CA1122604A - Complex platinum catalysts for hydrosilation reactions - Google Patents
Complex platinum catalysts for hydrosilation reactionsInfo
- Publication number
- CA1122604A CA1122604A CA304,414A CA304414A CA1122604A CA 1122604 A CA1122604 A CA 1122604A CA 304414 A CA304414 A CA 304414A CA 1122604 A CA1122604 A CA 1122604A
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- Prior art keywords
- bond
- substituted
- bonded
- platinum
- ligand
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/90—Compositions for taking dental impressions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
ABSTRACT OF THE DISCLOSURE
An improved catalytic process is provided for the addition of Si-bonded hydrogen to an aliphatic multiple bond or for curing, a mixture of an organopolysiloxane containing alkenyl groups, and an organopolysilox-une containing silicon-bonded hydrogen atoms, or for preparing a dental impression from such mixture. The reaction takes place in the presence of a platinum catalyst selected from the group consisting of (I) XPtY, (II)
An improved catalytic process is provided for the addition of Si-bonded hydrogen to an aliphatic multiple bond or for curing, a mixture of an organopolysiloxane containing alkenyl groups, and an organopolysilox-une containing silicon-bonded hydrogen atoms, or for preparing a dental impression from such mixture. The reaction takes place in the presence of a platinum catalyst selected from the group consisting of (I) XPtY, (II)
Description
2~
The present invention relates to a process for th~ addition of Si-bonded hydrogen to an aliphatic m~ltiple bond and ~Dre particularly to a process for the addition of Si-bonded hydrogen to an aliphatic multiple bond in the presence of a platinum catalyst.
Heretofore it has been kncwn that a number of platinumrcontaining materials will catalyze the addition of silicon-bonded hydrogen atoms across the double bonds of compounds containing olefinic unsaturation. This addition is sometLmes referred to as "hy~rosilation" and may be illustrated by n~ans of the follcwing equation:
-Sili~ C=C ~ -SiC-CH
M~ny of the kncwn hydrosilation pr3cesses involve the employment of a platinum catalyst in the form of a halogenated platinum compound, e.g.
described in U.S. Patent No. 2,823,218 to Speier which utilizes chlor~pla-tinic acid as the platillum catalyst. Other hydrosilation processes inv~lve the employment of platinum catalysts in the form of platinum-vinylsiloxanes which are substantially free of chemically combined halogen such as described in U.S. Patents 3,715,334; 3,779,452 and 3,814,730 to Karstedt. Additional processes are shown in U.S. Patents 3,159,601 to ~shby and 3,723,497 to Baney.
Alt~ough the above~described platinum materials catalyze the addition of silicon-konded hydrogen atoms to alipha~ic double bonds, the catalysts used in the process of aspects of this invention are substantially ~ore effective than the catalysts known heretofore. Thus, in order to achieve the same results, smaller amounts of platinum may be employed in the process of aspects of this invention ~len using the catalysts described herein as compared to the catalysts known heretofore. In o~herwords, t~h~n the same amDunt of platinum is used in the process of aspects of this in-vention, the reaction time is substantially less ~lan ~hen the catalysts ~ 2 -l~Z260~
known heretofore were employed in the hydrosilation processes.
Therefore, it is an object of one aspect of this invent on to provide for the platinum catalyzed addition of silicon-bonded hydrogen atoms to compounds containing aliphatic multiple bonds.
An object of another aspect of this invention is to provide a hydrosilation process which utilizes a platinum catalyst that is substanti-ally more effective than the platinum catalysts used heretofore. An object of a further aspect of this invention is to provide a process for the addition of silicon-bonded hydrogen atoms to compounds containing aliphatic bonds.
In accordance with a broad aspect of this invention, an improve-ment is provided in a process for effecting the addition of silicon-bonded hydrogen atoms to compounds containing aliphatic multiple bonds in the presence of a platinum catalyst, which improved process comprises: contact-ing a silicon compound containing Si-bonded hydrogen with compounds contain-ing an aliphatic multiple bond in the presence of a platinum catalyst selected from the class consisting of (I) XPtY, ~II) X'Pt~ z ~PtXI (III) APt(Y'~X", and mixtures thereof, in which A is a halogen, X is an unsub-stituted hydrocarbon radical or a substituted such hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 aliphatic double bonds,which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substitu~ed with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded-to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bnnd, X" is an un-substituted hydrocarbon or a substitited such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
The present invention relates to a process for th~ addition of Si-bonded hydrogen to an aliphatic m~ltiple bond and ~Dre particularly to a process for the addition of Si-bonded hydrogen to an aliphatic multiple bond in the presence of a platinum catalyst.
Heretofore it has been kncwn that a number of platinumrcontaining materials will catalyze the addition of silicon-bonded hydrogen atoms across the double bonds of compounds containing olefinic unsaturation. This addition is sometLmes referred to as "hy~rosilation" and may be illustrated by n~ans of the follcwing equation:
-Sili~ C=C ~ -SiC-CH
M~ny of the kncwn hydrosilation pr3cesses involve the employment of a platinum catalyst in the form of a halogenated platinum compound, e.g.
described in U.S. Patent No. 2,823,218 to Speier which utilizes chlor~pla-tinic acid as the platillum catalyst. Other hydrosilation processes inv~lve the employment of platinum catalysts in the form of platinum-vinylsiloxanes which are substantially free of chemically combined halogen such as described in U.S. Patents 3,715,334; 3,779,452 and 3,814,730 to Karstedt. Additional processes are shown in U.S. Patents 3,159,601 to ~shby and 3,723,497 to Baney.
Alt~ough the above~described platinum materials catalyze the addition of silicon-konded hydrogen atoms to alipha~ic double bonds, the catalysts used in the process of aspects of this invention are substantially ~ore effective than the catalysts known heretofore. Thus, in order to achieve the same results, smaller amounts of platinum may be employed in the process of aspects of this invention ~len using the catalysts described herein as compared to the catalysts known heretofore. In o~herwords, t~h~n the same amDunt of platinum is used in the process of aspects of this in-vention, the reaction time is substantially less ~lan ~hen the catalysts ~ 2 -l~Z260~
known heretofore were employed in the hydrosilation processes.
Therefore, it is an object of one aspect of this invent on to provide for the platinum catalyzed addition of silicon-bonded hydrogen atoms to compounds containing aliphatic multiple bonds.
