Crosslinkable thermoplastic polyurethane

Patent metadata

Field	Value
Publication number	US-9650477-B2
Application number	US-201414519275-A
Country	US
Kind code	B2
Filing date	Oct 21, 2014
Priority date	Jan 22, 2010
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

The TPU of this invention contains unsaturation in its polymeric backbone. The unsaturation can be present in the soft segment or in the hard segment or in both the soft and hard segments of the TPU. The TPU can be molded like a thermoplastic, and can be subsequently crosslinked by exposure to electron beam irradiation into thermoset articles having excellent chemical resistance, dimensional stability, set properties, heat resistance, oxidative resistance, and creep resistance. In one embodiment, the TPUs of this invention are the reaction product (1) a hydroxyl terminated intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds, such as the allyl moieties present in trimethylolpropane monoallyl ether. In another embodiment of this invention, the thermoplastic polyurethane which is crosslinkable by e-beam irradiation is comprised of the reaction product of (1) a saturated hydroxyl terminated intermediate, (2) an unsaturated hydroxyl terminated intermediate, wherein the unsaturated hydroxyl terminated intermediate contains carbon-carbon double bonds, (3) a polyisocyanate, and (4) a saturated glycol chain extender.

First claim

What is claimed is:

1. A process for manufacturing a molded article which comprises (a) heating a crosslinkable thermoplastic polyurethane composition to a temperature which is above the melting point of the thermoplastic polyurethane composition, wherein the thermoplastic polyurethane composition is comprised of the reaction product of (1) a hydroxyl terminated intermediate, wherein the hydroxyl terminated intermediate is an unsaturated hydroxyl terminated intermediate of the structural formula:

wherein A independently represents —R 1 OH and a moiety selected from the structure represented as follows:

and R 1 , R 2 , R 3 , and R 4 can be the same or different and represent divalent linear and branched alkylene moieties that contain from 1 to about 10 carbon atoms, R 1 can also represent a divalent ether group represented by —R 5 —O—R 5 , wherein R 5 independently is selected from a divalent alkylene moiety containing 1 to 5 carbon atoms, the ratio of n:m ranges from about 0 to about 35, and y is an integer ranging from about 1 to about 20, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds; (b) injecting the thermoplastic polyurethane composition into a mold; (c) cooling the thermoplastic polyurethane composition in the mold to a temperature which is below the melting point of the thermoplastic polyurethane composition to produce the molded article; (d) removing the molded article from the mold; and (e) exposing the molded article to irradiation to crosslink the thermoplastic polyurethane composition into a thermoset.

2. A process as specified in claim 1 wherein the irradiation is electron beam irradiation.

3. A process for manufacturing a thermoset tube which comprises (a) heating a crosslinkable thermoplastic polyurethane composition to a temperature which is above the melting point of the thermoplastic polyurethane composition, wherein the thermoplastic polyurethane composition is the thermoplastic polyurethane composition specified in claim 1 ; (b) extruding the thermoplastic polyurethane composition into a hot extruded tube; (c) cooling the hot extruded tube to below the melting point of the thermoplastic polyurethane composition to produce an uncured extruded tube; and (d) exposing the uncured extruded tube to irradiation to crosslink the thermoplastic polyurethane composition into a thermoset and to produce the thermoset tube.

4. A process for manufacturing a coated electrical wire which comprises (a) passing a metal wire through a tubing type cross-head die; (b) extruding a crosslinkable thermoplastic polyurethane composition is the thermoplastic polyurethane composition specified in claim 1 , (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds into a tube which surrounds the metal wire which is exiting the tubing type cross-head die at a speed lower than that at which the wire is exiting the tubing type cross-head die; (c) applying a vacuum to the die cavity so as to cause the tube of thermoplastic polyurethane composition to collapse onto the wire as it exits the tubing type cross-head dye to produce a wire having an uncured coating thereon; and (d) exposing the wire having the uncured coating thereon to irradiation to crosslink the thermoplastic polyurethane composition into a thermoset and to produce the coated electrical wire.

5. A wire and cable construction comprising:
(a) at least one metal conductor wherein said conductor is insulated with a non-conducting polymeric material; and
(b) a jacket covering said insulated metal conductor; wherein said jacket is a crosslinkable thermoplastic polyurethane composition comprising the reaction product of:
(i) at least one polyisocyanate;
(ii) at least one saturated glycol chain extender;
(iii) at least one glycol chain extender containing carbon-carbon double bonds;
(iv) at least one saturated hydroxyl terminated intermediate of the structural formula:

wherein A independently represents —R 1 OH and a moiety selected from the structure represented as follows:

and R 1 , R 2 , R 3 , and R 4 can be the same or different and represent divalent linear and branched alkylene moieties that contain from 1 to about 10 carbon atoms, R 1 can also represent a divalent ether group represented by —R 5 —O—R 5 , wherein R 5 independently is selected from a divalent alkylene moiety containing 1 to 5 carbon atoms, the ratio of n:m ranges from about 0 to about 35, and y is an integer ranging from about 1 to about 20;
(v) optionally at least one unsaturated hydroxyl terminated intermediate containing carbon-carbon double bonds.

6. The wire and cable construction of claim 5 , wherein said construction has from 2 to 8 insulated metal conductors.

7. The wire and cable construction of claim 5 , wherein said thermoplastic polyurethane further comprises at least one flame retardant.

Assignees

• Lubrizol Advanced Mat Inc

Inventors

• Makal Umit G
• Loeber George H
• Brandewiede Louis J

Classifications

• C08G18/676 Primary

  containing the unsaturation at least partially in a non-aromatic carbocyclic ring · CPC title

• C08J5/00 Primary

  Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00) · CPC title

• B29K2995/0016

  Non-flammable or resistant to heat · CPC title

• C08G18/6607

  with compounds of group C08G18/3203 · CPC title

• C08G18/68

  Unsaturated polyesters · CPC title