CA1261502A - Heat curable silicones having improved room temperature stability - Google Patents
Heat curable silicones having improved room temperature stabilityInfo
- Publication number
- CA1261502A CA1261502A CA000470770A CA470770A CA1261502A CA 1261502 A CA1261502 A CA 1261502A CA 000470770 A CA000470770 A CA 000470770A CA 470770 A CA470770 A CA 470770A CA 1261502 A CA1261502 A CA 1261502A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- value
- group
- radicals
- plus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- C08K5/01—Hydrocarbons
-
- 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
- C08K5/54—Silicon-containing compounds
-
- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- 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
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Abstract
HEAT CURABLE SILICONES HAVING IMPROVED ROOM
TEMPERATURE STABILITY
Abstract Improved inhibitor systems are disclosed for the reaction of silicon hydride containing silicones with vinyl containing and/or hydroxyl containing silicones. The improved inhibitors are mixtures of conjugated ane-ynes and vinylcyclosiloxanes. Inhibition of cure at room temperature is combined with rapid cure at elevated temperature when the improved inhibitors are used.
TEMPERATURE STABILITY
Abstract Improved inhibitor systems are disclosed for the reaction of silicon hydride containing silicones with vinyl containing and/or hydroxyl containing silicones. The improved inhibitors are mixtures of conjugated ane-ynes and vinylcyclosiloxanes. Inhibition of cure at room temperature is combined with rapid cure at elevated temperature when the improved inhibitors are used.
Description
5Ci ~
w L
IIE~T CU~ABLE SILICONES HAVING I~PROVED ROC~I
TEMPERATU~E STABILITY
This invention relates to heat curable 3ilicones having improved room temperature stability. More specifically, this invention deals with silicone compositions that are curable at elevated temperatures by the catalyzed reaction of silane, hereinafter also SiH, groups to silicon-bonded vinyl groups, hereinafter also SiVi, and/or silicon bonded hydroxyl groups, hereinafter also SiOH.
The reaction of SiH groups with SiVi and/or SiOH
groups is a well known reaction for crosslinking silicone resins, elastomers, and coatings. ' While this reaction provides rapid cure at elevated temperatures, there is an unfortunate tendency for cure to proceed'slowly at room temperature. This tendency limits the amount of time a composition can be stored before use, as well as the work life of a composition in an industrial process.
This problem has been dea~ with in two ~eneral ways: separation of the reactants until just before use, and the use of inhibitors.
Separation of the reactants before use is generally accomplished by providing the heat'curable composition in two parts. One of these parts contains the SiH containing component, while the other contains the SiVi and/or SiOH containing component, and the catalyst. These two parts are then mixed prior to use.
There are disadvantages to the use of such two part systems however. .4mong other disadvantages, expenses related ~o pack~ging, sh~pping, harcl3ing, and stor~ge are increased.
.,. ~.
5~2 In addition, in such applicatlons as release coatings, where very rapid cure is essent$al, high levels of reactive groups and catalyst are used. A release coating supplied in two parts must still maintaln a reasonable stab1lity, after the two parts are mixed, to be practical.
The use of inhibitors is another solution to the problem of lack of room temperature stability.
The patent literature, for example, discloses the following classes of compounds as inh~bitors for the reaction of SiH groups with SiVi and/or SiOH groups:
vinyl amides hydroperoxides aminoalkyl silanes various ~etal salts suloxides acrylonitrile derivatives acetylene derivatives, such as dialkylacetylene dicarboxylates and ethynylically unsa~urated isocyanurates, phosphir.es, phosphites, nitrogen-containing hydrocarbons, such as pyridine, dithiocarbamate derivatives, and the like.
U.S. Patent No., 4,340,709, issued July 20, l982, discloses the use of methylvinylcyclotetra~iloxahe, tri~lkylcyanurates, alkyl maleates, and mixtures of the above three t-jpes of compounds as inhib~tors.
U.S. Patent No. 4,465,8l8 issue~ August 14, 19~4, and entitled "P~oom Temperature Stable, ~ea~
Activated Organopolvsiloxane Co~positions" disclosas the use of conJugated ene-ynes as inhibitors of the reaction of SiH and Si~i.
l5~3~
Con;u~ated ene-ynes are hydrocarbons containing a triple bond, i.e. an "yne" bond, and a double bond, i~e. an "ene" boad in con~ugation with one another.
U.S. Patent No. 4,340,710, issued July 20, 1982, discloses the use of ethynylically unsaturated isocyanurates snd dialkyla~etylenecarboxylates con;ointly as inhibitors.
The present invention deals with ~he use, as the inhibitor, of vinylcyclosiioxanes in combination with one or more conjugated ene-yne(s). Surprisin~ly, the use of this combination results ln room temperature inhibition of cure that is 5 or more times as effectlve as the room temperature inhibition of cure observed for comparable levels of either the ene-yne or the vinylcyclosiloxane independently. In addition, no significant reduction in the rate of cure at elevated temperature has been noted.
In some cases, actual acceleration of the elevated temperature cure rate has been observed.
It i9 an object of this invention to provide a silicone composition that is curable at elevated temperature and has improved stability at room temperature.
It ls another object to provlde silicone coating co~posi~ions that are curable at elevated temperature and have improved stabili~y at room temperature. It is vet another object to p.ovide sili.one resins ~hat are curable at elevated temperatures and have improved stability at room temperature. It is a further object to provide silico~e elastomers that are curable at elevated temperatures and hsve improved stability at room temperature. It is another ob;ect to provide curable silicone composi~ions having extended work life. It is another object to provide imprGved inhibitors.
~i~'h ,,.~, ~2~ %
These ob~ects and others are attained by t~.e compositions of this invention9 which compositions comprise, in co~bination:
(A) a silicone containing SiVi groups and/or SiOH
groups;
(B) A silicone containing SiH groups;
(C) a catalyst;
(D) A conjugated ene-yne; and (E) vinylcyclosiloxanes.
This inventiqn relates to a curable silicone composition comprlsing the combination of:
(A) a polyorganosiloxane having the general formula 3 ( aQbslo(4-a-b)/2) x SiR3, wherein Rl is a non-olefinic monovalent hydrocarbon or haloganated hydrocarbon radical;
Q is a vinyl-containing radical of the general formula (Cn~2n)CH=CH2, wherein n has a ~alue of from O to 4;
R is selected from the group consisting of R
radicals, Q radicals, and hydroxyl radicals;
x has a value of from 18 to 6000;
a has a value of 0 9 1 or 2;
b has a value of 0, 1 or 2;
the average sum of the ~alues of a plus b is from 108 to 2.2;
there is at least one radical per polyorganosiloxane selected from the group CQnSiSting of Q radicals and hydroxyl radicals;
(B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a ca~alyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
,, 1) from 5 to 12 carbon aeoms;
w L
IIE~T CU~ABLE SILICONES HAVING I~PROVED ROC~I
TEMPERATU~E STABILITY
This invention relates to heat curable 3ilicones having improved room temperature stability. More specifically, this invention deals with silicone compositions that are curable at elevated temperatures by the catalyzed reaction of silane, hereinafter also SiH, groups to silicon-bonded vinyl groups, hereinafter also SiVi, and/or silicon bonded hydroxyl groups, hereinafter also SiOH.
The reaction of SiH groups with SiVi and/or SiOH
groups is a well known reaction for crosslinking silicone resins, elastomers, and coatings. ' While this reaction provides rapid cure at elevated temperatures, there is an unfortunate tendency for cure to proceed'slowly at room temperature. This tendency limits the amount of time a composition can be stored before use, as well as the work life of a composition in an industrial process.
This problem has been dea~ with in two ~eneral ways: separation of the reactants until just before use, and the use of inhibitors.
Separation of the reactants before use is generally accomplished by providing the heat'curable composition in two parts. One of these parts contains the SiH containing component, while the other contains the SiVi and/or SiOH containing component, and the catalyst. These two parts are then mixed prior to use.
There are disadvantages to the use of such two part systems however. .4mong other disadvantages, expenses related ~o pack~ging, sh~pping, harcl3ing, and stor~ge are increased.
.,. ~.
5~2 In addition, in such applicatlons as release coatings, where very rapid cure is essent$al, high levels of reactive groups and catalyst are used. A release coating supplied in two parts must still maintaln a reasonable stab1lity, after the two parts are mixed, to be practical.
The use of inhibitors is another solution to the problem of lack of room temperature stability.
The patent literature, for example, discloses the following classes of compounds as inh~bitors for the reaction of SiH groups with SiVi and/or SiOH groups:
vinyl amides hydroperoxides aminoalkyl silanes various ~etal salts suloxides acrylonitrile derivatives acetylene derivatives, such as dialkylacetylene dicarboxylates and ethynylically unsa~urated isocyanurates, phosphir.es, phosphites, nitrogen-containing hydrocarbons, such as pyridine, dithiocarbamate derivatives, and the like.
U.S. Patent No., 4,340,709, issued July 20, l982, discloses the use of methylvinylcyclotetra~iloxahe, tri~lkylcyanurates, alkyl maleates, and mixtures of the above three t-jpes of compounds as inhib~tors.
U.S. Patent No. 4,465,8l8 issue~ August 14, 19~4, and entitled "P~oom Temperature Stable, ~ea~
Activated Organopolvsiloxane Co~positions" disclosas the use of conJugated ene-ynes as inhibitors of the reaction of SiH and Si~i.
l5~3~
Con;u~ated ene-ynes are hydrocarbons containing a triple bond, i.e. an "yne" bond, and a double bond, i~e. an "ene" boad in con~ugation with one another.
U.S. Patent No. 4,340,710, issued July 20, 1982, discloses the use of ethynylically unsaturated isocyanurates snd dialkyla~etylenecarboxylates con;ointly as inhibitors.
The present invention deals with ~he use, as the inhibitor, of vinylcyclosiioxanes in combination with one or more conjugated ene-yne(s). Surprisin~ly, the use of this combination results ln room temperature inhibition of cure that is 5 or more times as effectlve as the room temperature inhibition of cure observed for comparable levels of either the ene-yne or the vinylcyclosiloxane independently. In addition, no significant reduction in the rate of cure at elevated temperature has been noted.
In some cases, actual acceleration of the elevated temperature cure rate has been observed.
It i9 an object of this invention to provide a silicone composition that is curable at elevated temperature and has improved stability at room temperature.
It ls another object to provlde silicone coating co~posi~ions that are curable at elevated temperature and have improved stabili~y at room temperature. It is vet another object to p.ovide sili.one resins ~hat are curable at elevated temperatures and have improved stability at room temperature. It is a further object to provide silico~e elastomers that are curable at elevated temperatures and hsve improved stability at room temperature. It is another ob;ect to provide curable silicone composi~ions having extended work life. It is another object to provide imprGved inhibitors.
~i~'h ,,.~, ~2~ %
These ob~ects and others are attained by t~.e compositions of this invention9 which compositions comprise, in co~bination:
(A) a silicone containing SiVi groups and/or SiOH
groups;
(B) A silicone containing SiH groups;
(C) a catalyst;
(D) A conjugated ene-yne; and (E) vinylcyclosiloxanes.
