Thermoplastic polyurethanes with crystalline chain ends

Patent metadata

Field	Value
Publication number	US-9546242-B2
Application number	US-201314438653-A
Country	US
Kind code	B2
Filing date	Oct 14, 2013
Priority date	Oct 31, 2012
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

The present invention relates to novel thermoplastic polyurethane (TPU) compositions that have crystalline chain ends. The TPU compositions of the invention can provide improved resiliency, lower surface free energy, and/or reduced stickiness, while maintaining other desirable physical properties. The present invention also provides the described TPU compositions that are further grafted with vinyl alkoxysilane moieties allowing for crosslinked networks of the TPU compositions. The present invention also provides plasticizer-free, very soft TPU compositions without the processing difficulties often associated with such materials. The invention further provides means of reducing the surface tension of a TPU composition which can allow for improved blend compositions, and means of crosslinking the described TPU compositions.

First claim

What is claimed is:

1. A thermoplastic polyurethane composition comprising the product of a reaction mixture comprising (i) a polyisocyanate component, (ii) at least one of a chain extender component or a polyol component, and (iii) a chain terminator component;
wherein the chain terminator component comprises a short chain crystalline compound containing 26 to 70 carbon atoms and a single NCO-reactive functional group capable of terminating a chain of a thermoplastic polyurethane resulting from the reaction of components (i) and (ii), wherein the short chain crystalline compound comprises one or more alpha-hydroxy terminated polyalphaolefins selected from a polyethylene, a polypropylene, a poly(ethylene-co-alphaolefin) copolymer, a poly(propylene-co-alphaolefin) copolymer, or any combination thereof; and
wherein the thermoplastic polyurethane composition comprises a crystalline end group formed by the chain terminator component.

2. The thermoplastic polyurethane composition of claim 1 wherein the thermoplastic polyurethane is represented by the following structure:

wherein each A is an end group derived from the short chain crystalline compound; each D is a group derived from the polyisocyanate component; each E is derived from the chain extender component; each P is derived from the polyol component; each m is an integer from 0 to 15; each n is an integer from 0 to 20; and x is an integer from 1 to 50; with the proviso that at least one of m and n is greater than 0.

3. The thermoplastic polyurethane composition of claim 1 wherein the reaction mixture comprises a chain extender component, comprising a diol, a diamine, or a combination thereof.

4. The thermoplastic polyurethane composition of claim 1 wherein the polyisocyanate component comprises MDI, H12MDI, HDI, TDI, IPDI, LDI, BDI, PDI, CHDI, TODI, NDI or a combination thereof.

5. The thermoplastic polyurethane composition of claim 1 wherein the reaction mixture comprises at least 75 percent by weight polyol component.

6. The thermoplastic polyurethane composition of claim 1 wherein the reaction mixture comprises a polyol component comprising a polyether polyol, a polyester polyol, a polycarbonate polyol, a polysiloxane polyol, or a combination thereof.

7. The thermoplastic polyurethane composition of claim 1 wherein the reaction mixture comprises a polyol component comprising a poly(ethylene glycol), poly(tetramethylene glycol), poly(trimethylene oxide), ethylene oxide capped poly(propylene glycol), poly(butylene adipate), poly(ethylene adipate), poly(hexamethylene adipate), poly(tetramethylene-co-hexamethylene adipate), poly(3-methyl- 1, 5-pentamethylene adipate), polycaprolactone diol, poly(hexamethylene carbonate) glycol, poly(pentamethylene carbonate) glycol, poly(trimethylene carbonate) glycol, polydimethyl siloxane polyol, or any combination thereof.

8. The thermoplastic polyurethane composition of claim 1 wherein the reaction mixture comprises a chain extender component comprising ethylene glycol, butanediol, hexamethylenediol, pentanediol, heptanediol, nonanediol, dodecanediol, ethylenediamine, butanediamine, hexamethylenediamine, or a combination thereof.

9. The thermoplastic polyurethane composition of claim 1 wherein the thermoplastic polyurethane composition has a Shore hardness below 65 A.

10. The thermoplastic polyurethane composition of claim 9 where the thermoplastic polyurethane composition is free of a plasticizer.

11. The thermoplastic polyurethane composition of claim 1 wherein the thermoplastic polyurethane composition has a surface tension lower than that of a thermoplastic polyurethane composition made without the chain terminator component.

12. The thermoplastic polyurethane composition of claim 1 wherein the composition further comprises a photoinitiator.

13. The thermoplastic polyurethane composition of claim 1 wherein the thermoplastic polyurethane composition is crosslinkable by E-Beam or gamma beam irradiation.

14. The thermoplastic polyurethane composition of claim 1 wherein the crystalline end group is grafted with a vinyl alkoxysilane moiety in the presence of a peroxide.

15. The thermoplastic polyurethane of claim 14 wherein the thermoplastic polyurethane composition is crosslinked by formation of siloxane crosslinks upon hydrolysis and subsequent condensation of the alkoxysilane groups;
resulting in a crosslinked network of thermoplastic polyurethane with crystalline end groups.

16. A blend comprising the thermoplastic polyurethane composition of claim 1 , and a polyolefin.

17. An article comprising a film, a sheet, or a non-woven fabric, where said article is made from a composition comprising the blend of claim 16 .

18. A method of making a thermoplastic polyurethane composition comprising the steps of: (I) reacting (i) a polyisocyanate component, (ii) at least one of a chain extender component or a polyol component, and (iii) a chain terminator component;
wherein the chain terminator component comprises a short chain crystalline compound containing 26 to 70 carbon atoms and a single functional group capable of terminating the chain of a thermoplastic polyurethane resulting from the reaction of components (i) and (ii), wherein the short chain crystalline compound comprises one or more alpha-hydroxy terminated polyalphaolefins selected from a polyethylene, a polypropylene, a poly(ethylene-co-alphaolefin) copolymer, a poly(propylene-co-alphaolefin) copolymer, or any combination thereof;
resulting in a thermoplastic polyurethane with crystalline end groups.

19. The method of claim 18 further comprising the step of reacting the resulting thermoplastic polyurethane with crystalline end groups with a crosslinkable vinyl alkoxysilane moiety in the presence of a peroxide;
resulting in a thermoplastic polyurethane with crystalline end groups where the crystalline end groups contain a crosslinkable vinyl alkoxysilane group.

Assignees

• Lubrizol Advanced Mat Inc

Inventors

• Makal Umit G
• Steinmetz Bryce W
• Lu Qiwei
• Day Roger W

Classifications

• C08G18/285

  Nitrogen containing compounds · CPC title

• C08G18/283

  Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/664

  with compounds of group C08G18/3203 · CPC title

• C08G18/4833

  Polyethers containing oxyethylene units · CPC title