Polycarbonate polyol compositions and methods
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.
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 CO 2 , wherein the poly(propylene carbonate)polyol has:
at least 95% —OH end groups;
a PDI less than 1.6; and
an 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 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 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 CO 2 copolymer characterized in that the composition contains polymer chains P 1 having two or more hydroxy end groups and polymer chains P 2 having only one hydroxyl group,
where, P 1 chains have a formula T-Y-A-(Y-T) n ,
P 2 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 —CH 2 CH(CH 3 )— group derived from propylene oxide, and
n is an integer between 1 and 10 inclusive, and
p ranges from 5 to 10,000,
characterized in that the composition:
has a ratio of P 1 polymer chains to P 2 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, and
at least 95% carbonate linkages.
36. The polycarbonate polyol composition of claim 35 , wherein ratio of P 1 polymer chains to P 2 polymer chains is greater than 20:1.
37. The polycarbonate polyol composition of claim 36 , wherein ratio of P 1 polymer chains to P 2 polymer chains is greater than 40:1.
38. The polycarbonate polyol composition of claim 37 , wherein ratio of P 1 polymer chains to P 2 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 P 1 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 P 1 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.