This inventiqn relates to a curable silicone composition comprlsing the combination of:
(A) a polyorganosiloxane having the general formula 3 ( aQbslo(4-a-b)/2) x SiR3, wherein Rl is a non-olefinic monovalent hydrocarbon or haloganated hydrocarbon radical;
Q is a vinyl-containing radical of the general formula (Cn~2n)CH=CH2, wherein n has a ~alue of from O to 4;
R is selected from the group consisting of R
radicals, Q radicals, and hydroxyl radicals;
x has a value of from 18 to 6000;
a has a value of 0 9 1 or 2;
b has a value of 0, 1 or 2;
the average sum of the ~alues of a plus b is from 108 to 2.2;
there is at least one radical per polyorganosiloxane selected from the group CQnSiSting of Q radicals and hydroxyl radicals;
(B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a ca~alyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
,, 1) from 5 to 12 carbon aeoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group; and (E) a vinylcyclosiloxane having the general formula (R5CH2-CHSio)-m wherein each R is selected from methyl, e~hyl~ and phenvl groups, and m has an average value of from 3 to 6.
In other aspects, this invention deals with heat curable silicone coating co~positions, with heat curable silicone elastomer composltions, and wlth heat curable silicone resin composltions, all of said compositions having enhanced roo~ temperature stability, and to the p oducts obtainet bv curing the above compo~i~ions.
The present invention~ in a further aspect, resides in a catalyst inhibitor consisting essentially of from 1 to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having l) from 5 to 12 carbon atoms; 2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group; and from l to 99 parts by weight of a vinylcyclosiloxane having the general formula RSCH2=CHSiO)m;
wherein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
In a still further aspect, the present invention provides an improvement in a curable silicone composition comprising a vinyl-containing or hydroxyl-containing polyorganosiloxane, a polyorgano-hydrogensiloxane containing hydrogen atoms bonded to silicone atoms, a catalyst, and a catalyst inhibitor, which improvement comprises the use of, as the catalyst inhibitor, a composition consisting essentially of from l to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having l) from 5 to 12 carbon atoms; 2) a terminal ethynyl group; 3~ an ethenyl group in conjugation with said ethynyl group; and from l to 99 parts by weight of a vinylcyclosiloxane having the general formula .~
, . . .
%
(R CH2-CHSiO)m wherein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
Component ~A) of the compositions of this invention is an SiYi or SiOH containing polyorganosiloxane havlng the general formula 1 3 ( aQbsio(4-a-b)/23 x SiR3, wherein R is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical; Q is a vinyl-containing ra~ical of the general formula (Cn~2n)CH~C~2, whereln n has a value of from O to 4; R is selected from 'the group consisting of ~1 radicals, Q radicals 9 and hydroxyl radicals; x has a value of from 18 to 6000; a has a value of 0, 1 or 2; b has a value of 0, 1 or 2; the average sum of the values of a plus b is from 1.8 to 2.2; there is at least one radical per polyorganosiloxane selected from the group consisting of Q radicals and hydroxyl radicals.
Those o~ skill in the art will recognize that side chains present ln such polyorganosiloxanes are terminated by R3SiO~groups, just as the main chain is.
~' ., ,.~ .
~6~S~:
~ y non-olefinic hydrocarbon radical, it is mean~
herein that said radical is singly bonded to a silicon atom, ~hat said radical contains only single bonds, and that said radical is composed of carbon and hydrogen atoms.
By non-olefinic, monovalent, halogenated hydrocarbon, it is meant herein a non-olefinic hydrocarbon radical as defined above in which some or all of the hydrogen atoms have been replaced with halogen atoms, such as fluorine, chlorine, or bromine.
Examples of suitable non-olefinic monovalent hydrocarbon and halogenated hydrocarbon radicals include alkyl radicals9 such as methyl, ethyl, propyl, butyl, and the like; halogenated alkyl radicals such as chloropropyll 3,3,3-trifluoropropyl and the like; cycloaliphatic radicals such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like; aryl radicals such as phenyl, tolyl, xylyl and the like; and aralkyl radicals such as 2-phenyloctyl, ben2yl, 2-ethyltolyl and the like. More preferably, most or all of the non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radicals discussed in this specification are salected from the group consisting of methyl, phenyl, and 3,3,3-trifluoropropyl radicals.
Most preferably, most or all of the non-olefinic monovalent hydrocarbon or halogenated monovalent hydrocarbon radicals are methyl radicals.
Polyorganosiloxanes as described above are well known. Many can be obtained commercially; others can be synthesi~d from more basic starting materials using well known synthetic techniques.
~ or example, hydrolysis and subsequent condensation of monomers described by the formula Rl QbSiX4 a b~ wherein Rl, Q, a, and b are as hereinabove described, and X is a hydroly~able radical, such as a nalogen atom o. an alko~y radical, will result in polyorganosiloxanes suitable for use a~ component ~A~.
Specific examples of polyorganosiloxanes suitable for use as component (A) include:
HOMe2SiO(MeViSiO)s(Me2siO)95siMe2oH;
Me3si(Mevisi)20(Me2si)20si~le3;
Me2ViSiO(MeViSiO~6(Me2SiO)98SiMe2vi;
HOMe~SiO(Me2SiO)~O0osiMe2oH;
a resin composed of Me2ViSiO~ units, Me3SiO~ units and SiO4/2 unlts;
CF3CH2CH2Me2S1(~eViSi)15(CF3CH2CH2MeSi)85SiMe2CH2C~2C~3;
and other polyorganosiloxanes having SiVi groups and/or SiOH group. The term Me is used herein to represent the methyl radical, and the term Vi to represent the vinyl radical.
Component (B) of the compositions of this inven~ion is a polyorganosilo~ane containing one or more hydrogen atoms, bonded to silicon atoms. Component (B) is described by the general unit formula:
cHdSi(4-c-d)/2 ~ wherein R is a non-olefinic monovalent hyd.ocarbon or halogenated hydrocarbon radical as described for R' of component (A);
H is a hydrogen atom;
c has a value of 0, 1; 2 or 3; and d has a value of 0, 1 or 2; there being at least one unit wherein d has a value of I.
Units of the abGve description are combined to form linear, branched, or cyclic polymers.
Preferably, c has a value of O, 1 or 2, d has a value of 0 or 11 and the values of c and d are selected such that their sum is from 1.8 ~o 2.2.
.
., --8~
A pol~organosiloxane of this description is substantially linPar, and can be represented by the general fOr~ula R3SiO(Rc HdSi(4-c-d)/3~YSi 3' selected from ~ radicals and R radicals, and ~ has a value of from 18 to 6000. There must be at least one H atom present in said polyorganosiloxane on average.
Polyorganosiloxanes as described for component (B) are well known. Many are commercially available. The synthesis of such polyorganoslloxanes from raore basic starting materials is also well known.
For example, hydrolysis and condensation of ~onomers described by the general formula R 3HdSiX4 c d~ wherein R3, c, d, and X are all as hereinabove described, is a method for producing polyorganosiloxanes suitable for use as component (B).
Specific examples of polyorganosiloxanes sultable for use as component (B) include:
(MeHSiO)5;
Me2HSiO(MeHSi.O)5(M&2SiO)43siMe2H;
Me3sio(MeHsio)22~Mec6H5sio)28siMe3;
Me~sio(MeHsio~35siMe3;
Me3SiO~MeHS1O)30(Me2SiO)970SiMe3;
Me2HSiO(Me2SiO)450SiMe2H~
Me3SiO(Me~lSiO)24(CF3CH2CH2Mesi)74SiMe3;
resins containing MeHSiO units, Me3SiO~ units and SiO4/2 units; and other suitable polyorganosiloxanes containing SiH groups which will be familiar to those skilled in the art.
Component (C) of the composition of this invention is the catalys~. The catalyst is selected from the salts, compounds and elemental forms of platinum, rhodium, palladium, ruthenium, rheniuml osmium, and iridium.
~...
. .
V~
It is ?rererred that salts or compounds of the above metals ~hat are soluble in a mixture of components (~), (B), (D) and (E) be selected.
It is further preferred that the catalyst be selectsd from the soluble sa~lts and compounds of platinum and rhodium.
It is most preferred to use a pla~lntlm compound that is soluble in components (A)~ (B), (D) and (E).
A particularly preferred catalyst is the compound formed by heating chloroplatinic acid with an SiVi-containing polyorganosiloxane.
Catalysts as described above are well know~.
Component (D) of the compositions of this invention is thP conjuga~ed ene-yne. The conjugated ene-yne is characterized by containing:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group; and 3) an ethenyl group in conjugation with said ethyny~
- group.
The term '!conjuga~ion" as used herein is to be construed as follows: two multiple bonds ln a hydrocarbon may be said to be conjuga~ed if they are separated by one, and only one, single bond.
Componen~ (D) is a hydrocarbon, that is, component (D) is composed of hydrogen and carbon a~oms.
Rxamples of con,jugated ene-ynes suitable for use as component (D) are the following:
HC-C-C=CH-CH3, HC-C-C=CH-CH2CH3~
- 1 0~ Z
HC-C-C-CH-CH(GH3)~.
HC=C-C-C~2, HC-C-C=CH2, ~ HC-C ~ .
HC-C ~ , HC=C-CH ~ , HC-C-C=
~ CH3 CH3 HC-C ~ and HC-C ~ CH3 particularly preferred conjugated ene-ynes are HC-C ~ , and HC=C-C= ca- CH ( CH3)2 C~13 Conjugated ene-yneq suitable for use as component (D~ can be synthesiæed from available starting materials by methods well known in organic chemistry. The patent literature also discusses methods for the synthesis of conjugated ene-ynes sultable for use as component (D) of the compositions of this invention.
For example, ~he appropriate ethynyl group terminated alcohol can be dehydrated in pyridine by PC15 to form the corresponding conjugated ene-yne. This is illustrated by the follow~ng exemplary equation:
26~f~2 ~< pyridina IIC~C~3 C-CH
O~her methods of synthesizing conjugated ene-ynes are known by those skilled in the art.
Component (~) of the compositions of this invention9 is vinylcyclosiloxane. Vinylcyclosiloxane is represented by the general formula (R5ViSio) , wherein each m has an integer value of 3, 4, 5, 6, 7, ~, and higher lntegers. Each R5 is selected from methyl, ethyl, and phenyl groups. Preferably R5 is a methyl group.
Vinylcyclosiloxanes are frequently furnished a4 mixtures in which m has an average value bet~een 4 and 5. It is to be understood that this average value encompasses species wherein m is 3, 4, 5, 6, 7, 8, and higher integers. It is not known at ~his time whether the particular value, or average value, of m has any effect on the composition of this inventlon. It is al50 not known if the use of a mixture rather than a pure compound has any effect on the compositions of this invention. It is not believed that the inclusion of small amounts9 such as 10 or 15 mO18 percent, of other diorganosiloxane units has any significant effect. Examples of possible contaminatlng diorganosiloxane unit~s are ~Me2SiO) units, ~MeC6H5SiO) units and the like.
Vlnylcyclosiloxanes are well known lntermediates in organosilicon chemistry. They are readily commercially available.
