UV CURABLE SELF-BONDING SILICONE RUBBER
A method for manufacturing a composite article of polytetrafluoroethylene and silicone includes: (a) providing a UV-curable silicone: (b) applying the UV-curable silicone to a polytetrafluoroethylene backing; and (c) exposing the UV-curable silicone to UV radiation sufficient to cure the silicone.
1 . A method for manufacturing a composite article of polytetrafluoroethylene and silicone comprising the steps of:
a) providing a UV-curable silicone;
b) applying the UV-curable silicone to a polytetrafluoroethylene backing; and
c) exposing the UV-curable silicone to UV radiation sufficient to cure the silicone.
2 . The method of claim 1 wherein the step (a) of providing a UV-curable silicone comprises the combining of:
(i) at least one linear polyorganosiloxane having at least three alkenyl groups and an average number of diorganosiloxy units determined by GPC with polystyrene as standard of at least 3000,
(ii) optionally one or more polyorganosiloxane (ii) having alkenyl groups, other than the polyorganosiloxane according to the component (i),
(iii) at least one polyorganosiloxane (iii) having at least two SiH groups,
(iv) at least one photoactivatable transition metal catalyst,
(v) optionally one or more filler,
(vi) optionally one or more conventional additives, to provide an uncured silicone,
3 . The method of claim 2 wherein linear polyorganosiloxane (i) has the general formula (I):
R (3-x) R 1 x SiO(R 1 RSiO) a (R 2 SiO) b SiR (3-x) R 1 x (I),
in which x is preferably 0, 1, 2 or 3, a is an average value and is in the range of 0 to 100, b is an average value and is in the range of 3000 to 12000, with the proviso that the polydiorganosiloxane (i) of the general formula (I) has at least three alkenyl groups,
R=a saturated organic group,
R 1 =an unsubstituted or substituted C 2 -C 12 -alkenyl radical selected from n-, iso-, tert-, or cyclic C 2 -C 12 -alkenyl, vinyl, allyl, hexenyl, C 6 -C 30 -cycloalkenyl, cycloalkenylalkyl, norbornenylethyl, limonenyl, C 8 -C 30 -alkenylaryl, in which, if appropriate, one or more —O— atoms can be present (corresponding to ether radicals) and the radicals can have substitution by one or more F-atoms.
4 . The method of claim 3 wherein R is selected from n-, iso-, tert- or C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy(C 1 -C 12 )alkyl, C 5 -C 30 -cycloalkyl or C 6 -C 30 -aryl, C 1 -C 12 -alkyl(C 6 -C 10 )aryl, each of these radicals R optionally having substitution by one or more F atoms and/or can contain one or more —O— groups, and R 1 is selected from vinyl, allyl, 5-hexenyl, cyclohexenylethyl, limonenyl, norbornenylethyl, ethylidenenorbornyl, and styryl.
5 . The method of claim 3 wherein R is selected from methyl, phenyl, and 3,3,3-trifluoropropyl, and R 1 is vinyl.
6 . The method of claim 3 wherein the step (a) comprises the combining of one or more polyorganosiloxane (ii) having alkenyl groups, other than the polyorganosiloxane according to the component (i), wherein the polyorganosiloxane (ii) has the formula
R 2 R 1 SiO(R 2 SiO) u SiR 2 R 1 (II′),
in which the index ‘u’ is an average value and is in the range of 3000 to 12000, preferably 5000 to 11000, more preferably 6000 to 10000, and R and R 1 have the same meanings as given above for formula (I).
7 . The method of claim 2 wherein the polyorganosiloxane (iii) has the formula
[M a2 D b2 T c2 Q d2 R 2 e2 ] m (III)
in which
M=R 3 R 2 SiO 1/2 ,
D=R 3 RSiO 2/2 ,
T=R 3 SiO 3/2 ,
Q=SiO 4/2 , in which
R=n-, iso-, tert- or C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy(C 1 -C 12 )alkyl, C 5 -C 30 -cycloalkyl or C 6 -C 30 -aryl, C 1 -C 12 -alkyl(C 6 -C 10 )aryl, each of these radicals R optionally having substitution by one or more fluorine atoms and/or can contain one or more —O— groups,
R 3 =R, R 1 or hydrogen, with the proviso that at least two radicals R 3 per molecule are hydrogen attached to a silicon atom, R being defined above,
R 2 =a divalent aliphatic n-, iso-, tert-, or cyclic C 1 -C 14 -alkylene radical, or a C 6 -C 14 -arylene or, respectively, alkylenearyl radical, which in each case bridges two siloxy units M, D or T,
m=from 1 to 1000
a2=from 1 to 10
b2=from 0 to 1000
c2=from 0 to 50
d2=from 0 to 1
e2=from 0 to 300.
8 . The method of claim 7 wherein R is methyl and R 1 is vinyl.
