Patent Application
20230323031
The present disclosure relates broadly to a polymer comprising a plurality of active amine groups in the backbone of the polymer, a derivative thereof and use of said polymer. The present disclosure also relates to methods of preparing said polymer and a derivative thereof.
There is increasing demand for amine containing polymers in a wide range of applications such as in the chemicals, pharmaceuticals, cosmetics, consumer and personal care industries.
However, the search for a suitable amine containing polymer is often challenging.
This is because amine polymers have several limitations and are far from desirable. This is further elaborated below.
Amine polymers often lack biocompatibility and biodegradability. There are also very few amine polymers that are soluble in water. One of the most commercially utilized amine polymer is polyethylene imine (PEI). Particularly, the branched form of PEI is commonly used due to its unique structure of having all primary, secondary and tertiary amine groups, which makes PEI a strong metal chelating and highly interacting polymer. However, there are concerns over its cytotoxicity (mainly due to the plurality of —NH2 group). Attempts have been made to reduce/avoid cytotoxicity of PEI. For example, modifications have been made on PEI with either polyethylene glycol (PEG) groups or subjecting PEI to ethoxylation. However, such modified polymers are still far from desirable as they still lack biocompatibility and biodegradability.
In view of the above, there is a need to address or at least ameliorate the above-mentioned problems. In particular, there is a need to provide a polymer comprising a plurality of active amine groups in the backbone of the polymer, a derivative of and related methods that address or at least ameliorate the above-mentioned problems.
In one aspect, there is provided a polymer or derivative thereof comprising a plurality of active amine groups in the backbone, wherein the polymer is a reaction product of a reaction between one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups.
In one embodiment, the polymer is a bio-based polymer and at least one of the bis-carbonates and/or at least one of the amine compounds having at least two terminal amino groups is derived from a bio-based source.
In one embodiment, the content of the polymer derived from a bio-based source ranges from 30% to 90% by weight of the polymer.
In one embodiment, the plurality of active amine groups comprise a plurality of different amine functionalities.
In one embodiment, the one or more amine compounds having at least two terminal amino groups are represented by general formula (1) and the one or more bis-carbonates are represented by general formula (2):
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof.
In one embodiment, the polymer comprises one or more structural units represented by general formula (3), one or more structural units represented by general formula (4):
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester or combinations thereof.
In one embodiment, the structural units represented by general formula (3) are linked to structural units represented by general formula (4) via carbamate/urethane linkages.
In one embodiment, A is selected from the following general formula (5), (6), (7) or (8):
In one embodiment, ring N1 and N2 are each independently selected from the group consisting of 3-pyrroline, 2-pyrroline, 2H-pyrrole, 1H-pyrrole, 2-pyrazoline, 2-imidazoline, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, isoxazole, isothiazole, thiazole, 1,2,5-oxadiazole, 1,2,3-oxadizole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, diphenylamine, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, 1,3,5-triazine, oxazine, thiazine, pyrazolidine, imidazolidine, piperidine, N-methylpiperidine, N-phenylpiperidine, pyrrolidine, piperazine, morpholine, thiomorpholine, 1,4-diazepane, quinoline, acridine and combinations thereof.
In one embodiment, B is selected from the following general formula (9), (10) or (11):
In one embodiment, R1 to R7 are each independently selected from a single bond, optionally substituted C1-C20 alkyl, C1-C20 optionally substituted alkenyl, C1-C20 optionally substituted alkynyl, C1-C20 optionally substituted cycloalkyl and C1-C20 optionally substituted cycloalkenyl; and Ra and Rb are each independently selected from the group consisting of H, optionally substituted C1-C20 alkyl, optionally substituted C1-C20 alkenyl and optionally substituted C1-C20 alkynyl.
In one embodiment, the one or more amine compounds having at least two terminal amino groups are selected from the group consisting of diethylenetriamine (DETA), diamino-N-methyldiethylamine (DMA), triethylenetetramine (TETA), diamino-N-methyldipropylamine (DMPA), pentaethylenehexamine (PEHA), bis(3-aminopropyl)piperazine (BAP), spermine, spermidine, lysine salt (LyS) and diaminopentane (DAP):
In one embodiment, the one or more bis-carbonates are selected from the group consisting of succinic bis-carbonate (SuBC), adipic bis-carbonate (ABC), butanediol bis-carbonate (BBC), isomers of pyridine bis-carbonate (PBC1), (PBC2), (PBC3), (PBC4), (PBC5) and/or (PBC6):
In one embodiment, the polymer or derivative of any one of the preceding claims selected from the following:
In one embodiment, the polymer or derivative thereof further comprises at least one of a hydroxyl group and an active amine group originally present in the polymer that has been functionalized.
In one embodiment, the polymer or derivative thereof is a grafted polymer obtained by grafting the polymer on a substrate or another polymer.
In one embodiment, the polymer or derivative thereof has one or more of the following properties: water-soluble; hydrolysable; biodegradable; and biocompatible.
In one aspect, there is provided a use of the polymer or derivative thereof disclosed herein as an anti-redepositioning agent, an anti-bacterial agent, an adhesive, an adhesion promoter, a fiber modifier, a pigment dispersant, a chelating agent, a flocculating agent, a wet strength improving additive, a pour point depressant, or a carbon dioxide capture agent.
In one aspect, there is provided a method of preparing the polymer or derivative thereof disclosed herein, the method comprising: polymerizing one or more diamines represented by general formula (1) with one or more biscarbonates represented by general formula (2) to obtain the polymer:
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof.
In one embodiment, the method comprises a) mixing one or more diamines represented by general formula (1) with one or more biscarbonates represented by general formula (2) to obtain a reaction mixture; and b) precipitating the polymer.
In one embodiment, the method further comprises a step of functionalising at least one of a hydroxyl group and an active amine group present in the polymer.
In one embodiment, the method further comprises a step of grafting to at least one of a hydroxyl group and an active amine group present in the polymer to another polymer or substrate.
The term “polymer” as used herein refers to a chemical compound comprising repeating units and is created through a process of polymerization.
The units composing the polymer are typically derived from monomers and/or macromonomers. A polymer typically comprises repetition of a number of constitutional units.
The terms “monomer” or “macromonomer” as used herein refer to a chemical entity that may be covalently linked to one or more of such entities to form a polymer.
The terms “bio-based” or “bio-derived” as used herein broadly refer to the quality of being derived or being originated from living organisms or once-living organisms. Such living organisms may be animal or plants. Therefore, “bio-based source” includes, but is not limited to, a biofeedstock, a plant-based source or combinations thereof.
The term “biocompatible” as used herein broadly refers to a property of being compatible with biological systems or parts of the biological systems without substantially or significantly eliciting an adverse physiological response such as a toxic reaction, an immune reaction, an injury or the like. Such biological systems or parts include blood, cells, tissues, organs or the like.
The term “bond” refers to a linkage between atoms in a compound or molecule. The bond may be a single bond, a double bond, or a triple bond.
The term “alkyl” as a group or part of a group refers to a straight or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of suitable straight and branched alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hexyl, amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 5-methylheptyl, 1-methylheptyl, octyl, nonyl, decyl and the like. The group may be a terminal group or a bridging group.
The term “alkenyl” as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched having 2 to 20 carbon atoms, 2 to 10 carbon atoms, 2 to 6 carbon atoms, or 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms in the chain. The group may contain a plurality of double bonds and the orientation about each double bond is independently E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, vinyl, allyl, 1-methylvinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butentyl, 1,3-butadienyl, 1-pentenyl, 2-pententyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,4-pentadienyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 2-methylpentenyl, 1-heptenyl, 2-heptentyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl and the like. The group may be a terminal group or a bridging group.
The term “alkynyl” as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond and which may be straight or branched having 2 to 20 carbon atoms, 2 to 10 carbon atoms, 2 to 6 carbon atoms, or 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms in the chain. The group may contain a plurality of triple bonds. Exemplary alkynyl groups include, but are not limited to, acetylenyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonynyl, 2-nonynyl, 8-nonynyl, 1-decynyl, 2-decynyl, 9-decynyl and the like. The group may be a terminal group or a bridging group.
The term “cyclic” as used herein broadly refers to a structure where one or more series of atoms are connected to form at least one ring. The term includes, but is not limited to, both saturated and unsaturated 5-membered and saturated and unsaturated 6-membered rings. Examples of groups having a cyclic structure include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, benzene and the like. The term “cyclic” as used herein includes “heterocyclic”.
The term “heterocyclic” as used herein broadly refers to a structure where two or more different kinds of atoms are connected to form at least one ring. For example, a heterocyclic ring may be formed by carbon atoms and at least another atom (i.e. heteroatom) selected from oxygen (O), nitrogen (N) or (NR) and sulfur (S), where R is independently a hydrogen or an organic group. The term also includes, but is not limited to, saturated and unsaturated 5-membered, and saturated and unsaturated 6-membered rings. Examples of groups having a heterocyclic structure include, but are not limited to furan, thiophene, 1H-pyrrole, 2H-pyrrole, 1-pyrroline, 2-pyrroline, 3-pyrroline, 1-pyrazoline, 2-pyrazoline, 3-pyrazoline, 2-imidazoline, 3-imidazoline, 4-imidazoline, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-oxadiazole, disubstituted 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, 1,3-dioxolane, 1,2-oxathiolane, 1,3-oxathiolane, pyrazolidine, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, thiazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,4-dioxin, 2H-thiopyran, 4H-thiopyran, tetrahydropyran, thiane, piperidine, 1,4-dioxane, 1,2-dithiane, 1,3-dithiane, 1,4-dithiane, 1,3,5-trithiane, piperazine, morpholine, thiomorpholine and the like.
