Aliphatic polycarbonate polyol compositions

Abstract

The present invention encompasses CO.sub.2-based polycarbonate polyols that do not degrade from the chain ends to form cyclic carbonate. Importantly, the inventive polyol compositions retain OH end group functionality desirable for thermoset applications.

Claims

1. A method comprising the steps of: i) reacting a polycarbonate polyol of formula P1-OH, ##STR00138## with a cyclic acid anhydride having a formula ##STR00139## to provide a polycarbonate polyol of formula P1-CO.sub.2H, ##STR00140## and ii) further treating this polyol with an epoxide of formula ##STR00141## to yield a polymer composition of formula P1, ##STR00142## wherein: is a multivalent moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; each n is independently, on average in the composition, within a range from about 2 to about 200; Q is an optionally substituted bivalent moiety; and x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

2. The method of claim 1, wherein the moiety ##STR00143## at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of: ##STR00144## ##STR00145## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

3. The method of claim 1, wherein the moiety ##STR00146## at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of: ##STR00147## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

4. The method of claim 1, wherein the moiety ##STR00148## at each occurrence in the aliphatic polycarbonate chains is ##STR00149##

5. The method of claim 1, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00150## where R.sup.a and R.sup.b are each independently selected from the group consisting of: H, halogen, optionally substituted C.sub.1-8 aliphatic, and optionally substituted C.sub.1-8 heteroaliphatic, where two or more R.sup.a and/or R.sup.b groups (whether on the same or different carbon atoms) may be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more heteroatoms, and where two R.sup.a and R.sup.b groups on the same carbon atom or on adjacent carbon atoms may optionally be taken together to form an alkene or, if on the same carbon atom, an oxo group; q is an integer from 1 to 10; R.sup.d is optionally present, and if present are, independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

6. The method of claim 1, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00151## where R.sup.d is independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

7. The method of claim 1, wherein Q is: ##STR00152##

8. The method of claim 1, wherein Q is: ##STR00153##

9. The method of claim 1, wherein: R.sup.3 is selected from the group consisting of an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group; and R.sup.1, R.sup.2, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

10. The method of claim 1, wherein the moiety ##STR00154## is at each occurrence in the aliphatic polycarbonate chains is: ##STR00155##

11. The method of claim 1, wherein the moiety ##STR00156## is at each occurrence in the aliphatic polycarbonate chains is: ##STR00157##

12. The method of claim 1, further comprising in step (i) the use of one or more catalysts.

13. The method of claim 1, further comprising in step (ii) the use of one or more catalysts.

14. The method of claim 13, wherein at least one catalyst is selected from the group consisting of: (salcy)MX (salcy=N,N-bis(3,5-di-tert-butylsalicylidene)-1,2 diaminocyclohexane; M=Al, Co, Cr, Mn; X=halide or carboxylate), zinc glutarate, TPPM-X (TPP=tetraphenylphorphyrin; M=Al, Co, Cr; X=halide or alkoxide), and (beta-diiminate)zinc acetate.

15. The method of claim 13, wherein at least one catalyst is cobalt(III) salcy (salcy=N,N-bis(3,5-di-tert-butylsalicylidene).

16. A composition made by the method of claim 1, wherein the composition comprises a polymer having formula P1, ##STR00158##

17. The composition of claim 16, wherein comprises one or more atoms selected from the group consisting of carbon, nitrogen, phosphorus, sulfur, and boron.

18. The composition of claim 16, wherein comprises one or more carbon atoms.

19. The composition of claim 16, wherein is: ##STR00159##

20. The composition of claim 16, wherein is derived from a polyfunctional chain transfer agent.

21. The composition of claim 16, wherein the moiety ##STR00160## is at each occurrence in the aliphatic polycarbonate chains independently selected from the group consisting of: ##STR00161## ##STR00162## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

22. The composition of claim 16, wherein the moiety ##STR00163## at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of: ##STR00164## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

23. The composition of claim 16, wherein the moiety ##STR00165## at each occurrence in the aliphatic polycarbonate chains is ##STR00166##

24. The composition of claim 16, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00167## where R.sup.a and R.sup.b are each independently selected from the group consisting of: H, halogen, optionally substituted C.sub.1-8 aliphatic, and optionally substituted C.sub.1-8 heteroaliphatic, where two or more R.sup.a and/or R.sup.b groups (whether on the same or different carbon atoms) may be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more heteroatoms, and where two R.sup.a and R.sup.b groups on the same carbon atom or on adjacent carbon atoms may optionally be taken together to form an alkene or, if on the same carbon atom, an oxo group; q is an integer from 1 to 10; and R.sup.d is optionally present, and if present are, independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

25. The composition of claim 16, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00168## where R.sup.d is independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

26. The composition of claim 16, wherein Q is: ##STR00169##

27. The composition of claim 16, wherein Q is: ##STR00170##

28. The composition of claim 16, wherein: R.sup.3 is selected from the group consisting of an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group; and R.sup.1, R.sup.2, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

29. The composition of claim 16, wherein the moiety ##STR00171## at each occurrence in the aliphatic polycarbonate chains is: ##STR00172##

30. The composition of claim 16, wherein the moiety ##STR00173## at each occurrence in the aliphatic polycarbonate chains is: ##STR00174##

31. The composition of claim 16, comprising an aliphatic polycarbonate polyol selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, and mixtures of any two or more of these: ##STR00175## wherein each n is, on average in the composition, within a range from about 2 to about 200, and t is from 0 to 10.

32. The composition of claim 31, wherein the composition comprises: Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; or Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups.

33. The composition of claim 16, comprising an aliphatic polycarbonate polyol selected from the group consisting of Q9, Q10, Q11, Q12, Q13, Q14, and mixtures of any two or more of these: ##STR00176## wherein each n is, on average in the composition, within a range from about 2 to about 200, and t is from 0 to 10.

34. The composition of claim 33, wherein the composition comprises: Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; or Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups.

35. The composition of claim 16, comprising an aliphatic polycarbonate polyol represented by the formula: ##STR00177##

36. An aliphatic epoxide-CO.sub.2 based polycarbonate polyol composition comprising polymer chains of formula P1: ##STR00178## wherein: is a multivalent moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; each n is independently, on average in the composition, within a range from about 2 to about 200; Q is an optionally substituted bivalent moiety; and x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

37. The composition of claim 36, wherein comprises one or more atoms selected from the group consisting of carbon, nitrogen, phosphorus, sulfur, and boron.

38. The composition of claim 36, wherein comprises one or more carbon atoms.

39. The composition of claim 36, wherein is: ##STR00179##

40. The composition of claim 36, wherein is derived from a polyfunctional chain transfer agent.

41. The composition of claim 36, wherein the moiety ##STR00180## is at each occurrence in the aliphatic polycarbonate chains independently selected from the group consisting of: ##STR00181## ##STR00182## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

42. The composition of claim 36, wherein the moiety ##STR00183## at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of: ##STR00184## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

43. The composition of claim 36, wherein the moiety ##STR00185## at each occurrence in the aliphatic polycarbonate chains is ##STR00186##

44. The composition of claim 36, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00187## where R.sup.a and R.sup.b are each independently selected from the group consisting of: H, halogen, optionally substituted C.sub.1-8 aliphatic, and optionally substituted C.sub.1-8 heteroaliphatic, where two or more R.sup.a and/or R.sup.b groups (whether on the same or different carbon atoms) may be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more heteroatoms, and where two R.sup.a and R.sup.b groups on the same carbon atom or on adjacent carbon atoms may optionally be taken together to form an alkene or, if on the same carbon atom, an oxo group; q is an integer from 1 to 10; and R.sup.d is optionally present, and if present are, independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

45. The composition of claim 36, wherein Q is an optionally substituted bivalent moiety selected from the group consisting of: ##STR00188## where R.sup.d is independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group.

46. The composition of claim 36, wherein Q is: ##STR00189##

47. The composition of claim 36, wherein Q is: ##STR00190##

48. The composition of claim 36, wherein: R.sup.3 is selected from the group consisting of an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group; and R.sup.1, R.sup.2, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

49. The composition of claim 36, wherein the moiety ##STR00191## at each occurrence in the aliphatic polycarbonate chains is: ##STR00192##

50. The composition of claim 36, wherein the moiety ##STR00193## at each occurrence in the aliphatic polycarbonate chains is: ##STR00194##

51. The composition of claim 36, comprising an aliphatic polycarbonate polyol selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, and mixtures of any two or more of these: ##STR00195## wherein each n is, on average in the composition, within a range from about 2 to about 200, and t is from 0 to 10.

52. The composition of claim 51, wherein the composition comprises: Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; or Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups.

53. The composition of claim 36, comprising an aliphatic polycarbonate polyol selected from the group consisting of Q9, Q10, Q11, Q12, Q13, Q14, and mixtures of any two or more of these: ##STR00196## wherein each n is, on average in the composition, within a range from about 2 to about 200, and t is from 0 to 10.

54. The composition of claim 53, wherein the composition comprises: Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; or Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups.

55. The composition of claim 36, comprising an aliphatic polycarbonate polyol represented by the formula: ##STR00197##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 depicts a .sup.1H-NMR of the product of step 1a of Example 1.

(2) FIG. 2 depicts a .sup.1H-NMR of a polycarbonate composition of formula Q3.

(3) FIG. 3 depicts the results of a comparative thermal stability study on aliphatic polycarbonate compositions of formula Q3.

(4) FIG. 4 depicts comparative stability of aliphatic polycarbonate compositions in the presence of trimethylamine.

(5) FIG. 5 depicts comparative stability of aliphatic polycarbonate compositions in the presence of dibutylamine.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

(6) I. Polyol Compositions

(7) The present invention provides, among other things, novel aliphatic polycarbonate polyols. These materials comprise polymer chains having repeat units conforming to the formula:

(8) ##STR00012## where R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are, at each occurrence in the polymer chain, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

(9) In certain embodiments, aliphatic polycarbonate polyols of the invention incorporate copolymers derived from one or more epoxides and carbon dioxide. In certain embodiments, copolymers are derived from ethylene oxide, propylene oxide, 1,2 butene oxide, 1,2 hexene oxide, oxides of higher alpha olefins (e.g. C.sub.6-40 alpha olefins), butadiene monoepoxide, styrene oxide, epichlorohydrin, ethers or esters of glycidol, cyclopentene oxide, cyclohexene oxide, 3 vinyl cyclohexene oxide, 3-ethyl cyclohexene oxide, and combinations of any two or more of these.

(10) In certain embodiments, aliphatic polycarbonate polyols of the invention incorporate copolymers derived from propylene oxide. In certain embodiments, aliphatic polycarbonate polyols of the invention incorporate copolymers derived from propylene oxide and one or more additional epoxides. In certain embodiments, aliphatic polycarbonate polyols of the invention incorporate copolymers derived from ethylene oxide. In certain embodiments, aliphatic polycarbonate polyols of the invention incorporate copolymers derived from ethylene oxide and one or more additional epoxides.

