# US 9,000,101 B2 · Anhydride end-capping of polymers

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- Number: US 9,000,101 B2
- Document ID: US9000101B2
- Status: Granted
- Kind: B2
- Application number: 13/938,255
- Filed: 2013-07-10
- Published: 2015-01-15
- Granted: 2015-04-07
- Earliest claimed: 2013-07-10
- Assignees: Xerox Corporation
- Applicants: Xerox Corporation; National Research Council of Canada
- Inventors: Andrew J. Myles; Jordan H. Wosnick; Karen A. Moffat; Valerie M. Farrugia
- Web page: https://patentgrep.com/patent/US9000101B2

## CPC

- C08G 63/91: Polymers modified by chemical after-treatment
- C08G 63/64: Polyesters containing both carboxylic ester groups and carbonate groups
- C08G 63/912: {derived from hydroxycarboxylic acids}
- C08G 64/42: Chemical after-treatment
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The disclosure describes a neat, one-pot scheme for reacting a hydroxyl propagating end of a polymer with a cyclic acid anhydride to form a free acid terminus.

## Claims

### Claim 1

A process comprising:
polymerizing a first cyclic component and an optional second cyclic component to form a homopolymer or a copolymer resin using a ring opening polymerization (ROP) process; and,
reacting a cyclic acid anhydride with a propagating terminal hydroxyl group of the homopolymer or copolymer with at least one catalyst and an optional initiator to form a free acid end group,
wherein the polymerizing and reacting occur under neat Conditions, and standard pressure and humidity, in a single vessel.

### Claim 2 (depends on 1)

The process of claim 1, wherein the cyclic acid anhydride is selected from the group consisting of phthalic anhydride, trimellitic anhydride, maleic anhydride, hexahydrophthalic anhydride, glutaric anhydride, itaconic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, pyromellitic dianhydride, humic anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenylsuccinic anhydride, and chlorendic anhydride.

### Claim 3 (depends on 1)

The process of claim 1, wherein the at last one catalyst comprises two components of a nucleophilic transesterification system.

### Claim 4 (depends on 3)

The process of claim 3, wherein the at least one catalyst comprises 4-(dimethylamino)pyridine (OMAP) and DMAP:HX, wherein FIX is selected from the group consisting of HCl, HBr, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, triflic acid, and combinations thereof.

### Claim 5 (depends on 4)

The process of claim 4, wherein FIX comprises DMAP:HO3SCF3.

### Claim 6 (depends on 1)

The process of claim 1, wherein the at least one optional initiator comprises a nonalcohol.

### Claim 7 (depends on 1)

The process of claim 1, wherein the at least one optional initiator is selected from the group consisting of hexanol, methyl alcohol, ethyl alcohol, propyl alcohol, allyl alcohol, cyclo-hexanol, furfuryl alcohol, benzyl alcohol, trifluoroethanol, heptafluorobutanol, heptadecylfluorooctanol, pentafluoropropanol, pentafluorobutanol, nonafluorohexanol and a fluoroalkylethanol.

### Claim 8 (depends on 1)

The process of claim 1, where said copolymer comprises a block copolymer.

### Claim 9 (depends on 8)

The process of claim 8, wherein said block copolymer comprises a first and a second cyclic monomers selected from the group consisting of glycolide, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone, D,D-lactide, L,L-lactide, D,L-lactide, 4-(benzyloxymethyl)-1,3-dioxolan-2-one (BDMC), 4-(hydroxymethyl)-1,3-dioxolan-2-one (DMCOH), succinic anhydride, glutaric anhydride, maleic anhydride, styrene oxide, cyclohexene oxide, 4-(sulfonatophenyl)caprolactone, cyclopentane-1,2-dicarboxylic anhydride, cyclohexene 1,2-dicarboxylic anhydride, 2,3-bicyclo[2,2,2]octadicarboxylic anhydride, phthalic anhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylic anhydride, thiophene-dicarboxylic anhydride and combinations thereof.

### Claim 10 (depends on 9)

The process of claim 9, further comprising a third cyclic monomer.

### Claim 11 (depends on 10)

The process of claim 10, wherein said third cyclic monomer comprises a carbonate selected from the group of organic monomers consisting of unsaturated carbonate monomers, symmetrical carbonate monomers, asymmetrical carbonate monomers, aliphatic carbonate monomers, cyclic carbonate monomers, aromatic carbonate monomers, aliphatic-aromatic carbonate monomers, alicyclic carbonate monomers, thio-carbonate monomers, imido-carbonate monomers, linear carbonate monomers, branched carbonate monomers, substituted carbonate monomers, functionalized carbonate monomers, and combinations thereof.

### Claim 12 (depends on 10)

The process of claim 10, wherein said carbonate monomer comprises Formula (I):

### Claim 13

A process comprising;
polymerizing as first cyclic, monomer with at least one catalyst and at least one optional initiator to form a homopolymer;
polymerizing a carbonate monomer to said homopolymer to form a second block of a diblock copolymer;
polymerizing a second cyclic component to said second block of the diblock copolymer to form a third block of a triblock copolymer, wherein said third block comprises a terminal propagating hydroxyl group; and
reacting a cyclic acid anhydride with said hydroxyl group to form a terminal free acid group, wherein the polymerizing and reacting steps are carried out under neat conditions in a single vessel under standard pressure and ambient humidity.

### Claim 14 (depends on 13)

The process of claim 13, wherein said cyclic acid anhydride is selected from the group consisting of phthalic anhydride, trimellitic anhydride, maleic anhydride, hexahydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, tetrachlorophthalic anhydride, pyromellitic dianhydride, humic anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenylsuccinic anhydride and chlorendic anhydride.

### Claim 15 (depends on 13)

The process of claim 13, wherein the first and second cyclic monomers, each is selected from the group consisting of glycolide, β-propiolactone, γ-butyrolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone, 4-(benzyloxymethyl)-1,3-dioxolan-2-one (BDMC), 4-(hydroxymethyl)-1,3-dioxolan-2-one (DMCOH), succinic anhydride, itaconic anhydride, glutaric anhydride, maleic anhydride, styrene oxide, cyclohexene oxide, 4-(sulfonatophenyl)caprolactone, cyclopentane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylic anhydride, 2,3-bicyclo[2,2,2]octadicarboxylic anhydride, phthalic anhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylic anhydride, thiophene-dicarboxylic anhydride and combinations thereof.

### Claim 16 (depends on 13)

The process of claim 13, wherein the first cyclic monomer comprises ε-caprolactone and said second cyclic comprises a lactide.

### Claim 17 (depends on 13)

The process of claim 13, wherein the at least one catalyst comprises 4-(dimethylamino)pyridine (DMAP) and DMAP:HX, wherein HX is selected from the group consisting of HCl, HBr, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, triflic acid and combinations thereof.

### Claim 18 (depends on 13)

The process of claim 13, wherein said carbonate monomer comprises Formula (I):

### Claim 19 (depends on 13)

The process of claim 13, wherein said at least one optional initiator comprises a monoalcohol.

### Claim 20 (depends on 13)

The process of claim 13, wherein the at least one initiator is selected from the group consisting of hexanol, methyl alcohol, ethyl alcohol, propyl alcohol, allyl alcohol, cyclohexanol, furfuryl alcohol, benzyl alcohol, trifluoroethanol, heptafluorobutanol, heptadecylfluorooctanol, pentafluoropropanol, pentafluorobutanol, nonafluorohexanol and a fluoroalkylethanol.