High-uniformity spandex and process for making spandex
First Claim
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1. Spandex comprising a polyurethaneurea which is the reaction product of:
- a) a capped glycol comprising the reaction product of;
i) a polymeric glycol selected from the group consisting of polyether glycols, polyester glycols, and polycarbonate glycols;
ii) a diisocyanate; and
iii) an aliphatic primary monoalcohol comprising 1-10 carbons;
b) an aliphatic diamine chain extender comprising 2-12 carbons; and
c) a primary aliphatic monoamine chain terminator comprising 5-12 carbons;
wherein the polyurethaneurea has;
monoalkylurea ends and alkylurethane ends;
a ratio of monoalkylurea ends to alkylurethane ends of at least about 0.5;
1; and
a ratio of monoalkylurea ends to alkyurethane ends of at most about 10;
1; and
wherein the spandex has a coefficient of denier variation which is lower, by at least about 15%, than that of spandex comprising an otherwise identical polyurethaneurea having dialkylurea and amine ends.
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Abstract
The invention provides a highly uniform spandex fiber and a method for making it. The polyurethaneurea component of the spandex has both alkylurethane and monoalkylurea ends, with a ratio of monoalkylurea ends to alkylurethane ends of from 0.5:1 to 10:1.
15 Citations
20 Claims
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1. Spandex comprising a polyurethaneurea which is the reaction product of:
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a) a capped glycol comprising the reaction product of;
i) a polymeric glycol selected from the group consisting of polyether glycols, polyester glycols, and polycarbonate glycols;
ii) a diisocyanate; and
iii) an aliphatic primary monoalcohol comprising 1-10 carbons;
b) an aliphatic diamine chain extender comprising 2-12 carbons; and
c) a primary aliphatic monoamine chain terminator comprising 5-12 carbons;
wherein the polyurethaneurea has; monoalkylurea ends and alkylurethane ends;
a ratio of monoalkylurea ends to alkylurethane ends of at least about 0.5;
1; and
a ratio of monoalkylurea ends to alkyurethane ends of at most about 10;
1; and
wherein the spandex has a coefficient of denier variation which is lower, by at least about 15%, than that of spandex comprising an otherwise identical polyurethaneurea having dialkylurea and amine ends.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10)
the polymeric glycol a polyether glycol;
the diisocyanate is an aromatic diisocyanate;
the monoalcohol comprises at least 4 carbons;
the monoalcohol comprises at most 7 carbons;
the diamine is selected from the group consisting of ethylene diamine, 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 1,3-cyclohexanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, and mixtures thereof;
the monoamine comprises at least 6 carbons; and
the monoamine comprises at most 7 carbons.
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3. The spandex of claim 1 wherein:
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the polymeric glycol is selected from the group consisting of poly(tetramethyleneether) glycol and poly(tetramethylene-ether-co-2-methyltetramethyleneether) glycol;
the diisocyanate is selected from the group consisting of 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene and mixtures thereof with 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene; and
the monoamine is selected from the group consisting of n-hexylamine, cyclohexylamine, 1-amino-3-methylcyclohexane, 1-amino-2-methylcyclohexane, and n-heptylamine.
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4. The spandex of claim 1 wherein:
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the polymeric glycol is a polyether glycol containing at least about 10 ppm and at most about 125 ppm of a compound selected from the group consisting of acids and acid-producing compounds;
the monoamine comprises at least 6 carbons;
the monoamine comprises at most 7 carbons; and
the spandex has a coefficient of denier variation of at most about 15.
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5. The spandex of claim 1 wherein:
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the polyurethaneurea has at least about 5 meq/kg alkylurethane ends, based on polyurethaneurea weight; and
the polyurethaneurea has at most about 30 meq/kg alkylurethane ends, based on polyurethaneurea weight.
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6. The spandex of claim 1 wherein:
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the polyurethaneurea has at least about 2 meq/kg monoalkylurea ends, based on polyurethaneurea weight; and
the polyurethaneurea has at most about 55 meq/kg monoalkylurea ends, based on polyurethaneurea weight.
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7. The spandex of claim 1 wherein:
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the diisocyanate is a mixture of 1-isocyanato-4-[(4-isocyanatophenyl)-methyl]benzene and 1-isocyanato-2-[(4-isocyanatophenyl)methyl]-benzene wherein;
the 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene is present in an amount of at least about 5 mol %, based on total diisocyanate; and
the 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene is present in an amount of at most about 30 mol %, based on total diisocyanate;
the capped glycol has an NCO content of at least about 2.0 wt % based on capped glycol;
the capped glycol has an NCO content of at most about 3.5 wt % based on capped glycol; and
the diamine is selected from the group consisting of ethylene diamine and mixtures thereof with at most about 10 mole percent, based on total diamines, of a diamine selected from the group consisting of 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-cyclohexanediamine, and 1,3-diaminopentane.
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8. The spandex of claim 1 wherein:
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the polymeric glycol is selected from the group consisting of poly(tetramethyleneether) glycol having a number-average molecular weight in the range of about 1500 to 2500 daltons and poly(tetramethylene-ether-co-2-methyltetramethyleneether) glycol having a number-average molecular weight in the range of about 2000 to 4000 daltons;
the diisocyanate is substantially 1-isocyanato-4-[(4′
-isocyanatophenyl)-methyl]benzene;
the capped glycol has an NCO content of;
at least about 2.0 wt %, based on total capped glycol, when the polymeric glycol is poly(tetramethyleneether-co-2-methyltetra-methyleneether) glycol;
at most about 5.5 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether-co-2-methyltetramethyleneether) glycol;
at least about 2.5 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether) glycol; and
at most about 6.0 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether) glycol; and
the diamine is a mixture of ethylene diamine with at least about 50 mol % of a diamine, based on total diamines, selected from the group consisting of 2-methyl-1,5-pentanediamine and 1,3-diaminopentane.
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9. The spandex of claim 1 wherein the polymeric glycol is poly(2,2-dimethyl-1,3-propane dodecanedioate) glycol.
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10. The spandex of claim 1 wherein:
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the polymeric glycol is a poly(tetramethylene terephthalate) glycol having a number-average molecular weight of about 1500 to 2500 daltons;
the diisocyanate is substantially 1-isocyanato-4-[(4′
-isocyanatophenyl)-methyl]benzene;
the diamine is ethylene diamine mixed with at least about 10 mole percent, based on total diamines, of a second diamine;
the diamine is ethylene diamine mixed with at most about 20 mole percent, based on total diamines, of a second diamine;
the monoamine comprises at least 6 carbons; and
the monoamine comprises at most 7 carbons;
wherein the second diamine is selected from the group consisting of 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-cyclohexanediamine, and 1,3-diaminopentane.
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11. A process for making spandex comprising the steps of:
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a) providing a polymeric glycol selected from the group consisting of polyether glycols, polyester glycols, and polycarbonate glycols;
b) providing a diisocyanate;
c) providing an aliphatic primary monoalcohol comprising 1-10 carbons;
d) contacting the glycol, diisocyanate, and monoalcohol to form a capped glycol;
e) providing an aliphatic diamine chain extender comprising 2-12 carbons;
f) providing a primary aliphatic monoamine chain terminator comprising 5-12 carbons;
g) contacting the capped glycol, the diamine, and the monoamine in a solvent to form a polyurethaneurea solution; and
h) spinning the polyurethaneurea solution to form the spandex, wherein; a mole ratio of monoamine to monoalcohol is at least about 0.5;
1; and
a mole ratio of monoamine to monoalcohol is at most about 10;
1.- View Dependent Claims (12, 13, 14, 15, 16, 17, 18, 19, 20)
providing a polyether glycol in step a);
providing an aromatic diisocyanate in step b);
providing a monoalcohol comprising at least 4 carbons in step c);
providing a monoalcohol comprising at most 7 carbons in step c);
selecting the diamine in step e) from the group consisting of ethylene diamine, 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 1,3-cyclohexanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, and mixtures thereof;
providing a monoamine comprising at least 6 carbons in step f); and
providing a monoamine comprising at most 7 carbons in step f); and
wherein step h) is a dry-spinning step.