(11) In another embodiment, aliphatic polycarbonate polyol compositions encompassed by the present invention comprise polymer chains having a formula P1:

(12) ##STR00013## where each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined above and in the classes and subclasses herein; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence, independently selected from the group consisting of H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; n is, on average in the composition, within a range from about 2 to about 200; Q is any bivalent moiety derived from a cyclic acid anhydride;

(13) ##STR00014## is a multivalent moiety; and x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

(14) In certain embodiments, for polymer chains of formula P1, Q is an optionally substituted bivalent moiety. In certain embodiments, for polymer chains of formula P1, Q is an optionally substituted bivalent moiety selected from the group consisting of: saturated or unsaturated, straight or branched, C.sub.2-C.sub.30 aliphatic group, wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), OC(O)N(R.sup.y), N(R.sup.y)C(O)O, OC(O)O, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), C(NOR.sup.y), or NN; C.sub.7-12 arylalkyl; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; where each occurrence of R.sup.y is independently hydrogen or an optionally substituted C.sub.1-6 aliphatic group.

(15) In certain embodiments, for polymer chains of formula P1, Q is an optionally substituted bivalent moiety selected from the group consisting of:

(16) ##STR00015##
where R.sup.a and R.sup.b are each independently selected from the group consisting of: H, halogen, optionally substituted C.sub.1-8 aliphatic, and optionally substituted C.sub.1-8 heteroaliphatic, where two or more R.sup.a and/or R.sup.b groups (whether on the same or different carbon atoms) may be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more heteroatoms, and where two R.sup.a and R.sup.b groups on the same carbon atom or on adjacent carbon atoms may optionally be taken together to form an alkene or, if on the same carbon atom, a carbonyl group (e.g., oxo); q is an integer from 1 to 10; and R.sup.d groups are optionally present, and if present are, independently at each occurrence selected from the group consisting of: halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2, CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; where two or more R.sup.d groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

(17) In certain embodiments, for polymer chains of formula P1, Q is selected from the group consisting of:

(18) ##STR00016##
where R.sup.d is as defined above.

(19) In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from a cyclic acid anhydride selected from the group consisting of:

(20) ##STR00017##
e.g., Section II below.

(21) In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from Succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from methyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from dimethylsuccinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from phenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from octadecenylsuccinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from hexadecenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from eicosodecenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 2-methylene succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from n-octenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from nonenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from tetrapropenyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 14 dodecyl succinic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from glutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 3-methylglutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from phenyl glutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from diglycolic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 2-ethyl 3-methyl glutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 3,3-dimethyl glutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 2,2-dimethyl glutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 3,3-tetramethyleneglutaric anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from phthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 4-methyl phthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 4-t-butyl phthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from tetrahydrophthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from hexahydrophthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from maleic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 2-methyl maleic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 3,4,5,6-tetrahydrophthalic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from 1-cyclopentene-1,2-dicarboxylic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from dimethyl maleic anhydride. In certain embodiments, for polymer chains of formula P1, Q is a bivalent moiety derived from diphenyl maleic anhydride.

(22) In certain embodiments, a multivalent moiety embedded within aliphatic polycarbonate chains described herein is derived from a polyfunctional chain transfer agent having two or more sites from which epoxide/CO.sub.2 copolymerization can occur. In certain embodiments, the multivalent moiety comprises one or more atoms selected from the group consisting of carbon, nitrogen, phosphorous, sulfur, and boron. In certain embodiments, comprises one or more carbon atoms. In certain embodiments, comprises a phosphorous atom. In certain embodiments, comprises a polymer chain. In certain embodiments, is derived from any of the polyfunctional chain transfer agents as exemplified in published PCT application WO 2010/028362, the entirety of which is incorporated herein by reference.

(23) In certain embodiments, a polyfunctional chain transfer agent has a formula:

(24) ##STR00018##
where , x, and y are as defined above and described in classes and subclasses herein.

(25) In certain embodiments, aliphatic polycarbonate chains in the inventive polymer compositions herein are derived from the copolymerization of one or more epoxides with carbon dioxide in the presence of such polyfunctional chain transfer agents as shown in scheme 2:

(26) ##STR00019##

(27) In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P2:

(28) ##STR00020##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, , and n are as defined above and described in classes and subclasses herein, and the moiety Y has the formula

(29) ##STR00021##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, and Q are as defined above and in the classes and subclasses herein.

(30) In certain embodiments, where aliphatic polycarbonate chains have a structure P2, a moiety is derived from a dihydric alcohol. In such instances the moiety represents the carbon-containing backbone of the dihydric alcohol, while the two oxygen atoms adjacent to are derived from the OH groups of the diol. For example, if the dihydric alcohol were derived from ethylene glycol, then would be CH.sub.2CH.sub.2 and P2 would have the following structure:

(31) ##STR00022##

(32) In certain embodiments, where is derived from a dihydric alcohol, the dihydric alcohol comprises a C.sub.2-40 diol. In certain embodiments, the dihydric alcohol 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, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

(33) In certain embodiments, is derived from a dihydric alcohol having the formula:

(34) ##STR00023##

(35) In certain embodiments, where is derived from a dihydric alcohol, the dihydric alcohol 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 glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.

(36) In certain embodiments, where is derived from a dihydric alcohol, the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

(37) In certain embodiments, where is derived from a dihydric alcohol, the dihydric alcohol comprises a polymeric diol. In certain embodiments, a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol.

(38) In certain embodiments, is derived from a polyhydric alcohol with more than two hydroxy groups. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where a moiety is derived from a triol. In certain embodiments, such aliphatic polycarbonate chains have the structure P3:

(39) ##STR00024##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and described in classes and subclasses herein.

(40) In certain embodiments, where is derived from a triol, the triol is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol, hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

(41) In certain embodiments, is derived from an alkoxylated derivative of a trifunctional carboxylic acid or trifunctional hydroxy acid. In certain embodiments, alkoxylated polymeric derivatives comprise ethoxylated or propoxylated compounds.

(42) In certain embodiments, where is derived from a polymeric triol, the polymeric triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated polymeric triols comprise ethoxylated or propoxylated compounds.

(43) In certain embodiments, is derived from a polyhydric alcohol with four hydroxy groups. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety is derived from a tetraol. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P4:

(44) ##STR00025##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and described in classes and subclasses herein.

(45) In certain embodiments, is derived from a polyhydric alcohol with more than four hydroxy groups. In certain embodiments, is derived from a polyhydric alcohol with six hydroxy groups. In certain embodiments, the polyhydric alcohol is dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P5:

(46) ##STR00026##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and described in classes and subclasses herein.

(47) In certain embodiments, aliphatic polycarbonates of the present invention comprise a combination of bifunctional chains (e.g. polycarbonates of formula P2) in combination with higher functional chains (e.g. one or more polycarbonates of formulae P3 to P5).

(48) In certain embodiments, is derived from a hydroxy acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P6:

(49) ##STR00027##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and described in classes and subclasses herein.

(50) In such instances, represents the carbon-containing backbone of the hydroxy acid, while ester and carbonate linkages adjacent to are derived from the CO.sub.2H group and the hydroxy group of the hydroxy acid. For example, if were derived from 3-hydroxy propanoic acid, then would be CH.sub.2CH.sub.2 and P6 would have the following structure:

(51) ##STR00028##

(52) In certain embodiments, is derived from an optionally substituted C.sub.2-40 hydroxy acid. In certain embodiments, is derived from a polyester. In certain embodiments, such polyesters have a molecular weight less than about 2000 g/mol. In certain embodiments, a hydroxy acid is an alpha-hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic, citric acid, and mandelic acid.

(53) In certain embodiments, a hydroxy acid is a beta-hydroxy acid. In certain embodiments, a 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.

(54) In certain embodiments, a hydroxy acid is a - hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of optionally substituted C.sub.3-20 aliphatic - hydroxy acids and oligomeric esters.

(55) In certain embodiments, is derived from a hydroxy acid selected from the group consisting of:

(56) ##STR00029## ##STR00030##

(57) In certain embodiments, is derived from a polycarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P7:

(58) ##STR00031##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and described in classes and subclasses herein, and y is from 1 to 5, inclusive.

(59) In embodiments where the aliphatic polycarbonate chains have a structure P7, represents the carbon-containing backbone (or a bond in the case of oxalic acid) of the polycarboxylic acid, while the ester groups adjacent to are derived from the CO.sub.2H groups of the polycarboxylic acid. For example, if were derived from succinic acid (HO.sub.2CCH.sub.2CH.sub.2CO.sub.2H), then would be CH.sub.2CH.sub.2 and P7 would have the following structure:

(60) ##STR00032##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, and n are as defined above and in the classes and subclasses herein.

(61) In certain embodiments, is derived from a dicarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P8:

(62) ##STR00033##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, , and n are as defined above and in the classes and subclasses herein.

(63) In certain embodiments, is derived from a dicarboxylic acid 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.

(64) In certain embodiments, derived from a dicarboxylic acid selected from the group consisting of:

(65) ##STR00034## ##STR00035##

(66) In certain embodiments, is derived from a phosphorous-containing molecule. In certain embodiments, has a formula P(O)(OR).sub.k where each R is independently hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group and k is 0, 1, or 2. In certain embodiments, is derived from a phosphorous-containing molecule selected from the group consisting of:

(67) ##STR00036##

(68) In certain embodiments, has a formula P(O)(OR).sub.j(R).sub.k where R is hydrogen, an optionally substituted C.sub.1-20 aliphatic group, or an optionally substituted aryl group, j is 1 or 2, and k is 0 or 1, wherein the sum of j and k is not more than 2. In certain embodiments, is derived from a phosphorous-containing molecule selected from the group consisting of:

(69) ##STR00037##
where R.sup.d is as defined above.

(70) In certain embodiments, in aliphatic polycarbonate chains of any of formulae P1 through P8, a majority of the polymer chain ends comprise Y groups. In certain embodiments, in aliphatic polycarbonate chains of any of structures P1 through P8, a majority of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions. In certain embodiments, at least 75% of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions. In certain embodiments, at least 80% of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions. In certain embodiments, at least 85% of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions. In certain embodiments, at least 90% of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions. In certain embodiments, at least 95% of the polymer chain ends comprise Y groups capable of participating in epoxide ring-opening reactions.

(71) In certain embodiments, a moiety

(72) ##STR00038##
in the structures herein above, is at each occurrence in the aliphatic polycarbonate chains independently selected from the group consisting of:

(73) ##STR00039## ##STR00040## wherein each R.sup.x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

(74) In certain embodiments, a moiety

(75) ##STR00041##
in the structures hereinabove, is at each occurrence in the aliphatic polycarbonate chains independently selected from the group consisting of:

(76) ##STR00042##

(77) wherein R.sup.x is as defined above.

(78) In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and one epoxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide.

(79) In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide.

(80) In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclohexene oxide.

(81) In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclopentene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3-vinyl cyclohexene oxide.

(82) In other embodiments, aliphatic polycarbonate chains comprise a terpolymer of carbon dioxide and two different epoxides. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glycidyl esters, glycidyl ethers, and epoxides of higher alpha olefins. In certain embodiments, these terpolymers contain a majority of repeat units derived from propylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 60% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% propylene oxide-derived repeat units.

