CA1136639A - Addition of si-bonded hydrogen to an aliphatic multiple bond - Google Patents
Addition of si-bonded hydrogen to an aliphatic multiple bondInfo
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- CA1136639A CA1136639A CA000338416A CA338416A CA1136639A CA 1136639 A CA1136639 A CA 1136639A CA 000338416 A CA000338416 A CA 000338416A CA 338416 A CA338416 A CA 338416A CA 1136639 A CA1136639 A CA 1136639A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0801—General processes
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- 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
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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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- 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
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- 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
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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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
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/30—Use of anatomy in making a mold or using said mold
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/901—Room temperature curable silicon-containing polymer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- General Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
- Chemical Vapour Deposition (AREA)
- Silicon Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Silicon containing compounds having Si-bonded hydrogen are added to an aliphatic multiple bond in the presence of a platinum catalyst which is either platinum compounds of the formula (R1)PtX2, or (R2SO)(Z)PtY2 R1 represents a cyclic hydrocarbon radical or a substituted cyclic hydro-carb n radical having 2 aliphatic carbon-carbon double bonds, where R
represents the same or different hydrocarbon radicals or substituted hydrocarbon radicals, x is the same or different halogen atoms and/or the same or different alkyl radicals, Z represents a hydrocarbon having a car-bon-carbon double bond and Y represents the same or different halogen atoms. An example of a platinum compound having the general formula (R1)PtX2, is dicyclopentadiene-platinum dichloride, while an example of a platinum compound having the general formula (R2SO) (Z)PtY2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloridde. The catalyst is more effective in promoting hydrosilation, is available in substantially pure state and is effective at room temperature.
Silicon containing compounds having Si-bonded hydrogen are added to an aliphatic multiple bond in the presence of a platinum catalyst which is either platinum compounds of the formula (R1)PtX2, or (R2SO)(Z)PtY2 R1 represents a cyclic hydrocarbon radical or a substituted cyclic hydro-carb n radical having 2 aliphatic carbon-carbon double bonds, where R
represents the same or different hydrocarbon radicals or substituted hydrocarbon radicals, x is the same or different halogen atoms and/or the same or different alkyl radicals, Z represents a hydrocarbon having a car-bon-carbon double bond and Y represents the same or different halogen atoms. An example of a platinum compound having the general formula (R1)PtX2, is dicyclopentadiene-platinum dichloride, while an example of a platinum compound having the general formula (R2SO) (Z)PtY2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloridde. The catalyst is more effective in promoting hydrosilation, is available in substantially pure state and is effective at room temperature.
Description
, 11366~9 The present invention relates to the addition of organosilicon compounds containing silicon bonded hydrogen to compounds containing ali-phatic unsaturation and more particularly to a process for adding organo-silicon compounds containing silicon bonded hydrogen to a compound having aliphatic unsaturation in the presence of a platinum catalyst.
The addition of organosilicon compounds containing Si-bonded hy-drogen to an aliphatic multiple bond is well known and is often referred to as "hydrosilation". Likewise, it is known that hydrosilation can be accel-erated with catalyst, e.g. platinum catalysts. Hydrosilation is further described in U.S. Patent No. 3,814,730 issued June 4, 1974 to ~arstedt, in which platinum catalysts are used to effect the addition of an organo-silicon compound having a silicon bonded hydrogen atom to an aliphatically unsaturated compound having either olefinic or acetylenic unsaturation and thereby form an adduct having a new silicon carbon linkage.
It is an object of one aspect of this inventlon to provide a catalyst for effecting the addition of organosilicon compounds containing silicon bonded hydrogen to unsaturated organic compounds.
An ob;ect of another aspect of this invention is to provide a catalyst which is more effective in promoting hydrosilation.
An ob;ect of still another aspect of this invention is to provide a catalyst which is available in substantially pure state and is effective at room temperature.
An object of a further aspect of this invention is to provide a process for promoting the addition of organosilicon compounds having sili-L ~ .
`` 1~3~6~9 con bonded hydrogen to a compound having aliphatic unsaturation.
In accordance with an aspect of this invention, an improvedprocess is provided for the addition of an organosilicon compound con-taining Si-bonded hydrogen to a compound having an aliphatic multiple bond in the presence of a platinum catalyst, the improvement comprising conducting the addition in the presence of a platinum catalyst selected from the group consisting of complexes of the formula (R )PtX2 , and (R2S0) (Z)PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-carbon double bond and Y
is the same or different halogen atom.
By a variant thereof, R ls dicyclopentadiene and X is chlorine.
By another variant, Rl~is dicyclopentadiene and X is an alkyl radical having from 1 to 4 carbon atoms.
By yet another variant, the plàtinum complex having the formula (R2S0)(Z)Pt 2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
By a further variant, the organosilicon compound is an organo-polysiloxane containing Si-bonded hydrogen and the organie compound is an organopolysiloxane containing alkenyl groups.
By another aspect of this invention, a composition is provided comprising an organosilicon compound containing Si-bonded hydrogen and an organic compound containing an aliphatie multiple bond and a platinum cata-lyst selected from the group consisting of complexes of ithe formula (R )PtX2 , and (R2SO)(Z)PtY2 1~36639 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of the same or different halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-car-bon double bond and Y is the same or different halogen atom.
By a variant thereof, R is a dicyclopentadiene and X is chlor-ine.
By another variant, R is dicyclopentadiene and X is an alkyl radical having from 1 to 4 carbon atoms.