The relative amounts of components (A) thru (E) that are used in the composition of this invention are not narrowly critical, and can vary widely. The relative ~2~
1~--amounts ot the components used depends largely upon the desired use of the composition.
All amounts set forth herein are expressed in parts by weight, based upon 100 total parts of component (A), (B), (D), and (E).
8roadly:
component (A) is present from O.S to 99.48 parts;
component (B) is present from 0.5 to 99.48 parts;
component (C) is present from 0.000001 to 1.0 parts;
component (D) is present from 0.01 to 10 parts;
and component (E) is present from 0.01 to 10 parts, all of the above parts based upon 100 total parts of (A) plus (B) plus ~D) plus (E).
More preferably:
component (A) is present from 92 to 98.5 parts;
componen~ (B) is present from 1.4 to 10 parts, component (C~ is present from 0.004 to 0.50 parts;
component (D) is present from 0.05 to 5 parts;
component (E) is present from 0~05 to ~ parts;
all o the above parts based upon 100 total parts of (A) plus (B) plus (D) plus (E).
The compositions of this invention can contain other, optional ingredients. For example, the compositions of this invention can contain fillers, solvents, flame retardants, antimicrobial preparations, surfactants, oxidation inhibitors, dyes, pigments, perfumes, and the like.
Of course, any addi~ives which are known, or are discovered, to poison the catalyst or other~Jise render the compositions unusable, are to be avoided.
~26~2 When accounting for the amounts of such other, optional ingredients~ the amounts referred to herein are on the basis of 100 total par~s of components (A), (B), (D), and (E). Thus, as an example, the addition oE an equal amount of filler to a composition of this invention is expressed as 100 parts of filler added to 100 parts components (A), (B), (D) and (E) of this invention.
Examples of fillers useful in the composi~ions of this invention include ~einforcing fillers and extending fillers. Examples of reinforcing fillers include: sllica, such as fume silica and precipitated silica; and treated silica, such as fume or precipitated sllica that has been reacted with eOgO an organchalosilane, a disiloxane, or a disilazane.
Examples of extending fillers include crushed quartz, aluminum oxide, aluminum silicateJ zirconium silicate, magnesium oxide, zinc o~ide, talc, diatomaceous earth, iron oxide, calcium carbonate, clay, titania, ~irconia, mica, glass, such as ground glass or glass fiber, sand, carbon black, graphite, barium sulfate, zinc sulfate, wood flour, cork, fluorocarbon polymer powder, rice hulls, ground peanut shells, and the like.
Solvents sultable for use with the compositions of this invention include well known solvents for silicones having chemical compositions similar to those described for component (A) or component (B).
Examples of such solvents include aliphatic hydrocarbons, such as pentane, hexane~ heptane, octane, nonane and the like; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, and butanol; ketones such as acetone, methylethyl keto.e and methyl-isobutyl ketone; and halogenated solvents such as fluorine-, chlorine-, and bromine-substituted aliphatic or ,, .
aromatic hydrocarbons, such as trichloroethane, perchloroethylene, bromobenzene and the like. Two or more solvents may be used together.
The compositions of this invention are made by mixing together the desired quantities of component (A3, (B), (C), (D), (E), and any optional ingredients in suitable mixing equipment.
Suitable mixi~g equlpment is very w211 known and widely available. Selection of a specific type of mixing equipment will be guided by the vlscosity of the mixture of components (A)~ (B), (C), (D), and (E).
For example, if the viscosity of the mixture is expected to be low, such as lO to 500 centistokes, mechanical stirrers such as paddle stirrers can be used to produce a mixture of components (A) and (B~. If a viscosity from 500 centipoise to 100,000 centistokes is expected, such equipment as three roll mills, sigmoid blade mixers, bread dough mixers and the like can also be used.
If a viscosity in excess of 100,000 centipoise is expected, such equipment as two roll mills, or Baker Perkins mixers may be required.
The compositions of thls invention are cured by exposure to elevated temperature. The specific times and temperaturss that are to be used can vary widely, depending upon the specific use intended for the cured composition, the relative amounts of SiH, SiVi, and SiOH groups present, the amounts of catalyst~ amounts of inhibitor, and other factors.
For example, a composition having a high amount of SiH, SiVi and catalyst can be cured in a few seconds at 70C. hs another example, a composition having low amoun~s of SiH, SiOH and catalyst may require 3 or 4 hours at l20C
or so.
-l5 Three specific embodiments of the c~mpositions o.
chis invention are particularly contemplaced: flr~t, a heat curable silicone resin composition, second a heat curable silicone coating compositlon, and third a heat curable elastomer composition.
The curable silicone resin composition comprises the combination o~:
(A) a polyorganosiloxane having the general formula 3 ( aQbsio(4-a-b)/2) x SiR3, wherein pl is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q i~ a vinyl-containing radical of the general formula (H2n)CH-CH2, wherein n has a value of from 0 to 4;
R is selected from the group consisting of R
radicals, Q radicals, and hydroxyl radieals;
x has a value of ~rom 18 to 6000;
a has a value of 0, 1 or 2;
b has a value of 0, 1 or 2, the average sum of the values of a plus b is from 1.8 to 2.2;
there is at least one radical per polyorgdnosiloxane selected f rom the group consisting of Q radicals and hydroxyl radicals;
~B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a catalyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said etnynyl group;
(~) A vinylcyclosiloxane having the general formula -l6-(~ CH2-CHSlo~
~herein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to ~ ; and (F) a filler.
The curable resin compositîon of this invention is useful in encapsulating componen~s, such as electronic components; it is useful as a potting compound for electronic circuitry; and it is useful for other well known applica~ions of curable silicone resins.
The curable resin can be fabricated in various ~ well known processes, such as press molding, transfer molding, extrusion, potting, or other processes.
The second specific embodiment of the composition of the present invention is a curable coating composition for substrates, said coating composition comprising:
- (A) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula l 3 ~ aQbsio(4-a-b)/2) x SiR3, wherein R is a nsn-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R is selected from ~he group consisting of Q
radicals, Rl radicals, and OH radicals;
a has a value of O, 1 or 2;
_ has a value of O, 1, or 2;
the average sum of the values of a plus b is from 1.8 to 2.2, and X has a value of from 18 to 4000, there being at least one vinyl or OH group per molecule;
~ B) from 0.5 ~o 99.48 parts of a polyorganosiloxane having the formula 3 ( cHdsio(4-c-d)/2)ysiR3~ wher~in R3 is a non-olefinic monovalent hydrocarbon or halogenat2d hydrocarbon ~adical;
H is a hydrogen atom;
R is selected from the group consisting of ~ atoms, and R radicals;
c has a value of 0, 1 or 2;
_ has a value of 0, 1, or 2;
the average sum oP the values of c plus d i8 Erom 1.8 to 2.2; and has a value of from 13 to 500, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, of a catalyst;
(D) from 0.1 to 10 parts of an inhibitor, said inhibitor being a hydrocarbon containing:
1) from 5 to 12 carbon atoms;
2) a ter~inal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group;
(E~ from 0.01 to 10 parts-of a vinylcyclosilo~ane having the general formula (R CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6; and (G) from O to 4000 parts of a solvent, all of the above parts being parts by weight based on 100 total parts of Components (A) plus (B) plus (D) plus (E).
While the coating compositlon of the present invention can be furnished and used eithar with a solvent or without a solvent, it is preferred to furnish and use said composition without a solvent. Use without a solvent is facilitated by selecting components (A) and (B) that are relatively low in viscosity, e. a, 100 to 5000 centistokes.
~ ~ , The coating compositions of thP pre~ent invention can be applied to a variety of substrates. Examples of such sllbstrates include: na~ural products, such as wood and stone; paper products, such as paper, cardboard and the like; plastics, such as polyethylene, polypropylene, and polymethylpentene, polyethylene terephthalate, polybutylene terephthalate and the like; metals, such as aluminum, copper, zinc, magnesium, iron, steel, nickel, chromium and the like; and other substrates.
Application of the coating composition to the substrate can be accomplished by an appropriate coating technique. Examples o F coa~ing techniques useful with the coating composition of this invention include spray coating, direc~ gravure coating, offset gravure coating, Mayer rod coating, two-roll coating, kiss coating, air ~nife coating and other known coating techniques.
The coating compositions of this invention can be used to fabricate release paper of excellent quali~y.
The third specific embodiment of the composition of the present i~vention is a curable silicone elastomer composition, said composition comprisi~C
(A) from 0.5 to 99.48 parts of a polyorOanosiloxane having the formula 3 ( aQbsio(4-a-b)/2) x SiR3, wherein Rl is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R is selected from the group consisting of Q
radicals, Rl radicals, and OH radicals;
a has a value of O, 1 or 2;
b has a value of O, 1, or 2;
the average sum of the val~es of a plus b is fro~
to 2.2; and . . .
~;26~
has a value of from 50 to 6000, there being a~ least one vinyl or OH group per molecule;
~ B) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R3SiO(R cHdSi(4 c d)~2)ySiR3~ wherein R is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
H is a hydrogen atom;
R is selected from the group consisting of H atoms, and R radicals;
c has a value of 0, 1 or 2;
d has a value of 0, 1, or 2;
the average sum of the values of c plus d is from 1.8 to 2.2; and has a value of from 50 to 6000, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, o~ a catalyst;
(D).from 0.01 to 10 parts of an inhibitor, said inhibi~or being a hydrocarbon containing:
1~ from 5 to 12 carbon atoms;
2) a terminal ethynyl group; and 3~ an ethenyl group in conjugation with said ethynyl group;
(E~ from 0.01 to 10 parts of a vinylcyclosilo~ane having the general formula -(R CH2=CHSiO~m wherein each R5 is selec~ed from methyl, ethyl,and phenyl groups, and m has an average value of from 3 to 6; and (F) from 0 to 400 parts of a filler, all of the above parts being parts by weight based on 100 total parts of Components (A) pl.us (B) plus (D) plus (E).
, , , .
The curable silicone elastomer composition can be fabricated by any of the conventional silicone elastomer fabrication techniques, such as compression molding, in~ection molding, extrusion9 and other well known silicone rubber fabrication teehniques.
The following examples are presented to further illustrate making and using the compositions of this invention. These examples are not to be construed as placing limits on the scope of this invention. In the examples, all parts and percentages noted are by ~eight unless otherwise specified. Me in the examples denotes a methyl radical and Vi denotes a vinyl radical.
The vinylcyclosiloxanes used in the following examples were methylvinylcyclosiloxan~s represented by the formula (MeViSiO) . The relative amount3 of different cyclic species in the particular methylvinylcyclosiloxanes used in the examples are set forth in Table 1.
Table 1 Distribution of Methylvinylcyclosiloxane Species m Pe~rcenta~e by Wei~ht 3 12.6%
In other aspects, this invention deals with heat curable silicone coating co~positions, with heat curable silicone elastomer composltions, and wlth heat curable silicone resin composltions, all of said compositions having enhanced roo~ temperature stability, and to the p oducts obtainet bv curing the above compo~i~ions.