(83) In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glycidyl esters, glycidyl ethers, and epoxides of higher alpha olefins. In certain embodiments, these terpolymers contain a majority of repeat units derived from ethylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than about 60% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% propylene oxide-derived repeat units.

(84) In certain embodiments, in polymer compositions described hereinabove, aliphatic polycarbonate chains have a number average molecular weight (M.sub.n) in the range of 500 g/mol to about 250,000 g/mol.

(85) In certain embodiments, aliphatic polycarbonate chains have an M.sub.n less than about 100,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n less than about 70,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n less than about 50,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n between about 500 g/mol and about 40,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n less than about 25,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n between about 500 g/mol and about 20,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n between about 1000 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n between about 1,000 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n of about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n of about 4,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n of about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n of about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M.sub.n of about 2,000 g/mol.

(86) In certain embodiments, in polymer compositions described hereinabove, aliphatic polycarbonate chains are characterized in that they have a narrow molecular weight distribution. This can be indicated by the polydispersity indices (PDI) of the aliphatic polycarbonate polymers. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 2. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.8. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.5. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.4. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.2. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.1.

(87) In certain embodiments, where aliphatic polycarbonates are derived from monosubstituted epoxides (e.g. such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, or a glycidol derivative), the aliphatic polycarbonates are characterized in that they are regioregular. Regioregularity may be expressed as the percentage of adjacent monomer units that are oriented in a head-to-tail arrangement within the polymer chain. In certain embodiments, aliphatic polycarbonate chains in the inventive polymer compositions have a head-to-tail content higher than about 80%. In certain embodiments, a head-to-tail content is higher than about 85%. In certain embodiments, a head-to-tail content is higher than about 90%. In certain embodiments, a head-to-tail content is greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 97%, or greater than about 99%.

(88) In certain embodiments, the structures of aliphatic polycarbonate chains derived from the polymerization of carbon dioxide with one or more epoxides as described above are represented by the ensuing non-limiting examples.

(89) Structures P2a through P2s below are representative of aliphatic polycarbonates derived from a diol chain transfer agent and one or more aliphatic epoxides such as propylene oxide, ethylene oxide, butylene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, 3-ethyl cyclohexene oxide, and esters or ethers of glycidol. It is to be understood that many variations on these compounds are possible including the use of additional or different epoxides, use of different chain transfer agents (such as higher polyhydric alcohols, hydroxy acids, and polyacids), and the introduction of different Y groups. Such variations will be apparent to one skilled in the art based on the disclosure and teachings of the present application and are specifically encompassed within the scope of the present invention.

(90) In certain embodiments, aliphatic polycarbonate chains comprise

(91) ##STR00043##
where , Y, and n are as defined above and described in classes and subclasses herein.

(92) In certain embodiments, aliphatic polycarbonate chains comprise

(93) ##STR00044##
where Y and n are as defined above and described in classes and subclasses herein.

(94) In certain embodiments, aliphatic polycarbonate chains comprise

(95) ##STR00045##
where Y, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and n are as defined above and described in classes and subclasses herein.

(96) In certain embodiments, aliphatic polycarbonate chains comprise

(97) ##STR00046##
where Y and n are as defined above and described in classes and subclasses herein.

(98) In certain embodiments, aliphatic polycarbonate chains comprise

(99) ##STR00047##
where , Y, and n are as defined above and described in classes and subclasses herein.

(100) In certain embodiments, aliphatic polycarbonate chains comprise

(101) ##STR00048##
where Y and n are as defined above and described in classes and subclasses herein.

(102) In certain embodiments, aliphatic polycarbonate chains comprise

(103) ##STR00049##
where , Y, and n are as defined above and described in classes and subclasses herein.

(104) In certain embodiments, aliphatic polycarbonate chains comprise

(105) ##STR00050##
where Y and n are as defined above and described in classes and subclasses herein.

(106) In certain embodiments, aliphatic polycarbonate chains comprise

(107) ##STR00051##
where , Y, and n are as defined above and described in classes and subclasses herein.

(108) In certain embodiments, aliphatic polycarbonate chains comprise

(109) ##STR00052##
where Y and n are as defined above and described in classes and subclasses herein.

(110) In certain embodiments, aliphatic polycarbonate chains comprise

(111) ##STR00053##
where , Y and n are as defined above and described in classes and subclasses herein.

(112) In certain embodiments, aliphatic polycarbonate chains comprise

(113) ##STR00054##
where Y and n are as defined above and described in classes and subclasses herein.

(114) In certain embodiments, aliphatic polycarbonate chains comprise

(115) ##STR00055##
where , Y, R.sup.x, and n are as defined above and described in classes and subclasses herein.

(116) ##STR00056##
where Y, R.sup.x, and n are as defined above and described in classes and subclasses herein.

(117) In certain embodiments, aliphatic polycarbonate chains comprise

(118) ##STR00057##
where , Y, and n are as defined above and described in classes and subclasses herein.

(119) In certain embodiments, aliphatic polycarbonate chains comprise

(120) ##STR00058##
where , Y, and n are as defined above and described in classes and subclasses herein, and is a single or double bond.

(121) In certain embodiments, aliphatic polycarbonate chains comprise

(122) ##STR00059##
where Y and n are as defined above and described in classes and subclasses herein.

(123) In certain embodiments, aliphatic polycarbonate chains comprise

(124) ##STR00060##
where Y, , and n are as defined above and described in classes and subclasses herein.

(125) In certain embodiments, aliphatic polycarbonate chains comprise

(126) ##STR00061##
where , Y, R.sup.x, and n are as defined above and described in classes and subclasses herein.

(127) In certain embodiments, aliphatic polycarbonate chains comprise

(128) ##STR00062##
where Y, R.sup.x, and n are as defined above and described in classes and subclasses herein.

(129) In certain embodiments, aliphatic polycarbonate chains comprise

(130) ##STR00063##
where , Y, and n are as defined above and described in classes and subclasses herein.

(131) In certain embodiments, aliphatic polycarbonate chains comprise

(132) ##STR00064##
where Y, , and n are as defined above and described in classes and subclasses herein.

(133) In certain embodiments, aliphatic polycarbonate chains comprise

(134) ##STR00065##
where Y and n are as defined above and described in classes and subclasses herein.

(135) In certain embodiments, aliphatic polycarbonate chains comprise

(136) ##STR00066##
where Y, , and n are as defined above and described in classes and subclasses herein.

(137) In certain embodiments, aliphatic polycarbonate chains comprise

(138) ##STR00067##
where , Y, and n are as defined above and described in classes and subclasses herein.

(139) In certain embodiments, in polycarbonates of structures P2a through P2r having a group, is derived from or selected from the group consisting of: ethylene glycol; diethylene glycol, triethylene glycol, 1,3 propane diol; 1,4 butane diol, hexylene glycol, propylene glycol, dipropylene glycol, tripopylene glycol, and alkoxylated derivatives of any of these.

(140) In certain embodiments, aliphatic polycarbonate chains comprise

(141) ##STR00068##
where Y and n are as defined above and described in classes and subclasses herein.

(142) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(143) ##STR00069##
where R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are as defined above and described in classes and subclasses herein.

(144) In certain embodiments, in polycarbonates of structure P2a through P2s, Y is selected from the group consisting of:

(145) ##STR00070##

(146) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(147) ##STR00071##

(148) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(149) ##STR00072##

(150) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(151) ##STR00073##
where R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are as defined above and described in classes and subclasses herein.

(152) In certain embodiments, in polycarbonates of structure P2a through P2s, Y is selected from the group consisting of:

(153) ##STR00074##

(154) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(155) ##STR00075##

(156) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(157) ##STR00076##

(158) In certain embodiments, in polycarbonates of structure P2a through P2s, Y is selected from the group consisting of:

(159) ##STR00077##

(160) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(161) ##STR00078##

(162) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(163) ##STR00079##

(164) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(165) ##STR00080##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.d, are as defined above and described in classes and subclasses herein.

(166) In certain embodiments, in polycarbonates of structure P2a through P2s, Y is selected from the group consisting of:

(167) ##STR00081##
where R.sup.d, is as defined above and described in classes and subclasses herein.

(168) In certain embodiments, in polycarbonates of structure P2a through P2s, Y is selected from the group consisting of:

(169) ##STR00082##

(170) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(171) ##STR00083##

(172) In certain embodiments, in polycarbonates of structure P2a through P2s, Y has the formula:

(173) ##STR00084##

(174) In certain embodiments, the aliphatic polycarbonate polyol compositions of the present invention are selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, and mixtures of any two or more of these.

(175) ##STR00085## wherein n is as defined above and in classes and subclasses herein, and t is from 0 to 10. In some embodiments, t is from 1 to 10.

(176) In certain embodiments, the present invention encompasses compositions comprising: Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(propylene carbonate) of any of formulae Q1 through Q8 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups.

(177) In certain embodiments, the aliphatic polycarbonate polyol compositions of the present invention are selected from the group consisting of Q9, Q10, Q11, Q12, Q13, Q14, and mixtures of any two or more of these.

(178) ##STR00086## wherein n is as defined above and in classes and subclasses herein, and t is from 0 to 10. In some embodiments, t is from 1 to 10.

(179) In certain embodiments, the present invention encompasses compositions comprising: Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups; Poly(ethylene carbonate) of any of formulae Q9 through Q14 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% OH end groups;
II. Methods of Making

(180) In another aspect, the present invention encompasses methods of producing the polyol compositions described above. In certain embodiments, such methods comprise the steps of reacting a polycarbonatepool with end groups of formula

(181) ##STR00087##
with a cyclic acid anhydride having a formula

(182) ##STR00088##
to provide a polycarbonate polyol with chain ends having a formula

(183) ##STR00089##
and then further treating this polyol with an epoxide of formula

(184) ##STR00090##
to yield a polymer composition with end groups having formula E1,

(185) ##STR00091##
where each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1, R.sup.2, R.sup.3, R.sup.4, n, and Q are as defined above and in the classes and subclasses herein.

(186) In certain embodiments, aliphatic polycarbonate polymers described above are derived from a polycarbonate polyol of formula P1-OH by end-capping with a suitable cyclic acid anhydride, followed by addition of an epoxide. In certain embodiments, such reactions conform to the Scheme 1 below, where each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1, R.sup.2, R.sup.3, R.sup.4, n, , and Q are as defined above and in the classes and subclasses herein.

(187) ##STR00092##

(188) In certain embodiments, methods of the present invention comprise the step of treating a polymer of formula P1-OH with a cyclic acid anhydride to provide a polymer of formula P1-CO.sub.2H. In certain embodiments, the cyclic anhydride has a formula

(189) ##STR00093##
where Q is as defined above and in the classes and subclasses herein.

(190) In certain embodiments, the present invention comprises the step of treating a polymer of formula P1-OH with succinic anhydride. In certain embodiments, the present invention comprises the step of treating a polymer of formula P1-OH with maleic anhydride. In certain embodiments, the present invention comprises the step of treating a polymer of formula P1-OH with glutaric anhydride. In certain embodiments, the present invention comprises the step of treating a polymer of formula P1-OH with phthalic anhydride. In certain embodiments, the present invention comprises the step of treating a polymer of formula P1-OH with methyl succinic anhydride.

