CA2134768A1 - Siloxane copolymers containing vinyloxy groups, their preparation and use - Google Patents
Siloxane copolymers containing vinyloxy groups, their preparation and useInfo
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- CA2134768A1 CA2134768A1 CA002134768A CA2134768A CA2134768A1 CA 2134768 A1 CA2134768 A1 CA 2134768A1 CA 002134768 A CA002134768 A CA 002134768A CA 2134768 A CA2134768 A CA 2134768A CA 2134768 A1 CA2134768 A1 CA 2134768A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
New siloxane copolymers having vinyloxy groups contain: (a) siloxane units having the formula (I): RaSi(OR1)bO(4-(a+b))/2 , and (b) at least one unit per molecule selected from the grou p of units having the formulae (II), (III), (IV) or (V), in which R, R1, Y, a, b, c, and x have the meaning given in the first claim.
Description
- 213~8 ~' WO 93J22368 - 1 - PCT/EP93/01113 ~ C~
Siloxane copolymer con~aining ~inyloxy group~, their preparation and their use The in~ention ralates to siloxane copolymers containing ~inyloxy groupa a~d to a process for their preparation. The in~e~tion further~ore relate~ to com-position~ which c~ be cro~slinked by light and are based on siloxane copolymers containi~g ~inyloxy group~.
Organopoly iloxane~ which contain, per molecule, at least one Si-bonded ~inyloxy-fu~ctional group of the ~ormula ~2C=CH-O-G-wherein ~ i~ an alkylene radical or an alkylene radical which is interrupted by at leaat one divalent hetero radical, ~uch as -O-, a di~alent phe~ylene radical or a ~ubstituted di~alent phenylene radical, or combinations of ~uch hetero radicals, are know~ from EP-~ 105 341.
These organopolysiloxanes are obtained by preparation of a compou~d ha~i~g an allyl and a vinyloxy group and addition of this compound onto the SiH groups of the organopolysiloxane~, hydrosilylation taking place only on the allyl group. EP-B 105 341 furthermore describes composition~ w~ich can be cros~linked by light and compri~e the abo~ementioned organopoly~iloxanes, and also onium salt~ which cataly~e the ~ationic polymerisation of the~e organopolyRiloxanes.
A ~ila~e which has one vinyloxypropyl group and at least one trimethylsiloxy group and which is obtained by hydrosilylation of allyl ~inyl ether with a silane containing trimethylsiloxy groups, addition taking place on the allyl group, i8 known for the production o~
pla~tic lenses from Chemical Abstracts 107, 176221q.
Orga~opoly~iloxanes which contain propenyloxy groups and siloxane copolymers which contain propenyloxy groupR are deRcribed in US-A 5,057,549 and C~-A
20 35 396, these compou~ds being prepared in a two-stage process by addition of compounds ha~ing two or more than - ~13~7~'' two allyloxy group~ onto si~ groups of organopolysilox-anes and ~ub~equent conversion o~ the allyloxy groups into the propenyloxy groups by addition o~ the double ¦bond.
Organopolysiloxanes which have any number of substituted vinyl ether groups and are prepared by hydrosilylation, that is to say by reaction of an organo-polysiloxane containing SiH group~ with a polyoxyalkylene ether, for example of the for~ula C-~2--c~i--cx2--o--(C~iz_c:w-O--) loH r C~2 C'~i ' C~
addition taking place on the allyl group, are known from US-A 5,145,915.
There was the obj,ect of providing siloxane copolymer~ which contain ~inyloxy groups and can be prepared in a simple process, the process allowing more than one ~inyloxy group to be introduced on one Rilicon atom. There was furthermore the object of pro~iding ~iloxane copolymers which contain ~inyloxy group~ and crosslink particularly rapidly under the action of light, in particular ultraviolet light, with cationic polymerisation. This object is achieved by the in~ention.
The invention relates to siloxane copolymers which contain vinyloxy groups and comprise (a) siloxane units of the formula . ~asi(OR )b4-(a~b) (I) wherein R denote~ identical or di~ferent, optionally halogenated hydrocarbon radicals having 1 to 18 21~317~Q
carbon ato~( 8 ) per radical, Rl denotes identical or differe~t alkyl radicals having 1 ko 4 carbon atom(~ per radical, which ca~
be subGtituted by a~ ether oxygen atom, a iB 0, 1, 2 or 3, b i~ 0, 1, 2 or 3 a~d the ~um of a+b i8 not greater than 3, (b) at least one unit per molecule chose~ from the group co~pri~ing U~i tB 0 f the for~ula ~ 4-(c'l) (II) 04 (c+l)RcSi-G -SiRco4_(c~l) (III) 4-(cll~Rcsi-G -SiRco4 ( (IV) and 2 liRc4_(c+l) : , 2 --S iRc4 ( c ' 1 ) O R Si l~ SiR o 2 SiRc4-(cll) (V) wherein R has the meaning gi~en above for thi~
radical, c i~ 0, 1 or 2, G denotes a radical of the formula - CH2CH20Y (OCH=C}I2) X-l wherein `-- 213Li7G~
Y denotes a divalent, trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having 1 to 20 carbon atoms per radical, which can be #ub~tituted by groups of the for~ula - 0~ .
2 (wherein R2 denotes an alkyl radical having 1 to 6 carbon atom(s) per radical) - osiR3 (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyi radical) - OCR2 (wherein R2 has the meaning given above 0 for this radical) or - X (wherein X denotes a halogen atom) -15 or can be interrupted by at least one oxygen atom, one carboxyl or one car~onyl group, and x is 2, 3, 4, 5 or 6, G1 denotes a radical of the formula ( C~I=CH2 ) X-Z
-Cx2cH20-~-ocH2c~2 ~2 denoteq a radical of the ~ormula ~ (OCH=CX2)x-3 ; ~ 20 -CH2C~2~-Y-0C~2c~2 and lCX2C~2-':~
:
G3 denotes a radical of the formula : (Cx=c~2)x-4 -CY.2 C~20~Y-~cx2 CX2 . (~C~C~2-)2 : wherein Y and x have the meaning given above for these eymbols~
The siloxane copolymers containing vinyloxy ~'~i.
21~ ~7~
groups preferably compri~e Riloxane unit3 of the formula (I), at least one siloxa~e unit of the formula (II~ per molecule and at least o~e unit 3elected from the group comprising the unit~ of the formulae (III), tIV) and (V) per molecule.
The in~ention furthermora relate~ to a proces for the preparation of the siloxa~e copolymers containing vinyloxy groups, characterised i~ that an organic com-pound (l) containing more than one vi~yloxy group, of the general formula y (oc~I=c~2) x (1) _ where Y and x have the meaning giYen above for these ~ymbol~ i~ reacted with a~ organopolysiloxane (2) ha~ing at lea~t ona Si-bonded hydroge~ atom per molecule, in the presence of a cataly~t (3) which promoten the addition of Si-bonded ~ydrogen onto an aliphatic double bond, the ratio employed of aliphatic double bond in the organic compound (1) to Si-bonded hydrogen in tha-organopoly-siloxane (2) i~ ch that siloxane copolymer~ containing ~inyloxy group~, having on a~erage at least one vinyloxy group of the formula -OC~=CH~
are obtained.
In the prior art, as in the abo~ementioned EP-B
105 341, neither ar~ siloxane copolymer8 containing vinyloxy groups described nor was it to be expected that such copolymers can be obtained by addition (hydrosilyla-tion) of SiH groups onto vinyloxy groups, since according to EP-B 105 341, the introduction of a ~inyloxy group into an organopolysiloxane i8 achieved only by hydro-silylation of a compound which containQ an allyl group and a ~inyloxy group, the addition taking place on the allyl group.
Preferably, x is 2, 3 or 4 and Y is a di~alent, tri~alent or tetravalent radical.
21~47~8 The organopolysiloxa~es according to the inven-tion whlch contain ~inyloxy group~ preferably have a ~i~cosity of 5 to 5x105 mPa s at 25C, preferably 50 to 50000 mPa-~ at 25C.
5The ~iloxane content in the ~iloxane copolymer~
according to the in~ention which contain ~inyloxy groups i8 preferably 20 to 90% by weight, ba~ed on the total weight of ~iloxane copolymers containing vinyloxy groups.
Examples of radicals R are alkyl radicals, such as the methyl~ ethyl, n-propyl, i~o-propyl, 1-n-butyl, 2-n-butyl, i80 -butyl~ tert-butyl, n-pentyl, i 80 -pentyl, neo-pentyl and tert-pentyl radical; hexyl radicals, such as the n-hexyl radical; heptyl radical&l ~uch as the _ n-heptyl radical; octyl radicals, such a~ the n-octyl 15radical aad i80~0ctyl radical~, 2uch a~ the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radical~, such as the n-decyl radical; dodecyl radical~, such as the n-dodecyl radical;
octadecyl radicals, such as the n-octadecyl radical;
cycloalk~l radical~, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicaln, su~h as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals; xylyl radical~ and ethylphenyl radical~; and aralkyl radicals, 3uch a~ the benzyl radical and the a and ~-phenylethyl radical. The methyl radical is preferred.
Examples of halogenated radicals R are halogeno-alkyl radicals, such as the 3,3,3-trifluoro-n-propyl 30radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and halogenoaryl radicals, 3uch as the o-, m- and p-chlorophenyl radical.
Examplea of alkyl radical~ R~ are the methyl, ethyl, n-propyl, iso-pr.opyl, 1-n-butyl, 2-n-butyl, i80-butyl and tert-butyl radical~ The methyl and ethyl r~dical are preferred. Exa~ple~ of alkyl radical~ R1 which are ~ubstituted by an ether oxygen atom are the methoxyethylene and ethoxyethylene radical.
Example~ of alkyl radical~ Ra are the methyl, - ~13~
, - 7 ethyl, n-propyl, i~o-propyl, 1-n-butyl, 2-n-butyl, i~o-butyl, tert-butyl, n-pe~tyl, iso-pentyl, neo-pentyl and tert-pentyl radical and hexyl radicals, such aR the n-hexyl radical.