The term “aromatic” as used herein when referring to hydrocarbons, refers broadly to hydrocarbons having a ring-shaped or cyclic structure with delocalised electrons between carbon atoms. The term encompasses, but is not limited to, monovalent (“aryl”), divalent (“arylene”) monocyclic aromatic groups having 5 to 6 atoms. Examples of such groups include, but are not limited to, benzene, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, benzofuran, benzothiophene, benzopyrrole, benzodifuran, benzodithiophene, benzodipyrrole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine and the like.
The term “heteroaromatic” as used herein when referring to hydrocarbons, refers broadly to aromatic hydrocarbons that have one or more carbon atoms replaced by a heteroatom. The term encompasses, but is not limited to, monovalent (“aryl”), divalent (“arylene”) monocyclic, polycyclic conjugated or fused aromatic groups having 5 to 14 atoms, where 1 to 6 atoms in each aromatic ring are heteroatoms selected from oxygen (O), nitrogen (N) or (NH) and sulfur (S). Examples of such groups include, but are not limited to, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, benzofuran, benzothiophene, benzopyrrole, benzodifuran, benzodithiophene, benzodipyrrole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine and the like.
The term “optionally substituted,” when used to describe a chemical structure or moiety, refers to the chemical structure or moiety wherein one or more of its hydrogen atoms is optionally substituted with a chemical moiety or functional group such as alcohol, alkoxy, alkanoyloxy, alkoxycarbonyl, alkenyl, alkyl (e.g., methyl, ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (—OC(O)alkyl), amide (—C(O)NH-alkyl- or -alkylNHC(O)alkyl), tertiary amine (such as alkylamino, arylamino, arylalkylamino), aryl, aryloxy, azo, carbamoyl (—NHC(O)O-alkyl- or —OC(O)NH-alkyl), carbamyl (e.g., CONH2, as well as CONH-alkyl, CONH-aryl, and CONH-arylalkyl), carboxyl, carboxylic acid, carboxylic acid salt (e.g., —COO—Na+), cyano, ester, ether (e.g., methoxy, ethoxy), halo, haloalkyl (e.g., —CCl3, —CF3, —C(CF3)3), heteroalkyl, isocyanate, isothiocyanate, nitrile, nitro, phosphodiester, sulfide, sulfonamido (e.g., SO2NH2), sulfone, sulfonyl (including alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl), sulfoxide, thiol (e.g., sulfhydryl, thioether) or urea (—NHCONH-alkyl-).
The term “alkoxy” as used herein refers to straight chain or branched alkyloxy groups. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like.
The term “alkoxyalkyl” as used herein is intended to broadly refer to a group containing —R—O—R′, where R and R′ are alkyl as defined herein. The group may be a terminal group or a bridging group.
The term “alkylcarbonyl” as used herein is intended to broadly refer to a group containing —R—C(═O)—, where R is alkyl as defined herein. The group may be a terminal group or a bridging group.
The term “alkylcarbonylalkyl” as used herein is intended to broadly refer to a group containing —R—C(═O)—R′, where R and R′ are alkyl as defined herein.
The group may be a terminal group or a bridging group.
The term “carboxylalkyl” as used herein is intended to broadly refer to a group containing —C(═O)—O—R, where R is alkyl as defined herein. The group may be a terminal group or a bridging group.
The term “oxycarbonylalkyl” as used herein is intended to broadly refer to a group containing —O—C(═O)—R, where R is alkyl as defined herein. The group may be a terminal group or a bridging group.
The term “alkylcarboxylalkyl” as used herein is intended to broadly refer to a group containing —R—C(═O)—O—R′, where R and R′ are alkyl as defined herein.
The group may be a terminal group or a bridging group.
The term “alkoxycarbonylalkyl” as used herein is intended to broadly refer to a group containing —R—O—C(═O)—R′, where R and R′ are alkyl as defined herein. The group may be a terminal group or a bridging group.
The term “oxy” as used herein is intended to broadly refer to a group containing —O—.
The term “carbonyl” as used herein is intended to broadly refer to a group containing —C(═O)—.
The term “oxycarbonyl” as used herein is intended to broadly refer to a group containing —O—C(═O)—.
The term “carboxyl” as used herein is intended to broadly refer to a group containing —C(═O)—O—R, where R is hydrogen or an organic group.
The term “halogen” represents chlorine, fluorine, bromine or iodine. The term “halo” represents chloro, fluoro, bromo or iodo.
The term “amine group” or the like is intended to broadly refer to a group containing —NR2, where R is independently a hydrogen or an organic group. The group may be a terminal group or a bridging group.
The term “amide group” or the like is intended to broadly refer to a group containing —C(═O)NR2, where R is independently a hydrogen or an organic group. The group may be a terminal group or a bridging group.
The term “micro” as used herein is to be interpreted broadly to include dimensions from about 1 micron to about 1000 microns.
The term “nano” as used herein is to be interpreted broadly to include dimensions less than about 1000 nm, less than about 500 nm, less than about 100 nm or less than about 50 nm.
The term “particle” as used herein broadly refers to a discrete entity or a discrete body. The particle described herein can include an organic, an inorganic or a biological particle. The particle used described herein may also be a macro-particle that is formed by an aggregate of a plurality of sub-particles or a fragment of a small object. The particle of the present disclosure may be spherical, substantially spherical, or non-spherical, such as irregularly shaped particles or ellipsoidally shaped particles. The term “size” when used to refer to the particle broadly refers to the largest dimension of the particle. For example, when the particle is substantially spherical, the term “size” can refer to the diameter of the particle; or when the particle is substantially non-spherical, the term “size” can refer to the largest length of the particle.
The terms “coupled” or “connected” as used in this description are intended to cover both directly connected or connected through one or more intermediate means, unless otherwise stated.
The term “associated with”, used herein when referring to two elements refers to a broad relationship between the two elements. The relationship includes, but is not limited to a physical, a chemical or a biological relationship.
For example, when element A is associated with element B, elements A and B may be directly or indirectly attached to each other or element A may contain element B or vice versa.
The term “adjacent” used herein when referring to two elements refers to one element being in close proximity to another element and may be but is not limited to the elements contacting each other or may further include the elements being separated by one or more further elements disposed therebetween.
The term “and/or”, e.g., “X and/or Y” is understood to mean either “X and Y” or “X or Y” and should be taken to provide explicit support for both meanings or for either meaning.
Further, in the description herein, the word “substantially” whenever used is understood to include, but not restricted to, “entirely” or “completely” and the like. In addition, terms such as “comprising”, “comprise”, and the like whenever used, are intended to be non-restricting descriptive language in that they broadly include elements/components recited after such terms, in addition to other components not explicitly recited. For example, when “comprising” is used, reference to a “one” feature is also intended to be a reference to “at least one” of that feature. Terms such as “consisting”, “consist”, and the like, may in the appropriate context, be considered as a subset of terms such as “comprising”, “comprise”, and the like. Therefore, in embodiments disclosed herein using the terms such as “comprising”, “comprise”, and the like, it will be appreciated that these embodiments provide teaching for corresponding embodiments using terms such as “consisting”, “consist”, and the like. Further, terms such as “about”, “approximately” and the like whenever used, typically means a reasonable variation, for example a variation of +/−5% of the disclosed value, or a variance of 4% of the disclosed value, or a variance of 3% of the disclosed value, a variance of 2% of the disclosed value or a variance of 1% of the disclosed value.
Furthermore, in the description herein, certain values may be disclosed in a range. The values showing the end points of a range are intended to illustrate a preferred range. Whenever a range has been described, it is intended that the range covers and teaches all possible sub-ranges as well as individual numerical values within that range. That is, the end points of a range should not be interpreted as inflexible limitations. For example, a description of a range of 1% to 5% is intended to have specifically disclosed sub-ranges 1% to 2%, 1% to 3%, 1% to 4%, 2% to 3% etc., as well as individually, values within that range such as 1%, 2%, 3%, 4% and 5%. It is to be appreciated that the individual numerical values within the range also include integers, fractions and decimals. Furthermore, whenever a range has been described, it is also intended that the range covers and teaches values of up to 2 additional decimal places or significant figures (where appropriate) from the shown numerical end points. For example, a description of a range of 1% to 5% is intended to have specifically disclosed the ranges 1.00% to 5.00% and also 1.0% to 5.0% and all their intermediate values (such as 1.01%, 1.02% . . . 4.98%, 4.99%, 5.00% and 1.1%, 1.2% . . . 4.8%, 4.9%, 5.0% etc.) spanning the ranges. The intention of the above specific disclosure is applicable to any depth/breadth of a range.
Additionally, when describing some embodiments, the disclosure may have disclosed a method and/or process as a particular sequence of steps. However, unless otherwise required, it will be appreciated that the method or process should not be limited to the particular sequence of steps disclosed. Other sequences of steps may be possible. The particular order of the steps disclosed herein should not be construed as undue limitations. Unless otherwise required, a method and/or process disclosed herein should not be limited to the steps being carried out in the order written. The sequence of steps may be varied and still remain within the scope of the disclosure.