An object of another aspect of this invention is to provide a hydrosilation process which utilizes a platinum catalyst that is substanti-ally more effective than the platinum catalysts used heretofore. An object of a further aspect of this invention is to provide a process for the addition of silicon-bonded hydrogen atoms to compounds containing aliphatic bonds.
In accordance with a broad aspect of this invention, an improve-ment is provided in a process for effecting the addition of silicon-bonded hydrogen atoms to compounds containing aliphatic multiple bonds in the presence of a platinum catalyst, which improved process comprises: contact-ing a silicon compound containing Si-bonded hydrogen with compounds contain-ing an aliphatic multiple bond in the presence of a platinum catalyst selected from the class consisting of (I) XPtY, ~II) X'Pt~ z ~PtXI (III) APt(Y'~X", and mixtures thereof, in which A is a halogen, X is an unsub-stituted hydrocarbon radical or a substituted such hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 aliphatic double bonds,which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substitu~ed with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded-to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bnnd, X" is an un-substituted hydrocarbon or a substitited such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
- 3 -~L~2~604 By another aspect of this invention, an lmprovement is provided in a process for curing an organopolysiloxane containing alkenyl groups and an organopolysiloxane containing silicon-bonded hydrogen atoms in the presence of a platinum catalyst, the improvement comprising mixing the alkenyl-containing organopolysiloxane with the silicon-bonded hydro-gen-containing organopolysiloxane in the presence of a platinum catalyst selected from the group consisting of (I) XPtY, ~II) X'Pt~ z -PtX', (III) APt(Y~)X", and mixtures thereof, in which A is a halogen, X is an unsub-stituted hydrocarbon radical or a substituted such hydrocarbon radical substieuted with an alkoxy or acyloxy group and has from 1 to 3 aliphatic double bonds,which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an un-substituted hydrocarbon or a substituted such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-dike-tonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
By another aspect , an improvement is provided in a process for preparing a dental compression, including the steps of applying a mix-ture containing an organopolysiloxane having alkenyl groups and an organo-hydrogenpolysiloxane containin~ silicon-bonded hydrogen atoms and a plati-num catalyst to a tooth of which an impression is to be ta~en, curing the material and thereafter removing the resultant impression from the tooth, the improvement COmprising usl.ng,as a platinum catalyst, a catalyst selec-ted from the group consisting of (1) XPtY, ~II) X'Pt ~z, PtX', (III) APt(Y')X", and mixtures thereof, in which A is halogen, X is an unsub-stituted hydrocarbon radical or a substituted such hydrocarbon radical substituted wit~ an alkoxy or acyloxy group and has from 1 to 3 aliphatic llZZ60~
double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy gro~p and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an un-substituted hydrocarbon or a substituted such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-dikaton-ate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
By one variant, the platinum catalyst has the formula:
( C1~3~) 2 C~
~ t ~ .
f ~
C1~3 Cl~ cll3 By another variantl the platinum catalyst has the formula:
P~
Pt \
Cl fl Pt ~?~
~ ~ 5 -By a variant thereof, the platinum catalyst i5 acetylacetona-techloro(ethylene~-platinum-(II).
By another variant, the organopolysiloxane contains at least two alkenyl groups per molecule and the organohydrogenpolyslloxane con-tains at least three silicon bonded hydrogen atoms per molecule.
By a further variant, the catalytic reaction is affected at a temperature up to 150C.
Thè radicals represented by X and X',which may be the same or different, are substituted or unsubstituted hydrocarbon radicals. Pre-ferably by variants of this invention these hydrocarbon radicals have only one aliphatic double bond. Examples of groups which may be linked to the hydrocarbon radicals X are the acetylacetonyl radical, as well as alkoxy and acyloxy groups having from 1 to 3 carbon atoms. It is preferred by other variants that the alkoxy or acyloxy groups linked to the hydrocarbon radicals X' have from 1 to 3 carbon atoms. Furthermore, it is preferred `t~ - 5 a -by still otl~er variants of this invention that Z be Cl or RC00 radicals, where R is a hydrocarbon radical and more preferably a hydrocarbon radical having from 1 to 3 carbon atoms, e.g., the methyl, n-propyl, isopropyl, vinyl or allyl radical. Because of their availability, it is preferred that A be chlorine and that X" by ethylene.
Compounds represented by class (I~ and their processes of pre-paration are de~cri~ed for example by B.F.G. Johnson and associates in the "Journal of the Chemical Society", section A, 1968, pages 1993 to 2001, as well as by J.K. Stille and associates, in the "Journal of the American Chemical Society", Volume 92, 1970, pages 1274 to 1278. Excellent results according to one variant of this Lnvention are obtained using a oo~pound having the following form~la: -A
~cH3 o)2~ ?
o, o C~ `. ~c ~hich may be referred to as "(acac-C ~8)Pttacac~"O
Cbmpounds represented by class (II~ and their methods of prepara tion are descriked for example by J. Chatt and associates, in the l'Journal of the Chemical Society", 1957, pages 2496 to 2505~ Excellent results are obtained according to another variant of this invention with a campound o~rres~onaing to the following form~la:
_ 6 C1130~
\ ~
Pt / \
Cl Cl \ /
P~: .
which may be referred to as "[(CH30-CloH12)PtCl]~".
Co~pounds represented by Class (III) and their processes of pre-p æ ation æe described for example by C.E. Hollch~ay and associates in the "Journal of the Chemical Society", section A, 1970, pages 1653 to 1658.
Outstanding results accordLng to another variant are achiev,ed. using acetylacetonatochloro~ethylene)-platinum~ which can be a~breviated as "(C2H41PtCl(acac)".
Examples of compounds relating to class (I) having chelate-like bonded beta-diketonate ligands according to another væiant æ e the follcw~
- ing:
(acac-C7H8~Pt(acac) (Bzac-C7H8~Pt(9zac) (acac-C8H12)Pt(acac) (Bzac~ 8H12)Pt(Bzac) (acac-C10Hl2)Pt(acac) (szac-cloHl~pt(Bzac) -~ ~ (R~-C7H8~Pt(acac) ( ~C8H12) t( ~m) (R~C8H12)Pt(acac) 7H8)Pt(dbm) Hl2)pt~Etac) ,.
~1 - 7 -_ _, . . . .... .