Preferred ~iloxane copolymer~ containing vinyloxy grol~p~ are those which compri~e (a) siloxane u~itR of the formula R2SiO ~I') , (b) per molecule, at least two siloxane unit~ of the formula GR2SiO1~2 ~II') a~d per molecule, at least one unit of the formula 0l/2R2siGlsiR2ol~2 (III') wherein R, G~and G1 ha~e the meaning gi~en a~ove for 1~ these radicals.
Examples of the organic compound (1) which contains ~ore than one ~inyloxy group and i 8 employed in the proce~s according to the invention are those of the formula 20CH2=C~-O-CH2-CH2-0-CH=CH2 CH2=CH----( CH2 ) 4--0--CH=CH2 , CH2=C~----(CH2CH20)3-CH=CH2 CH2=c~-o-tc~2c~2c~2c~2o)n-cH-c~2 n=2-6 C~;2 -C~2 CH2=C~-O--C~2-c~ CH-C}I2-0-c~=c~2 cX2 -CH2 `- ~13 1~
.- 8 -O-CH=CH2 CH2=CX--0--CH--C:i2 -0-CH=CH2 1 ~2----CH=c-i2 CX3-C-CH2-0-cH=c~2 CY2-0-C~=CX2 C~3-cLc~2-otc~c~2o)m-cH=c~2~3 m=l-10 CH2-0-C~=CEi2 C~3--C~2- 1C--C~2--0--CH=CH2 ~n2 ~0~C~=Cn2 3-c~2-ctc~2-o(c~2cH2o)m-cH=c~2]~ m=l-10 CX2 -0--C~=CX2 }IO--CH2 -C-C~2 -0--CH=C~2 ~ ~ CH2--0--C~=CH2 ,. - ~, .
c~2--o--CH=C~2 CH2=CH-O--CH2--C-C~2-0-CH=CH2 C~2 -0-CX=C~2 (C~2=C~-0)2C~C~(O-cH=c~2)2 - (C~2=cH-~)2c~cH2c~(o-cH-c~2)2 CH3C(O-CH=cH2)3 (CX2=CY-o)cx2~cH(o-c~=c~2)]3cH2(o-~x=~2) and 13 i 7~ g ( cU.2=cu.-O ) C~2 t C~I ( O--C~=CH2 ) ] 4 CH2 ( 0--cH=cH2 ) Pref err~d example~ of the organic compound ( 1 ) are C~2~C~-o--~ C~I2 C~i~ O ) 3 -CH=C~I2 C~I2 -CH~
I
~2=~ ~-0-C~2-C~ C~--CH2-0-C~=CX2 C~i2 -CH2 CH3 -C ~ C~2--0--CH--C~2 ] 3 CH3-c~c~2-o (cH2cx2o~m-/~H=cH2] 3 m=l-10 CH3 -CX2-C ~ C~I2-0-CH=C~2 ~ 3 and CX3-C~2-C ~ C~2- (CH2C~20) m-CH=CH2 ] 3 m=l-lo .
Exam~?les of the radical Y are therefore those of the fonnula - (C}I2) 2 ~ (C~2) ~ ~
- (C~I2cH20) 2-C' 2-C~2-( CH2 Cr~2C~2 C~20 ) n- ~ C~2 C~2 CH2 CH2 - n=2--6 C~i2-C'' 2 -CX2-CY' C':.-CH2-c~;2 -Ci2 --C~--CY2--2 1 3 4 ~
CH3 -C-CX2 ~
CH2 - .
CH3 -C ~ CH2 - ( CH2 CX20 ) m-1C~2 C~2 ~ ] 3 m--1-10 lcx2-CY.3--C~2--c--c~2 C~i3-CH2~C~CX2-0(cH2c~2c))m-lc~2c~2~~3 m=l-10 I
HO--CH2 -C-C~2 -C~;2-'~ I ' -CX2-C-C~2-C~2---C~--CY--I I I
-CX2-CH-CH-CH-C~2- and 11 - 213 17!~g -'CH2 -CH-C~-C.i-C}i-C~2 -Proce~se~ for the preparation of the organlc ¦ compound (1) are described, for example, in PCT Applica-tion WO 91/05756- The basis of the prepara~ioIl iB the Reppe ~inylation which i8 known to the expert, in which alcohols are reacted catalytically with acetylene.
Typical impurities of industrial ~inyl ethers are vinyl ether-alcohols, which are retained a~ "intermediate ~tages" due to incomplete ~i~ylation, and, where approp-- riate, secondary products thereof formed by self-cyclisa-: 10 tion, such as, for example:
. .
-CH2 C'i2-OH
\ /
~ ~ C - >
I \
~, :CH2--CK--O--CH2 CH2--0-CX=cH2 CX3 -CH2 C~2 -C C~-CX3 CH2=cH-o-cx2 CX2-0 Organopolysiloxanes (2) ha~ing at least one Si-bo~ded hydrogen atom which are preferably employed in the ~:: process according to the in~ention are those of th~
general fornula HeRfSiO4-(e~f~ (VI) :: 2 wherein R has the meaning gi~en abo~e for this radical, ~: e i8 0 or 1, on a~erage 0.005 to 1.0, f i3 O, 1, 2 or 3, on a~erage 1.0 to 2.5, and the 8um of elf is not greater than 3.
Organopolysiloxanes (2) ha~ing at least one Si-~:~ bonded hydrogen atom which are preferably employed in the 213~7~o proce~fi according to the in~ention are those of the general formula EdR3 dsio (siR2o) 0 (SiR~o) pSi:lR3dH~, (VII) wherein R has the meaning given above for thi3 radical, S d is identical or different and i~ 0 or 1, o denotes 0 or an i~teger rom 1 to 1000 and p denotes 0 or an integer from 1 to 6.
The organopoly6iloxane~ (2) employed in the process according to the invention particularly prefer-ably contain 2 to 6 Si-bonded hydrogen atoms per mole-cule.
_ The organopoly~iloxane~ (23 which have at lea~t one Si-bonded hydrogen atom per molecule pre erably have a visco~ity of 0.5 to 20,000 mP~ 8 at 25C, preferably to lO00 mPa 8 at 25C.
Preferred example~ of organopolysiloxane~ of the formula (VII~ are copolymers of dimethylh~drido~iloxane and dimethylsiloxane unit~, copolymers of dimethyl-hydridosiloxane, dimethylsiloxane and methylhydrido-~iloxane units, copolymers of trimethylsiloxane andmethylhydridosiloxane units and copolymers of trimethyl-siloxane, dimethyl~iloxane and methylhydrido~iloxane unit~.
Processes for the preparation of organopolysilox-anes which have at least one Si-bonded hydrogen atom per molecule, including tho~e of the preferred type, are generally known.
- The organic co~pound (l) i8 employed in the process according to the invention in amounts such that the aliphatic double bond in the organic compound (1) is present in a ratio to the Si-bonded hydrogen in the organopoly~iloxane (2) of preferably 1.5:1 to 20:1, preferably 2:1 to 10:1. The organic compound (1) can be combined with the organopolysiloxane (2) almost as desired within very wide limit~, depending on its ~unc-tionality and its molecular weight. However, a C=C:SiH
ratio of greater than 20:1 leads exclu~ively to mono-~ 1 3 ~
hydrosilylation of the orgacic compou~d (1), which.is not preferred.
The reaction of the organic compound (1), ~uch as triethylene glycol di~inyl ether, with the organopoly-siloxane (2), such as a,~-dihydridodimethylpoly~iloxane, in the presence of the catalyst (3) proceeds in accord-ance with the following equation:
. HSiMe20(9iMe20)~,,SiMe2X + C~12=C~IO- (CH2CH20)3-CH=C}I2 ------~
- CH2=~Ho-(c~2cH2o)3-cH2cH2siMe2o(siMe2o)~siMe2cH2cx2o-- (Cx2cx2) 3-C~2CH25iMe20 (SiMe20) 3SiMe2C}I2CH2o-(CH2CX20) 3CH=~H2 The cour3e of the reaction and therefore the : resulting end product depends decisi~ely on the ratio : employed between the C=C double bond in the organic - :: 15 compound (1) and the -Si-bonded hydrogen in the organo-polysiloxane (2). Depending on the ratio of C=C:SiH
employed - where the C=C:SiH ratio must always be greater : than 1 - ~iloxane copolymers which contain free ~inyloxy groups of the formula -OC~=C~, . :
~:~ : at the chain end and along the chain (for example if an orga~nic compound (1) ha~ing more than two vinyloxy groups usedj are obtained, it being possible for branchings to occur along the chain by further reaction of the free ~ 25 vinyloxy groups along the chain with the Si-bonded , hydrogen atoms of the organopolysiloxane (2).
Catalysts (3) which promote the addition of Si-~; ~ bonded hydrogen onto an aliphatic multiple bond and which can be employed in the process according to the in~ention ;~ 30 are al~o the same catalysts which it has also been possible to employ to date for promoting addition of Si-bonded hydrogen onto an aliphatic double bond~ The : cataly~ts (3) are preferably a metal from the group of ; platinum metal~ or a compound or a complex from the group 1317(~8 of platinum metals. ~xamples of such catalysts are metallic and finely divided platinum, which can be on support~, ~uch as silicon dioxide, al~l~inium oxide or active charcoal, compounds and complexes of platinum, such as platinum halides, for example PtCl" ~2PtClc~6H20 or Na2PtCl~4H20, platinum-olefin complexe~, platinum-alcohol complexes, platinum-alcoholate complexes, plati-num-ether complexes, platinum-aldehyde complexes, ; platinum-ketone.complexes, including reaction products of H2PtClc*6H30 and cyclohexanone, plati~um-~inyl~iloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetra-methy}disiloxane complexes with or without a content of detecta~le inorganically bonded halogen, bis-(gamma-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, dimethyl sulphoxide-ethyle~e-platinum(II) dichloride and reaction products of platinum tetra-~:: chloride with an olefin and primary amine or secondary amine or a primary and secondary amine according to US-A
: 20 4,292,434, such as the reaction product of platinum tetrachloride diRsolved in 1-octene with sec-butylamine, and ammonium-platinum complexes according to EP-B
110 370, and compounds and complexes of rhodium, such as the rhodium complexes according to EP-A 476 426.
