SULFUR-CONTAINING POLYURETHANE

• US 20090176945A1
• Filed: 03/17/2009
• Published: 07/09/2009
• 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, Robinson, Daryl J., Rukavina, Thomas G.
• Application Number:
  US12/405,720
• Publication Number:
  US 20090176945A1
• Time in Patent Office: Days
• US Class Current: 525/453
• 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 18/3206 aliphatic
• CPC Class Codes: C08G 18/3876 containing mercapto groups
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings

Abstract

Sulfur-containing polyurethane comprising the reaction product of:

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

Claims

1. Sulfur-containing polyurethane comprising the reaction product of:

(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; and

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

2. The sulfur-containing polyurethane of claim 1 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 (c) reactant.

3. The sulfur-containing polyurethane of claim 1 prepared by reacting (a) and (b) to form polyurethane prepolymer and chain-extending said prepolymer with (c).

4. The sulfur-containing polyurethane of claim 1 wherein (a), (b), and (c) are reacted in a one-pot process.

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

6. The polyurethane 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 sulfur-containing polyurethane of claim 3 wherein said polyurethane prepolymer is sulfur-containing.

8. The sulfur-containing polyurethane of claim 7 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.

9. The sulfur-containing polyurethane of claim 7 wherein said sulfur-containing polyurethaneprepolymer 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 mixture of trifunctional or higher-functional polythiol and trifunctional or higher-functional polyol.

10. The sulfur-containing polyurethane 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;

propylene glycol;

diethylene glycol;

dipropylene glycol; and

mixtures thereof.

11. The sulfur-containing polyurethane of claim 1 wherein said trifunctional or higher-functional polyol is chosen from, trimethylolethane, trimethylolpropane, and mixtures thereof.

12. The sulfur-containing polyurethane of claim 1 wherein said polyurethane is adapted to an optical article having a refractive index of at least 1.55 and an Abbe number of at least 30.

13. The sulfur-containing polyurethane of claim 1 wherein said polyurethane is adapted to an optical article having a refractive index of at least 1.57 and an Abbe number of at least 30.

14. The sulfur-containing polyurethane of claim 1 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.

15. A sulfur-containing polyurethane 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; and

(c) dithiol having molecular weight of less than or equal to 600 grams/mole, wherein said dithiol 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 (c) reactant.

16. The sulfur-containing polyurethane of claim 15 wherein said trifunctional or higher-functional polythiol is chosen from trifunctional polythiol, tetrafunctional polythiol, and mixtures thereof.

18. The sulfur-containing polyurethane of claim 15 wherein (c) further comprises at least one of trifunctional or higher-functional polyol, trifunctional or higher-functional polythiol, or mixtures thereof.

17. A sulfur containing polyurethane 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; and

(c) dithiol having molecular weight of less than or equal to 600 grams/mole, wherein said dithiol 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 (c) reactant.

19. The sulfur-containing polyurethane of claim 17 wherein (c) further comprises at least one of trifunctional or higher-functional polyol, trifunctional or higher functional polythiol, or mixtures thereof.

20. A sulfur-containing polyurethane comprising reaction product of:

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

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

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

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

wherein the ratio of the sum of the number of equivalents of (b) to the sum of the number of equivalents in (a) is from 0.05;

1.0 to 0.4;

1.0.

21. A sulfur-containing polyurethane of claim 20 wherein said dithiol in (c) comprises dithiol oligomer having number average molecular weight 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 (c) reactant.

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

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

to form polyurethane prepolymer, and

(b) reacting said prepolymer with at least one active hydrogen-containing 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, or mixtures thereof,

wherein at least one of (a) or (b) is sulfur-containing.

23. The method of claim 22 wherein said dithiol in (b) 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 active hydrogen-containing in (b).

24. A method of preparing sulfur-containing polyurethane comprising reacting

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

(b) at least one 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, or mixtures thereof; and

(c) at least one 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, or mixtures thereof,

in a one-pot process, wherein at least one of (a), (b) or (c) is sulfur-containing.

25. The method of claim 24 wherein said dithiol of (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 (c) reactant.