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13. The process of claim 11 comprising the steps of:
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selecting the polymeric glycol in step a) from the group consisting of poly(tetramethyleneether) glycol and poly(tetramethylene-ether-co-2-methyltetramethyleneether) glycol;
selecting the diisocyanate in step b) from the group consisting of 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene and mixtures thereof with 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene; and
selecting the monoamine in step f) from the group consisting of n-hexylamine, cyclohexylamine, 1-amino-3-methylcyclohexane, 1-amino-2-methylcyclohexane, and n-heptylamine.
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14. The process of claim 11 comprising the steps of:
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providing a polyether glycol in step a);
providing a monoamine comprising at least 6 carbons in step f); and
providing a monoamine comprising at most 7 carbons in step f); and
further comprising, between steps a) and d), the step of adding to the polyether glycol at least about 10 ppm and at most about 125 ppm of a compound selected from the group consisting of acids and acid-producing compounds.
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15. The process of claim 11 comprising the steps of:
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providing the monoalcohol in step c) in an amount of at least about 5 meq/kg, based on total ingredients; and
providing the monoalcohol in step c) in an amount of at most about 30 meq/kg based on total ingredients.
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16. The process of claim 11 comprising the steps of:
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providing the monoamine in step f) in an amount of at least about 2 meq/kg based on total ingredients; and
providing the monoamine in step f) in an amount of at most about 55 meq/kg, based on total ingredients.
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17. The process of claim 11 comprising the steps of:
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in step b), providing a mixture of 1-isocyanato4-[(4-isocyanatophenyl)-methyl]benzene and 1-isocyanato-2-[(4-isocyanatophenyl)methyl]-benzene wherein;
the 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene is present in an amount of at least about 5 mol %, based on total diisocyanate; and
the 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene is present in an amount of at most about 30 mol %, based on total diisocyanate;
in step d), forming a capped glycol having an NCO content of at least about 2.0 wt % based on capped glycol;
in step d), forming a capped glycol having an NCO content of at most about 3.5 wt % based on capped glycol; and
in step e), selecting the diamine from the group consisting of ethylene diamine and mixtures thereof with at most about 10 mole percent, based on total diamines, of a diamine selected from the group consisting of 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-cyclohexanediamine, and 1,3-diaminopentane.
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18. The process of claim 11 comprising the steps of:
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selecting the polymeric glycol in step a) from the group consisting of poly(tetramethyleneether) glycol having a number-average molecular weight in the range of about 1500 to 2500 daltons and poly(tetramethylene-ether-co-2-methyltetramethyleneether) glycol having a number-average molecular weight in the range of about 2000 to 4000 daltons;
in step b), providing substantially 1-isocyanato-4-[(4′
-isocyanatophenyl)-methyl]benzene;
in step d), forming a capped glycol having an NCO content of;
at least about 2.0 wt %, based on total capped glycol, when the polymeric glycol is poly(tetramethyleneether-co-2-methyltetra-methyleneether) glycol;
at most about 5.5 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether-co-2-methyltetramethyleneether) glycol;
at least about 2.5 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether) glycol; and
at most about 6.0 wt %, based on total capped glycol, when the glycol is poly(tetramethyleneether) glycol; and
in step e), providing a mixture of ethylene diamine with at least about 50 mol % of a diamine, based on total diamines, selected from the group consisting of 2-methyl-1,5-pentanediamine and 1,3-diaminopentane.
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19. The process of claim 11 comprising providing poly(2,2-dimethyl-1,3-propane dodecanedioate) glycol in step a).
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20. The process of claim 11 comprising the steps of:
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in step a), providing poly(tetramethylene terephthalate) glycol having a number-average molecular weight of about 1500 to 2500 daltons;
in step b), providing substantially 1-isocyanato-4-[(4′
-isocyanatophenyl)-methyl]benzene;
in step e), providing ethylene diamine mixed with at least about 10 mole percent, based on total diamines, of a second diamine;
in step e), providing ethylene diamine mixed with at most about 20 mole percent, based on total diamines, of a second diamine;
providing a monoamine comprising at least 6 carbons in step f); and
providing a monoamine comprising at most 7 carbons in step f);
wherein the second diamine is selected from the group consisting of 1,2-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-cyclohexanediamine, and 1,3-diaminopentane.
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Specification