Polycarbonate polyol compositions and methods

Patent metadata

Field	Value
Publication number	US-2016264728-A1
Application number	US-201615161684-A
Country	US
Kind code	A1
Filing date	May 23, 2016
Priority date	Sep 8, 2008
Publication date	Sep 15, 2016
Grant date	—

Abstract

In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO 2 and epoxides comprising 1) a catalyst including a metal coordination compound having a permanent ligand set and at least one ligand that is a polymerization initiator, and 2) a chain transfer agent having two or more sites that can initiate polymerization. In a second aspect, the present disclosure encompasses methods for the synthesis of polycarbonate polyols using the inventive polymerization systems. In a third aspect, the present disclosure encompasses polycarbonate polyol compositions characterized in that the polymer chains have a high percentage of —OH end groups and a high percentage of carbonate linkages. The compositions are further characterized in that they contain polymer chains having an embedded polyfunctional moiety linked to a plurality of individual polycarbonate chains.

First claim

What is claimed is:

1 . A polymerization system for the copolymerization of CO 2 and epoxides, the system comprising:
a metal complex including a permanent ligand set and at least one ligand that is a polymerization initiator, and a chain transfer agent having a plurality of sites capable of initiating copolymerization of epoxides and CO 2 .

2 . The polymerization system of claim 1 , wherein the chain transfer agent has a structure Y-A-(Y) n , where:
each —Y group is independently a functional group capable of initiating chain growth of epoxide CO 2 copolymers and each Y group may be the same or different; -A- is a covalent bond or a multivalent moiety; and n is an integer between 1 and 10, inclusive.

3 . The polymerization system of claim 2 , wherein each Y group is independently selected from the group consisting of: —OH, —C(O)OH, —C(OR y )OH, —OC(R y )OH, —NHR y , —NHC(O)R y , —NHC═NR y ; —NR y C═NH; —NR y C(NR y 2 )═NH; —NHC(NR 2 )═NR y ; —NHC(O)OR y , —NHC(O)NR 2 ; —C(O)NHR y , —C(S)NHR y , —OC(O)NHR y , —OC(S)NHR y , —SH, —C(O)SH, —B(OR y )OH, —P(O) a (R y ) b (OR) c (O) d H, —OP(O) a (R y ) b (OR) c (O) d H, —N(R y )OH, —ON(R y )H; ═NOH, ═NN(R y )H, where each occurrence of R y is independently —H, or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic, C 1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b, and c is 1 or 2 and where an acidic hydrogen atom bound in any of the above functional groups may be replaced by a metal atom or an organic cation.

4 . The polymerization system of claim 2 , wherein each Y group is independently selected from the group consisting of: —OH, and —C(O)OH.

5 . The polymerization system of claim 2 , wherein -A- is an optionally substituted radical selected from the group consisting of: C 2-30 aliphatic, C 2-30 heteroaliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5- to 12-membered heteroaryl, polyolefins, polyesters, polyethers, polycarbonates, polyoxymethylene and mixtures of two or more of these.

6 . The polymerization system of claim 2 , wherein n is 1 to 4.

7 . The polymerization system of claim 2 , wherein n is 1.

8 . The polymerization system of claim 2 , wherein n is 2.

9 . The polymerization system of claim 2 , wherein n is 3.

10 . The polymerization system of claim 1 , wherein the chain transfer agent is a polyhydric alcohol.

11 . The polymerization system of claim 1 , wherein the chain transfer agent is a diol.

12 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexanediethanol.

13 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), preferrably those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) preferrably those having number average molecular weights of from 234 to about 2000 g/mol.

14 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of: 4,4′-(1-methylethylidene)bis[cyclohexanol], 2,2′-methylenebis[phenol], 4,4′-methylenebis[phenol], 4,4′-(phenylmethylene)bis[phenol], 4,4′-(diphenylmethylene)bis[phenol], 4,4′-(1,2-ethanediyl)bis[phenol], 4,4′-(1,2-cyclohexanediyl)bis[phenol], 4,4′-(1,3-cyclohexanediyl)bis[phenol], 4,4′-(1,4-cyclohexanediyl)bis[phenol], 4,4′-ethylidenebis[phenol], 4,4′-(1-phenylethylidene)bis[phenol], 4,4′-propylidenebis[phenol], 4,4′-cyclohexylidenebis[phenol], 4,4′-(1-methylethylidene)bis[phenol], 4,4′-(1-methylpropylidene)bis[phenol], 4,4′-(1-ethylpropylidene)bis[phenol], 4,4′-cyclohexylidenebis[phenol], 4,4′-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2, 1-ethanediyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4′-(1-methylidene)bis[2-methylphenol], 4,4′-(1-methylethylidene)bis[2-(1-methylethyl)phenol], and 2,2′-methylenebis[4-methyl-6-(1-methylethyl)phenol].

15 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of:

16 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of: 1,3 propane diol, 1,4 butane diol, dipropylene glycol, diethylene glycol, and isosorbide.

17 . The polymerization system of claim 1 , wherein the chain transfer agent is a hydroxy acid.

18 . The polymerization system of claim 17 , wherein the hydroxy acid is an alpha-hydroxy acid.

19 . The polymerization system of claim 18 , wherein the hydroxy acid is selected from the group consisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic, citric acid and mandelic acid.

20 . The polymerization system of claim 17 , wherein the hydroxy acid is a beta-hydroxy acid.

21 . The polymerization system of claim 20 , wherein the hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3 hydroxybutryic acid, L 3-hydroxybutyric acid, DL-3-hydroxy valeric acid, D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, and derivatives of salicylic acid.

22 . The polymerization system of claim 17 , wherein the hydroxy acid is a α-ω hydroxy acid.

23 . The polymerization system of claim 17 , wherein the hydroxy acid is selected from the group consisting of: of optionally substituted C 3-20 aliphatic α-ω hydroxy acids and polyester oligomeric esters.

24 . The polymerization system of claim 17 , wherein the hydroxy acid is selected from the group consisting of:

25 . The polymerization system of claim 1 , wherein the chain transfer agent is a polycarboxylic acid.

26 . The polymerization system of claim 1 , wherein the chain transfer agent is diacid.

27 . The polymerization system of claim 26 , wherein the chain transfer agent is selected from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

28 . The polymerization system of claim 1 , wherein the chain transfer agent is selected from the group consisting of:

Assignees

• Novomer Inc

Inventors

• Allen Scott D
• Coates Geoffrey W
• Cherian Anna E
• Simoneau Chris A
• Gridnev Alexei A
• Farmer Jay J

Classifications

• C08G64/0208

  saturated · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G18/44

  Polycarbonates · CPC title

• C08G64/0216

  containing a chain-terminating or -crosslinking agent · CPC title