By a further variant, the platinum complex having the formula (R250) (Z)PtY2is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
By another aspect of this invention, an improved method is pro-vided for making dental impressions which comprises applying a composition containing an organopolysiloxane having alkenyl groups, an organopolysiloxane containing Si-bonded hydrogen and a platinum catalyst to a tooth and there-after removing the crosslinked organopolysiloxane impression, the improve-ment which comprises adding a platinum catalyst selected from the group con-sisting of complexes of the formula (Rl)PtX2 and (R2SO)(Z~PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group consisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals
The addition of organosilicon compounds containing Si-bonded hy-drogen to an aliphatic multiple bond is well known and is often referred to as "hydrosilation". Likewise, it is known that hydrosilation can be accel-erated with catalyst, e.g. platinum catalysts. Hydrosilation is further described in U.S. Patent No. 3,814,730 issued June 4, 1974 to ~arstedt, in which platinum catalysts are used to effect the addition of an organo-silicon compound having a silicon bonded hydrogen atom to an aliphatically unsaturated compound having either olefinic or acetylenic unsaturation and thereby form an adduct having a new silicon carbon linkage.
It is an object of one aspect of this inventlon to provide a catalyst for effecting the addition of organosilicon compounds containing silicon bonded hydrogen to unsaturated organic compounds.
An ob;ect of another aspect of this invention is to provide a catalyst which is more effective in promoting hydrosilation.
An ob;ect of still another aspect of this invention is to provide a catalyst which is available in substantially pure state and is effective at room temperature.
An object of a further aspect of this invention is to provide a process for promoting the addition of organosilicon compounds having sili-L ~ .
`` 1~3~6~9 con bonded hydrogen to a compound having aliphatic unsaturation.
In accordance with an aspect of this invention, an improvedprocess is provided for the addition of an organosilicon compound con-taining Si-bonded hydrogen to a compound having an aliphatic multiple bond in the presence of a platinum catalyst, the improvement comprising conducting the addition in the presence of a platinum catalyst selected from the group consisting of complexes of the formula (R )PtX2 , and (R2S0) (Z)PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-carbon double bond and Y
is the same or different halogen atom.
By a variant thereof, R ls dicyclopentadiene and X is chlorine.
By another variant, Rl~is dicyclopentadiene and X is an alkyl radical having from 1 to 4 carbon atoms.
By yet another variant, the plàtinum complex having the formula (R2S0)(Z)Pt 2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
By a further variant, the organosilicon compound is an organo-polysiloxane containing Si-bonded hydrogen and the organie compound is an organopolysiloxane containing alkenyl groups.
By another aspect of this invention, a composition is provided comprising an organosilicon compound containing Si-bonded hydrogen and an organic compound containing an aliphatie multiple bond and a platinum cata-lyst selected from the group consisting of complexes of ithe formula (R )PtX2 , and (R2SO)(Z)PtY2 1~36639 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of the same or different halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-car-bon double bond and Y is the same or different halogen atom.
By a variant thereof, R is a dicyclopentadiene and X is chlor-ine.
By another variant, R is dicyclopentadiene and X is an alkyl radical having from 1 to 4 carbon atoms.
By a further variant, the platinum complex having the formula (R250) (Z)PtY2is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
By another aspect of this invention, an improved method is pro-vided for making dental impressions which comprises applying a composition containing an organopolysiloxane having alkenyl groups, an organopolysiloxane containing Si-bonded hydrogen and a platinum catalyst to a tooth and there-after removing the crosslinked organopolysiloxane impression, the improve-ment which comprises adding a platinum catalyst selected from the group con-sisting of complexes of the formula (Rl)PtX2 and (R2SO)(Z~PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group consisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals
- 2 a -having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of the same or different halogen atoms and the same or different alkyl radicals, Z is a hydrocar~oh having a carbon-carbon double bond and Y is the same or different halogen atom.
Compared to the catalysts known heretofore for the addition of Si-bonded hydrogen to an aliphatic multiple bond, the platinum complexes used in aspects of this invention have the advantage that they are more effective and or can be obtained more readily in a pure state from the precipitation reaction and consequently can be diluted to the proper con-centration more readily than the conventional platinum catalysts used heretofore.
Examples of cyclic hydrocarbons represented by R which have 2aliphatic car~bon-carbon double bonds are dicyclopentadiene and 1,5-cyclo-octadiene.
The halogen atoms represented by X are fluorine, chlorine, bromine or iodine atoms, with chlorine being the preferred halogen.
The alkyl radicals represented by X preferably contain from l to 4 carbon atoms and are for example the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals.
The preferred platinum complex represented by the formula . (R )PtX2 ls d$cyclopentadiene-platinum dichloride, (CloH12)PtC12 , since it is very reactive even at room temperature.
Additional examples of platinum complexes having the general formula (Rl)PtX2' are compounds corresponding to the following formulas:
(ClOH12) PtBr2 (CloHl2)ptI2 (C8H12)PtC12 (C8H12) PtBr2 (c8Hl2)pt(cH3) (C8H12)Pt (CH3)2 (C8Hl2)Pt(c2H5)2 (CloH12)Pt (CH3)2 - (CloHl2)Pt(c2H5)2 (CloHl2)pt(c4H9)2 In the above formulas ''CloH12ll represents dicyclopentadiene and "C8H12" represents 1,5-cyclooctadiene.
A platinum complex other than the dicyclopentadiene-platinum dichloride is a dicyclopentadiene-platinum complex -having Cl to C4-alkyl radicals of the formula X' X' - where X' is an alkyl radical having from 1 to 4 carbon atoms.
Platinum complexes of the general formula (R )PtX2 and their process of preparation are described by J. Chatt et al, 15 Journal of the Chemical Society, 1957 J pages 2496 through 2505 and by H. C. Clark et al, Journai of Organometallic Chemistry 59 (1973), pages 411 through 428.
