Patent Application
20220289873
The present invention relates to a process for polymerization of a radically polymerizable compound comprising at least one ethylenic bond, in the presence of a complex of borane with an amine.
Radical polymerization constitutes one of the industrially most exploited polymerization processes due to the variety of polymerizable monomers, its ease of implementation and the variety of synthesis processes employed (bulk, emulsion, solution, suspension).
The use of organoboranes for the radical polymerization of compounds comprising an ethylenic bond is known in the prior art. However, due to the unstable and pyrophoric nature of organoboranes, they must be complexed with an amine in order to avoid oxidative decomposition.
Generally, before the initiation of the polymerization, the presence of a compound such as an oxidizing agent (such as a peroxide) is necessary for the initiation of the polymerization. However, these types of compounds are very reactive as well, which can make their use during the polymerization dangerous.
Generally, the initiation of the reaction requires either the presence of an organoborane or the presence of an initiator (such as a peroxide) in combination with an amine-borane complex.
Document U.S. Pat. No. 2,973,337 describes the polymerization of unsaturated compounds comprising one or more ethylenic bonds, using borazanes in combination with oxidizing agents of persulfate type.
Document U.S. Pat. No. 3,036,048 describes the polymerization of unsaturated compounds comprising one or more ethylenic bonds, using organoborane-amine complexes in combination with catalysts such as titanium and zirconium salts.
Document U.S. Pat. No. 3,236,823 describes the polymerization of unsaturated compounds comprising one or more ethylenic bonds, using organoborane-amines.
Document U.S. Pat. No. 8,202,932 relates to polymerizable (meth)acrylic compositions and adhesive systems prepared from these compositions. These compositions comprise an alkylated borohydride or a tetraalkylborane metal or ammonium salt and an aminosilane. According to this document, these compositions are suitable for bonding applications involving at least one low-energy surface.
Document U.S. Pat. No. 6,632,908 relates to (meth)acrylic compositions used for the adhesion of metal, plastic or glass substrates to substrates of the same nature or of a different nature, such as substrates having a low-energy surface. The (meth)acrylic compositions described in this document comprise a (meth)acrylate compound and an initiator system comprising an organometallic compound, a peroxide compound, an aziridine-based compound and a compound having an acid function.
Document U.S. Pat. No. 9,315,701 describes a two-part adhesive composition comprising an organoborane-amine complex, a polyamine, a radically polymerizable compound and a polyisocyanate compound. These compositions are particularly suitable for the adhesion of substrates having a low surface energy.
However, in certain cases, despite the complexation of the organoborane with the amine, the high reactivity of the organoborane-amine complexes prevents effective control of their reactivity during the crosslinking of the monomer(s) (in other words, they crosslink very rapidly).
There is therefore a real need to provide an efficient process for polymerization of a radically polymerizable compound, with it being possible for the compound used for the polymerization to be stored for a prolonged period, to be used safely and to have a controllable reactivity.
The invention firstly relates to a process for polymerization of at least one radically polymerizable compound comprising at least one ethylenic bond, in the presence of a complex of borane BH3 with an amine as radical initiator, comprising the steps of:
According to certain embodiments:
According to certain embodiments, the amine is chosen from triethylamine, diisopropylamine, tert-butylamine, dicyclohexylamine, tetramethylpiperidine, morpholine, diisopropylethylamine, 2,6-dimethylpyridine, a polyetheramine, and combinations thereof.
According to certain embodiments, the radically polymerizable compound is chosen from a styrene, vinyl, acrylic, or methacrylic monomer, and combinations thereof.
According to certain embodiments, the radically polymerizable compound is a monomer chosen from an acrylate, an acrylic acid, an acrylamide, an acrylonitrile, a methacrylate, a methacrylic acid, a methacrylamide, a methacrylonitrile, and combinations thereof.
According to certain embodiments, the complex of borane BH3 with an amine is present at a content by mass of 0.01% to 25%, and preferably of 0.1% to 20%, relative to the mass of the radically polymerizable compound.
According to certain embodiments, the radically polymerizable compound has a content by mass of 5% to 100%, and preferably of 50% to 100%, relative to the total mass of the composition.
According to certain embodiments, the process comprises a heating step after bringing the complex into contact with the composition comprising at least one polymerizable compound.
According to certain embodiments, the heating step is carried out at a temperature of 20 to 100° C., and preferably of 35 to 85° C.
According to certain embodiments, the composition additionally comprises one or more additives chosen from fillers, plasticizers, tackifying resins, solvents, UV stabilizers, moisture absorbers, fluorescent materials, rheological additives, and combinations thereof.
The invention also relates to a composition comprising at least one radically polymerizable compound comprising at least one ethylenic bond and a complex of borane BH3 with an amine, the composition being devoid of oxidizing agent and/or additional radical initiator other than the complex of borane BH3 with an amine.
According to certain embodiments:
According to certain embodiments, the amine is chosen from triethylamine, diisopropylamine, tert-butylamine, dicyclohexylamine, tetramethylpiperidine, morpholine, diisopropylethylamine, 2,6-dimethylpyridine, a polyetheramine, and combinations thereof.
According to certain embodiments, the radically polymerizable compound is chosen from a styrene, vinyl, acrylic, or methacrylic monomer, and combinations thereof.
According to certain embodiments, the radically polymerizable compound is a monomer chosen from an acrylate, an acrylic acid, an acrylamide, an acrylonitrile, a methacrylate, a methacrylic acid, a methacrylamide, a methacrylonitrile, and combinations thereof.
The invention also relates to the use of the composition as described above as a material with its intrinsic properties.
The invention also relates to the use of the composition as described above as an adhesive for binding two substrates together.
The invention also relates to the use of the composition as described above as a coating on the surface of a substrate.
The invention also relates to the use of the composition as described above as a primer on the surface of a substrate.
According to certain embodiments, the substrate or at least one of the two substrates has a surface energy of less than or equal to 45 mJ/m2, preferably of less than or equal to 40 mJ/m2, and more preferably of less than or equal to 35 mJ/m2.
According to certain embodiments, the substrate or at least one of the two substrates consists of polyolefin(s), preferably chosen from polyethylene, polypropylene, polybutene, polyisoprene, polybutadiene, polyfarnesene, polymyrcene, polyvinyl fluoride, poly(vinylidene fluoride), polytetrafluoroethylene, and the copolymers thereof or mixtures thereof.
The invention also relates to an article comprising at least one layer obtained by crosslinking the composition as described above.
According to certain embodiments, the layer is an adhesive layer.
The present invention makes it possible to meet the need expressed above. It more particularly provides an efficient process for polymerization of a radically polymerizable compound, with it being possible for the compound used for the polymerization to be stored for a prolonged period, to be used safely and to have a controllable reactivity.
This is accomplished by virtue of the use of a borane-amine (i.e. BH3-amine) complex. Borane-amine complexes offer improved stability compared to complexes comprising organoboranes, allowing prolonged storage. In addition, the lower reactivity of these complexes compared to the organoborane-amine complexes enables better control of the reactivity of the composition during its crosslinking.
In addition, the absence of reactive compounds (such as oxidants, co-initiators, peroxides, metal salts) facilitates and simplifies the polymerization process.
The possibility of using such a complex satisfactorily is a genuine surprise, insofar as the polymerization mechanism initiated by such a complex is necessarily different from that initiated by an organoborane complex as employed in the prior art.
The invention is now described in greater detail and in a nonlimiting way in the description which follows.
The polymerization according to the invention is carried out with a complex of borane with an amine.
The term “borane”, or “trihydridoboron” according to systematic nomenclature, is understood to mean a molecule having the formula “BH3”.