(191) In certain embodiments, the step of treating the polymer of formula P1-OH with a cyclic acid anhydride comprises contacting the polymer with the cyclic anhydride in the presence of one or more catalysts. In certain embodiments, a catalyst comprises an esterification catalyst. In certain embodiments, an esterification catalyst is selected from the group consisting of: Esterification and acylation catalysts such as those reported in Grasa, G. A.: et al. Synthesis 2004, 7, 971. and Otera, J. Chem. Rev. 1993, 93, 1449; Aromatic and alkyl amines, for example: Pyridine, lutidine, 4-dimethylaminopyridine, tetramethylethylenedaimine, triethylamine, disopropylethylamine, DBU, TBD, MTBD, DABCO, guanidines; Phosphines and phosphazenes, for example: tributylphosphine, triphenylphosphine, and Bis(triphenylphoshphine) iminium chloride (PPNCl); Metal salts. For example, halide, triflate or perchlorate salts derived from: trimethylsilyl, lithium, magnesium, indium, tin, bismuth, titanium, copper, scandium, nickel, cobalt, ruthenium, silver, lanthium, and zinc; Other nitrogen-containing heterocycles. For example, imidazoles, such as 1-methylimidazole, 1-phenethylimidazole, 1-isopropylimidazole, imidazole and the like; Bronsted Acids, for example: HCl, H.sub.2SO.sub.4, methanesulfonic acid, toluenesulfonic acid, and H.sub.3PO.sub.4; Lewis acids, for example: bismuth 2-ethylhexanoate, tin(2-ethylhexanoate), tin(II)sterate, tin(II)acetate, dibutyltin dilaurate, molybdenum dichloro dioxide, iron trichloride, zinc oxide, tin oxide, silica chloride; Organometallic catalysts known to form polycarbonates from epoxides and carbon dioxide, for example: (salcy)MX (salcy=N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; M=Al, Co, Cr, Mn; X=halide or carboxylate), zinc glutarate, TPPM-X (TPP=tetraphenylphorphyrin; M=Al, Co, Cr; X=halide or alkoxide), (beta-diiminate)zinc acetate; Solid acids or bases and ion exchange resins, for example: Amberlyst-15, poly(4-vinylpyridine), montmorillite K-10, montmorillite KSF, zeolite, alumina, silica, solid supported sulfonic acids, Naffion-H, HBF.sub.4 on SiO.sub.2, HClO.sub.4 on SiO.sub.2.

(192) In certain embodiments, the step of treating the polymer of formula P1-OH with a cyclic acid anhydride comprises contacting the polymer with the cyclic anhydride in the presence of a catalyst utilized to copolymerize the epoxide(s) and CO.sub.2. In certain embodiments, the present invention comprises quenching a copolymerization of CO.sub.2 and one or more epoxides with a cyclic acid anhydride to provide a product of formula P1-CO.sub.2H.

(193) In certain embodiments, methods of the present invention comprise the additional step of treating the product of formula P1-CO.sub.2H with epoxide to provide a product of formula P1. In certain embodiments, the epoxide is selected from ethylene oxide, propylene oxide, and mixtures of these.

(194) In certain embodiments, methods of the present invention comprise contacting the product of formula P1-CO.sub.2H with epoxide. In certain embodiments, the step of contacting with epoxide is performed in the presence of one or more second catalysts. In certain embodiments, the step of contacting with epoxide is performed with heating. In certain embodiments, the second catalyst is characterized in that it catalyzes the ring-opening of epoxide by carboxylic acids or their salts. In certain embodiments, the second catalyst is characterized in that it catalyzes the ring-opening of epoxide by carboxylic acids or their salts, but does not catalyze the ring-opening of epoxide by alcohols. In certain embodiments, a second catalyst is selected from the group consisting of: Bronsted bases capable of deprotonation of carboxylic acids, for example: triethylamine, pyridine, lutidine, 4-dimethylaminopyridine, tetramethylethylenedaimine, triethylamine, disopropylethylamine, DBU, TBD, MTBD, DABCO, guanidine, ammonia, K.sub.3PO.sub.4, K.sub.2CO.sub.3, NaHCO.sub.3, and NaOH; Lewis and Bronsted acids known to activate epoxides for nucleophilic addition, for example: boron trifluoride, H.sub.3PO.sub.4, toluenesulfonic acid, tetrabutylammonium bromide, tetrabutylphosphonium bromide, cesium triflate, chromium acetate; Organometallic catalysts known to form polycarbonates from epoxides and carbon dioxide, for example: (salcy)MX (salcy=N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; M=Al, Co, Cr, Mn; X=halide or carboxylate), zinc glutarate, TPPM-X (TPP=tetraphenylphorphyrin; M=Al, Co, Cr; X=halide or alkoxide), (beta-diiminate) zinc acetate; Solid supported bases and ion exchange resins, for example: Poly(4-vinylpyridine, zeolite, alumina, Amberlyst A-21, Amberlite IRA-743.

(195) In certain embodiments, the present invention provides methods of quenching a reaction mixture resulting from the copolymerization of CO.sub.2 and one or more epoxides. In certain embodiments, the said copolymerization is catalyzed by a metal complex and the reaction mixture contains the metal complex or residues thereof. In certain embodiments, the reaction comprises treating a polymerization reaction mixture or aliphatic polycarbonate polyol with a cyclic acid anhydride of formula

(196) ##STR00094##
optionally in the presence of an esterification catalyst.

(197) In certain embodiments, where the reaction mixture to be quenched contains unreacted epoxide and the copolymerization was catalyzed by a metal complex, the product of the quenching method is a compound of formula P1. In certain embodiments of the inventive quench methods, the treatment of the reaction mixture with the acid anhydride results first in formation of an intermediate product of formula P1-CO.sub.2H and the metal complex or residues thereof further catalyze reaction of residual epoxide from the copolymerization reaction with intermediate P1-CO.sub.2H to provide the product P1. In certain embodiments, such methods include the additional step of removing CO.sub.2 pressure from the copolymerization mixture prior to treating with the cyclic acid anhydride.

(198) III. Higher Polymers

(199) In another aspect, the present invention encompasses higher polymers resulting from the reaction of polymers of formula P1 with cross-linking agents. In certain embodiments, such cross-linking agents comprise polyisocyanates, melamine, phenol formaldehyde resins, and the like. In certain embodiments, such high polymers comprise the reaction product of any of the inventive polyols described herein above with one or more polyisocyanates. In certain embodiments, the present invention encompasses higher polymers resulting from the reaction of polymers of formula P1 as defined above and in the classes and subclasses herein with any of the isocyanates described in APPENDIX I.

(200) In certain embodiments, the present invention encompasses higher polymers resulting from the reaction of polymers of formula P1 as defined above and in the classes and subclasses herein in combination with any of the coreactants described in APPENDIX II with any of the isocyanates described in APPENDIX I.

(201) In certain embodiments, the present invention encompasses articles of manufacture comprising from polyol compositions of formula P1 as defined above and in the classes and subclasses herein. In certain embodiments, the present invention encompasses coatings, adhesives, foams, thermoplastics, composites, sealants, or elastomers derived from polyol compositions of formula P1.

EXEMPLIFICATION

Example 1

Synthesis of Aliphatic a Polycarbonate Composition of Formula Q3

(202) ##STR00095##
Step 1a Synthesis of Acid-Terminated Polymer

(203) 100 g of poly(propylene carbonate) polyol of formula

(204) ##STR00096##
and having a number average molecular weight (Mn) of 1,490 g/mol, a PDI of 1.1, and a carbonate content greater than 99% was combined with acetonitrile (100 mL) in a 500 mL round bottom flask. Succinic anhydride (20 g, 0.2 mol) was charged and the reaction was allowed to stir at rt for 20 min. 4-dimethylaminopyridine (DMAP) (12 g, 0.1 mol) was added portion-wise over 1 min and the reaction was held at rt, under nitrogen, for 21 h.

(205) The reaction was concentrated, in vacuo, at 50 C. and diluted with dichlormethane (100 mL) and quenched with IN HCl (50 mL). The reaction mixture was allowed to stir at rt for 15 min, then layers separated. The organic layer was washed with water (350 mL), brine (20 mL), and dried over MgSO.sub.4. The organic layer was filtered and concentrated, in vacuo, at 65 C. to produce a faint yellow polyol (101 g, 80% yield). The product conforms to formula:

(206) ##STR00097##
GPC: Mn=1,743 g/mol, PDI=1.1; Acid#81.5 mg KOH/g; .sup.1H NMR (DMSO-d.sub.6, 400 MHz, see FIG. 1).
Step 1b Reaction of the Acid-Terminated Polymer with Epoxide

(207) 100 g of product from Step 1a was combined with acetonitrile (25 mL) and propylene oxide (50 mL, 0.71 mol) in a 250 mL round bottom flask and stirred at rt, under nitrogen, for 1 h. (7.010.sup.4 mol) of a cobalt(III) salcy catalyst was charged and the reaction was stirred at rt for 16 h, then concentrated, in vacuo. The reaction mixture was diluted with 50 mL acetonitrile, stirred over celite, filtered and concentrated, in vacuo, to provide a polymer of formula Q3 as a faint yellow viscous liquid (77 g, 80% yield): M.sub.n=1980 g/mol, PDI=1.1; OH#77 mg KOH/g. .sup.1H NMR (CDCl.sub.3, 400 MHz, FIG. 2)

Example 2

Synthesis of an Aliphatic Polycarbonate Composition of Formula

(208) P2a:

(209) ##STR00098##
where is

(210) ##STR00099##
and Y is

(211) ##STR00100##
Step 2a Synthesis of Acid-Terminated Polymer

(212) 100 g of poly(propylene carbonate) polyol of formula

(213) ##STR00101##
and having a number average molecular weight (Mn) of 1,490 g/mol and a PDI of 1.1, is treated according to the conditions of Example 1, Step 1a, except glutaric anhydride is used in place of succinic anhydride to afford a product of formula P1-CO.sub.2H

(214) ##STR00102##
where is

(215) ##STR00103##
R.sup.1, R.sup.2, and R.sup.3 are H, R.sup.4 is CH.sub.3, Q is CH.sub.2CH.sub.2CH.sub.2, x is 2 and y is 0.
Step 2b Reaction of the Acid-Terminated Polymer with Epoxide

(216) The product of Step 2a is combined with acetonitrile (25 mL) and propylene oxide (50 mL, 0.71 mol) in a 250 mL round bottom flask and stirred at rt, under nitrogen, for 1 h. (7.010.sup.4 mol) of a cobalt(III) salcy catalyst is added and the reaction is stirred at rt for 16 h, then concentrated, in vacuo. The reaction mixture is diluted with acetonitrile (50 mL), stirred over celite, filtered and concentrated, in vacuo, to provide the desired product.