Furthermore, it will be appreciated that while the present disclosure provides embodiments having one or more of the features/characteristics discussed herein, one or more of these features/characteristics may also be disclaimed in other alternative embodiments and the present disclosure provides support for such disclaimers and these associated alternative embodiments.
Exemplary, non-limiting embodiments of a polymer comprising a plurality of active amine groups in the backbone of the polymer, a derivative thereof, use of said polymer, and a method of preparing said polymer or a derivative thereof are disclosed hereinafter.
There is provided a polymer comprising a plurality of active amine groups.
In various embodiments, the active amine groups comprise active amine groups present in the backbone of the polymer. Advantageously, the active amine groups are designed to be tunable and/or customizable, depending on the application the polymer is to be used for. In various embodiments, the functionalities and/or properties of the polymer can be changed or tuned, depending on the type of amine groups present in the polymer. The active amine groups may be selected from the group consisting of secondary (2°) amine, tertiary (3°) amine, quaternary ammonium cations (i.e. NR4+) and combinations thereof. For example, a polymer having secondary (2°) amine groups are preferred for applications as additives such as in shampoo, detergents and/or cosmetics due to its anti-redepositioning property. A polymer having secondary (2°) amine groups are also preferred for applications as anti-bacterial materials due to its anti-bacterial property. A polymer having secondary (2°) amine groups are also preferred for applications as adhesive or adhesion promoter due to its hydrogen bonding ability. A polymer having secondary (2°) amine groups are also preferred for water treatment applications as chelating or flocculating agents due to its metal chelation or metal binding ability.
In various embodiments, the plurality of active amine groups comprise a plurality of different amine functionalities. The amine group/functionality may be selected from the group consisting of secondary (2°) amine, tertiary (3°) amine, quaternary ammonium cations (i.e. NR4+) and combinations thereof. In various embodiments, the active amine groups comprise aliphatic amine groups, aromatic amine groups, cyclic amine groups, or combinations thereof. The aliphatic amine may comprise aliphatic secondary amines, aliphatic tertiary amines, aliphatic quaternary ammonium cations, or combinations thereof. The cyclic amine may comprise cyclic secondary amines such as piperazine, imidazolidine, 1,4-diazepane, piperidine, pyrrolidine; cyclic tertiary amines such as N-methylpiperidine and N-phenylpiperidine; cyclic quaternary ammonium cations, or combinations thereof. The aromatic amine may comprise aromatic secondary amines such as diphenylamine; aromatic tertiary amines such as pyridine, pyrimidine, quinoline, acridine; aromatic quaternary ammonium cations, or combinations thereof.
In various embodiments, the nitrogen (N) content of the polymer ranges from about 1% to about 30%, from about 2% to about 29%, from about 3% to about 28%, from about 4% to about 27%, from about 5% to about 26%, from about 6% to about 25%, from about 7% to about 24%, from about 8% to about 23%, from about 9% to about 22%, from about 10% to about 21%, from about 11% to about 20%, from about 12% to about 19%, from about 13% to about 18%, from about 14% to about 17%, or from about 15% to about 16% by weight of the polymer.
Advantageously, due to the presence of a plurality of active amine groups in the backbone, embodiments of the polymer disclosed herein have a higher water solubility and/or water dispersibility than conventional amine functional polymers. For example, the polymer may be more water soluble/dispersible as compared to conventional amine functional polymers such as polyaniline (2° amine), poly(4-aminostyrene) (1° amine), poly(4-vinylpyridine) (aromatic amine), poly(2-(dimethylamino)ethyl methacrylate) or poly(DMAEMA) (3° amine), poly(allylamine) (1° amine), poly(vinylamine) (1° amine), polylysine (1° amine), linear polyethylenimine (PEI) (2° amine), branched polyethylenimine (PEI) (that contains 1°, 2° and 3° amine groups) and branched PEI-g-PEG (that contains 1° and 2° amine groups).
In various embodiments, the polymer is a water-soluble/dispersible polymer, for example, under ambient conditions such as a temperature of about 20° C. to 40° C. The polymer may be soluble in water in both acidic and basic conditions. For example, the polymer can dissolve at a pH below about 3 or in the range of from about 3 to about 10. In some embodiments, the polymer can dissolve at a pH of about 0, pH of about 1, pH of about 2, pH of about 3, pH of about 4, pH of about 5, pH of about 6, pH of about 7, pH of about 8, pH of about 9 or pH of about 10.
In various embodiments, the polymer is organic solvent-soluble polymer. The polymer may be soluble in an organic solvent, e.g. dimethylformamide (DMF), tetrahydrofuran (THF), acetone, dichloromethane (DCM), acetonitrile (ACN), acetone, dimethyl sulfoxide (DMSO) and an alkyl alcohol such as methanol (MeOH), ethanol or propanol.
In various embodiments, the polymer is a cationic polymer. In various embodiments, the polymer is positively charged or comprises an overall net positive charge(s). In various embodiments, the active amine groups (e.g., 2° amine and/or 3° amine groups) present in the polymer becomes partially or completely protonated (e.g., gains protons) via an adjustment in pH value. For example, by lowering the pH value, the 2° amine groups (—NH—) present in the polymer may gain protons (H+) to form positively charged cations (—NH2+—). Advantageously, the positive charge(s) on the polymer allows for embodiments of the polymer to possess anti-redepositioning property, making the polymer ideal/attractive/suitable for use as an additive in shampoo, detergent and/or cosmetics. Without being bound by theory, it is believed that the positive charge(s) on the polymer allow for embodiments of the polymer to be adsorb onto negatively charged particles (e.g., clay or soil particles/deposits), which results in a repulsive force and thereby preventing redeposition of such negatively charged particles during washing.
In various embodiments, the polymer further comprises at least one of an ester group, an ether group, a hydroxyl group, a carbamate/urethane group or combinations thereof. In some embodiments, the polymer comprises at least one ester group, at least one ether group, at least one hydroxyl group, at least one carbamate/urethane group, and a plurality of amine groups. In some embodiments, a plurality of ester groups, a plurality of ether groups, a plurality of hydroxyl group, a plurality of carbamate/urethane groups, and a plurality of amine groups are present in the polymer.
In various embodiments, the polymer comprises monomeric units that are joined/linked together via carbamate/urethane linkages. In various embodiments therefore, the polymer is a polyurethane (PU) polymer.
In various embodiments, the polymer comprises a plurality of hydroxyl groups and a plurality of carbamate/urethane linkages. In various embodiments therefore, the polymer is a polyhydroxyurethane (PHU) polymer.
Advantageously, embodiments of the polymer is substantially devoid of a toxic isocyanate or phosgene. In various embodiments, the polymer is a non-isocyanate polymer, a non-isocyanate polyurethane or a non-isocyanate polyhydroxyurethane.
In various embodiments, the polymer is hydrolysable. Advantageously, the hydrolysability (e.g., due to presence of a plurality of ester groups and/or urethane groups) of the polymer allows for embodiments of the polymer to be degradable, hydrolytic degradable, biodegradable and/or broken down naturally, making the polymer ideal/attractive/suitable for use in applications which require materials used therein to be biocompatible, non-toxic and/or non-skin irritant, for e.g., as antibacterial or anti-fungal agents. In various embodiments, the polymer is compatible with biological systems or parts of the biological systems without substantially or significantly eliciting an adverse physiological response such as a toxic reaction/response, an immune reaction/response, an injury or the like when used on the human or animal body. In various embodiments, the polymer is substantially devoid of materials that elicit an adverse physiological response. It will be appreciated that most conventional amine functional polymers such as polyaniline (2° amine), poly(4-aminostyrene) (1° amine), poly(4-vinylpyridine) (aromatic amine), poly(2-(dimethylamino)ethyl methacrylate) or poly(DMAEMA) (3° amine), poly(allylamine) (1° amine), poly(vinylamine) (1° amine), linear polyethylenimine (PEI) (2° amine), branched polyethylenimine (PEI) (that contains 1°, 2° and 3° amine groups) and branched PEI-g-PEG (that contains 1° and 2° amine groups) are non-degradable.
In various embodiments, the polymer has a rate of hydrolysis, degradation and/or hydrolytic degradation that is higher/faster at a higher pH, for e.g., at a pH above 8.5, at a pH of from about pH 9 to about pH 13, from about pH 10 to about pH 12, or about pH 11. In various embodiments, the rate of hydrolysis and/or degradation is higher at a higher temperature, for e.g., at a temperature that is higher than room temperature, at a temperature above about 25° C., above about 50° C., above about 100° C. or above about 125° C.
In various embodiments, the polymer has a degradability, hydrolytic degradability, biodegradability or biodegradable rate of at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or about 100% (e.g., complete biodegradation) over a time period of about 6 hours, about 12 hours, about 24 hours, about 2 days, about 3 days, about 4 days, about 5 days, about 6 days, about 7 days, about 8 days, about 9 days, about 10 days, about 15 days, about 20 days, about 25 days, about 30 days, about 35 days, about 40 days, about 45 days, about 50 days, about 55 days, about 60 days, about 70 days or about 80 days. The polymer may be substantially susceptible to degradation by biological activity.
