Sulfur-containing oligomers and high index polyurethanes prepared therefrom

• US 8,017,720 B2
• Filed: 12/16/2005
• Issued: 09/13/2011
• Est. Priority Date: 12/16/2005
• Status: Active Grant

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Smith, Robert A., Graham, Marvin J., Herold, Robert D., McDonald, William H., Bojkova, Nina V.
• Primary Examiner(s): Cano; Milton I
• Assistant Examiner(s): LEONARD, MICHAEL L
• Application Number:
  US11/303,707
• Publication Number:
  US 20070142605A1
• Time in Patent Office: 2,097 Days
• Field of Search: 528/44, 528/76, 528/376, 528/59, 528/61, 528/65, 528/80, 528/85, 528/60, 528/373, 528/374, 528/375, 525/212, 525/123, 525/131, 525/127, 525/457, 525/458, 526/286, 252/182.17, 252/182.2, 252/182.24, 252/182.28, 348/902, 359/241, 359/580, 523/123, 523/131, 523/127, 523/457, 523/458
• US Class Current: 528/375
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/1816 having carbocyclic groups
• CPC Class Codes: C08G 18/3876 containing mercapto groups
• CPC Class Codes: C08G 18/52 Polythioethers
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings

Abstract

The present invention provides polythiol oligomer formed by the reaction of at least two or more different dienes and at least one or more dithiol wherein stoichiometric ratio of the sum of the number of equivalents of all polythiols to the sum of the number of equivalents of all dienes used to form the polythiol oligomer is greater than 1.0:1.0; and wherein the two or more different dienes comprise

• • (a) at least one non-cyclic diene and at least one cyclic diene; or
  • (b) at least one aromatic ring-containing diene and at least one non-aromatic cyclic diene; or
  • (c) at least one non-aromatic monocyclic diene and at least one non-aromatic polycyclic diene;
    Sulfur-containing polyurethane of the present invention can be prepared by combining polyisocyanate, polyisothiocyanate, or mixture thereof; the polythiol oligomer described above; and active hydrogen-containing material.

Claims

1. A sulfur-containing polyurethane comprising the reaction product of:

(I) polyisocyanate, polyisothiocyanate, or mixture thereof;

(II) polythiol oligomer; and

(III) active hydrogen-containing material including at least one material selected from trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, trifunctional or higher-functional material containing both hydroxyl and SH groups, or mixtures thereof;

wherein said polythiol oligomer (II) is the reaction product of;

(a) two or more different dienes comprising

(i) at least one first diene comprising

an aromatic ring-containing diene, having the following structural formula;

2. The sulfur-containing polyurethane of claim 1 wherein said aromatic ring-containing diene is selected from 1,3-diispropenyl benzene, divinyl benzene, and mixtures thereof.

3. The sulfur-containing polyurethane of claim 1 wherein said stoichiometric ratio is from 1.1:

1.0 to 1.5;

1.0.

4. The sulfur-containing polyurethane of claim 1 wherein said polythiol oligomer further comprises trifunctional or higher-functional polythiol.

5. The sulfur-containing polyurethane of claim 1 wherein said active hydrogen-containing material further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

6. The sulfur-containing polyurethane of claim 5 wherein said dithiol includes dithiol oligomer.

7. The sulfur-containing polyurethane of claim 1 having a refractive index of at least 1.55 and an Abbe number of at least 30, when polymerized.

8. The sulfur-containing polyurethane of claim 1 having a refractive index of at least 1.55 and an Abbe number of at least 35, when polymerized.

9. The sulfur-containing polyurethane of claim 1 having a refractive index of at least 1.57, and an Abbe number of at least 30, when polymerized.

10. The sulfur-containing polyurethane of claim 1 having a refractive index of at least 1.57 and an Abbe number of at least 35, when polymerized.

11. The sulfur-containing polyurethane of claim 1 having a refractive index of at least 1.59 and an Abbe number of at least 30, when polymerized.

12. The sulfur-containing polyurethane of claim 1 prepared by:

(A) reacting

(i) polyisocyanate, polyisothiocyanate, or mixture thereof;

(ii) polythiol oligomer formed by the reaction of two or more different dienes and

one or more dithiols, said dienes comprising

at least one first diene comprising an aromatic ring-containing diene having the following structural formula;

13. The sulfur-containing polyurethane of claim 12 wherein said active hydrogen-containing material of (iii) further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

14. The sulfur-containing polyurethane of claim 13 wherein said dithiol includes dithiol oligomer.

15. The sulfur-containing polyurethane of claim 12 wherein said polythiol of (ii) includes dithiol oligomer.

16. The sulfur-containing polyurethane of claim 1 prepared by:

reacting polyisocyanate, polyisothiocyanate, or mixture thereof; and

polythiol oligomer formed by the reaction of

two or more different dienes and one or more dithiol, said dienes comprising

(i) at least one first diene comprising aromatic ring-containing diene having the following structural formula;

17. The sulfur-containing polyurethane of claim 16 wherein (iii) further comprises active hydrogen-containing material including at least one material selected from polyol, polythiol, polyfunctional material containing both hydroxyl and SH groups, or mixtures thereof.

18. The sulfur-containing polyurethane of claim 17 wherein said polythiol includes dithiol oligomer.

19. The sulfur-containing polyurethane of claim 16 wherein said active hydrogen-containing material further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

20. The sulfur-containing polyurethane of claim 19 wherein said dithiol includes dithiol oligomer.

21. The sulfur-containing polyurethane of claim 1 prepared by reacting

polyisocyanate, polyisothiocyanate, or mixture thereof;

polythiol oligomer formed by the reaction of two or more different dienes and one or more dithiol, said dienes comprising

(i) at least one first diene comprising aromatic ring-containing diene having the following structural formula;

22. The sulfur-containing polyurethane of claim 21 wherein said active hydrogen-containing material further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

23. The sulfur-containing polyurethane of claim 22 wherein said dithiol includes dithiol oligomer.

24. The sulfur-containing polyurethane of claim 1 wherein said polyisocyanate is chosen from aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, cyclic dimers and cyclic trimers thereof, and mixtures thereof.

25. The sulfur-containing polyurethane of claim 24 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;

or mixtures thereof.

26. The sulfur-containing polyurethane of claim 12 wherein said polyisocyanate, polyisothiocyanate, or mixture thereof used to prepare said sulfur-containing polyurethane prepolymer is polyisocyanate.

27. The sulfur-containing polyurethane of claim 26 wherein the amount of said polyisocyanate, the amount of said polythiol oligomer, and the amount of said active hydrogen-containing are selected such that the equivalent ratio of (NCO):

(SH+OH) is from 2.0;

1.0 to 5.5;

1.0.

28. The sulfur-containing polyurethane of claim 12 wherein the amount of said sulfur-containing polyurethane prepolymer and the amount of said active hydrogen-containing of (B) to form sulfur-containing polyurethane are selected such that the equivalent ratio of (OH+SH):

(NCO) is from 1.1;

1.0 to 0.85;

1.0.

29. The sulfur-containing polyurethane of claim 16 wherein said polyisocyanate, polyisothiocyanate, or mixture thereof used to prepare said sulfur-containing polyurethane prepolymer is polyisocyanate.

30. The sulfur-containing polyurethane of claim 29 wherein the amount of said polyisocyanate, and the amount of said polythiol oligomer are selected such that the equivalent ratio of (NCO):

(SH) is from 2.0;

1.0 to 5.5;

1.0.

31. The sulfur-containing polyurethane of claim 16 wherein the amount of said sulfur-containing polyurethane prepolymer and the amount of said active hydrogen-containing material to form sulfur-containing polyurethane are selected such that the equivalent ratio of (OH+SH):

(NCO) is from 1.1;

1.0 to 0.85;

1.0.

41. The sulfur-containing polyurethane of claim 1 wherein said trifunctional or higher functional polythiol includes at least one material selected from pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and materials represented by the following structural formulas:

42. The sulfur-containing polyurethane of claim 1 wherein said dithiol is chosen from aliphatic dithiols, cycloaliphatic dithiols, aromatic dithiols, dithiols having heterocyclic group, polymeric dithiols, dithiols containing ether linkages, dithiols containing one or more sulfide linkages and/or disulfide linkages, or combinations thereof.

43. The sulfur-containing polyurethane of claim 1 wherein said polythiol is chosen from aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, polythiols having herocyclic group, polymeric polythiols, polythiols containing ether linkages, polythiols containing one or more sulfide linkages and/or disulfide linkages, or combinations thereof.

32. A method of preparing sulfur-containing polyurethane comprising:

(a) reacting

polyisocyanate, polyisothiocyanate, or mixture thereof;

polythiol oligomer formed by the reaction of two or more different dienes and one or more dithiol, said dienes comprising

(i) at least one first diene comprising aromatic ring-containing diene having the following structural formula;

33. Method of claim 32 wherein said active hydrogen-containing material of (a) further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

34. Method of claim 32 wherein said polythiol of (b) includes dithiol oligomer.

35. Method of preparing sulfur-containing polyurethane comprising:

(a) reacting

polyisocyanate, polyisothiocyanate, or mixture thereof; and

polythiol oligomer formed by the reaction of two or more different dienes and one or more dithiol, said dienes comprising

(i) at least one first diene comprising aromatic ring-containing diene having the following structural formula;

36. Method of claim 35 wherein a) further comprises active hydrogen-containing material including at least one material selected from polyol, polythiol, polyfunctional material containing both hydroxyl and SH groups, or mixtures thereof.

37. Method of claim 35 wherein said active hydrogen-containing material of (b) further comprises at least one material selected from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

38. A method of preparing sulfur-containing polyurethane comprising reacting:

(a) polyisocyanate, polyisothiocyanate, or mixture thereof;

(b) polythiol oligomer formed by the reaction of two or more different dienes and one or more dithiol, said dienes comprising

(i) at least one first diene comprising aromatic ring-containing diene having the following structural formula;

39. Method of claim 38 wherein (c) further comprises at least one material chosen from diol, dithiol, difunctional material containing both hydroxyl and SH groups, or mixtures thereof.

40. Method of claim 39 wherein said dithiol includes dithiol oligomer.

44. An optical article comprising a sulfur-containing polyurethane, wherein said sulfur-containing polyurethane comprises the reaction product of:

(I) polyisocyanate, polyisothiocyanate, or mixture thereof;

(II) polythiol oligomer; and

(III) active hydrogen-containing material including at least one material selected from trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, trifunctional or higher-functional material containing both hydroxyl and SH groups, or mixtures thereof;

wherein said polythiol oligomer (II) is the reaction product of;

(a) two or more different dienes comprising

(i) at least one first diene comprising

aromatic ring-containing diene having the following structural formula;

45. A photochromic article comprising (A) a sulfur-containing polyurethane;

(B) a polymerized substrate; and

(C) a photochromic amount of a photochromic material wherein said photochromic material is imbibed into said substrate, and wherein said sulfur-containing polyurethane (A) comprises the reaction product of;

(I) polyisocyanate, polyisothiocyanate, or mixture thereof,

(II) polythiol oligomer, and

(III) active hydrogen-containing material including at least one material selected from trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, trifunctional or higher-functional material containing both hydroxyl and SH groups, or mixtures thereof;

wherein said polythiol oligomer (II) is the reaction product of;

(a) two or more different dienes comprising

(i) at least one first diene comprising

aromatic ring-containing diene having the following structural formula;

46. The photochromic article of claim 45 wherein said photochromic substance comprises at least one naphthopyran.

47. The photochromic article of claim 45 wherein said photochromic substance is chosen from spiro(indoline)naphthoxazines, spiro(indoline)benzoxazines, benzopyrans, naphthopyrans, organo-metal dithizonates, fulgides and fulgimides, and mixtures thereof.