Spandex from poly(tetramethylene-co-ethyleneether) glycols having low ethyleneether content
The invention provides a polyurethaneurea composition comprising at least one diisocyanate compound and a poly(tetramethylene-co-ethyleneether)glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide, wherein the portion of the units derived from the ethylene oxide is present in the poly(tetramethylene-co-ethyleneether)glycol at less than about 15 mole percent. The invention further relates to the use of such low ethyleneether content poly(tetramethylene-co-ethyleneether)glycols in spandex compositions. The invention also relates to new polyurethane compositions comprising poly(tetramethylene-co-ethyleneether)glycols with such low 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 at less than about 15 mole percent;
(b) at least one diisocyanate; and
(c) at least one diamine chain extender.
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 at between about 5 and less than about 15 mole percent.
3 . The polyurethaneurea of claim 1 wherein the portion of the units derived from ethylene oxide is present in the poly(tetramethylene-co-ethyleneether)glycol at between about 10 and less than about 15 mole percent.
4 . Spandex comprising a polyurethaneurea reaction product of claim 1 .
5 . Spandex comprising a polyurethaneurea reaction product of claim 2 .
6 . Spandex comprising a polyurethaneurea reaction product of claim 3 .
7 . The spandex of claim 4 wherein said poly(tetramethylene-co-ethyleneether)glycol has a molecular weight between about 650 Dalton and about 4000 Dalton.
8 . The spandex of claim 4 wherein said polyurethaneurea has a molar ratio of diisocyanate to poly(tetramethylene-co-ethyleneether)glycol between about 1.2 and about 2.3.
9 . The spandex of claim 4 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.
10 . The spandex of claim 4 wherein the diamine chain extender is selected from the group consisting of ethylene diamine, 2-methylpentanediamine, and 1,2-propanediamine, and mixtures thereof.
11 . The spandex of claim 4 having a tenacity equal to or greater than 1.0 gram per denier.
12 . The spandex of claim 4 having an unload power at 100 percent elongation equal to or greater than about 0.016 grams per denier.
13 . The spandex of claim 11 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
14 . The spandex of claim 12 wherein the spandex is spun at a speed in excess of about 800 meters per minute
15 . 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 at less than about 15 mole percent;
(b) at least one diisocyanate; and
(c) at least one diol chain extender.
16 . Spandex comprising a polyurethane reaction product of claim 15 .
17 . 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 at less than about 15 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.
18 . The process of claim 17 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.
19 . The process of claim 17 wherein the diamine chain extender is selected from the group consisting of ethylene diamine, 2-methylpentanediamine, and 1,2-propanediamine, or mixtures thereof.
20 . The process of claim 17 wherein the spinning to form spandex is dry-spinning and the poly(tetramethylene-co-ethyleneether)glycol has a molecular weight of about 650 Dalton to about 4000 Dalton.
21 . The process of claim 20 wherein the spandex is spun at a speed in excess of about 800 meters per minute.
22 . A fabric comprising the spandex of claim 4 .
23 . A fabric comprising the spandex of claim 15 .
24 . A garment or textile article comprising the fabric of claim 22 .
25 . A garment or textile article comprising the fabric of claim 23 .
26 . A dispersion, a coating, a film, an adhesive, an elastomer, or a shaped article comprising the polyurethaneurea of claim 1 .
27 . A dispersion, a coating, a film, an adhesive, an elastomer, or a shaped article comprising the polyurethane of claim 15.