In various embodiments, the polymer is capable of undergoing hydrogen bonding. Advantageously, this property of the polymer allows for embodiments of the polymer to be used as adhesive or adhesion promoter. For example, active amine groups (e.g., 2° amine), hydroxyl groups and/or urethane groups present in the polymer may undergo hydrogen bonding. The polymer may undergo hydrogen bonding in aqueous medium (e.g., water), ammonia, alcohols or carboxylic acids.
In various embodiments, the polymer comprises metal-chelating/binding property. In various embodiments, the polymer is capable of binding/chelating metal. Advantageously, this property of the polymer allows for embodiments of the polymer to be used in the formation of metal chelate complex, metal coordination or complex compound. For example, active amine group(s) (e.g., 2° amine, 3° amine, and/or quaternary ammonium cations) present in the polymer may react with or bind to a metal (e.g., metal atom or ion) to form a metal coordination or complex compound. Hydroxyl group(s) present in the polymer may also react with or bind to a metal (e.g., metal atom or ion) to form a metal coordination or complex compound. In various embodiments, the polymer comprises N-chelating groups and/or OH-chelating groups. In various embodiments, the polymer is capable of binding/chelating metal or forming metal chelate complex with metal, e.g. transition metals such as copper, nickel, cobalt, iron, manganese, chromium, vanadium, titanium, zinc, ruthenium, rhodium, palladium or the like. The metal may be a metal atom or metal ion.
In various embodiments, the polymer comprises antibacterial property. Advantageously, this property of the polymer (e.g., due to the presence of 2° amine and/or 3° amine groups) allows for embodiments of the polymer to be used as antibacterial or anti-fungal agents. For example, the polymer may be functionalized with acrylates (e.g., fluorinated acrylates) to make hydrophobic anti-bacterial materials.
In various embodiments, the polymer is capable of undergoing quaternization. For example, active amine groups (e.g., 3° amine and aromatic amine) present in the polymer may undergoes quaternization.
In various embodiments, the polymer is capable of undergoing nucleophilic addition reactions such as Aza-Michael reaction (e.g. room temperature atom-efficient Aza-Michael) and/or amine-epoxide nucleophilic addition reaction with another reactant. The reactant may be α,β-unsaturated carbonyl compounds and epoxy compounds. Advantageously, in various embodiments, the polymer may be functionalized/grafted through nucleophilic addition reactions in the absence of catalyst and/or formation of by-products. The nucleophilic addition reactions such as Aza-Michael reaction and/or amine-epoxide reaction may occur at one or more of the chemical moieties selected from an ester group, an ether group, a hydroxyl group, a carbamate/urethane group or an active amine group (e.g., 2° amine groups) present in the polymer.
In various embodiments, the polymer is capable of being cross-linked. The polymer may be a crosslinkable polymer. In various embodiments, the polymer is cross-linked by using cross-linking agents which include, but is not limited to, acrylates (e.g., bisacrylates) and epoxy compounds (e.g., bisepoxy compounds). Advantageously, this property of the polymer allows for embodiments of the polymer to be made/synthesized into hydrogels. For example, the polymer (hydroxyl and/or amine groups in the polymer) may be cross-linked/functionalized with poly(ethylene glycol) diglycidyl ether (PEGE) to form hydrogels. Advantageously, this property of the polymer also allow for embodiments of the polymer to form a crosslinked coating. For example, the polymer (hydroxyl and/or amine groups in the polymer) may be cross-linked/functionalized with 1,4-butanediol diacrylate (BDDA) to form a crosslinked coating or insoluble film.
In various embodiments, the polymer is capable of forming reversible cross-links. In various embodiments therefore, the polymer is a reversibly crosslinkable polymer.
In various embodiments, the polymer is capable of capturing carbon dioxide (CO2) or being used as a carbon dioxide (CO2) capture material. In one embodiment, the polymer is capable of being used for CO2 capture with capture effectiveness that is similar/comparable/superior to polyethylenimine (PEI)/aminoethanol. In various embodiments, the polymer is capable of releasing captured CO2 at a temperature that is lower than that of commercial/conventional system such as monoethanolamine (MEA) solution. In various embodiments, the polymer is capable of releasing captured CO2 at a temperature of about 120° C., below about 120° C., below about 110° C., below about 100° C., below about 90° C., below about 80° C. or below about 70° C.
In various embodiments, the polymer is capable of interacting fibers and surfaces of like cotton, polyesters (may be hair, pigments, clay as well) and may be used as a surface modification additive. Because of this interaction, embodiments of the polymer may be used as an anti-redepositioning agent for fabrics.
In various embodiments, the polymer is capable of being functionalised to produce at least one of a crosslinked coating, a hydrogel, an antibacterial polymer (e.g permanently cationic), an antifouling agent, a hydrophobic polymer, a fluorinated functional polymer, an oil-soluble polymer, a pour point polymer/depressant, a cationic polymer, zwitterionic polymer, anionic polymer, oleophobic polymer, an enhanced bio-based polymer with increased bio-content, or a precursor to a graft polymer, optionally in the absence of a catalyst.
In various embodiments, the polymer is capable of being functionalised to produce a long chain fatty acid modified amine polymer that is capable of reducing pour point and/or viscosity and/or storage modulus of wax or oil such as synthetic oil and crude oil. In various embodiments, the functionalised polymer displays a pour point depressant property that is better than commercial/conventional system such as poly(octadecyl acrylate).
In various embodiments, the polymer is a reaction product of a reaction between one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups.
In various embodiments, the polymer is a bio-based polymer. In various embodiments, at least one of the monomers (i.e. bis-carbonates and the amine compounds having at least two terminal amino groups) is derived from a bio-based source. In one embodiment, at least the amine compound is bio-based. In one embodiment, at least the bis-carbonate is bio-based. In one embodiment, both monomers (i.e. bis-carbonates and the amine compounds having at least two terminal amino groups) are bio-based or derived from a bio-based source. The polymers disclosed herein are advantageous over conventional amine polymers at least in that the monomers are bio-based/bio-derived. In various embodiments therefore, the reaction products disclosed herein are innocuous biocompatible polymers, making them attractive as alternative sustainable materials for future applications.
In various embodiments, the polymer comprises a high bio-content. The content of the polymer derived from a bio-based source may range from about 20% to about 90% by weight of the polymer. The content of the content of the polymer derived from a bio-based source may range from about 20% to about 90%, from about 25% to about 85%, from about 30% to about 80%, from about 35% to about 75%, from about 40% to about 70%, from about 45% to about 65%, from about 50% to about 60%, or about 55% by weight of the polymer.
In various embodiments, the polymer is a reaction product of a reaction between one or more amine compounds having at least two terminal amino groups represented by general formula (1), one or more bis-carbonates represented by general formula (2), and optionally one or more amine compounds having at least two terminal amino groups represented by general formula (12):
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one amine group (e.g., active amine group);
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof; and C comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons.
In various embodiments, the polymer comprises one or more structural units represented by general formula (3), one or more structural units represented by general formula (4), and optionally one or more structural units represented by general formula (13):
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one amine group (e.g., active amine group);
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester or combinations thereof; and
C comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons.
In various embodiments, the structural units represented by general formula (3) are linked to structural units represented by general formula (4) via carbamate/urethane linkages. For example, the polymer may comprise one or more of the following structural units:
In various embodiments, the polymer comprises structural units represented by general formula (13). For example, the structural units represented by general formula (13) may also be linked to structural units represented by general formula (4) via carbamate/urethane linkages.
In various embodiments, the repeating/structural units represented by general formula (3) present in the polymer may have the same or different types of A. In various embodiments, the repeating/structural units represented by general formula (4) present in the polymer may have the same or different types of B. In various embodiments, the repeating/structural units represented by general formula (13) present in the polymer may have the same or different types of C.
In various embodiments, A is selected from the following general formula (5), (6), (7) or (8):
In various embodiments, R1, R2 and R3 are each independently selected from a single bond, optionally substituted C1-C20 alkyl, C1-C20 optionally substituted alkenyl, C1-C20 optionally substituted alkynyl, C1-C20 optionally substituted cycloalkyl and C1-C20 optionally substituted cycloalkenyl. In various embodiments, Ra and Rb are each independently selected from the group consisting of H, optionally substituted C1-C20 alkyl, optionally substituted C1-C20 alkenyl and optionally substituted C1-C20 alkynyl.
In various embodiments, R1, R2 and R3 are each independently C1-C20 alkyl substituents. In various embodiments, Ra and Rb are each independently selected from the group consisting of H and C1-C20 alkyl substituents. The C1-C20 alkyl substituents may be straight or branched substituents selected from methyl, ethyl, n-propyl, 2-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hexyl, amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 5-methylheptyl, 1-methylheptyl, octyl, nonyl, decyl or the like. For example, R1, R2 and R3 may be each independently selected from the group consisting of —CH—, —CH2CH2—, —CH2CH2CH2— and —CH2CH2CH2CH2—. Ra and Rb may be each independently selected from the group consisting of —H and —CH3.
