogen single bonds, carbon-oxygen double bond wherein the carbon is bonded to another two oxygens via single bonds; preferably the double covalent bonds are selected from the group consisting of carbon-carbon double bond, carbon-nitrogen double bond, sulphur-oxygen double bond, carbon-oxygen double bond wherein the carbon is a member of a ring structure, and carbon-oxygen double bond wherein the carbon is bonded to another two carbons via carbon-carbon single bonds, carbon-oxygen double bond wherein the carbon is bonded to another oxygen via single bond and to a nitrogen via a single bond, carbon-oxygen double bond wherein the carbon is bonded to two nitrogens via carbon-nitrogen single bonds.
Preferably, the aggregate number of carbon and hydrogen atoms in X1 and/or X2 and/or X3 and/or X4 and/or X5 is at least 5, preferably at least 10, more preferably at least 15, most preferably at least 20, for example at least 25, for example at least 30, for example at least 35, for example at least 40, for example at least 45, for example at least 50, for example at least 55, for example at least 60, for example at least 65, for example at least 70, for example at least 75, for example at least 80, for example at least 85, for example at least 90, for example at least 95, for example at least 97, for example at least 98, for example at least 99, for example 100% as to the aggregate number of all the atoms present in X1 and/or X2 and/or X3 and/or X4 and/or X5, respectively.
Preferably, the aggregate number of all the atoms present in X1 and/or X2 and/or X3 and/or X4 and/or X5 is at most 600, preferably at most 550, more preferably at most 500, most preferably at most 450, for examples at most 400, for example at most 350, for example at most 300, for example at most 250, for example at most 200.
Preferably, the AZ-component is selected from the group consisting of i) to v): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ5 of Formula A5 (AZ5-compound), and vi) mixtures thereof, and
wherein
the AZ1-compound is selected from the group consisting of compounds having the Formula A1a, and compounds having the Formula A1b, as each of these Formulae A1a-A1d is described below
wherein each of the n in Formula A1a is independently selected, and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4; and
wherein the R in Formula A1b is a C3-C10 saturated hydrocarbylene, and wherein each of the n in Formula A1b is independently selected and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4; and
wherein each of the n in Formula A1c is independently selected, and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, and
wherein the R in Formula A1d is a C3-C10 saturated hydrocarbylene, and wherein each of the n in Formula A1d is independently selected and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 10, more preferably from and including 2 up to and including 7, most preferably from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 7, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, and
wherein
the AZ2-compound is selected from the group consisting of compounds having the Formula A2a, compounds having the Formula A2b, compounds having the Formula A2c, compounds having the Formula A2d, compounds having the Formula A2e, as each of these Formulae A2a-A2e is described below
wherein the n in Formula A2a is an integer ranging from and including 2 up to and including 20, for example from and including 2 up to and including 10, for example from and including 2 up to and including 8, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 8, for example from and including 4 up to and including 20, for example from and including 4 up to and including 10, for example from and including 4 up to and including 8, for example from and including 5 up to and including 20, for example from and including 5 up to and including 10, for example from and including 5 up to and including 8, for example from and including 6 up to and including 20, for example from and including 6 up to and including 10, for example from and including 6 up to and including 8, for example n is equal to 7;
and
wherein each of the n in Formula A2b is independently selected and each of the n in Formula A2b is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 12, most preferably from and including 2 up to and including 11, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15 for example from and including 3 up to and including 12 for example from and including 3 up to and including 11, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15 for example from and including 4 up to and including 12 for example from and including 4 up to and including 11, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15 for example from and including 5 up to and including 12 for example from and including 5 up to and including 11, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15 for example from and including 6 up to and including 12 for example from and including 6 up to and including 11, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15 for example from and including 7 up to and including 12 for example from and including 7 up to and including 11, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15 for example from and including 8 up to and including 12 for example from and including 8 up to and including 11, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15 for example from and including 9 up to and including 12 for example from and including 9 up to and including 11, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15 for example from and including 10 up to and including 12 for example from and including 10 up to and including 11, for example n is equal to 11;
and
wherein each of the n in Formula A2c is independently selected and each of the n in Formula A2c is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 12, most preferably from and including 2 up to and including 11, for example from and including 3 up to and including 20, for example from and including 3 up to and including 15 for example from and including 3 up to and including 12 for example from and including 3 up to and including 11, for example from and including 4 up to and including 20, for example from and including 4 up to and including 15 for example from and including 4 up to and including 12 for example from and including 4 up to and including 11, for example from and including 5 up to and including 20, for example from and including 5 up to and including 15 for example from and including 5 up to and including 12 for example from and including 5 up to and including 11, for example from and including 6 up to and including 20, for example from and including 6 up to and including 15 for example from and including 6 up to and including 12 for example from and including 6 up to and including 11, for example from and including 7 up to and including 20, for example from and including 7 up to and including 15 for example from and including 7 up to and including 12 for example from and including 7 up to and including 11, for example from and including 8 up to and including 20, for example from and including 8 up to and including 15 for example from and including 8 up to and including 12 for example from and including 8 up to and including 11, for example from and including 9 up to and including 20, for example from and including 9 up to and including 15 for example from and including 9 up to and including 12 for example from and including 9 up to and including 11, for example from and including 10 up to and including 20, for example from and including 10 up to and including 15 for example from and including 10 up to and including 12 for example from and including 10 up to and including 11, for example n is equal to 11;
and
and
wherein
the AZ3-compound is selected from the group consisting of compounds having the Formula A3a
wherein each of the n in Formula A3a is independently selected, and each of the n in Formula A3a is an integer ranging from and including 2 up to and including 20, preferably from and including 2 up to and including 15, more preferably from and including 2 up to and including 10, most preferably from and including 2 up to and including 9, for example from and including 2 up to and including 8, for example from and including 2 up to and including 7, for example from and including 2 up to and including 6, for example from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 2 up to and including 3, for example n is equal to 3, for example n is equal to 2;
and
wherein
the AZ5-compound is selected from the group consisting of compounds having the Formula A5a
wherein each of the n in Formula A5a is independently selected and each of the n in Formula A5a is an integer ranging from and including 2 up to and including 40, preferably from and including 2 up to and including 30, more preferably from and including 2 up to and including 20, most preferably from and including 2 up to and including 10, for example from and including 2 up to and including 9, for example from and including 2 up to and including 8, for example from and including 2 up to and including 7, for example from and including 2 up to and including 6, for example from and including 2 up to and including 5, for example from and including 2 up to and including 4, for example from and including 3 up to and including 40, for example from and including 3 up to and including 30, for example from and including 3 up to and including 20, for example from and including 3 up to and including 10, for example from and including 3 up to and including 9, for example from and including 3 up to and including 8, for example from and including 3 up to and including 7, for example from and including 3 up to and including 6, for example from and including 3 up to and including 5, for example from and including 3 up to and including 4, for example n is equal to 4, for example n is equal to 3.
Preferably, the X1 and/or the X2 and/or the X3 and/or the X4 and/or the X5 does not contain any structural unit of (or equally derived from) phenol formaldehyde resins (also known as phenolic resins); examples of phenol-formaldehyde (PF) resins include novolacs (acid-catalyzed PF resins with a formaldehyde to phenol ratio of equal to or lower than one), and resols (base-catalyzed PF resins with a formaldehyde to phenol ratio of greater than one, usually equal to 1.5).
