[미국특허]
Polycarbonate polyol compositions and methods
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08G-064/00
C08G-018/44
C08G-064/02
C08G-064/34
C08G-063/02
출원번호
US-0040001
(2013-09-27)
등록번호
US-8921508
(2014-12-30)
발명자
/ 주소
Allen, Scott D.
Coates, Geoffrey W.
Cherian, Anna E.
Simoneau, Chris A.
Gridnev, Alexei A.
Farmer, Jay J.
출원인 / 주소
Novomer, Inc.
대리인 / 주소
Choate, Hall & Stewart, LLP
인용정보
피인용 횟수 :
25인용 특허 :
29
초록▼
In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO2 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 age
In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO2 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.
대표청구항▼
1. A poly(propylene carbonate)polyol composition made by a method comprising the step of contacting a reaction mixture comprising propylene oxide and carbon dioxide with a metal complex including a permanent ligand set and at least one ligand that is a polymerization initiator, and a chain transfer
1. A poly(propylene carbonate)polyol composition made by a method comprising the step of contacting a reaction mixture comprising propylene oxide and carbon dioxide with 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 CO2, wherein the poly(propylene carbonate)polyol has: at least 95% —OH end groups;a PDI less than 1.6; andan Mn between 300 g/mol and 20,000 g/mol. 2. The poly(propylene carbonate)polyol composition 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 CO2 copolymers and each Y group may be the same or different;-A- is a covalent bond or a multivalent moiety; andn is an integer between 1 and 10, inclusive. 3. The poly(propylene carbonate)polyol composition of claim 2, wherein n is 1. 4. The poly(propylene carbonate)polyol composition of claim 3, wherein the chain transfer agent is a diol. 5. The poly(propylene carbonate)polyol composition of claim 3, wherein the diol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycol) such as those having number average molecular weights of from 234 to about 2000 g/mol. 6. The poly(propylene carbonate)polyol composition of claim 5, wherein the diol is dipropylene glycol. 7. The poly(propylene carbonate)polyol composition of claim 5, wherein the diol is polyethylene glycol. 8. The poly(propylene carbonate)polyol composition of claim 7, wherein the polyethylene glycol has an Mn from 220 to 2,000 g/mol. 9. The poly(propylene carbonate)polyol composition of claim 8, wherein the polyethylene glycol is poly(ethylene glycol) having an Mn of 400 g/mol. 10. The poly(propylene carbonate)polyol composition of claim 5, wherein the diol is poly(propylene glycol). 11. The poly(propylene carbonate)polyol composition of claim 10, wherein the poly(propylene glycol) has an Mn from 234 to about 2000 g/mol. 12. The poly(propylene carbonate)polyol composition of claim 4, wherein the diol 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 poly(propylene carbonate)polyol composition of claim 12, wherein the diol is 1,6-hexane diol. 14. The poly(propylene carbonate)polyol composition of claim 1, wherein the chain transfer agent is a polyhydric alcohol. 15. The poly(propylene carbonate)polyol composition of claim 14, wherein the polyhydric alcohol is a triol. 16. The poly(propylene carbonate)polyol composition of claim 14, wherein the polyhydric alcohol is a tetraol. 17. The poly(propylene carbonate)polyol composition of claim 14, wherein the polyhydric alcohol is a higher polyol having more than four OH groups. 18. The poly(propylene carbonate)polyol composition of claim 15, wherein the triol is an aliphatic triol having a molecular weight less than 500. 19. The poly(propylene carbonate)polyol composition of claim 15, wherein the triol is selected from the group consisting of: trimethylolethane; trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene oxide triol; and polyester triols. 20. The poly(propylene carbonate)polyol composition of claim 15, wherein the triol is a polypropylene oxide triol. 21. The poly(propylene carbonate)polyol composition of claim 16, wherein the tetraol is selected from the group consisting of: erythritol, pentaerythritol; 2,2′-dihydroxymethyl-1,3-propanediol; and 2,2′-(oxydimethylene)bis-(2-ethyl-1,3-propanediol). 22. The poly(propylene carbonate)polyol composition of claim 16, wherein the tetraol is propoxylated pentaerythritol. 23. The poly(propylene carbonate)polyol composition of claim 1, wherein the composition comprises less than 10% cyclic carbonate. 24. The poly(propylene carbonate)polyol composition of claim 23, wherein the composition comprises less than 5% cyclic carbonate. 25. The poly(propylene carbonate)polyol composition of claim 24, wherein the composition comprises less than 1% cyclic carbonate. 26. The poly(propylene carbonate)polyol composition of claim 1, wherein the PDI of the polyol is less than 1.2. 