Thermoplastic polyurethane and associated method and article

Patent metadata

Field	Value
Publication number	US-9422394-B2
Application number	US-201313929961-A
Country	US
Kind code	B2
Filing date	Jun 28, 2013
Priority date	Jun 28, 2013
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

A thermoplastic polyurethane is formed by the reaction of a specific hydroxy-diterminated poly(phenylene ether) and an organic diisocyanate. The polyurethane-forming reaction optionally employs diols other than the hydroxy-diterminated poly(phenylene ether). Compared to thermoplastic polyurethanes lacking the residue of the hydroxy-diterminated poly(phenylene ether), the thermoplastic polyurethanes described herein exhibit properties including one or more of improved heat and oxidation resistance, improved resistance to acids, bases, and solvent, and reduced water absorption.

First claim

The invention claimed is:

1. A linear thermoplastic polyurethane comprising:
at least three poly(phenylene ether) repeat units having the structure

 wherein each occurrence of Q 1 is independently halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q 2 is independently hydrogen, halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R 1 and R 2 is independently hydrogen, halogen, C 1 -C 12 hydrocarbylthio, hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; and Y is selected from

 wherein each occurrence of R 3 -R 6 is independently hydrogen or C 1 -C 12 hydrocarbyl; and
at least three diisocyanate residue repeat units having the structure

 wherein R 7 is, independently in each repeat unit, C 4 -C 18 hydrocarbylene;
wherein at least one terminal oxygen atom of each poly(phenylene ether) repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate residue repeat unit to form a urethane moiety.

2. The linear thermoplastic polyurethane of claim 1 , wherein the poly(phenylene ether) repeat units have the structure

wherein each occurrence of Q 5 and Q 6 is independently methyl or di-n-butylaminomethyl; and each occurrence of a and b is independently 0 to 20, provided that the sum of a and b is at least 3.

3. The linear thermoplastic polyurethane of claim 1 , wherein each diisocyanate residue repeat units independently has a structure selected from

4. The linear thermoplastic polyurethane of claim 1 , further comprising at least three diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

5. The linear thermoplastic polyurethane of claim 1 , comprising 5 to 95 weight percent of the poly(phenylene ether) repeat units, and 5 to 40 weight percent of the diisocyanate residue repeat units.

6. The linear thermoplastic polyurethane of claim 5 , further comprising 5 to 70 weight percent of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

7. The linear thermoplastic polyurethane of claim 1 , having a weight average molecular weight of 10,000 to 250,000 atomic mass units.

8. The linear thermoplastic polyurethane of claim 1 ,
wherein the poly(phenylene ether) repeat units have the structure

 wherein each occurrence of Q 5 and Q 6 is independently methyl or di-n-butylaminomethyl; and each occurrence of a and b is independently 0 to 20, provided that the sum of a and b is at least 3;
wherein the diisocyanate residue repeat units have a structure selected from

 and
wherein the linear thermoplastic polyurethane further comprises at least three diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

9. An article comprising a linear thermoplastic polyurethane comprising:
at least three poly(phenylene ether) repeat units having the structure

 wherein each occurrence of Q 1 is independently halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q 2 is independently hydrogen, halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R 1 and R 2 is independently hydrogen, halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; and Y is selected from

 wherein each occurrence of R 3 -R 6 is independently hydrogen or C 1 -C 12 hydrocarbyl; and
at least three diisocyanate residue repeat units having the structure

 wherein R 7 is, independently in each repeat unit, C 4 -C 18 hydrocarbyl;

wherein at least one terminal oxygen atom of each poly(phenylene ether) repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate residue repeat unit to form a urethane moiety.

10. The article of claim 9 , wherein the article is selected from the group consisting of films, cable sheathing, spiral tubing, pneumatic tubing, blow molded bellows, ski boot shells, sport shoe soles, caster tires, automotive body panels, and automotive rocker panels.

11. A method of forming a linear thermoplastic polyurethane, the method comprising:
reacting a hydroxy-diterminated poly(phenylene ether) with an organic diisocyanate to form a linear thermoplastic polyurethane;
wherein the hydroxy-diterminated poly(phenylene ether) has the structure

 wherein each occurrence of Q 1 is independently halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q 2 is independently hydrogen, halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy

Assignees

• Sabic Global Technologies Bv

Inventors

• Peters Edward Norman

Classifications

• Y10T428/139

  Open-ended, self-supporting conduit, cylinder, or tube-type article · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/4854

  Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group · CPC title

• C08G18/10

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G18/3206

  aliphatic · CPC title