Granted Patent B2

US 8,765,901 · App. 11/429,897 · Granted Jul 1, 2014

Abstract

Claims (52)

1. Spandex comprising a polyurethane reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate; and

(c) at least one diamine chain extender;

wherein the spandex is spun at a speed in excess of about 750 meters per minute.

2. The spandex of claim 1 wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 55 mole percent.

3. The spandex of claim 1 wherein the spandex is spun at a speed in excess of about 1000 m/min.

4. The spandex of claim 1 wherein the diisocyanate is selected from the group consisting of 1-isocyanato-4-[(4-isocyanato-phenyl)methyl]benzene, 1-isocyanate-2-[(4-isocyanato-phenyl)methyl]benzene and mixtures thereof.

5. The spandex of claim 1 wherein the chain extender is selected from the group consisting of hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-cyclohexanediamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine, 4,4′-methylene-bis-cyclohexylamine, and mixtures thereof.

6. The spandex of claim 4 wherein the poly(tetramethylene-co-ethyleneether) glycol has a number-average molecular weight of about 650 to about 4000 Dalton and the molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol is about 1.2:1 to about 2.3:1.

7. The spandex of claim 5 wherein the diisocyanate is selected from the group consisting of 1-isocyanato-4-[(4-isocyanato-phenyl)methyl]benzene, 1-isocyanato-2-[(4-isocyanato-phenyl)methyl]benzene and mixtures thereof and the molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol is about 1.2:1 to about 2.3:1.

8. The spandex of claim 5 wherein the diisocyanate is 1-isocyanato-4-[(4-isocyanato-phenyl)methyl]benzene and the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol in an amount of about 50 mole percent.

9. A process for preparing spandex comprising:

(a) contacting a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent with at least one diisocyanate to form a capped glycol;

(b) dissolving the capped glycol in a solvent;

(c) contacting the solution of the capped glycol of (b) with at least one diamine chain extender; and

(d) spinning the solution of (c) so that the filaments are spun at a speed in excess of 750 meters per minute to form the spandex.

10. The process of claim 9 wherein the diisocyanate is 1-isocyanato-4-[(4-isocyanato-phenyl)methyl]benzene, the molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol is about 1.2:1 to about 2.3:1, and the chain extender is selected from the group consisting of hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine, 1,3-cyclohexanediamine, 1,2-diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, and mixtures thereof.

11. The process of claim 9 wherein the spinning step to form spandex is a dry-spinning step and the poly(tetramethylene-co-ethyleneether) glycol has a number-average molecular weight of about 650 to about 4000 Dalton.

12. Spandex comprising a reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate;

(c) at least one diamine chain extender; and

wherein the spandex has an unload power at 100% elongation of at least 0.018 g/denier.

13. Spandex comprising a reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate;

(c) one or more diamine chain extenders; and

wherein the chain extender comprises one or more diamines and wherein the spandex has a retractive force at 100% elongation of at least 0.017 g/denier and a load power at 100% elongation less than 0.106 g/denier.

14. Spandex comprising a reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate;

(c) one or more diamine chain extenders; and

wherein the chain extender comprises one or more diamines and wherein the spandex has a retractive force at 200% elongation of at least 0.0341 g/denier and a load power at 200% elongation less than 0.16 g/denier.

15. Spandex comprising a reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate;

(c) one or more diamine chain extenders; and

wherein the chain extender comprises one or more diamines and wherein the spandex has a retractive force at 200% elongation of at least 0.0341 g/denier and a load power at 300% elongation less than 0.227 g/denier.

16. Spandex comprising a reaction product of:

(a) a poly(tetramethylene-co-ethyleneether) glycol consisting of constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate;

(c) one or more diamine chain extenders; and

wherein the chain extender comprises one or more diamines and wherein the spandex has a tenacity of at least 0.495 g/denier and a load power at 200% elongation less than 0.16 g/denier.

17. Spandex comprising a polyurethane reaction product of:

(a) poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 50 to about 70 mole percent;

(b) at least one diisocyanate; and

(c) at least one diamine chain extender;

(d) a polymeric glycol selected from the group consisting of a poly(tetramethylene ether) glycol, a poly(tetramethylene-co-2-methyltetramethyleneether) glycol, a poly(ethylene ether) glycol, a poly(propylene ether) glycol, a polycarbonate glycol, a polyester glycol, and combinations thereof;

wherein the spandex is spun at a speed in excess of about 750 meters per minute.

18. The spandex of claim 17 , wherein the polymeric glycol is poly(ethylene ether) glycol and wherein the combined poly(tetramethylene-co-ethyleneether) glycol and poly(ethylene ether) glycol in the spandex has an overall percentage of units derived from ethylene oxide from about 35 to about 70 mole percent.

19. The spandex of claim 17 , wherein the polymeric glycol is selected from the group consisting of a poly(tetramethylene ether) glycol, a poly(tetramethylene-co-2-methyltetramethyleneether) glycol, a poly(propylene ether) glycol, a polycarbonate glycol, a polyester glycol, or combinations thereof and wherein the combined poly(tetramethylene-coethyleneether) glycol and the polymeric glycol has an overall percentage of units derived from ethylene oxide less than or equal to about 35 mole percent.

Assignments (8)