α,ω-functionalized polyoxyalkylene-siloxane polymers and copolymers made therefrom
View Patent ↗An α,ω-functionalized polyoxyalkylene-siloxane polymer having the general structural Formula (I): provides improved hydrophilicity and hemocompatibility. The α,ω-functionalized polyoxyalkylene-siloxane polymer may be used to make various polycarbonate/α,ω-functionalized polyoxyalkylene-siloxane copolymers and polymer blends, as well as articles including such copolymers and blends.
1. An α,ω-functionalized polyoxyalkylene-siloxane polymers having the structural Formula (I):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R 2 is different from at least one R 3 ;
R 12 is independently hydrogen or methyl;
A is
wherein R 4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R 5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R 6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and p is 1;
wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2.
2. The α,ω-functionalized polyoxyalkylene-siloxane polymer of claim 1 , wherein R 1 is independently an alkyl group of from 1 to 4 carbon atoms or phenyl; R 2 is independently an alkyl group of from 1 to 4 carbon atoms or phenyl; R 3 is independently an alkyl group of from 1 to 16 carbon atoms, phenyl, 2-phenylethyl, 2,2-diphenylethyl, 2-phenyl-2-methylethyl, 3-phenylpropyl, 3-phenyl-2-methylpropyl, or phenyl-4-oxabutyl; R 4 is independently an alkylene group of 2 to 6 carbon atoms; R 5 is independently hydrogen, chloro, methoxy, ethoxy; R 6 is independently —OH, —NH 2 or —C(═O)Cl; R 12 is methyl; wherein m, n, n′, p, x and y are integers, and wherein m is from 0 to 100; n is from 1 to 100; n′ is from 1 to 6; p is 1; x is from 1 to 275; and y is from 0 to 80.
3. The α,ω-functionalized polyoxyalkylene-siloxane polymer of claim 2 , wherein R 1 is methyl; R 2 is methyl, R 3 is independently methyl or phenyl; R 4 is —CH 2 CH 2 —, —CH(CH 3 )CH 2 —, —CH 2 CH 2 CH 2 — or —CH 2 CH(CH 3 )CH 2 —; R 5 is independently hydrogen or methoxy; R 6 is —OH; wherein m, n, n′, p, x and y are integers, and wherein m is from 0 to 100; n is from 1 to 100; n′ is from 1 to 3; p is 1; x is from 1 to 275; and y is from 0 to 80.
4. A composition comprising an α,ω-functionalized polyoxyalkylene-siloxane polymer of claim 1 and at least one polymer selected from the group consisting of polycarbonate homopolymers, polycarbonate copolymers, polycarbonate-polyesters, polyesters, polysulfones, polyethersulfones, polyetheretherketones, polyimides and polyetherimides and combinations thereof.
5. An article comprising the composition of claim 4 , wherein the article is one or more of a medical article, a medical tube, a medical bag, a mobile phone housing, a frozen food service equipment article, a helmet, an automotive windshield, a motorcycle windshield, an automotive sunroof, a dashboard, a headlamp, or an electric screen.
6. A method of making an article comprising molding, shaping, or forming the composition of claim 4 into the article.
7. A method preparing an α,ω-functionalized polyoxyalkylene-siloxane polymers having the structural Formula (I):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R 2 is different from at least one R 3 ;
R 12 is independently hydrogen or methyl;
A is
wherein R 4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R 5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R 6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and p 1;
wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2, comprising:
(a) reacting a hydride terminated siloxane represented by the structural Formula (IV):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R 2 is different from at least one R 3 ; and x is an integer from 1 to 300 and y is an integer from 0 to 100 with bis-unsaturated polyalkylene containing terminal carbon-carbon double bonds in the presence of a hydrosilylation catalyst to obtain hydride terminated polyoxyalkylene siloxane represented by the structural Formula (V):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein R 2 and R 3 are not the same;
R 12 is independently hydrogen or methyl;
wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2; and
(b) reacting the hydride terminated polyoxyalkylene siloxane of step (a) with substituted phenyl containing a carbon-carbon double bond, represented by the Formula (VI):
wherein R 12 is independently hydrogen or methyl; R 13 is independently a divalent linear or branched alkylene group having from 1 to 8 carbon atoms, an aralkylene group having from 7 to 10 carbon atoms, an unsubstituted or substituted arylene group having from 6 to 16 carbon atoms, a hydrocarbylene group having from 2 to 8 carbon atoms and containing at least one heteroatom of oxygen, R 5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R 6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and the subscript q is an integer 0 or 1, to obtain an α,ω-functionalized polyoxyalkylene-siloxane polymer.