Since borane is a highly reactive molecule, its complexation with an amine is necessary in order to avoid its decomposition and in order to enable its storage.
The amine may be a monoamine (comprising a single amine group) or a polyamine (comprising more than one amine group, for example two, three or four amine groups). In the case of polyamines comprising a main chain, the amine groups may be present at the ends of the main chain and/or in the form of side or pendant groups along the main chain.
Preferably, the amine is a monoamine.
When the amine is a monoamine, it may be chosen from a primary, secondary or tertiary monoamine.
According to certain embodiments, the monoamine can be of formula (I):
R1, R2 and R3 may independently represent a hydrogen atom or a group comprising from 1 to 20 carbon atoms. This group may be linear or branched and saturated or unsaturated.
R1, R2 and R3 may comprise one or more heteroatoms chosen from an oxygen atom, a sulfur atom and a halogen (such as fluorine, chlorine, bromine and iodine).
According to certain embodiments, R1, R2 and R3 may independently be chosen from an alkyl group, a cycloalkyl group, an alkoxy group, or an aryl group. By way of example, R1, R2 and R3 may independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a tert-butyl group, an isobutyl group, an n-butyl group, a sec-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an alkyl group substituted by an aryl group (arylalkyl) such as an alkyl phenyl, a methoxy group, an ethoxy group, a propoxy group, a butoxy, preferably tert-butoxy, group, a phenoxy group, a phenyl group which is unsubstituted or substituted by one or more groups such as an alkyl group (alkylaryl) or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a naphthyl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a heteroaryl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group. As examples of heteroaryl groups, mention may be made of pyridines, pyrroles and carbazoles. Alternatively, two of R1, R2 and R3 may form part of a ring, for example of a pyrrolidine, of a piperidine, of a morpholine, of a thiomorpholine, or of one of the higher homologs thereof. Still alternatively, two of R1, R2 and R3 may form part of several rings such as for example 1-azabicyclo[2.2.2]octane (or quinuclidine).
According to certain embodiments, R1, R2 and R3 may be identical.
According to other embodiments, R1, R2 and R3 may be different from one another.
According to certain embodiments, at least two of R1, R2 and R3 are identical.
According to certain embodiments, at least one of R1, R2 and R3 is a hydrogen.
According to other embodiments, none of R1, R2 and R3 is a hydrogen.
According to certain embodiments, at least two of R1, R2 and R3 form part of a ring such as a morpholine or a piperidine.
According to certain embodiments, R1, R2 and R3 form part of a ring such as a substituted or unsubstituted pyridine.
According to preferred embodiments, when the monoamine of formula (I) is a primary amine, it may be tert-butylamine.
According to preferred embodiments, when the monoamine of formula (I) is a secondary amine, it may be diisopropylamine or dicyclohexylamine or morpholine, or 2,6-dimethylpyridine, and preferably diisopropylamine.
According to preferred embodiments, when the monoamine of formula (I) is a tertiary amine, it may be diisopropylethylamine or an aromatic amine such as 2,6-dimethylpyridine.
According to other embodiments, the monoamine may be a polyetheramine, i.e. an amine comprising multiple ether functions.
According to preferred embodiments, the monoamine is a primary polyetheramine.
According to other embodiments, the monoamine is a secondary or tertiary polyetheramine.
Thus, in the case of a monoamine which is a polyetheramine, it can be of formula (II):
R4, R5 and R10 may independently represent a hydrogen atom or a group comprising from 1 to 10 carbon atoms. This group may be linear or branched and saturated or unsaturated. Preferably, R4, R5 and R10 independently represent a linear or branched group comprising from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms and more preferably from 1 to 3 carbon atoms.
According to certain embodiments, R4 may be chosen from an alkyl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, or an aryl group, the alkyl, cycloalkyl, arylalkyl, arylalkyl and aryl groups being as described above.
Preferably, R4 is an alkyl group, preferably comprising from 1 to 7 carbon atoms, and preferably from 1 to 3 carbon atoms.
According to certain embodiments, R5 may be chosen from an alkyl group, a cycloalkyl group, or an aryl group, these groups being as described above. Preferably, R5 is an alkyl group, preferably comprising from 1 to 2 carbon atoms. More preferably, R5 is chosen from a methyl group and an ethyl group.
According to certain embodiments, R10 may be chosen from an alkyl group, a cycloalkyl group, or an aryl group, the alkyl, cycloalkyl and aryl groups being as described above. Preferably, R10 is an alkyl group, preferably comprising from 1 to 2 carbon atoms. More preferably, R10 is chosen from a methyl group and an ethyl group.
According to certain preferred embodiments, R4, R5 and R10 may be identical.
According to other embodiments, R4, R5 and R10 may be different from one another.
According to preferred embodiments, R5 and R10 are different from one another. For example, one of R5 and R10 may be an ethyl group and the other of R5 and R10 may be a methyl group.
According to preferred embodiments, at least one of R4, R5 and R10 is a methyl group.
Ri and Rii may independently represent a hydrogen atom or a group comprising from 1 to 20 carbon atoms. This group may be linear or branched and saturated or unsaturated.
According to certain embodiments, Ri and Rii may independently be chosen from an alkyl group, a cycloalkyl group, an aryl group, or an arylalkyl group. By way of example, Ri and Rii may independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a tert-butyl group, an isobutyl group, an n-butyl group, a sec-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an alkyl group substituted by an aryl group such as an alkyl phenyl, a phenyl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a naphthyl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a heteroaryl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group. As examples of heteroaryl groups, mention may be made of pyridines, pyrroles and carbazoles. Alternatively, Ri and Rii may form part of a ring, for example of a pyrrolidine, of a piperidine, of a morpholine, of a thiomorpholine, or of one of the higher homologs thereof.
According to certain preferred embodiments, Ri and Rii are both hydrogen atoms. In this case, it is a primary polyetheramine.
According to other embodiments, at least one of Ri and Rii is a group comprising from 1 to 20 carbon atoms. In this case, it is a secondary polyetheramine.
According to other embodiments, both of Ri and Rii are independently groups comprising from 1 to 20 carbon atoms. In this case, it is a tertiary polyetheramine.
According to certain embodiments, t, x and y may independently represent a number from 0 to 90, preferentially from 0 to 70, preferentially from 0 to 50, and even more preferentially from 0 to 30. Thus, t, x and y may independently represent a number from 0 to 10, or from 10 to 20; or from 20 to 30; or from 30 to 40; or from 40 to 50; or from 50 to 60; or from 60 to 70; or from 70 to 80; or from 80 to 90.
When t is other than 0, the number t represents the number of ethoxy groups substituted by a group R10 (preferably propoxy groups when R10 is methyl or butoxy groups when R10 is ethyl) present in the monoamine of formula (II).
The number t may or may not be an integer. For example, if a mixture of different alkylene oxides is used, t corresponds to the average degree of ethoxylation of the ethoxy groups substituted by a group R10 (preferably to the average degree of propoxylation when R10 is methyl or butoxylation when R10 is ethyl).
When x is other than 0, the number x represents the number of ethoxy groups present in the monoamine of formula (II).
The number x may or may not be an integer. For example, if a mixture of different molecules is used, x corresponds to the average degree of ethoxylation.
When y is other than 0, the number y represents the number of ethoxy groups substituted by a group R5 (preferably propoxy groups when R5 is methyl or butoxy groups when R5 is ethyl) present in the monoamine of formula (II).