~ .
Dlcyclopentadiene-platinum dichloride can be obtained not only by reacting Na2PtC14 4H20 with dicyclopentadiene in n-propanol, but also by reacting K2PtC14 with dicyclopentadiene in. ; 50 percent by weight of aqueous acetic acid. Dicyclo-pentadiene-platinum dibromide can be obtained by reacting dicyclopentadiene-platinum dichloride with lithium bromide in acetone and dicyclopentadiene-platinum diiodide can be obtained by reacting dicyclopentadiene-platinum dichloride with sodium iodide in acetone.
The substituted radicals represented by R may be ali-phatic or aromatic hydrocarbon radicals. It is preferred that they contain from 1 to 10 carbon atoms. The examples cited above for alkyl radicals represented by X are equally applicable to the hydrocarbon radicals represented by R. Additional examples of hydrocarbon radicals represented by R are the phenyl and the benzyl radicals. Examples of substituted hydrocarbon radicals represented by R are the 2-chloroethyl radical, a radi-cal of the formula -CH2COOH, the o-chlorophenyl radical, the o-carboxyphenyl radical and the o-nitrophenyl radical. The radicals represented by R may be connected to form a ring con-figuration e.g. occurs in the case of the tetramethylene radical.
The hydrocarbon radicals represented by Z having a carbon-carbon double bond may be linear, branched or cyclic. It is preferred that they contain from 2 to 10 carbon atoms.
Examples of hydrocarbon radicals represented by Z are ethylene, propylene, n-l-butene, n-l-pentenej cyclopentene, styrene, cis-2-hexene and l-nonene.
The halogen atoms represented by Y are fluorine, chlorine, bromine or iodine. Preferably the halogen atoms are chlorine and bromine.
It is preferred that the platinum complex having the following formula ( R2 S O ) (Z ) PtY2 be dimethylsulfoxide-ethylene-platinum-(II)-dichloride, [(CH3)2SO](C2H4)PtC12, since it is very reactive even at room temperature.
1136~39 Additional examples of platinum complexes having the general formula (R2SO) (Z,)PtY2 are compounds of the following formulas:
[ (cH3)2so] (C3H6)PtC12 [(CH3)2SO] (C4H8)PtC12 [ (CH3)2SO] (C5Hlo)Ptcl2 [(CH3)2SO] (C5H8)PtC12 [(CH3)2S0](c6HscH CH2)PtC 2 [ (CH3)2SO] (C2H4)PtBr2 [(CH3)2SO](C3H6)PtBr2 [(C6H5)(cH3)sO](c2H4)ptcl2 [(C6H5)(CH3)sO](c3H6)ptcl2 [(C6H5)(CH3)SO](C6H5CH=CH2)PtC12 [(C6H5)(CH3)SO](c2H4)PtBr2-In the above formulas "C4H8" represents n-l-butene and "C5Hlo" represents n-l-pentene.
Platinum complexes of the following general formula (R2SO) (Z)PtY2 and their preparation are generally known in the art and their preparation is described by H. Boucher et al, Journal of the Chemical Society, Volume 99, 1977, pages 6253 through 6261.
In the sulfoxide-ethylene-platinum-~I~dihalides, higher boiling hydrocarbons having a carbon-carbon double bond may be substituted for the ethylene.
The amount of platinum catalyst required to promote the addition of a silicon compound containing Si-bonded hydro-gen to a compound having an aliphatic multiple bond, may bethe same amount of platinum catalyst which have been or could have been used heretofore in the addition of Si-bonded hydrogen to an aliphatic multiple bond. Preferably a sufficient amount of catalyst should be used so that at least lO lO gram atom, and more preferably 10 8 to 10 3 gram atom of platinum is present, based on elemental platinum, for each gram atom of Si-bonded 1~3~6~39 hydrogen.
The temperature used in the addition process of one aspect of this invention may be the same as that uséd or could have been used heretofore in the known processes for the aZdition of Si-bonded hydrogen to an aliphatic multiple bond in the presence of a platinum catalyst. Thus the temperature ranges from about room temperature up to 150C, at atmospheric pressure, i.e., one bar or approximately one bar. However, higher or lower temperatures may be used if desired.
The process of an aspect of this invention may be used whenever monomeric or polymeric silicon compounds having Si-bonded hydrogen are to be added to monomeric or polymeric compounds having an aliphatic multiple bond. Depending on the compounds which are to be added, other monomeric silicon compounds or dimeric or polymeric, silicon-containing compounds can be prepared or modified by the process of an aspect of this invention.
An Example of monomeric silicon compounds which may be prepared by the process of an aspect of this invention are 3-chloropropyltrichlorosilane in which trichlorosilane is reacted with allyl chloride. Also 3-chloro-propylmethyldichlorosilane may be prepared by reacting methyldichlorosilane with allyl chloride. Likewise n-propyltrichlorosilane may be prepared by reacting propene with trichlorosilane. Furthermore, methacryloxypropyl-trichlorosilane may be prepared by reacting allylmethacrylate with tri~
chlorosilane and vinylmethyldichlorosilane may be prepared by reacting ace-tylene with methyldichlorosilane~.
An Example of dimeric or polymeric silicon containing compounds which may be prepared by the process of this invention are bis-(1,2-tri-chlorosilyl)-ethane which is prepared by reacting vinyltrichlorosilane with trichlorosilane. Also organosiloxanes having SiC-bonded ester groups are prepared by the addition of at least one diester of allylsuccinic acid to an organosilane having an Si-bonded hydrogen. Likewise the number of ali-113f~6~9 phatic multiple bonds in polymers may be decreased in, for example, poly-(oxyalkylene)-polyols, by reacting polymers of this type containing ali-,phatic multiple bonds with organopolysiloxanes having at least two Si-bonded hydrogen atoms per molecule.