3L:lZZ60~
E~lmples of ccn~ounds o: class (I~ having chelate~ e bonded arylcarbo.~ylate ligands according to another variant are the following:
(C6l~5cOc-c7H8~Pt(c6H5 (o-rmr,p~l3C6H4COO-C7H8~Pt(o ,m ~P-~3 6 4 (C6El5OQO-cloHl2~Pt~c6 5 P- 3 6 4COO CloHl2)pt(o-rm-~p-cH3c6El4coo) Additional examples of compounds of cla~ss (II~ according to another variant are:
[(R~-C7H8~PtC1]2 ` 10 O-C8lll2)Ptc~]2 [(Ro-C10l1l2)rtcl]2 0-C7~18)rtBr~2 [(CU3C00-C71-18)Pt(C113C0)]2 [(C~13C00-C811l2)It(CH3C00)]2 [(C1~3COC~-CloHl2)rt(C113C00)]2 - [(R0-c6Hlo)Ptcl]2 Examples of compounds of class (III) according bo ano~
variant are the following:
(C21~)PtC].(acac) (C2114)PtCl(Bzac) (C2114)PtCl(3Facac) (C2~4)PtBr(acac) (C3~16)PtCl(acac) (C3116)PLCl(Bz~c) (C3116)PtCl(3Facac) (C112=C11011)rtCl(acac) In tlle preceding examples of compounds of classes (I), (II) and (III) the above abbreviations represent the following 20 radicals:
acac = acetylacetonate radical Bzac = benzoylacetonate radical 3Facac = trifluoroacetylacetonate radical dbm = diben70y].methyl radical Etac = ethylacetoacetate radical R = C~13, C2115 or n C3 7 C7~]8 = norbornadiene C8Hl~ = ]5-cyclooctadiene CloHl2 = dicyclopentadiene 6 ~0 .= ]lexadiene-(1.5) o-,m-,p-, = ortho, meta or para-substitlltion on the benzene ring l~le "hy~rosilation" process of aspects of this invention could be described as the addition of a silicon compound having Si-bonded h~drogen to cc~pounds containing an aliphatic multiple bond. The amounts ofcatalyst used in the process of aspects of this invention may be the same as those which have been used heretofore in tlle addition of Si-bonded hy-drogen to an aliphatic multiple hond in the pres~ce of a platinum catalyst.
Generally, the amount of catalyst is at least 10 10 gram atom, and more preferably frcm 10 8 to 10 3 gram atom of platinum, calculated as elemental platinum, for each gram atom of Si-bonded hydrogen. Nevertheless, it should 10 be noted that smaller amounts of catalyst, calculated as elem~ntal platinum, are required in the process of aspects of this invention than were required - in the processes kncwn hereto~ore for the addition Si-bonded hydrogen to an aliphatic multiple bond in the presence of platinum catalyst under identi-cal conditions, i.e., temperature and time.
me pressure and temperatures used in the process of aspects of this invention may be same as those which were used in the processes known heretofore for the addition of Si-bonded hydrogen to an aliphatic m~ltiple bond in the presence of a platinum catalyst. The process is generally carried out at te~peratures between room temperature and 150C and at 20 atmospheric pressure, i.e., 760 mm Hg (abs.~ or approxlmately 760 mm Hg (abs.~.
m e process of aspects of this invention may be used whenever monomeric or polymeric silicon compounds having Si-bonded hydrogen are to be added to m~nomeric or polymeric compounds having an aliphatic multiple bond. Depending upon which compounds are to be added, the addition can produce other moncmeric compounds. Fbr example 3-chloropropyltrichlorosil-ane can he prepared by reacting trichlorosilane with allyl chloride, or n-propyltrichlorosilane can be prepared by reacting pro~ne with trichloro-sik~ne. ~lso methacryloxy~ropyltrichlorosilane can be prepared by the addition o~ ~richlorosilane to allylmethacryla~e or vin~lmethyldichlorosil-- lG -~Z;~:6~
and can be prepared by rPacting acetylene with methyldichlorosilane. In addition, modified dimeric or polymeric compounds containing silicon can be prepared by the addition of Si-bonded hydrogen to compounds containing aliphatic multiple bonds. For example, vinyltrichlorosilane can be reacted with trichlorosilane to form bis-(1,2-trichlorosilyl)-ethane. Also the number of aliphatic multiple bonds in polymers, for example poly(oxyalkyl-ene)polyols, can be decreased by reacting polymers containing aliphatic multiple bonds with organopolysiloxanes having at least two Si-bonded hy-drogen atoms per molecule.
10Surprisin~ly, the platinum catalysts used in accordance with the process of aspects of this invention are more effective during cross-linking, i.e., curing of vulcanization of compounds which contain alkenyl groups, especially vinyl groups, and organopolysiloxanes containing Si-bonded hydrogen. Consequently~ the process of aspects of this invention i5 preferred for the crosslinking of such compounds which may for example be used as potting or coating substances including substances used for ad-hesive repellent coatings, on for example paper or molds especially those used in the pouring of concrete. These catalysts are especially effective - in the preparation of materials used for making human or animal dental im-pressions.
When the platinum catalysts are used in accordance with aspects of this invention for cross-linking organopolysiloxane compositions, the organopolysiloxane composition contains (a) an organopolysiloxane contain-ing preferably at least two alkenyl groups and (b) organohydrogenpolysilox-anes having silicon-bonded hydrogen atoms.
Organopolysiloxanes (a) containing alkenyl groups are known in the art and are described, for example in U.S. Patents 3,723,497 issued March 19, 1973 to Banly and 3,950,300 lssued April 4, 1976 to Hittmair et al. Suitable examples of organopolysiloxanes are preferably diorganopoly-,'3 .~
6~4 siloxanes having triorganosiloxy terminal groups having at least one vinylgroup in each terminal unit. These organopolysiloxanes have a viscosity of from 500 to 300,000 cs. and more preferably from 2000 up to 100,000 cs.
at 25C.
The organohydrogenpolysiloxanes (b) containing silicon-bonded atoms are described, for example in the above identified U.S. Patents 3,723,497 and 3,950~300. Preferably these organohydrogenpolysiloxanes have at least three silicon-bonded hydrogen atoms per molecule. Generally, these organohydrogenpolysiloxanes contain from 0.01 to 1.7 percent by weight of silicon-bonded hydrogen atoms and the silicon vanences not satis-fied by hydrogen atoms and siloxane oxygen atoms are satisfied by sut-stituted and unsubstituted monovalent hydrocarbon radicals free of alipha-tic unsaturation.