8. The method of claim 7 , further comprising purifying the α,ω-functionalized polyoxyalkylene-siloxane polymer.
9. A copolymer comprising a structural unit of Formula (II):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R 2 is different from at least one R 3 ;
R 12 is independently hydrogen or methyl;
A 1 is
wherein R 4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R 5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, W is independently a divalent group selected from the group consisting of −O—, —NR—, —C(═O)O— and —S(═O) 2 O—, and the subscript p is 1;
wherein m, n, n′, x and y are integers, wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2.
10. The copolymer of claim 9 , further comprising a structural unit having the Formula (VII)
wherein each R 7 is a hydrocarbon radical having 1 to 60 carbon atoms, a divalent hydrocarbon group, a group derived from the structural unit having the Formula (III):
where R 8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having from 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; and R 9 is independently a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group; and X is a compound represented by a structural formula selected from the group consisting of:
wherein R 10 , R 11 are independently a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group.
11. A composition comprising the copolymer of claim 9 and at least one of a polycarbonate homopolymer, a polycarbonate-polyester, a polyester, a polysulfone, a polyethersulfone, a polyetheretherketone, a polyimide, a polyetherimide, a polycarbonate copolymer.
12. An article comprising the composition of claim of claim 11 , wherein the article is one or more of a medical article, a medical tube, a medical bag, a mobile phone housing, a frozen food service equipment, a helmet, an automotive windshield, a motorcycle windshield, an automotive sunroof, a dashboard, a headlamp, or an electric screen.
13. A method of making an article comprising: molding, shaping, or forming a composition of claim 11 to obtain the article.
14. A method of preparing a copolymer comprising polymerizing α,ω-functionalized polyoxyalkylene-siloxane polymer is a polymer having the structural Formula (I):
wherein each R 1 , R 2 and R 3 is independently a linear or branched aliphatic group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 16 carbon atoms, an alicyclic group containing 3 to 16 carbon atoms, a heteronuclear aromatic group containing 3 to 16 carbon atoms, a hydrocarbyl group having from 3 to 16 carbon atoms and containing at least one heteroatom of oxygen, nitrogen or sulfur and/or containing at least one ester, nitrile or halo group, wherein at least one R 2 is different from at least one R 3 ;
R 12 is independently hydrogen or methyl;
A is
wherein R 4 is independently a divalent linear or branched alkylene group having from 2 to 10 carbon atoms, an aralkylene group having from 8 to 12 carbon atoms, an unsubstituted or substituted arylene group having from 8 to 18 carbon atoms, or a hydrocarbylene group having from 2 to 10 carbon atoms and containing at least one oxygen heteroatom, R 5 is independently a hydrogen, a halogen, an aliphatic group containing from 1 to 12 carbon atoms, an aromatic group containing from 6 to 12 carbon atoms, an alkoxy group containing form 1 to 12 carbon atoms or an aryloxy group containing from 6 to 12 carbon atoms, R 6 is independently a hydroxyl group, an amine group, a carboxylic acid chloride group or a sulfonyl halide group, and the subscript p is 1;
wherein m, n, n′, x and y are integers, and wherein m is from 0 to 120, n is from 1 to 120, n′ is from 1 to 10, x is from 1 to 300, and y is from 0 to 100, with the proviso that the sum of n+m is greater than or equal to 2,
with a compound of Formula (III):
where R 8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having from 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; and R 9 is independently a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group; and X is a compound represented by a structural formula selected from the group consisting of:
wherein R 10 , R 11 are independently a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group in the presence of a carbonate precursor.
15. The method of claim 14 , wherein the carbonate precursor is chosen from phosgene, diphosgene, diarylcarbonates, bis(methylsalicyl)carbonate, or a combination thereof.
16. The method of claim 14 , wherein the polymerizing step is an interfacial polymerization process conducted in the presence of a solvent and optionally one or more catalysts.
17. The method of claim 14 , wherein the polymerizing step is an interfacial polymerization process conducted in the presence of a solvent, a caustic, and optionally one or more catalysts, and wherein the carbonate precursor is chosen from phosgene, diphosgene, triphosgene, diarylcarbonates, bis(methylsalicyl)carbonate, or a combination thereof.
18. The method of claim 14 , wherein the polymerizing step comprises reacting bisphenol A with triphosgene in a biphasic solvent in the presence of a phase transfer catalyst to form a bischloroformate; and adding the α,ω-functionalized polyoxyalkylene-siloxane polymer to form the copolymer.
19. The method of claim 18 , wherein the bischloroformate is formed in a tube reactor, and then added into an interfacial polycondensation reactor with a catalyst.