Example 3

Synthesis of an Aliphatic Polycarbonate Composition of Formula

(217) P2a:

(218) ##STR00104##
where is

(219) ##STR00105##
and Y is

(220) ##STR00106##
Step 3a Synthesis of Acid-Terminated Polymer

(221) 100 g of poly(propylene carbonate) polyol of formula

(222) ##STR00107##
and having a number average molecular weight (Mn) of 1,490 g/mol and a PDI of 1.1, is treated according to the conditions of Example 1, Step 1a, except phthalic anhydride is used in place of succinic anhydride to afford a product of formula P1-CO.sub.2H

(223) ##STR00108##
where is

(224) ##STR00109##
R.sup.1, R.sup.2, and R.sup.3 are H, R.sup.4 is CH.sub.3, Q is

(225) ##STR00110##
x is 2 and y is 0.
Step 3b Reaction of the Acid-Terminated Polymer with Epoxide

(226) The product of Step 3a is combined with acetonitrile (25 mL) and propylene oxide (50 mL, 0.71 mol) in a 250 mL round bottom flask and stirred at rt, under nitrogen, for 1 h. (7.010.sup.4 mol) of a cobalt(III) salcy catalyst is added and the reaction is stirred at rt for 16 h, then concentrated, in vacuo. The reaction mixture is diluted with acetonitrile (50 mL), stirred over celite, filtered and concentrated, in vacuo, to provide the desired product.

Example 4

Synthesis of Aliphatic a Polycarbonate Composition of Formula Q7

(227) ##STR00111##

(228) 100 g of product from Step 1a of Example 1 above is combined with acetonitrile (25 mL) and ethylene oxide (0.71 mol) in a 250 mL round bottom flask and stirred at rt, under nitrogen, for 1 h. (7.010.sup.4 mol) of a cobalt(III) salcy catalyst is charged and the reaction is stirred at rt for 16 h, then concentrated, in vacuo. The reaction mixture is diluted with 50 mL acetonitrile, stirred over celite, filtered and concentrated, in vacuo, to provide a polymer of formula Q7.

Example 5

Examples of Improved Thermal and Base Stability of the Inventive Polymers

Example 5a

Experimental Determination of Thermal Stability of Aliphatic Polycarbonate Compositions of Formula Q3

(229) ##STR00112##

(230) 10 g of poly(propylene carbonate) polyol of formula Q3 having an a number average molecular weight (Mn) of 1,743 g/mol, and a PDI=1.1 and 10 g of a control poly(propropylene carbonate) polyol of formula:

(231) ##STR00113##
having an Mn of 1,490 g/mol and a PDI of 1.1 were placed in 4 oz steel cans and heated in a 120 C. convection oven. Samples were removed at 24 h intervals and analyzed by .sup.1H NMR for formation of cyclic carbonate. The results in FIG. 3 show that the aliphatic polycarbonate with composition Q3 produced <1 wt % cyclic carbonate over 3 days at 120 C., while the control poly(propropylene carbonate) polyol had decomposed to >50 wt % cyclic carbonate.

Example 5b

Experimental Determination of Improved Stability of Aliphatic Polycarbonate Compositions of Formula Q3 in the Presence of Triethylamine

(232) ##STR00114##

(233) 0.5 g of poly(propylene carbonate) polyol of formula Q3 and 0.5 g of the control poly(propropylene carbonate) polyol (both as described in Example 5a) were placed in 20 mL glass vials, charged with triethylamine (25 mg, 5 wt %) and heated to 50 C. in an aluminum reaction block. Samples were removed after 16 h and analyzed by .sup.1H NMR for formation of cyclic carbonate (FIG. 4). The results confirm that the inventive polycarbonate Q3 is more stable to triethylamine than the unmodified polyol.

Example 5c

Experimental Determination of Improved Stability of Aliphatic Polycarbonate Compositions of Formula Q3 in the Presence of Dibutylamine

(234) 0.5 g of poly(propylene carbonate) polyol of formula Q3 and 0.5 g of the control poly(propropylene carbonate) polyol (both as described in Example 5a) were placed in 20 mL glass vials, charged with dibutylamine (25 mg, 5 wt %), and heated to 50 C. using an aluminum reaction block. Samples were removed after 16 h and analyzed by 1H NMR for formation of cyclic carbonate (FIG. 5). The results confirm that the inventive polycarbonate Q3 is more stable to tributylamine than the unmodified polyol.

Example 6

Two-Step, One-Pot Reaction to the Ester End-Capped Polyol

Synthesis of an Aliphatic Polycarbonate Composition of Formula

(235) P2a:

(236) ##STR00115##
where is

(237) ##STR00116##
and Y is

(238) ##STR00117##

(239) 428 g of poly(propylene carbonate) polyol of formula

(240) ##STR00118##
and having a number average molecular weight (Mn) of 1,490 g/mol, a PDI of 1.1, and a carbonate content greater than 99% was combined with methyl propionate (135 mL) in a 500 mL round bottom flask. Succinic anhydride (89 g, 0.88 mol) was charged and the reaction was allowed to stir at 75 C. for 30 min. Di-isopropyl ethyl amine (10.8 g, 0.09 mol) was added portion-wise over 6 minutes and the reaction was stirred at 75 C., under nitrogen, for 4 hours. A sample of the reaction mixture indicated >99% conversion to the desired acid end-capped polyol P1-CO.sub.2H

(241) ##STR00119##
where is

(242) ##STR00120##
R.sup.1, R.sup.2, and R.sup.3 are H, R.sup.4 is CH.sub.3, Q is

(243) ##STR00121##
x is 2 and y is 0. The reaction mixture was cooled to room temperature and propylene oxide (99 g, 1.7 mol) was added. A salcy cobalt(III) catalyst (2.110.sup.3 mol) was added and the mixture was stirred for an additional 4 hours. A sample was taken to show that intermediate polyol P1-CO.sub.2H was converted to the desired product P2a:

(244) ##STR00122##
where is

(245) ##STR00123##
and Y is

(246) ##STR00124##
The polyol solution was stirred over Microcel C (60 g) resin to remove the catalysts, filtered and then the solvent was removed in vacuo to provide the desired end-capped product.

Example 7

Two-Step, One-Pot Reaction to the Ester End-Capped Polyol

(247) Synthesis of an Aliphatic Polycarbonate Composition of Formula

(248) P2a:

(249) ##STR00125##
where is

(250) ##STR00126##
and Y is

(251) ##STR00127##
94 g of poly(propylene carbonate) polyol of formula

(252) ##STR00128##
and having a number average molecular weight (Mn) of 1,490 g/mol, a PDI of 1.1, and a carbonate content greater than 99% was combined with dibasic ester (106 g) in a 1000 mL round bottom flask and heated to 50 C. Succinic anhydride (21.6 g, 0.22 mol) was charged to the flask and the reaction was allowed to stir at 50 C. for 10 min. Triethyl amine (14.3 g, 0.14 mol) was added portion-wise over 2 minutes and the reaction was stirred at 50 C., under nitrogen, for 1.5 hours. A sample of the reaction mixture indicated >99% conversion to the desired acid end-capped polyol P1-CO.sub.2H

(253) ##STR00129##
where is

(254) ##STR00130##
R.sup.1, R.sup.2, and R.sup.3 are H, R.sup.4 is CH.sub.3, Q is

(255) ##STR00131##
x is 2 and y is 0. Propylene oxide (33 g, 0.56 mol) was added and the mixture was stirred at 50 C. for 23 h. A sample was taken to show that intermediate polyol P1-CO.sub.2H was converted to the desired product P2a:

(256) ##STR00132##
where is

(257) ##STR00133##
and Y is

(258) ##STR00134##

Example 8

Terminating an Epoxide/CO2 Co-Polymerization with Cyclic Anhydride to Produce an Acid End-Capped Polyol, Followed by Conversion to Hydroxy End-Capped Polyol with Residual Propylene Oxide

(259) Propylene oxide (30 g, 0.52 mol), neopentyl glycol (3.5 g, 0.033 mol) and a salcy cobalt(III) catalyst (45 mg) (see, e.g., WO2010/028362) are added to a 300 mL Parr autoclave. The reactor is brought up to 35 C. and pressurized to 300 psi with CO.sub.2. The reaction mixture is stirred for 18 hours (attaining about 90% propylene oxide conversion) and then a mixture of succinic anhydride (6.8 g, 0.068 mol) in methyl propionate (100 mL) is added. The reactor is vented to atmospheric pressure and the temperature is increased to 70 C. for 8 hours.

(260) The reaction mixture is cooled to room temperature, slurried with celite, filtered and the solvent is removed in vacuo to provide the desired product P2a:

(261) ##STR00135##
where is

(262) ##STR00136##
and Y is

(263) ##STR00137##

Example 9

(264) The same procedure of Example 1 is followed, except DMAP is replaced with N-methyl imidazole, triethyl amine, or di-isopropyl amine.

Example 10

(265) The same procedure as Example 6 is followed, except di-isopropyl ethyl amine is replaced with triethyl amine, or a mixture of di-isopropyl amine and triethyl amine is used.

Example 11

(266) The same procedure as Example 7 is followed, except a mixture of di-isopropyl amine and triethyl amine is used.

Example 12

(267) The same procedure as Example 8 is followed, but after venting the reactor, additional catalyst is added.

Example 13

(268) The same procedure as Example 8 is followed, but after venting the reactor, additional propylene oxide is added.

Example 14

(269) The same procedure as Example 8 is followed, but after venting the reactor, triethyl amine (0.5 equivalents relative to neopentyl glycol) is added.

Example 15

(270) The same procedure as Example 8 is followed, but after venting the reactor, a mixture of triethyl amine (0.5 equivalents relative to neopentyl glycol) and di-isoproyl amine (0.5 equivalents relative to neopentyl glycol) are added.

(271) The complete disclosures of all patents, patent applications including provisional patent applications, and publications, and electronically available material cited herein are incorporated by reference. The foregoing detailed description and examples have been provided for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described; many variations will be apparent to one skilled in the art and are intended to be included within the invention defined by the claims.

APPENDIX I

Isocyanate Reagents

(272) As described above, certain compositions of the present invention comprise higher polymers derived from reactions with polyisocyanate reagents. The purpose of these isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols to form higher molecular weight structures through chain extension and/or cross-linking.

(273) The art of polyurethane synthesis is well advanced and a very large number of isocyanates and related polyurethane precursors are known in the art. While this section of the specification describes isocyanates suitable for use in certain embodiments of the present invention, it is to be understood that it is within the capabilities of one skilled in the art of polyurethane formulation to use alternative isocyanates along with the teachings of this disclosure to formulate additional compositions of matter within the scope of the present invention. Descriptions of suitable isocyanate compounds and related methods can be found in: Chemistry and Technology of Polyols for Polyurethanes Ionescu, Mihail 2005 (ISBN 978-1-84735-035-0), and H. Ulrich, Urethane Polymers, Kirk-Othmer Encyclopedia of Chemical Technology, 1997, the entirety of each of which is incorporated herein by reference.

(274) In certain embodiments, the isocyanate reagents comprise two or more isocyanate groups per molecule. In certain embodiments, the isocyanate reagents are diisocyanates. In other embodiments, the isocyanate reagents are higher polyisocyanates such as triisocyanates, tetraisocyanates, isocyanate polymers or oligomers, and the like, which are typically a minority component of a mix of predominantly diisocyanates. In certain embodiments, the isocyanate reagents are aliphatic polyisocyanates or derivatives or oligomers of aliphatic polyisocyanates. In other embodiments, the isocyanates are aromatic polyisocyanates or derivatives or oligomers of aromatic polyisocyanates. In certain embodiments, the isocyanates may comprise mixtures of any two or more of the above types of isocyanates.