The number y may or may not be an integer. For example, if a mixture of different alkylene oxides is used, y corresponds to the average degree of ethoxylation of the ethoxy groups substituted by a group R5 (preferably to the average degree of propoxylation when R5 is methyl or butoxylation when R5 is ethyl).
When t and y are other than 0, the sum t+y represents the number of ethoxy groups substituted by groups R5 and R10 (preferably propoxy groups when R5 and R10 are methyl or butoxy groups when R5 and R10 are ethyl) present in the amine of formula (II).
According to certain embodiments, when t is equal to 0, y is other than 0.
According to other embodiments, when y is equal to 0, t is other than 0.
According to yet other embodiments, in particular when R5 and R10 are different, t and y are both other than 0.
According to certain embodiments, when y and/or t is equal to 0, x is other than 0.
According to other embodiments, when x is equal to 0, y and/or t is other than 0.
The monoamines of formula (II) may have a molecular mass of 200 to 5500 g/mol, and preferably of 500 to 2500 g/mol. For example, the monoamines of formula (II) may have a molecular mass of 200 to 500 g/mol; or of 500 to 750 g/mol; or of 750 to 1000 g/mol; or of 1000 to 1250 g/mol; or of 1250 to 1500 g/mol; or of 1500 to 1750 g/mol; or of 1750 to 2000 g/mol; or of 2000 to 2250 g/mol; or of 2250 to 2500 g/mol; or of 2500 to 2750 g/mol; or of 2750 to 3000 g/mol; or of 3000 to 3250 g/mol; or of 3250 to 3500 g/mol; or of 3500 to 3750 g/mol; or of 3750 to 4000 g/mol; or of 4000 to 4250 g/mol; or of 4250 to 4500 g/mol; or of 4500 to 4750 g/mol; or of 4750 to 5000 g/mol; or of 5000 to 5250 g/mol; or of 5250 to 5500 g/mol.
This type of polyetheramines is for example sold under the name Jeffamine M series by the company Huntsman.
When the amine is a polyamine, it may be chosen from a primary and/or secondary and/or tertiary polyamine. Preferably, it is a primary polyamine, i.e. all of its amine groups are primary amine groups. More preferably, it is a diamine. However, polyamines comprising more than two amine groups (for example three or four) such as polyethyleneimines (PEIs) may be used.
According to certain embodiments, the polyamine can be of formula (III):
R6 may represent a divalent group comprising from 2 to 60 carbon atoms, preferably from 2 to 40 carbon atoms and more preferably from 2 to 15 carbon atoms.
R6 may be linear or branched, cyclic or alicyclic, and saturated or unsaturated.
R6 may comprise one or more heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen. Preferably, a single heteroatom may be present in R6.
In addition, R6 may be chosen from a divalent alkyl radical, a divalent cycloalkyl radical, a divalent alicyclic radical, a divalent arylalkyl radical or a divalent aryl radical. Preferably, R6 is an alkyl group.
Ri and Rii are as detailed above.
Riii and Riv may independently represent a hydrogen atom or a group comprising from 1 to 20 carbon atoms. This group may be linear or branched and saturated or unsaturated.
According to certain embodiments, Riii and Riv may independently be chosen from an alkyl group, a cycloalkyl group, an aryl group, or an arylalkyl group. By way of example, Riii and Riv may independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a tert-butyl group, an isobutyl group, an n-butyl group, a sec-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an alkyl group substituted by an aryl group such as an alkyl phenyl, a phenyl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a naphthyl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group, a heteroaryl group which is unsubstituted or substituted by one or more groups such as an alkyl or cycloalkyl group, an alkoxy group, a halogen, a nitro group, and a carbonyl group. As examples of heteroaryl groups, mention may be made of pyridines, pyrroles and carbazoles. Alternatively, Riii and Riv may form part of a ring, for example of a pyrrolidine, of a piperidine, of a morpholine, of a thiomorpholine, or of one of the higher homologs thereof.
According to certain preferred embodiments, Ri and Rii and/or Riii and Riv are all hydrogen atoms.
According to other embodiments, at least one of Ri and Rii and/or at least one of Riii and Riv is a group comprising from 1 to 20 carbon atoms.
According to other embodiments, both of Ri and Rii and/or both of Riii and Riv are independently groups comprising from 1 to 20 carbon atoms.
According to preferred embodiments, the polyamine of formula (III) may be chosen from ethylenediamine, 1,3-propanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, isophoronediamine, 4,4′-methylenedianiline, 2-methylbenzene-1,4-diamine, diethylenetriamine, 4,6-diethyl-2-methylbenzene-1,3-diamine, 4,4′-methylenedicyclohexanamine, 2,4,6-trimethyl-1,3-phenylenediamine, and naphthalene-1,8-diamine.
More preferably, the polyamine of formula (III) may be chosen from ethylenediamine and 1,3-propanediamine, and preferably the polyamine of formula (III) is 1,3-propanediamine.
According to other embodiments, the polyamine may be a polyetheramine comprising two amine groups, preferably primary amine groups. Alternatively, the polyamine may be a secondary or tertiary polyamine comprising two amine groups.
Thus, when it is a polyetheramine comprising two amine groups, it can be of formula (IV):
R7, R9 and R9 may independently represent a group comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and more preferably from 1 to 2 carbon atoms. These groups may be linear or branched and saturated or unsaturated.
R7, R8 and R9 may independently be chosen from an alkyl group, a cycloalkyl group, or an aryl group, these groups being as described above. Preferably, at least one of R7, R8 and R9 is an alkyl group, and more preferably a methyl group or an ethyl group.
According to certain preferred embodiments, R7, R8 and R9 may be identical.
According to other embodiments, R7, R8 and R9 may be different from one another.
According to preferred embodiments, at least one of R7, R8 and R9 is a methyl group, and preferably R7, R8 and R9 are methyl groups.
According to preferred embodiments, R8 and R9 are different from one another.
According to other embodiments, at least one of R8 and R9 is a methyl group, and the other of R8 and R9 is an ethyl group.
Ri, Rii, Riii and Riv are as detailed above.
According to certain preferred embodiments, Ri and Rii and/or Riii and Riv are all hydrogen atoms.
According to other embodiments, at least one of Ri and Rii and/or at least one of Riii and Riv is a group comprising from 1 to 20 carbon atoms.
According to other embodiments, both of Ri and Rii and/or both of Riii and Riv are independently groups comprising from 1 to 20 carbon atoms.
According to certain embodiments, v, w and z may independently represent a number from 0 to 90, preferentially from 0 to 70. Thus, v, w and z may independently represent a number from 0 to 10, or from 10 to 20; or from 20 to 30; or from 30 to 40; or from 40 to 50; or from 50 to 60; or from 60 to 70; or from 70 to 80; or from 80 to 90.
According to certain embodiments, z is equal to 0 and v is other than 0.
According to other embodiments, z is other than 0 and v is equal to 0.
According to yet other embodiments, z and v are both other than 0.
When z and v are other than 0, the sum z+v represents the number of substituted ethoxy groups (preferably propoxy or butoxy groups) present in the polyamine of formula (IV).
The sum z+v may or may not be an integer. For example, if a mixture of different molecules is used, z+v corresponds to the average degree of ethoxylation of the substituted ethoxy groups (preferably to the degree of propoxylation or butoxylation).
When v is equal to 0, the number z represents the number of substituted ethoxy groups (preferably propoxy groups when R8 is methyl or butoxy groups when R8 is ethyl) present in the polyamine of formula (IV).
When z is equal to 0, the number v represents the number of substituted ethoxy groups (preferably propoxy groups when R9 is methyl or butoxy groups when R9 is ethyl) present in the polyamine of formula (IV).