2~5 The catalyst (3) i8 preferably employed in amounts of 2 to 1000 ppm by weight (parts by weight per million partq by weight), preferably in amounts of 10 ~o 50 ppm by weight, in each case calculated as elemental platinum and based on the totaI weight of organic com-pound (1) and organopolysiloxane (2).
The process according to the invention is prefer-ably carried out under the pressure of the surrounding atmosphere, that is to say under about 1020 hPa (abso-lute); but it can also be carried out under higher or lower pressures. Furthermore, the process according to the invention is preferably carried out at a temperature of 50C to 170C, preferably 80C to 150C.
Inert, organic solvents can be co-used in the process according to the invention, although the co-use - 2 1 ~
of inert organic ~olvent~ is not preferred. Example~ of inert oxganic ~ol~ent~ are toluene, xylene, octane isomers, butyl acetate, 1,2-dimethoxyethane, tetrahydro-furan and cyclohexane.
Exce~s organic compound (1) and any inert organic sol~ent which haR been co-used are preferably remo~ed by di~tillation from the ~ilox ne copolymers prepared by the process according to the invention and containing ~inyl-oxy groups.
The siloxane copol~mer~ prepared by the process according to the invention and containing ~inyloxy group~
are equilibrated with an organopolysiloxane (41, if appropriate.
_ Organopoly~iloxane~ t4) which are used are preferably those chosen from the group co~prising linear organopolysiloxane~ co~taining terminal triorganosiloxy group~, of the formula R3SiO(5iR2O)rSiR3 wherein R has the meaning gi~en above for this radical and r i~ 0 or~an integer ha~ing a ~alue from 1 to 1500, linear organopolysiloxanes containing terminal hydroxyl groups, of the formula HO(SiR2O),H
wherein R has the meaning given abo~e for this radical and 8 is an integer having a ~alue from 1 to 1500, cyclic organopolysiloxane~ of the formula (R2SiO) ~
wherein R haR the meaning gi~en abo~e for this radical a~d t is an integ~er from 3 to 12, and copolymers of units of the formula R2SiO and Rsi3~a -- ~13~7~
wher in R has the meaning gi~e~ abo~e for thi~ radical.
The ratio of the amount~ of the orga~opoly~ilox-ane (4) employed in the equilibration which i~ to be carried out if appropriate and th~ siloxane copolymers containing ~i~yloxy group3 i5 determined ~erely by the desired content of ~inyloxy group~ in the siloxane copolymers produced by the equilibration which i~ carried out if appropriate and by the de~ired average chain length.
Basic catalyst3 which pro~ote the eguilibration are preferably employed in the e~uilibration which i8 carried out if appropriate. Examples of ~uch cataly8t8 are alkali metal hydroxides, ~uch as sodium hydroxide and - potas~ium hydroxide, trimethylbenzylammonium hydroxide and tetra~ethylammonium hydroxide. Alkali metal hydrox ides are preferred. Alkali metal hydroxide~ are preer-ably u~ed in amou~ts of 50 to 10,000 ppm by weight (= parts per millio~), in particular 500 to 2000 ppm by weight, in each case based o~ the total weight of ~ilox-ane copolymer containing vinyloxy group~ employed and organopolysiloxane (4) employed. Although it is possible to use acid equilibratio~ cataly~ts, this i8 not pre-ferred.
The equilibration which i8 carried out if approp-riate is preferably carried out at 100C to 150C under the pre~Qure of the surrounding atmosphere, that i~ to say at about 1020 hPa (absolute). If desired, howe~er, higher or lower pressures can also be used. The equili-bration i8 preferably carried out in a concentration of 5 to 20~ by weight, based on the total weight of the particular siloxane copolymer containing ~inyloxy groups employed and organopolysiloxane (4) employed, in a water-immi~cible sol~ent, ~uch as toluene. The catalyst can be rendered inacti~e before the mixture obtained in the equilibration is worked up.
The proces~ according to the in~ention can be carried out batchwise, ~emi-continuously or completely continuously.
The siloxane copolymers according to the in~en-. ~
213~
tion which contain ~inyloxy groups can be cros~linked cationically, for example by addition of acids, such a~
hydrochloric acids, ~ulphuric acid~ or p-toluene~ulpho~ic acids. The siloxane copolymer~ according to the in~ention which contain ~inyloxy groups are pr.eferably cros~linked in a cationic polymeri~ation iaitiated by light. Cata-ly ts which are used for the cros~linking initiated by light are preferably onium salts, such a~ diaryliodonium salts or triarylsulphonium salt~, which are known from EP-B 105 341 and the German application by the Applicant Company ha~ing the application number P 41 42 327.5.
Examples of such onium salts are the bis-(dodecylphenyl)-iodonium salts described in EP-B 105 341, such as bis-- (dodecylphenyl)iodonium hexafluoroantimon~te or bi3-~dodecylphenyl)iodonium hexafluoroar~enate, or the iodonium ~alts of the formula ~ J~- ~ D X~
wherein D danotes a radical of the formula -O-R~-SiR3 wherein R~ denotes a di~alent hydrocarbon radical ha~ing 1 to 18 carbon atoms per radical, which i~ optionally interrupted by at least one oxygen atom and/or one sulphur atom and/or one carboxyl group, R5 denotes a mono~alent hydrocarbon radical ha~ing 1 to 18 car~on atoms per radical, which is optionally inter-rupted by at least one oxygen atom, and X~ is a tosylate anion or a weakly nucleophilic or non-nucleophilic anion Y~ chosen from the group comprising CF3CO2-, BF~-, PF6-, AsF6, SbFC-, ClO~, ~SO~, CF3SO3 and C~FgSO3~
which are described in the German applicat~on having the application number P 41 42 327.5.
The in~ention therefore relates to the use of siloxane copolymers containing ~inyloxy groups, prefer-- ~13~7~
ably compri~ing units of the formula (I), (II) and if appropriate at least one of the units of the formula (III), (IV) or ~V), preferably comprising unit~ of the formulae (I'), (II') and (III'), in compo~itions which can be crosslinked by light and are based on the abo~e-mentioned ~iloxane copolymers.
The siloxane copol~mer~ according to the inven-tion which contain vinyloxy group~ are preferably cro~-linked by ultra~iolet light, that ha~ing wavelengths in the range from 200 to 400 nm being preferred. The ultraviolet light can be generated, for example, in xenon or low, medium or high pressure mercury lamp6.
Ultra~iolet light ha~ing a wa~elength of 400 ts 600 nm, _ that i_ to say Qo-called "halogen light" i8 al80 suitable for the crosslinking by light. The siloxane copolymers according to the in~ention which contain vinyloxy groups can be cro~slinked by light in the ~isible range if ; commercially a~ailable photosensitisers are also u_ed.
Thz cationic polymeri~ation of the silox~ne copolymers according to the in~ention which contain ~inyloxy groupQ can of course also be initiated by Bro~sted or Lewis acids customary for this purpose.
Finally, the invention also relates to the use of the siloxane copolymer~ according to the in~ention which contain ~inyloxy group_ for the production of coatingQ
which can be crosslinked by light.
The siloxane copolymers according to the inven-tion which contain Yinyloxy groups can be used in radia-tion-curing printing inks.
Example~ of surfaces onto which the coatings according to the in~ention can be applied are those of paper, wood, cork, fil~s of plastic, for example poly-ethylene film~ or polypropylene film~, ceramic objects, glass, including glass fibres, metals, pa~teboard, including that of asbestos, and wo~en and non-wo~en cloth of naturally occurring or synthetic organic ~ibre~.
The application of the siloxane copolymers according to the in~ention which contain ~inyloxy groups to the surfaces to be coated can be carried out in any .
o' ¦ desired ~aDner which i8 suitable a~d in many cases known for the production of coatings from liquid substance , for example by dipping, brushing, pouring, spraying, rolling, prin ing, for example by ~e~s of an o~fset gravure coating device, or knife or doctor blade coating.
Example 1:
238 g of a copolymer of hydridodimethylsiloxane and dimethylsiloxane units ha~ing a viscosity of 11 mm2/s at 25C, corresponding to 0.5 g o~ Si-bonded hydroge~, together with 78.5 g of the ~inyl ether of the formula C~i2 -C~2 `CH2=CX--O--C~2-C~ C~-C~2--0--CH=CH2 obtainable from GAF Chem. Corp. under the trade ~ame Rapi-Cure CXVE, are heated at 50C under a nitrogen atmosphere. 4 mg of platinum are added in the form of a 1~ ~olution of ~2PtCl6xH20 in isopropanol, after which the te~perature of~the reaction mixtura rises to about 130C.
The mixture is allowed to react at thi~ temperature for a further hour, a con~ersion o~ more than 99~ being achieved. 315 g of a copolymer which comprises alternat-ing siloxane and aliphatic ether blocks and has a vis-cosity of 9O 32/~ at 25C are obtained. In accordance with the preparation method, the linear block copolymer containQ ~inyl ether end groups, the average molecular weight being 1900. The product has a surface tension of 22 mN m~l.
Example 2:
336 g of of an a,~-dihydridodimethylpolysiloxane having a content of 0.149% of Si-bonded hydrogen are - mixed under turbulent conditions with 67 g of triethylene ~0 glycol divinyl ether (obtainable under the trade name Rapi-Cure DVE-3 from GAF Corp.) and the mixture is heated to about 80C. A solution of 14 mg of platinum tetra-chloride in a little 1-octene i8 added under a nitrogen 2 1 '~
atmosphere, after which the mixture heat~ up to 135C.
This temperature i~ maintained for a further hour and the mixture i~ cooled. In accordance with the ~ynthesis, the product has the structure of a linear block copolymer of S dimethylpolysiloxa~e and polyglycol chains having 2-~inyl ether end groups- The viscosity at 25C i~ 23S mml/s, and the a~erage molecular weight iB about 6000. The siloxane content is about 83~ by weight (from the lH-N~R
spectrum).