In various embodiments, ring N1 and N2 are cyclic and/or aromatic amines. In various embodiments, ring N1 and N2 are each independently selected from the group consisting of 3-pyrroline, 2-pyrroline, 2H-pyrrole, 1H-pyrrole, 2-pyrazoline, 2-imidazoline, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, isoxazole, isothiazole, thiazole, 1,2,5-oxadiazole, 1,2,3-oxadizole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, diphenylamine, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, 1,3,5-triazine, oxazine, thiazine, pyrazolidine, imidazolidine, piperidine, N-methylpiperidine, N-phenylpiperidine, pyrrolidine, piperazine, morpholine, thiomorpholine, 1,4-diazepane, quinoline, acridine and combinations thereof.
In various embodiments, p≥1. For example, p may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, or 50. In various embodiments, q≥0. For example, q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, or 50.
In some embodiments, R1 and R2 are each —CH2CH2—, A is general formula (5) and Ra is —H. In such embodiments, the polymer comprises a reaction product derived from diethylenetriamine (DETA). In some embodiments, R1 and R2 are each —CH2CH2—, A is general formula (5) and Ra is —CH3. In such embodiments, the polymer comprises a reaction product derived from diamino-N-methyldiethylamine (DMA). In some embodiments, R1 and R2 are each —CH2CH2CH2—, A is general formula (5) and Ra is —H. In such embodiments, the polymer comprises a reaction product derived from spermidine. In some embodiments, R1 and R2 are each —CH2CH2CH2—, A is general formula (5) and Ra is —CH3. In such embodiments, the polymer comprises a reaction product derived from diamino-N-methyldipropylamine (DMPA). In some embodiments, R1, R2 and R3 are each —CH2CH2—, A is general formula (6) and Ra is —H. In such embodiments, the polymer comprises a reaction product derived from triethylenetetramine (TETA) and/or pentaethylenehexamine (PEHA). In some embodiments, R1 and R3 are each —CH2CH2CH2—, R2 is —CH2CH2CH2CH2—, A is general formula (6) and Ra is —H. In such embodiments, the polymer comprises a reaction product derived from spermine. In some embodiments, R1 and R2 are each —CH2CH2CH2—, A is general formula (7) and ring N1 is piperazine. In such embodiments, the polymer comprises a reaction product derived from bis(3-aminopropyl)piperazine (BAP).
In various embodiments, the one or more bis-carbonates represented by general formula (2) are derived from long chain or aromatic bis olefins. For example, B in general formula (2) comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons.
In various embodiments, B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one of an ether, amine, ester and combinations thereof.
In various embodiments, B is selected from the following general formula (9), (10) or (11):
wherein
R4, R5, R6 and R7 are each independently selected from a single bond, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted cycloalkenyl;
X1 and X2 are each independently selected from the group consisting of a single bond, —O—, —NRc—, —C(═O)—O— and —O—C(═O)—, wherein Rc is selected from the group consisting of H, optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl; and
ring Z is an optionally substituted 5-membered or 6-membered hydrocarbon cyclic ring or an optionally substituted 5-membered or 6-membered heterocyclic ring having up to three heteroatoms independently selected from the group consisting of O, N, S and NH.
It will be appreciated that X1 and/or X2 may be bonded to any available positions on ring Z and R5 and/or R6 may be bonded to any available positions on ring Z.
In various embodiments, R4, R5, R6 and R7 are each independently selected from a single bond, optionally substituted C1-C20 alkyl, C1-C20 optionally substituted alkenyl, C1-C20 optionally substituted alkynyl, C1-C20 optionally substituted cycloalkyl and C1-C20 optionally substituted cycloalkenyl. In various embodiments, Rc is selected from the group consisting of H, optionally substituted C1-C20 alkyl, optionally substituted C1-C20 alkenyl and optionally substituted C1-C20 alkynyl.
In various embodiments, R4, R5, R6 and R7 are each independently C1-C20 alkyl substituents. In various embodiments, Rc is selected from the group consisting of H and C1-C20 alkyl substituents. The C1-C20 alkyl substituents may be straight or branched substituents selected from methyl, ethyl, n-propyl, 2-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hexyl, amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 5-methylheptyl, 1-methylheptyl, octyl, nonyl, decyl or the like. For example, R4, R5, R6 and R7 may be each independently selected from the group consisting of —CH—, —CH2CH2—, —CH2CH2CH2— and —CH2CH2CH2CH2—.
In various embodiments, ring Z is a 5-membered heterocyclic ring having three heteroatoms, two heteroatoms or one heteroatom independently selected from the group consisting of O, N, S and NH. For example, ring Z may be selected from a furan (e.g. disubstituted furan), a thiophene (e.g. disubstituted thiophene), a pyrrole (e.g. disubstituted 1H-pyrrole, disubstituted 2H-pyrrole), pyrone, a pyrroline (e.g. disubstituted 1-pyrroline, disubstituted 2-pyrroline, disubstituted 3-pyrroline), a pyrazoline (e.g. disubstituted 1-pyrazoline, disubstituted 2-pyrazoline, disubstituted 3-pyrazoline), an imidazoline (e.g. disubstituted 2-imidazoline, disubstituted 3-imidazoline, disubstituted 4-imidazoline), a pyrazole (e.g. disubstituted pyrazole), a imidazole (e.g. disubstituted imidazole), a oxazole (e.g. disubstituted oxazole, disubstituted isoxazole), a thiazole (e.g. disubstituted thiazole, disubstituted isothiazole), a triazole (e.g. disubstituted 1,2,3-triazole, disubstituted 1,2,4-triazole), a oxadiazole (e.g. disubstituted 1,2,3-oxadiazole, disubstituted 1,2,4-oxadiazole, disubstituted 1,2,5-oxadiazole, disubstituted 1,3,4-oxadiazole), a thiadiazole (e.g. disubstituted 1,2,3-thiadiazole, disubstituted 1,2,4-thiadiazole, disubstituted 1,2,5-thiadiazole, disubstituted 1,3,4-thiadiazole), a tetrahydrofuran (e.g. disubstituted tetrahydrofuran), a tetrahydrothiophene (e.g. disubstituted tetrahydrothiophene), a pyrrolidine (e.g. disubstituted pyrrolidine), a dioxolane (e.g. disubstituted 1,3-dioxolane, disubstituted 1,2-oxathiolane, disubstituted 1,3-oxathiolane), a pyrazolidine (e.g. disubstituted pyrazolidine), a imidazolidine (e.g. disubstituted imidazolidine) and the like. It will be appreciated that in various embodiments, ring Z may be termed as a disubstituted ring due to it having two bonds to X1 and X2 or R5 and R6.
In various embodiments, the 5-membered heterocyclic ring is heteroaromatic. In such embodiments, ring Z is selected from disubstituted furan, disubstituted thiophene, disubstituted pyrrole, disubstituted pyrazole, disubstituted imidazole, oxazole, disubstituted thiazole, disubstituted triazole, disubstituted oxadiazole, disubstituted thiadiazole and the like.
In various embodiments, ring Z is a 6-membered hydrocarbon cyclic ring. For example, ring Z may be selected from disubstituted cyclohexane, disubstituted cyclohexene and disubstituted benzene.
In various embodiments, ring Z is a 6-membered heterocyclic ring having three heteroatoms, two heteroatoms or one heteroatom independently selected from the group consisting of O, N, S and NH. For example, ring Z may be selected from disubstituted pyridine, disubstituted pyridazine, disubstituted pyrimidine, disubstituted pyrazine, disubstituted 1,2-oxazine, disubstituted 1,3-oxazine, disubstituted 1,4-oxazine, disubstituted thiazine, disubstituted 1,2,3-triazine, 1,2,4-triazine, disubstituted 1,3,5-triazine, disubstituted 2H-pyran, disubstituted 4H-pyran, disubstituted 1,4-dioxin, disubstituted 2H-thiopyran, disubstituted 4H-thiopyran, disubstituted tetrahydropyran, disubstituted thiane, disubstituted piperidine, disubstituted 1,4-dioxane, disubstituted 1,2-dithiane, disubstituted 1,3-dithiane, disubstituted 1,4-dithiane, disubstituted 1,3,5-trithiane, disubstituted piperazine, disubstituted morpholine, disubstituted thiomorpholine and the like.
In various embodiments, the 6-membered hydrocarbon ring Z is heteroaromatic. In such embodiments, ring Z is selected from disubstituted pyridine, disubstituted pyridazine, disubstituted pyrimidine, disubstituted pyrazine, disubstituted 1,2,3-triazine, disubstituted 1,2,4-triazine and disubstituted 1,3,5-triazine and the like.
In various embodiments, ring Z is selected from the group consisting of disubstituted furan, disubstituted tetrahydrofuran and disubstituted pyridine. In various embodiments, ring Z is selected from the group consisting of 2,5-disubstituted furan, 3,4-disubstituted furan, 2,3-disubstituted furan, 2,4-disubstituted furan, 2,5-disubstituted pyridine, 2,6-disubstituted pyridine, 2,3-disubstituted pyridine, 2,4-disubstituted pyridine, 3,5-disubstituted pyridine, 3,4-disubstituted pyridine, 3,4-disubstituted tetrahydrofuran, 2,5-disubstituted tetrahydrofuran, 2,3-disubstituted tetrahydrofuran and 2,4-disubstituted tetrahydrofuran. In some embodiments, ring Z is 2,5-disubstituted furan, 2,5-disubstituted pyridine, 2,6-disubstituted pyridine, 2,4-disubstituted pyridine, 3,5-disubstituted pyridine, or 3,4-disubstituted tetrahydrofuran.