9 . The method of claim 7 wherein the polyorganosiloxne (iii) is selected from polyhydrogensiloxanes having structures corresponding to formula (IIIa-IIIf)
HR 2 SiO(R 2 SiO) 2 (RHSiO) p SiR 2 H (IIIa)
Me 2 SiO(Me 2 SiO) z (MeHSiO) p SiMe 2 H (IIIb)
Me 3 SiO(Me 2 SiO) z (MeHSiO) p SiMe 3 (IIIc)
Me 3 SiO(MeHSiO) p SiMe 3 (IIId)
{[R 2 R 3 SiO 1/2 ] 0-3 [R 3 SiO 3/2 ][R 4 O) n-2 } m2 (IIIe)
{[SiO 4/2 ][R 4 O 1/2 ][R 2 R 3 SiO 1/2 ] 0.01-10 [R 3 SiO 3/2 ] 0-50 [RR 3 SiO 2/2 ] 1000 } m2 (IIIf)
where
z=from 0 to 1000
p=from 0 to 100
z+p=b4=from 1 to 1000
n2=from 0.001 to 4
m2=from 1 to 1000
in which R 4 O 1/2 is an alkoxy radical on silicon, and R 3 is defined as above.
10 . The method of claim 2 wherein the at least one polyorganosiloxane (iii) comprises a mixture of a polyhydrogen siloxane (iii-1) selected from the group consisting of
HMe 2 SiO-(Me 2 SiO) z SiMe 2 H, and
Me 3 SiO-(Me 2 SiO) z (MeHSiO) 2 SiMe 3
[(Me 2 SiO) z (MeHSiO) 2 ].
and a polyhydrogen siloxane (iii-2) selected from the group consisting of
Me 3 SiO-(MeHSiO) p SiMe 3 ,
HMe 2 SiO(Me 2 SiO) z (MePhSiO) z (MeHSiO) p SiMe 2 H,
(MeHSiO) p ,
(HMe 2 SiO) 4 Si
MeSi(OSiMe 2 H) 3 ,
in which p is from 0 to 100 and z is from 0 to 1000.
11 . The method of claim 2 wherein the catalyst (iv) comprises a η 5 -(optionally substituted)-cyclopentadienyl platinum complex compounds having sigma-bonded alkyl ligands.
12 . The method of claim 2 wherein the catalyst (iv) comprises one or more platinum complexes selected from the group consisting of:
(Cp)trimethylplatinum
(Cp)ethyldimethylplatinum
(Cp)triethylplatinum
(Cp)triallylplatinum
(Cp)tripentylplatinum
(Cp)trihexylplatinum
(methyl-Cp)trimethylplatinum
(trimethylsilyl-Cp)trimethyl platinum
(phenyldimethylsilyl-Cp)trimethylplatinum
(Cp)acetyldimethylplatinum
(Cp)diethylmethylplatinum
(Cp)triisopropylplatinum
(Cp)tri(2-butyl)platinum
(Cp)triallyiplatinum
(Cp)trinonylplatinum
(Cp)tridodecylplatinum
(Cp)tricyclopentylplatinum
(Cp)tricyclohexylplatinum
(chloro)-Cp)trimethyl platinum
(fluoro-Cp)trimethylplatinum
(Cp)dimethylbenzylplatinum
(triethylsilyl-Cp)trimethylplatinum
(dimethylphenylsilyl-Cp)trimethylplatinum
(methyldiphenylsilyl-Cp)trimethylplatinum
(triphenylsilyl-Cp)trihexylplatinum
1,3-bis(trimethylsilyl)-Cp]trimethylplatinum
(dimethyloctadecylsilyl-Cp)trimethylplatinum
1,3-bis[(Cp)trimethylplatinum]tetramethyldisiloxane
1,3-bis[(Cp)trimethylplatinum]dimethyldiphenyfdisiloxane
1,3-bis[(Cp)dimethylphenylplatinum]tetramethyldisiloxane
1,3,5-tris[(Cp)trimethylplatinum]pentamethyltrisiloxane
1,3,5,7-tetra[(Cp)trimethylplatinum]heptamethyltetrasiloxane
(methoxy-Cp)trimethylplatinum
(ethoxymethyl-Cp)ethyldimethylplatinum
(methyoxycarbonyl-Cp)trimethylplatinum
(1,3-dimethyl-Cp)trimethylplatinum
(methyl-Cp)triisopropylplatinum
(1,3-diacetyl-Cp)diethylmethylplatinum
(1,2,3,4,5-pentachloro-Cp)trimethylplatinum
(phenyl-Cp)trimethylplatinum
(Cp)acetyldimethylplatinum
(Cp)propionyldimethylplatinum
(Cp)acrloyldimethylplatinum
(Cp)di(methacryloyl)ethylplatinum
(Cp)dodecanoyldimethylplatinum
trimethylplatinumcyclopentadienyl-terminated polysiloxane.
(1,5-COD)diphenylplatinum
(1,3,5,7-COT)diphenylplatinum
(2,5-NBD)diphenylplatinum
(3a,4,7,7a-tetrahydro-4,7-methanoindene)diphenylplatinum
(1,5-COD)-bis(4-methylphenyl)platinum
(1,5-COD)-bis(2-methylphenyl)platinum
(1,5-COD)-bis(2-methoxyphenyl)platinum
(1,5-COD)-bis(3-methoxyphenyl)platinum
(1,5-COD)-bis(4-phenoxyphenyl)platinum
(1,5-COD)-bis(4-methylthiophenyl)platinum
(1,5-COD)-bis(3-chlorophenyl)platinum
(1,5-COD)-bis(4-fluorophenyl)platinum
(1,5-COD)-bis(4-bromophenyl)platinum
(1,5-COD)-bis(4-trifluoromethylphenyl)platinum
(1,5-COD)-bis(3-trifluoromethylphenyl)platinum
(1,5-COD)-bis(2,4-bis(trifluoromethyl)phenyl)platinum
(1,5-COD)-bis(4-dimethylaminophenyl)platinum
(1,5-COD)-bis(4-acetylphenyl)platinum
(1,5-COD)-bis(trimethylsilyloxyphenyl)platinum
(1,5-COD)-bis(trimethylsilylphenyl)platinum
(1,5-COD)-bis(pentafluorophenyl)platinum
(1,5-COD)-bis(4-benzylphenyl)platinum
(1,5COD)-bis(1-naphthyl)platinum
(1,5-COD)-naphthylphenylplatinum
(1,5-COD)-bis(2H-chromen-2-yl)platinum
(1,5-COD)-bis(xanthen-1-phenyl)platinum
(1,3,5-cycloheptatriene)diphenylplatinum
(1-chloro-1,5-COD)diphenylplatinum
(1,5-dichloro-1,5-COD)diphenylplatinum
(1-fluoro-1,3,5,7-COT)diphenylplatinum
(1,2,4,7-tetramethyl-1,3,5,7-COT)-bis(4-methylphenyl)platinum
(7-chloro-2,5-NBD)diphenylplatinum
(1,3-cyclohexadiene)diphenylplatinum
(1,4-cyclohexadiene)diphenylplatinum
(2,4-hexadiene)diphenylplatinum
(2,5-heptadiene)diphenylplatinum
(1,3-dodecadiene)diphenylplatinum
bis[η 2 -2-(2-propenyl)phenyl]platinum
bis[η 2 -2-(ethenylphenyl)]platinum
bis[η 2 -2-(cyclohexen-1-ylmethyl)phenyl]platinum.
(1,5-COD)Pt(methyl) 2
(1,5-COD)Pt(benzyl) 2
(1,5-COD)Pt(hexyl) 2 ;
wherein “Cp” signifies cyclopentadienyl, “COD” signifies cyclooctadiene, “COT” signifies cyclooctatetraene, and “NBD” signifies norbornadiene
13 . The method of claim 2 wherein the catalyst (i) is, methylcyclopentadienyl-trimethyl-platinum.
14 . The method of claim 2 wherein the UV curable silicone includes a filler (v) selected from silicates, carbonates, nitrides, oxides, carbon blacks, or silicas having a particle size of no more than 100 microns, the filler being present in an amount of from 1 to 100 parts by weight based on 100 parts by weight of component (i) and optionally (ii).
15 . The method of claim 14 wherein the filler is fumed silica.
16 . The method of claim 2 wherein the UV-curable silicone further comprises an additive (vi) selected from the group consisting of organic dyes or pigments, stabilizers plasticizers, polydimethylsiloxane oils, fatty acid derivatives or fatty alcohol derivatives, fluoroalkyl surfactants, organic salts or complexes of Fe-, Mn-, Ti-, Ce- or La-compounds, PTFE-powders, boron oxide derivatives, fluoroalkyl surfactants, 1,3-divinyltetra-methyldisiloxane, tetravinyl-tetramethyl-tetracyclosiloxanes ethynylcyclohexanol, 3-methylbutynol, and dimethyl maleate.
17 . The method of claim 1 further including the step of modifying the surface of the polytetrafluoroethylene backing to which the UV-curable silicone is to be applied.
18 . The method of claim 17 wherein the step of modifying the surface of the polytetrafluoroethylene backing comprises etching the surface with a caustic agent and applying a primer to the etched surface of the PTFE backing.
19 . A composite article of polytetrafluoroethylene and silicone manufactured in accordance with the method of claim 1 .
20 . The composite article of claim 19 having a peel strength of at least 11 pounds/in as measured by running a standard 180 degree peel test at a crosshead speed of 2 inches/minute 72 hours after preparation of the composite.