Example 3:
403 g of ~,~-dihydridod~methylpolysiloxane ha~ing a total of 0.25 g of Si-bonded hydrogen are mixed with 42 g of triethylene glycol di~inyl ether (obtainable - under the trade name Rapi-Cure DVE-3 from G~F Corp.) at 90C under nitrogen. 24 mg of hexachloroplatinic acid dis olved in a little isopropanol are added. A~ter the internal te~perature has risen, the mixture is allowed to react at 130C for another 3 hours, until a conversion of more than 99% is reached. Volatile co~titue~ts are removed at 100C under 5 hPa, after which a clear oil ha~ing a viscosity of 220 mm2/s at 25C i8 obtained. The strUcture in principle corresponds to the polymer product from Example 2; the siloxane chain length is now greater but the dimethylpolysiloxane chains alternate less often with the polyglycol chains. The siloxane content is now 91% by weight, at about the Qame a~erage molecular weight.
Example 4:
170 g of copolymer of trimethylsiloxane, dimethylsiloxane and hydridomethylsiloxane units having a ~iscosity of 90 mm2/s at 25C and a total of 80 mg of Si-bonded hydrogen are mixed with 29.5 g of the ~inyl ether Rapi-Cure CHVE, which is described in Example 1, and 4 mg of platinum in the form of a solution of PtCl~
in 1-octene. The mlxture i8 heated at 120C ~nder nitrogen for 3 hours, ~olatile contents are stripped off under 5 hPa, and a clear oil ha~ing a ~iscosity of 28Q
mm2/s at 25C is obtained. The copolymer has a branched structure, siloxane chains being bridged by aliphatic -213~76 ethers and at the same time having lateral vinyl ether groups~ It contains about 0.3 mol of vinyl ether double bonds per kg.
Example 5:
170 g of copolymer of trimethylsiloxane, di-methylsiloxane and hydridomethyl~iloxane u~its having a viscosity of 90 mm2/R at 25C are mixed with 20 g of the vinyl eth~r Rapi-Cure DVE-3~ which i8 described in Example 2, and the mixture i8 heated to 100C under a nitrogen atmosphere. After addition of 10 mg of ~2PtCl6 x X20, dissolYed in a little isopropanol, the internal temperature rises to just about 120C, where it i~ kept for a further 3 hours. After removal of volatile con-~ stituents in vacuo under 5 hPa, 175 g of a branched block copolymer of ~iloxane chain~ with polyglycol bridges and SiC-bonded vinyl ether groups are obtained after filtra-tion. The polymer product has a viscosity of 1200 mm~/8 at 25C and about 0.25 ~ol of vinyl ether double bonds per kg.
Example 6:
Siloxane copolymer con~aining ~inyloxy group~, their preparation and their use The in~ention ralates to siloxane copolymers containing ~inyloxy groupa a~d to a process for their preparation. The in~e~tion further~ore relate~ to com-position~ which c~ be cro~slinked by light and are based on siloxane copolymers containi~g ~inyloxy group~.
Organopoly iloxane~ which contain, per molecule, at least one Si-bonded ~inyloxy-fu~ctional group of the ~ormula ~2C=CH-O-G-wherein ~ i~ an alkylene radical or an alkylene radical which is interrupted by at leaat one divalent hetero radical, ~uch as -O-, a di~alent phe~ylene radical or a ~ubstituted di~alent phenylene radical, or combinations of ~uch hetero radicals, are know~ from EP-~ 105 341.
These organopolysiloxanes are obtained by preparation of a compou~d ha~i~g an allyl and a vinyloxy group and addition of this compound onto the SiH groups of the organopolysiloxane~, hydrosilylation taking place only on the allyl group. EP-B 105 341 furthermore describes composition~ w~ich can be cros~linked by light and compri~e the abo~ementioned organopoly~iloxanes, and also onium salt~ which cataly~e the ~ationic polymerisation of the~e organopolyRiloxanes.
A ~ila~e which has one vinyloxypropyl group and at least one trimethylsiloxy group and which is obtained by hydrosilylation of allyl ~inyl ether with a silane containing trimethylsiloxy groups, addition taking place on the allyl group, i8 known for the production o~
pla~tic lenses from Chemical Abstracts 107, 176221q.
Orga~opoly~iloxanes which contain propenyloxy groups and siloxane copolymers which contain propenyloxy groupR are deRcribed in US-A 5,057,549 and C~-A
20 35 396, these compou~ds being prepared in a two-stage process by addition of compounds ha~ing two or more than - ~13~7~'' two allyloxy group~ onto si~ groups of organopolysilox-anes and ~ub~equent conversion o~ the allyloxy groups into the propenyloxy groups by addition o~ the double ¦bond.
Organopolysiloxanes which have any number of substituted vinyl ether groups and are prepared by hydrosilylation, that is to say by reaction of an organo-polysiloxane containing SiH group~ with a polyoxyalkylene ether, for example of the for~ula C-~2--c~i--cx2--o--(C~iz_c:w-O--) loH r C~2 C'~i ' C~
addition taking place on the allyl group, are known from US-A 5,145,915.
There was the obj,ect of providing siloxane copolymer~ which contain ~inyloxy groups and can be prepared in a simple process, the process allowing more than one ~inyloxy group to be introduced on one Rilicon atom. There was furthermore the object of pro~iding ~iloxane copolymers which contain ~inyloxy group~ and crosslink particularly rapidly under the action of light, in particular ultraviolet light, with cationic polymerisation. This object is achieved by the in~ention.
The invention relates to siloxane copolymers which contain vinyloxy groups and comprise (a) siloxane units of the formula . ~asi(OR )b4-(a~b) (I) wherein R denote~ identical or di~ferent, optionally halogenated hydrocarbon radicals having 1 to 18 21~317~Q
carbon ato~( 8 ) per radical, Rl denotes identical or differe~t alkyl radicals having 1 ko 4 carbon atom(~ per radical, which ca~
be subGtituted by a~ ether oxygen atom, a iB 0, 1, 2 or 3, b i~ 0, 1, 2 or 3 a~d the ~um of a+b i8 not greater than 3, (b) at least one unit per molecule chose~ from the group co~pri~ing U~i tB 0 f the for~ula ~ 4-(c'l) (II) 04 (c+l)RcSi-G -SiRco4_(c~l) (III) 4-(cll~Rcsi-G -SiRco4 ( (IV) and 2 liRc4_(c+l) : , 2 --S iRc4 ( c ' 1 ) O R Si l~ SiR o 2 SiRc4-(cll) (V) wherein R has the meaning gi~en above for thi~
radical, c i~ 0, 1 or 2, G denotes a radical of the formula - CH2CH20Y (OCH=C}I2) X-l wherein `-- 213Li7G~
Y denotes a divalent, trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having 1 to 20 carbon atoms per radical, which can be #ub~tituted by groups of the for~ula - 0~ .
2 (wherein R2 denotes an alkyl radical having 1 to 6 carbon atom(s) per radical) - osiR3 (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyi radical) - OCR2 (wherein R2 has the meaning given above 0 for this radical) or - X (wherein X denotes a halogen atom) -15 or can be interrupted by at least one oxygen atom, one carboxyl or one car~onyl group, and x is 2, 3, 4, 5 or 6, G1 denotes a radical of the formula ( C~I=CH2 ) X-Z
-Cx2cH20-~-ocH2c~2 ~2 denoteq a radical of the ~ormula ~ (OCH=CX2)x-3 ; ~ 20 -CH2C~2~-Y-0C~2c~2 and lCX2C~2-':~
:
G3 denotes a radical of the formula : (Cx=c~2)x-4 -CY.2 C~20~Y-~cx2 CX2 . (~C~C~2-)2 : wherein Y and x have the meaning given above for these eymbols~
The siloxane copolymers containing vinyloxy ~'~i.
21~ ~7~
groups preferably compri~e Riloxane unit3 of the formula (I), at least one siloxa~e unit of the formula (II~ per molecule and at least o~e unit 3elected from the group comprising the unit~ of the formulae (III), tIV) and (V) per molecule.
The in~ention furthermora relate~ to a proces for the preparation of the siloxa~e copolymers containing vinyloxy groups, characterised i~ that an organic com-pound (l) containing more than one vi~yloxy group, of the general formula y (oc~I=c~2) x (1) _ where Y and x have the meaning giYen above for these ~ymbol~ i~ reacted with a~ organopolysiloxane (2) ha~ing at lea~t ona Si-bonded hydroge~ atom per molecule, in the presence of a cataly~t (3) which promoten the addition of Si-bonded ~ydrogen onto an aliphatic double bond, the ratio employed of aliphatic double bond in the organic compound (1) to Si-bonded hydrogen in tha-organopoly-siloxane (2) i~ ch that siloxane copolymer~ containing ~inyloxy group~, having on a~erage at least one vinyloxy group of the formula -OC~=CH~
are obtained.
In the prior art, as in the abo~ementioned EP-B
105 341, neither ar~ siloxane copolymer8 containing vinyloxy groups described nor was it to be expected that such copolymers can be obtained by addition (hydrosilyla-tion) of SiH groups onto vinyloxy groups, since according to EP-B 105 341, the introduction of a ~inyloxy group into an organopolysiloxane i8 achieved only by hydro-silylation of a compound which containQ an allyl group and a ~inyloxy group, the addition taking place on the allyl group.
Preferably, x is 2, 3 or 4 and Y is a di~alent, tri~alent or tetravalent radical.
21~47~8 The organopolysiloxa~es according to the inven-tion whlch contain ~inyloxy group~ preferably have a ~i~cosity of 5 to 5x105 mPa s at 25C, preferably 50 to 50000 mPa-~ at 25C.
5The ~iloxane content in the ~iloxane copolymer~
according to the in~ention which contain ~inyloxy groups i8 preferably 20 to 90% by weight, ba~ed on the total weight of ~iloxane copolymers containing vinyloxy groups.
