Polyurethane (ureas) and sulfur-containing polyurethane (ureas) methods of preparation

• US 20070142606A1
• Filed: 12/16/2005
• Published: 06/21/2007
• Est. Priority Date: 12/16/2005
• Status: Abandoned Application

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Bojkova, Nina, Rukavina, Thomas, Robinson, Daryl
• Application Number:
  US11/303,892
• Publication Number:
  US 20070142606A1
• Time in Patent Office: Days
• US Class Current: 528/44
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/324 containing only one aromatic ring
• CPC Class Codes: C08G 18/3876 containing mercapto groups
• CPC Class Codes: C08G 2120/00 Compositions for reaction injection moulding processes

Abstract

The present invention relates to polyurethane(ureas), sulfur-containing polyurethane(ureas) and methods for their preparation. Polyurethane(urea) of the present invention can be prepared by combining polyisocyanate; trifunctional or higher-functional polyol diol and diamine. Sulfur-containing polyurethane(urea) of the present invention can be prepared by combining (a) polyisocyanate and/or polyisothiocyanate; (b) trifunctional or higher-functional (c) polyol and/or trifunctional or higher-functional polythiol and diol and/or dithiol and/or dithiol oligomer and (d) diamine wherein at least one of (a), (b), (c) and (d) is sulfur-containing.

Claims

1. Polyurethane(urea) comprising the reaction product of polyisocyanate, trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole, diol having molecular weight of less than or equal to 200 grams/mole, and diamine.

2. The polyurethane(urea) of claim 1 prepared by:

(a) reacting said polyisocyanate and said trifunctional or higher-functional polyol to form polyurethane prepolymer; and

(b) reacting said polyurethane prepolymer and said diol and said diamine to form said polyurethane(urea).

3. The polyurethane(urea) of claim 2 wherein (b) further comprises material chosen from trifunctional or higher-functional polyamine, trifunctional or higher-functional polyol or mixtures thereof.

4. The polyurethane(urea) of claim 1 prepared by reacting said polyisocyanate, said trifunctional or higher-functional polyol, said diol and said diamine in a one-pot process.

5. The polyurethane(urea) of claim 1 wherein said polyisocyanate is chosen from aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.

6. The polyurethane(urea) of claim 5 wherein said polyisocyanate is chosen from 1,3-bis(1-isocyanato-1-methylethyl) benzene;

3-isocyanato-methyl-3,5,5,-trimethyl cyclohexyl isocyanate ;

4,4′

-methylene bis(cyclohexyl isocyanate);

meta-xylylene diisocyanate;

and mixtures thereof.

7. The polyurethane(urea) of claim 1 wherein said trifunctional or higher-functional polyol is chosen from triols, tetraols, and mixtures thereof.

8. The polyurethane(urea) of claim 1 wherein said trifunctional or higher-functional polyol is chosen from trimethylolethane, trimethylolpropane, and mixtures thereof.

9. The polyurethane(urea) of claim 1 wherein said diol is chosen from 1,2-butanediol;

1,4-butanediol;

1,3-butanediol;

1,5-pentanediol;

2,4-pentanediol;

1,6 hexanediol;

2,5-hexanediol;

2,4-heptanediol;

2-ethyl-1,3-hexanediol;

2,2-dimethyl-1,3-propanediol;

1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and mixtures thereof.

10. The polyurethane(urea) of claim 1 wherein said diamine is chosen from 2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene, and mixtures thereof;

4,4′

-methylenebis(3-chloro-2,6-diethylaninline);

4,4′

-methylenebis(2-chloroaniline);

materials having the following chemical formula;

wherein R₁ and R₂ is each independently methyl, ethyl, propyl, or isopropyl, and R₃ is hydrogen or chlorine;

and mixtures thereof.

11. The polyurethane(urea) of claim 1 wherein said diamine is primary diamine.

12. The polyurethane(urea) of claim 1 wherein said diamine is cyclic diamine.

13. The polyurethane(urea) of claim 12 wherein said cyclic diamine is aromatic diamine.

14. The polyurethane(urea) of claim 1 further comprising trifunctional or higher-functional polyamine.

15. The polyurethane(urea) of claim 1 when adapted to an optical article, having a refractive index of at least 1.50 and an Abbe number of at least 40.

16. The polyurethane(urea) of claim 1 when adapted to an optical article, having a refractive index of at least 1.55 and Abbe number of at least 30.

17. The polyurethane(urea) of claim 1 wherein the ratio of the number of equivalents of said trifunctional or higher-functional polyol to the number of equivalents of said polyisocyanate is from 0.05:

1.0 to 0.4;

1.0.

18. The polyurethane(urea) of claim 1 wherein the ratio of the number of equivalents of said diamine to the number of equivalents of said polyisocyanate is from 0.05:

1.0 to 0.4;

1.0.

21. The polyurethane(urea)of claim 2 wherein (a) further comprises diol.

59. A solid optical article comprising the polyurethane(urea) of claim 1.

60. A photochromic article comprising the polyurethane(urea) of claim 1.

19. A polyurethane(urea) comprising the reaction product of polyisocyanate, trifunctional or higher-functional polyol, diol and diamine wherein the ratio of the number of equivalents of said trifunctional or higher-functional polyol to the number of equivalents of said polyisocyanate is from 0.05:

1.0 to 0.4;

1.0.

20. A polyurethane(urea) comprising the reaction product of polyisocyanate, trifunctional or higher-functional polyol, diol and diamine wherein the ratio of the number of equivalents of said diamine to the number of equivalents of said polyisocyanate is from 0.05:

1.0 to 0.4;

1.0.

22. A polyurethane(urea) prepared by:

(a) reacting polyisocyanate, trifunctional or higher-functional polyol, and diol to form polyurethane prepolymer; and

(b) reacting said prepolymer with diol having a molecular weight of less than or equal to 200 grams/mole and diamine to form said polyurethane(urea).

23. The polyurethane(urea) of claim 22 wherein said diol of (a) comprises polycaprolactone diol.

24. The polyurethane(urea) of claim 23 wherein number average molecular weight of said polycaprolactone diol is from 200 to 5,000 grams/mole.

25. The polyurethane(urea) of claim 24 wherein (a) and (b) are free of catalyst.

26. A method of preparing polyurethane(urea) comprising:

(a) reacting polyisocyanate with trifunctional or higher functional polyol, said polyol having molecular weight of less than or equal to 200 grams/mole, to form polyurethane prepolymer;

and

(b) reacting said polyurethane prepolymer with diol, said diol having molecular weight of less than or equal to 200 grams/mole, and diamine to form said polyurethane(urea).

27. A method of preparing polyurethane(urea) comprising reacting polyisocyanate, trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole, diol having molecular weight of less than or equal to 200 grams/mole, and diamine, in a one-pot process.

28. A sulfur-containing polyurethane(urea) comprising the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixture thereof;

(b) at least one of trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole, trifunctional or higher-functional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 700 grams/mole, trifunctional or higher-functional polythiol having molecular weight of less than or equal to 700 grams/mole, or mixture thereof;

(c) at least one of diol having molecular weight of less than or equal to 200 grams/mole, dithiol having molecular weight of less than or equal to 600 grams/mole difunctional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 600 grams/mole, or mixture thereof;

and

(d) diamine, wherein at least one of (a), (b) and (c) is sulfur-containing.

29. The sulfur-containing polyurethane(urea) of claim 28 wherein said dithiol in (c) comprises dithiol oligomer having number average molecular weight of less than or equal to 600 grams/mole, with the proviso that said dithiol oligomer constitutes less than or equal to 70 mole percent of reactant in (c).

30. The sulfur-containing polyurethane(urea) of claim 28 prepared by reacting (a) and (b) to form polyurethane prepolymer and chain-extending said prepolymer with (c) and (d).

31. The sulfur-containing polyurethane(urea) of claim 28 wherein (a), (b), (c), and (d) are reacted in a one-pot process.

32. The sulfur-containing polyurethane(urea) of claim 30 wherein (d) further comprises material chosen from trifunctional or higher-functional polyamine, trifunctional or higher-functional polyol, trifunctional or higher functional polythiol having molecular weight of less than or equal to 700, trifunctional or higher-functional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 700, and mixtures thereof.

33. The polyurethane(urea) of claim 28 wherein said polyisocyanate is chosen from aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.

34. The polyurethane(urea) of claim 33 wherein said polyisocyanate is chosen from 1,3-bis(1-isocyanato-1-methylethyl) benzene;

3-isocyanato-methyl-3,5,5,-trimethyl cyclohexyl isocyanate;

4,4′

-methylene bis(cyclohexyl isocyanate);

meta-xylylene diisocyanate;

and mixtures thereof.

35. The sulfur-containing polyurethane(urea) of claim 30 wherein said polyurethane prepolymer is sulfur-containing.

36. The sulfur-containing polyurethane(urea) of claim 35 wherein said sulfur-containing polyurethane prepolymer comprises the reaction product of:

(a) at least one of polyisothiocyanate or mixture of polyisothiocyanate and polyisocyanate; and

(b) at least one of trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, or mixture thereof.

37. The sulfur-containing polyurethane(urea) of claim 35 wherein said sulfur-containing polyurethane prepolymer comprises the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixture thereof; and

(b) at least one of trifunctional or higher-functional polythiol or a mixture of trifunctional or higher-functional polythiol and trifunctional or higher-functional polyol.

38. The sulfur-containing polyurethane(urea) of claim 28 wherein said diol is chosen from 1,2-butanediol;

1,4-butanediol;

1,3-butanediol;

1,5-pentanediol;

2,4-pentanediol;

1,6 hexanediol;

2,5-hexanediol;

2,4-heptanediol;

2-ethyl-1,3-hexanediol;

2,2-dimethyl-1,3-propanediol;

1,4-cyclohexanedimethanol;

ethylene glycol;

propylene glycol;

diethylene glycol;

dipropylene glycol;

and mixtures thereof.

39. The sulfur-containing polyurethane(urea) of claim 28 wherein said trifunctional or higher-functional polyol is chosen from, trimethylolethane, trimethylolpropane, and mixtures thereof.

40. The sulfur-containing polyurethane(urea) of claim 28 wherein said diamine is a chosen from 2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene, and mixtures thereof;

4,4′

-methylenebis(3-chloro-2,6 -diethylaninline);

4,4′

-methylenebis(2-chloroaniline);

materials having the following chemical formula;

wherein R₁ and R₂ is each independently methyl, ethyl, propyl, or isopropyl, and R₃ is hydrogen or chlorine;

and mixtures thereof.

41. The sulfur-containing polyurethane(urea) of claim 28 wherein said diamine is primary diamine.

42. The sulfur-containing polyurethane(urea) of claim 28 wherein said diamine is cyclic diamine.

43. The sulfur-containing polyurethane(urea) of claim 42 wherein said cyclic diamine is aromatic diamine.

44. The sulfur-containing polyurethane(urea) of claim 28 when adapted to an optical article, having a refractive index of at least 1.55, and an Abbe number of at least 30.

45. The sulfur-containing polyurethane(urea) of claim 28 when adapted to an optical article, having a refractive index of at least 1.57 and an Abbe number of at least 30.

46. The sulfur-containing polyurethane(urea) of claim 28 wherein the ratio of the sum of the number of equivalents in (b) to the sum of the number of equivalents in (a) is from 0.05:

1.0 to 0.4;

1.0.

47. The sulfur-containing polyurethane(urea) of claim 28 wherein the ratio of the sum of the number of equivalents in (d) to the sum of the number of equivalents in (a) is from 0.05:

1.0 to 0.4;

1.0.

48. The sulfur-containing polyurethane(urea) of claim 28 wherein (d) further comprises trifunctional or higher-functional polyamine.

49. A sulfur-containing polyurethane(urea) comprising the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixture thereof;

(b) trifunctional or higher-functional polythiol having molecular weight of less than or equal to 700 grams/mole;

(c) dithiol having molecular weight of less than or equal to 600 grams/mole, and (d) diamine.

51. The sulfur-containing polyurethane(urea) of claim 49 wherein (d) further comprises material chosen from trifunctional or higher-functional polyamine, polyol, polythiol and mixtures thereof.

50. A sulfur-containing polyurethane(urea) comprising the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixture thereof;

(b) trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole;

(c) dithiol having molecular weight of less than or equal to 600 grams/mole; and

(d) diamine.

52. The sulfur-containing polyurethane(urea) of claim 50 wherein (d) further comprises material chosen from trifunctional or higher-functional polyamine, polyol, polythiol and mixtures thereof.

53. A sulfur-containing polyurethane(urea) comprising the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixtures thereof;

(b) at least one of trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, trifunctional or higher-functional material containing both hydroxyl and SH groups, or mixtures thereof;

(c) at least one of dithiol, diol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof; and

(d) diamine,

wherein at least one of (a), (b) and (c)is sulfur-containing and wherein the ratio of the sum of the number of equivalents in (b) to the sum of the number of equivalents in (a) is from 0.05;

1.0 to 0.4;

1.0.

54. A sulfur-containing polyurethane(urea) comprising the reaction product of:

(a) at least one of polyisocyanate, polyisothiocyanate or mixtures thereof;

(b) at least one of trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, trifunctional or higher-functional material containing both hydroxyl and SH groups, or mixtures thereof;

(c) at least one of diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof; and

(d) diamine, wherein at least one of (a), (b) or (c) is sulfur-containing and wherein the ratio of the sum of the number of equivalents in (d) to the sum of the number of equivalents in (a) is from 0.05;

1.0 to 0.4;

1.0.

55. A method of preparing sulfur-containing polyurethane(urea), comprising

(a) reacting material chosen from polyisocyanate, polyisothiocyanate and mixtures thereof, and material chosen from trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole, trifunctional or higher-functional polythiol having molecular weight less of than or equal to 700 grams/mole, trifunctional or higher-functional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 700 grams/mole, and mixtures thereof, to form polyurethane prepolymer ;

and

(b) reacting said prepolymer with diamine and material chosen from diol having molecular weight of less than or equal to 200 grams/mole, dithiol having molecular weight of less than or equal to 600 grams/mole, difunctional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 600 grams/mole, and mixtures thereof; and

(d) diamine,

wherein at least one of (a), (b) and (c) is sulfur-containing .

56. The method of claim 55 wherein (d) further comprises materials chosen from trifunctional or higher-functional polyamine, trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol having molecular weight less than or equal to 700 grams/mole, trifunctional or higher-functional material containing both hydroxyl and SH groups having molecular weight less than or equal to 700 grams, and mixtures thereof.

57. A method of preparing sulfur-containing polyurethane(urea) comprising reacting:

(a) material chosen from polyisocyanate, polyisothiocyanate or mixtures thereof;

(b) material chosen from trifunctional or higher-functional polyol having molecular weight of less than or equal to 200 grams/mole, trifunctional or higher-functional polythiol having molecular weight of less than or equal to 700 grams/mole, trifunctional or higher-functional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 700 grams/mole, and mixtures thereof;

(c) material chosen from diol having molecular weight of less than or equal to 200 grams/mole, dithiol having molecular weight less of than or equal to 600 grams/mole, difunctional material containing both hydroxyl and SH groups having molecular weight of less than or equal to 600 grams/mole, and mixtures thereof; and

(d) diamine,

wherein (a), (b), (c) and (d) are reacted in a one-pot process wherein at least one of (a), (b) and (c) is sulfur-containing.

58. The method of claim 57 wherein (d) further comprises trifunctional or higher-functional polyamine.