The present invention~ in a further aspect, resides in a catalyst inhibitor consisting essentially of from 1 to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having l) from 5 to 12 carbon atoms; 2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group; and from l to 99 parts by weight of a vinylcyclosiloxane having the general formula RSCH2=CHSiO)m;
wherein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
In a still further aspect, the present invention provides an improvement in a curable silicone composition comprising a vinyl-containing or hydroxyl-containing polyorganosiloxane, a polyorgano-hydrogensiloxane containing hydrogen atoms bonded to silicone atoms, a catalyst, and a catalyst inhibitor, which improvement comprises the use of, as the catalyst inhibitor, a composition consisting essentially of from l to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having l) from 5 to 12 carbon atoms; 2) a terminal ethynyl group; 3~ an ethenyl group in conjugation with said ethynyl group; and from l to 99 parts by weight of a vinylcyclosiloxane having the general formula .~
, . . .
%
(R CH2-CHSiO)m wherein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
Component ~A) of the compositions of this invention is an SiYi or SiOH containing polyorganosiloxane havlng the general formula 1 3 ( aQbsio(4-a-b)/23 x SiR3, wherein R is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical; Q is a vinyl-containing ra~ical of the general formula (Cn~2n)CH~C~2, whereln n has a value of from O to 4; R is selected from 'the group consisting of ~1 radicals, Q radicals 9 and hydroxyl radicals; x has a value of from 18 to 6000; a has a value of 0, 1 or 2; b has a value of 0, 1 or 2; the average sum of the values of a plus b is from 1.8 to 2.2; there is at least one radical per polyorganosiloxane selected from the group consisting of Q radicals and hydroxyl radicals.
Those o~ skill in the art will recognize that side chains present ln such polyorganosiloxanes are terminated by R3SiO~groups, just as the main chain is.
~' ., ,.~ .
~6~S~:
~ y non-olefinic hydrocarbon radical, it is mean~
herein that said radical is singly bonded to a silicon atom, ~hat said radical contains only single bonds, and that said radical is composed of carbon and hydrogen atoms.
By non-olefinic, monovalent, halogenated hydrocarbon, it is meant herein a non-olefinic hydrocarbon radical as defined above in which some or all of the hydrogen atoms have been replaced with halogen atoms, such as fluorine, chlorine, or bromine.
Examples of suitable non-olefinic monovalent hydrocarbon and halogenated hydrocarbon radicals include alkyl radicals9 such as methyl, ethyl, propyl, butyl, and the like; halogenated alkyl radicals such as chloropropyll 3,3,3-trifluoropropyl and the like; cycloaliphatic radicals such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like; aryl radicals such as phenyl, tolyl, xylyl and the like; and aralkyl radicals such as 2-phenyloctyl, ben2yl, 2-ethyltolyl and the like. More preferably, most or all of the non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radicals discussed in this specification are salected from the group consisting of methyl, phenyl, and 3,3,3-trifluoropropyl radicals.
Most preferably, most or all of the non-olefinic monovalent hydrocarbon or halogenated monovalent hydrocarbon radicals are methyl radicals.
Polyorganosiloxanes as described above are well known. Many can be obtained commercially; others can be synthesi~d from more basic starting materials using well known synthetic techniques.
~ or example, hydrolysis and subsequent condensation of monomers described by the formula Rl QbSiX4 a b~ wherein Rl, Q, a, and b are as hereinabove described, and X is a hydroly~able radical, such as a nalogen atom o. an alko~y radical, will result in polyorganosiloxanes suitable for use a~ component ~A~.
Specific examples of polyorganosiloxanes suitable for use as component (A) include:
HOMe2SiO(MeViSiO)s(Me2siO)95siMe2oH;
Me3si(Mevisi)20(Me2si)20si~le3;
Me2ViSiO(MeViSiO~6(Me2SiO)98SiMe2vi;
HOMe~SiO(Me2SiO)~O0osiMe2oH;
a resin composed of Me2ViSiO~ units, Me3SiO~ units and SiO4/2 unlts;
CF3CH2CH2Me2S1(~eViSi)15(CF3CH2CH2MeSi)85SiMe2CH2C~2C~3;
and other polyorganosiloxanes having SiVi groups and/or SiOH group. The term Me is used herein to represent the methyl radical, and the term Vi to represent the vinyl radical.
Component (B) of the compositions of this inven~ion is a polyorganosilo~ane containing one or more hydrogen atoms, bonded to silicon atoms. Component (B) is described by the general unit formula:
cHdSi(4-c-d)/2 ~ wherein R is a non-olefinic monovalent hyd.ocarbon or halogenated hydrocarbon radical as described for R' of component (A);
H is a hydrogen atom;
c has a value of 0, 1; 2 or 3; and d has a value of 0, 1 or 2; there being at least one unit wherein d has a value of I.
Units of the abGve description are combined to form linear, branched, or cyclic polymers.
Preferably, c has a value of O, 1 or 2, d has a value of 0 or 11 and the values of c and d are selected such that their sum is from 1.8 ~o 2.2.
.
., --8~
A pol~organosiloxane of this description is substantially linPar, and can be represented by the general fOr~ula R3SiO(Rc HdSi(4-c-d)/3~YSi 3' selected from ~ radicals and R radicals, and ~ has a value of from 18 to 6000. There must be at least one H atom present in said polyorganosiloxane on average.
Polyorganosiloxanes as described for component (B) are well known. Many are commercially available. The synthesis of such polyorganoslloxanes from raore basic starting materials is also well known.
For example, hydrolysis and condensation of ~onomers described by the general formula R 3HdSiX4 c d~ wherein R3, c, d, and X are all as hereinabove described, is a method for producing polyorganosiloxanes suitable for use as component (B).
Specific examples of polyorganosiloxanes sultable for use as component (B) include:
(MeHSiO)5;
Me2HSiO(MeHSi.O)5(M&2SiO)43siMe2H;
Me3sio(MeHsio)22~Mec6H5sio)28siMe3;
Me~sio(MeHsio~35siMe3;
Me3SiO~MeHS1O)30(Me2SiO)970SiMe3;
Me2HSiO(Me2SiO)450SiMe2H~
Me3SiO(Me~lSiO)24(CF3CH2CH2Mesi)74SiMe3;
resins containing MeHSiO units, Me3SiO~ units and SiO4/2 units; and other suitable polyorganosiloxanes containing SiH groups which will be familiar to those skilled in the art.
Component (C) of the composition of this invention is the catalys~. The catalyst is selected from the salts, compounds and elemental forms of platinum, rhodium, palladium, ruthenium, rheniuml osmium, and iridium.
~...
. .
V~
It is ?rererred that salts or compounds of the above metals ~hat are soluble in a mixture of components (~), (B), (D) and (E) be selected.
It is further preferred that the catalyst be selectsd from the soluble sa~lts and compounds of platinum and rhodium.
It is most preferred to use a pla~lntlm compound that is soluble in components (A)~ (B), (D) and (E).
A particularly preferred catalyst is the compound formed by heating chloroplatinic acid with an SiVi-containing polyorganosiloxane.
Catalysts as described above are well know~.
Component (D) of the compositions of this invention is thP conjuga~ed ene-yne. The conjugated ene-yne is characterized by containing:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group; and 3) an ethenyl group in conjugation with said ethyny~
- group.
The term '!conjuga~ion" as used herein is to be construed as follows: two multiple bonds ln a hydrocarbon may be said to be conjuga~ed if they are separated by one, and only one, single bond.
Componen~ (D) is a hydrocarbon, that is, component (D) is composed of hydrogen and carbon a~oms.
Rxamples of con,jugated ene-ynes suitable for use as component (D) are the following:
HC-C-C=CH-CH3, HC-C-C=CH-CH2CH3~
- 1 0~ Z
HC-C-C-CH-CH(GH3)~.
HC=C-C-C~2, HC-C-C=CH2, ~ HC-C ~ .
HC-C ~ , HC=C-CH ~ , HC-C-C=
~ CH3 CH3 HC-C ~ and HC-C ~ CH3 particularly preferred conjugated ene-ynes are HC-C ~ , and HC=C-C= ca- CH ( CH3)2 C~13 Conjugated ene-yneq suitable for use as component (D~ can be synthesiæed from available starting materials by methods well known in organic chemistry. The patent literature also discusses methods for the synthesis of conjugated ene-ynes sultable for use as component (D) of the compositions of this invention.
For example, ~he appropriate ethynyl group terminated alcohol can be dehydrated in pyridine by PC15 to form the corresponding conjugated ene-yne. This is illustrated by the follow~ng exemplary equation:
26~f~2 ~< pyridina IIC~C~3 C-CH
O~her methods of synthesizing conjugated ene-ynes are known by those skilled in the art.
Component (~) of the compositions of this invention9 is vinylcyclosiloxane. Vinylcyclosiloxane is represented by the general formula (R5ViSio) , wherein each m has an integer value of 3, 4, 5, 6, 7, ~, and higher lntegers. Each R5 is selected from methyl, ethyl, and phenyl groups. Preferably R5 is a methyl group.
Vinylcyclosiloxanes are frequently furnished a4 mixtures in which m has an average value bet~een 4 and 5. It is to be understood that this average value encompasses species wherein m is 3, 4, 5, 6, 7, 8, and higher integers. It is not known at ~his time whether the particular value, or average value, of m has any effect on the composition of this inventlon. It is al50 not known if the use of a mixture rather than a pure compound has any effect on the compositions of this invention. It is not believed that the inclusion of small amounts9 such as 10 or 15 mO18 percent, of other diorganosiloxane units has any significant effect. Examples of possible contaminatlng diorganosiloxane unit~s are ~Me2SiO) units, ~MeC6H5SiO) units and the like.
Vlnylcyclosiloxanes are well known lntermediates in organosilicon chemistry. They are readily commercially available.
The relative amounts of components (A) thru (E) that are used in the composition of this invention are not narrowly critical, and can vary widely. The relative ~2~
1~--amounts ot the components used depends largely upon the desired use of the composition.
All amounts set forth herein are expressed in parts by weight, based upon 100 total parts of component (A), (B), (D), and (E).
8roadly:
component (A) is present from O.S to 99.48 parts;
component (B) is present from 0.5 to 99.48 parts;
component (C) is present from 0.000001 to 1.0 parts;
component (D) is present from 0.01 to 10 parts;
and component (E) is present from 0.01 to 10 parts, all of the above parts based upon 100 total parts of (A) plus (B) plus ~D) plus (E).
More preferably:
component (A) is present from 92 to 98.5 parts;
componen~ (B) is present from 1.4 to 10 parts, component (C~ is present from 0.004 to 0.50 parts;
component (D) is present from 0.05 to 5 parts;
component (E) is present from 0~05 to ~ parts;
all o the above parts based upon 100 total parts of (A) plus (B) plus (D) plus (E).
The compositions of this invention can contain other, optional ingredients. For example, the compositions of this invention can contain fillers, solvents, flame retardants, antimicrobial preparations, surfactants, oxidation inhibitors, dyes, pigments, perfumes, and the like.
Of course, any addi~ives which are known, or are discovered, to poison the catalyst or other~Jise render the compositions unusable, are to be avoided.