In various embodiments, C comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons. In various embodiments, C comprises optionally substituted C1-C20 alkyl, C1-C20 optionally substituted alkenyl, C1-C20 optionally substituted alkynyl, C1-C20 optionally substituted cycloalkyl and C1-C20 optionally substituted cycloalkenyl. The C1-C20 alkyl substituents may be straight or branched substituents selected from methyl, ethyl, n-propyl, 2-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hexyl, amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 5-methylheptyl, 1-methylheptyl, octyl, nonyl, decyl or the like. For example, C may be selected from the group consisting of —CH—, —CH2CH2—, —CH2CH2CH2— and —CH2CH2CH2CH2—. C may also be optionally substituted with carboxylic acid salt (e.g., —COO—Na+).
Advantageously, embodiments of the polymer disclosed herein are highly customizable. Depending on the application that the polymer is intended, an amine compound having at least two terminal amino groups with the desired amine functionalities (i.e. A) may be selected to combine with a bis-carbonate with the desired chemical functionalities (i.e. B) to eventually obtain the polymer with the desired structural/repeating units represented by general formulae (3) and (4).
In various embodiments, the polymer is derived from two or more different types of bis-carbonates. In various embodiments, the polymer is derived from 2, 3, 4, 5, 6, 7, 8, 9 or 10 different types of bis-carbonates.
In various embodiments, the polymer is derived from two or more different types of amine compounds having at least two terminal amino groups. In various embodiments, the polymer is derived from 2, 3, 4, 5, 6, 7, 8, 9 or 10 different types of amine compounds having at least two terminal amino groups.
In various embodiments, the one or more bis-carbonates represented by general formula (2) are selected from the group consisting of succinic bis-carbonate (SuBC), adipic bis-carbonate (ABC), butane diol bis-carbonate (BBC), isomers of pyridine bis-carbonate (PBC1), (PBC2), (PBC3), (PBC4), (PBC5) and (PBC6):
In various embodiments, the bio-carbonates disclosed herein (namely SuBC, ABC, BBC, PBC1, PBC2, PBC3, PBC4, PBC5 and/or PBC6) are/may be obtained/derived from a bio-based source. Advantageously, using such bio-based/derived bis-carbonates as monomers increase the bio-content of polymer, and consequently the biocompatibility of the polymer, making the polymer compatible with biological systems or parts of the biological systems. It will be appreciated that in various embodiments, embodiments of the method disclosed herein may include the use of bio-carbonates that are not obtained/derived from a bio-based source.
In various embodiments, the one or more amine compounds having at least two terminal amino groups represented by general formula (1) are selected from the group consisting of diethylenetriamine (DETA), diamino-N-methyldiethylamine (DMA), triethylenetetramine (TETA), diamino-N-methyldipropylamine (DMPA), pentaethylenehexamine (PEHA), bis(3-aminopropyl)piperazine (BAP), spermine and spermidine:
In various embodiments, the one or more amine compounds having at least two terminal amino groups represented by general formula (12) are selected from the group consisting of lysine salt (LyS) and diaminopentane (DAP):
In various embodiments, spermine, spermidine, LyS and/or DAP are obtained/derived from a bio-based source. Advantageously, besides imparting amine functionality to the polymer, the use of such amine compounds disclosed herein further increases the bio-content of the polymer, and consequently the biocompatibility of the polymer, making the polymer compatible with biological systems or parts of the biological systems.
In various embodiments, the polymer is selected from the following:
or a derivative thereof, wherein n is an integer that is indicative of the degree of polymerization.
In various embodiments, n≥1. For example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 100, 200, 300, 400, 500 or 1,000.
In various embodiments, the polymer has a glass transition temperature (Tg) of from about −30° C. to about 80° C., from about −25° C. to about 75° C., from about −20° C. to about 70° C., from about −15° C. to about 65° C., from about −10° C. to about 60° C., from about −5° C. to about 55° C., from about 0° C. to about 50° C., from about 5° C. to about 45° C., from about 10° C. to about 40° C., from about 15° C. to about 35° C., from about 20° C. to about 30° C., or about 25° C.
In various embodiments, the polymer has a number average molecular weight (Mn) of from about 500 to about 100,000, from about 1,000 to about 90,000, from about 1,500 to about 80,000, from about 2,000 to about 70,000, from about 2,500 to about 60,000, from about 3,000 to about 50,000, from about 3,500 to about 40,000, from about 4,000 to about 30,000, from about 4,500 to about 20,000, from about 5,000 to about 10,000, from about 5,500 to about 9,500, from about 6,000 to about 9,000, from about 6,500 to about 8,500, from about 7,000 to about 8,000, or about 7,500.
In various embodiments, the polymer has a peak molecular weight (Mp) of from about 500 to about 100,000, from about 1,000 to about 90,000, from about 1,500 to about 80,000, from about 2,000 to about 70,000, from about 2,500 to about 60,000, from about 3,000 to about 50,000, from about 3,500 to about 40,000, from about 4,000 to about 30,000, from about 4,500 to about 20,000, from about 5,000 to about 10,000, from about 5,500 to about 9,500, from about 6,000 to about 9,000, from about 6,500 to about 8,500, from about 7,000 to about 8,000, or about 7,500.
As may be appreciated, the present disclosure also provides a derivative of the polymer/reaction product disclosed above. For example, the derivative may be obtained from functionalizing at least one of a hydroxyl group and an active amine group present in the polymer, or the derivative may be obtained from grafting at least one of a hydroxyl group and an active amine group present in the polymer to another polymer or substrate. In one embodiment, the derivative comprises a functionalized amine derivative and/or a functionalized hydroxyl derivative.
In various embodiments, the polymer further comprises at least one of a hydroxyl group and an active amine group originally present in the polymer that has been functionalised. For example, hydroxyl group(s) and/or active amine group(s) may be functionalized with acrylates (e.g., halogenated acrylates such as fluorinated acrylates) to make hydrophobic anti-bacterial materials. In various embodiments therefore, there is also provided a functionalised product/polymer.
In various embodiments, there is also provided a crosslinked coating/hydrogel/antibacterial polymer (e.g permanently cationic)/antifouling agent/hydrophobic polymer/fluorinated functional polymer/oil-soluble polymer/pour point polymer/pour point depressant/cationic polymer/zwitterionic polymer/anionic polymer/oleophobic polymer/enhanced bio-based polymer with increased bio-content comprising the functionalised product/polymer.
In various embodiments, the polymer is a grafted polymer obtained by grafting the polymer onto another polymer or a substrate. For example, the polymer may be grafted to another polymer or substrate via hydroxyl group(s) and/or active amine group(s) present in the polymer. In various embodiments therefore, there is also provided a grafted product/polymer. The substrate may be a porous and/or solid adsorbent selected from the group consisting of zeolites, metal organic frameworks (MOFs), zeolitic imidazolate frameworks (ZIFs), silica gel, adsorbing porous polymers, carbon, activated carbon and combinations thereof.
In various embodiments, there is also provided use of the polymer as an anti-redepositioning agent, an anti-bacterial agent, an adhesive, an adhesion promoter, a fiber modifier, a pigment dispersant, a chelating agent, a flocculating agent, a wet strength improving additive, a pour point depressant, or a carbon dioxide capture agent.
There is also provided a method of preparing a polymer, the method comprising: polymerizing one or more amine compounds having at least two terminal amino groups represented by general formula (1) with one or more bis-carbonates represented by general formula (2), and optionally one or more amine compounds having at least two terminal amino groups represented by general formula (12):
wherein
A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one amine group (e.g., active amine group);
B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof; and
C comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons.
In various embodiments, the method comprises a) mixing one or more amine compounds having at least two terminal amino groups represented by general formula (1) with one or more bis-carbonates represented by general formula (2), and optionally one or more amine compounds having at least two terminal amino groups represented by general formula (12) to obtain a reaction mixture; and b) precipitating the polymer.
In various embodiments, the mixing step a) is carried out or undertaken at a temperature of from about 10° C. to about 100° C., from about 15° C. to about 95° C., from about 20° C. to about 90° C., from about 25° C. to about 85° C., from about 30° C. to about 80° C., from about 35° C. to about 75° C., from about 40° C. to about 70° C., from about 45° C. to about 65° C., from about 50° C. to about 60° C., about 55° C., or at room temperature.
In various embodiments, the mixing step a) is carried out or undertaken for a time period of from about 30 mins to about 3 days. The mixing step a) may be carried out for about 30 mins, about 35 mins, about 40 mins, about 45 mins, about 50 mins, about 55 mins, about 60 mins, about 65 mins, about 70 mins, about 75 mins, about 80 mins, about 85 mins, about 90 mins, about 100 mins, about 120 mins, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 20 hours, about 24 hours, about 48 hours, or about 72 hours.
In some embodiments, the mixing step a) is carried out in an inert atmosphere or in the absence of oxygen (e.g., by degassing with an inert gas such as nitrogen or argon). In other embodiments, the mixing step a) is carried out in the presence of oxygen (e.g., reaction works in the presence of oxygen).
In various embodiments, the mixing step a) is carried out in the absence of a solvent (e.g. an organic solvent). In various embodiments, the method is substantially devoid of a step containing the use of isocyanates as a reactant. Advantageously, embodiments of the presently disclosed method provide a green and sustainable strategy to produce a polymer having a plurality of active amine groups as use of toxic isocyanates and phosgene are avoided and polymerization may be conducted in the absence of a solvent, i.e. under solvent-less conditions. Embodiments of the method disclosed herein may also be easily scaled up without requiring any specialized external energy input etc. and/or without the production of by-product.
In various embodiments, the method is substantially devoid of a step containing the use of a catalyst. Advantageously, embodiments of the presently disclosed method provide an easy and straightforward strategy to produce a polymer having a plurality of active amine groups as use of catalyst is avoided.
In various embodiments, the mixing step a) is optionally carried out in the presence of an aqueous solution (for e.g., in water) or an organic solvent selected from the group consisting of dimethylformamide (DMF), tetrahydrofuran (THF), 2-methyl tetrahydrofuran, anisole, acetone, dichloromethane (DCM), acetonitrile (ACN), dimethyl sulfoxide (DMSO), γ-valerolactone (GVL), propylene carbonate (PC), dimethylcarbonate (DMC), dioxane, dioxolane, diglyme, acetone, methyl ethyl ketone (MEK), alcohols, esters, ethers, water, sodium hydroxide solution, potassium hydroxide solution and the like and combinations thereof. It is to be appreciated that the type of solvent used is dependent on the type of reactants/monomers used and is not limited to the above.
In various embodiments, the method further comprises one or more post precipitation steps. For example, the method may comprise a step of purifying the polymer formed in the mixture to remove impurities such as excess monomers. The step of purifying the polymer may comprise washing the mixture, filtering the mixture to obtain the polymer and allowing the polymer to dry. The step of washing may be repeated once, twice or thrice. The step of washing may comprise adding a washing medium (e.g., water, diethyl ether). The step of drying may be conducted under vacuum. The step of drying may also be conducted with heat.
In various embodiments, the method further comprises a step of functionalising at least one of a hydroxyl group and an active amine group present in the polymer.
In various embodiments, the method further comprises a step of grafting at least one of a hydroxyl group and an active amine group present in the polymer to another polymer or substrate.
In various embodiments, the step of functionalising and/or grafting comprises nucleophilic addition reactions. In various embodiments, the polymer is functionalized or grafted via nucleophilic addition reactions. The nucleophilic addition reactions may be Aza-Michael addition and/or amine-epoxide addition. Advantageously, in various embodiments, the nucleophilic addition reaction is performed in the absence of catalyst and/or formation of by-products. The nucleophilic addition reaction may also be performed at a temperature of from about 10° C. to about 100° C., from about 15° C. to about 95° C., from about 20° C. to about 90° C., from about 25° C. to about 85° C., from about 30° C. to about 80° C., from about 35° C. to about 75° C., from about 40° C. to about 70° C., from about 45° C. to about 65° C., from about 50° C. to about 60° C., about 55° C., or at room temperature.
In various embodiments, the step of functionalising and/or grafting comprises Aza-Michael addition with α,β-unsaturated carbonyl compounds. For example, by reacting with a suitable α,β-unsaturated carbonyl compound, the polymer may undergoes hydrophobic functionalisation, oleophobic functionalisation, cationic functionalisation, anionic functionalisation and/or zwitterionic functionalisation. The polymer may also be crosslinked/functionalized with acrylates (e.g., bisacrylates such as 1,4-butanediol diacrylate (BDDA) to form a cross-linked coating via Aza-Michael addition. The polymer may also be functionalized with acrylates (e.g., halogenated acrylates such as fluorinated acrylates).
In various embodiments, the step of functionalising and/or grafting comprises amine-epoxide nucleophilic addition with an epoxide or epoxy compounds. For example, the polymer may be crosslinked/functionalized with poly(ethylene glycol) diglycidyl ether (PEGE) to form hydrogels via an amine-epoxide nucleophilic addition.
Example embodiments of the disclosure will be better understood and readily apparent to one of ordinary skill in the art from the following examples, tables and if applicable, in conjunction with the figures. It should be appreciated that other modifications related to structural, and chemical changes may be made without deviating from the scope of the invention. Example embodiments are not necessarily mutually exclusive as some may be combined with one or more embodiments to form new example embodiments. The example embodiments should not be construed as limiting the scope of the disclosure.
A method for the synthesis/construction of novel water soluble/dispersible polymers with tunable (diverse type of aliphatic and aromatic) active amine groups present in the backbone has been developed. Embodiments of the method disclosed herein allow for green synthesis of polymer. The polymer may be synthesized in the presence of water/moisture or in the absence of a solvent, i.e. under solvent-less conditions. Embodiments of the method disclosed herein allow for easy synthesis of polymer without production of by-product(s) and/or in the absence of a catalyst. The polymer may also be synthesized at room temperature. Embodiments of the method disclosed herein may also be easily scaled up without requiring any specialized external energy input etc. and/or without the production of by-product.
The present disclosure provides a strategy to create a new type of amine polymers with tunable structure and properties. Bis-carbonates may be easily copolymerized with amine compounds having at least two terminal amino groups to construct amine polymers. Scheme 1 shows the structures of some examples of monomers that can be used to synthesize water soluble/dispersible polymers with tunable active amine groups present in the backbone.
Scheme 2 shows the synthesis of water soluble succinic acid based active amine polymers from one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups. As shown in Scheme 2, succinic bis-carbonate (SuBC) was used as an example of a bis-carbonate to obtain a water soluble succinic acid based polymer with active amine groups.
Polymers from succinic acid based bis-carbonate (SuBC) with active amine groups were synthesized using the protocol described in Scheme 2. These polymers can be synthesized in different solvents including water, or even in the absence of a solvent, i.e. under a solvent-less condition. Polymerization can be performed at a temperature ranging from room temperature to about 70° C. In various examples, heating the reaction mixture may speed up reaction and/or increase conversion.
Polymers obtained were characterized with 1H & 13C NMR spectroscopy, gel permeation chromatography (GPC). Conversion, yield and molecular weight data were reported in Table 1. Table 1 also shows the bio-content of polymers synthesized that usually ranges from 50 to 75% by weight. Most of these polymers are soluble in water (in both acidic and basic pH) unlike traditional polyhydroxyurethanes (PHUs) (Table 2). Without being bound by theory, it is believed that the water solubility of the polymers is mainly attributed to the presence of active amine groups. Bio-content of such polymer could also be increased by the use of amines from natural sources. Polymers from butanediol bis-carbonate (BBC) and adipic acid bis-carbonate (ABC) were also reported in Table 1. Pyridine bis-carbonate (PBC) was an optional monomer useful when targeting to introduce aromatic amine into the polymer structure. R-12 is a representative polymer where all type of amine groups (2°, 3° and aromatic) are present in the backbone.
= Form cloudy solution, turns into clear solution after some time
Scheme 3 shows that a polymer designed in accordance with various embodiments disclosed herein can contain ester, urethane, hydroxyl, amine (2°, 3° and aromatic) groups. Amount of bio-content and amine can also be controlled. Such polymers can be crosslinked (using bis-acrylate or bis-epoxy), used to make hydrogel or can also be functionalized with fluorinated acrylates to make hydrophobic antibacterial materials etc.
Examples of applications of polymers with active amine functionality include:
Particularly, the polymer in accordance with various embodiments disclosed herein are useful as additive to laundry products as anti-redepositioning agent, as an adhesive/adhesion promoter, as additive/binder for waterborne coating (e.g., for pigment dispersion and for anti-bacterial formulations).
As shown in
Amine containing polymers (Scheme 4) are useful for a range of applications such as additive to shampoo, detergent & cosmetics (as antibacterial or redepositioning agent), fibre modification (
In the following examples, it is shown that the polymer designed/synthesized in accordance with various embodiments disclosed herein can be used for diverse range of specialty applications. The polymers designed in accordance with various embodiments disclosed herein can be synthesized from bio-based monomers (e.g., succinic acid-based monomers) and are easily synthesizable (even in water or bulk) in large quantities. Embodiments of the polymers disclosed herein have also shown/proven to be hydrolysable and are therefore, potentially bio-degradable. Apart from the presence of amine groups, embodiments of the polymers disclosed herein also contain urethane and hydroxyl groups for improved properties and can be further functionalized via catalyst-free room temperature Aza-Michael and amine-epoxy addition reactions for diverse applications. Examples of applications of these polymers include applications as additive (e.g., anti-redepositioning agent) for detergents, cosmetics, as adhesive or adhesion promoter, coatings and as anti-bacterial materials.
The presence of amine groups of polymers were confirmed by performing chelation experiments with copper salt. Polymers R-12 and R-14 produced characteristic blue coloration when mixed with copper (I) bromide (CuBr) in water (
Hydrolytic degradability of succinic acid based PHUs designed in accordance with various embodiments disclosed herein were studied initially at pH 10-11 and at elevated temperature (Scheme 5). Degradability of such polymers at lower pH and at room temperature (RT) was also proven to be successful although degradation was slower (at lower pH and at RT). The degraded products were characterized with NMR and GPC. The results are shown in Table 3 below.