. .
60~
Tllc le~ t;ve amoullt ot componcnts (a) alld (b) emp]oyed are such that Crom 0.75 to 5 gram atoms oF s:ili.con-botlded hydrogen are presellt Lrom coml-onent (b) per ~ram molecule of alkenyl group prcsent from component (a).
In order o prepare a cross-linkable compo.sltion, components (a) and (b) and optionally oLher addi.tivcs are normally mixed with the platinum catalYst at environmental tempera;ures and pre.ssures i.c., from : room temperature and 760 mm llg (abs.).
In the examples, all parts and percentages are by weigllt unless oLllerwi.se spcciied.
EXA~IPLE 1 - Mixtu_e_A
400 grams of a mixture consisting of 150 parts of a dimethylpolysi].oxane having vinyldimethy]siJ.oxy terminal groups and a viscosity of 1200 cP at 23C, 68 parts of a dimethyl-~olysiloxane having vinyld:imethylsiloxy terminal groups and a viscosity of 22,000 cP at 23C, 174 parts of cristobalite meal and 8.6 parts of a commercially available treatcd silicon dioxide pyrogenically produced in the gaseous phase and havi.ng a surface area of 200 m /gm, which has been rendercd 60 percent hydrophobic by reacting with dimethyldiclllorosilane, are mixed - with 1.6 grams of a 1 percent platinum (calculated as the element) solution of (acac-C7l~8)Pt(acac) in methy].ene ch]oride, so as to form a mixturc whicll contains 40 ppm of platinum, (calculated as the element).
Mixtllre B
_ .
- 60 parts of the dimetlly]po]ysi]oxane having vinyldimethylsiloxy terminal groups and a viscosity of 1200 cP at 23C are mixecl with 31 parts of the dimethylpolysiloxane havi.llg vinyldimethylsiloxy terminal groups and a viscosity of 22,000 cP at 23C, 83 parts of cristobalite meal, 5 parts of the trcatcd silicon dioxide described in the preparation of mixture A, and 25 parts of a copolymer having a viscosity of 7700 c~ at 23C
and consisting of dimethylsiloxane~ methyl.hydrogensiloxane and trimethylsiloxane units, with the molar ratio of the dimethyl-siloxane units to the methylcllogensiloxane units being 9:1.
Mixtures A and B are stored at room temperature for 3 days and then mixed togethcr in a weight ratio of 1:1. At room tcml~erO;ure, the time elal~sod beLween thc mixing of mixt~lres 13 and A and t~e cross:linliing of the compounds is 50 seconds .
Example 2 The procedure described in Example ] is repeated, except that 1.6 grams of a ] percent: platinum so]ution (calculatecl as the elem~nt) of [(Cli3-C10ll12)PtCl]2 is substituted for (acac-C7H8(Pt(acac).
At room temperature, the elapsed timc between the initial addition of mixture 13 al-d mixture A and observable rross-linking of the composition is 70 seconds.
Example 3 The procedure describcd in Example 1 is repeated, except that 1.6 grams of a 1 percent platinum solution (cal-culated as the elemellt) of (C2H4)PtCl(acac) in methylene chlorideis substituted for (acac--C7]18)Pt(acac)-At room temperature, the elapsed time between theinitial addition of mixture B to mixture A and observable cross-linking is 30 seconds.
Comparison Example a T~e proceduL-e described in Example 1 is repeated, except that 1.6 grams of a 1 percent platinum solution (calculated as the element) of a platinum-diviny]tetramethyldisiloxane in di-methylpolysiloxane having vinyldimethylsiloxy terminal groups is substituted for (acac-C7H8)Pt(acac). The procedure for preparing the catalyst is described in ~xample 6 of U.S. Patent No.
3,814,730.
To a mixture containing 10 parts of H2PtC16 6}l20 and 20 parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 50 parcs ethanol, was added 20 parts of sodium hicarbonate. For 30 minutes the mixture was refluxed under coDstant agitation and then allowed to stand for 15 hours. After filtration the volatile components were removed from the filtrate by distillation at approximately 12 mm Hg (abs.). The residue was dissolved in benzene and the solution filtered and the benzene removed from the filtrate by distillation. The residue was tllen dissolved in dimethylpolysiloxane having vinyldimethylsiloxy terminal groups and a viscosity of 1400 cP at 23C at a ra~e so that the so.lution con':ains ] percellt plati.lulll, calcll]ated as the elemer~.
~ 1~ room tclllpcr.lt-lre, tlle e:lap~sed ti.me beLween thc init:ial acldi~-ltll o~ mixture B to mixture A alld observab]e cross-linkin~ was 2 min~l~es ant1 lO seconds.
Co~ iso~ E~t~ r~
The process described in Example 1 was repeated except that 1.6 gram~s of a 1 percent platinum solution (calcu].ated as - element) of (PtC12'C2114)2 in methylene chloride (descri.bed in U.S. Patent 3,159,601) is substituted for (acac-C7H8)Pt(acac).
~ At room temperature, the elapsed t:ime between the initial incorporatioil of mixture B in mixture A and observable cross]inking of the compos;.tion was 10 minutes.
Comparison F.xam~_~ c The procedtlre described in ~xample l. was repeated, except Illat l.G grams of a 1 percent platinum solution (ca]culated as the element) o' platinum-(II)-diacetylacetonate in methylene chloride (described in U.S. Patent 3,723,497) was substituted ' for the (acac-C7H8)Pt(acac).
At room temperature, the elapsed time between the initial incorporation of mixture B in mixture A and observable crossli.nking of tlle composition was 3 hours.