Although the process of-an aspect of this invention may be used - - 6 a -1~3t~639 to modify polymeric silicon-containing compounds, it is equally applicable for crosslinking, i.e., the curing or vulcanization of compositions containing alkenyl groups, es-pecially vinyl groups, and organopolysiloxanes containing Si-bonded hydrogen. In the crosslinking of compositions contain-ing alkenyl groups and organopolysiloxanes containing Si-bonded hydrogen, the activity of the catalyst at room temper-ature can be of great importance in order to achieve rapid crosslinking at temperatures in the range of from 18 to 35C.
lC Thus, the process of an aspect of this invention is preferred for the crosslinking of such compositions which may, for example, be used for potting or encapsulating electrical or electronic devices or which may be used as coatings or as compositions which may be used in preparing coatings which repel adhesive sub-stances, such as for coating paper. Such compositions may alsobe used for pre-cast concrete molds and for making impressions of human or animal teeth.
In making dental impressions, a mixture containing (a) organopolysiloxanes having silicon bond hydrogen, (b) organopoly-siloxanes having aliphatic unsaturation, (c) the platinum cata-lyst of this invention and ~d) other additives, if desired, are applied to the tooth or teeth of which an impression is to be taken and after the material has hardened, the resultant impression is removed from the tooth or teeth.
Agents which retard or inhibit the addition of Si-bonded hydrogen to an aliphatic multiple bond at room tempera-ture may of course be used when necessary or desired. Examples of such retardants are benzotriazole, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and/or 2-methyl-3-butyn-2-ol.
In the following examples all parts and percentages are by weight un~ess otherwise specified.
a) A mixture containing dicylcopentadiene-platinum di-chloride and diluent which is used in the examples is prepared in the following manner:
~0.2 g of dicyclopentadiene-platinum dichloride is dissolved in 20 ml of methylene chloride. The solution is mixed with 100 g of a dimethylpolysiloxane having terminal vinyldimethylsiloxy units and a viscosity of 1000 mPa at 23C.
The mixture is stirred at room temperature and at 1 bar until 11366~
the methylene chloride evaporates. The resultant mixture con-tains 0.1 percent of platinum, calculated as elemental platinum.
b) A mixture containing dimethylsulfoxide-ethylene-platinum-(II)-dichloride and diluent which is used in the follow-ing examples is prepared in accordance with the procedure des-cribed in (a) above, except that 0.2 g of dimethylsulfoxide-ethylene-platinum-(II)-dichloride is used instead of the 0.2 g of dicyclopentadiene-platinum dichloride. 'The mixture thus obtained also contains 0.1 percent of platinum, calculated as elemental platinum.
Exalmple 1 I - 90 g of dimethylpolysiloxane having terminal vinyldimethysiloxy units and a viscosity of 1000 mPa at 23 C, are mixed with 2 g of the platinum complex prepared in accordance with the procedure described in (a) above. The mixture thus obtained is stored for 5 days at room temperature. 10 g of a copolymer having a viscosity of 700 mPa at 23C and contain-ing dimethylsiloxane, methylhydrogensiloxane and trimethyl-siloxane units are added to the mixture. The'mole ratio of the dimethylsiloxane units to the methylhydrogensiloxane units in the mixture is 1:9. The time which el`apsed after the mixing of the copolymer and observable crosslinking of the composition is 2 minutes. The resultant mixture contains 20 ppm of platinum, calculated as elemental plati'num. 5 Example 2 The procedure of Example 1 is repeated, except that 2 g of the platinum complex prepared in accordance with (b) above is substituted for the platinum complex prepared in ac-cordance with (a) above. The organopolysiloxane containing the platinum complex is stored for 5 days before being mixed with the organopolysiloxane containing Si-bonded hydrogen. Cross-linking is observed 45 seconds after the organopolysilox-ane containing the platinum complex is initially mixed with the organopolysiloxane containing Si-bonded hydrogen.
Comparison Example a) 1~3~i6~9 The procedure described in Example 1 is repeated, except that 0.2 g of a 1 percent platinum solution, calculated as elemental platinum of a platinum-divinyltetramethyldisilox-ane complex in dimethylpolysiloxane having terminal vinyl-dimethylsiloxy groups is substituted for 2 g of the platinumcomplex prepared in accordance with (a) above. This solution is prepared in accordance with the following procedure which is described in Example 6 of U. S. Patent No. 3,814,730.
To a mixture containing 10 parts of H2PtC16-6H20, 20 10parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 50 parts of ethanol, are added 20 parts of sodium bicarbonate. The mixture is boiled under reflux for 30 minutes, then allowed to stand for 15 hours and subsequently filtered. The volatile components are removed from the filtrate by distillation at 1516 mbar. The residue is then dissolved in benzene, filtered and the benzene distilled from the filtrate. The resi-due is dissolved in a sufficient amount of a dimethylpolysilox-ane having terminal vinyldimethylsiloxy groups and a viscosity of 1000 mPa at 23C to provide a solution containing 1 percent platinum, calculated as elemental platinum.
The organopolysiloxane platinum complex is stored for 5 days before it is mixed with the organopolysiloxane contain-ing Si-bonded hydrogen. Crosslinking is observed 2.5 minutes after the two organopolysiloxanes are mixed.