~26~2 When accounting for the amounts of such other, optional ingredients~ the amounts referred to herein are on the basis of 100 total par~s of components (A), (B), (D), and (E). Thus, as an example, the addition oE an equal amount of filler to a composition of this invention is expressed as 100 parts of filler added to 100 parts components (A), (B), (D) and (E) of this invention.
Examples of fillers useful in the composi~ions of this invention include ~einforcing fillers and extending fillers. Examples of reinforcing fillers include: sllica, such as fume silica and precipitated silica; and treated silica, such as fume or precipitated sllica that has been reacted with eOgO an organchalosilane, a disiloxane, or a disilazane.
Examples of extending fillers include crushed quartz, aluminum oxide, aluminum silicateJ zirconium silicate, magnesium oxide, zinc o~ide, talc, diatomaceous earth, iron oxide, calcium carbonate, clay, titania, ~irconia, mica, glass, such as ground glass or glass fiber, sand, carbon black, graphite, barium sulfate, zinc sulfate, wood flour, cork, fluorocarbon polymer powder, rice hulls, ground peanut shells, and the like.
Solvents sultable for use with the compositions of this invention include well known solvents for silicones having chemical compositions similar to those described for component (A) or component (B).
Examples of such solvents include aliphatic hydrocarbons, such as pentane, hexane~ heptane, octane, nonane and the like; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, and butanol; ketones such as acetone, methylethyl keto.e and methyl-isobutyl ketone; and halogenated solvents such as fluorine-, chlorine-, and bromine-substituted aliphatic or ,, .
aromatic hydrocarbons, such as trichloroethane, perchloroethylene, bromobenzene and the like. Two or more solvents may be used together.
The compositions of this invention are made by mixing together the desired quantities of component (A3, (B), (C), (D), (E), and any optional ingredients in suitable mixing equipment.
Suitable mixi~g equlpment is very w211 known and widely available. Selection of a specific type of mixing equipment will be guided by the vlscosity of the mixture of components (A)~ (B), (C), (D), and (E).
For example, if the viscosity of the mixture is expected to be low, such as lO to 500 centistokes, mechanical stirrers such as paddle stirrers can be used to produce a mixture of components (A) and (B~. If a viscosity from 500 centipoise to 100,000 centistokes is expected, such equipment as three roll mills, sigmoid blade mixers, bread dough mixers and the like can also be used.
If a viscosity in excess of 100,000 centipoise is expected, such equipment as two roll mills, or Baker Perkins mixers may be required.
The compositions of thls invention are cured by exposure to elevated temperature. The specific times and temperaturss that are to be used can vary widely, depending upon the specific use intended for the cured composition, the relative amounts of SiH, SiVi, and SiOH groups present, the amounts of catalyst~ amounts of inhibitor, and other factors.
For example, a composition having a high amount of SiH, SiVi and catalyst can be cured in a few seconds at 70C. hs another example, a composition having low amoun~s of SiH, SiOH and catalyst may require 3 or 4 hours at l20C
or so.
-l5 Three specific embodiments of the c~mpositions o.
chis invention are particularly contemplaced: flr~t, a heat curable silicone resin composition, second a heat curable silicone coating compositlon, and third a heat curable elastomer composition.
The curable silicone resin composition comprises the combination o~:
(A) a polyorganosiloxane having the general formula 3 ( aQbsio(4-a-b)/2) x SiR3, wherein pl is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q i~ a vinyl-containing radical of the general formula (H2n)CH-CH2, wherein n has a value of from 0 to 4;
R is selected from the group consisting of R
radicals, Q radicals, and hydroxyl radieals;
x has a value of ~rom 18 to 6000;
a has a value of 0, 1 or 2;
b has a value of 0, 1 or 2, the average sum of the values of a plus b is from 1.8 to 2.2;
there is at least one radical per polyorgdnosiloxane selected f rom the group consisting of Q radicals and hydroxyl radicals;
~B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a catalyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said etnynyl group;
(~) A vinylcyclosiloxane having the general formula -l6-(~ CH2-CHSlo~
~herein each R is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to ~ ; and (F) a filler.
The curable resin compositîon of this invention is useful in encapsulating componen~s, such as electronic components; it is useful as a potting compound for electronic circuitry; and it is useful for other well known applica~ions of curable silicone resins.
The curable resin can be fabricated in various ~ well known processes, such as press molding, transfer molding, extrusion, potting, or other processes.
The second specific embodiment of the composition of the present invention is a curable coating composition for substrates, said coating composition comprising:
- (A) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula l 3 ~ aQbsio(4-a-b)/2) x SiR3, wherein R is a nsn-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R is selected from ~he group consisting of Q
radicals, Rl radicals, and OH radicals;
a has a value of O, 1 or 2;
_ has a value of O, 1, or 2;
the average sum of the values of a plus b is from 1.8 to 2.2, and X has a value of from 18 to 4000, there being at least one vinyl or OH group per molecule;
~ B) from 0.5 ~o 99.48 parts of a polyorganosiloxane having the formula 3 ( cHdsio(4-c-d)/2)ysiR3~ wher~in R3 is a non-olefinic monovalent hydrocarbon or halogenat2d hydrocarbon ~adical;
H is a hydrogen atom;
R is selected from the group consisting of ~ atoms, and R radicals;
c has a value of 0, 1 or 2;
_ has a value of 0, 1, or 2;
the average sum oP the values of c plus d i8 Erom 1.8 to 2.2; and has a value of from 13 to 500, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, of a catalyst;
(D) from 0.1 to 10 parts of an inhibitor, said inhibitor being a hydrocarbon containing:
1) from 5 to 12 carbon atoms;
2) a ter~inal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group;
(E~ from 0.01 to 10 parts-of a vinylcyclosilo~ane having the general formula (R CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6; and (G) from O to 4000 parts of a solvent, all of the above parts being parts by weight based on 100 total parts of Components (A) plus (B) plus (D) plus (E).
While the coating compositlon of the present invention can be furnished and used eithar with a solvent or without a solvent, it is preferred to furnish and use said composition without a solvent. Use without a solvent is facilitated by selecting components (A) and (B) that are relatively low in viscosity, e. a, 100 to 5000 centistokes.
~ ~ , The coating compositions of thP pre~ent invention can be applied to a variety of substrates. Examples of such sllbstrates include: na~ural products, such as wood and stone; paper products, such as paper, cardboard and the like; plastics, such as polyethylene, polypropylene, and polymethylpentene, polyethylene terephthalate, polybutylene terephthalate and the like; metals, such as aluminum, copper, zinc, magnesium, iron, steel, nickel, chromium and the like; and other substrates.
Application of the coating composition to the substrate can be accomplished by an appropriate coating technique. Examples o F coa~ing techniques useful with the coating composition of this invention include spray coating, direc~ gravure coating, offset gravure coating, Mayer rod coating, two-roll coating, kiss coating, air ~nife coating and other known coating techniques.
The coating compositions of this invention can be used to fabricate release paper of excellent quali~y.
The third specific embodiment of the composition of the present i~vention is a curable silicone elastomer composition, said composition comprisi~C
(A) from 0.5 to 99.48 parts of a polyorOanosiloxane having the formula 3 ( aQbsio(4-a-b)/2) x SiR3, wherein Rl is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R is selected from the group consisting of Q
radicals, Rl radicals, and OH radicals;
a has a value of O, 1 or 2;
b has a value of O, 1, or 2;
the average sum of the val~es of a plus b is fro~
to 2.2; and . . .
~;26~
has a value of from 50 to 6000, there being a~ least one vinyl or OH group per molecule;
~ B) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R3SiO(R cHdSi(4 c d)~2)ySiR3~ wherein R is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
H is a hydrogen atom;
R is selected from the group consisting of H atoms, and R radicals;
c has a value of 0, 1 or 2;
d has a value of 0, 1, or 2;
the average sum of the values of c plus d is from 1.8 to 2.2; and has a value of from 50 to 6000, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, o~ a catalyst;
(D).from 0.01 to 10 parts of an inhibitor, said inhibi~or being a hydrocarbon containing:
1~ from 5 to 12 carbon atoms;
2) a terminal ethynyl group; and 3~ an ethenyl group in conjugation with said ethynyl group;
(E~ from 0.01 to 10 parts of a vinylcyclosilo~ane having the general formula -(R CH2=CHSiO~m wherein each R5 is selec~ed from methyl, ethyl,and phenyl groups, and m has an average value of from 3 to 6; and (F) from 0 to 400 parts of a filler, all of the above parts being parts by weight based on 100 total parts of Components (A) pl.us (B) plus (D) plus (E).
, , , .
The curable silicone elastomer composition can be fabricated by any of the conventional silicone elastomer fabrication techniques, such as compression molding, in~ection molding, extrusion9 and other well known silicone rubber fabrication teehniques.
The following examples are presented to further illustrate making and using the compositions of this invention. These examples are not to be construed as placing limits on the scope of this invention. In the examples, all parts and percentages noted are by ~eight unless otherwise specified. Me in the examples denotes a methyl radical and Vi denotes a vinyl radical.
The vinylcyclosiloxanes used in the following examples were methylvinylcyclosiloxan~s represented by the formula (MeViSiO) . The relative amount3 of different cyclic species in the particular methylvinylcyclosiloxanes used in the examples are set forth in Table 1.
Table 1 Distribution of Methylvinylcyclosiloxane Species m Pe~rcenta~e by Wei~ht 3 12.6%
4 73.3%
10.0%
>5 4.1%
Test Procedures The following test procedures were used to evaluate cured films in the following examples.
Smear - Smear of a coating was evaluated by lightly rubbing the cured coa~ing with a finger. A wholly cured coating will not change in appearance upon rubbing. ~o change in , .
appearance in ~ne smear test is recorded in the following examples as "none".
Rub-off - Rub-off of a coating was evaluated by vigorously rubbing the cured coatlng with a finger. The result "none' indicates that the coating could not be removed in this manner. The result "ruboEf" indicate4 that the coating was easily removed.
Migration - Migration was evaluated herein by: first, adhering a strip of standard adhesive-coated tape to the cured coating by firmly pressing the side coated with adhesive to the cured coatlng; second, removing the tape from the cured coating by peeling the tape up; third, doubling the removed tape back upon itself with the adhesive-coated side adhering to itself; and fourth9 comparing the force required to peel the doubled tape to the force required to peel a freshly prepared, similarly doubled tape which had never been adhered to the coating.
If the force required is substantially the same, no migration of the coating or componen~s thereof has occurred. This result is recorded as "none" with respect to migration. Total loss of adherence indica~es that migration of coating components has taken place. This result is recorded as "migration".
Example 1 In this example, the following components were mixed together:
Component (A): 97.7 parts or a polymer having the approximate average formula Me2ViSiO(Me2SiO)3400(MeViSiO)70 2 Component (B): 1.6 parts of a polyorganohydrogen-siloxane having the average formula:
Me3SiO(MeHSiO)35Si~e3.
Component (C): 0.008 parts, based on the weight of platinum, of the reaction product of chloroplatinic acid and (Me2ViSi)23-Component (D): 0.52 parts of HC-C ~ .
Component (~3 0.16 parts of mathylvinylcyclo-siloxane.