(275) In certain embodiments, isocyanate reagents usable for the production of the polyurethane adhesive include aliphatic, cycloaliphatic, and aromatic diisocyanate compounds.

(276) Suitable aliphatic and cycloaliphatic isocyanate compounds include, for example, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4,-dicyclohexylmethane diisocyanate, 2,2-diethylether diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate-biuret.

(277) Suitable aromatic isocyanate compounds include, for example, p-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4-diphenyl diisocyanate, 2,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), 3,3-methyleneditolylene-4,4-diisocyanate, tolylenediisocyanate-trimethylolpropane adduct, triphenylmethane triisocyanate, 4,4-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, 3,3-dichloro-4,4-diphenylmethane diisocyanate, and triisocyanate phenylthiophosphate.

(278) In certain embodiments, the isocyanate compound employed comprises one or more of: 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene hexamethylene diisocyanate and isophorone diisocyanate. In certain embodiments, the isocyanate compound employed is 4,4-diphenylmethane diisocyanate. The above-mentioned diisocyanate compounds may be employed alone or in mixtures of two or more thereof.

(279) In certain embodiments, an isocyanate reagent is selected from the group consisting of: 1,6-hexamethylaminediisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4 methylene-bis(cyclohexyl isocyanate) (H.sub.12MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenylmethane-4,4-diisocyanate (MDI), diphenylmethane-2,4-diisocyanate (MDI), xylylene diisocyanate (XDI), 1,3-Bis(isocyanatomethyl)cyclohexane (H6-XDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI), p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-1,8-ictane diisocyanate (TIN), triphenylmethane-4,4,4triisocyanate, Tris(p-isocyanatomethyl)thiosulfate, 1,3-Bis(isocyanatomethyl)benzene, 1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysine diisocyanate, HDI allophonate trimer, HDI urethdione and HDI-trimer and mixtures of any two or more of these.

(280) In certain embodiments, an isocyanate reagent is selected from the group consisting of 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate. In certain embodiments, an isocyanate reagent is 4,4-diphenylmethane diisocyanate. In certain embodiments, an isocyanate reagent is 1,6-hexamethylene diisocyanate. In certain embodiments, an isocyanate reagent is isophorone diisocyanate.

(281) Isocyanates suitable for certain embodiments of the present invention are available commercially under various trade names. Examples of suitable commercially available isocyanates include materials sold under trade names: Desmodur (Bayer Material Science), Tolonate (Perstorp), Takenate (Takeda), Vestanat (Evonik), Desmotherm (Bayer Material Science), Bayhydur (Bayer Material Science), Mondur (Bayer Material Science), Suprasec (Huntsman Inc.), Lupranate (BASF), Trixene (Baxenden), Hartben (Benasedo), Ucopol (Sapici), and Basonat (BASF). Each of these trade names encompasses a variety of isocyanate materials available in various grades and formulations. The selection of suitable commercially-available isocyanate materials as reagents to produce polyurethane compositions for a particular application is within the capability of one skilled in the art of polyurethane coating technology using the teachings and disclosure of this patent application along with the information provided in the product data sheets supplied by the above-mentioned suppliers.

(282) Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Lupranate (BASF). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 1, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

(283) TABLE-US-00001 TABLE 1 Nominal Products Description % NCO Funct. Lupranate M 4,4 MDI 33.5 2 Lupranate MS 4,4 MDI 33.5 2 Lupranate MI 2,4 and 4,4 MDI Blend 33.5 2 Lupranate LP30 Liquid Pure 4,4 MDI 33.1 2 Lupranate 227 Monomeric/Modified MDI Blend 32.1 2 Carbodiimide Modified MDI Lupranate 5143 Carbodiimide Modified 4,4 MDI 29.2 2.2 Lupranate MM103 Carbodiimide Modified 4,4 MDI 29.5 2.2 Lupranate 219 Carbodiimide Modified 4,4 MDI 29.2 2.2 Lupranate 81 Carbodiimide Modified MDI 29.5 2.2 Lupranate 218 Carbodiimide Modified MDI 29.5 2.2 Polymeric MDI (PMDI) Lupranate M10 Low Funct. Polymeric 31.7 2.2 Lupranate R2500U Polymeric MDI Variant 31.5 2.7 Lupranate M20S Mid-Functionality Polymeric 31.5 2.7 Lupranate M20FB Mid-Functionality Polymeric 31.5 2.7 Lupranate M70L High-Functionality Polymeric 31 3 Lupranate M200 High-Functionality Polymeric 30 3.1 Polymeric MDI Blends and Derivatives Lupranate 241 Low Functionality Polymeric 32.6 2.3 Lupranate 230 Low Viscosity Polymeric 32.5 2.3 Lupranate 245 Low Viscosity Polymeric 32.3 2.3 Lupranate TF2115 Mid Functionality Polymeric 32.3 2.4 Lupranate 78 Mid Functionality Polymeric 32 2.3 Lupranate 234 Low Functionality Polymeric 32 2.4 Lupranate 273 Low Viscosity Polymeric 32 2.5 Lupranate 266 Low Viscosity Polymeric 32 2.5 Lupranate 261 Low Viscosity Polymeric 32 2.5 Lupranate 255 Low Viscosity Polymeric 31.9 2.5 Lupranate 268 Low Viscosity Polymeric 30.6 2.4 Select MDI Prepolymers Lupranate 5010 Higher Functional Prepolymer 28.6 2.3 Lupranate 223 Low Visc. Derivative of Pure MDI 27.5 2.2 Lupranate 5040 Mid Functional, Low Viscosity 26.3 2.1 Lupranate 5110 Polymeric MDI Prepolymer 25.4 2.3 Lupranate MP102 4,4 MDI Prepolymer 23 2 Lupranate 5090 Special 4,4 MDI Prepolymer 23 2.1 Lupranate 5050 Mid Functional, Mid NCO Prepol 21.5 2.1 Lupranate 5030 Special MDI Prepolymer 18.9 NA Lupranate 5080 2,4-MDI Enhanced Prepolymer 15.9 2 Lupranate 5060 Low Funct, Higher MW Prepol 15.5 2 Lupranate 279 Low Funct, Special Prepolymer 14 2 Lupranate 5070 Special MDI Prepolymer 13 2 Lupranate 5020 Low Functionality, Low NCO 9.5 2 Toluene Diisocyanate (TDI) Lupranate T80- 80/20:2,4/2,6 TDI 48.3 2 Lupranate T80- High Acidity TDI 48.3 2 Lupranate 8020 80/20:TDI/Polymeric MDI 44.6 2.1

(284) Other isocyanates suitable for certain embodiments of the present invention are sold under the trade name Desmodur available from Bayer Material Science. In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 2, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