Examples of radicals R are alkyl radicals, such as the methyl~ ethyl, n-propyl, i~o-propyl, 1-n-butyl, 2-n-butyl, i80 -butyl~ tert-butyl, n-pentyl, i 80 -pentyl, neo-pentyl and tert-pentyl radical; hexyl radicals, such as the n-hexyl radical; heptyl radical&l ~uch as the _ n-heptyl radical; octyl radicals, such a~ the n-octyl 15radical aad i80~0ctyl radical~, 2uch a~ the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radical~, such as the n-decyl radical; dodecyl radical~, such as the n-dodecyl radical;
octadecyl radicals, such as the n-octadecyl radical;
cycloalk~l radical~, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicaln, su~h as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals; xylyl radical~ and ethylphenyl radical~; and aralkyl radicals, 3uch a~ the benzyl radical and the a and ~-phenylethyl radical. The methyl radical is preferred.
Examples of halogenated radicals R are halogeno-alkyl radicals, such as the 3,3,3-trifluoro-n-propyl 30radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and halogenoaryl radicals, 3uch as the o-, m- and p-chlorophenyl radical.
Examplea of alkyl radical~ R~ are the methyl, ethyl, n-propyl, iso-pr.opyl, 1-n-butyl, 2-n-butyl, i80-butyl and tert-butyl radical~ The methyl and ethyl r~dical are preferred. Exa~ple~ of alkyl radical~ R1 which are ~ubstituted by an ether oxygen atom are the methoxyethylene and ethoxyethylene radical.
Example~ of alkyl radical~ Ra are the methyl, - ~13~
, - 7 ethyl, n-propyl, i~o-propyl, 1-n-butyl, 2-n-butyl, i~o-butyl, tert-butyl, n-pe~tyl, iso-pentyl, neo-pentyl and tert-pentyl radical and hexyl radicals, such aR the n-hexyl radical.
Preferred ~iloxane copolymer~ containing vinyloxy grol~p~ are those which compri~e (a) siloxane u~itR of the formula R2SiO ~I') , (b) per molecule, at least two siloxane unit~ of the formula GR2SiO1~2 ~II') a~d per molecule, at least one unit of the formula 0l/2R2siGlsiR2ol~2 (III') wherein R, G~and G1 ha~e the meaning gi~en a~ove for 1~ these radicals.
Examples of the organic compound (1) which contains ~ore than one ~inyloxy group and i 8 employed in the proce~s according to the invention are those of the formula 20CH2=C~-O-CH2-CH2-0-CH=CH2 CH2=CH----( CH2 ) 4--0--CH=CH2 , CH2=C~----(CH2CH20)3-CH=CH2 CH2=c~-o-tc~2c~2c~2c~2o)n-cH-c~2 n=2-6 C~;2 -C~2 CH2=C~-O--C~2-c~ CH-C}I2-0-c~=c~2 cX2 -CH2 `- ~13 1~
.- 8 -O-CH=CH2 CH2=CX--0--CH--C:i2 -0-CH=CH2 1 ~2----CH=c-i2 CX3-C-CH2-0-cH=c~2 CY2-0-C~=CX2 C~3-cLc~2-otc~c~2o)m-cH=c~2~3 m=l-10 CH2-0-C~=CEi2 C~3--C~2- 1C--C~2--0--CH=CH2 ~n2 ~0~C~=Cn2 3-c~2-ctc~2-o(c~2cH2o)m-cH=c~2]~ m=l-10 CX2 -0--C~=CX2 }IO--CH2 -C-C~2 -0--CH=C~2 ~ ~ CH2--0--C~=CH2 ,. - ~, .
c~2--o--CH=C~2 CH2=CH-O--CH2--C-C~2-0-CH=CH2 C~2 -0-CX=C~2 (C~2=C~-0)2C~C~(O-cH=c~2)2 - (C~2=cH-~)2c~cH2c~(o-cH-c~2)2 CH3C(O-CH=cH2)3 (CX2=CY-o)cx2~cH(o-c~=c~2)]3cH2(o-~x=~2) and 13 i 7~ g ( cU.2=cu.-O ) C~2 t C~I ( O--C~=CH2 ) ] 4 CH2 ( 0--cH=cH2 ) Pref err~d example~ of the organic compound ( 1 ) are C~2~C~-o--~ C~I2 C~i~ O ) 3 -CH=C~I2 C~I2 -CH~
I
~2=~ ~-0-C~2-C~ C~--CH2-0-C~=CX2 C~i2 -CH2 CH3 -C ~ C~2--0--CH--C~2 ] 3 CH3-c~c~2-o (cH2cx2o~m-/~H=cH2] 3 m=l-10 CH3 -CX2-C ~ C~I2-0-CH=C~2 ~ 3 and CX3-C~2-C ~ C~2- (CH2C~20) m-CH=CH2 ] 3 m=l-lo .
Exam~?les of the radical Y are therefore those of the fonnula - (C}I2) 2 ~ (C~2) ~ ~
- (C~I2cH20) 2-C' 2-C~2-( CH2 Cr~2C~2 C~20 ) n- ~ C~2 C~2 CH2 CH2 - n=2--6 C~i2-C'' 2 -CX2-CY' C':.-CH2-c~;2 -Ci2 --C~--CY2--2 1 3 4 ~
CH3 -C-CX2 ~
CH2 - .
CH3 -C ~ CH2 - ( CH2 CX20 ) m-1C~2 C~2 ~ ] 3 m--1-10 lcx2-CY.3--C~2--c--c~2 C~i3-CH2~C~CX2-0(cH2c~2c))m-lc~2c~2~~3 m=l-10 I
HO--CH2 -C-C~2 -C~;2-'~ I ' -CX2-C-C~2-C~2---C~--CY--I I I
-CX2-CH-CH-CH-C~2- and 11 - 213 17!~g -'CH2 -CH-C~-C.i-C}i-C~2 -Proce~se~ for the preparation of the organlc ¦ compound (1) are described, for example, in PCT Applica-tion WO 91/05756- The basis of the prepara~ioIl iB the Reppe ~inylation which i8 known to the expert, in which alcohols are reacted catalytically with acetylene.
Typical impurities of industrial ~inyl ethers are vinyl ether-alcohols, which are retained a~ "intermediate ~tages" due to incomplete ~i~ylation, and, where approp-- riate, secondary products thereof formed by self-cyclisa-: 10 tion, such as, for example:
. .
-CH2 C'i2-OH
\ /
~ ~ C - >
I \
~, :CH2--CK--O--CH2 CH2--0-CX=cH2 CX3 -CH2 C~2 -C C~-CX3 CH2=cH-o-cx2 CX2-0 Organopolysiloxanes (2) ha~ing at least one Si-bo~ded hydrogen atom which are preferably employed in the ~:: process according to the in~ention are those of th~
general fornula HeRfSiO4-(e~f~ (VI) :: 2 wherein R has the meaning gi~en abo~e for this radical, ~: e i8 0 or 1, on a~erage 0.005 to 1.0, f i3 O, 1, 2 or 3, on a~erage 1.0 to 2.5, and the 8um of elf is not greater than 3.
Organopolysiloxanes (2) ha~ing at least one Si-~:~ bonded hydrogen atom which are preferably employed in the 213~7~o proce~fi according to the in~ention are those of the general formula EdR3 dsio (siR2o) 0 (SiR~o) pSi:lR3dH~, (VII) wherein R has the meaning given above for thi3 radical, S d is identical or different and i~ 0 or 1, o denotes 0 or an i~teger rom 1 to 1000 and p denotes 0 or an integer from 1 to 6.
The organopoly6iloxane~ (2) employed in the process according to the invention particularly prefer-ably contain 2 to 6 Si-bonded hydrogen atoms per mole-cule.
_ The organopoly~iloxane~ (23 which have at lea~t one Si-bonded hydrogen atom per molecule pre erably have a visco~ity of 0.5 to 20,000 mP~ 8 at 25C, preferably to lO00 mPa 8 at 25C.
Preferred example~ of organopolysiloxane~ of the formula (VII~ are copolymers of dimethylh~drido~iloxane and dimethylsiloxane unit~, copolymers of dimethyl-hydridosiloxane, dimethylsiloxane and methylhydrido-~iloxane units, copolymers of trimethylsiloxane andmethylhydridosiloxane units and copolymers of trimethyl-siloxane, dimethyl~iloxane and methylhydrido~iloxane unit~.
Processes for the preparation of organopolysilox-anes which have at least one Si-bonded hydrogen atom per molecule, including tho~e of the preferred type, are generally known.
- The organic co~pound (l) i8 employed in the process according to the invention in amounts such that the aliphatic double bond in the organic compound (1) is present in a ratio to the Si-bonded hydrogen in the organopoly~iloxane (2) of preferably 1.5:1 to 20:1, preferably 2:1 to 10:1. The organic compound (1) can be combined with the organopolysiloxane (2) almost as desired within very wide limit~, depending on its ~unc-tionality and its molecular weight. However, a C=C:SiH
ratio of greater than 20:1 leads exclu~ively to mono-~ 1 3 ~
hydrosilylation of the orgacic compou~d (1), which.is not preferred.
The reaction of the organic compound (1), ~uch as triethylene glycol di~inyl ether, with the organopoly-siloxane (2), such as a,~-dihydridodimethylpoly~iloxane, in the presence of the catalyst (3) proceeds in accord-ance with the following equation:
. HSiMe20(9iMe20)~,,SiMe2X + C~12=C~IO- (CH2CH20)3-CH=C}I2 ------~
- CH2=~Ho-(c~2cH2o)3-cH2cH2siMe2o(siMe2o)~siMe2cH2cx2o-- (Cx2cx2) 3-C~2CH25iMe20 (SiMe20) 3SiMe2C}I2CH2o-(CH2CX20) 3CH=~H2 The cour3e of the reaction and therefore the : resulting end product depends decisi~ely on the ratio : employed between the C=C double bond in the organic - :: 15 compound (1) and the -Si-bonded hydrogen in the organo-polysiloxane (2). Depending on the ratio of C=C:SiH
employed - where the C=C:SiH ratio must always be greater : than 1 - ~iloxane copolymers which contain free ~inyloxy groups of the formula -OC~=C~, . :
~:~ : at the chain end and along the chain (for example if an orga~nic compound (1) ha~ing more than two vinyloxy groups usedj are obtained, it being possible for branchings to occur along the chain by further reaction of the free ~ 25 vinyloxy groups along the chain with the Si-bonded , hydrogen atoms of the organopolysiloxane (2).