Preferably, the AZ-component is selected from the group consisting of AZ1-compound and wherein the AZ1-compound is the compound of the following formula
Preferably, the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
Preferably, the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
Preferably, the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula
Preferably, the AZ1-compound and/or the AZ2-compound and/or the AZ3-compound and/or the AZ4-compound and/or the AZ5-compound comprises polyoxyethylene (—O—CH2—CH2—)x group(s), and/or polyoxypropylene (—O—CHCH3—CH2—)x group(s) and/or polytetrahydrofurane (—O—CH2—CH2—CH2—CH2)x groups, preferably in an amount of at least 10 and at most 92, more preferably at least 15 and at most 85, even more preferably at least 25 and at most 75, for example at least 30 and at most 65, for example at least 35 and at most 55 mol % relative to the corresponding AZ1-compound and/or the AZ2-compound and/or the AZ3-compound and/or the AZ4-compound and/or the AZ5-compound to which these mol % refer to.
Preferably, the AZ1-compound and/or the AZ2-compound and/or the AZ3-compound and/or the AZ4-compound and/or the AZ5-compound comprises methoxy poly(ethylene glycol) (MPEG) and/or poly(ethylene glycol) (PEG) groups (each of these groups with a calculated number average molecular weight (Mn) higher than 1600, preferably 2200 Da), preferably in an amount of at least 1 and at most 35, more preferably at least 3 and at most 30, even more preferably at least 5 and at most 27, for example at least 7 and at most 20, for example at least 8 and at most 17, for example at least 9 and at most 15, for example at least 10 and at most 13 mol % relative to the corresponding AZ1-compound and/or the AZ2-compound and/or the AZ3-compound and/or the AZ4-compound and/or the AZ5-compound to which these mol % refer to.
Preferably, the AZ1-compound and/or the AZ2-compound and/or the AZ3-compound and/or the AZ4-compound and/or the AZ5-compound comprise groups which have a sulfonate functionality, which can, for instance, be obtained by reacting epoxy groups with amino-functional sulfonic acid groups like 2-(cyclohexylamino) ethane sulfonic acid and 3-(cyclohexyl-amino)propane sulfonic acid. These groups which have a sulfonate functionality are preferably neutralized with a base, more preferably with an inorganic base. The reaction between an epoxy group and a group having a sulfonate functionality can, for instance, be done by reacting part of the epoxy groups of the polyepoxide prior to reaction with an aziridine-AZIR—as this is defined in the specification; see section 2—, or during the reaction with the aziridine-AZIR or stopping the reaction between the polyepoxide and the aziridine-AZIR at a certain moment, e.g. by distilling off the excess of the aziridine-AZIR followed by reacting some or all of the remaining epoxy groups with the amino-functional sulfonic acid molecules [2-(cyclohexylamino) ethane sulfonic acid and 3-cyclohexyl-amino)propane sulfonic acid]. Alternatively, a salt of taurine can be used as well, and preferably the taurine is neutralized with sodium hydroxide or potassium hydroxide or lithium hydroxide.
Preferably the AZ-component may be cured at a temperature of at least 0 and at most 85, preferably at least 15 and at most 80, more preferably at least 23 and at most 70, most preferably at least 30 and at most 85, for example at least 15 and at most 30° C., for time periods that may vary and are preferably of at most 60, more preferably at most 30, even more preferably at most 15 minutes.
In principle, the (aziridinyl hydroxy)-functional organic component (AZ-component) as this is described in the specification, is preferably obtained by reacting an aziridine of Formula AZIR (abbreviated as ‘aziridine-AZIR’) with at least a polyepoxide having at least two and at most six epoxy groups.
wherein
Exemplary aziridines of Formula AZIR include but are not limited to propylene imine, 1,2-dimethyl aziridine, 2,2-dimethyl aziridine, 2-ethyl aziridine, butyl aziridine.
More particularly, the AZ1-compound (as this is described in the specification) is preferably obtained by reacting an aziridine of Formula AZIR with at least a polyepoxide having two epoxy groups. Exemplary polyepoxides having two epoxy groups include but are not limited to any glycidyl ether of a dihydroxy compound (which dihydroxy compound has a molecular weight of at least 374 Da), for instance, a polypropylene glycol diglycidyl ether like the ERISYS® GE-24 available by CVC Thermoset Specialties.
More particularly, the AZ2-compound (as this is described in the specification) is preferably obtained by reacting an aziridine of Formula AZIR with at least a polyepoxide having three epoxy groups. Exemplary polyepoxides having three epoxy groups include but are not limited to any glycidyl ether of a tri functional hydroxy compound with a molecular weight of at least 261 Da, as well as the ERISYS® GE-36, and EPALLOY® 9000 both available by CVC Thermoset Specialties.
More particularly, the AZ3-compound (as this is described in the specification) is preferably obtained by reacting an aziridine of Formula AZIR with at least a polyepoxide having four epoxy groups. Exemplary polyepoxides having four epoxy groups include but are not limited to any glycidyl ether of a tetra hydroxy compound with a molecular weight of at least 148 Da, like for instance the glycidyl ether of ethoxylated penta like Polyol R4410, available from Perstop.
More particularly, the AZ4-compound (as this is described in the specification) is preferably obtained by reacting an aziridine of Formula AZIR with at least a polyepoxide having five epoxy groups. Exemplary polyepoxides having five epoxy groups include but are not limited to any glycidyl ether of a penta hydroxy compound.
More particularly, the AZ5-compound (as this is described in the specification) is preferably obtained by reacting an aziridine of Formula AZIR with at least a polyepoxide having six epoxy groups. Exemplary polyepoxides having six epoxy groups include but are not limited to any glycidyl ether of a hexa hydroxy compound for instance the hexaglycidyl ether of dipentaerythritol.
The reaction (the terms refers to and encompasses any and all of the reactions mentioned just above in this section) takes places at any temperature from 20 to 110° C., more preferably from 50 to 95° C., and most preferably from 70 to 90° C. and its progress can be monitored via 1H-NMR spectroscopy. The reaction is carried out for as long as the epoxy groups are reacted; this is monitored and verified by 1H-NMR spectroscopy where the characteristic 1H-NMR chemical shift of the epoxy protons (2.5-3 ppm) is disappeared. Preferably the reaction is carried out without solvent. However, if desired (for instance to reduce the viscosity), one or more solvents, e.g. methanol, ethanol, toluene, can be used during or after the reaction. If a solvent is used, it is often convenient to first dissolve the polyepoxide in the solvent (or mixture of solvents) before adding the aziridine-AZIR to the reaction mixture. The molar ratio of the mol of the aziridine groups of the aziridine-AZIR to the mol of the epoxy groups of the polyepoxide is at least 1 and at most 8, more preferably at least 1 and at most 4, even more preferably at least 1.1 and at most 3 and most preferably at least 1.2 and at most 2.2. Once the reaction is completed, the residual aziridine-AZIR is distilled off, preferably at a temperature from 60 to 90° C., more preferably from 65 to 80° C., and at reduced pressure, for example from 20 to 50 mbar, preferably from 30-45 mbar. Preferably once the reaction is completed, the residual aziridine-AZIR is distilled off at reduced pressure from 20 to 50 mbar at 70° C., more preferably from 30 to 45 mbar at 70° C. Subsequently, a further distillation step for the removal of any unreacted aziridine-AZIR and any other volatiles is carried out at 25 to 40° C. at 2 to 4 mbar, until no aziridine-AZIR could be detected by 1H-NMR spectroscopy. It is often useful to add an additional solvent to the reaction mixture prior to or during distillation, to facilitate the removal of the excess of the aziridine-AZIR. If desired, a base can be used during the reaction, to reduce possible sources of acid. Bases include both organic bases, like tertiary amines or inorganic bases like sodium or potassium carbonate or for instance calcium hydroxide. The inorganic bases can be filtered off after the reaction is completed.
