US 5,332,798 AGranted

Fluorinated polyurethanes and polyurethane-ureas, and methods for preparing them

AssigneeAusimont S.p.A.

InventorsEnrico Ferreri, Francesco Giavarini, Claudio Tonelli, Tania Trombetta, Ronald E. Zielinski

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Abstract

Fluorinated polyurethanes and polyurethane-ureas, of heat-processable, elastomeric type, constituted by rubber-like blocks and hard blocks, comprising segments derived from: (a) a macroglycol or polybutadiene-diol; (b) a perfluoropolyether-diol of formula HO(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 --Q--CH.sub.2 --(OCH.sub.2 CH.sub.2).sub.n OH wherein Q is a perfluoropolyether chain and "n" is comprised within the range of from 1 to 5; (c) an aromatic, aliphatic, or cycloaliphatic diisocyanate; and (d) an aliphatic, cycloaliphatic or aromatic diol or diamine, containing from 2 to 14 carbon atoms. They contain from 4 to 30% by weight of fluorine, from 10 to 60% by weight of hard components, with the molar ratio of rubber-like components (a): (b) comprised within the range of from 2 to 20. At least 80% of rubber-like segments deriving from (b) component are connected, at least at one of their sides, through a segment deriving from (c) component, with a rubber-like segment deriving from (a) component.

Heat-processable, elastomeric fluorinated polyurethanes constituted by rubber-like blocks and hard blocks, comprising segments derived from:

(a) a diol of polyether or polyester type, or polybutadienediol, having an average molecular weight comprised within the range of from 500 to 4,000;
(b) a perfluoropolyether- or fluoropolyether-diol having an average molecular weight comprised within the range of from 400 to 10,000, of formula:
HO(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 --Q--CH.sub.2 (OCH.sub.2 CH.sub.2).sub.n OH
wherein:
n is comprised within the range of from 1 to 5, and
Q is a perfluoropolyether or fluoropolyether chain selected from the group consisting of:
(1) --CF.sub.2 --O--(CF.sub.2 CF.sub.2 O).sub.m (CF.sub.2 O).sub.p --CF.sub.2 -- (I)
wherein (CF.sub.2 CF.sub.2 O) and (CF.sub.2 O) units are randomly distributed along the chain, and the ratio of m/p is comprised within the range of from 0.2 to 2;
(2) --CF.sub.2 CH.sub.2 --(OCF.sub.2 CF.sub.2 CH.sub.2).sub.r --O--R.sup.1 --O--(CH.sub.2 CF.sub.2 CF.sub.2 O).sub.s --CH.sub.2 CF.sub.2 --(II)
wherein R.sup.1 is a fluoroalkylene radical of from 1 to 10 carbon atoms, and the ratio of r/s is comprised within the range of from 0.8 to 1.2;
##STR4## in which the units ##STR5## are randomly distributed along the chain;
X=F or CF.sub.3 ;
t/u=0.6-2.0;
u/v is higher than 10;
##STR6## in which R.sup.2 is a perfluoroalkylene radical of from 1 to 10 carbon atoms, and c/f=0.8-1.2,
(c) an aromatic, aliphatic or cycloaliphatic diisocyanate having a molecular weight not higher than 500;
(d) an aliphatic, cycloaliphatic or aromatic diol of from 2 to 14 carbon atoms;
with said fluorinated polyurethanes being furthermore characterized in that:
(i) the hard components (c) and (d) represent, together, from 10 to 60% of total components, by weight;
(ii) the molar ratio of the rubber-like component (b) to the rubber-like component (b) is comprised within the range of from 2 to 20;
(iii) the amount of rubber-like component (b) is such that the polymer contains from 4 to 30% by weight of fluorine;
(iv) at least 80% of perfluoropolyether or fluoropolyether segments deriving from (b) component are connected, at at least one of their sides, through a segment deriving from a diisocyanate component (c), with a rubber-like segment deriving from an (a) component.

19 more elements

Abstract

Claims14