Component (G) 215 parts of toluene and 1227 parts of heptane.
The resulting coating composition of ~his invention was coated onto 40 pound s~percalendered Kraft paper by means of a No. 12 Mayer rod~ The coated paper was then cured in a forced alr oven set at 170~F until the coating showed no smear, no migration, and no rub-off.
The coating and curing procedure above was repeated periodically to determine any changes in cure time as the coating composition aged. The following results were noted:
initial cure time : 35 seconds after 1 hour aging: 45 seco~ds zfter 5 hour aging: 90 seconds The above example was repeated with a composition identical to ~xample 1 but with no methylvinylcyclo-siloxanes added. The following results were noted:
initial cure time : 150 seconds after 1 hour aging: ~40 seconds Example 2 The procedure of Exa~ple 1 was duplicated for the following co~position:
(A) 97.9 parts of component (A~ of Example l;
(B) 1.63 parts of component (B) of Example l;
5V~
~23-(C) 0.078 parts of the catalyst of Example 1;
(D) .359 parts of HCsC-C~CH-C~(CH3)2 (E) 0.097 parts Qf methylvinylcqclosiloxanes.
The following results were noted in evaluating minimum cure time as a function of aging:
initial cure time : 45 seconds after 1 hour aging : 75 seconds after 2 hours aging : 90 seconds after 3 hours aging : 90 ~econds after 5 hours aging : 195 seconds As a comparison, Example 2 was repeated without the methylvinylsiloxane. The following results were noted:
initial cure timP : 180 seconds after 1 hour aging : 300 seconds As another comparison, Example 2 was repeated without the conjugated ene-yne. The following results were noted.
initial cure time : 180 minutes after 2 hours aging: 300 minutes Example 3 In this example, the following components were mixed together:
(A) 95.0 parts of a polyorganosiloxane having approximately 1.8 mole percent MeViSiO unlts, 98.2 mole percent Me2S~0 units, and having a viscosity of about 300 centipoise;
(B) 3.87 parts of component ~B) of Example l;
tC~ 0.009 parts, by weight of rhodium, as a soluble rhodium compound;
(D) 0.116 parts of C~-C ~
(E) 1.014 parts of methylvinylcyclosiloxane.
. . .
When applied to paper, the above coating composition showed no smear, no migratlon~ and no rubofE
after being cured for 20 seconds at 300F~
The viscosity of thls coating composition was monitored as a function of time. The viscosity was found to have doubled in 48 hours.
In a parallel experiment in which tha methyl-vinylcyclosiloxane was not included, the viscosity was found to have doubled in only 30 hours.
Example 4 The following components were mixed together:
(A) 95.91 parts of a polyorganosiloxane having the average formula HoMe2sio(Me2sio)24oo ' (B) 1. 62 parts of component tB) from Example l;
(C) 0.0044 parts of the platinum catalyst of Example 1 ;
(3) 2.7 parts of CHsC ~ ;
(E) 0.934 parts of methylvinylcyclosiloxane;
(F) 109 parts heptane; and 10 parts of toluene.
The viscosity of this solution was monitored as a function of time aged at room temperature; the viscosity showed no change after 144 hours.
In a parallel experiment, all the above components except the methylvinyl,cyclosiloxane were mixed together. The viscosity was found to increase from 60 centistokes to 75 centistokes in 72 hours, and to 77.5 centistokes after 144 hours.
Comparison E~periment ' In this experiment, the following components were mixed toge~her. This comparison is not an embodiment of the present invention because it contains no component (AJ~
~z~LS~
3~24 parts me~hylvinylcyclosiloxane;
95.38 parts of a polymer having the formula Me3sio(M~2sio)7oosi~ 3;
1.31 parts of component (B) of Example l;
0.0073 parts of the platinum catalyst of Example l; and 0.0655 parts of CH-C ~
The resulting mixture was dissolved in a mixture of heptane and toluene, such that the above components constituted approximately 1%.
The above coating composition was coated on paper following the procedure of Example 1. After 5 minutes exposure to 300F, smearing of the coating was observed.
Example_5 The following elastomer composition of the present invention was formulated:
(A) 98.33 parts of a polymer having the average formula Me2ViSiO(Me2SiO)1gOSiMe2Vi (B) 1.54 parts of a polymer consisting of 46~ (Me~SiO) units and 54% (Me2SiO) units and Me3SiO~ units (C) .077 parts o~ tne platinum catalyst of Example 1 (D) .064 parts of HC=C ~
(E) .064 parts of methylvinylcyclosiloxanes (F) 94 parts of trimethylsilylated silica . After being thoroughly mixed, the above composition was placed in an air circulating ove~ set at 55~C. After 15 hours the composition gelled.
, ~2~
-~6-In a parallel experiment, a similar composition ~ith no methylvinylcyclosiloxane was found to gel in 6 hours at 55C. In another parallel experiment wi~h neither the conjugated ene-yne nor the methylvinylcyclosiloxanes present, the composition was found to gel in less than minutes~
10.0%
>5 4.1%
Test Procedures The following test procedures were used to evaluate cured films in the following examples.
Smear - Smear of a coating was evaluated by lightly rubbing the cured coa~ing with a finger. A wholly cured coating will not change in appearance upon rubbing. ~o change in , .
appearance in ~ne smear test is recorded in the following examples as "none".
Rub-off - Rub-off of a coating was evaluated by vigorously rubbing the cured coatlng with a finger. The result "none' indicates that the coating could not be removed in this manner. The result "ruboEf" indicate4 that the coating was easily removed.
Migration - Migration was evaluated herein by: first, adhering a strip of standard adhesive-coated tape to the cured coating by firmly pressing the side coated with adhesive to the cured coatlng; second, removing the tape from the cured coating by peeling the tape up; third, doubling the removed tape back upon itself with the adhesive-coated side adhering to itself; and fourth9 comparing the force required to peel the doubled tape to the force required to peel a freshly prepared, similarly doubled tape which had never been adhered to the coating.
If the force required is substantially the same, no migration of the coating or componen~s thereof has occurred. This result is recorded as "none" with respect to migration. Total loss of adherence indica~es that migration of coating components has taken place. This result is recorded as "migration".
Example 1 In this example, the following components were mixed together:
Component (A): 97.7 parts or a polymer having the approximate average formula Me2ViSiO(Me2SiO)3400(MeViSiO)70 2 Component (B): 1.6 parts of a polyorganohydrogen-siloxane having the average formula:
Me3SiO(MeHSiO)35Si~e3.
Component (C): 0.008 parts, based on the weight of platinum, of the reaction product of chloroplatinic acid and (Me2ViSi)23-Component (D): 0.52 parts of HC-C ~ .
Component (~3 0.16 parts of mathylvinylcyclo-siloxane.
Component (G) 215 parts of toluene and 1227 parts of heptane.
The resulting coating composition of ~his invention was coated onto 40 pound s~percalendered Kraft paper by means of a No. 12 Mayer rod~ The coated paper was then cured in a forced alr oven set at 170~F until the coating showed no smear, no migration, and no rub-off.
The coating and curing procedure above was repeated periodically to determine any changes in cure time as the coating composition aged. The following results were noted:
initial cure time : 35 seconds after 1 hour aging: 45 seco~ds zfter 5 hour aging: 90 seconds The above example was repeated with a composition identical to ~xample 1 but with no methylvinylcyclo-siloxanes added. The following results were noted:
initial cure time : 150 seconds after 1 hour aging: ~40 seconds Example 2 The procedure of Exa~ple 1 was duplicated for the following co~position:
(A) 97.9 parts of component (A~ of Example l;
(B) 1.63 parts of component (B) of Example l;
5V~
~23-(C) 0.078 parts of the catalyst of Example 1;
(D) .359 parts of HCsC-C~CH-C~(CH3)2 (E) 0.097 parts Qf methylvinylcqclosiloxanes.
The following results were noted in evaluating minimum cure time as a function of aging:
initial cure time : 45 seconds after 1 hour aging : 75 seconds after 2 hours aging : 90 seconds after 3 hours aging : 90 ~econds after 5 hours aging : 195 seconds As a comparison, Example 2 was repeated without the methylvinylsiloxane. The following results were noted:
initial cure timP : 180 seconds after 1 hour aging : 300 seconds As another comparison, Example 2 was repeated without the conjugated ene-yne. The following results were noted.
initial cure time : 180 minutes after 2 hours aging: 300 minutes Example 3 In this example, the following components were mixed together:
(A) 95.0 parts of a polyorganosiloxane having approximately 1.8 mole percent MeViSiO unlts, 98.2 mole percent Me2S~0 units, and having a viscosity of about 300 centipoise;
(B) 3.87 parts of component ~B) of Example l;
tC~ 0.009 parts, by weight of rhodium, as a soluble rhodium compound;
(D) 0.116 parts of C~-C ~
(E) 1.014 parts of methylvinylcyclosiloxane.
. . .
When applied to paper, the above coating composition showed no smear, no migratlon~ and no rubofE
after being cured for 20 seconds at 300F~
The viscosity of thls coating composition was monitored as a function of time. The viscosity was found to have doubled in 48 hours.
In a parallel experiment in which tha methyl-vinylcyclosiloxane was not included, the viscosity was found to have doubled in only 30 hours.
Example 4 The following components were mixed together:
(A) 95.91 parts of a polyorganosiloxane having the average formula HoMe2sio(Me2sio)24oo ' (B) 1. 62 parts of component tB) from Example l;
(C) 0.0044 parts of the platinum catalyst of Example 1 ;
(3) 2.7 parts of CHsC ~ ;
(E) 0.934 parts of methylvinylcyclosiloxane;
(F) 109 parts heptane; and 10 parts of toluene.
The viscosity of this solution was monitored as a function of time aged at room temperature; the viscosity showed no change after 144 hours.
In a parallel experiment, all the above components except the methylvinyl,cyclosiloxane were mixed together. The viscosity was found to increase from 60 centistokes to 75 centistokes in 72 hours, and to 77.5 centistokes after 144 hours.
Comparison E~periment ' In this experiment, the following components were mixed toge~her. This comparison is not an embodiment of the present invention because it contains no component (AJ~
~z~LS~
3~24 parts me~hylvinylcyclosiloxane;
95.38 parts of a polymer having the formula Me3sio(M~2sio)7oosi~ 3;
1.31 parts of component (B) of Example l;
0.0073 parts of the platinum catalyst of Example l; and 0.0655 parts of CH-C ~
The resulting mixture was dissolved in a mixture of heptane and toluene, such that the above components constituted approximately 1%.
The above coating composition was coated on paper following the procedure of Example 1. After 5 minutes exposure to 300F, smearing of the coating was observed.
Example_5 The following elastomer composition of the present invention was formulated:
(A) 98.33 parts of a polymer having the average formula Me2ViSiO(Me2SiO)1gOSiMe2Vi (B) 1.54 parts of a polymer consisting of 46~ (Me~SiO) units and 54% (Me2SiO) units and Me3SiO~ units (C) .077 parts o~ tne platinum catalyst of Example 1 (D) .064 parts of HC=C ~
(E) .064 parts of methylvinylcyclosiloxanes (F) 94 parts of trimethylsilylated silica . After being thoroughly mixed, the above composition was placed in an air circulating ove~ set at 55~C. After 15 hours the composition gelled.