Example 3 Mixture A: A mixture containing 102.5 parts of a dimethylpolysiloxane having terminal vinyldimethylsiloxy groups and a viscosity of 22,000 mPa at 23C, 145 parts of cristobal-lite meal and 5.5 parts of a commercially available silicon dioxide produced pyrogenically in the gaseous phase with a BET
surface area of 200 m /g which has been treated with dimethyl-dichlorosilane to impart hydrophobic properties to about 60 per-cent of its surface area, is mixed with 10 parts of the platinum complex prepared in accordance with the procedure described in (a) above. The resultant mixture contains 40 ppm of platinum, calculated as elemental platinum.
Mixture B: 97 parts of dimethylpolysiloxane having terminal vinyldimethylsiloxy groups and a viscosity of _ g _ 1~3t;6~39 22,000 mPa at 23C, are mixed with 137 parts of cristobalite meal, 9.2 parts of the treated silicon dioxide described in mixture (A) above, and 9.8 parts of a copolymer having a vis-cosity of 200 mPa at 23C and consisting of dimethylsiloxane, methylhydrogensiloxane and trimethylsiloxane units, in which the molar ratio of the dimethylsiloxane units to the methyl-hydrogensiloxane units is 6:1.
: Mixtures (A) and (B) are stored for 3 days at room tem-perature and then mixed toge her in a weight ratio of l:l.
Crosslinking is observed 50 seconds after mixtures (A) and (B) arelcombined at room temperature.
Example 4 The procedure described in Example 3 is repeated, except that 10 parts of the platinum complex prepared in accor-dance with (b) above are substituted for the platinum complexprepared in (a) above.
Crosslinking is observed 30 seconds after mixture (B) is combined with mixture (A) at room temperature.
Compared to the catalysts known heretofore for the addition of Si-bonded hydrogen to an aliphatic multiple bond, the platinum complexes used in aspects of this invention have the advantage that they are more effective and or can be obtained more readily in a pure state from the precipitation reaction and consequently can be diluted to the proper con-centration more readily than the conventional platinum catalysts used heretofore.
Examples of cyclic hydrocarbons represented by R which have 2aliphatic car~bon-carbon double bonds are dicyclopentadiene and 1,5-cyclo-octadiene.
The halogen atoms represented by X are fluorine, chlorine, bromine or iodine atoms, with chlorine being the preferred halogen.
The alkyl radicals represented by X preferably contain from l to 4 carbon atoms and are for example the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals.
The preferred platinum complex represented by the formula . (R )PtX2 ls d$cyclopentadiene-platinum dichloride, (CloH12)PtC12 , since it is very reactive even at room temperature.
Additional examples of platinum complexes having the general formula (Rl)PtX2' are compounds corresponding to the following formulas:
(ClOH12) PtBr2 (CloHl2)ptI2 (C8H12)PtC12 (C8H12) PtBr2 (c8Hl2)pt(cH3) (C8H12)Pt (CH3)2 (C8Hl2)Pt(c2H5)2 (CloH12)Pt (CH3)2 - (CloHl2)Pt(c2H5)2 (CloHl2)pt(c4H9)2 In the above formulas ''CloH12ll represents dicyclopentadiene and "C8H12" represents 1,5-cyclooctadiene.
A platinum complex other than the dicyclopentadiene-platinum dichloride is a dicyclopentadiene-platinum complex -having Cl to C4-alkyl radicals of the formula X' X' - where X' is an alkyl radical having from 1 to 4 carbon atoms.
Platinum complexes of the general formula (R )PtX2 and their process of preparation are described by J. Chatt et al, 15 Journal of the Chemical Society, 1957 J pages 2496 through 2505 and by H. C. Clark et al, Journai of Organometallic Chemistry 59 (1973), pages 411 through 428.
~ .
Dlcyclopentadiene-platinum dichloride can be obtained not only by reacting Na2PtC14 4H20 with dicyclopentadiene in n-propanol, but also by reacting K2PtC14 with dicyclopentadiene in. ; 50 percent by weight of aqueous acetic acid. Dicyclo-pentadiene-platinum dibromide can be obtained by reacting dicyclopentadiene-platinum dichloride with lithium bromide in acetone and dicyclopentadiene-platinum diiodide can be obtained by reacting dicyclopentadiene-platinum dichloride with sodium iodide in acetone.
The substituted radicals represented by R may be ali-phatic or aromatic hydrocarbon radicals. It is preferred that they contain from 1 to 10 carbon atoms. The examples cited above for alkyl radicals represented by X are equally applicable to the hydrocarbon radicals represented by R. Additional examples of hydrocarbon radicals represented by R are the phenyl and the benzyl radicals. Examples of substituted hydrocarbon radicals represented by R are the 2-chloroethyl radical, a radi-cal of the formula -CH2COOH, the o-chlorophenyl radical, the o-carboxyphenyl radical and the o-nitrophenyl radical. The radicals represented by R may be connected to form a ring con-figuration e.g. occurs in the case of the tetramethylene radical.
The hydrocarbon radicals represented by Z having a carbon-carbon double bond may be linear, branched or cyclic. It is preferred that they contain from 2 to 10 carbon atoms.
Examples of hydrocarbon radicals represented by Z are ethylene, propylene, n-l-butene, n-l-pentenej cyclopentene, styrene, cis-2-hexene and l-nonene.
The halogen atoms represented by Y are fluorine, chlorine, bromine or iodine. Preferably the halogen atoms are chlorine and bromine.
It is preferred that the platinum complex having the following formula ( R2 S O ) (Z ) PtY2 be dimethylsulfoxide-ethylene-platinum-(II)-dichloride, [(CH3)2SO](C2H4)PtC12, since it is very reactive even at room temperature.