(285) TABLE-US-00002 TABLE 2 Trade Name Description Desmodur 2460 M Monomeric diphenylmethane diisocyanate with high 2,4- isomer content Desmodur 44 M A monomeric diphenylmethane-4,4-diisocyanate (MDI). Desmodur 44 MC Desmodur 44 MC Flakes is a monomeric diphenylmethane- 4,4-diisocyanate (MDI). Desmodur BL 1100/1 Blocked aromatic polyisocyanate based on TDI Desmodur BL 1265 MPA/X Blocked aromatic polyisocyanate based on TDI Desmodur BL 3175 SN Blocked, aliphatic polyisocyanate based on HDI Desmodur BL 3272 MPA Blocked aliphatic polyisocyanate based on HDI Desmodur BL 3370 MPA Blocked aliphatic polyisocyanate based on HDI Desmodur BL 3475 BA/SN Aliphatic crosslinking stoving urethane resin based on HDI/ IPDI Desmodur BL 3575/1 MPA/SN Blocked aliphatic polyisocyanate based on HDI Desmodur BL 4265 SN Blocked, aliphatic polyisocyanate based on IPDI Desmodur BL 5375 Blocked aliphatic polyisocyanate based on H 12 MDI Desmodur CD-L Desmodur CD-L is a modified isocyanate based on diphenylmethane-4,4-diisocyanate. Desmodur CD-S Desmodur CD-S is a modified isocyanate based on diphenylmethane-4,4-diisocyanate. Desmodur D XP 2725 Hydrophilically modified polyisocyanate Desmodur DA-L Hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate Desmodur DN Aliphatic polyisocyanate of low volatility Desmodur E 1160 Aromatic polyisocyanate prepolymer based on toluene diisocyanate Desmodur E 1361 BA Aromatic polyisocyanate prepolymer based on toluylene diisocyanate Desmodur E 1361 MPA/X Aromatic polyisocyanate prepolymer based on toluene diisocyanate Desmodur E 14 Aromatic polyisocyanate prepolymer based on toluene diisocyanate Desmodur E 15 Aromatic polyisocyanate prepolymer based on toluene diisocyanate. Desmodur E 1660 Aromatic polyisocyanate prepolymer based on toluene diisocyanate. Desmodur E 1750 PR Polyisocyanate prepolymer based on toluene diisocyanate Desmodur E 20100 Modified polyisocyanate prepolymer based on diphenylmethane diisocyanate. Desmodur E 21 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI). Desmodur E 2190 X Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI) Desmodur E 22 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate. Desmodur E 2200/76 Desmodur E 2200/76 is a prepolymer based on (MDI) with isomers. Desmodur E 23 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI). Desmodur E 29 Polyisocyanate prepolymer based on diphenylmethane diisocyanate. Desmodur E 305 Desmodur E 305 is a largely linear aliphatic NCO prepolymer based on hexamethylene diisocyanate. Desmodur E 3265 MPA/SN Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate (HDI) Desmodur E 3370 Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate Desmodur E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate Desmodur E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate Desmodur E XP 2715 Aromatic polyisocyanate prepolymer based on 2,4- diphenylmethane diisocyanate (2,4-MDI) and a hexanediol Desmodur E XP 2723 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI). Desmodur E XP 2726 Aromatic polyisocyanate prepolymer based on 2,4- diphenylmethane diisocyanate (2,4-MDI) Desmodur E XP 2727 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate. Desmodur E XP 2762 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI). Desmodur H Monomeric aliphatic diisocyanate Desmodur HL Aromatic/aliphatic polyisocyanate based on toluylene diisocyanate/hexamethylene diisocyanate Desmodur I Monomeric cycloaliphatic diisocyanate. Desmodur IL 1351 Aromatic polyisocyanate based on toluene diisocyanate Desmodur IL 1451 Aromatic polyisocyanate based on toluene diisocyanate Desmodur IL BA Aromatic polyisocyanate based on toluene diisocyanate Desmodur IL EA Aromatic polyisocyante resin based on toluylene diisocyanate Desmodur L 1470 Aromatic polyisocyanate based on toluene diisocyanate Desmodur L 67 BA Aromatic polyisocyanate based on tolulene diisocyanate Desmodur L 67 MPA/X Aromatic polyisocyanate based on tolulene diisocyanate Desmodur L 75 Aromatic polyisocyanate based on tolulene diisocyanate Desmodur LD Low-functionality isocyanate based on hexamethylene diisocyanate (HDI) Desmodur LS 2424 Monomeric diphenylmethane diisocyanate with high 2,4- isomer content Desmodur MT Polyisocyanate prepolymer based on diphenylmethane diisocyanate Desmodur N 100 Aliphatic polyisocyanate (HDI biuret) Desmodur N 3200 Aliphatic polyisocyanate (low-viscosity HDI biuret) Desmodur N 3300 Aliphatic polyisocyanate (HDI trimer) Desmodur N 3368 BA/SN Aliphatic polyisocyanate (HDI trimer) Desmodur N 3368 SN Aliphatic polyisocyanate (HDI trimer) Desmodur N 3386 BA/SN Aliphatic polyisocyanate (HDI trimer) Desmodur N 3390 BA Aliphatic polyisocyanate (HDI trimer) Desmodur N 3390 BA/SN Aliphatic polyisocyanate (HDI trimer) Desmodur N 3400 Aliphatic polyisocyanate (HDI uretdione) Desmodur N 3600 Aliphatic polyisocyanate (low-viscosity HDI trimer) Desmodur N 3790 BA Aliphatic polyisocyanate (high functional HDI trimer) Desmodur N 3800 Aliphatic polyisocyanate (flexibilizing HDI trimer) Desmodur N 3900 Low-viscosity, aliphatic polyisocyanate resin based on hexamethylene diisocyanate Desmodur N 50 BA/MPA Aliphatic polyisocyanate (HDI biuret) Desmodur N 75 BA Aliphatic polyisocyanate (HDI biuret) Desmodur N 75 MPA Aliphatic polyisocyanate (HDI biuret) Desmodur N 75 MPA/X Aliphatic polyisocyanate (HDI biuret) Desmodur NZ 1 Aliphatic polyisocyanate Desmodur PC-N Desmodur PC-N is a modified diphenyl-methane-4,4- diisocyanate (MDI). Desmodur PF Desmodur PF is a modified diphenyl-methane-4,4- diisocyanate (MDI). Desmodur PL 340, 60% BA/SN Blocked aliphatic polyisocyanate based on IPDI Desmodur PL 350 Blocked aliphatic polyisocyanate based on HDI Desmodur RC Solution of a polyisocyanurate of toluene diisocyanate (TDI) in ethyl acetate. Desmodur RE Solution of triphenylmethane-4,4,4-triisocyanate in ethyl acetate Desmodur RFE Solution of tris(p-isocyanatophenyl) thiophosphate in ethyl acetate Desmodur RN Solution of a polyisocyanurate with aliphatic and aromatic NCO groups in ethyl acetate. Desmodur T 100 Pure 2,4-toluene diisocyanate (TDI) Desmodur T 65 N 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 67:33 Desmodur T 80 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80:20 Desmodur T 80 P 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80:20 with an increased content of hydrolysable chlorine Desmodur VH 20 N Polyisocyanate based on diphenylmethane diisocyanate Desmodur VK Desmodur VK products re mixtures of diphenylmethane-4,4- diisocyanate (MDI) with isomers and higher functional Desmodur VKP 79 Desmodur VKP 79 is a modified diphenylmethane-4,4- diisocyanate (MDI) with isomers and homologues. Desmodur VKS 10 Desmodur VKS 10 is a mixture of diphenylmethane-4,4- diisocyanate (MDI) with isomers and higher functional Desmodur VKS 20 Desmodur VKS 20 is a mixture of diphenylmethane-4,4- diisocyanate (MDI) with isomers and higher functional Desmodur VKS 20 F Desmodur VKS 20 F is a mixture of diphenylmethane-4,4- diisocyanate (MDI) with isomers and higher functional Desmodur VKS 70 Desmodur VKS 70 is a mixture of diphenylmethane-4,4- diisocyanate (MDI) with isomers and homologues. Desmodur VL Aromatic polyisocyanate based on diphenylmethane diisocyanate Desmodur VP LS 2078/2 Blocked aliphatic polyisocyanate based on IPDI Desmodur VP LS 2086 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate Desmodur VP LS 2257 Blocked aliphatic polyisocyanate based on HDI Desmodur VP LS 2371 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate. Desmodur VP LS 2397 Desmodur VP LS 2397 is a linear prepolymer based on polypropylene ether glycol and diphenylmethane Desmodur W Monomeric cycloaliphatic diisocyanate Desmodur W/1 Monomeric cycloaliphatic diisocyanate Desmodur XP 2404 Desmodur XP 2404 is a mixture of monomeric polyisocyanates Desmodur XP 2406 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate Desmodur XP 2489 Aliphatic polyisocyanate Desmodur XP 2505 Desmodur XP 2505 is a prepolymer containing ether groups based on diphenylmethane-4,4-diisocyanates (MDI) with Desmodur XP 2551 Aromatic polyisocyanate based on diphenylmethane diisocyanate Desmodur XP 2565 Low-viscosity, aliphatic polyisocyanate resin based on isophorone diisocyanate. Desmodur XP 2580 Aliphatic polyisocyanate based on hexamethylene diisocyanate Desmodur XP 2599 Aliphatic prepolymer containing ether groups and based on hexamethylene-1,6-diisocyanate (HDI) Desmodur XP 2617 Desmodur XP 2617 is a largely linear NCO prepolymer based on hexamethylene diisocyanate. Desmodur XP 2665 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI). Desmodur XP 2675 Aliphatic polyisocyanate (highly functional HDI trimer) Desmodur XP 2679 Aliphatic polyisocyanate (HDI allophanate trimer) Desmodur XP 2714 Silane-functional aliphatic polyisocyanate based on hexamethylene diisocyanate Desmodur XP 2730 Low-viscosity, aliphatic polyisocyanate (HDI uretdione) Desmodur XP 2731 Aliphatic polyisocyanate (HDI allophanate trimer) Desmodur XP 2742 Modified aliphatic Polyisocyanate (HDI-Trimer), contains SiO2-nanoparticles

(286) Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Tolonate (Perstorp). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 3, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

(287) TABLE-US-00003 TABLE 3 Tolonate D2 a blocked aliphatic polyisocyanate, supplied at 75 % solids in aromatic solvent Tolonate HDB a viscous solvent-free aliphatic polyisocyanate Tolonate HDB-LV a solvent free low viscosity aliphatic polyisocyanate Tolonate HDB 75 B an aliphatic polyisocyanate, supplied at 75% solids in methoxy propyl acetate Tolonate HDB 75 BX an aliphatic polyisocyanate, supplied at 75% solids Tolonate HDT a medium viscosity, solvent-free aliphatic polyisocyanate Tolonate HDT-LV is a solvent free low viscosity aliphatic polyisocyanate Tolonate HDT-LV2 a solvent free, very low viscosity aliphatic polyisocyanate Tolonate HDT 90 an aliphatic polyisocyanate, based on HDI-trimer (isocyanurate), supplied at 90% solids Tolonate HDT 90 B an aliphatic polyisocyanate, based on HDI-trimer (isocyanurate), supplied at 90% solids Tolonate IDT 70 B an aliphatic polyisocyanate, based on HDI-trimer (isocyanurate), supplied at 70% solids Tolonate IDT 70 S an aliphatic polyisocyanate, based on HDI-trimer (isocyanurate), supplied at 70% solids Tolonate X FD 90 B a high functionality, fast drying aliphatic polyisocyanate based on HDI-trimer, supplied at 90% solids

(288) Other isocyanates suitable for certain embodiments of the present invention are sold under the trade name Mondur available from Bayer Material Science. In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 4, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