By another aspect , an improvement is provided in a process for preparing a dental compression, including the steps of applying a mix-ture containing an organopolysiloxane having alkenyl groups and an organo-hydrogenpolysiloxane containin~ silicon-bonded hydrogen atoms and a plati-num catalyst to a tooth of which an impression is to be ta~en, curing the material and thereafter removing the resultant impression from the tooth, the improvement COmprising usl.ng,as a platinum catalyst, a catalyst selec-ted from the group consisting of (1) XPtY, ~II) X'Pt ~z, PtX', (III) APt(Y')X", and mixtures thereof, in which A is halogen, X is an unsub-stituted hydrocarbon radical or a substituted such hydrocarbon radical substituted wit~ an alkoxy or acyloxy group and has from 1 to 3 aliphatic llZZ60~
double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy gro~p and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an un-substituted hydrocarbon or a substituted such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-dikaton-ate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
By one variant, the platinum catalyst has the formula:
( C1~3~) 2 C~
~ t ~ .
f ~
C1~3 Cl~ cll3 By another variantl the platinum catalyst has the formula:
P~
Pt \
Cl fl Pt ~?~
~ ~ 5 -By a variant thereof, the platinum catalyst i5 acetylacetona-techloro(ethylene~-platinum-(II).
By another variant, the organopolysiloxane contains at least two alkenyl groups per molecule and the organohydrogenpolyslloxane con-tains at least three silicon bonded hydrogen atoms per molecule.
By a further variant, the catalytic reaction is affected at a temperature up to 150C.
Thè radicals represented by X and X',which may be the same or different, are substituted or unsubstituted hydrocarbon radicals. Pre-ferably by variants of this invention these hydrocarbon radicals have only one aliphatic double bond. Examples of groups which may be linked to the hydrocarbon radicals X are the acetylacetonyl radical, as well as alkoxy and acyloxy groups having from 1 to 3 carbon atoms. It is preferred by other variants that the alkoxy or acyloxy groups linked to the hydrocarbon radicals X' have from 1 to 3 carbon atoms. Furthermore, it is preferred `t~ - 5 a -by still otl~er variants of this invention that Z be Cl or RC00 radicals, where R is a hydrocarbon radical and more preferably a hydrocarbon radical having from 1 to 3 carbon atoms, e.g., the methyl, n-propyl, isopropyl, vinyl or allyl radical. Because of their availability, it is preferred that A be chlorine and that X" by ethylene.
Compounds represented by class (I~ and their processes of pre-paration are de~cri~ed for example by B.F.G. Johnson and associates in the "Journal of the Chemical Society", section A, 1968, pages 1993 to 2001, as well as by J.K. Stille and associates, in the "Journal of the American Chemical Society", Volume 92, 1970, pages 1274 to 1278. Excellent results according to one variant of this Lnvention are obtained using a oo~pound having the following form~la: -A
~cH3 o)2~ ?
o, o C~ `. ~c ~hich may be referred to as "(acac-C ~8)Pttacac~"O
Cbmpounds represented by class (II~ and their methods of prepara tion are descriked for example by J. Chatt and associates, in the l'Journal of the Chemical Society", 1957, pages 2496 to 2505~ Excellent results are obtained according to another variant of this invention with a campound o~rres~onaing to the following form~la:
_ 6 C1130~
\ ~
Pt / \
Cl Cl \ /
P~: .
which may be referred to as "[(CH30-CloH12)PtCl]~".
Co~pounds represented by Class (III) and their processes of pre-p æ ation æe described for example by C.E. Hollch~ay and associates in the "Journal of the Chemical Society", section A, 1970, pages 1653 to 1658.
Outstanding results accordLng to another variant are achiev,ed. using acetylacetonatochloro~ethylene)-platinum~ which can be a~breviated as "(C2H41PtCl(acac)".
Examples of compounds relating to class (I) having chelate-like bonded beta-diketonate ligands according to another væiant æ e the follcw~
- ing:
(acac-C7H8~Pt(acac) (Bzac-C7H8~Pt(9zac) (acac-C8H12)Pt(acac) (Bzac~ 8H12)Pt(Bzac) (acac-C10Hl2)Pt(acac) (szac-cloHl~pt(Bzac) -~ ~ (R~-C7H8~Pt(acac) ( ~C8H12) t( ~m) (R~C8H12)Pt(acac) 7H8)Pt(dbm) Hl2)pt~Etac) ,.
~1 - 7 -_ _, . . . .... .
3L:lZZ60~
E~lmples of ccn~ounds o: class (I~ having chelate~ e bonded arylcarbo.~ylate ligands according to another variant are the following:
(C6l~5cOc-c7H8~Pt(c6H5 (o-rmr,p~l3C6H4COO-C7H8~Pt(o ,m ~P-~3 6 4 (C6El5OQO-cloHl2~Pt~c6 5 P- 3 6 4COO CloHl2)pt(o-rm-~p-cH3c6El4coo) Additional examples of compounds of cla~ss (II~ according to another variant are:
[(R~-C7H8~PtC1]2 ` 10 O-C8lll2)Ptc~]2 [(Ro-C10l1l2)rtcl]2 0-C7~18)rtBr~2 [(CU3C00-C71-18)Pt(C113C0)]2 [(C~13C00-C811l2)It(CH3C00)]2 [(C1~3COC~-CloHl2)rt(C113C00)]2 - [(R0-c6Hlo)Ptcl]2 Examples of compounds of class (III) according bo ano~
variant are the following:
(C21~)PtC].(acac) (C2114)PtCl(Bzac) (C2114)PtCl(3Facac) (C2~4)PtBr(acac) (C3~16)PtCl(acac) (C3116)PLCl(Bz~c) (C3116)PtCl(3Facac) (C112=C11011)rtCl(acac) In tlle preceding examples of compounds of classes (I), (II) and (III) the above abbreviations represent the following 20 radicals:
acac = acetylacetonate radical Bzac = benzoylacetonate radical 3Facac = trifluoroacetylacetonate radical dbm = diben70y].methyl radical Etac = ethylacetoacetate radical R = C~13, C2115 or n C3 7 C7~]8 = norbornadiene C8Hl~ = ]5-cyclooctadiene CloHl2 = dicyclopentadiene 6 ~0 .= ]lexadiene-(1.5) o-,m-,p-, = ortho, meta or para-substitlltion on the benzene ring l~le "hy~rosilation" process of aspects of this invention could be described as the addition of a silicon compound having Si-bonded h~drogen to cc~pounds containing an aliphatic multiple bond. The amounts ofcatalyst used in the process of aspects of this invention may be the same as those which have been used heretofore in tlle addition of Si-bonded hy-drogen to an aliphatic multiple hond in the pres~ce of a platinum catalyst.