Catalysts (3) which promote the addition of Si-~; ~ bonded hydrogen onto an aliphatic multiple bond and which can be employed in the process according to the in~ention ;~ 30 are al~o the same catalysts which it has also been possible to employ to date for promoting addition of Si-bonded hydrogen onto an aliphatic double bond~ The : cataly~ts (3) are preferably a metal from the group of ; platinum metal~ or a compound or a complex from the group 1317(~8 of platinum metals. ~xamples of such catalysts are metallic and finely divided platinum, which can be on support~, ~uch as silicon dioxide, al~l~inium oxide or active charcoal, compounds and complexes of platinum, such as platinum halides, for example PtCl" ~2PtClc~6H20 or Na2PtCl~4H20, platinum-olefin complexe~, platinum-alcohol complexes, platinum-alcoholate complexes, plati-num-ether complexes, platinum-aldehyde complexes, ; platinum-ketone.complexes, including reaction products of H2PtClc*6H30 and cyclohexanone, plati~um-~inyl~iloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetra-methy}disiloxane complexes with or without a content of detecta~le inorganically bonded halogen, bis-(gamma-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, dimethyl sulphoxide-ethyle~e-platinum(II) dichloride and reaction products of platinum tetra-~:: chloride with an olefin and primary amine or secondary amine or a primary and secondary amine according to US-A
: 20 4,292,434, such as the reaction product of platinum tetrachloride diRsolved in 1-octene with sec-butylamine, and ammonium-platinum complexes according to EP-B
110 370, and compounds and complexes of rhodium, such as the rhodium complexes according to EP-A 476 426.
2~5 The catalyst (3) i8 preferably employed in amounts of 2 to 1000 ppm by weight (parts by weight per million partq by weight), preferably in amounts of 10 ~o 50 ppm by weight, in each case calculated as elemental platinum and based on the totaI weight of organic com-pound (1) and organopolysiloxane (2).
The process according to the invention is prefer-ably carried out under the pressure of the surrounding atmosphere, that is to say under about 1020 hPa (abso-lute); but it can also be carried out under higher or lower pressures. Furthermore, the process according to the invention is preferably carried out at a temperature of 50C to 170C, preferably 80C to 150C.
Inert, organic solvents can be co-used in the process according to the invention, although the co-use - 2 1 ~
of inert organic ~olvent~ is not preferred. Example~ of inert oxganic ~ol~ent~ are toluene, xylene, octane isomers, butyl acetate, 1,2-dimethoxyethane, tetrahydro-furan and cyclohexane.
Exce~s organic compound (1) and any inert organic sol~ent which haR been co-used are preferably remo~ed by di~tillation from the ~ilox ne copolymers prepared by the process according to the invention and containing ~inyl-oxy groups.
The siloxane copol~mer~ prepared by the process according to the invention and containing ~inyloxy group~
are equilibrated with an organopolysiloxane (41, if appropriate.
_ Organopoly~iloxane~ t4) which are used are preferably those chosen from the group co~prising linear organopolysiloxane~ co~taining terminal triorganosiloxy group~, of the formula R3SiO(5iR2O)rSiR3 wherein R has the meaning gi~en above for this radical and r i~ 0 or~an integer ha~ing a ~alue from 1 to 1500, linear organopolysiloxanes containing terminal hydroxyl groups, of the formula HO(SiR2O),H
wherein R has the meaning given abo~e for this radical and 8 is an integer having a ~alue from 1 to 1500, cyclic organopolysiloxane~ of the formula (R2SiO) ~
wherein R haR the meaning gi~en abo~e for this radical a~d t is an integ~er from 3 to 12, and copolymers of units of the formula R2SiO and Rsi3~a -- ~13~7~
wher in R has the meaning gi~e~ abo~e for thi~ radical.
The ratio of the amount~ of the orga~opoly~ilox-ane (4) employed in the equilibration which i~ to be carried out if appropriate and th~ siloxane copolymers containing ~i~yloxy group3 i5 determined ~erely by the desired content of ~inyloxy group~ in the siloxane copolymers produced by the equilibration which i~ carried out if appropriate and by the de~ired average chain length.
Basic catalyst3 which pro~ote the eguilibration are preferably employed in the e~uilibration which i8 carried out if appropriate. Examples of ~uch cataly8t8 are alkali metal hydroxides, ~uch as sodium hydroxide and - potas~ium hydroxide, trimethylbenzylammonium hydroxide and tetra~ethylammonium hydroxide. Alkali metal hydrox ides are preferred. Alkali metal hydroxide~ are preer-ably u~ed in amou~ts of 50 to 10,000 ppm by weight (= parts per millio~), in particular 500 to 2000 ppm by weight, in each case based o~ the total weight of ~ilox-ane copolymer containing vinyloxy group~ employed and organopolysiloxane (4) employed. Although it is possible to use acid equilibratio~ cataly~ts, this i8 not pre-ferred.
The equilibration which i8 carried out if approp-riate is preferably carried out at 100C to 150C under the pre~Qure of the surrounding atmosphere, that i~ to say at about 1020 hPa (absolute). If desired, howe~er, higher or lower pressures can also be used. The equili-bration i8 preferably carried out in a concentration of 5 to 20~ by weight, based on the total weight of the particular siloxane copolymer containing ~inyloxy groups employed and organopolysiloxane (4) employed, in a water-immi~cible sol~ent, ~uch as toluene. The catalyst can be rendered inacti~e before the mixture obtained in the equilibration is worked up.
The proces~ according to the in~ention can be carried out batchwise, ~emi-continuously or completely continuously.
The siloxane copolymers according to the in~en-. ~
213~
tion which contain ~inyloxy groups can be cros~linked cationically, for example by addition of acids, such a~
hydrochloric acids, ~ulphuric acid~ or p-toluene~ulpho~ic acids. The siloxane copolymer~ according to the in~ention which contain ~inyloxy groups are pr.eferably cros~linked in a cationic polymeri~ation iaitiated by light. Cata-ly ts which are used for the cros~linking initiated by light are preferably onium salts, such a~ diaryliodonium salts or triarylsulphonium salt~, which are known from EP-B 105 341 and the German application by the Applicant Company ha~ing the application number P 41 42 327.5.
Examples of such onium salts are the bis-(dodecylphenyl)-iodonium salts described in EP-B 105 341, such as bis-- (dodecylphenyl)iodonium hexafluoroantimon~te or bi3-~dodecylphenyl)iodonium hexafluoroar~enate, or the iodonium ~alts of the formula ~ J~- ~ D X~
wherein D danotes a radical of the formula -O-R~-SiR3 wherein R~ denotes a di~alent hydrocarbon radical ha~ing 1 to 18 carbon atoms per radical, which i~ optionally interrupted by at least one oxygen atom and/or one sulphur atom and/or one carboxyl group, R5 denotes a mono~alent hydrocarbon radical ha~ing 1 to 18 car~on atoms per radical, which is optionally inter-rupted by at least one oxygen atom, and X~ is a tosylate anion or a weakly nucleophilic or non-nucleophilic anion Y~ chosen from the group comprising CF3CO2-, BF~-, PF6-, AsF6, SbFC-, ClO~, ~SO~, CF3SO3 and C~FgSO3~
which are described in the German applicat~on having the application number P 41 42 327.5.
The in~ention therefore relates to the use of siloxane copolymers containing ~inyloxy groups, prefer-- ~13~7~
ably compri~ing units of the formula (I), (II) and if appropriate at least one of the units of the formula (III), (IV) or ~V), preferably comprising unit~ of the formulae (I'), (II') and (III'), in compo~itions which can be crosslinked by light and are based on the abo~e-mentioned ~iloxane copolymers.
The siloxane copol~mer~ according to the inven-tion which contain vinyloxy group~ are preferably cro~-linked by ultra~iolet light, that ha~ing wavelengths in the range from 200 to 400 nm being preferred. The ultraviolet light can be generated, for example, in xenon or low, medium or high pressure mercury lamp6.
Ultra~iolet light ha~ing a wa~elength of 400 ts 600 nm, _ that i_ to say Qo-called "halogen light" i8 al80 suitable for the crosslinking by light. The siloxane copolymers according to the in~ention which contain vinyloxy groups can be cro~slinked by light in the ~isible range if ; commercially a~ailable photosensitisers are also u_ed.
Thz cationic polymeri~ation of the silox~ne copolymers according to the in~ention which contain ~inyloxy groupQ can of course also be initiated by Bro~sted or Lewis acids customary for this purpose.
Finally, the invention also relates to the use of the siloxane copolymer~ according to the in~ention which contain ~inyloxy group_ for the production of coatingQ
which can be crosslinked by light.
The siloxane copolymers according to the inven-tion which contain Yinyloxy groups can be used in radia-tion-curing printing inks.
Example~ of surfaces onto which the coatings according to the in~ention can be applied are those of paper, wood, cork, fil~s of plastic, for example poly-ethylene film~ or polypropylene film~, ceramic objects, glass, including glass fibres, metals, pa~teboard, including that of asbestos, and wo~en and non-wo~en cloth of naturally occurring or synthetic organic ~ibre~.
The application of the siloxane copolymers according to the in~ention which contain ~inyloxy groups to the surfaces to be coated can be carried out in any .
o' ¦ desired ~aDner which i8 suitable a~d in many cases known for the production of coatings from liquid substance , for example by dipping, brushing, pouring, spraying, rolling, prin ing, for example by ~e~s of an o~fset gravure coating device, or knife or doctor blade coating.
Example 1:
238 g of a copolymer of hydridodimethylsiloxane and dimethylsiloxane units ha~ing a viscosity of 11 mm2/s at 25C, corresponding to 0.5 g o~ Si-bonded hydroge~, together with 78.5 g of the ~inyl ether of the formula C~i2 -C~2 `CH2=CX--O--C~2-C~ C~-C~2--0--CH=CH2 obtainable from GAF Chem. Corp. under the trade ~ame Rapi-Cure CXVE, are heated at 50C under a nitrogen atmosphere. 4 mg of platinum are added in the form of a 1~ ~olution of ~2PtCl6xH20 in isopropanol, after which the te~perature of~the reaction mixtura rises to about 130C.
The mixture is allowed to react at thi~ temperature for a further hour, a con~ersion o~ more than 99~ being achieved. 315 g of a copolymer which comprises alternat-ing siloxane and aliphatic ether blocks and has a vis-cosity of 9O 32/~ at 25C are obtained. In accordance with the preparation method, the linear block copolymer containQ ~inyl ether end groups, the average molecular weight being 1900. The product has a surface tension of 22 mN m~l.
Example 2:
336 g of of an a,~-dihydridodimethylpolysiloxane having a content of 0.149% of Si-bonded hydrogen are - mixed under turbulent conditions with 67 g of triethylene ~0 glycol divinyl ether (obtainable under the trade name Rapi-Cure DVE-3 from GAF Corp.) and the mixture is heated to about 80C. A solution of 14 mg of platinum tetra-chloride in a little 1-octene i8 added under a nitrogen 2 1 '~
atmosphere, after which the mixture heat~ up to 135C.
This temperature i~ maintained for a further hour and the mixture i~ cooled. In accordance with the ~ynthesis, the product has the structure of a linear block copolymer of S dimethylpolysiloxa~e and polyglycol chains having 2-~inyl ether end groups- The viscosity at 25C i~ 23S mml/s, and the a~erage molecular weight iB about 6000. The siloxane content is about 83~ by weight (from the lH-N~R
spectrum).
Example 3:
403 g of ~,~-dihydridod~methylpolysiloxane ha~ing a total of 0.25 g of Si-bonded hydrogen are mixed with 42 g of triethylene glycol di~inyl ether (obtainable - under the trade name Rapi-Cure DVE-3 from G~F Corp.) at 90C under nitrogen. 24 mg of hexachloroplatinic acid dis olved in a little isopropanol are added. A~ter the internal te~perature has risen, the mixture is allowed to react at 130C for another 3 hours, until a conversion of more than 99% is reached. Volatile co~titue~ts are removed at 100C under 5 hPa, after which a clear oil ha~ing a viscosity of 220 mm2/s at 25C i8 obtained. The strUcture in principle corresponds to the polymer product from Example 2; the siloxane chain length is now greater but the dimethylpolysiloxane chains alternate less often with the polyglycol chains. The siloxane content is now 91% by weight, at about the Qame a~erage molecular weight.
Example 4:
170 g of copolymer of trimethylsiloxane, dimethylsiloxane and hydridomethylsiloxane units having a ~iscosity of 90 mm2/s at 25C and a total of 80 mg of Si-bonded hydrogen are mixed with 29.5 g of the ~inyl ether Rapi-Cure CHVE, which is described in Example 1, and 4 mg of platinum in the form of a solution of PtCl~
in 1-octene. The mlxture i8 heated at 120C ~nder nitrogen for 3 hours, ~olatile contents are stripped off under 5 hPa, and a clear oil ha~ing a ~iscosity of 28Q
mm2/s at 25C is obtained. The copolymer has a branched structure, siloxane chains being bridged by aliphatic -213~76 ethers and at the same time having lateral vinyl ether groups~ It contains about 0.3 mol of vinyl ether double bonds per kg.
Example 5:
170 g of copolymer of trimethylsiloxane, di-methylsiloxane and hydridomethyl~iloxane u~its having a viscosity of 90 mm2/R at 25C are mixed with 20 g of the vinyl eth~r Rapi-Cure DVE-3~ which i8 described in Example 2, and the mixture i8 heated to 100C under a nitrogen atmosphere. After addition of 10 mg of ~2PtCl6 x X20, dissolYed in a little isopropanol, the internal temperature rises to just about 120C, where it i~ kept for a further 3 hours. After removal of volatile con-~ stituents in vacuo under 5 hPa, 175 g of a branched block copolymer of ~iloxane chain~ with polyglycol bridges and SiC-bonded vinyl ether groups are obtained after filtra-tion. The polymer product has a viscosity of 1200 mm~/8 at 25C and about 0.25 ~ol of vinyl ether double bonds per kg.
Example 6:
4 mg of platinum in the form of a platinum-1,3-divinyl-1,1,3;3-tetramethyldisiloxane complex are added to 202 g of the vinyl ether Rapi-Cure DYE-3, which is described in Example 2, and the mixture is heated to 90C
under a nitrogen atmosphere. A total of 69 g of 1,3-dihydridotetramethyldisiloxane are metered in over a period of about 1.5 hour~, and the reaction is brought to completion at about 130C. After removal of volatile compound~ at 160C under 5 hPa, a polymeric difunctional vinyl ether having a ~iscosity of 44 mm2/s at 25C is obtained in a quantitative yield. It can be seen from the ~_NMR spectrum that the C=C/SiCH2 ratio has a ~alue of 0.61. The product contains 2.6 mol of vinyl ether double ~onds per kg. It has a surface ten~ion of 28 mN m-l.
Example 7:
To prepare a vinyl ether/siloxane copolymer branched via the ether blocks, Example 1 is repeated with 100 g of trimethylolpropane trivinyl ether instead of the divinyl ether used therein. After the end of the - 2i3~7~
hydrosilyl~tion reaction, the excess vinyl ether i~
removed at 160C under 3 hPa, after which a clear ail having a viscosity-of 145 mm2/s at 25C i3 obtained. The branched block copolymer contains di~inyl ether end groups and a siloxane content of 76% by weight. It contains about 1.6 mol of vinyl ether dou~le bonds per kg.
Example 8:
10 g of the block copolymer prepared in Example 6 are mixed with 0.1 g of [4-[2-(3-dioctylmethylsilyl-propyloxy)ethoxy]phenyl]-iodonium hexafluoroantimonate (preparation described in the German application ha~ing the application number P 41 42 327.5) at 22C and the mixture is applied in a thin layer of about 4 ~m to polyethylene-coated paper using a glass rod. After an exposure t~me of 0.15 second using a medium pressure mercury lamp (80 watt/cm) at a distance of 10 cm, the b}ock copolymer has hardened to an abrasion-resistant p~roduct.
Example 9: ~
17C g of the copolymer used in Example 4 are mixed together with 17 g of butane-1,4-diol divinyl ether, inhibited with 100 ppm of ROH, and 2 mg of plati-num in the form of its 1,3-di~inyltetramethylsiloxane complex,~ and the mixture i~ heated to 136C. After a reaction time of 3 hours under nitrogen, more than 97% of the acti~e hydrogen groups ha~e been consumed, after - which excess di~inyl ether is remo~ed at 160C under 5 hPa. A branched copolymer of aliphatic ether units and 30 siloxane blocks ha~ing a ~i8c08ity of 330 mm2 8~l at 25C
j - ~ i8 obtained. It contains about 0.27 mol of ~inyl ether double bonds per kg.
~.' .
:
under a nitrogen atmosphere. A total of 69 g of 1,3-dihydridotetramethyldisiloxane are metered in over a period of about 1.5 hour~, and the reaction is brought to completion at about 130C. After removal of volatile compound~ at 160C under 5 hPa, a polymeric difunctional vinyl ether having a ~iscosity of 44 mm2/s at 25C is obtained in a quantitative yield. It can be seen from the ~_NMR spectrum that the C=C/SiCH2 ratio has a ~alue of 0.61. The product contains 2.6 mol of vinyl ether double ~onds per kg. It has a surface ten~ion of 28 mN m-l.
Example 7:
To prepare a vinyl ether/siloxane copolymer branched via the ether blocks, Example 1 is repeated with 100 g of trimethylolpropane trivinyl ether instead of the divinyl ether used therein. After the end of the - 2i3~7~
hydrosilyl~tion reaction, the excess vinyl ether i~
removed at 160C under 3 hPa, after which a clear ail having a viscosity-of 145 mm2/s at 25C i3 obtained. The branched block copolymer contains di~inyl ether end groups and a siloxane content of 76% by weight. It contains about 1.6 mol of vinyl ether dou~le bonds per kg.
Example 8:
10 g of the block copolymer prepared in Example 6 are mixed with 0.1 g of [4-[2-(3-dioctylmethylsilyl-propyloxy)ethoxy]phenyl]-iodonium hexafluoroantimonate (preparation described in the German application ha~ing the application number P 41 42 327.5) at 22C and the mixture is applied in a thin layer of about 4 ~m to polyethylene-coated paper using a glass rod. After an exposure t~me of 0.15 second using a medium pressure mercury lamp (80 watt/cm) at a distance of 10 cm, the b}ock copolymer has hardened to an abrasion-resistant p~roduct.
Example 9: ~
17C g of the copolymer used in Example 4 are mixed together with 17 g of butane-1,4-diol divinyl ether, inhibited with 100 ppm of ROH, and 2 mg of plati-num in the form of its 1,3-di~inyltetramethylsiloxane complex,~ and the mixture i~ heated to 136C. After a reaction time of 3 hours under nitrogen, more than 97% of the acti~e hydrogen groups ha~e been consumed, after - which excess di~inyl ether is remo~ed at 160C under 5 hPa. A branched copolymer of aliphatic ether units and 30 siloxane blocks ha~ing a ~i8c08ity of 330 mm2 8~l at 25C
j - ~ i8 obtained. It contains about 0.27 mol of ~inyl ether double bonds per kg.
~.' .
:
Claims (9)
1. Siloxane copolymers containing vinyloxy groups and comprising (a) siloxane units of the formula (I) wherein R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different alkyl radicals having 1 to 4 carbon atoms per radical, which can be substituted by an ether oxygen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and the sum of a+b is not greater than 3, (b) at least one unit per molecule chosen from the group comprising units of the formula (II) (III) (IV) and (V) wherein R has the meaning given above for this radical, c is 0, 1 or 2, G denotes a radical of the formula - CH2CH2OY(OCH=CH2)x-1 wherein Y denotes a divalent, trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having 1 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH
- OR2 (wherein R2 denotes an alkyl radical hav-ing 1 to 6 carbon atoms per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) - O?R2 (wherein R2 has the meaning given above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x is 2, 3, 4, 5 or 6, G1 denotes a radical of the formula , G2 denotes a radical of the formula and G3 denotes a radical of the formula , wherein Y and x have the meaning given above for these symbols.
- OR2 (wherein R2 denotes an alkyl radical hav-ing 1 to 6 carbon atoms per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) - O?R2 (wherein R2 has the meaning given above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x is 2, 3, 4, 5 or 6, G1 denotes a radical of the formula , G2 denotes a radical of the formula and G3 denotes a radical of the formula , wherein Y and x have the meaning given above for these symbols.
2. Siloxane copolymers containing vinyloxy groups, according to Claim 1, characterised is that the siloxane units of the formula (I) contain, per molecule, at least one siloxane unit of the formula (II) and, per molecule, at least one unit selected from the group comprising the units of the formulae (III), (IV) and (V).
3. Siloxane copolymers containing vinyloxy groups, according to Claim 1 or 2, characterised in that they comprise (a) siloxane units of the formula R2SiO (I') , (b) per molecule, at least two siloxane units of the formula GR2SiO1/2 (II') and per molecule, at least one unit of the formula O1/2R2SiG1SiR2O1/2 (III') wherein R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, G denotes a radical of the formula - CH2CH2OY(OCH=CH2)x-1 and G1 denotes a radical of the formula wherein Y denotes a divalent, trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having 1 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH
- OR2 (wherein R2 denotes an alkyl radical hav-ing 1 to 6 carbon atoms per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) -O?R2 (wherein R2 has the meaning above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x denotes 2, 3, 4, 5 or 6.
- OR2 (wherein R2 denotes an alkyl radical hav-ing 1 to 6 carbon atoms per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) -O?R2 (wherein R2 has the meaning above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x denotes 2, 3, 4, 5 or 6.
4. Process for the preparation of the siloxane copolymers containing vinyloxy groups, characterised in that an organic compound (1) containing more than one vinyloxy group, of the general formula Y (OCH=CH2)x (1) wherein Y denotes a divalent, trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having 1 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH
- OR2 (wherein R2 denotes an alkyl radical having 1 to 6 carbon atom(s) per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) (wherein R2 has the meaning given above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x is 2, 3, 4, 5 or 6.
is reacted with an organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule, in the presence of a catalyst (3) which promotes the addition of Si-bonded hydrogen onto an aliphatic double bond, the ratio employed of aliphatic double bond in the organic compound (1) to Si-bonded hydrogen in the organopolysiloxane (2) is such that siloxane copolymers containing vinyloxy groups, having on average at least one vinyloxy group of the formula -OCH=CH2 are obtained.
- OR2 (wherein R2 denotes an alkyl radical having 1 to 6 carbon atom(s) per radical) - OSiR? (wherein R3 denotes a methyl, ethyl, isopropyl, tert-butyl or phenyl radical) (wherein R2 has the meaning given above for this radical) or - X (wherein X denotes a halogen atom) or can be interrupted by at least one oxygen atom, one carboxyl or one carbonyl group, and x is 2, 3, 4, 5 or 6.
is reacted with an organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule, in the presence of a catalyst (3) which promotes the addition of Si-bonded hydrogen onto an aliphatic double bond, the ratio employed of aliphatic double bond in the organic compound (1) to Si-bonded hydrogen in the organopolysiloxane (2) is such that siloxane copolymers containing vinyloxy groups, having on average at least one vinyloxy group of the formula -OCH=CH2 are obtained.
5. Process according to Claim 4, characterised in that CH2=CH-O-(CH2CH2O)3-CH=CH2 , CH3-CH2-C[CH2-O-CH=CH2]3 is used as the organic compound (1).
6. Process according to Claim 4, characterised in that the organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule which is used is one of the general formula HdR3-dSiO(SiR2O)o(SiRHO)pSiR3-dHd (VII) wherein R denotes identical or different, optionally halogenated hydrocarbon radicals with 1 to 18 carbon atom(s) per radical, d is identical or different and is 0 or 1, o denotes 0 or an integer from 1 to 1000 and p denotes 0 or an integer from 1 to 6.
7. Process according to Claim 4, 5 or 6, charac-terised in that the resulting siloxane copolymer contain-ing vinyloxy groups is equilibrated with an organopoly-siloxane (4) chosen from the group comprising linear organopolysiloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copoly-mers of diorganosiloxane and monoorganosiloxane units.
8. Use of the siloxane copolymers containing vinyl-oxy groups according to Claim 1, 2 or 3 in compositions which can be crosslinked by light and are based on the abovementioned siloxane copolymers.
9. Use of the siloxane copolymers containing vinyl-oxy groups according to Claim 1, 2 or 3 for the produc-tion of coatings which can be crosslinked by light.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4215076.0 | 1992-05-07 | ||
| DE4215076A DE4215076A1 (en) | 1992-05-07 | 1992-05-07 | Siloxane copolymers containing vinyloxy groups, their preparation and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2134768A1 true CA2134768A1 (en) | 1993-11-11 |
Family
ID=6458359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002134768A Abandoned CA2134768A1 (en) | 1992-05-07 | 1993-05-06 | Siloxane copolymers containing vinyloxy groups, their preparation and use |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0639205B1 (en) |
| JP (1) | JPH0832787B2 (en) |
| KR (1) | KR0152307B1 (en) |
| AT (1) | ATE141626T1 (en) |
| CA (1) | CA2134768A1 (en) |
| DE (2) | DE4215076A1 (en) |
| ES (1) | ES2090995T3 (en) |
| FI (1) | FI945178A (en) |
| TW (1) | TW225544B (en) |
| WO (1) | WO1993022368A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5594042A (en) * | 1993-05-18 | 1997-01-14 | Dow Corning Corporation | Radiation curable compositions containing vinyl ether functional polyorganosiloxanes |
| DE4420062A1 (en) * | 1994-06-08 | 1995-12-14 | Wacker Chemie Gmbh | Radically crosslinkable alkenyl ether siloxane compositions |
| DE19718634A1 (en) * | 1997-05-02 | 1998-11-05 | Wacker Chemie Gmbh | Radiation- or thermosetting organosiloxane compositions with (methyl) styrene groups |
| DE19731961A1 (en) * | 1997-07-24 | 1999-01-28 | Wacker Chemie Gmbh | Alkenyloxy group-containing organo-silicon compound |
| DE19856115A1 (en) | 1998-12-04 | 2000-06-21 | Wacker Chemie Gmbh | Siloxane copolymers containing alkenyl groups |
| DE10020670A1 (en) * | 2000-04-27 | 2001-08-09 | Clariant Gmbh | Organosiloxane derivatives with side chains derived from polyalkylene glycol vinyl ether compounds by hydrosilylation reactions, used as foam suppressants for paint and foam stabilizers for polyurethane foam |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0105341B1 (en) * | 1982-04-01 | 1987-01-07 | General Electric Company | Vinyloxy-functional organopolysiloxanes compositions |
| DE3914896A1 (en) * | 1989-05-05 | 1990-11-22 | Wacker Chemie Gmbh | ENOXY-FUNCTIONAL ORGANOSILICIUM COMPOUNDS, THEIR PRODUCTION AND USE |
| WO1991005756A1 (en) * | 1989-10-20 | 1991-05-02 | Gaf Chemicals Corporation | Trivinyl ethers of polyols |
| DE4002922A1 (en) * | 1990-02-01 | 1991-08-08 | Wacker Chemie Gmbh | Alkenyloxy gp.-contg. siloxane! copolymers |
| DE4002879A1 (en) * | 1990-02-01 | 1991-08-08 | Wacker Chemie Gmbh | Alkenyl gp.-contg. siloxane! copolymers |
| DE4009889C1 (en) * | 1990-03-28 | 1991-06-13 | Th. Goldschmidt Ag, 4300 Essen, De |
-
1992
- 1992-05-07 DE DE4215076A patent/DE4215076A1/en not_active Withdrawn
-
1993
- 1993-03-25 TW TW082102269A patent/TW225544B/zh active
- 1993-05-06 ES ES93909910T patent/ES2090995T3/en not_active Expired - Lifetime
- 1993-05-06 DE DE59303512T patent/DE59303512D1/en not_active Expired - Fee Related
- 1993-05-06 KR KR1019940703870A patent/KR0152307B1/en not_active IP Right Cessation
- 1993-05-06 JP JP5518938A patent/JPH0832787B2/en not_active Expired - Lifetime
- 1993-05-06 AT AT93909910T patent/ATE141626T1/en not_active IP Right Cessation
- 1993-05-06 EP EP93909910A patent/EP0639205B1/en not_active Expired - Lifetime
- 1993-05-06 WO PCT/EP1993/001113 patent/WO1993022368A1/en active IP Right Grant
- 1993-05-06 CA CA002134768A patent/CA2134768A1/en not_active Abandoned
-
1994
- 1994-11-03 FI FI945178A patent/FI945178A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2090995T3 (en) | 1996-10-16 |
| DE59303512D1 (en) | 1996-09-26 |
| EP0639205B1 (en) | 1996-08-21 |
| KR950701358A (en) | 1995-03-23 |
| JPH07502776A (en) | 1995-03-23 |
| ATE141626T1 (en) | 1996-09-15 |
| TW225544B (en) | 1994-06-21 |
| DE4215076A1 (en) | 1993-11-11 |
| FI945178A0 (en) | 1994-11-03 |
| KR0152307B1 (en) | 1998-10-15 |
| JPH0832787B2 (en) | 1996-03-29 |
| WO1993022368A1 (en) | 1993-11-11 |
| EP0639205A1 (en) | 1995-02-22 |
| FI945178A (en) | 1994-11-03 |
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