The numbers z and v may or may not be integers.
The number w represents the number of ethoxy groups present in the polyamine.
The number w may or may not be an integer. For example, if a mixture of different molecules is used, w corresponds to the average degree of ethoxylation.
According to certain embodiments, v and w may be 0. This type of polyetheramines is for example sold under the names Jeffamine D series and Jeffamine SD series by the company Huntsman.
According to other embodiments, w may be other than 0, while v is greater than 0.
According to other embodiments, v and w may be greater than 0. In this case, the sum z+v may be from 1 to 10, and preferably from 1 to 8. For example, this sum may be from 1 to 2; or from 2 to 3; or from 3 to 4; or from 4 to 5; or from 5 to 6; or from 6 to 7; or from 7 to 8; or from 8 or 9; or from 9 to 10. This type of polyetheramines is for example sold under the name Jeffamine ED series by the company Huntsman.
The polyetheramines of formula (IV) may have a molecular mass of 100 to 5000 g/mol, and preferably of 200 to 4000 g/mol. For example, the polyetheramines of formula (IV) may have a molecular mass of 100 to 500 g/mol; or of 500 to 750 g/mol; or of 750 to 1000 g/mol; or of 1000 to 1250 g/mol; or of 1250 to 1500 g/mol; or of 1500 to 1750 g/mol; or of 1750 to 2000 g/mol; or of 2000 to 2250 g/mol; or of 2250 to 2500 g/mol; or of 2500 to 2750 g/mol; or of 2750 to 3000 g/mol; or of 3000 to 3250 g/mol; or of 3250 to 3500 g/mol; or of 3500 to 3750 g/mol; or of 3750 to 4000 g/mol; or of 4000 to 4250 g/mol; or of 4250 to 4500 g/mol; or of 4500 to 4750 g/mol; or of 4750 to 5000 g/mol.
According to other embodiments, the polyetheramine comprising two amine groups can be of formula (V):
Ri, Rii, Riii and Riv are as described above.
According to certain preferred embodiments, Ri and Rii and/or Riii and Riv are all hydrogen atoms.
According to other embodiments, at least one of Ri and Rii and/or at least one of Riii and Riv is a group comprising from 1 to 20 carbon atoms.
According to other embodiments, both of Ri and Rii and/or both of Riii and Riv are independently groups comprising from 1 to 20 carbon atoms.
According to certain embodiments, a and b may independently represent a number from 1 to 20 and preferably from 2 to 11.
According to certain preferred embodiments, a and b are identical. Preferably, a and b are equal to 2 or 3.
According to other embodiments, a and b are different. In this case, at least one of a and b is preferably equal to 2 or 3.
The polyetheramines of formula (V) may have a molecular mass of 150 to 1500 g/mol, and preferably of 150 to 1000 g/mol. For example, the polyetheramines of formula (V) may have a molecular mass of 150 to 160 g/mol; or of 160 to 170 g/mol; or of 170 to 180 g/mol; or of 180 to 190 g/mol; or of 190 to 200 g/mol; or of 200 to 300 g/mol; or of 300 to 400 g/mol; or of 400 to 500 g/mol; or of 500 to 600 g/mol; or of 600 to 700 g/mol; or of 700 to 800 g/mol; or of 800 to 900 g/mol; or of 900 to 1000 g/mol; or of 1000 to 1100 g/mol; or of 1100 to 1200 g/mol; or of 1200 to 1300 g/mol; or of 1300 to 1400 g/mol; or of 1400 to 1500 g/mol.
This type of polyetheramines (formula (V)) is for example sold under the name Jeffamine EDR series by the company Huntsman.
According to other embodiments, the polyamine may be a primary polyetheramine comprising three amine groups. Alternatively, the polyamine may be a secondary or tertiary polyamine comprising three amine groups.
Thus, when it is a polyetheramine comprising three amine groups, it can be of formula (VI):
R18, R19, R28, R29, R29, R38, and R39 may independently represent a group comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and more preferably from 1 to 2 carbon atoms. These groups may be linear or branched and saturated or unsaturated.
R18, R19, R28, R29, R29, R38, and R39 may independently be chosen from an alkyl group, a cycloalkyl group, or an aryl group, these groups being as described above. Preferably, at least one of R18, R19, R28, R29, R29, R38, and R39 is an alkyl group. More preferably, R18, R19, R28, R29, R29, R38, and R39 are chosen from a methyl group or an ethyl group.
According to certain preferred embodiments, R18, R19, R28, R29, R29, R38, and R39 may be identical, for example they are all a methyl group.
According to other embodiments, R18, R19, R28, R29, R29, R38, and R39 may be different from one another.
According to certain embodiments, R18 is different from R28 and/or R39.
According to certain embodiments, R19 is different from R29 and/or R39.
According to preferred embodiments, at least one of R18, R19 and/or at least one of R28, R29 and/or at least one of R38, R39 and/or is a methyl group and the other of R18, R19 and/or R28, R29 and/or R38, R39 and/or is an ethyl group.
R may represent a hydrogen atom or a group comprising from 1 to 10 carbon atoms, and preferably from 1 to 3 carbon atoms. This group may be linear or branched.
According to certain embodiments, R may be chosen from an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group, the alkyl, cycloalkyl, arylalkyl and aryl groups being as described above.
When R is a group comprising from 1 to 10 carbon atoms, it is preferably an alkyl group, preferably comprising from 1 to 3 carbon atoms, and preferably from 1 to 2 carbon atoms.
According to certain embodiments, R is a hydrogen atom.
According to other embodiments, R is an ethyl group.
Ri, Rii, Riii and Riv are also as detailed above.
According to certain embodiments, z1, z2 and z3 may represent a number from 0 to 80, and preferably from 0 to 70. For example, z1, z2 and Z3 may be from 0 to 5; or from 5 to 10; or from 10 to 15; or from 15 to 20; or from 20 to 25; or from 25 to 30; or from 30 to 35; or from 35 to 40; or from 40 to 45; or from 45 to 50; or from 50 to 55; or from 55 to 60; or from 60 to 65; or from 65 to 70; or from 70 to 75; or from 75 to 80. The numbers z1, z2 and z3 may or may not be an integer.
According to certain embodiments, w1, w2 and w3 may represent a number from 0 to 50, and preferably from 0 to 40. For example, w1, w2 and w3 may be from 0 to 5; or from 5 to 10; or from 10 to 15; or from 15 to 20; or from 20 to 25; or from 25 to 30; or from 30 to 35; or from 35 to 40. The numbers w1, w2 and w3 may or may not be an integer.
According to certain embodiments, v1, v2 and v3 may represent a number from 0 to 20, and preferably from 0 to 10. For example, v1, v2 and v3 may be from 0 to 2; or from 2 to 4; or from 4 to 6; or from 6 to 8; or from 8 to 10; or from 10 to 12; or from 12 to 14; or from 14 to 16; or from 16 to 18; or from 18 to 20. The numbers v1, v2 and v3 may or may not be an integer.
According to certain embodiments, at least one of z1, z2 and z3 is other than 0.
According to certain embodiments, at least one of v1, v2 and v3 is other than 0.
According to other embodiments, at least one of z1, z2 and z3 is other than 0, and v1, v2 and v3 are equal to 0.
According to certain embodiments, at least one of w1, w2 and w3 is other than 0.
According to other embodiments, at least one of w1, w2 and w3 is equal to 0, and preferably at least two of w1, w2 and w3 and preferably all three of w1, W2 and w3 are equal to 0.
According to certain embodiments, at least one of v1 and z1 is equal to 0 and/or at least one of v2 and z2 is equal to 0 and/or at least one of v3 and z3 is equal to 0.
According to preferred embodiments, at least one of v1 and z1 is equal to 0 and/or at least one of v2 and z2 is equal to 0 and/or at least one of v3 and z3 is equal to 0 and at least one of w1, w2 and w3 is equal to 0, preferably at least two of w1, w2 and w3 and preferably all three of w1, w2 and w3 are equal to 0.
The sum w1+w2+w3 represents the number of ethoxy groups present in the polyamine of formula (VI).
The sum v1+v2+v3+z1+z2+z3 represents the number of ethoxy groups substituted by R18, R18, R28, R29, R38 and R39 (preferably propoxy or butoxy groups) present in the polyamine of formula (VI).
The sum v1+v2+v3+z1+z2+z3 may or may not be an integer. For example, if a mixture of different alkylene oxides is used, this sum corresponds to the average degree of ethoxylation of the ethoxy groups substituted by R18, R18, R28, R29, R38 and R39 (preferably to the degree of propoxylation and/or butoxylation).
The sums z1+z2+z3, v1+v2+v3 and w1+w2+w3 may independently represent a number from 0 to 90, preferentially from 0 to 70, preferentially from 0 to 50 and even more preferentially from 0 to 30. Thus, this number may be from 0 to 10; or from 10 to 20; or from 20 to 30; or from 30 to 40; or from 40 to 50; or from 50 to 60; or from 60 to 70; or from 70 to 80; or from 80 to 90.
According to certain embodiments, when w1, w2, w3, z1, z2 and z3 are equal to 0, v1+v2+v3 may be from 2 to 90, and preferably from 4 to 90. For example, this sum may be from 2 to 5; or from 5 to 10; or from 10 to 20; or from 20 to 30; or from 30 to 40; or from 40 to 50; or from 50 to 60; or 60 or 70; or from 70 to 80; or 80 to 90.
The number n may represent a number from 0 to 30, preferably from 1 to 20, and more preferably from 1 to 10. For example, n may be from 0 to 5; or from 5 to 10; or from 10 to 15; or from 15 to 20; or from 20 to 25; or from 25 to 30.
According to certain preferred embodiments, n may be 0 or 1.
The polyetheramines of formula (VI) may have a molecular mass of 300 to 6000 g/mol, and preferably of 300 to 5000 g/mol. For example, the polyetheramines of formula (VI) may have a molecular mass of 300 to 500 g/mol; or of 500 to 750 g/mol; or of 750 to 1000 g/mol; or of 1000 to 1250 g/mol; or of 1250 to 1500 g/mol; or of 1500 to 1750 g/mol; or of 1750 to 2000 g/mol; or of 2000 to 2250 g/mol; or of 2250 to 2500 g/mol; or of 2500 to 2750 g/mol; or of 2750 to 3000 g/mol; or of 3000 to 3250 g/mol; or of 3250 to 3500 g/mol; or of 3500 to 3750 g/mol; or of 3750 to 4000 g/mol; or of 4000 to 4250 g/mol; or of 4250 to 4500 g/mol; or of 4500 to 4750 g/mol; or of 4750 to 5000 g/mol; or of 5000 to 5250 g/mol; or of 5250 to 5500 g/mol; or of 5500 to 5750 g/mol; or of 5750 to 6000 g/mol.
This type of polyetheramines (formula (VI)) is for example sold under the names Jeffamine T series and Jeffamine ST series by the company Huntsman.
In all of the formulae above, the groups with indices t, x, y, v, w, z, vi, wi, and zi may or may not be adjacent in the molecule. For example, ethoxy groups may alternate randomly (according to a certain statistical distribution) with propoxy and/or butoxy groups along the same chain.
Alternatively, other types of polyamines that may be used in the context of the present invention are polyethyleneimines (or polyaziridines), that is to say a polymer comprising a repeating unit composed of the amine group and of the biradical “—CH2CH2—” group. These types of polyamines may be linear, branched or dendrimers. Examples include tetraethylenepentamine, EPOMIN SP012 and also the polyethyleneimines of the Lupasol® name (in particular Lupasol® FG) sold by the company BASF.
According to the invention, the borane can form a complex with the amine, with a molar ratio of borane to the amine of 0.1 to 10, and preferably of 0.5 to 5. Preferably, this ratio is from 0.5 to 2. This ratio may in particular be from 0.1 to 0.5; or from 0.5 to 1; or from 1 to 2; or from 2 to 4; or from 4 to 6; or from 6 to 8; or from 8 to 10. For example, when a monoamine is involved, this ratio is preferably approximately 1. However, when a diamine is involved, this ratio is preferably approximately 2.
The borane-amine complex may be used at a content by mass of 0.01% to 25%, and preferably of 0.1% to 20%, relative to the mass of the radically polymerizable compound. This content may in particular be from 0.01% to 0.1%; or from 0.1% to 1%; or from 1% to 2%; or from 2% to 3%; or from 3% to 4%; or from 4% to 5%; or from 5% to 6%; or from 6% to 7%; or from 7% to 8%; or from 8% to 9%; or from 9% to 10%; or from 10% to 11%; or from 11% to 12%; or from 12% to 13%; or from 13% to 14%; or from 14% to 15%; or from 15% to 16%; or from 16% to 17%; or from 17% to 18%; or from 18% to 19%; or from 19% to 20%; or from 20% to 21%; or from 21% to 22%; or from 22% to 23%; or from 23% to 24%; or from 24% to 25%.
More particularly, the content of borane-amine complex must be sufficient to allow a complete reaction.
According to certain embodiments, the borane-amine complex may be prepared according to the process described in the patent EP 2189463 or according to the process described in the article by P. Veeraraghavan Ramachand ran et al. (Amine-boranes bearing borane-incompatible functionalities: application to selective amine protection and surface functionalization, Chem. Commun., 2016, 52, 11885). More particularly, the borane-amine complex may be prepared by reacting an amine as described above with a borohydride compound, such as sodium borohydride, potassium borohydride or lithium borohydride. This reaction may in particular be carried out in the presence of an acid such as an inorganic acid such as sulfuric acid, methanesulfonic acid, hydrochloric acid, nitric acid, boric acid, and preferably in the presence of sulfuric acid.
The borane present in the borane-amine complex can thus initiate the polymerization of a radically polymerizable compound.
The composition which will be polymerized comprises at least one radically polymerizable compound. The radically polymerizable compound comprises at least one ethylenic bond. “Radical polymerization” is a chain polymerization which involves radicals as active species. It involves initiation, propagation, termination and chain transfer reactions. Thus, the borane present in the borane-amine complex can initiate the polymerization of the polymerizable compound(s) to form a network of polymer(s).
The radically polymerizable compound may comprise any monomer, oligomer or polymer, and also mixtures thereof, comprising an olefinic unsaturation and being radically polymerizable. For example, the radically polymerizable compound may be chosen from styrene, vinyl, acrylic and methacrylic monomers. These may include styrene, α-methylstyrene, vinyl esters such as vinyl neodecanoate and vinyl acetate, acrylic and methacrylic monomers or oligomers such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid amides (or acrylamides), methacrylic acid amides (or methacrylamides), acrylic acid esters (or acrylates) and methacrylic acid esters (or methacrylates).
According to preferred embodiments, the radically polymerizable compound is an acrylic or methacrylic monomer such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, acrylates and methacrylates.
The radically polymerizable compound may for example be chosen from acrylic acid, methacrylic acid, acrylate monomers, methacrylate monomers, and mixtures thereof, the alkyl group of the acrylic esters (acrylates) and methacrylic esters (methacrylates) preferably comprising from 1 to 22 carbon atoms, being saturated or unsaturated, linear, branched or cyclic, and possibly including at least one heteroatom (O, S) or one ester function (—COO—); and the alkyl group preferably comprising from 1 to 12 carbon atoms and being linear, branched or cyclic.
Advantageously, the radically polymerizable compound may be chosen from alkyl and cycloalkyl acrylates and methacrylates such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate (SR440 sold by Sartomer), 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate (SR395 sold by Sartomer), lauryl acrylate (SR335 sold by Sartomer), tridecyl acrylate (SR489 sold by Sartomer), C12-C14 alkyl acrylate (SR336 sold by Sartomer), n-octadecyl acrylate (SR484 sold by Sartomer), C16-C18 alkyl acrylate (SR257C sold by Sartomer), cyclohexyl acrylate, t-butylcyclohexyl acrylate (SR217 sold by Sartomer), 3,3,5-trimethylcyclohexyl acrylate (SR420 sold by Sartomer), isobornyl acrylate (SR506D sold by Sartomer), methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, allyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, tridecyl methacrylate, and mixtures thereof. Particularly preferred compounds are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
In addition, the radically polymerizable compound may be chosen from acrylates and methacrylates comprising heteroatoms, that is to say acrylates and methacrylates which contain at least one atom which is not a carbon or hydrogen in the group of the alcohol part of the ester (without taking into account the atoms of the ester group itself). Preferably, the atom is an oxygen. Thus, the radically polymerizable compound may be chosen from tetrahydrofurfuryl acrylate (SR285 sold by Sartomer), tetrahydrofurfuryl methacrylate (SR203H sold by Sartomer), glycidyl acrylate, 2-hydroxyethyl acrylate, 2- and 3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- and 3-ethoxypropyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate (SR256 sold by Sartomer), methoxypolyethylene glycol acrylate (preferably comprising 2 to 8 (ethoxy) repeating units), polyethylene glycol acrylate (preferably comprising 2 to 8 (ethoxy) repeating units), polypropylene glycol acrylate (preferably comprising 2 to 8 (propoxy) repeating units), polycaprolactone acrylate (SR495B sold by Sartomer), 2-phenoxyethyl acrylate (SR339C sold by Sartomer), 2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethyl acrylate (SR410 sold by Sartomer), 2-[2-[2-(2-nonylphenoxyethoxy)ethoxy]ethoxy]ethyl acrylate (SR504D sold by Sartomer), cyclic trimethylolpropane formal acrylate (SR531 sold by Sartomer), cyclic glycerol formal acrylate, 2-[2-[2-(2-dodecyloxyethoxy)ethoxy]ethoxy]ethyl acrylate (SR9075 sold by Sartomer), glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2- and 3-ethoxypropyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, methoxypolyethylene glycol methacrylate (preferably comprising 2 to 8 (ethoxy) repeating units), polyethylene glycol methacrylate (preferably comprising 2 to 8 (ethoxy) repeating units), polypropylene glycol methacrylate (preferably comprising 2 to 8 (propoxy) repeating units), cyclic trimethylolpropane formal methacrylate, cyclic glycerol formal methacrylate (Visiomer® Glyfoma sold by Evonik), and mixtures thereof. Acrylates and methacrylates of ethylene glycol, diethylene glycol, trimethylpropane, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and pentapropylene may also be used. Particularly preferred compounds are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polycaprolactone acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and polycaprolactone methacrylate.
Diacrylate and dimethacrylate compounds may also be used within the context of this invention. Such compounds include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate (SR238 sold by Sartomer), 3-methyl-1,5-pentanediol diacrylate (SR341 sold by Sartomer), cyclohexanedimethanol diacrylate, neopentyl glycol diacrylate, 1,10-decanediol diacrylate (SR595 sold by Sartomer), tricyclodecanedimethanol diacrylate (SR833S sold by Sartomer), esterdiol diacrylate (SR606A sold by Sartomer), alkoxylated aliphatic diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate (SR272 sold by Sartomer), dipropylene glycol diacrylate (SR508 sold by Sartomer), tripropylene glycol diacrylate (SR306 sold by Sartomer), tetraethylene glycol diacrylate (SR268G sold by Sartomer), ethoxylated and/or propoxylated cyclohexanedimethanol diacrylates, ethoxylated and/or propoxylated hexanediol diacrylates, ethoxylated and/or propoxylated neopentyl glycol diacrylates, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, dipropylene glycol diacrylate, ethoxylated (3) bisphenol A diacrylate (SR349 sold by Sartomer), ethoxylated (10) bisphenol A diacrylate (SR602 sold by Sartomer), ethoxylated (30) bisphenol A diacrylate, ethoxylated (40) bisphenol A diacrylate, polyethylene glycol (200) diacrylate (SR259 sold by Sartomer), polyethylene glycol (400) diacrylate (SR344 sold by Sartomer), polyethylene glycol (600) diacrylate (SR610 sold by Sartomer), propoxylated neopentyl glycol diacrylates, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-hexanediol monoacrylate monomethacrylate, cyclohexanedimethanol dimethacrylate, neopentyl glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, alkoxylated aliphatic methacrylates such as triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethoxylated and/or propoxylated cyclohexanedimethanol dimethacrylates, ethoxylated and/or propoxylated hexanediol dimethacrylates, ethoxylated and/or propoxylated neopentyl glycol dimethacrylates, caprolactone-modified neopentyl glycol hydroxypivalate dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, ethoxylated (10) bisphenol A dimethacrylate, ethoxylated (3) bisphenol A dimethacrylate, ethoxylated (30) bisphenol A dimethacrylate, ethoxylated (40) bisphenol A dimethacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) dimethacrylate, ethoxylated and/or propoxylated neopentyl glycol dimethacrylates, and mixtures thereof.
Triacrylate and trimethacrylate compounds may also be used within the context of this invention. Such compounds include glycerol trimethacrylate, glycerol triacrylate, ethoxylated and/or propoxylated glycerol triacrylates, trimethylolpropane triacrylate (SR351 sold by Sartomer), ethoxylated and/or propoxylated trimethylolpropane triacrylates, pentaerythritol triacrylate (SR444D sold by Sartomer), ethoxylated and/or propoxylated trimethylolpropane triacrylates, trimethylolpropane trimethacrylate, and tris(2-hydroxyethyl)isocyanurate triacrylate (SR368 sold by Sartomer), tris(2-hydroxyethyl)isocyanurate trimethacrylate, ethoxylated and/or propoxylated glycerol trimethacrylates, ethoxylated and/or propoxylated tri methylolpropane trimethacrylates, and pentaerythritol trimethacrylate.
Compounds comprising more than three acrylate or methacrylate groups may also be used such as, for example, pentaerythritol tetraacrylate (SR295 sold by Sartomer), ditrimethylolpropane tetraacrylate (SR355 sold by Sartomer), dipentaerythritol pentaacrylate (SR399 sold by Sartomer), ethoxylated and/or propoxylated pentaerythritol tetraacrylates, pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentamethacrylate and ethoxylated and/or propoxylated pentaerythritol tetramethacrylates.
In addition, the radically polymerizable compound may be chosen from acrylic and methacrylic oligomers such as urethane-acrylates and urethane-methacrylates, polyester-acrylates, polyester-methacrylates, polybutadiene-acrylates (SR307 sold by Sartomer) and polybutadiene-methacrylates. Preferred compounds in this category are for example CN1963, CN1964, CN992, CN981, CN9001, CN9002, CN9012, CN9200, CN964A85, CN965, CN966H90, CN991, CN9245S, CN998B80, CN9210, CN9276, CN9209, PRO21596, CN9014NS, CN9800, CN9400, CN9167, CN9170A86, CN9761, and CN9165A, sold by Sartomer.
Radically polymerizable compounds which may be used within the context of the invention may also include acrylamides and methacrylamides. For example, these monomers may be chosen from acrylamide, methacrylamide, N-(hydroxymethyl)acrylamide, N-(hydroxyethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-(3-methoxypropyl)acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, N-isopropylacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, diacetone acrylamide, N,N′-methylenedimethacrylamide, N,N′-methylenediacrylamide, N,N′-(1,2-dihydroxyethylene)bismethacrylamide and N,N′-(1,2-dihydroxyethylene)bisacrylamide and also from the acrylamides and methacrylamides formed after reaction of acrylic or methacrylic acid (or of the acyl chloride of this acid) with primary and/or secondary (poly)amines such as 1,3-diaminopropane, N,N′-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, polyamidoamines and polyoxyalkylenepolyamines.
The radically polymerizable compound(s) may be present in the composition at a content by mass of 5% to 100%, and preferably of 50% to 100%, relative to the total mass of the composition. This content may for example be from 5% to 10%; or from 10% to 15%; or from 15% to 20%; or from 20% to 25%; or from 25% to 30%; or from 30% to 35%; or from 35% to 40%; or from 40% to 45%; or from 45% to 50%; or from 50% to 55%; or from 55% to 60%; or from 60% to 65%; or from 65% to 70%; or from 70% to 75%; or from 75% to 80%; or from 80% to 85%; or from 85% to 90%; or from 90% to 95%; or from 95% to 100%.
The polymerization process according to the invention comprises the steps of:
Aside from the radically polymerizable compound, the composition may also comprise one or more additives chosen from fillers, plasticizers, tackifying resins, solvents, UV stabilizers, moisture absorbers, fluorescent materials and rheological additives.
The fillers may be chosen from talc, mica, kaolin, bentonite, aluminum oxides, titanium oxides, iron oxides, barium sulfate, hornblende, amphiboles, chrysotile, carbon black, carbon fibers, fumed or pyrogenic silicas, molecular sieves, calcium carbonate, wollastonite, glass beads, glass fibers, and combinations thereof. The fillers may also include nanofillers, such as carbon nanofibers, carbon nanotubes, etc.
As regards the plasticizer, this may be chosen from those known to a person skilled in the art in the coating or adhesive industries. Mention may be made, for example, of plasticizers based on phthalates, polyol esters (such as, for example, pentaerythritol tetravalerate, sold by Perstorp), epoxidized oil, alkylsulfonic esters of phenol (the Mesamoll® product sold by Lanxess), and mixtures thereof.
The tackifying resin may in particular be chosen from: resins obtained by polymerization of terpene hydrocarbons and of phenols, in the presence of Friedel-Crafts catalysts, such as the Dertophene® 1510 resin available from DRT having a molar mass of approximately 870 Da, Dertophene® H150 available from the same company with a molar mass equal to approximately 630 Da, Sylvarez® TP 95 available from Arizona Chemical having a molar mass of approximately 1200 Da; resins obtained by a process comprising the polymerization of a-methylstyrene such as the Norsolene® W100 resin available from Cray Valley, which is obtained by polymerization of α-methylstyrene without the action of phenols, with a number-average molar mass of 900 Da, Sylvarez® 510 which is also available from Arizona Chemical with a molar mass of approximately 1740 Da, the process for the production of which also comprises the addition of phenols; natural-origin or modified rosins, and derivatives thereof which are hydrogenated, dimerized, polymerized or esterified with monoalcohols or polyols such as the Sylvalite® RE 100 resin which is an ester of rosin and of pentaerythritol available from Arizona Chemical and has a molar mass of approximately 1700 Da; resins obtained by hydrogenation, polymerization or copolymerization of mixtures of unsaturated aliphatic hydrocarbons having approximately 5, 9 or 10 carbon atoms obtained from petroleum fractions; terpene resins; copolymers based on natural terpenes; and acrylic resins having a viscosity at 100° C. of less than 100 Pa·s.
The solvent may be a solvent which is volatile at ambient temperature (temperature of the order of 23° C.). The volatile solvent may, for example, be chosen from alcohols which are volatile at ambient temperature, such as ethanol or isopropanol. Alternatively, the solvent may be tetrahydrofuran (THF). The volatile character of the solvent makes it possible for the polymer, obtained after crosslinking the composition, to no longer contain solvent.
The UV stabilizers may be chosen from benzotriazoles, benzophenones, “hindered” amines, such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and mixtures thereof. Mention may be made, for example, of the products Tinuvin® 328 or Tinuvin™ 770, sold by BASF.
The fluorescent material may for example be 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) (Uvitex® OB).
As regards the rheological additives, these may be chosen from those known to a person skilled in the art in the coating or adhesive industries. Mention may be made, for example, of silica (in particular pyrogenic silica), or a micronized amide wax (such as, for example, the Crayvallac series sold by Arkema).
The additives may be present in the composition at a content by mass of 0.01% to 5%, and preferably of 0.01% to 3%, relative to the total mass of the composition. Thus, the additives may in particular be present in the composition at a content by mass of 0.01% to 0.5%; or of 0.05% to 0.1%; or of 0.1% to 0.5%; or of 0.5% to 1%; or of 1% to 1.5%; or of 1.5% to 2%; or of 2% to 2.5%; or of 2.5% to 3%; or of 3% to 3.5%; or of 3.5% to 4%; or of 4% to 4.5%; or of 4.5% to 5%.
The borane-amine complex may be brought into contact with the composition for example by mixing the composition with the complex. This mixing may for example be carried out at ambient temperature.
After the step of bringing the borane-amine complex into contact with the composition, the process according to the invention may comprise a step of heating the mixture of borane-amine complex and composition so as to facilitate the crosslinking of the polymerizable compound. According to certain embodiments, the heating can be carried out at a temperature of 20 to 100° C., and preferably of 35 to 85° C. Thus, this temperature can in particular be from 20 to 25° C.; or from 25 to 30° C.; or from 30 to 35° C.; or from 35 to 40° C.; or from 40 to 45° C.; or from 45 to 50° C.; or from 50 to 55° C.; or from 55 to 60° C.; or from 60 to 65° C.; or from 65 to 70° C.; or from 70 to 75° C.; or from 75 to 80° C.; or from 80 to 85° C.; or from 85 to 90° C.; or from 90 to 95° C.; or from 95 to 100° C.
The polymerization according to the invention is carried out in the absence of oxidizing agent and/or additional radical initiator other than the borane-amine complex. Thus, the polymerization of the radically polymerizable compound is initiated solely by the action of the borane-amine complex on the polymerizable compound, without the aid of additional compounds.
The term “oxidizing agent” or “oxidizer” or “oxidant” is understood to mean an elementary substance, a compound or an ion which receives at least one electron from another chemical species during an oxidation-reduction reaction. The oxidant which has accepted at least one electron during this reaction is said to be reduced, whereas the chemical species which has given up at least one electron is said to be oxidized.
In particular, radical initiators of the azoisobutyronitrile (AIBN) type and di-tert-butyl hyponitrite (DTBHN) are absent from the reactive mixture.
In particular, the following oxidizing agents are absent from the reactive mixture: peroxide compounds, persulfate compounds, hypochlorite compounds, permanganate compounds, and perborate compounds.