Generally, the amount of catalyst is at least 10 10 gram atom, and more preferably frcm 10 8 to 10 3 gram atom of platinum, calculated as elemental platinum, for each gram atom of Si-bonded hydrogen. Nevertheless, it should 10 be noted that smaller amounts of catalyst, calculated as elem~ntal platinum, are required in the process of aspects of this invention than were required - in the processes kncwn hereto~ore for the addition Si-bonded hydrogen to an aliphatic multiple bond in the presence of platinum catalyst under identi-cal conditions, i.e., temperature and time.
me pressure and temperatures used in the process of aspects of this invention may be same as those which were used in the processes known heretofore for the addition of Si-bonded hydrogen to an aliphatic m~ltiple bond in the presence of a platinum catalyst. The process is generally carried out at te~peratures between room temperature and 150C and at 20 atmospheric pressure, i.e., 760 mm Hg (abs.~ or approxlmately 760 mm Hg (abs.~.
m e process of aspects of this invention may be used whenever monomeric or polymeric silicon compounds having Si-bonded hydrogen are to be added to m~nomeric or polymeric compounds having an aliphatic multiple bond. Depending upon which compounds are to be added, the addition can produce other moncmeric compounds. Fbr example 3-chloropropyltrichlorosil-ane can he prepared by reacting trichlorosilane with allyl chloride, or n-propyltrichlorosilane can be prepared by reacting pro~ne with trichloro-sik~ne. ~lso methacryloxy~ropyltrichlorosilane can be prepared by the addition o~ ~richlorosilane to allylmethacryla~e or vin~lmethyldichlorosil-- lG -~Z;~:6~
and can be prepared by rPacting acetylene with methyldichlorosilane. In addition, modified dimeric or polymeric compounds containing silicon can be prepared by the addition of Si-bonded hydrogen to compounds containing aliphatic multiple bonds. For example, vinyltrichlorosilane can be reacted with trichlorosilane to form bis-(1,2-trichlorosilyl)-ethane. Also the number of aliphatic multiple bonds in polymers, for example poly(oxyalkyl-ene)polyols, can be decreased by reacting polymers containing aliphatic multiple bonds with organopolysiloxanes having at least two Si-bonded hy-drogen atoms per molecule.
10Surprisin~ly, the platinum catalysts used in accordance with the process of aspects of this invention are more effective during cross-linking, i.e., curing of vulcanization of compounds which contain alkenyl groups, especially vinyl groups, and organopolysiloxanes containing Si-bonded hydrogen. Consequently~ the process of aspects of this invention i5 preferred for the crosslinking of such compounds which may for example be used as potting or coating substances including substances used for ad-hesive repellent coatings, on for example paper or molds especially those used in the pouring of concrete. These catalysts are especially effective - in the preparation of materials used for making human or animal dental im-pressions.
When the platinum catalysts are used in accordance with aspects of this invention for cross-linking organopolysiloxane compositions, the organopolysiloxane composition contains (a) an organopolysiloxane contain-ing preferably at least two alkenyl groups and (b) organohydrogenpolysilox-anes having silicon-bonded hydrogen atoms.
Organopolysiloxanes (a) containing alkenyl groups are known in the art and are described, for example in U.S. Patents 3,723,497 issued March 19, 1973 to Banly and 3,950,300 lssued April 4, 1976 to Hittmair et al. Suitable examples of organopolysiloxanes are preferably diorganopoly-,'3 .~
6~4 siloxanes having triorganosiloxy terminal groups having at least one vinylgroup in each terminal unit. These organopolysiloxanes have a viscosity of from 500 to 300,000 cs. and more preferably from 2000 up to 100,000 cs.
at 25C.
The organohydrogenpolysiloxanes (b) containing silicon-bonded atoms are described, for example in the above identified U.S. Patents 3,723,497 and 3,950~300. Preferably these organohydrogenpolysiloxanes have at least three silicon-bonded hydrogen atoms per molecule. Generally, these organohydrogenpolysiloxanes contain from 0.01 to 1.7 percent by weight of silicon-bonded hydrogen atoms and the silicon vanences not satis-fied by hydrogen atoms and siloxane oxygen atoms are satisfied by sut-stituted and unsubstituted monovalent hydrocarbon radicals free of alipha-tic unsaturation.
. .
60~
Tllc le~ t;ve amoullt ot componcnts (a) alld (b) emp]oyed are such that Crom 0.75 to 5 gram atoms oF s:ili.con-botlded hydrogen are presellt Lrom coml-onent (b) per ~ram molecule of alkenyl group prcsent from component (a).
In order o prepare a cross-linkable compo.sltion, components (a) and (b) and optionally oLher addi.tivcs are normally mixed with the platinum catalYst at environmental tempera;ures and pre.ssures i.c., from : room temperature and 760 mm llg (abs.).
In the examples, all parts and percentages are by weigllt unless oLllerwi.se spcciied.
EXA~IPLE 1 - Mixtu_e_A
400 grams of a mixture consisting of 150 parts of a dimethylpolysi].oxane having vinyldimethy]siJ.oxy terminal groups and a viscosity of 1200 cP at 23C, 68 parts of a dimethyl-~olysiloxane having vinyld:imethylsiloxy terminal groups and a viscosity of 22,000 cP at 23C, 174 parts of cristobalite meal and 8.6 parts of a commercially available treatcd silicon dioxide pyrogenically produced in the gaseous phase and havi.ng a surface area of 200 m /gm, which has been rendercd 60 percent hydrophobic by reacting with dimethyldiclllorosilane, are mixed - with 1.6 grams of a 1 percent platinum (calculated as the element) solution of (acac-C7l~8)Pt(acac) in methy].ene ch]oride, so as to form a mixturc whicll contains 40 ppm of platinum, (calculated as the element).
Mixtllre B
_ .
- 60 parts of the dimetlly]po]ysi]oxane having vinyldimethylsiloxy terminal groups and a viscosity of 1200 cP at 23C are mixecl with 31 parts of the dimethylpolysiloxane havi.llg vinyldimethylsiloxy terminal groups and a viscosity of 22,000 cP at 23C, 83 parts of cristobalite meal, 5 parts of the trcatcd silicon dioxide described in the preparation of mixture A, and 25 parts of a copolymer having a viscosity of 7700 c~ at 23C
and consisting of dimethylsiloxane~ methyl.hydrogensiloxane and trimethylsiloxane units, with the molar ratio of the dimethyl-siloxane units to the methylcllogensiloxane units being 9:1.