1136~39 Additional examples of platinum complexes having the general formula (R2SO) (Z,)PtY2 are compounds of the following formulas:
[ (cH3)2so] (C3H6)PtC12 [(CH3)2SO] (C4H8)PtC12 [ (CH3)2SO] (C5Hlo)Ptcl2 [(CH3)2SO] (C5H8)PtC12 [(CH3)2S0](c6HscH CH2)PtC 2 [ (CH3)2SO] (C2H4)PtBr2 [(CH3)2SO](C3H6)PtBr2 [(C6H5)(cH3)sO](c2H4)ptcl2 [(C6H5)(CH3)sO](c3H6)ptcl2 [(C6H5)(CH3)SO](C6H5CH=CH2)PtC12 [(C6H5)(CH3)SO](c2H4)PtBr2-In the above formulas "C4H8" represents n-l-butene and "C5Hlo" represents n-l-pentene.
Platinum complexes of the following general formula (R2SO) (Z)PtY2 and their preparation are generally known in the art and their preparation is described by H. Boucher et al, Journal of the Chemical Society, Volume 99, 1977, pages 6253 through 6261.
In the sulfoxide-ethylene-platinum-~I~dihalides, higher boiling hydrocarbons having a carbon-carbon double bond may be substituted for the ethylene.
The amount of platinum catalyst required to promote the addition of a silicon compound containing Si-bonded hydro-gen to a compound having an aliphatic multiple bond, may bethe same amount of platinum catalyst which have been or could have been used heretofore in the addition of Si-bonded hydrogen to an aliphatic multiple bond. Preferably a sufficient amount of catalyst should be used so that at least lO lO gram atom, and more preferably 10 8 to 10 3 gram atom of platinum is present, based on elemental platinum, for each gram atom of Si-bonded 1~3~6~39 hydrogen.
The temperature used in the addition process of one aspect of this invention may be the same as that uséd or could have been used heretofore in the known processes for the aZdition of Si-bonded hydrogen to an aliphatic multiple bond in the presence of a platinum catalyst. Thus the temperature ranges from about room temperature up to 150C, at atmospheric pressure, i.e., one bar or approximately one bar. However, higher or lower temperatures may be used if desired.
The process of an aspect of this invention may be used whenever monomeric or polymeric silicon compounds having Si-bonded hydrogen are to be added to monomeric or polymeric compounds having an aliphatic multiple bond. Depending on the compounds which are to be added, other monomeric silicon compounds or dimeric or polymeric, silicon-containing compounds can be prepared or modified by the process of an aspect of this invention.
An Example of monomeric silicon compounds which may be prepared by the process of an aspect of this invention are 3-chloropropyltrichlorosilane in which trichlorosilane is reacted with allyl chloride. Also 3-chloro-propylmethyldichlorosilane may be prepared by reacting methyldichlorosilane with allyl chloride. Likewise n-propyltrichlorosilane may be prepared by reacting propene with trichlorosilane. Furthermore, methacryloxypropyl-trichlorosilane may be prepared by reacting allylmethacrylate with tri~
chlorosilane and vinylmethyldichlorosilane may be prepared by reacting ace-tylene with methyldichlorosilane~.
An Example of dimeric or polymeric silicon containing compounds which may be prepared by the process of this invention are bis-(1,2-tri-chlorosilyl)-ethane which is prepared by reacting vinyltrichlorosilane with trichlorosilane. Also organosiloxanes having SiC-bonded ester groups are prepared by the addition of at least one diester of allylsuccinic acid to an organosilane having an Si-bonded hydrogen. Likewise the number of ali-113f~6~9 phatic multiple bonds in polymers may be decreased in, for example, poly-(oxyalkylene)-polyols, by reacting polymers of this type containing ali-,phatic multiple bonds with organopolysiloxanes having at least two Si-bonded hydrogen atoms per molecule.
Although the process of-an aspect of this invention may be used - - 6 a -1~3t~639 to modify polymeric silicon-containing compounds, it is equally applicable for crosslinking, i.e., the curing or vulcanization of compositions containing alkenyl groups, es-pecially vinyl groups, and organopolysiloxanes containing Si-bonded hydrogen. In the crosslinking of compositions contain-ing alkenyl groups and organopolysiloxanes containing Si-bonded hydrogen, the activity of the catalyst at room temper-ature can be of great importance in order to achieve rapid crosslinking at temperatures in the range of from 18 to 35C.
lC Thus, the process of an aspect of this invention is preferred for the crosslinking of such compositions which may, for example, be used for potting or encapsulating electrical or electronic devices or which may be used as coatings or as compositions which may be used in preparing coatings which repel adhesive sub-stances, such as for coating paper. Such compositions may alsobe used for pre-cast concrete molds and for making impressions of human or animal teeth.
In making dental impressions, a mixture containing (a) organopolysiloxanes having silicon bond hydrogen, (b) organopoly-siloxanes having aliphatic unsaturation, (c) the platinum cata-lyst of this invention and ~d) other additives, if desired, are applied to the tooth or teeth of which an impression is to be taken and after the material has hardened, the resultant impression is removed from the tooth or teeth.
Agents which retard or inhibit the addition of Si-bonded hydrogen to an aliphatic multiple bond at room tempera-ture may of course be used when necessary or desired. Examples of such retardants are benzotriazole, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and/or 2-methyl-3-butyn-2-ol.
In the following examples all parts and percentages are by weight un~ess otherwise specified.
a) A mixture containing dicylcopentadiene-platinum di-chloride and diluent which is used in the examples is prepared in the following manner:
~0.2 g of dicyclopentadiene-platinum dichloride is dissolved in 20 ml of methylene chloride. The solution is mixed with 100 g of a dimethylpolysiloxane having terminal vinyldimethylsiloxy units and a viscosity of 1000 mPa at 23C.
