Fluorinated polyurethane elastomers prepared from polyether prepolymers formed from mono-substituted fluorinated oxetane monomers and tetrahydrofuran
View Patent ↗The present invention provides, inter alia, novel fluorinated polyurethane elastomers (e.g., fluorinated thermoset polyurethane elastomers and fluorinated thermoplastic elastomers) prepared from polyether prepolymers formed from mono-substituted fluorinated oxetane monomers (FOX monomers) and tetrahydrofuran (THF). In addition, the present invention provides methods of making such fluorinated polyurethane elastomers.
1. A fluorinated polyurethane elastomer having FOX/THF segments and comprising a mixture of monomeric repeat units having the formulae:
wherein:
each n is independently selected and is a number from 1 to 3;
each R is independently selected from the group consisting of methyl and ethyl;
each R f is independently selected from the group consisting of linear and branched perfluorinated alkyls and isoalkyls having from 1 to about 20 carbons, and oxa-perfluorinated polyethers having from about 4 to about 60 carbons;
x is about 10 to about 250;
z is 1 to about 250;
R 1 is a divalent hydrocarbyl radical; and
w is 1 to about 50.
2. The fluorinated polyurethane elastomer in accordance with claim 1 , wherein said fluorinated polyurethane elastomer is a fluorinated thermoset polyurethane elastomer.
3. The fluorinated polyurethane elastomer in accordance with claim 1 , wherein said fluorinated polyurethane elastomer is a fluorinated thermoplastic polyurethane elastomer.
4. The fluorinated polyurethane elastomer in accordance with claim 1 , wherein the isocyanate segment is produced from a member selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-methylene diphenyl-isocyanate (MDI), polymeric MDI, toluene diisocyanates, hydrogenated MDI (HMDI), polymeric HDI, trimethylhexane diisocyanate and mixtures of at least two thereof.
5. The fluorinated polyurethane elastomer in accordance with claim 1 , further comprising a cross-link formed from a cross-linking agent or a chain-extender selected from the group consisting of low molecular weight polyols and polyamines.
6. The fluorinated polyurethane elastomer in accordance with claim 5 , wherein said cross-linking agent is selected from the group consisting of trimethylolpropane, pentaerythritol, trimethylolethane, triethanolamine, 1,4-butanediamine, xylene diamine, diethylenetriamine, methylene dianiline and diethanolamine.
7. The fluorinated polyurethane elastomer in accordance with claim 5 , wherein said chain extender is a member selected from the group consisting of 1,4-butanediol; 1,3-propanediol; and benzenedimethanol.
8. The fluorinated polyurethane elastomer in accordance with claim 5 , wherein said chain extender is 1,4-butanediol.
9. The fluorinated polyurethane elastomer in accordance with claim 1 , wherein the fluorinated polyether segment is produced from at least one mono-substituted FOX monomer selected from the group consisting of 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methyloxetane; 3-(2,2,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl)oxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca-fluorooctyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl)-3-methyloxetane; and 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10,11,11,12,12,12-heneicosafluorododecyloxymethyl)-3-methyloxetane.