Mixtures A and B are stored at room temperature for 3 days and then mixed togethcr in a weight ratio of 1:1. At room tcml~erO;ure, the time elal~sod beLween thc mixing of mixt~lres 13 and A and t~e cross:linliing of the compounds is 50 seconds .
Example 2 The procedure described in Example ] is repeated, except that 1.6 grams of a ] percent: platinum so]ution (calculatecl as the elem~nt) of [(Cli3-C10ll12)PtCl]2 is substituted for (acac-C7H8(Pt(acac).
At room temperature, the elapsed timc between the initial addition of mixture 13 al-d mixture A and observable rross-linking of the composition is 70 seconds.
Example 3 The procedure describcd in Example 1 is repeated, except that 1.6 grams of a 1 percent platinum solution (cal-culated as the elemellt) of (C2H4)PtCl(acac) in methylene chlorideis substituted for (acac--C7]18)Pt(acac)-At room temperature, the elapsed time between theinitial addition of mixture B to mixture A and observable cross-linking is 30 seconds.
Comparison Example a T~e proceduL-e described in Example 1 is repeated, except that 1.6 grams of a 1 percent platinum solution (calculated as the element) of a platinum-diviny]tetramethyldisiloxane in di-methylpolysiloxane having vinyldimethylsiloxy terminal groups is substituted for (acac-C7H8)Pt(acac). The procedure for preparing the catalyst is described in ~xample 6 of U.S. Patent No.
3,814,730.
To a mixture containing 10 parts of H2PtC16 6}l20 and 20 parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 50 parcs ethanol, was added 20 parts of sodium hicarbonate. For 30 minutes the mixture was refluxed under coDstant agitation and then allowed to stand for 15 hours. After filtration the volatile components were removed from the filtrate by distillation at approximately 12 mm Hg (abs.). The residue was dissolved in benzene and the solution filtered and the benzene removed from the filtrate by distillation. The residue was tllen dissolved in dimethylpolysiloxane having vinyldimethylsiloxy terminal groups and a viscosity of 1400 cP at 23C at a ra~e so that the so.lution con':ains ] percellt plati.lulll, calcll]ated as the elemer~.
~ 1~ room tclllpcr.lt-lre, tlle e:lap~sed ti.me beLween thc init:ial acldi~-ltll o~ mixture B to mixture A alld observab]e cross-linkin~ was 2 min~l~es ant1 lO seconds.
Co~ iso~ E~t~ r~
The process described in Example 1 was repeated except that 1.6 gram~s of a 1 percent platinum solution (calcu].ated as - element) of (PtC12'C2114)2 in methylene chloride (descri.bed in U.S. Patent 3,159,601) is substituted for (acac-C7H8)Pt(acac).
~ At room temperature, the elapsed t:ime between the initial incorporatioil of mixture B in mixture A and observable cross]inking of the compos;.tion was 10 minutes.
Comparison F.xam~_~ c The procedtlre described in ~xample l. was repeated, except Illat l.G grams of a 1 percent platinum solution (ca]culated as the element) o' platinum-(II)-diacetylacetonate in methylene chloride (described in U.S. Patent 3,723,497) was substituted ' for the (acac-C7H8)Pt(acac).
At room temperature, the elapsed time between the initial incorporation of mixture B in mixture A and observable crossli.nking of tlle composition was 3 hours.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In an improved process for effecting the addition of sili-con-bonded hydrogen atoms to compounds containing aliphatic multiple bonds in the presence of a platinum catalyst, the improvement which comprises:
contacting a compound containing at least one silicon-bonded hydrogen atom with a compound containing aliphatic carbon atoms linked by multiple bonds, in the presence of a platinum catalyst selected from the group con-sisting of (I) XPtY, (II) (III) APt(Y')X" and mixtures thereof, in which A is halogen, X is an unsubstituted hydrocarbon radical or a substituted such hydrocarbon radical substituted with an al-koxy or acyloxy group and has from 1 to 3 aliphatic double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an unsubstitued hydro-carbon or a substituted such hydrocarbon substituted with an alkoxy or acyl-oxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
contacting a compound containing at least one silicon-bonded hydrogen atom with a compound containing aliphatic carbon atoms linked by multiple bonds, in the presence of a platinum catalyst selected from the group con-sisting of (I) XPtY, (II) (III) APt(Y')X" and mixtures thereof, in which A is halogen, X is an unsubstituted hydrocarbon radical or a substituted such hydrocarbon radical substituted with an al-koxy or acyloxy group and has from 1 to 3 aliphatic double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an unsubstitued hydro-carbon or a substituted such hydrocarbon substituted with an alkoxy or acyl-oxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
2. In an improved process for curing an organopolysiloxane con-taining alkenyl groups and an organopolysiloxane containing silicon-bonded hydrogen atoms in the presence of a platinum catalyst, the improvement comprising: mixing said alkenyl-containing organopolysiloxane with said silicon-bonded hydrogen-containing organopolysiloxane, in the presence of a platinum catalyst select ed from the group consisting of (I) XPtY, (II) (III) APt (Y')X" and mixtures thereof, in which A is a halogen, X is an unsubstituted hydrocar-bon radical or a substituted such hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 aliphatic double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an unsubstituted hy-drocarbon or a substituted such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand or arylcarboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
3. In an improved process for preparing a dental impression which comprises applying a mixture containing an organopolysiloxane having alkenyl groups and an organohydrogenpolysiloxane containing silicon-bonded hydrogen atoms and a platinum catalyst to a tooth of which an impression is to be taken, curing the material and thereafter removing the resultant impression from the tooth, the improvement which comprises: using as said platinum catalyst, a catalyst selected from the group consisting of (I) XPtY, (II) (III) APt(Y')X" and mixtures thereof, in which A is halogen, X is an unsubstituted hydrocarbon radical or a substituted such hydrocarbon radical substituted with an al-koxy or acyloxy group and has from 1 to 3 aliphatic double bonds which is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X' is a hydrocarbon radical substituted with an alkoxy or acyloxy group and has from 1 to 3 double bonds and is bonded to the platinum atom via a PtC-sigma bond and a Pt-olefin-Pi-bond, X" is an unsubstituted hydrocar-bon or a substituted such hydrocarbon substituted with an alkoxy or acyloxy group and has an aliphatic double bond which is bonded to the platinum atom via a Pt-olefin-Pi-bond, Y is a chelated beta-diketonate ligand or aryl-carboxylate ligand, Y' is a beta-diketonate ligand and Z is a double link bridge ligand.
4. The improved process of claims 1, 2 or 3 wherein said platinum catalyst has the formula:
5. The improved process of claims 1, 2 or 3 wherein said platinum catalyst has the formula:
6. The improved process of claims 1, 2 or 3 wherein said platinum catalyst is acetylacetonatechloro(ethylene)-platinum-(II).
7. The improved process of claims 1, 2 or 3 wherein said catalytic reaction is affected at a temperature up to 150°C.
8. The improved process of claims 2 or 3, wherein said organopolysiloxane contains at least two alkenyl groups per molecule and the organohydrogenpolysiloxane contains at least three silicon-bonded hydrogen atoms per molecule.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772724822 DE2724822A1 (en) | 1977-06-02 | 1977-06-02 | PROCESS FOR ADDING SI-BONDED HYDROGEN TO ALIPHATIC MULTIPLE BONDING |
| DEP2724822.2 | 1977-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122604A true CA1122604A (en) | 1982-04-27 |
Family
ID=6010463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA304,414A Expired CA1122604A (en) | 1977-06-02 | 1978-05-30 | Complex platinum catalysts for hydrosilation reactions |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4177341A (en) |
| JP (3) | JPS543015A (en) |
| AU (1) | AU521156B2 (en) |
| BE (1) | BE867748A (en) |
| CA (1) | CA1122604A (en) |
| DE (1) | DE2724822A1 (en) |
| FR (1) | FR2401169A1 (en) |
| GB (1) | GB2000165B (en) |
| NL (1) | NL7804694A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2846621A1 (en) * | 1978-10-26 | 1980-05-08 | Wacker Chemie Gmbh | METHOD FOR APPLYING SI-TIED HYDROGEN TO ALIPHATIC MULTIPLE BINDING |
| JPS55154354A (en) * | 1979-05-16 | 1980-12-01 | Toray Silicone Co Ltd | Silicone composition for treating glass fiber |
| DE3131734A1 (en) * | 1981-08-11 | 1983-02-24 | Bayer Ag, 5090 Leverkusen | HEAT-CURABLE ORGANOPOLYSILOXANE MIXTURES |
| US4530879A (en) * | 1983-03-04 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Radiation activated addition reaction |
| US5145886A (en) * | 1988-05-19 | 1992-09-08 | Minnesota Mining And Manufacturing Company | Radiation activated hydrosilation reaction |
| US4916169A (en) * | 1988-09-09 | 1990-04-10 | Minnesota Mining And Manufacturing Company | Visible radiation activated hydrosilation reaction |
| JPH089006B2 (en) * | 1989-11-15 | 1996-01-31 | 信越化学工業株式会社 | Platinum catalyst composition and method for producing the same |
| DE59104822D1 (en) * | 1990-04-26 | 1995-04-06 | Wacker Chemie Gmbh | ORGANO (POLY) SILOXANES WITH ORGANYLOXY AND HYDROGEN GROUPS HAVING FINAL SILOXANE UNITS. |
| US6562470B2 (en) * | 2001-01-10 | 2003-05-13 | General Electric Company | Method for making coated substrates and articles made thereby |
| DE102009002231A1 (en) | 2009-04-06 | 2010-10-07 | Wacker Chemie Ag | Self-adherent Pt-catalyzed addition-crosslinking silicone compositions at room temperature |
| KR102443609B1 (en) * | 2014-08-12 | 2022-09-15 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Hydrosilylation reaction catalyst |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159601A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
| US3516946A (en) * | 1967-09-29 | 1970-06-23 | Gen Electric | Platinum catalyst composition for hydrosilation reactions |
| US3723497A (en) * | 1971-11-19 | 1973-03-27 | Dow Corning | Silicone compositions catalyzed with platinum ii diacetylacetonate |
| GB1428552A (en) * | 1972-02-16 | 1976-03-17 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
| US3950300A (en) * | 1972-10-11 | 1976-04-13 | Wacker-Chemie Gmbh | Dental impression materials |
| US3884866A (en) * | 1973-04-13 | 1975-05-20 | Gen Electric | High strength organopolysiloxane compositions |
-
1977
- 1977-06-02 DE DE19772724822 patent/DE2724822A1/en active Granted
-
1978
- 1978-05-02 NL NL7804694A patent/NL7804694A/en not_active Application Discontinuation
- 1978-05-24 US US05/909,094 patent/US4177341A/en not_active Expired - Lifetime
- 1978-05-29 AU AU36573/78A patent/AU521156B2/en not_active Expired
- 1978-05-30 CA CA304,414A patent/CA1122604A/en not_active Expired
- 1978-05-30 JP JP6488178A patent/JPS543015A/en active Granted
- 1978-06-01 GB GB7826223A patent/GB2000165B/en not_active Expired
- 1978-06-01 FR FR7816401A patent/FR2401169A1/en active Granted
- 1978-06-02 BE BE188264A patent/BE867748A/en not_active IP Right Cessation
-
1981
- 1981-04-13 JP JP56054473A patent/JPS5932477B2/en not_active Expired
- 1981-04-13 JP JP56054472A patent/JPS607998B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2000165A (en) | 1979-01-04 |
| JPS5715118B2 (en) | 1982-03-29 |
| DE2724822C2 (en) | 1987-06-19 |
| JPS5932477B2 (en) | 1984-08-09 |
| FR2401169B1 (en) | 1980-04-04 |
| US4177341A (en) | 1979-12-04 |
| AU3657378A (en) | 1979-12-06 |
| AU521156B2 (en) | 1982-03-18 |
| BE867748A (en) | 1978-12-04 |
| FR2401169A1 (en) | 1979-03-23 |
| JPS607998B2 (en) | 1985-02-28 |
| JPS543015A (en) | 1979-01-11 |
| JPS56152839A (en) | 1981-11-26 |
| GB2000165B (en) | 1982-01-13 |
| NL7804694A (en) | 1978-12-05 |
| DE2724822A1 (en) | 1978-12-07 |
| JPS56167728A (en) | 1981-12-23 |
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