The mixture is stirred at room temperature and at 1 bar until 11366~
the methylene chloride evaporates. The resultant mixture con-tains 0.1 percent of platinum, calculated as elemental platinum.
b) A mixture containing dimethylsulfoxide-ethylene-platinum-(II)-dichloride and diluent which is used in the follow-ing examples is prepared in accordance with the procedure des-cribed in (a) above, except that 0.2 g of dimethylsulfoxide-ethylene-platinum-(II)-dichloride is used instead of the 0.2 g of dicyclopentadiene-platinum dichloride. 'The mixture thus obtained also contains 0.1 percent of platinum, calculated as elemental platinum.
Exalmple 1 I - 90 g of dimethylpolysiloxane having terminal vinyldimethysiloxy units and a viscosity of 1000 mPa at 23 C, are mixed with 2 g of the platinum complex prepared in accordance with the procedure described in (a) above. The mixture thus obtained is stored for 5 days at room temperature. 10 g of a copolymer having a viscosity of 700 mPa at 23C and contain-ing dimethylsiloxane, methylhydrogensiloxane and trimethyl-siloxane units are added to the mixture. The'mole ratio of the dimethylsiloxane units to the methylhydrogensiloxane units in the mixture is 1:9. The time which el`apsed after the mixing of the copolymer and observable crosslinking of the composition is 2 minutes. The resultant mixture contains 20 ppm of platinum, calculated as elemental plati'num. 5 Example 2 The procedure of Example 1 is repeated, except that 2 g of the platinum complex prepared in accordance with (b) above is substituted for the platinum complex prepared in ac-cordance with (a) above. The organopolysiloxane containing the platinum complex is stored for 5 days before being mixed with the organopolysiloxane containing Si-bonded hydrogen. Cross-linking is observed 45 seconds after the organopolysilox-ane containing the platinum complex is initially mixed with the organopolysiloxane containing Si-bonded hydrogen.
Comparison Example a) 1~3~i6~9 The procedure described in Example 1 is repeated, except that 0.2 g of a 1 percent platinum solution, calculated as elemental platinum of a platinum-divinyltetramethyldisilox-ane complex in dimethylpolysiloxane having terminal vinyl-dimethylsiloxy groups is substituted for 2 g of the platinumcomplex prepared in accordance with (a) above. This solution is prepared in accordance with the following procedure which is described in Example 6 of U. S. Patent No. 3,814,730.
To a mixture containing 10 parts of H2PtC16-6H20, 20 10parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 50 parts of ethanol, are added 20 parts of sodium bicarbonate. The mixture is boiled under reflux for 30 minutes, then allowed to stand for 15 hours and subsequently filtered. The volatile components are removed from the filtrate by distillation at 1516 mbar. The residue is then dissolved in benzene, filtered and the benzene distilled from the filtrate. The resi-due is dissolved in a sufficient amount of a dimethylpolysilox-ane having terminal vinyldimethylsiloxy groups and a viscosity of 1000 mPa at 23C to provide a solution containing 1 percent platinum, calculated as elemental platinum.
The organopolysiloxane platinum complex is stored for 5 days before it is mixed with the organopolysiloxane contain-ing Si-bonded hydrogen. Crosslinking is observed 2.5 minutes after the two organopolysiloxanes are mixed.
Example 3 Mixture A: A mixture containing 102.5 parts of a dimethylpolysiloxane having terminal vinyldimethylsiloxy groups and a viscosity of 22,000 mPa at 23C, 145 parts of cristobal-lite meal and 5.5 parts of a commercially available silicon dioxide produced pyrogenically in the gaseous phase with a BET
surface area of 200 m /g which has been treated with dimethyl-dichlorosilane to impart hydrophobic properties to about 60 per-cent of its surface area, is mixed with 10 parts of the platinum complex prepared in accordance with the procedure described in (a) above. The resultant mixture contains 40 ppm of platinum, calculated as elemental platinum.
Mixture B: 97 parts of dimethylpolysiloxane having terminal vinyldimethylsiloxy groups and a viscosity of _ g _ 1~3t;6~39 22,000 mPa at 23C, are mixed with 137 parts of cristobalite meal, 9.2 parts of the treated silicon dioxide described in mixture (A) above, and 9.8 parts of a copolymer having a vis-cosity of 200 mPa at 23C and consisting of dimethylsiloxane, methylhydrogensiloxane and trimethylsiloxane units, in which the molar ratio of the dimethylsiloxane units to the methyl-hydrogensiloxane units is 6:1.
: Mixtures (A) and (B) are stored for 3 days at room tem-perature and then mixed toge her in a weight ratio of l:l.
Crosslinking is observed 50 seconds after mixtures (A) and (B) arelcombined at room temperature.
Example 4 The procedure described in Example 3 is repeated, except that 10 parts of the platinum complex prepared in accor-dance with (b) above are substituted for the platinum complexprepared in (a) above.
Crosslinking is observed 30 seconds after mixture (B) is combined with mixture (A) at room temperature.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition comprising an organosilicon compound contain-ing Si-bonded hydrogen and an organic compound containing an aliphatic multiple bond and a platinum catalyst selected from the group consisting of complexes of the formula (R1)PtX2, and (R2SO)(Z)PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of the same or different halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-carbon double bond and Y is the same or different halogen atom.
2. The composition of claim 1, wherein R is dicyclopentadiene and X is chlorine.
3. The composition of claim 1, wherein R1 is dicyclo-pentadiene and X is an alkyl radical having from 1 to 4 carbon atoms.
