Spandex from poly(tetramethylene-co-ethyleneether)glycols having high ethyleneether content
The invention provides a polyurethaneurea composition comprising poly(tetramethylene-co-ethyleneether) glycol having from about 37 to about 70 mole percent ethyleneether content and ethylene diamine as the extender. The invention further relates to the use of high ethyleneether content poly(tetramethylene-co-ethyleneether) glycol as the soft segment base material in spandex compositions. The invention also relates to new polyurethane compositions comprising poly(tetramethylene-co-ethyleneether) glycols with such high ethyleneether content, and their use in spandex.
1 . A polyurethaneurea comprising the reaction product of:
(a) a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from greater than about 37 to about 70 mole percent;
(b) at least one diisocyanate; and
(c) an ethylene diamine chain extender having between 0 and 10 mole percent co-extenders.
2 . The polyurethaneurea of claim 1 wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 48 to about 58 mole percent.
3 . Spandex comprising the polyurethaneurea of claim 1 .
4 . Spandex comprising the polyurethaneurea of claim 2 .
5 . The spandex of claim 3 wherein said poly(tetramethylene-co-ethyleneether) glycol has a molecular weight between about 650 Dalton and about 4000 Dalton.
6 . The spandex of claim 3 wherein said polyurethaneurea has a molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol between about 1.2 and about 2.3.
7 . The spandex of claim 3 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.
8 . The spandex of claim 3 having a load power at 300% elongation between about 0.11 and about 0.24 grams per denier on the first elongation cycle.
9 . The spandex of claim 3 having an unload power at 200% elongation between about 0.027 and about 0.043 grams per denier on the fifth elongation cycle.
10 . The spandex of claim 3 having a load power at 200% elongation between about 0.075 and about 0.165 grams per denier on the first elongation cycle.
11 . The spandex of claim 3 having a heat set efficiency of about 77 percent to about 95 percent when held for 120 seconds at 190° C. at 1.5× stretch.
12 . The spandex of claim 8 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
13 . The spandex of claim 9 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
14 . The spandex of claim 10 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
15 . The spandex of claim 11 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
16 . Spandex comprising a polyurethaneurea reaction product of:
(a) a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from greater than about 37 to about 70 mole percent;
(b) at least one diisocyanate;
(c) a chain-extender or a mixture thereof;
(d) at least one chain terminator; and
wherein the spandex has a heat-set efficiency of at least about 85% when held for 120 seconds at 190° C. at 1.5× stretch.
17 . A polyurethane comprising a reaction product of:
(a) a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from greater than about 37 to about 70 mole percent;
(b) at least one diisocyanate; and
(c) at least one diol chain extender having between 0 and about 10 mole percent co-extenders.
18 . The polyurethane of claim 17 wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from about 48 to about 58 mole percent.
19 . Spandex comprising a polyurethane of claim 17 .
20 . A process for preparing spandex comprising:
(a) contacting a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from greater than about 37 to about 70 mole percent with at least one diisocyanate to form a capped glycol;
(b) optionally adding a solvent to the product of (a);
(c) contacting the product of (b) with at least one diamine or diol chain extender; and
(d) spinning the product of (c) to form spandex.
21 . The process of claim 20 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 wherein the molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol is about 1.2 to about 2.3.
22 . The process of claim 20 wherein the one or more diamine chain extenders is an ethylene diamine having between 0 and 10 mole percent co-extenders.
23 . A fabric comprising the spandex of claim 3 .
24 . A fabric comprising the spandex of claim 16 .
25 . A fabric comprising the spandex of claim 19 .
26 . A garment or textile article comprising the fabric of claim 23 .
27 . A garment or textile article comprising the fabric of claim 24 .
28 . A garment or textile article comprising the fabric of claim 25 .
29 . A dispersion, a coating, a film, an adhesive, an elastomer, or a shaped article comprising the polyurethaneurea of claim 1 .
30 . A dispersion, a coating, a film, an adhesive, an elastomer, or a shaped article comprising the polyurethane of claim 17 .
31 . A method for making spandex having a heat set efficiency of about 77 percent to about 95 percent when held for 120 seconds at 190° C. at 1.5× stretch, the method comprising:
(a) contacting a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether) glycol from greater than about 37 to about 70 mole percent with at least one diisocyanate in a molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether) glycol between about 1.2 and about 2.3;
(b) adding a solvent to the product of (a);
(c) contacting the product of (b) with an ethylene diamine chain extender having between 0 and about 10 mole percent co-extenders and at least one chain terminator; and
(d) spinning the product of (c) to form spandex.