# US 7,745,561 B2 · Processes for making copolymers using macrocyclic oligoesters, and copolymers therefrom > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,561 B2 - Document ID: US7745561B2 - Status: Granted - Kind: B2 - Application number: 11/345,057 - Filed: 2006-01-31 - Published: 2010-05-13 - Granted: 2010-06-29 - Earliest claimed: 2006-01-31 - Assignees: Cyclics Corporation - Inventors: Steven R. Bahr; James Pawlson - Web page: https://patentgrep.com/patent/US7745561B2 ## CPC - C08G 63/672: Dicarboxylic acids and dihydroxy compounds - C08G 63/00: Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule (polyester-amides C08G69/44; polyester-imides C08G73/16) - C08G 63/16: Dicarboxylic acids and dihydroxy compounds - C08G 63/60: derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The invention provides alternatives to traditional polycondensation processes for preparing copolymers. For example, in certain embodiments, the invention provides a process that includes an extrusion step and a solid state polymerization step to prepare high molecular weight block copolymer with a “hard block” contributed by a macrocyclic polyester oligomer (MPO) and a “soft block” contributed by a dihydroxyl-functionalized polymer, an oligoether, and/or a dimerized fatty acid (i.e. a polyol). The invention also provides new copolymer compositions made possible by the new processes—for example, copolymers of higher molecular weight, copolymers with higher weight ratio of soft block units to hard block units, copolymers made with higher molecular weight polyol, and copolymers with hard block units that are themselves random copolyesters of units contributed by a MPO and a cyclic ester. ## Claims ### Claim 1 A method of making a block copolymer with hard and soft blocks, the method comprising the steps of: (a) shearing together at elevated temperature (i) a macrocyclic oligoester and (ii) at least one member selected from the group consisting of a dihydroxyl-functionalized polymer, an oligoether, and a dimerized fatty acid in the presence of a catalyst, thereby forming a block copolymer, wherein the macrocyclic oligoester has a structural repeat unit of formula: wherein A is an alkylene, a cycloalkylene, or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group; and (b) increasing the molecular weight of the block copolymer by heating at a temperature above 80° C. under vacuum. ### Claim 2 (depends on 1) The method of claim 1, wherein step (a) is performed using at least one member selected from the group consisting of an extruder, a mixer, and a blender. ### Claim 3 (depends on 1) The method of claim 1, wherein step (a) is performed using an extruder and wherein step (b) is performed using solid-state polymerization equipment. ### Claim 4 (depends on 1) The method of claim 1, wherein the mixture comprises a dihydroxyl-functionalized polymer having molecular weight greater than 1000. ### Claim 5 (depends on 1) The method of claim 1, wherein the mixture comprises a dihydroxyl-functionalized polymer having molecular weight greater than 2500. ### Claim 6 (depends on 1) The method of claim 1, wherein the weight ratio of block units contributed by component (ii) to component (i) in the block copolymer is at least about 10:90. ### Claim 7 (depends on 1) The method of claim 1, wherein the weight ratio of block units contributed by component (ii) to component (i) in the block copolymer is at least about 25:75. ### Claim 8 (depends on 1) The method of claim 1, wherein step (a) comprises charging an extruder with at least a 25:75 weight ratio of component (ii) to component (i). ### Claim 9 (depends on 1) The method of claim 1, wherein the block copolymer comprises a hard block and a soft block and wherein component (i) contributes to the hard block and component (ii) contributes to the soft block. ### Claim 10 (depends on 9) The method of claim 9, wherein the weight ratio of the soft block to the hard block in the block copolymer is selected to provide a desired property or combination of properties. ### Claim 11 (depends on 9) The method of claim 9, wherein the weight ratio of the soft block to the hard block in the block copolymer is high enough to make the block copolymer inherently dissipative. ### Claim 12 (depends on 1) The method of claim 1, wherein the catalyst is a transesterification catalyst. ### Claim 13 (depends on 1) The method of claim 1, wherein the catalyst comprises a tin compound, a titanate compound, or both. ### Claim 14 (depends on 1) The method of claim 1, wherein step (b) comprises heating the block copolymer to increase its molecular weight by a factor of at least about 2. ### Claim 15 (depends on 1) The method of claim 1, wherein step (b) comprises heating the block copolymer to increase its molecular weight by a factor of at least about 5. ### Claim 16 (depends on 1) The method of claim 1, wherein the block copolymer has molecular weight of at least about 150,000 after step (b). ### Claim 17 (depends on 1) The method of claim 1, wherein the block copolymer has molecular weight of at least about 200,000 after step (b). ### Claim 18 (depends on 1) The method of claim 1, wherein step (a) comprises extruding the mixture at a temperature from about 130° C. to about 300° C. ### Claim 19 (depends on 1) The method of claim 1, wherein step (a) comprises extruding the mixture at a temperature from about 230° C. to about 260° C. ### Claim 20 (depends on 1) The method of claim 1, wherein step (b) comprises heating at a temperature from about 190° C. to about 240° C. ### Claim 21 (depends on 1) The method of claim 1, wherein step (b) comprises heating at a temperature within a range from about 200° C. to about 220° C. ### Claim 22 (depends on 1) The method of claim 1, wherein step (b) comprises heating the block copolymer for a period of time from about 4 hours to about 8 hours. ### Claim 23 (depends on 1) The method of claim 1, wherein step (b) comprises heating the block copolymer at a pressure no greater than about 20 torr. ### Claim 24 (depends on 1) The method of claim 1, wherein the block copolymer is in a solid state during step (b). ### Claim 25 (depends on 1) The method of claim 1, wherein the macrocyclic oligoester comprises at least one monomeric unit selected from the group consisting of butylene terephthalate, ethylene terephthalate, and propylene terephthalate. ### Claim 26 (depends on 1) The method of claim 1, wherein the mixture comprises a dihydroxyl-functionalized polymer. ### Claim 27 (depends on 26) The method of claim 26, wherein the dihydroxyl-functionalized polymer comprises at least one member selected from the group consisting of a dihydroxyl-functionalized poly(alkylene terephthalate), a dihydroxyl-functionalized poly(ethylene terephthalate), a dihydroxyl-functionalized poly(butylene terephthalate), a dihydroxyl-functionalized poly(propylene terephthalate), a dimer diol, a polyolefin diol, a polycaprolactone diol, a polyperfluoroether diol, and a polysiloxane diol. ### Claim 28 (depends on 1) The method of claim 1, wherein the mixture comprises an oligoether. ### Claim 29 (depends on 28) The method of claim 28, wherein the oligoether comprises at least one member selected from the group consisting of poly(ethylene ether) glycol, poly(propylene ether) glycol, poly(tetramethylene ether) glycol, and poly(tetramethylene oxide). ### Claim 30 (depends on 1) The method of claim 1, wherein the mixture comprises a dimerized fatty acid. ### Claim 31 (depends on 30) The method of claim 30, wherein the dimerized fatty acid comprises a dimerization product of at least one member selected from the group consisting of oleic acid, linoleic acid, palmitoleic acid, elaidic acid, eucric acid, sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil, and tall oil. ### Claim 32 (depends on 1) The method of claim 1, further comprising the step of: (c) contacting the block copolymer after step (b) with an ester in the presence of a transesterification catalyst at an elevated temperature, thereby producing a copolyester comprising structural units from component (i) of the mixture, component (ii) of the mixture, and the ester, wherein the ester comprises at least one structural unit of formula: —R1—O—C(O)—R2— wherein each of R1 and R2 is independently a divalent organic moiety. ### Claim 33 (depends on 32) The method of claim 32, wherein the block copolymer comprises a soft block comprising units contributed by component (ii) of the mixture, and the block copolymer comprises a hard block comprising units contributed by component (i) of the mixture and the ester of step (c). ### Claim 34 (depends on 33) The method of claim 33, wherein the hard block comprises randomized units contributed by component (i) of the mixture and the ester of step (c). ### Claim 35 (depends on 32) The method of claim 32, wherein the ester comprises a cyclic ester. ### Claim 36 (depends on 35) The method of claim 35, wherein the cyclic ester is a lactone. ### Claim 37 (depends on 36) The method of claim 36, wherein the lactone is caprolactone. ### Claim 38 (depends on 32) The method of claim 32, wherein the ester comprises an aliphatic or aromatic polyester. ### Claim 39 (depends on 32) The method of claim 32, wherein step (c) is conducted at a temperature within a range from about 100° C. to about 300° C. ### Claim 40 (depends on 32) The method of claim 32, wherein R1 is not —O-A′- if R2 is —B′—C(O)—, where A′ is an alkylene, a cycloalkylene, or a mono- or polyoxyalkylene group and B′ is a divalent aromatic or alicyclic group. ### Claim 41 A block copolymer comprising: (a) a first block unit comprising, within its polymeric backbone, at least one structural unit of formula: wherein A is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group, and B is a divalent aromatic or alicyclic group; and at least one structural unit of formula: —R1—O—C(O)—R2— wherein each of R1 and R2 is independently a divalent organic moiety, wherein R1 is not —O-A′- if R2 is —B′—C(O)—, where A′ is an alkylene, a cycloalkylene, or a mono- or polyoxyalkylene group and B′ is a divalent aromatic or alicyclic group; and (b) a second block unit comprising, within its polymeric backbone, at least one structural unit of formula: -D- wherein D is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group, and wherein one or more of the carbon atoms in D may be replaced with an oxygen atom, a nitrogen atom, or a sulfur atom, wherein D comprises at least one member selected from the group consisting of a polyalkylene ether, a polyethylene ether, a polypropylene ether, a polymethylene ether, a polyolefin, a polycaprolactone, a polyperfluoroether, a dimer diol, and a polysiloxane diol. ### Claim 42 (depends on 41) The block copolymer of claim 41, wherein the first block unit of the block copolymer comprises a random configuration of the structural units of formula and formula —R1—O—C(O)—R2—. ### Claim 43 (depends on 41) The block copolymer of claim 41, having molecular weight of at least about 150,000. ### Claim 44 (depends on 41) The block copolymer of claim 41, having molecular weight of at least about 200,000. ### Claim 45 (depends on 41) The block copolymer of claim 41, wherein the weight ratio of second block units to first block units is at least about 10:90. ### Claim 46 (depends on 41) The block copolymer of claim 41, wherein the weight ratio of second block units to first block units is at least about 25:75. ### Claim 47 (depends on 41) The block copolymer of claim 41, wherein the block copolymer is inherently dissipative. ### Claim 48 A blend comprising: (a) a block copolymer comprising: (i) a first block unit comprising, within its polymeric backbone, at least one structural unit of formula: wherein A is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group, and B is a divalent aromatic or alicyclic group; and (ii) a second block unit comprising, within its polymeric backbone, at least one structural unit of formula: -D- wherein D is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group, one or more of the carbon atoms in D may be replaced with an oxygen atom, a nitrogen atom, or a sulfur atom, wherein D comprises at least one member selected from the group consisting of a polyalkylene ether, a polyethylene ether, a polypropylene ether, a polymethylene ether, a polyolefin, a polycaprolactone, a polyperfluoroether, a dimer diol, and a polysiloxane diol; and (b) at least one of a hydroxyl-functionalized polymer, an oligoether, and a dimerized fatty acid. ### Claim 49 (depends on 48) The blend of claim 48 wherein component (b) of the blend comprises polyethylene glycol.