4. The composition of claim 1, wherein the platinum complex having the formula ( R2SO)(Z)PtY2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
5. An improved process for the addition of an organo-silicon compound containing Si-bonded hydrogen to an organic compound containing an aliphatic multiple bond in the presence of a platinum catalyst, the improvement which comprises conducting the addition in the presence of a platinum catalyst selected from the group consisting of complexes of the formula (R1)PtX2 , and (R2SO) (Z)PtY2 11 .
where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R1 is selected from the group consist-ing of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-carbon double bond and Y is the same or different halogen atom.
where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R1 is selected from the group consist-ing of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds, X is selected from the group consisting of halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-carbon double bond and Y is the same or different halogen atom.
6. The improved process of Claim 5, wherein R1 is dicyclopenta-diene and X is chlorine.
7. The improved process of claim 5, wherein R1 is dicyclopenta-diene and X is an alkyl radical having from 1 to 4 carbon atoms.
8. The improved process of claim 5, wherein the platinum com-plex having the formula (R2SO) (Z)PtY2 is dimethylsulfoxide-ethylene-platinum-(II)-dichloride.
9. The improved process of claims 5 or 6 wherein the organo-silicon compound is an organopolysiloxane containing Si-bonded hydrogen and the organic compound is an organopolysiloxane containing alkenyl groups.
10. The improved process of claims 7 or 8 wherein the organo-silicon compound is an organopolysiloxane containing Si-bonded hydrogen and the organic compound is an organopolysiloxane containing alkenyl groups.
11. An improved method for making dental impressions which comprises applying a composition containing an organopolysiloxane having alkenyl groups, an organopolysiloxane containing Si-bonded hydrogen and a platinum catalyst to a tooth and thereafter removing the crosslinked organopolysiloxane impression, the improvement which comprises adding a platinum catalyst selected from the group consisting of complexes of the formula (R1)PtX2 and (R2SO)(Z)PtY2 where R is selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R1 is selected from the group con-sisting of cyclic hydrocarbon radicals and substituted cyclic hydrocarbon radicals having two aliphatic carbon-carbon double bonds X is selected from the group consisting of the same or different halogen atoms and the same or different alkyl radicals, Z is a hydrocarbon having a carbon-car-bon double bond and Y is the same or different halogen atom.
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|---|---|---|---|
| DEP2846621.9 | 1978-10-26 | ||
| DE19782846621 DE2846621A1 (en) | 1978-10-26 | 1978-10-26 | METHOD FOR APPLYING SI-TIED HYDROGEN TO ALIPHATIC MULTIPLE BINDING |
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| CA1136639A true CA1136639A (en) | 1982-11-30 |
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| CA000338416A Expired CA1136639A (en) | 1978-10-26 | 1979-10-25 | Addition of si-bonded hydrogen to an aliphatic multiple bond |
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| US (1) | US4276252A (en) |
| EP (1) | EP0011714B1 (en) |
| JP (1) | JPS5931533B2 (en) |
| AT (1) | ATE325T1 (en) |
| AU (1) | AU529001B2 (en) |
| BR (1) | BR7906596A (en) |
| CA (1) | CA1136639A (en) |
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| US3453234A (en) * | 1968-01-31 | 1969-07-01 | Dow Corning | Latent catalyst containing platinum and sulfoxide |
| US3814730A (en) * | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
| DE2724822A1 (en) * | 1977-06-02 | 1978-12-07 | Consortium Elektrochem Ind | PROCESS FOR ADDING SI-BONDED HYDROGEN TO ALIPHATIC MULTIPLE BONDING |
| JPS5476529A (en) * | 1977-11-28 | 1979-06-19 | Shin Etsu Chem Co Ltd | Addition reaction method |
| JPS5476530A (en) * | 1977-11-30 | 1979-06-19 | Shin Etsu Chem Co Ltd | Addition reaction method |
-
1978
- 1978-10-26 DE DE19782846621 patent/DE2846621A1/en not_active Withdrawn
-
1979
- 1979-08-28 MX MX179081A patent/MX153329A/en unknown
- 1979-09-27 AU AU51256/79A patent/AU529001B2/en not_active Ceased
- 1979-10-11 BR BR7906596A patent/BR7906596A/en unknown
- 1979-10-17 US US06/085,572 patent/US4276252A/en not_active Expired - Lifetime
- 1979-10-25 NO NO793423A patent/NO793423L/en unknown
- 1979-10-25 CA CA000338416A patent/CA1136639A/en not_active Expired
- 1979-10-25 ES ES485359A patent/ES485359A1/en not_active Expired
- 1979-10-26 JP JP54137896A patent/JPS5931533B2/en not_active Expired
- 1979-10-26 EP EP79104155A patent/EP0011714B1/en not_active Expired
- 1979-10-26 DE DE7979104155T patent/DE2961081D1/en not_active Expired
- 1979-10-26 AT AT79104155T patent/ATE325T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2846621A1 (en) | 1980-05-08 |
| DE2961081D1 (en) | 1981-12-24 |
| AU5125679A (en) | 1980-05-01 |
| JPS5931533B2 (en) | 1984-08-02 |
| EP0011714A2 (en) | 1980-06-11 |
| ES485359A1 (en) | 1980-05-16 |
| AU529001B2 (en) | 1983-05-19 |
| ATE325T1 (en) | 1981-11-15 |
| NO793423L (en) | 1980-04-29 |
| EP0011714A3 (en) | 1980-06-25 |
| JPS5559198A (en) | 1980-05-02 |
| US4276252A (en) | 1981-06-30 |
| BR7906596A (en) | 1980-07-15 |
| MX153329A (en) | 1986-09-17 |
| EP0011714B1 (en) | 1981-10-21 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |