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US 6,184,329 B2Granted
Polyfunctional, perhalogenated polyorganosiloxanes and methods for preparation thereof
AssigneeRhone-Poulenc Chimie
InventorsPhilippe Jost, Philippe Karrer, Gérard Mignani, Philippe Olier
Life of this patent
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Abstract
Chemicaly stable, perflourinated, linear or cyclic polyorganosiloxanes (POS), and a process for the preparation thereof. Antifoams, agents for lowering surface tension, dirt repellents, antiadhesives, lubricants, oleophobic and/or hydrophobic agents, coatings and other compositions containing the perfluorinated POS are disclosed.
Claims20
A polymer of formula (I), (I.1) or formula (II):
- {(H)d1(R1)c1SiO½}-(R2GfSiO{fraction (2/2)})z-(R2ESiO{fraction (2/2)})e-(HR2SiO{fraction (2/2)})y1-{(R2)2SiO{fraction (2/2)}}y-{(H)d2(R1)c2SiO½} (I.1)
- wherein,
- 1) a+b+p=3,
- a=2 or 3,
- b=0or 1, and
- p=0 or 1;
- and at least one b is 1;
- 2) z is 1 to about 200,
- y1 is 0 to about 10,
- y is 0 to about 50, and
- e is 1 to about 200,
- provided that,
- i) 5≦z+y1+y+e ≦200 and (z/(z+y1+y+e+2))100≧3;
- 3) 1≦z1≦9,
- 0≦y1′≦0.5, and
- 0≦y′≦5;
- (z1+y1′+y′+e1)<10;
- wherein e1 is at least one;
- 4) R1 and R2 are the same or different, and are linear or branched C1-2 - alkyl, C3-12-cycloalkyl, aryl, aralkyl, or alkylaryl group wherein each of R1 and R2 may be identical or different from other R1 and R2;
- 5) Gf is present at least once in the formulae (I) and (II), and is a monovalent radical of formula (III)
- [Brketopenst](Z1)h-(Z2)g-((Z3)j-Rf)k (III)
- wherein,
- a) [Brketopenst] is a free valence attached directly or indirectly to the silicon;
- b) h, g, and j are independently 0 or 1, with the proviso that when b=1 in Formula I then g=1;
- c) k is 1 or 2;
- d) Z1 is a divalent radical of formula (IV),
- [Parenopenst]CmH2m[Parenclosest] (IV)
- wherein m is ≧2, with the proviso that when m is 2, g is 1;
- e) Z2 is a radical having one of the formulae (V) to (XII)
- wherein
- i) in formula (V) at least one of the free valences of the carbonyl group(s) is joined to—(Z3)j—Rf, and if only one free valence is joined to—(Z3)j—Rf, the other free valence is joined to a hydroxyl group;
- ii) in formula (VI) at least one of the free valences of the carbonyl group(s) is joined to—(Z3)j—Rf, and if only one free valence is joined to —(Z3)j—Rf, the other free valence is joined to a linear or branched C1-C6 alkoxy, and
- Ra is hydrogen, aryl, or linear or branched C1-C6 alkyl;
- iii) in formula (X), h in Gf is 0, at least one of the free valences of the carbonyl group(s) is joined to —(Z3)j—Rf, and if only one free valence is joined to —(Z3)j—Rf, the other is joined to a hydroxy group or to linear or branched C1-C6 alkoxy;
- iv) in formula (XI) at least one of the two free valences other than the valence [Brketopenst] is joined to —(Z3)j—Rf, and where only one of the two valences is joined to —(Z3)j—Rf, the other is joined to a hydroxy group or to linear or branched C1-C6 alkoxy;
- v) in formula (XII) at least one of the two free valences other than the valence [Brketopenst] is joined to —(Z3)j—Rf and, where only one of the two valences is joined to —(Z3)j—Rf, the other is joined to a hydroxy group or to a linear or branched C1-C6 alkoxy, and Rb is hydrogen or linear or branched C1-C6 alkyl;
- and
- vi) in formulae (V), (VIII), (VIII), and (IX), W is a cyclic or non-cyclic hydrocarbon group;
- f) Z3 is a divalent radical of the formula (XIII)
- [Brketopenst]U—CnH2n— (XIII)
- wherein,
- i) n≧1,
- ii) U is O, S, NH, or NHSO2, and
- g) Rf is a perhalogenated group or is a linear or branched fluoroalkyl radical having one of the formulae:
- —CqF2q—H wherein q≧1;
- —NRrfSO2CqF2q—CF3 wherein q≧0 and Rrf=H, aryl or linear or branched C1-C6-lower alkyl;
- or
- —NRrfSO2CqF2q—H wherein q≧1;
- and
- 6) all E radicals are different than Gf and may be the same or different, and are selected from E1-E2, E4-E6, and E8-E13;
- wherein:
- E1 has the formula (XIV)
- [Brketopenst](Z1)h—(Z2)g (XIV)
- wherein,
- a) Z1 and h are as defined for Gf where m≧2 and g is 1;
- b) Z2 is a radical of formula (Va)-(XIIa);
- [Brketopenst]W—N=C=O (XVII)
- wherein in formula (Va)
- the free valences of the carbonyl groups are each joined to a hydroxyl group or the two free valences are both joined to the same oxygen atom;
- wherein in formula (XV) the two free valences of the carbonyls are each joined to a linear or branched C1-C6-alkoxy group;
- wherein in formula (IXa) the free valence of the carbonyl is joined to a linear or branched C1-C6-alkoxy or to a hydroxyl group;
- wherein in formula (Xa) the free valences of the carbonyl groups are bonded to a hydroxyl or a linear or branched C1-C6-alkoxy, or these two free valences are both joined to the same oxygen atom;
- wherein in formula (XIa) the two free valences other than the valence [Brketopenst] are joined to a hydroxy group or to linear or branched C1-C6 alkoxy;
- Rb
- wherein in formula (XIIa) Rb is hydrogen or linear or branched C1-C6 lower alkyl;
- and the two free valences other than the valence [Brketopenst] are joined to a hydroxy group,
- wherein in formulae (Va), (XVII), (XVIII), and (IXa), W is a cyclic or noncyclic hydrocarbon group;
- E2 is amine;
- E4 is acyl, E5 is acyloxy, E6 is hydroxyl, E8 is amide, E9 is an ester, E10 is phenol, E11 is arylalkoxy, E12 is aryloxy, and E13 is ether-hydroxy;
- with the proviso that in Formula I.1, h and g are 1, or h is 1 and g is 0 for Gf;
- c1+d1=3 wherein d1 is at least one;
- c2+d2=3;
- 1≦z≦90;
- and
- 1≦e≦100.
72 more elements
A process for preparing the compounds of claim 1, comprising reacting at least one polyalkylhydrogenosiloxane oil with at least one halogenated olefin which is a precursor of Gf and has the formula:
- (Z1p)h—(Z2)g—[(Z3)j—Rf]k
- wherein Z1p is the olefinic precursor of the radical Z1 defined in claim 53;
- Z2, Z3, Rf, h, g, j, and k are as defined in claim 53, provided that if h=0, then g=1 and Z2 becomes an olefinic precursor Z2p;
- in the presence of an effective amount of a metal hydrosilylation catalyst;
- wherein the precursor of Gf has one of the following formulae:
- wherein in the above formulae
- Ra and R9 independently are H or linear or branched C1-6-lower alkyl;
- R10 and R11 independently are OH, linear or branched C1-6-alkoxy or —(Z3)j—Rf, at least one of the radicals R10 and R11 being —(Z3)j—Rf;
- and
- i is 0 to 10.
7 more elements
A process for preparing the compounds of claim 1, comprising
- a) reacting at least one Si—H linkage in a polyalkylhydrogenosiloxane oil with at least one halogenated olefin which is a precursor of Gf and has the formula
- (Z1P)h—(Z2)g—{(Z3)j—Rf}k
- wherein
- Z1p is the olefinic precursor of the radical Z1 as defined in claim 53
- Z2, Z3, Rf, h, g, j, and k are as defined in claim 53,
- provided that if h=0,
- then g=1 and
- Z2 becomes an olefinic precursor Z2P;
- in the presence of an effective amount of a metal hydrosilylation catalyst and
- b) reacting the reaction product of step a) with Ep, which is an olefinic precursor to E
- wherein the olefin(s) in (Z1p)h(Z2)g((Z3)j—Rf) are selected based on the anticipated bond between the precursor and the silicon atom(s) containing the Si—H bond(s) participating in the hydrosilation reaction.
8 more elements
Dependencies are inferred from the claim text.