, ~2~
-~6-In a parallel experiment, a similar composition ~ith no methylvinylcyclosiloxane was found to gel in 6 hours at 55C. In another parallel experiment wi~h neither the conjugated ene-yne nor the methylvinylcyclosiloxanes present, the composition was found to gel in less than minutes~
Claims (8)
1. A curable silicone composition comprising the combination of:
(A) a polyorganosiloxane having the general formula R?SiO(R1aQbSiO(4-a-b)/2) x SiR?, wherein R1 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical of the general formula (CnH2n)CH=CH2, wherein n has a value of from 0 to 4;
R2 is selected from the group consisting of R1 radicals, Q radicals, and hydroxyl radicals;
x has a value of from 18 to 6000;
a has a value of 0, 1 or 2;
b has a value of 0, 1 or 2;
the average sum of the values of a plus b is from 1.8 to 2.2;
there is at lea t one radical per polyorganosiloxane selected from the group consisting of Q radicals and hydroxyl radicals;
(B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a catalyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group; and (E) a vinylcyclosiloxane having the general formula (R5CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6.
(A) a polyorganosiloxane having the general formula R?SiO(R1aQbSiO(4-a-b)/2) x SiR?, wherein R1 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical of the general formula (CnH2n)CH=CH2, wherein n has a value of from 0 to 4;
R2 is selected from the group consisting of R1 radicals, Q radicals, and hydroxyl radicals;
x has a value of from 18 to 6000;
a has a value of 0, 1 or 2;
b has a value of 0, 1 or 2;
the average sum of the values of a plus b is from 1.8 to 2.2;
there is at lea t one radical per polyorganosiloxane selected from the group consisting of Q radicals and hydroxyl radicals;
(B) a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms;
(C) a catalyst;
(D) a conjugated ene-yne, said conjugated ene-yne characterized by having:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group; and (E) a vinylcyclosiloxane having the general formula (R5CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6.
2. A curable silicone composition as claimed in claim 1 wherein component (A) is present from 0.5 to 99.43 parts; component (B) is present from 0.5 to 99.48 parts;
component (C) is present from 0.000001 to 1.0 parts;
component (D) is present from 0.01 to 10 parts; and component (E) is present from 0.01 to 10 parts; there being 100 total parts of components (A) plus (B) plus (D) plus (E), all parts being by weight.
component (C) is present from 0.000001 to 1.0 parts;
component (D) is present from 0.01 to 10 parts; and component (E) is present from 0.01 to 10 parts; there being 100 total parts of components (A) plus (B) plus (D) plus (E), all parts being by weight.
3. A curable silicone composition as claimed in claim 1 wherein component (D) is
4. A curable resin composition as claimed in claim 1, said composition further comprising:
(F) a filler.
(F) a filler.
5. A curable coating composition for substrates, said coating composition comprising:
(A) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R?SiO(R1aQbSiO((4-a-b)/2) x SiR?, wherein R1 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R2 is selected from the group consisting of Q
radicals, R1 radicals, and OH radicals;
a has a value of 0, 1 or 2;
b has a value of 0, 1, or 2;
the average sum of the values of a plus b is from 1.8 to 2.2; and x has a value of from 18 to 4000, there being at least one vinyl or OH group per molecule;
(B) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R?SiO(R3cHdSiO(4-c-d)/2)ySiR?, wherein R3 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
H is a hydrogen atom;
R4 is selected from the group consisting of H atoms, and R3 radicals;
c has a value of 0, 1 or 2;
d has a value of 0, 1, or 2;
the average sum of the values of c plus d is from 1.8 to 2.2; and y has a value of from 18 to 500, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, of a catalyst;
(D) from 0.1 to 10 parts of an inhibitor, said inhibitor being a hydrocarbon containing:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group;
(E) from 0.01 to 10 parts of a vinylcyclosiloxane having the general formula (R5CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, and (G) from 0 to 4000 parts of a solvent, all of the above parts being parts by weight based on 100 total parts of Components (A) plus (B) plus (D) plus (E).
(A) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R?SiO(R1aQbSiO((4-a-b)/2) x SiR?, wherein R1 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
Q is a vinyl-containing radical;
R2 is selected from the group consisting of Q
radicals, R1 radicals, and OH radicals;
a has a value of 0, 1 or 2;
b has a value of 0, 1, or 2;
the average sum of the values of a plus b is from 1.8 to 2.2; and x has a value of from 18 to 4000, there being at least one vinyl or OH group per molecule;
(B) from 0.5 to 99.48 parts of a polyorganosiloxane having the formula R?SiO(R3cHdSiO(4-c-d)/2)ySiR?, wherein R3 is a non-olefinic monovalent hydrocarbon or halogenated hydrocarbon radical;
H is a hydrogen atom;
R4 is selected from the group consisting of H atoms, and R3 radicals;
c has a value of 0, 1 or 2;
d has a value of 0, 1, or 2;
the average sum of the values of c plus d is from 1.8 to 2.2; and y has a value of from 18 to 500, there being at least one H atom bonded to silicon present per molecule;
(C) from 0.000001 to 1.0 parts, based on the weight of metal, of a catalyst;
(D) from 0.1 to 10 parts of an inhibitor, said inhibitor being a hydrocarbon containing:
1) from 5 to 12 carbon atoms;
2) a terminal ethynyl group;
3) an ethenyl group in conjugation with said ethynyl group;
(E) from 0.01 to 10 parts of a vinylcyclosiloxane having the general formula (R5CH2=CHSiO)m wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, and (G) from 0 to 4000 parts of a solvent, all of the above parts being parts by weight based on 100 total parts of Components (A) plus (B) plus (D) plus (E).
6. A catalyst inhibitor consisting essentially of from 1 to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having 1) from 5 to 12 carbon atoms; 2) a terminal ethynyl group; 3) an ethenyl group in conjugation with said ethynyl group; and from 1 to 99 parts by weight of a vinylcyclosiloxane having the general formula (R5CH2=CHSiO)m, wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
7. In a curable silicone composition comprising a vinyl-containing or hydroxyl containing polyorgano-siloxane, a polyorganohydrogensiloxane containing hydrogen atoms bonded to silicon atoms, a catalyst, and a catalyst inhibitor, the improvement comprising the use of, as the catalyst inhibitor, a composition consisting essentially or from 1 to 99 parts by weight of a conjugated ene-yne, said conjugated ene-yne characterized by having 1) from 5 to 12 carbon atoms; 2) a terminal ethynyl group; 3) an ethenyl group in conjugation with said ethynyl group; and from 1 to 99 parts by weight of a vinylcyclusiloxane having the general formula (R5CH2=CHSiO)m, wherein each R5 is selected from methyl, ethyl, and phenyl groups, and m has an average value of from 3 to 6, there being 100 total parts.
8. The cured product of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US576,985 | 1984-02-06 | ||
| US06/576,985 US4472563A (en) | 1984-02-06 | 1984-02-06 | Heat curable silicones having improved room temperature stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1261502A true CA1261502A (en) | 1989-09-26 |
Family
ID=24306818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000470770A Expired CA1261502A (en) | 1984-02-06 | 1984-12-21 | Heat curable silicones having improved room temperature stability |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4472563A (en) |
| EP (1) | EP0154411B1 (en) |
| JP (1) | JPS60188461A (en) |
| KR (1) | KR920009395B1 (en) |
| AU (1) | AU571052B2 (en) |
| CA (1) | CA1261502A (en) |
| DE (1) | DE3567667D1 (en) |
Families Citing this family (66)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1984000034A1 (en) * | 1982-06-15 | 1984-01-05 | Toray Silicone Co | Composition for forming releasable film |
| US4830924A (en) * | 1983-10-03 | 1989-05-16 | General Electric Company | Modified silicone release coating compositions |
| US4460712A (en) * | 1983-12-23 | 1984-07-17 | Dow Corning Corporation | Compositions producing aminofunctional silicone foams and coatings |
| JPS6114235A (en) * | 1984-06-29 | 1986-01-22 | Toray Silicone Co Ltd | Prevention of evolution of hydrogen gas from cured silicone product |
| IT1177317B (en) * | 1984-11-23 | 1987-08-26 | Pirelli Cavi Spa | FILLER FOR CABLES AND COMPONENTS OF FIBER OPTIC CABLES AND FIBER OPTIC CABLES AND THEIR INCORPORATING COMPONENTS SUCH FILLER |
| EP0184598A1 (en) * | 1984-12-06 | 1986-06-18 | Toray Silicone Company Limited | Ultraviolet and electron-beam curable polyorganosiloxane composition |
| JPS61197448A (en) * | 1985-02-22 | 1986-09-01 | Toray Silicone Co Ltd | Coating agent for optical fiber for optical communication |
| US4640956A (en) * | 1985-06-13 | 1987-02-03 | General Electric Company | Iodine resistant silicone rubber compositions |
| US4645815A (en) * | 1985-10-31 | 1987-02-24 | General Electric Company | Heat curable organopolysiloxane compositions |
| FR2600660B1 (en) * | 1986-06-24 | 1988-11-18 | Rhone Poulenc Chimie | AQUEOUS EMULSIONS OF ORGANOPOLYSILOXANE POLYADDITION COMPOSITIONS FOR COATING FLEXIBLE MATERIALS |
| FR2600661B1 (en) * | 1986-06-24 | 1988-11-10 | Rhone Poulenc Chimie | POLYADDITION ORGANOPOLYSILOXANE COMPOSITIONS FOR COATING FLEXIBLE MATERIALS |
| US5004792A (en) * | 1986-08-22 | 1991-04-02 | Dow Corning Corporation | Method for extending the working life of organosiloxane compositions curable by a platinum catalyzed hydrosilation reaction |
| US4785066A (en) * | 1986-08-22 | 1988-11-15 | Dow Corning Corporation | Novel organosiloxane inhibitors for hydrosilation reactions |
| US4710559A (en) * | 1986-12-22 | 1987-12-01 | Wacker Silicones Corporation | Heat curable organopolysiloxane compositions |
| US4774111A (en) * | 1987-06-29 | 1988-09-27 | Dow Corning Corporation | Heat-curable silicone compositions comprising fumarate cure-control additive and use thereof |
| JP2808001B2 (en) * | 1988-11-25 | 1998-10-08 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane composition for forming release cured film |
| JPH0791471B2 (en) * | 1988-11-25 | 1995-10-04 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane composition for peelable film formation |