For example, an AZ2-compound of Formula A2d
may be prepared by reacting EPALLOY® 9000 (6.26 mmol) (available by CVC Thermoset Specialties) with propylene imine (70.22 mmol) at 80° C. for 3 h in the presence of potassium carbonate (250 mg).
A high excess of propylene imine is typically used to dissolve EPALLOY® 9000 (the molar ratio of the mol of aziridine-AZIR to the mol of the epoxy groups. The reaction may be monitored via 1H-NMR. After 3 h at 80° C., the chemical shifts of the epoxide protons were not visible in the 1H-NMR; only some small peaks due to impurities. There has been no change in the 1H-NMR spectrum once the reaction mixture was left at 80° C. from 3 to 22 h. The reaction mixture was cooled down to room temperature; it was diluted with toluene. The potassium carbonate was filtered off, and the excess of propylene imine was distilled off with toluene at 70° C. and 40 mbar. The residue was held at 90-95° C. and at a reduced pressure of 3-4 mbar (oil pump) for 2 h, to remove any residual propylene imine and the toluene. The reaction product solidified quickly after cooling. The 1H-NMR did not show any peaks attributed to any residual propylene imine.
In principle, a process for making an AZ-compound wherein the Y is a monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B2, or a monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B3, is preferably obtained by reacting a hydroxy cyclohexene oxide with an isocyanurate of a diisocyanate, followed by a reaction with an aziridine-AZIR, e.g. propylene imine. For example, an AZ-component wherein the Y is a monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B2, monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B3, may be prepared by 1-hydroxy cyclohexene oxide (see Formula below)
which is obtained by reacting peracetic acid epoxidation of 1-hydroxy cyclohexene. The 1-hydroxy cyclohexene oxide is reacted with the isocyanurate of hexamethylene diisocyanate and subsequently reacted with a 3-fold excess of propylene imine, at 80° C. for 24 h. Afterwards, the excess of propylene imine is distilled off at a temperature of 50° C. and at reduced pressure. The resulting AZ-compound has a molecular weight of 1018 Da.
Alternatively, a polyoxyalkylene which comprises either at least one amino-functional group (preferably a secondary amino-functional group) or at least one carboxylic acid functional group, is reacted with some epoxy groups of a polyepoxide, before the reaction of the polyepoxide with the aziridine-AZIR, as this was described above. This may be a reaction scheme that may introduce polyether groups in any one of the X1 to X5.
Alternatively, an aziridine-AZIR may be partly reacted with a polyoxyalkylene which comprises at least one carboxylic acid functional group, prior to the reaction of the aziridine-AZIR with the polyepoxide, as this was described above. This may be a reaction scheme that may introduce polyether groups in any one of the X1 to X5.
Preferably, a mono-hydroxy or mono-amine functional polyether can be reacted in a 1:1 molar ratio with 2,4-toluene diisocyanate, and the reaction of which can be subsequently reacted with some of the hydroxyl groups which are formed after the reaction of the imine with the epoxy compound.
The liquid compositions of the invention are as disclosed in the entire specification, including the claims. The term ‘liquid compositions of the invention’ (or alternatively ‘inventive liquid compositions’) as used in the specification includes any and all of its preferments, combinations of its features and ranges as well as combinations of any and all of its preferments with any and all of the combinations of its features and ranges. Thus, any and all of the inventive liquid compositions disclosed in this section 3 includes any and all of their preferments, combinations of their features and ranges as well as combinations of any and all of their preferments with any and all of the combinations of their features and ranges, are collectively referred to—in the entire specification including the claims—as the inventive liquid compositions.
The inventive liquid compositions are according to any one of A19 to A34 and as disclosed in the entire specification, including the claims. More specifically, the inventive liquid compositions at 23±1° C. and at atmospheric pressure, comprise
The inventive liquid compositions may be prepared by mixing the liquid medium—as this disclosed in the entire specification including the claims with the AZ-component—as this is disclosed in the entire specification including the claims. The mixing of the liquid medium and the AZ-component may be carried out at standard conditions.
The inventive liquid compositions may be solutions in an organic solvent, solutions in water, aqueous dispersions (with or without an organic solvent). Solubilizing the AZ-component in an organic solvent can be done by gentle stirring, if desired under mild heating, e.g. up to 40° C. to facilitate and accelerate the dissolution. If desired, mixtures of organic solvents or mixtures of water and organic solvents can be used. If desired other components can be combined in the solution of the AZ-component, including for example plasticizers, bases (preferred bases for neutralization are inorganic bases like the hydroxides of sodium, potassium or lithium, secondary amines, and tertiary amines), and dispersants. If desired the AZ-component can be dispersed in water by any technique, preferably using one or more bases like tertiary amines or inorganic bases like sodium hydroxide, by either using the AZ-component as such or first solubilizing the AZ-component in a preferably water-miscible solvent, adding a dispersant preferably a non-ionic dispersant; even more preferably, the dispersant is polymeric in nature and contains ionic functional groups, e.g. polyethylene oxide groups and/or sulphonate groups. Water is added to the mixture above under stirring and the mixture can be diluted with additional water if desired to reach the targeted solids content of the final dispersion. If desired, the solvent can be removed once the aqueous dispersion is obtained.
Preferably, the inventive liquid compositions are aqueous dispersions comprising water in an amount of at least 20 and at most 55 wt % on the total weight of the liquid composition (in this case on the total weight of the aqueous dispersion), and wherein and said aqueous dispersions have a pH determined according to the ISO 976:2013 and according to the description, of at least 7.5 and at most 14.0, preferably at least 8.0 and at most 14.0, for example at least 8.5 and at most 13.5, for example at least 9.0 and at most 13.0, for example at least 9.2 and at most 12.5, for example at least 9.4 and at most 12.0, for example at least 10 and at most 13, for example at least 10.5 and at most 12.0, for example at least 10.5 and at most 11.6, for example at least 10.5 and at most 11.5. Dispersions in water facilitate dosing to aqueous polymer systems and can reduce VOC levels since less or no organic solvent is needed to obtain a manageable viscosity for dosing. The dispersions can optionally be made with the help of an organic solvent which can be removed after dissipating the components in water. Typically, the removal of the organic solvent is done by distillation.
Preferably, the inventive liquid composition comprises water in an amount of at most 90, preferably at most 85, more preferably at most 80, most preferably at most 75, for example at most 70, for example at most 65, for example at most 60, for example at most 55, for example at most 50, for example at most 45, for example at most 40, for example at most 35, for example at most 30, for example at most 25, for example at most 20, for example at most 15, for example at most 10, for example at most 5, for example at most 2, for example at most 1 wt % on the total weight of the inventive liquid composition, for example the inventive liquid composition is free of water.
Preferably, the inventive liquid composition comprises water in an amount of at least 70 and at most 90, preferably at least 75 and at most 85 wt % on the total weight of the inventive liquid composition, and the AZ-compound in an amount of at least 10 and at most 30, preferably at least 15 and at most 25 wt % on the total weight of the inventive liquid composition.
Preferably, the inventive liquid composition comprises water in an amount of at least 50 and at most 75, preferably at least 55 and at most 70 wt % on the total weight of the inventive liquid composition, and the AZ-compound in an amount of at least 25 and at most 50, preferably at least 30 and at most 45 wt % on the total weight of the inventive liquid composition.
Preferably, the inventive liquid composition comprises water in an amount of at least 40 and at most 70, preferably at least 45 and at most 65 wt % on the total weight of the inventive liquid composition, and the AZ-compound in an amount of at least 30 and at most 60, preferably at least 35 and at most 55 wt % on the total weight of the inventive liquid composition.
Preferably, the water—in the inventive liquid composition—is present in an amount of at least 30 and at most 95, preferably at least 40 and at most 85, for example at least 45 and at most 85, for example at least 50 and at most 70, for example at least 55 and at most 65 wt % on the total weight of the inventive liquid composition, and wherein the total amount of all the components that make up the inventive liquid composition totals 100 wt %.
Preferably, the inventive liquid composition comprises an organic solvent in an amount of at most 40, preferably at most 30, for example at most 25, for example at most 20, for example at most 12, for example at most 10, for example at most 8, for example at most 5, for example at most 4, for example at most 3, for example at most 2, for example at most 1, for example at most 0.5, for example at most 0.2, for example at most 0.1 wt % on the total weight of the inventive liquid composition.
Preferably, the inventive liquid composition is free of an organic solvent.
Preferably, the inventive liquid composition has a pH determined according to the ISO 976:2013 and according to the description, of at least 7.5 and at most 14.0, preferably at least 8.0 and at most 14.0, for example at least 8.5 and at most 13.5, for example at least 9.0 and at most 13.0, for example at least 9.2 and at most 12.5, for example at least 9.4 and at most 12.0, for example at least 10 and at most 13, for example at least 10.5 and at most 12.0, for example at least 10.5 and at most 11.6, for example at least 10.5 and at most 11.5, with the proviso that the inventive liquid composition comprises water in an amount of at least 20, preferably at least 25, more preferably at least 30, most preferably at least 35 wt % on the total weight of the inventive liquid composition.
Preferably, the inventive liquid composition comprises a component T selected from the group consisting of: i) organic compounds having a molecular weight determined via MALDI-TOF MS according to the description, lower than 600 Da and comprising at least one aziridine ring, and ii) mixtures thereof, in an amount, determined via LC-MS according to the description, of at most 5, preferably at most 4, more preferably at most 3, for example at most 2, for example at most 1, for example at most 0.5, for example at most 0.1, for example at most 0.05 wt % on the total weight of the AZ-compound.
Preferably, the inventive liquid composition is free of component T.
The inventive liquid composition may comprise chloride; preferably the amount of chloride determined according to the ASTM D1726-11(2019), is at most 0.3, preferably at most 0.2, more preferably at most 0.1, for example at most 0.05, for example at most 0.03 wt % on the total weight of the inventive liquid composition.
Preferably, the inventive liquid composition is free of chloride.
Preferably, the inventive liquid composition further comprises:
When the inventive liquid compositions further comprise a polymer—as this disclosed in the entire specification—then such inventive liquid composition may be prepared by mixing the liquid medium—as this disclosed in the entire specification including the claims with the AZ-component—as this is disclosed in the entire specification including the claims and the polymer—as this is disclosed in the entire specification-. The mixing of the liquid medium and the AZ-component and the polymer may be carried out at standard conditions.
Preferably, the polymer is selected from the group consisting of polyesters, polyamides, polycarbonates, polyimides, alkyds, uralkyds, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, preferably the polymer is selected from the group consisting of polyamides, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, most preferably the polymer is selected from the group consisting of polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof.
Preferably, the polymer is present in an amount of at least 5 and at most 65, preferably at least 10 and at most 60, more preferably at least 20 and at most 55, for example at least 30 and at most 50 wt % on the total weight of the aqueous composition, and wherein the total amount of all the components that make up the mixture totals 100 wt %.
Preferably, the inventive liquid compositions are coating compositions, preferably liquid coating compositions.
The inventive liquid compositions may optionally (further) comprise other components, such as pigments and/or waxes, and/or the usual (processing) additives, for example degassing agents—if the inventive liquid compositions are used in powder coatings-, smoothness, appearance enhancing agents or (light) stabilizers.
Suitable stabilizers include for example primary and/or secondary antioxidants and UV stabilizers for example quinones, (sterically hindered) phenolic compounds, phosphonites, phosphites, thioethers and HALS (hindered amine light stabilizers). Examples of suitable degassing agents include cyclohexane dimethanol bisbenzoate, benzoin.
In yet another aspect, the invention provides for a cured form of an inventive liquid composition as the latter disclosed in the entire specification.
The curing of the inventive liquid compositions may take place either by chemical reaction (resulting in the formation of irreversible covalent chemical bonds) or a combination of physical drying and chemical reaction. The curing of an inventive liquid composition may take place either at standard conditions (as these are defined in the specification), or by using heat, or by using pressure, or by applying vacuum, or by irradiation, e.g. UV-radiation, or by any combination thereof. Preferably an inventive liquid composition may be cured at a temperature of at least 0 and at most 85, preferably at least 15 and at most 80, more preferably at least 23 and at most 70, most preferably at least 30 and at most 85, for example at least 15 and at most 30° C., for time periods that may vary and are preferably of at most 60, more preferably at most 30, even more preferably at most 15 minutes.
The liquid compositions of the invention may be cured in the presence of a cationic initiator.
The liquid compositions of the invention may be cured in the presence of a suitable polymer such as for example a polymer (preferably employed in an aqueous dispersion) which has an acid value determined according to the ASTM D1639-90(1996)e1 in the range from 5 to 300, preferably from 8 to 200, more preferably from 10 to 150 mg KOH/g and wherein the polymer may optionally comprise ionic functional groups, at standard conditions for example 12-48 h (preferably 24-48 h), and/or by heat-curing at elevated temperatures and at atmospheric pressure for example 70-80° C. for 10-60 minutes (preferably 15-30 minutes, more preferably 20 minutes), and/or any combination of curing at room temperature and curing at elevated temperatures; annealing steps (e.g. 50° C. for 16 h) may also be included in between curing at elevated temperatures and at atmospheric pressure and curing at standard conditions, wherein the annealing step follows the curing at elevated temperatures and at atmospheric pressure. Such inventive liquid compositions may preferably be cured at a temperature of at least 0 and at most 85, preferably at least 15 and at most 80, more preferably at least 23 and at most 70, most preferably at least 30 and at most 85, for example at least 15 and at most 30° C., for time periods that may vary and are preferably of at most 60, more preferably at most 30, even more preferably at most 15 minutes.
Obviously, curing at elevated temperatures and at atmospheric pressure requires shorter curing time; curing may also be effected by using pressure or by applying vacuum, or by irradiation, e.g. UV-radiation, or by any combination thereof. Such polymers may be selected from the group consisting of polyesters, polyamides, polycarbonates, polyimides, alkyds, uralkyds, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, preferably the polymer is selected from the group consisting of polyamides, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, most preferably the polymer is selected from the group consisting of polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof.
In yet another aspect, the invention provides for a kit-of-parts comprising parts A and B which are physically separated from each other, wherein:
i) the part A comprises a liquid composition according to any one of A19 to A34 or any combination derived from the disclosure in sections 1 and 3 and as disclosed in the entire specification including the claims; and
ii) the part B comprises a polymer which has an acid value determined according to the ASTM D1639-90(1996)e1 in the range from 5 to 300, preferably from 8 to 200, more preferably from 10 to 150 mg KOH/g and wherein the polymer may optionally comprise ionic functional groups, and wherein the polymer is preferably selected from the group consisting of polyesters, polyamides, polycarbonates, polyimides, alkyds, uralkyds, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, more preferably the polymer is selected from the group consisting of polyamides, polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof, most preferably the polymer is selected from the group consisting of polyacrylics, polyurethanes, poly(urethane-acrylic)s, and mixtures thereof,
wherein the part A does not comprise the polymer of the part B, and the part B does not comprise the liquid composition of the part A.
In yet another aspect, the invention provides fora cured form of an AZ-component according to Ala or to any one of A1 to A18 or any combination derived from the disclosure in sections 1 and 3 and as disclosed in the entire specification including the claims, of a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 1 and 3 and as disclosed in the entire specification including the claims; preferably the cured form is a film.
In yet another aspect, the invention provides for an article comprising:
i) an AZ-component according to Ala or to any one of A1 to A18 or any combination derived from the disclosure in section 1 and as disclosed in the entire specification including the claims, or ii) a liquid composition according to any one of A19-A34 or any combination derived from the disclosure in sections 1 and 3 and as disclosed in the entire specification including the claims; preferably the article is selected from the group consisting of textile, glass, metal, composite, plastic, wood, engineered wood, wood-like, leather, artificial leather, paper, fibers.
In yet another aspect, the invention provides for a use of any one or any combination of the following:
In yet another aspect, the invention provides for a use of any one or any combination of the following:
Yet, another aspect of the invention is any one of the AZ-components shown in the Examples that is according to the invention (Examples 1, 2, 3 and 4).
Yet, another aspect of the invention is any one of the liquid compositions shown in the Examples that is according to the invention (Examples 1, 2, 3, and 4).
Many other variations and embodiments of the invention are apparent to those skilled in the art, and such variations are contemplated within the scope of the claims.
Any feature, element, component, embodiment, range and especially any preferred feature, preferred element, preferred embodiment, preferred range, preferred combination of ranges, preferment described in the entire specification including the claims can be combined with each other.
Further aspects of the invention and preferred features thereof are given in the claims in the specification.
The invention will now be described in detail with reference to the following non-limiting examples, which are by way of illustration only.
The invention is explained in more detail with reference to the following non-limiting examples.
All the Examples shown in this section were carried out in a controlled laboratory environment at standard conditions (as these are defined in the specification), a relative humidity of 50±1% and an airflow of 0.1 m/s, unless otherwise explicitly specified.
Triethylamine (purity 99.7%) was supplied by ARKEMA. Propylene imine (purity ≥99.0%) was supplied by Menadiona. Anhydrous potassium carbonate (K2CO3; purity ≥99.0%) was supplied by Alfa Aesar. The trimethylolpropane tris(2-methyl-1-aziridinepropionate) (CAS No. 64265-57-2; see structure in Example 1C) was supplied by DSM (commercial product name ‘crosslinker CX-100’). The DESMODUR® N 3600 is a low viscosity aliphatic polyisocyanate (trimer) based on hexamethylene diisocyanate (HDI) (NCO content: 23.0±0.5% (M105-ISO 11909); viscosity at 23° C.: 1200±300 mPa·s (M014-ISO 3219/A.3); color value (hazen): ≤40 (M017-EN 1557); monomeric HDI: ≤0.25% (M106-ISO 10283); equivalent weight: approx. 183; flash point: approx. 159° C. (DIN 53213/1); density at 20° C.: approx. 1.16 g/ml (DIN EN ISO 2811), supplied by Covestro. The DESMODUR® N 3900 is a low viscosity aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) (NCO content: 23.0±0.5% (M105-ISO 11909); viscosity at 23° C.: 730±100 mPa·s (M014-ISO 3219/A.3); color value (hazen): ≤40 (M017-EN 1557); monomeric HDI: ≤0.25% (M106-ISO 10283); equivalent weight: approx. 179; flash point: approx. 203° C. (DIN 53213/1); density at 20° C.: approx. 1.15 g/ml (DIN EN ISO 2811), supplied by Covestro. The ERISYS® GE-36 is a triglycidyl ether of propoxylated glycerine (see Scheme 1) (EEW: 620-680 g/eq; viscosity: 200-320 cps at 25° C.; hydrolysable chloride: <0.10%; flash point: >93° C., residual epichlorohydrin: <20 ppm) was supplied by CVC Thermoset Specialties (now HUNTSMAN). The ERISYS® GA-240 (see Scheme 2) is glycidyl amine of m-xylelenediamine (CAS No. 63738-22-7) (epoxy equivalent weight (EEW): 95-110 g/eq; specific gravity at 25° C.: 1.14-1.16 g/ml; flash point: >215° C.; colour (Gardner): max. 5; viscosity at 25° C.: 1600-3000 cP) supplied by CVC Thermoset Specialties (now HUNSTMAN). The Cardolite® NC-514S is a di-functional glycidyl ether epoxy resin (see Scheme 3) [reddish brown liquid; color (Gardner): (ASTM D1544); viscosity at 25° C.: 1000-3000 cP (ASTM D2196); epoxy equivalent weight (EEW): 320-420 (ASTM D1652-97); hydrolysable chlorine (%): 0.5 (ASTM D1726-11); volatile loss (% wt): 0.5 (ASTM D2369-98); density at 25° C.: 1.026 Kg/L (ASTM D1475); flash point: >205° C. (ASTM D93)] was supplied by Cardolite Corporation. The EPPALOY® 9000 is tris hydroxyl phenyl ethane (CAS No. 87093-13-8) (see Scheme 4) [average epoxy functionality: 3.0; epoxy equivalent weight (EEW): 160-180 g/eq; viscosity at 72° C.: 5500-6500 cP; colour (Gardner): max. 2) supplied by CVC Thermoset Specialties (now HUNSTMAN]. The bisphenol A diglycidyl ether (CAS No. 1675-54-3) was supplied from Tokyo Chemical Industry Co., Ltd. The N,N-diglycidyl-4-glycidyloxyaniline (CAS No. 5026-74-4) was supplied by Sigma-Aldrich. Mehtylethylketone was supplied by Sigma-Aldrich. The polypropylene glycol with a calculated number average molecular weight (Mn) of 2000 Da and an OH-value of 56±2 mg KOH/g polypropylene glycol), and the polypropylene glycol with a calculated number average molecular weight (Mn) of 1000 Da and an OH-value of 112±2 mg KOH/g polypropylene glycol, were supplied by DOW. The DOWANOL™ DPM Glycol Ether [dipropylene glycol mono methyl ether; CAS No.: 34590-94-8; boiling point 190° C. at 760 mmHg; density 0.948 g/mL; flash point (closed cup): 75° C.; freezing point: −83° C.; molecular weight: 148.2 Da; specific gravity (25° C.): 0.951; surface tension: 28 dynes/cm; viscosity (25° C.): 3.7 cP; vapor pressure (20° C.): 0.28 mmHg; solubility in water (25° C.): infinite (wt %)] is a (mid- to slow evaporating) organic solvent. Any other chemical that is not explicitly mentioned in this paragraph and used in the Examples section (and unless otherwise stated in the specification) has been supplied by Sigma-Aldrich.
A one-litre flask (equipped with a thermometer and an overhead stirrer), was charged with 29.9 grams of dimethylol propionic acid, 282.1 grams of a polypropylene glycol with a calculated number average molecular weight (Mn) of 2000 Da and an OH-value of 56±2 mg KOH/g polypropylene glycol), 166.5 grams of a polypropylene glycol with a calculated number average molecular weight (Mn) of 1000 Da and an OH-value of 112±2 mg KOH/g polypropylene glycol, and 262.8 grams of isophorone diisocyanate (the number average molecular weight of each of the polyols is calculated from its OH-value according to the equation: Mn=2*56100/[OH-value in mg KOH/g polypropylene glycol). The reaction mixture was placed under N2 atmosphere, heated to 50° C. and subsequently, 0.07 g dibutyltin dilaurate were added to the reaction mixture. An exothermic reaction was observed; however, proper care was taken in order for the reaction temperature not to exceed 97° C. The reaction was maintained at 95° C. for an hour. The NCO content of the resultant polyurethane A was 7.00% on solids determined according to the ISO 14896 Method A (year 2009) (theoretically 7.44%), and the acid value of the polyurethane A was 16.1±1 mg KOH/g polyurethane A. The polyurethane A was cooled down to 60° C., and 18.7 grams of triethylamine were added, and the resulting mixture was stirred for 30 minutes. Subsequently, an aqueous dispersion of the polyurethane A (abbreviated as ‘polyurethane A-AQD’) was prepared as follows: the thus prepared mixture of the polyurethane A and triethylamine was fed—at room temperature over a time period of 60 minutes- to a mixture of 1100 grams of demineralized water, 19.5 grams of nonylphenol ethoxylate (9 ethoxylate groups), and 4.0 grams of triethylamine. After the feed was completed, the mixture was stirred for additional 5 minutes, and subsequently, 111.2 grams of hydrazine (16 wt % solution in water) were added to the mixture. The aqueous dispersion of the polyurethane A thus prepared was stirred for an additional 1 h.
All MALDI-ToF-MS spectra were acquired using a Bruker UltrafleXtreme™ MALDI-ToF mass spectrometer. The instrument is equipped with a Nd:YAG laser emitting at 1064 nm and a collision cell (not used for these samples). Spectra were acquired in the positive-ion mode using the reflectron, using the highest resolution mode providing accurate masses (range 60-7000 m/z). Cesium Tri-iodide (range 0.3-3.5 kDa) was used for mass calibration (calibration method: IAV Molecular Characterization, code MC-MS-05). The laser energy was 20%. The samples were dissolved in THF at approx. 50 mg/mL. The matrix used was: DCTB (trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile), CAS Number 300364-84-5. The matrix solution was prepared by dissolving 20 mg in 1 mL of THF. Potassium trifluoroacetate (KTFA, CAS Number: 2923-16-2) or alternatively sodium iodide was used as salt (NaI, CAS Number 7681-82-5); 10 mg was dissolved in 1 ml THF with a drop of MeOH added. Ratio sample:matrix:salt=10:200:10 (μL), after mixing, 0.5 μL was spot on MALDI plate and 20 allowed to air-dry. Reported signals are the major peaks within 0.5 Da of the calculated mass of the multi-aziridine compounds which are theoretically present in the composition in the largest amounts. In all cases, the reported peaks are the sodium or potassium adducts of the measured ions. The MALDI-TOF MS signals reported correspond to the major peaks of the sodium or potassium adducts of the measured ions of the theoretical formula of a multi-aziridine compound (the sodium and potassium cations. The theoretical formula of a multi-aziridine compound may be determined via analytical techniques well-known to one skilled in the art of analytical chemistry, e.g. NMR spectroscopy and/or liquid chromatography-mass spectroscopy (LC-MS), and/or liquid chromatography-mass spectroscopy-mass spectroscopy (LC-MS-MS), and/or theoretically from its method of preparation (if reactants and conditions are known); once the theoretical formula of a multi-aziridine compound is determined, then its theoretical molecular weight may also be determined.
The multi-aziridine compounds are identified by comparing the molecular weight which is defined just below (MW), with the exact molecular mass (i.e. the sum of the non-isotopically averaged atomic masses of its constituent atoms) of a theoretical structure, using a maximum deviation of 0.5 Da. In the context of this specification, the molecular weight (MW) attributed to a multi-aziridine compound is calculated from the following equation:
MW=Obs.[M+Mcation]−[Mcation]
wherein
the Mcation is the exact molar mass of the sodium (22.99 Da), or potassium cation (38.96 Da) (depending on which cation was used in the MALDI-TOF MS method), and the Obs.[M+Mcation] is the MALDI-TOF MS signal (peak) which corresponds to the theoretical formula of the multi-aziridine compound.
The genotoxicity was determined according to the ToxTracker® assay (Toxys, Leiden, the Netherlands) as described below. The ToxTracker® assay can be applied for pure substances or for compositions which are the direct products obtained in the preparation of compounds bearing the aziridine ring.
The ToxTracker assay is a panel of several validated Green Fluorescent Protein (GFP)-based mouse embryonic stem (mES) reporter cell lines that can be used to identify the biological reactivity and potential carcinogenic properties of newly developed compounds in a single test. This methodology uses a two-step approach.
In the first step a dose range-finding was performed using wild-type mES cells (strain B4418). 20 different concentrations for each compound was tested, starting at 10 mM in DMSO as the highest concentration and nineteen consecutive 2-fold dilutions. Next, the genotoxicity of samples (inventive and comparative examples) was evaluated using specific genes linked to reporter genes for the detection of DNA damage; i.e. Bscl2 (as elucidated by U.S. Pat. No. 9,695,481B2 and EP2616484B1) and Rtkn (Hendriks et al. Toxicol. Sci. 2015, 150, 190-203) biomarkers. Genotoxicity was evaluated at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA). The independent cell lines were seeded in 96-well cell culture plates, 24 h after seeding the cells in the 96-well plates, fresh ES cell medium containing the diluted test substance was added to the cells. For each tested compound, five concentrations are tested in 2-fold dilutions. The highest sample concentration will induce significant cytotoxicity (50-70%). In case of no or low cytotoxicity, 10 mM or the maximum soluble mixture concentration is used as maximum test concentration. Cytotoxicity is determined by cell count after 24 h exposure using a Guava easyCyte 10HT flow cytometer (Millipore). GFP reporter induction is always compared to a vehicle control treatment. DMSO concentration is similar in all wells for a particular compound and never exceeds 1%. All compounds were tested in at least three completely independent repeat experiments. Positive reference treatment with cisplatin (DNA damage) was included in all experiments. Metabolic was evaluated by the addition of S9 liver extract. Cells are exposed to five concentrations of the test compound in the presence of S9 and required co-factors (RegenSysA+B, Moltox, Boone, N.C., USA) for 3 h. After washing, cells are incubated for 24 h in fresh ES cell medium. Induction of the GFP reporters is determined after 24 h exposure using a Guava easyCyte 10HT flow cytometer (Millipore). Only GFP expression in single intact cells is determined. Mean GFP fluorescence and cell concentrations in each well are measured, which is used for cytotoxicity assessment. Data were analyzed using ToxPlot software (Toxys, Leiden, the Netherlands). The induction levels reported are at compound concentrations that induce 10%, 25% and 50% cytotoxicity after 3 h exposure in the presence of S9 rat liver extract and 24 h recovery or alternatively after 24 h exposure when not in the presence of S9 rat liver extract. A positive induction level of the biomarkers is defined as equal to or higher than a 2-fold induction in at least one of 10, 25 and 50% cytotoxicity in the absence or presence of the metabolizing system rat S9 liver extract; a weakly positive induction as higher than 1.5-fold and lower than 2-fold induction in at least one of 10, 25 and 50% cytotoxicity (but lower than 2-fold at 10, 25 and 50% cytotoxicity) in the absence or presence of the metabolizing system rat S9 liver extract and a negative as lower than or equal to a 1.5-fold induction at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems. In the context of the specification by ‘non-genotoxic’ (or equally ‘not genotoxic’) is meant that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP is lower than 2-fold—preferably equal to or lower than 1.9-fold, more preferably equal to or lower than 1.8-fold, for example equal to or lower than 1.7-fold, for example equal to or lower than 1.6-fold for example equal to or lower than 1.5-fold at 10, 25 and 50% cytotoxicity in the absence and presence of rat S9 liver extract-based metabolizing systems (aroclor1254-induced rats, Moltox, Boone, N.C., USA).
The crosslinking efficiency of organic compounds bearing aziridine ring(s) in liquid compositions [or equally the crosslinking efficiency of liquid compositions comprising organic compounds bearing aziridine ring(s)] was assessed by determining the chemical resistance of films (cured coatings).
The chemical resistance of a film (cured coating) was tested based on the DIN 68861-1:2011-01. The film was prepared as follows: 0.43 parts of the composition were mixed with 0.57 parts of DOWANOL™ DPM Glycol Ether and incubated at 80° C. for 10 minutes under regular agitation. Subsequently, an amount of the resulting solution was added under continuous stirring to an amount of the polyurethane A-AQD, and the resulting mixture was stirred for additional 30 minutes to thus produce a liquid composition. These amounts were calculated on the basis that the molar ratio of the mol of aziridine rings present in the organic compound (or a mixture of organic compounds) bearing aziridine ring(s), e.g. AZ-component to the mol of carboxylic acid functional groups present in the polyurethane A was equal to 0.9. This liquid composition was filtered and subsequently applied onto Leneta test cards using a 100 μm wire rod applicator. The film was dried for 16 h at 25° C., then annealed at 50° C. for 1 h and subsequently dried for 24 h at 25° C.
Cotton wool pads (1×1 cm) were soaked in a solution of ethanol: demineralized water (1:1). They were then placed on the films and covered with Petri dishes for 240 minutes. Afterwards, the pads and the Petri dishes were removed; after 1 h the coatings were visually inspected for damages; the extent of damages was assessed according to the following rating scheme:
In the context of this specification, the above integers 0-5 are mentioned as ‘ranking points’.
The chemical resistance of a reference film (prepared from only polyurethane A-AQD) was poor (this applies for all examples inventive and comparatives shown in the Examples).
The pH of a sample was determined according to the ISO 976:2013. Samples were measured at room temperature using a Metrohm 691 pH-meter equipped with a combined glass electrode and a PT-1000 temperature sensor. The pH-meter was calibrated using buffer solutions of pH 7.00 and 9.21 prior to use.
The acid value of a polymer is determined according to the ASTM D1639-90(1996)e1. According to the procedure, the sample was dissolved in a good solvent, was titrated with alcoholic potassium hydroxide solution of a known concentration (KOH). The difference in titration volume between the sample and a blank is the measure of the acid value on solids, according to the following formula:
AV=[(Vblank−Vsample)*NKOH*56.1]/(W*S/100)
where
AV is the acid number on solids in mg KOH/g solid material, Vblank is the volume of KOH solution used in the blank, Vsample is the volume of KOH solution used in the sample, NKOH is the normality of the KOH solution, W is the sample weight in grams and S is the solids content of the sample in %. Measurements are performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (accepting the measurement if the difference between duplicates is <0.1 mg KOH/g solid material).
The NCO content of a sample is determined based on the ASTM D2572-19 standard. In the procedure, the sample is reacted with excess n-dibutylamine. The excess of n-dibutylamine is subsequently back-titrated with standard 1N hydrochloric acid (HCl). The difference in titration volume between the sample and a blank is the measure of the isocyanate content on solids, according to the following formula:
% NCOsolids=[(Vb−Vm)*N*4.2]/(A*s/100)
where
% NCOsolids is the isocyanate content on solids, Vb is the volume of HCl used in the blank, Vm is the volume of HCl used in the sample, N is the normality of the HCl solution, A is the sample weight in grams and s is the solids content of the sample in %. Measurements are performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (accepting the measurement if the difference between duplicates is <0.1%NCO).
1.8 Determination of the Amount of Component T [Liquid Chromatography Coupled with Mass Spectroscopy (LC-MS)]
The amount of component T (as the latter is defined in the specification including the claims; wt % on the total weight of the AZ-compound) was determined via liquid chromatography coupled with mass spectroscopy (LC-MS). Initially, a 0.01 wt % solution of sample in methanol was prepared. Subsequently, 0.5 μL of this solution was injected into an Agilent 1290 Infinity II Ultra High Pressure Liquid Chromatography (UHPLC) system equipped with: a) a High Strength Silica (HSS) technology C18 type T3 column supplied by Waters® [100×2.1 mm (length×diameter); 1.8 micron average particle size of the stationary phase] operating at 40° C., and b) an Agilent 6550 iFunnel QTOF detector [ElectroSpray Ionization-Time-of-Flight Mass Spectrometer (ESI-TOF-MS) detector]. Once the sample was injected, then a gradient of a mobile phase [from 80/20 v/v A/B to 1/99 v/v A/B, wherein A was 10 mM CH3COO−NH4+ (set to pH 9.0 with NH3) and B was acetonitrile; A and B making up the mobile phase], at a flow rate of 0.5 mL/min, for 10 min, was used to separate the various ingredients of the sample. Subsequently, a gradient of a mobile phase [from 1/99 v/v A/B to 1/49/50 A/B/C, wherein A was 10 mM CH3COO−NH4+ (set to pH 9.0 with NH3), B was acetonitrile and C was tetrahydrofuran (THF); A, B and C making up the mobile phase] at a flow rate of 0.5 mL/min, for 5 min was applied to purge the column. Assuming a linear MS response of all the ingredients of the sample over all response ranges and an equal ionization efficiency for all the ingredients of the sample, the signals of the:
The data acquisition was carried out via the MassHunter Build 10.1.48 software supplied by Agilent, while the data processing was carried out via the Qualitative Analysis Build 10.0.10305.0 software, also supplied by Agilent.
The amount of component T (wt % on the total weight of the AZ-compound) was determined by dividing the integrals of the extracted ion chromatograms of the component T by the integrals of the total ion current, multiplied by 100.
The amount of chloride in a liquid composition was determined according to the ASTM D1726-11(2019).
100 grams of ERISYS® GE-36, 26.5 grams of propylene imine and 5 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was then heated to 80° C. Samples were taken at regular intervals, and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. The reaction mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain from the filtrate was removed in vacuo to obtain a clear highly viscous liquid. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below (wherein x+y+z=33), and the theoretical molecular weight was calculated to be 2346.68 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 2346.50 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the (aziridinyl hydroxy)-functional organic compound obtained above (and its liquid composition) was very good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this (aziridinyl hydroxy)-functional organic compound was not genotoxic.
75 grams of EPALLOY® 9000 was dissolved in 75 mL of toluene and charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). Next, 55 grams of propylene imine and 5 grams of potassium carbonate were added to the flask. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 80° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 22 hours of reaction, the mixture was filtered. The solvent and excess of propylene imine were removed from the filtrate in vacuo to obtain an off-white solid. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below and the theoretical molecular weight was calculated to be 645.38 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 645.37 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the (aziridinyl hydroxy)-functional organic compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this (aziridinyl hydroxy)-functional organic compound was not genotoxic.
130 grams of DESMODUR® N 3600 was dissolved in 130 grams of toluene, charged to a reaction flask equipped with a thermometer and heated to 50° C. Next, 0.05 grams of triethylamine was added to the flask and over the course of 90 minutes 52 grams of glycidol was slowly added to the reaction mixture, while making sure that the reaction temperature stayed constant between 55-58° C. After stirring for another 60 minutes at this temperature, the mixture was cooled down to room temperature and stirred for 18 hours at room temperature. The solvent was removed in vacuo and the resulting yellowish oil was transferred to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). Next, 200 grams of toluene, 150 grams of propylene imine and 5 grams of potassium carbonate were added to the flask. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 60° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 18 hours of reaction, the mixture was filtered. The solvent and excess of propylene imine were removed from the filtrate in vacuo to obtain a high viscous liquid. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below and the theoretical molecular weight was calculated to be 897.55 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 897.58 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the (aziridinyl hydroxy)-functional organic compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this (aziridinyl hydroxy)-functional organic compound was not genotoxic.
30.0 grams of Cardolite® NC-514S, 19.2 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was than heated to 70° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 20 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain to obtain a high viscous brownish oil. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below and the theoretical molecular weight was calculated to be 622.47 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 622.43 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the (aziridinyl hydroxy)-functional organic compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this (aziridinyl hydroxy)-functional organic compound was not genotoxic.
The trimethylolpropane tris(2-methyl-1-aziridinepropionate) (commercial product name ‘crosslinker CX-100’) has the following structure:
The theoretical molecular weight was calculated to be 467.30 Da.
The crosslinking efficiency of the trimethylolpropane tris(2-methyl-1-aziridinepropionate) (and its liquid composition) was very good and given the ToxTracker® assay results on the genotoxicity shown in the table below, the trimethylolpropane tris(2-methyl-1-aziridinepropionate) was genotoxic.
75 grams of ERISYS® GA-240, 80 grams of propylene imine and 5 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 71° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 22 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a clear, transparent solid. The theoretical formula of the thus prepare multi-aziridine compound is shown below and the theoretical molecular weight was calculated to be 588.44 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 588.48 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the multi-aziridine compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this multi-aziridine compound was genotoxic.
24.0 grams of N,N-dilycidyl-4-glycidyloxyaniline, 42.0 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was than heated to 70° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 24 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous yellow material. The theoretical formula of the thus prepare multi-aziridine compound is shown below and the theoretical molecular weight was calculated to be 448.30 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 448.29 Da (=Obs. [M+MNa+]−[MNa+]).
This compound was disclosed in U.S. Pat. No. 3,329,674 in cl. 2, II. 29-39.
The crosslinking efficiency of the multi-aziridine compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this multi-aziridine compound was genotoxic.
299 grams of bisphenol A diglycidyl ether, 250 grams of toluene, 255 grams of propylene imine and 10 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 70° C. Samples were taken at regular intervals and the reaction progress was monitored using a 1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 19 hours of reaction, the mixture was filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous liquid. The theoretical formula of the thus prepare multi-aziridine compound is shown below and the theoretical molecular weight was calculated to be 454.28 Da.
The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 454.26 Da (=Obs. [M+MNa+]−[MNa+]).
The crosslinking efficiency of the multi-aziridine compound obtained above (and its liquid composition) was good, and given the ToxTracker® assay results on the genotoxicity shown in the table below, this multi-aziridine compound was genotoxic.
The U.S. Pat. No. 3,329,674 to Thiokol Chemical Corporation disclosed low molecular weight aziridinyl derivatives of polyfunctional epoxides. The molecular weight of these aziridinyl derivatives was well below 600 Da as explained in the specification. The U.S. Pat. No. 3,329,674 did not disclose (aziridinyl hydroxy)-functional organic compounds having a molecular weight of at least 600 and at most 10000 Da. The U.S. Pat. No. 3,329,674 failed to provide for (aziridinyl hydroxy)-functional organic compounds (and its liquid compositions) that would be non-genotoxic and have at least good crosslinking efficiency. Evidence for that is the Example 3C shown in the specification, which was genotoxic.
Upon comparing the results of the inventive Examples 1 to 4 and those of the comparative Examples 1C to 4C, it is evident that only the AZ-component of the invention (and the liquid compositions of the invention) were not genotoxic and had at least good crosslinking efficiency.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20153154.8 | Jan 2020 | EP | regional |
| 20153159.7 | Jan 2020 | EP | regional |
| 20153239.7 | Jan 2020 | EP | regional |
| 20153240.5 | Jan 2020 | EP | regional |
| 20153242.1 | Jan 2020 | EP | regional |
| 20153245.4 | Jan 2020 | EP | regional |
| 20153246.2 | Jan 2020 | EP | regional |
| 20153249.6 | Jan 2020 | EP | regional |
| 20153250.4 | Jan 2020 | EP | regional |
| 20153251.2 | Jan 2020 | EP | regional |
| 20153253.8 | Jan 2020 | EP | regional |
| 20153628.1 | Jan 2020 | EP | regional |
| 20153630.7 | Jan 2020 | EP | regional |
| 20187717.2 | Jul 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/051378 | 1/21/2021 | WO |