For example, the peroxide compounds may include organic and inorganic peroxides such as hydrogen peroxide, benzoyl peroxide, dibutyryl peroxide, and peracetic acid.
Persulfate compounds may include potassium persulfate, sodium persulfate, and ammonium persulfate.
Hypochlorite compounds may include sodium hypochlorite and calcium hypochlorite.
Permanganate compounds may include potassium permanganate.
Perborate compounds may include sodium perborate.
Also absent from the reactive mixture are additional radical initiators, such as: titanium salts (in particular titanium trichloride and titanium tetrachloride), zirconium salts (in particular zirconium tetrachloride), aluminum salts, iron salts, cobalt salts, nickel salts, osmium salts, ruthenium salts, rhodium salts, iridium salts, palladium salts, platinum salts, manganese salts, chromium salts, molybdenum salts, hafnium salts, tantalum salts, vanadium salts, uranium salts, neodymium salts, thorium salts, and tungsten salts.
The polymerization of the radically polymerizable compound may have a duration of from 15 minutes to 3 days, and preferably from 30 minutes to 2 days.
The polymerization process according to the invention makes it possible to obtain polymers having a number-average molar mass of 1000 to 1 000 000 g/mol, preferably from 1000 to 500 000 g/mol and preferably from 1000 to 250 000 g/mol. The number-average molecular mass can be measured by gel permeation chromatography (GPC).
The invention thus provides a polymerizable composition comprising at least one radically polymerizable compound (as described above) and a complex of borane BH3 with an amine (as described above). This composition is devoid of oxidizing agent and/or additional radical initiator other than the complex of borane BH3 with an amine. In other words, the polymerizable composition comprises the composition described above comprising the radically polymerizable compound and the borane-amine complex and it may be formed by mixing the composition described above comprising the radically polymerizable compound with the borane-amine complex.
The polymerizable composition according to the invention can in particular be used for the treatment of substrates having a low surface energy. More particularly, the polymerizable composition according to the invention can be used for the treatment of substrates having a surface energy of less than or equal to 45 mJ/m2, preferably of less than or equal to 40 mJ/m2, and more preferably of less than or equal to 35 mJ/m2. For example, this surface energy may be from 10 to 15 mJ/m2; or from 15 to 20 mJ/m2; or 20 to 25 mJ/m2; or from 25 to 30 mJ/m2; or 30 to 35 mJ/m2; or from 35 to 40 mJ/m2; or from 40 to 45 mJ/m2. Substrates exhibiting a low surface energy are, for example, polyolefins such as polyethylene, polypropylene, polybutadiene, polyisoprene, poly(vinylidene fluoride), polytetrafluoroethylene, and also the copolymers thereof. These surface energy values are well known in the prior art.
According to certain embodiments, the polymerizable composition may be coated onto the surface of the substrate at a temperature of 20 to 100° C., and preferably of 35 to 85° C.
Thus, the polymerizable composition can form a layer on the surface of the substrate. This layer may have a thickness of 1 μm to 500 mm, and preferably of 10 μm to 100 mm, and more preferably of 10 μm to 10 mm.
According to certain embodiments, the polymerizable composition according to the invention can be used as an adhesive composition, so as to bond two substrates together. Thus, after crosslinking, the composition can form an adhesive layer holding two substrates fixed together. More particularly, after coating the polymerizable composition on the surface of a substrate, the surface of an additional substrate can be brought into contact with the coated surface, so as to bond the two substrates. According to certain embodiments, bringing the additional substrate into contact with the coated surface, the assembly can be placed under a heating press so as to accelerate the bonding of the two substrates together. The temperature of this press can be for example from 60 to 110° C., and preferably from 80 to 100° C.
Preferably, at least one of the two substrates is a substrate having a low surface energy. The second substrate can also be a substrate having a low surface energy. Alternatively, the second substrate may be a material chosen from paper, a metal such as aluminum, a polymeric material other than low surface energy substrates, such as polyamides, polystyrene, vinyl polymers such as polyvinyl chloride, polyethers, polyurethanes, polyesters, acrylonitrile-butadiene-styrene, poly(methyl methacrylate), and natural or synthetic rubber.
According to other embodiments, the polymerizable composition according to the invention can be used as a coating on the surface of a substrate. Thus, after crosslinking, the composition can form a layer covering the surface of the substrate in order for example to modify one or more properties of its surface. Preferably, this substrate has a low surface energy, as described above.
According to yet other embodiments, the polymerizable composition according to the invention can be used as a primer. The term “primer” is understood to mean a layer coated on a substrate so as to improve one or more surface properties of this substrate (for example so as to improve the adhesion of the substrate to a material), so that additional layers can be applied to the substrate comprising the primer layer. For example, the coating of the polymerizable composition according to the invention on a low surface energy substrate can make it possible to increase the surface energy thereof in order to facilitate the application of another adhesive composition above the polymerizable composition.
Thus, the articles manufactured after application of the polymerizable composition according to the invention comprise at least one surface coated with the polymerizable composition.
When the polymerizable composition is used as a primer or coating, this is an external surface of the article.
When the polymerizable composition is used as an adhesive, this is an internal surface of the article, that is to say a surface of the article which is in contact with, for example, another surface of the article, with the polymerizable composition being located between these two surfaces.
The crosslinked polymerizable composition may exhibit an elongation at break of greater than or equal to 30%. This elongation at break may be, for example, from 30% to 40%; or from 40% to 50%; or from 50% to 60%; or from 60% to 70%; or from 70% to 80%; or from 80% to 90%; or from 90% to 100%; or greater than 100%. The elongation at break can be measured according to the standard ISO 37.
The crosslinked polymerizable composition may exhibit a modulus of elasticity of less than or equal to 100 MPa and more preferably of less than or equal to 60 MPa; it may, for example, be from 1 to 100 MPa, preferably from 3 to 50 MPa. The modulus of elasticity can be measured according to the standard ISO 37.
The examples that follow illustrate the invention without limiting it.
In example 1, different amines are used for the polymerization of methyl methacrylate by the borane-amine complex. The polymerization is carried out starting from a composition comprising 100% methyl methacrylate at different temperatures (40, 60 and 80° C.) and with different contents by mass of borane-amine complex (0.1%, 1% and 10% relative to the mass of methyl methacrylate). More particularly, the borane-amine complex is mixed with the composition comprising the methacrylic monomer and then this mixture is heated to 40, 60 or 80° C.
In example 2, the polymerization of the styrene is carried out with different borane-amine complexes at a content of 16% relative to the mass of the styrene and at a temperature of 60° C. The polymerization is carried out by mixing a composition comprising 100% styrene with a borane-amine complex and heating this mixture to 60° C.
The table below includes various amines present in the borane-amine complexes (reactions 1 to 22). According to these reactions, the polymerization is carried out with 10% borane-amine complex and at a temperature of 60° C.
The term “reaction time” is understood to mean the duration of polymerization from the moment at which the borane-amine complex is mixed with the polymerizable compound up to the moment that the polymer is formed (the polymer formed is in a solid state whereas the initial mixture of borane-amine complex with the polymerizable compound is in a liquid state).
It is observed that the process according to the invention makes it possible to synthesize methacrylic polymers in an efficient manner using different borane-amine complexes.
Next, the polymerization of styrene according to the process of the invention is studied. The table below includes various amines present in the borane-amine complexes (reactions 23 and 24). As mentioned above, the polymerization is carried out with 16% borane-amine complex and at a temperature of 60° C.
It is observed that the process according to the invention makes it possible to synthesize styrene polymers in an efficient manner using different borane-amine complexes.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR1908159 | Jul 2019 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2020/051239 | 7/9/2020 | WO |