27. The poly(propylene carbonate)polyol composition of claim 1, wherein the Mn of the polyol is between 500 and 10,000 g/mol. 28. The poly(propylene carbonate)polyol composition of claim 27, wherein the Mn of the polyol is between 1,000 and 5,000 g/mol. 29. The poly(propylene carbonate)polyol composition of claim 1, wherein the Mn of the polyol is about 3,000 g/mol. 30. The poly(propylene carbonate)polyol composition of claim 1, wherein the Mn of the polyol is about 2,000 g/mol. 31. The poly(propylene carbonate)polyol composition of claim 1, wherein the Mn of the polyol is about 1,000 g/mol. 32. A urethane composition comprising the reaction product of a poly(propylene carbonate)polyol composition of claim 1 with a polyisocyanate. 33. The urethane composition of claim 32, wherein the reaction product is selected from the group consisting of: a homogeneous or microcellular elastomer, a flexible or rigid foam, an adhesive, and a coating. 34. The urethane composition of claim 32, wherein the reaction product comprises a coating. 35. A polycarbonate polyol composition comprising an epoxide CO2 copolymer characterized in that the composition contains polymer chains P1 having two or more hydroxy end groups and polymer chains P2 having only one hydroxyl group, where, P1 chains have a formula T-Y-A-(Y-T)n,P2 chains have a formula —Y-A-(Y—)n— derives from a chain transfer consisting of a polyhydric alcohol where each —Y— is a hydroxyl group and -A- is a multivalent compound,X is a bound form of an anion capable of initiating only one polymer chain,-T is -E- is a —CH2CH(CH3)— group derived from propylene oxide, andn is an integer between 1 and 10 inclusive, andp ranges from 5 to 10,000,characterized in that the composition: has a ratio of P1 polymer chains to P2 polymer chains is greater than 9:1,a polydispersity index (PDI) of the composition is less than 2,an Mn is between 400 and 20,000 g/mol, andat least 95% carbonate linkages. 36. The polycarbonate polyol composition of claim 35, wherein ratio of P1 polymer chains to P2 polymer chains is greater than 20:1. 37. The polycarbonate polyol composition of claim 36, wherein ratio of P1 polymer chains to P2 polymer chains is greater than 40:1. 38. The polycarbonate polyol composition of claim 37, wherein ratio of P1 polymer chains to P2 polymer chains is greater than 100:1. 39. The polycarbonate polyol composition of claim 35, wherein n is 1. 40. The polycarbonate polyol composition of claim 35, wherein chains of type P1 have the formula: 41. The polycarbonate polyol composition of claim 40, wherein -A- is 42. The polycarbonate polyol of claim 41, wherein is a mixture of isomers. 43. The polycarbonate polyol of claim 42, wherein the Mn is between 800 and 4,000 g/mol. 44. The polycarbonate polyol of claim 43, wherein the Mn is between 1,000 and 3,000 g/mol. 45. The polycarbonate polyol of claim 43, wherein the Mn is about 3,000 g/mol. 46. The polycarbonate polyol of claim 40, wherein -A- is a polyether chain. 47. The polycarbonate polyol of claim 46, wherein -A- is polypropylene glycol. 48. The polycarbonate polyol of claim 46, wherein -A- is polyethylene glycol. 49. The polycarbonate polyol of claim 48, wherein -A- is poly(ethylene glycol) having an Mn of 400 g/mol. 50. The polycarbonate polyol of claim 35, wherein the chain transfer agent is a triol. 51. The polycarbonate polyol of claim 50, wherein chains of type P1 have the formula: where each z is 1. 52. The polycarbonate polyol of claim 50, wherein -A- is glycerol. 53. The polycarbonate polyol of claim 50, wherein -A- is a polymer chain or oligomer selected from the group consisting of polyolefins, polyethers, polyesters, polycarbonates, polycarbonate polyethers and polyoxymethylene. 54. The polycarbonate polyol of claim 50, wherein -A- is a polyether chain. 55. The polycarbonate polyol of claim 35, wherein the chain transfer agent is a tetraol. 56. The polycarbonate polyol of claim 55, wherein the tetraol is pentaerythritol. 57. The polycarbonate polyol of claim 55, wherein -A- is a polymer chain or oligomer selected from the group consisting of polyolefins, polyethers, polyesters, polycarbonates, polycarbonate polyethers and polyoxymethylene. 58. The polycarbonate polyol of claim 55, wherein -A- is a polyether. 59. The polycarbonate polyol of claim 56, wherein -A- is 60. The polycarbonate polyol of claim 35, wherein the chain transfer agent is a polyhydric alcohol with more than four OH groups. 61. The polycarbonate polyol of claim 35, wherein —Y-A-Y— is derived from propylene glycol. 62. The polycarbonate polyol of claim 61, wherein the Mn is between 800 and 4,000 g/mol. 63. The polycarbonate polyol of claim 62, wherein the Mn is between 1,000 and 3,000 g/mol. 64. The polycarbonate polyol of claim 62, wherein the Mn is about 1,000 g/mol. 65. A urethane composition comprising the reaction product of a poly(propylene carbonate)polyol composition of claim 35 with a polyisocyanate. 66. The urethane composition of claim 65, wherein the reaction product is selected from the group consisting of: a homogeneous or microcellular elastomer, a flexible or rigid foam, an adhesive, and a coating. 67. The urethane composition of claim 66, wherein the reaction product comprises a coating.
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