(289) TABLE-US-00004 TABLE 4 Trade Name Description MONDUR 445 TDI/MDI blend polyisocyanate; blend of toluene diisocyanate and polymeric diphenylmethane diisocyanate; NCO weight 44.5-45.2% MONDUR 448 modified polymeric diphenylmethane diisocyanate (pMDI) prepolymer; NCO weight 27.7%; viscosity 140 mPa .Math. s @ 25 C.; equivalent weight 152; functionality 2.2 MONDUR 489 modified polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 700 mPa .Math. s @ 25 C.; equivalent weight 133; functionality 3.0 MONDUR 501 modified monomeric diphenylmethane diisocyanate (mMDI); isocyanate-terminated polyester prepolymer; NCO weight 19.0%; viscosity 1,100 mPa .Math. s @ 25 C.; equivalent weight 221; functionality 2 MONDUR 541 polymeric diphenylmethane diisocyanate (pMDI); binder for composite wood products and as a raw material in adhesive formulations; NCO weight 31.5%; viscosity 200 mPa .Math. s @ 25 C. MONDUR 582 polymeric diphenylmethane diisocyanate (pMDI); binder for composite wood products and as a raw material in adhesive formulations; NCO weight 31.0%; viscosity 200 mPa .Math. s @ 25 C. MONDUR 541-Light polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.0%; viscosity 70 mPa .Math. s @ 25 C.; equivalent weight 131; functionality 2.5 MONDUR 841 modified polymeric MDI prepolymer; NCO, Wt 30.5%; Acidity, Wt 0.02%; Amine Equivalent 132; Viscosity at 25 C., mPa .Math. s 350; Specific gravity at 25 C. 1.24; Flash Point, PMCC, F. >200 MONDUR 1437 modified diphenylmethane diisocyanate (mMDI); isocyanate-terminated polyether prepolymer; NCO weight 10.0%; viscosity 2,500 mPa .Math. s @ 25 C.; equivalent weight 420; functionality 2 MONDUR 1453 modified diphenylmethane diisocyanate (mMDI); isocyanate-terminated polyether prepolymer based on polypropylene ether glycol (PPG); NCO weight 16.5%; viscosity 600 mPa .Math. s @ 25 C.; equivalent weight 254; functionality 2 MONDUR 1515 modified polymeric diphenylmethane diisocyanate (pMDI) prepolymer; used in the production of rigid polyurethane foams, especially for the appliance industry; NCO weight 30.5%; viscosity 350 mPa .Math. s @ 25 C. MONDUR 1522 modified monomeric 4,4-diphenylmethane diisocyanate (mMDI); NCO weight 29.5%; viscosity 50 mPa .Math. s @ 25 C.; equivalent weight 143; functionality 2.2 MONDUR MA-2300 modified monomeric MDI, allophanate-modified 4,4-diphenylmethane diisocyanate (mMDI); NCO weight 23.0%; viscosity 450 mPa .Math. s @ 25 C.; equivalent weight 183; functionality 2.0 MONDUR MA 2600 modified monomeric MDI, allophanate-modified 4,4-diphenylmethane diisocyanate (mMDI); NCO weight 26.0%; viscosity 100 mPa .Math. s @ 25 C.; equivalent weight 162; functionality 2.0 MONDUR MA 2601 aromatic diisocyanate blend, allophanate-modified 4,4-diphenylmethane diisocyanate (MDI) blended with polymeric diphenylmethane diisocyanate (pMDI) containing 2,4- isomer; NCO weight 29.0%; viscosity 60 mPa .Math. s @ 25 C.; equivalent weight 145; functionality 2.2 MONDUR MA 2603 MDI prepolymer; isocyanate-terminated (MDI) prepolymer blended with an allophanate- modified 4,4-diphenylmethane diisocyanate (MDI); NCO weight 16.0%; viscosity 1,050 mPa .Math. s @ 25 C.; equivalent weight 263; functionality 2.0 MONDUR MA-2902 modified monomeric MDI, allophanate-modified 4,4-diphenylmethane diisocyanate (mMDI); NCO weight 29.0%; viscosity 40 mPa .Math. s @ 25 C.; equivalent weight 145; functionality 2.0 MONDUR MA-2903 modified monomeric MDI; isocyanate-terminated (MDI) prepolymer; NCO weight 19.0%; viscosity 400 mPa .Math. s @ 25 C.; equivalent weight 221; functionality 2.0 MONDUR MA-2904 Allophanate-modified MDI polyether prepolymer; NCO weight 12.0%; viscosity 1,800 mPa .Math. s @ 25 C.; equivalent weight 350; functionality of 2.0 MONDUR MB high-purity grade difunctional isocyanante, diphenylmethane 4,4-diiscocyanate; used in production of polyurethane elastomers, adhesives, coatings and intermediate polyurethane products; appearance colorless solid or liquid; specific gravity @ 50 C. 15.5 1.19; flash point 202 C. PMCC; viscosity (in molten form) 4.1 mPa .Math. s; bult density 10 lb/gal (fused) or 9.93 lb/gal (molten); freezing temperature 39 C. MONDUR MLQ monomeric diphenylmethan diisocyanate; used in a foams, cast elastomers, coatings and ahdesives; appearance light yellow clear liquid, NCO 33.4% wt; 1.19 specific gravity at 25 C., 196 C. flash point, DIN 51758; 11-15 C. freezing temperature MONDUR MQ high-purity-grade difunctional isocyanate, diphenylmethane 4,4-diisocyanate (MDI); used in production of solid polyurethane elastomers, adhesives, coatings and in intermediate polyurethane products; appearance colorless solid or liquid; specific gravity 1.19 @ 50 C.; flash point 202 C. PMCC; viscosity 4.1 mPa .Math. s; bulk density 10 lb./gal (fused) or 9.93 lb./gal (molten); freezing temperature 39 C. MONDUR MR polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa .Math. s @ 25 C.; equivalent weight 133; functionality 2.8 MONDUR MR LIGHT polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa .Math. s @ 25 C.; equivalent weight 133; functionality 2.8 MONDUR MR-5 polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 50 mPa .Math. s @ 25 C.; equivalent weight 129; functionality 2.4 MONDUR MRS 2,4 rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa .Math. s @ 25 C.; equivalent weight 133; functionality 2.6 MONDUR MRS 2 2,4 rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 33.0%; viscosity 25 mPa .Math. s @ 25 C.; equivalent weight 127; functionality 2.2 MONDUR MRS-4 2,4 rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 40 mPa .Math. s @ 25 C.; equivalent weight 129; functionality 2.4 MONDUR MRS-5 2,4 rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.3%; viscosity 55 mPa .Math. s @ 25 C.; equivalent weight 130; functionality 2.4 MONDUR PC modified 4,4 diphenylmethane diisocyanate (mMDI); NCO weight 25.8%; viscosity 145 mPa .Math. s @ 25 C.; equivalent weight 163; functionality 2.1 MONDUR PF modified 4,4' diphenylmethane diisocyanate (mMDI) prepolymer; NCO weight 22.9%; viscosity 650 mPa .Math. s @ 25 C.; equivalent weight 183; functionality 2 MONDUR TD-65 monomeric toluene diisocyanate (TDI); 65/35 mixture of 2,4 and 2.6 TDI; NCO weight 48%; viscosity 3 mPa .Math. s @ 25 C.; equivalent weight 87.5; functionality 2 MONDUR TD-80 monomeric toluene diisocyanate (TDI); 80/20 mixture of the 2,4 and 2,6 isomer; NCO GRADE A weight 48%; viscosity 5 mPa .Math. s @ 25 C.; equivalent weight 87.5; functionality 2 MONDUR TD-80 monomeric toluene diisocyanate (TDI); 80/20 mixture of the 2,4 and 2,6 isomer; NCO GRADE A/GRADE B weight 48%; viscosity 5 mPa .Math. s @ 25 C.; equivalent weight 87.5; functionality 2

(290) In certain embodiments, one or more of the above-described isocyanate compositions is provided in a formulation typical of a mixture known in the art of polyurethane manufacture. Such mixtures may comprise prepolymers formed by the reaction of a molar excess of one or more isocyanates with reactive molecules comprising reactive functional groups such as alcohols, amines, thiols, carboxylates and the like. These mixtures may also comprise solvents, surfactants, stabilizers, and other additives known in the art.

APPENDIX II

Coreactants

(291) In addition to the aliphatic polycarbonate polyols and isocyanate reagents described above, some compositions of the present invention may comprise optional coreactants. Coreactants can include other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other classes of polycarbonate polyols), or small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, thiol groups, and the like. In certain embodiments, such coreactants comprise molecules with two or more functional groups reactive toward isocyanates.

(292) In certain embodiments, a coreactant comprises a polyhydric alcohol. In certain embodiments, a coreactant comprises a dihydric alcohol. In certain embodiments, the dihydric alcohol comprises a C.sub.2-40 diol. In certain embodiments, the dihydric alcohol 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, 2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane 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, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

(293) In certain embodiments, a coreactant comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights from 220 to about 3000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights from 234 to about 3000 g/mol.

(294) In certain embodiments, a coreactant comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

(295) In certain embodiments, a coreactant comprises a polymeric diol. In certain embodiments, a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol.

(296) In certain embodiments, a coreactant comprises a polyester polyol. In certain embodiments, the polyester polyol present comprises a material based on a diol and a diacid (e.g. a polymer based on adipic acid (AA); sebacic acid (SBA); succinic Acid (SA); dodecanedioic acid (DDA); isophthalic acid (iPA); azelaic acid (Az); ethylene glycol (EG); propylene glycol (PG); 1,3-propane diol; 1,4bButanediol (BDO); 1,6-hexanediol (HID); diethylene glycol (DEG); neopentyl glycol (NPG); 3-Methyl-1,5-pentanediol (MPD). Examples of these include, but are not limited to: AA-EG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-EG/BDO polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-PG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol AA-BDO polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-BDO/HID polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-DEG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-NPG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-NPG/HID polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-HID polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; AA-MPD polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; SEA-HID polyesters with molecular weights of 2,000, 3,000, 4,000 or 5,000 g/mol; DDA-HID polyesters with molecular weights of 2,000, 3,000, 4,000 or 5,000 g/mol; Az-EG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; Az/iPA-EG/NPG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; SA-EG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; SA-DEG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; SA-NPG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; and SA-PG polyesters with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol.

(297) In certain embodiments, polyester polyol is formed by ring-opening-polymerization of caprolactone or propiolactone. For example, polycaprolactone with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol; or polypropiolactone with molecular weights of 500, 1,000, 2,000 or 3,000 g/mol.

(298) In some embodiments, a coreactant comprises a triol or higher polyhydric alcohol. In certain embodiments, a coreactant is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol, hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

(299) In some embodiments, a coreactant comprises a polyhydric alcohol with four to six hydroxy groups. In certain embodiments, a coreactant comprises dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, coreactant comprises sorbitol or an alkoxylated analog thereof.

(300) In certain embodiments, a functional coreactant comprises a polyhydric alcohol containing one or more moieties that can be converted to an ionic functional group. In certain embodiments, the moiety that can be converted to an ionic functional group is selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.

(301) In certain embodiments, a coreactant comprises a hydroxy-carboxylic acid having the general formula (HO).sub.xQ(COOH).sub.y, wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are each integers from 1 to 3. In certain embodiments, a coreactant comprises a diol carboxylic acid. In certain embodiments, a coreactant comprises a bis(hydroxylalkyl) alkanoic acid. In certain embodiments, a coreactant comprises a bis(hydroxylmethyl) alkanoic acid. In certain embodiments the diol carboxylic acid is selected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4-bis(hydroxyphenyl) valeric acid. In certain embodiments, a coreactant comprises an N,N-bis(2-hydroxyalkyl)carboxylic acid.

(302) In certain embodiments, a coreactant comprises a polyhydric alcohol containing a sulfonic acid functional group. In certain embodiments, a coreactant comprises a diol sulfonic acid. In certain embodiments, a polyhydric alcohol containing a sulfonic acid is selected from the group consisting of: 2-hydroxymethyl-3-hydroxypropane sulfonic acid, 2-butene-1,4-diol-2-sulfonic acid, and materials disclosed in U.S. Pat. No. 4,108,814 and US Pat. App. Pub. No. 2010/0273029 the entirety of each of which is incorporated herein by reference.

(303) In certain embodiments, a coreactant comprises a polyhydric alcohol containing a sulfamic acid functional group. In certain embodiments, a polyhydric alcohol containing a sulfamic acid is selected from the group consisting of: [N,N-bis(2-hydroxyalkyl)sulfamic acid (where each alkyl group is independently a C.sub.2-6 straight chain, branched or cyclic aliphatic group) or epoxide adducts thereof (the epoxide being ethylene oxide or propylene oxide for instance, the number of moles of epoxide added being 1 to 6) also epoxide adducts of sulfopolycarboxylic acids [e.g. sulfoisophthalic acid, sulfosuccinic acid, etc.], and aminosulfonic acids [e.g. 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, etc.]

(304) In certain embodiments, a coreactant comprises a polyhydric alcohol containing a phosphate group. In certain embodiments, a coreactant comprises a bis (2-hydroxalkyl) phosphate (where each alkyl group is independently a C.sub.2-6 straight chain, branched or cyclic aliphatic group). In certain embodiments, a coreactant comprises bis (2-hydroxethyl) phosphate.

(305) In certain embodiments, a coreactant comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a coreactant comprises an amino diol. In certain embodiments, a coreactant comprises a diol containing a tertiary amino group. In certain embodiments, an amino diol is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)--amino pyridine, dipropanolamine, diisopropanolamine (DIPA), N-methyldiisopropanolamine, diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3-chloroaniline, 3-diethylaminopropane-1,2-diol, 3-dimethylaminopropane-1,2-diol and N-hydroxyethylpiperidine. In certain embodiments, a coreactant comprises a diol containing a quaternary amino group. In certain embodiments, a coreactant comprising a quaternary amino group is an acid salt or quaternized derivative of any of the amino alcohols described above.

(306) Compounds having at least one crosslinkable functional group can also be incorporated into the prepolymers of the present invention, if desired. Examples of such compounds include those having carbonyl, amine, epoxy, acetoacetoxy, urea-formaldehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsaturated groups optionally with UV activation, olefinic and hydrazide groups, blocked isocyanates, and the like, and mixtures of such groups and the same groups in protected forms (so crosslinking can be delayed until the composition is in its application (e.g., applied to a substrate) and coalescence of the particles has occurred) which can be reversed back into original groups from which they were derived (for crosslinking at the desired time).