A preliminary study aiming to apply the amine containing polymers designed in accordance with various embodiments disclosed herein as anti-redepositioning agent was performed via an interaction study with cotton fiber.
As shown in
There are numerous possibilities for further functionalization of amine polymers especially from polymer containing secondary —NH— group. As shown in
Results obtained from CO2 capture experiments are provided in Table 5.
N-functionalized polymers R-153 and R-190 which are oil/dodecane soluble, were synthesized according to Scheme 8. In R-153, 50% N-functionalization was achieved, whereby it contains 50% C18H37 by formula. In R-190, 100% N-functionalization was achieved, whereby it contains 100% C18H37 by formula.
The evaluation of pour point reduction on wax solutions by N-functionalised SuBC+PEHA NIPUs R-153 and R-190 are shown in
The rheological effects of NIPU on 10 wt % Wax A solution in dodecane are shown in
The anti-soil redepositioning (ASR) property of the polymers designed in accordance with various embodiments disclosed herein on cotton and polyester cloths were evaluated. Both cotton and polyester cloths were washed in SuBC-PEHA ASR agent, PEI ASR agent and without additives as a control. Cotton cloth was additionally washed using PEI-g-PEG as ASR agent as a commercial control. Images were captured before and after the washing experiment and shown in
Cell viability experiments were conducted on polymers designed in accordance with various embodiments.
Both SuBC-TETA and SuBC-PEHA were proved to be non-skin irritant and non-cytotoxic.
As shown in Scheme 9, secondary-amine containing NIPUs designed in accordance with various embodiments disclosed herein can be easily post-functionalized for improvement in functional properties. SuBC-TETA or SuBC-PEHA can be post-functionalized into SuBC-TETA-EH, SuBC-PEHA-EH, SuBC-PEHA-Sy or SuBC-TETA-HF, when reacted with 2-ethylhexyl acrylate, stearyl acrylate or hexafluorobutyl acrylate respectively.
Scheme 9 shows a specific post-functionalization procedure, whereby SuBC-TETA is reacted with hexafluorobutyl acrylate with DMF or DMSO to obtained SuBC-TETA-HF. The change in water contact angle which represents change in coating surface property was measured to determine the success in post-functionalization. From
Succinyl chloride (20 g, 129 mmol) was added slowly to dichloromethane (DCM) (100 mL) in a round bottom flask under nitrogen atmosphere. Glycerol carbonate (32 g, 271 mmol) was added dropwise to the succinyl chloride solution at 0° C. After addition, the reaction mixture was stirred at 35° C. under nitrogen atmosphere for 19 hrs. The precipitated solid was washed with 1 M NaOH solution (85 mL) followed by water (100 mL×2). The solid was dried partially and washed with cold acetone. The white solid was dried under vacuum at 50° C. for overnight and used for polymerization without further purification (27.5 g, yield 67%). 1H NMR (400 MHz, DMSO) δ 5.03 (m, 2H), 4.56 (t, 2H), 4.27 (m, 6H), 2.62 (s, 4H). 13C NMR (101 MHz, DMSO) δ 171.69, 154.81, 74.33, 66.04, 63.66, 28.48.
Adipoyl chloride (8 g, 43.7 mmol) was added slowly to dichloromethane (32 mL) in a round bottom flask under nitrogen atmosphere. Glycerol carbonate (10.8 g, 91.4 mmol) was added dropwise to the adipoyl chloride solution at 0° C. After addition, the reaction mixture was stirred at 35° C. under nitrogen atmosphere for 19 hrs. The reaction mixture was diluted with dichloromethane (40 mL), and washed with 1 M NaOH solution (15 mL) followed by water (15 mL) and brine (6 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a viscous liquid, which slowly crystallized into white solid. The white solid was dried under vacuum at 50° C. for overnight and used for polymerization without further purification (12.3 g, yield 81%). 1H NMR (400 MHz, DMSO) δ 5.02 (m, 2H), 4.56 (t, 2H), 4.25 (m, 6H), 2.36 (m, 4H), 1.54 (m, 4H). 13C NMR (101 MHz, DMSO) δ 172.31, 154.63, 74.22, 65.97, 63.25, 32.80, 23.58.
iii) Synthesis of Butanediol Bis-Carbonate (BBC)
The bis-epoxy product 1,4-bis(oxiran-2-ylmethoxy)butane (10 mmol, 2.02 g), tetrabutyl ammonium iodide (TBAI) (5 mol %, 185 mg, 0.5 mmol) and pyridinedimethanol (5 mol %, 70 mg, 0.5 mmol) were dissolved in 20 mL of dry tetrahydrofuran (THF), transferred into a Parr reactor and pressurized with CO2 up to 180 psig after purging with N2. The reaction was carried out under stirring at 105° C. for 24 h. After the reaction, the reactor was cooled to room temperature and depressurized. The solvent THF was removed and redissolved in 50 ml diethyl ether, and the product was precipitated from 30 mL petroleum ether. 1.8 g (63%) of the product was obtained as off white solid. 1H NMR (400 MHz, Chloroform-d) δ 4.84-4.76 (m, 2H), 4.49 (t, J=8.3 Hz, 2H), 4.42-4.35 (m, 2H), 3.74-3.56 (m, 4H), 3.53 (t, J=4.8 Hz, 4H), 1.69-1.61 (m, 4H).
iv) An Example of Polymerization Procedure of SuBC with TETA at High Temperature
SuBC (0.5 g, 1.57 mmol) and triethylenetetramine (TETA, 0.23 g, 1.57 mmol) were added into a reaction vial charged with magnetic stirring bar. A few drops of mesitylene were added as internal reference. Dimethylformamide (DMF) (1 mL) was added and the reaction mixture was degassed with nitrogen under stirring. After 15 minutes, the reaction mixture was stirred at 70° C. for 24 hours. The reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer (R-6, SuBC-TETA polymer) was washed with diethyl ether for three times followed by drying under vacuum at 60° C. for overnight (0.48 g, yield 66%). 1H NMR (400 MHz, DMSO) δ 7.05 (br, 2H), 5.07-4.70 (br, 1H), 4.12 (br, 2H), 4.05-3.84 (br, 6H), 3.77 (br, 1H), 3.42 (br, 4H), 2.98 (br, 4H), 2.49 (br, 12H).
SuBC (0.25 g, 0.79 mmol) and DMF (1 mL) were added into a reaction vial charged with magnetic stirring bar. A few drops of mesitylene were added as internal reference. Pentaethylenehexamine (PEHA, 0.183 g, 0.79 mmol) was added and the reaction mixture was degassed with nitrogen under stirring. After 15 minutes, the reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer was washed with diethyl ether for three times followed by drying under vacuum at 60° C. for overnight (0.3 g, yield 69%). 1H NMR (400 MHz, DMSO) δ 7.06 (br, 2H), 4.97 (br, 1H), 4.83 (br, 1H), 4.72 (br, 1H), 4.16-4.02 (br, 2H), 3.97-3.85 (br, 4H), 3.77 (br, 1H), 3.00 (br, 5H), 2.55-2.50 (br, 14H), 2.27 (br, 5H).
The NIPU solution was prepared by dissolving SUBC-TETA polymer (R-6,150 mg) in deionized water (0.75 mL). This NIPU solution was separated into three separate vials (0.25 mL each, 0.2 mmol based on mole of TETA), namely, Control, Sample 1 and Sample 2. Poly(ethylene glycol) diglycidyl ether (54 mg, 0.1 mmol) was added into Sample 1 and Sample 2 vials, respectively. After mixing, the Sample 1 and Sample 2 vials were capped and placed at room temperature and at 50° C., respectively, for 48 hrs. Control vial was used as control example without addition of poly(ethylene glycol) diglycidyl ether.
vii) Procedure for NIPU Functionalization with Hexafluorobutyl Acrylate
SUBC-TETA polymer (R-6, 200 mg, 0.43 mmol based on mole of TETA) was dissolved in DMF (0.5 mL) followed by addition of 2,2,3,4,4,4-hexafluorobutyl acrylate (200 mg, 0.86 mmol) in a reaction vial. A drop of mesitylene was added as internal reference for NMR analysis. The reaction mixture was stirred at 60° C. for 24 hrs. After cooling to room temperature, the reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer SUBC-TETA—HF (R-6-F) was washed with diethyl ether for 3 times and dried under vacuum at 60° C.
viii) Procedure for Contact Angle Measurement
R-6 and R-6-F solutions were prepared by dissolving polymer (40 mg) in DMF (0.25 mL). The polymer solution was dropped onto a pre-cleaned glass slide. After drop-casting, the glass slides were placed at room temperature for 2 hours and subsequently dried at 60° C. for 24 hours. The contact angles of water droplet on the R-6 and R-6-F coated glass slides were measured.
It will be appreciated by a person skilled in the art that other variations and/or modifications may be made to the embodiments disclosed herein without departing from the spirit or scope of the disclosure as broadly described. For example, in the description herein, features of different exemplary embodiments may be mixed, combined, interchanged, incorporated, adopted, modified, included etc. or the like across different exemplary embodiments. The present embodiments are, therefore, to be considered in all respects to be illustrative and not restrictive.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10202010612S | Oct 2020 | SG | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SG2021/050640 | 10/21/2021 | WO |