| US5187015A (en) * | 1989-02-17 | 1993-02-16 | Minnesota Mining And Manufacturing Company | Ice release composition, article and method |
| JPH0657797B2 (en) * | 1989-02-20 | 1994-08-03 | 信越化学工業株式会社 | Organopolysiloxane composition |
| JPH0655895B2 (en) * | 1989-03-16 | 1994-07-27 | 信越化学工業株式会社 | Curable silicone rubber composition |
| US4961963A (en) * | 1989-09-01 | 1990-10-09 | Dow Corning Corporation | Silicone release coatings containing rhodium |
| US5025073A (en) * | 1989-10-19 | 1991-06-18 | General Electric Company | One part heat curable organopolysiloxane compositions |
| US5036117A (en) * | 1989-11-03 | 1991-07-30 | Dow Corning Corporation | Heat-curable silicone compositions having improved bath life |
| US5125998A (en) * | 1989-11-03 | 1992-06-30 | Dow Corning Corporation | Process for improving the bath life and cure time of heat-curable silicone compositions |
| US5212048A (en) * | 1990-11-21 | 1993-05-18 | Presstek, Inc. | Silicone coating formulations and planographic printing plates made therewith |
| US5281656A (en) * | 1992-12-30 | 1994-01-25 | Dow Corning Corporation | Composition to increase the release force of silicone paper release coatings |
| DE4331608A1 (en) * | 1993-09-17 | 1995-03-23 | Goldschmidt Ag Th | Organopolysiloxanes modified with acrylate groups |
| JP3504692B2 (en) * | 1993-09-17 | 2004-03-08 | 東レ・ダウコーニング・シリコーン株式会社 | Silicone composition for peelable cured film formation |
| GB9322794D0 (en) * | 1993-11-05 | 1993-12-22 | Dow Corning | Silicone release compositions |
| US5486578A (en) * | 1993-12-30 | 1996-01-23 | Dow Corning Corporation | Curable silicone coatings containing silicone resins |
| US5412006A (en) * | 1994-03-14 | 1995-05-02 | Dow Corning Corporation | Electrorheological cels and a method for the preparation thereof |
| US5616403A (en) * | 1994-07-11 | 1997-04-01 | General Electric Company | Fluorosilicone coatings |
| US5625023A (en) * | 1994-12-09 | 1997-04-29 | Dow Corning Corporation | Aerosol suppressant compositions for silicone coatings |
| US5534609A (en) * | 1995-02-03 | 1996-07-09 | Osi Specialties, Inc. | Polysiloxane compositions |
| US5567764A (en) * | 1995-07-28 | 1996-10-22 | Dow Corning Corporation | Curable silicone coatings containing alkoxy and alkenyl functional siloxanes |
| JP2835588B2 (en) * | 1995-07-31 | 1998-12-14 | 信越化学工業株式会社 | Curable silicone rubber composition for roll members |
| JP3098946B2 (en) * | 1995-09-21 | 2000-10-16 | 東レ・ダウコーニング・シリコーン株式会社 | Removable cured film-forming organopolysiloxane composition |
| DE19541451A1 (en) * | 1995-11-07 | 1997-05-15 | Wacker Chemie Gmbh | Crosslinkable compositions |
| US5616672A (en) * | 1995-11-17 | 1997-04-01 | General Electric Company | Paper release compositions having improved release characteristics |
| GB9526498D0 (en) | 1995-12-23 | 1996-02-28 | Dow Corning | Silicone release coating compositions |
| US6677407B1 (en) | 1996-08-28 | 2004-01-13 | Dow Corning Corporation | Coating with organopolysiloxane, organohydrogensilicon, platinum catalyst and silylated acetylenic compound |
| US5994454A (en) * | 1996-10-25 | 1999-11-30 | Dow Corning Corporation | Aerosol suppressant compositions for silicone coatings |
| US5756598A (en) * | 1996-12-30 | 1998-05-26 | Dow Corning Corporation | Resin-containing organosiloxane compositions curable to silicone elastomers having low weep |
| US5777047A (en) * | 1996-12-30 | 1998-07-07 | Dow Corning Corporation | Organosiloxane compositions with fluorinated resins curable to silicone elastomers having low weep |
| US5708075A (en) * | 1996-12-30 | 1998-01-13 | Dow Corning Corporation | Silicone release coating compositions |
| US5932060A (en) * | 1997-09-12 | 1999-08-03 | General Electric Company | Paper release laminates having improved release characteristics |
| US6077611A (en) * | 1997-09-30 | 2000-06-20 | General Electric Company | Printable paper release compositions |
| GB9912653D0 (en) | 1999-05-28 | 1999-07-28 | Dow Corning Sa | Organosilicon composition |
| US6716533B2 (en) | 2001-08-27 | 2004-04-06 | General Electric Company | Paper release compositions having improved adhesion to paper and polymeric films |
| WO2004058705A2 (en) * | 2002-12-20 | 2004-07-15 | Chemocentryx | Inhibitors of the binding of chemokines i-tac or sdf-1 to the ccxckr2 receptor |
| US7090923B2 (en) * | 2003-02-12 | 2006-08-15 | General Electric Corporation | Paper release compositions having improved adhesion to paper and polymeric films |
| US7005475B2 (en) * | 2003-06-10 | 2006-02-28 | General Electric Company | Curable silicone compositions having improved adhesion to polymeric films |
| JP4801320B2 (en) * | 2003-12-19 | 2011-10-26 | 東レ・ダウコーニング株式会社 | Addition reaction curable organopolysiloxane resin composition |
| EP1866374B1 (en) * | 2005-04-06 | 2016-06-08 | Dow Corning Corporation | Organosiloxane compositions |
| GB0506939D0 (en) * | 2005-04-06 | 2005-05-11 | Dow Corning | Organosiloxane compositions |
| US7956123B2 (en) * | 2005-10-24 | 2011-06-07 | Momentive Performance Materials Inc. | Solvent resistant polyurethane adhesive compositions |
| AU2008275937A1 (en) * | 2007-07-19 | 2009-01-22 | Luzenac America, Inc. | Silicone coatings, methods of making silicone coated articles and coated articles therefrom |
| EP2145912A1 (en) | 2008-07-19 | 2010-01-20 | Momentive Performance Materials GmbH | Method of coating substrates |
| CN102300784B (en) * | 2009-01-29 | 2013-07-10 | 株式会社吉野工业所 | Container with folded-back bottom wall |
| GB0905205D0 (en) | 2009-03-26 | 2009-05-13 | Dow Corning | Preparation of organosiloxane polymer |
| GB0905204D0 (en) | 2009-03-26 | 2009-05-13 | Dow Corning | Preparation of organosiloxane polymers |
| US8933187B2 (en) | 2011-12-08 | 2015-01-13 | Momentive Performance Material Inc. | Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof |
| US9487677B2 (en) | 2014-05-27 | 2016-11-08 | Momentive Performance Materials, Inc. | Release modifier composition |
| WO2015196440A1 (en) | 2014-06-27 | 2015-12-30 | Dow Corning (China) Holding Co., Ltd. | Silicone release coating composition and low release force emulsion silicone release coating for films and papers having cured release coating |
| JP5956698B1 (en) * | 2014-12-18 | 2016-07-27 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Polyorganosiloxane composition for molding, optical member, lens or cover for light source, and molding method |
| WO2023227714A1 (en) | 2022-05-25 | 2023-11-30 | Momentive Performance Materials Gmbh | New substituted phosphite transition metal compounds |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340709A (en) * | 1980-07-16 | 1982-07-20 | General Electric Company | Addition curing silicone compositions |
| US4340710A (en) * | 1981-04-02 | 1982-07-20 | General Electric Company | Addition cure coating with improved adhesion |
| JPS6054991B2 (en) * | 1982-04-02 | 1985-12-03 | ト−レ・シリコ−ン株式会社 | Organopolysiloxane composition |
| JPS59133252A (en) * | 1983-01-19 | 1984-07-31 | Toray Silicone Co Ltd | Organopolysiloxane composition |
| FR2554118B1 (en) * | 1983-10-26 | 1986-01-17 | Rhone Poulenc Spec Chim | KETONIC INHIBITOR FOR PLATINUM METAL CATALYST AND ORGANOPOLYSILOXANE COMPOSITIONS CONTAINING THE SAME |
| US4562096A (en) * | 1984-12-24 | 1985-12-31 | Dow Corning Corporation | Heat-curable silicone compositions, use thereof and stabilizer therefor |
-
1984
- 1984-02-06 US US06/576,985 patent/US4472563A/en not_active Expired - Lifetime
- 1984-12-21 CA CA000470770A patent/CA1261502A/en not_active Expired
-
1985
- 1985-02-05 EP EP85300762A patent/EP0154411B1/en not_active Expired
- 1985-02-05 KR KR1019850000713A patent/KR920009395B1/en not_active IP Right Cessation
- 1985-02-05 AU AU38464/85A patent/AU571052B2/en not_active Ceased
- 1985-02-05 JP JP60019389A patent/JPS60188461A/en active Granted
- 1985-02-05 DE DE8585300762T patent/DE3567667D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| KR850005867A (en) | 1985-09-26 |
| DE3567667D1 (en) | 1989-02-23 |
| US4472563A (en) | 1984-09-18 |
| EP0154411B1 (en) | 1989-01-18 |
| JPH0129512B2 (en) | 1989-06-12 |
| KR920009395B1 (en) | 1992-10-16 |
| EP0154411A3 (en) | 1986-04-30 |
| JPS60188461A (en) | 1985-09-25 |
| AU3846485A (en) | 1985-08-15 |
| EP0154411A2 (en) | 1985-09-11 |
| AU571052B2 (en) | 1988-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1261502A (en) | Heat curable silicones having improved room temperature stability | |
| US4611042A (en) | Resinous copolymeric siloxanes containing alkenyldimethylsiloxanes | |
| US5432006A (en) | Solventless silicone release coating | |
| US3888815A (en) | Self-bonding two-package room temperature vulcanizable silicone rubber compositions | |
| US4143088A (en) | Rapidly curable, storage-stable organosilicon compositions | |
| US5861467A (en) | Radiation curable siloxane compositions containing vinyl ether functionality and methods for their preparation | |
| CA1129270A (en) | Method for coating a substrate using a curable silicone release composition | |
| US4262107A (en) | Rhodium catalyzed silicone rubber compositions | |
| US5708046A (en) | Silicone release coating compostions | |
| US5824761A (en) | Radiation curable compositions containing vinyl ether functionality and methods for their preparation | |
| JP2914710B2 (en) | Solvent-free silicone coating composition | |
| US4764576A (en) | Silicone-based coating composition for surface-releasing film | |
| CA2087766A1 (en) | Organopolysiloxane paper release compositions | |
| GB1570411A (en) | Manufacture of curable organopolysiloxane compositions | |
| EP0217334B1 (en) | Radiation-curable organopolysiloxane coating composition | |
| JPS60156755A (en) | Carboxy functional silicone curable material | |
| US5914192A (en) | Silicone release coating compositions | |
| JP4367670B2 (en) | Silicone composition for forming a peelable cured film | |
| US5223344A (en) | Heat curable platinum catalyzed silicone coating compositions | |
| EP0409272B1 (en) | Reaction products as adhesion additives for uv curable compositions and compositions containing same | |
| CA1105645A (en) | Curable organopolysiloxane compositions | |
| CA1142679A (en) | Rhodium catalyzed silicone rubber compositions | |
| EP0625533A1 (en) | Radiation curable siloxane compositions containing vinyl ether functionality and methods for their preparation | |
| JPS6228984B2 (en) | ||
| EP0618272B1 (en) | Curable organosilicone composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |