High productivity spandex fiber process and product
View Patent ↗Commercially acceptable spandex can be prepared with greater efficiency, improved consistency and at lower costs from a high-solids content polyurethaneurea polymer solution. The polyurethaneurea is prepared using a combination of 4,4′-MDI and 2,4′-MDI, and an amount of chain extenders and chain terminators such that the polymer solution, prior to spinning, is highly soluble and has an appropriate pre-spun IV and primary amine content.
1. A method of making a polyurethaneurea comprising the steps of:
(a) contacting at least one polymeric glycol selected from the group consisting of polyether glycols and polyester glycols; with a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI; wherein the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.5 and about 1:2;
(b) contacting the product of step (a) with a composition comprising:
(1) a solvent selected from the group consisting of N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N,N-dimethylpyrrolidinone, and mixtures thereof;
(2) at least one chain extender wherein ethylenediamine is at least about 90 mole percent of the total moles of chain extenders;
(3) at least one chain terminator
to form a polymer, wherein the pre-spun intrinsic viscosity (“TV”) of the polymer is between about 0.65 and about 0.90 dl/g and the primary amine content is between about 25 and about 55 meq/Kg.
2. The method of claim 1 wherein: (i) the polymeric glycol is a polyether glycol having a number average molecular weight between about 1600 and about 2500; (ii) the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.6 and about 1:1.8; (iii) the diisocyanate mixture comprises between about 80 and about 95 mole percent 4,4′-MDI and further comprises between about 5 and about 20 mole percent 2,4′-MDI; and (iv) at least one chain terminator is a secondary amine.
3. The method of claim 2 wherein; (i) the polyether glycol has a number average molecular weight between about 1800 and about 2000 and is selected from the group consisting of polyethyleneether glycol, polytrimethyleneether glycol, polytetramethyleneether glycol, polytetramethylene-co-2methyl-tetramethyleneether) glycol, polytetramethylene-co-tetraethyleneether glycol, and mixtures thereof; (ii) at least one secondary chain extender is present and selected from 2-methyl-1,5-pentanediamine and 1,2-propanediamine; and (iii) at least one chain terminator is selected from the group consisting of diethylamine, diisopropylamine, piperidine, and dibutylamine.
4. The method of claim 3 wherein: (i) the polyether glycol is polytetramethyleneether glycol having a number average molecular weight of about 1800; (ii) the diisocyanate mixture comprises between about 83 and about 91 mole percent 4,4′-MDI and further comprises between about 9 and about 17 mole percent 2,4′-MDI and further comprises less than 1 mole percent 2,2′-MDI; (iii) the at least one chain terminator is diethylamine; and (iv) the solvent is N,N-dimethylacetamide.
5. The method of claim 1 wherein: (i) the pre-spun intrinsic viscosity (“IV”) is between about 0.70 and about 0.80 dl/g; and (ii) the primary amine content is between about 35 and about 45 meq/Kg.
6. The method of claim 5 wherein: (i) the pre-spun intrinsic viscosity (“IV”) is about 0.75; and (ii) the primary amine content is about 40 meq/Kg.
7. A polyurethaneurea polymer formed by the reaction of:
(a) at least one polymeric glycol selected from the group consisting of polyether glycols and polyester glycols;
(b) a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI; wherein the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.5 and about 1:2; and
(c) a composition comprising:
(1) at least one chain extender wherein ethylenediamine is at least about 90 mole percent of the total moles of chain extenders; and
(2) at least one chain terminator;
wherein the resulting polyurethaneurea polymer has a pre-spun intrinsic viscosity (“IV”) between about 0.65 and about 0.90 dl/g and a primary amine content between about 25 and about 55 meq/Kg.
8. The polyurethaneurea polymer of claim 7 wherein: (i) the polymeric glycol is a polyether glycol having a number average molecular weight between about 1600 and about 2500; (ii) the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.6 and about 1:1.8; (iii) the diisocyanate mixture comprises between about 80 and about 95 mole percent 4,4′-MDI and further comprises between about 5 and about 20 mole percent 2,4′-MDI; and (iv) at least one chain terminator is a secondary amine.
9. The polyurethaneurea polymer of claim 5 wherein: (i) the polyether glycol has a number average molecular weight between about 1800 and about 2000 and is selected from the group consisting of polyethyleneether glycol, polytrimethyleneether glycol, polytetramethyleneether glycol, polytetramethylene-co-2-methyl-tetramethyleneether) glycol, polytetramethylene-co-tetraethyleneether glycol, and mixtures thereof; (ii) at least one secondary chain extender is present and selected from 2-methyl-1,5-pentanediamine and 1,2-propanediamine; and (iii) at least one chain terminator is selected from the group consisting of diethylamine. diisopropylamine, piperidine, and dibutylamine.
10. The polyurethaneurea polymer of claim 9 wherein: (i) the polyether glycol is polytetramethyleneether glycol having a number average molecular weight of about 1800; (ii) the diisocyanate mixture comprises between about 83 and about 91 mole percent 4,4′-MDI and further comprises between about 9 and about 17 mole percent 2,4′-MDI and further comprises less than 1 mole percent 2,2′-MDI; and (iii) the at least one chain terminator is diethylamine.
11. The polyurethaneurea polymer of claim 7 wherein: (i) the pre-spun intrinsic viscosity (“IV”) is between about 0.70 and about 0.80 dl/g; and (ii) the primary amine content is between about 35 and about 45 meq/Kg.
12. The polyurethaneurea polymer of claim 11 wherein: (i) the pre-spun intrinsic viscosity (“IV”) is about 0.75; and (ii) the primary amine content is about 40 meq/Kg.
13. A method of making spandex fiber comprising the steps of:
(a) preparing a polymer solution comprising:
(1) a solvent selected from the group consisting of N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide; N,N-dimethylpyrrolidinone, and mixtures thereof; and
(2) a polyurethaneurea prepared from at least one polymeric glycol and a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI at least one chain extender and at least one chain terminator, wherein the polyurethaneurea has a pore-spun intrinsic viscosity (“IV”) of between about 0.65 and about 0.9 dl/g and a primary amine content between about 25 and about 55 meq/Kg;
wherein the solids content of the polyurethaneurea in the polymer solution is greater than 38 and less than 50 weight percent; and
(b) dry spinning the polymer solution to form spandex fiber having the following properties at 40 denier: an intrinsic viscosity (“IV”) greater than 1.1 dl/g; a tenacity of at least 40 g; a load power less than 7 g; an unload power at least 0.9 g; and a coefficient of denier variation (“CDV”) of less than 15.
14. The method of claim 13 wherein the solids content is between about 40 and about 48 weight percent.
15. The method of claim 14 wherein the solids content is about 45 weight percent.
16. The method of claim 15 wherein the solvent is the solvent is N,N-dimethylacetamide.
17. Spandex prepared from a polyurethaneurea polymer formed by the reaction of:
(a) at least one polymeric glycol selected from the group consisting of polyester glycols and polyester glycols;
(b) a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI; wherein the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.5 and about 1:2; and
(c) a composition comprising:
(3) at least one chain extender wherein ethylenediamine is at least about 90 mole percent of the total moles of chain extenders; and
(4) at least one chain terminator;
wherein the polyurethaneurea polymer, used to make the spandex, has a pre-spun intrinsic viscosity (“IV”) between about 0.65 and about 0.90 dl/g and has a primary amine content between about 25 and about 55 meq/Kg.
18. The spandex of claim 17 wherein: (i) the polymeric glycol is a polyether glycol having a number average molecular weight between about 1600 and about 2500; (ii) the molar ratio of the at least one glycol to the total moles of diisocyanate is between about 1:1.6 and about 1:1.8; (iii) the diisocyanate mixture comprises between about 80 and about 95 mole percent 4,4′-MDI and further comprises between about 5 and about 20 mole percent 24′-MDI; and (iv) at least one chain terminator is a secondary amine.
19. The spandex of claim 18 wherein: (i) the polyether glycol has a number average molecular weight between about 1800 and about 2000 and is selected from the group consisting of polyethyleneether glycol, polytrimethyleneether glycol, polytetramethyleneether glycol, polytetramethylene-co-2-methyl-tetramethyleneether, glycol, polytetramethylene-co-tetraethyleneether glycol, and mixtures thereof; (ii) at least and one secondary chain extender is present and selected from 2-methyl-1,5-pentanediamine and 1,2-propanediamine; and (iii) at least one chain terminator is selected from the group consisting of diethylamine, diisopropylamine, piperidine, and dibutylamine.
20. The spandex of claim 19 wherein: (i) the polyether glycol is polytetramethyleneether glycol having a number average molecular weight of about 1800; (ii) the diisocyanate mixture comprises between about 83 and about 91 mole percent 4,4′-MDI and further comprises between about 9 and about 17 mole percent 2,4′-MDI and further comprises less than 1 mole percent 2,2′-MDI; and (iii) the at least one chain terminator is diethylamine.
21. The spandex of claim 17 wherein: (i) the pre-spun intrinsic viscosity (“IV”) is between about 0.70 and about 0.80 dl/g; and (ii) the primary amine content is between about 35 and about 45 meq/Kg.
22. The spandex of claim 21 wherein: (i) the pro-spun intrinsic viscosity (“IV”) is about 0.75; and (ii) the primary amine content is about 40 meq/Kg.
23. Spandex prepared by the steps comprising:
(a) preparing a polymer solution comprising:
(1) a solvent selected from the group consisting of N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N,N-dimethylpyrrolidinone, and mixtures thereof; and
(2) a polyurethaneurea prepared from at least one polymeric glycol and a diisocyanate mixture comprising at least about 78 mole percent 4,4′-MDI and at least about 5 mole percent 2,4′-MDI, at least one chain extender and at least one chain terminator, wherein the polyurethaneurea has a pre-spun intrinsic viscosity (“IV”) of between about 0.65 and about 0.9 dl/g and a primary amine content between about 25 and about 55 meq/Kg;
wherein the solids content of the polyurethaneurea in the polymer solution is greater than 38 and less than 50 weight percent; and
(b) dry spinning the polymer solution
wherein the spandex produced has the following properties at 40 denier: an intrinsic viscosity (“IV”) greater than 1.1 dl/g; a tenacity of at least 40 g; a load power less than 7 g; an unload power at least 0.9 g; and a coefficient of denier variation (“CDV”) of less than 15.
24. The spandex of claim 23 wherein the solids content is between about 40 and about 48 weight percent.
25. The spandex of claim 24 wherein the solids content is about 45 weight percent.
26. The spandex of claim 25 wherein the solvent is the solvent is N,N-dimethylacetamide.