CA2184441A1 - Crosslinkable mixtures, a method of preparing them and their use - Google Patents
Crosslinkable mixtures, a method of preparing them and their useInfo
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- CA2184441A1 CA2184441A1 CA002184441A CA2184441A CA2184441A1 CA 2184441 A1 CA2184441 A1 CA 2184441A1 CA 002184441 A CA002184441 A CA 002184441A CA 2184441 A CA2184441 A CA 2184441A CA 2184441 A1 CA2184441 A1 CA 2184441A1
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- alkyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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Abstract
A crosslinkable mixture, containing a) at least one polysiloxane which contains at least two olefinic ally or acetylenically unsaturated multiple bonds, b) at least one polyhydrogensiloxane which contains at least two hydrogen atoms directly bonded to silicon, c) at least one substance which catalyzes hydrosilylation, d) at least one inhibitor, and e) at least one phosphorus compound of the formula PR3 (1) wherein R each independently is H, C1-C18-alkyl, C6-C30-aryl, C7-C31-alkylaryl, or OR1, R1 each independently is C1-C18-alkyl, C6-C30-aryl, C7-C31-alkylaryl, and wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals, f) optionally other auxiliary materials for the coating of a substrate.
Description
' Le A 31 2$6-Eiorei~n Cr~lln~rieal Bs /ngb/S-P 2 1 ~ ~ 4 ~ 1 . ~
I
Cl~ kq~ mixtures, a method of nre~arin~ them and their use The present invention relates to crosslinkable mixtures, to a method of preparing 5 them and to thei} use.
The use of silicones for the adhesive coating of substrates such as paper, plastics or metal foils, for example, i.e. for coatings which repel adhesive substances, has been hnown for some time. In this connection, a liquid mixture comprising a vinyl-containing polydiorganosiloxane, an Si-H-containing polydiorgqnr~eiloYqn~
10 (polyhydrogensiloxane) and a suitable catalyst is applied to the paper and is cured at elevated Lt~ rldLulu~ by what is termed a hydrosilylation reaction (addition-u~u~ hillg systems). A solid silicone layer which adheres to the substrate is formed in the course of this procedure. The silicone layer is applied to the substrate via rollers, which take up the liquid, reactive silicone mixture from a vat 15 and transfer it to the substrate. If a substrate coating machine such as this breaks down for an extended period of time for technical reasons, the silicone film is capable of crosslinhing on the rollers even at room Ltlllp~,.a~ul~. This results in silicone residues on the rollers which are extremely difficult to remove, and which make it impossible to achieve trouble-free operation again aRer the machine has 20 been re-started.
Since problems which are similar in principle also arise in other applications of addition-crosslinhing silicone systems (e.g. lLS~), numerous additives (inhibitors) have been developed in the past, the function of all of which is to keep the reactive mixtures liquid for longer at }oom ~tUll~ldLUlt:. Thus US-A-4 329 275, 25 for example, discloses the use of phosphorus compounds in combination with peroxides as worhing life extenders. However, the addition of peroxides is associated with safety risks during the production and processing of mixtures ofthis type. US-A-4 645 815 relates to the use of cyclometallized Pt phosphite complexes. In this disclosure the catalyst complex is produced in a separate step, 30 which is associated with additional costs. However, both of the aforementioned possible solutions have a further, very senous disadvantage. They were developedfor systems which employ relatively low concentrations of catalyst (10 ppm).
Silicone mixtures which have a considerably higher content of catalyst (100 ppm)are used for the coating of substrates, however. In systems with high catalyst 35 concentrations such as this, the aforementioned inhibitors do not fulfil the requirements which are desired by the market as regards room temperature .. . . ..... . . . . ..... ... .. .
Le A 31 28eS-Forei~n Countries 2 1 8 4 4 ~ 1 . ~
stability. US-A-4 851 452 ptoposes the use of Pt-vinylsiloxane complexes in eombination with Pt-phosphine complexes as catalysts which haYe a signifieantly decreased activity at room temperature. However, phosphines have the disadvantage that the activity of the catalyst is also decreased to an appreciable 5 extent at elevated ~l..p~ld~Ulc~ (T=180C), i.e. under curing eonditions. For this reason, they are only of very limited value for substrate coating applications.
a-hydroxyacetylenes, whieh are deseribed in detail in US-A-3 445 420, eonstitute -another group of inhibitors which can be used. These e~mro~m~i~ do in fact prolong the working life of the system "in bulk", but are extremely I '` y 10 as regards prolonging the working life of thin films such as those which are present on the rollers during the coating operation.
The object of this invention is therefore to provide suitable mixtures which decrease the aetivity of the catalyst at room Lclllpcld~UIc, even in rapid, addition-~,lu~lillkillg silicone systems, without prolonging the curing times under reaction 15 conditions. At the same time, an object is to be able to prepare the mixture in a simple manner and without safety risks.
It llas now been found that these problems can be solved with addition-erosslinking polysiloxane mixtures which contain Pt compounds or elemental Pt, an a-hydlu~yacc~ylene or an ester of a dicarboxy acid and at least one 20 organophosphorus eompound of the type speeified in detail below.
The present invention therefore relates to ulu~ kal)le mixtures eûntaining a) at least one polysiloxane which contains at least two olefinically or acetylenically unsaturated multiple bonds, b) at least ore polyll~.llu~;c..siloxane which eontains at least two hydrogen atoms direetly bonded to silieon, e) at least one substanee which eatalyzes hydrosilylation, d) at least one inhibitor, and e) at least one phosphorus eompound of formula (1) Le A 31 ~ oreign Countrie3 2 1 8 4 4 4 1 ' ~
PR3 (1) wherein R each independently is H, Cl-CI8-alkyl, C6-C30-aryl, C7-C3l-alkylaryl, or ORI
S Rl each in~ r~n~ is Cl-C18-alkyl, C6-C30-aryl, C7-C3l-alkylaryl, and wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals and R and Rl may have a different meaning within the molecule, and f) optionally other auxiliary materials.
Component a) in the sense of the invention is preferably a cyclic, linear or branched polysiloxane which is synthesized from units of tlle general formula (II) (R3)a(R4)bsio(4 -a-b) 2 (Il) Here, R3 represents a C2-C8 alkenyl radical, e.g. vinyl, allyl, I-butenyl, I-hexenyl, etc. The alkenyl radicals may be bonded to silicon atoms within the chain or at the end of the chain. R4 is a ~ luv 1~..., saturated lly~l~JuallJwl radical containing up to 10 carbon atoms, from the group comprising substituted and .~
alkyl, aryl and arylalkyl radicals. Examples of monovalent radicals R4 include methyl, ethyl, propyl, isopropyl, butyl, octyl, etc., cyclobutyl, cyclopentyl, 20 cyclohexyl, etc., phenyl, tolyl, xylyl, naphthyl, etc., and benzyl, phenylethyl or phenylpropyl. The relationships 0 < a < 3, 0 < b < 3 and 0 < a + b < 4 apply to the integers a and b. . a is preferably equal to 0 or 1. In radicals R4 of the present invention, some or all of the hydrogen atoms may be substituted by fluorine and / or chlorine, bromine, or iodine atoms or cyano radicals This means 25 that R4 may also be a chloromethyl, trinu~"o~",yl, chlorophenyl, dibromophenyl, ~3-cyanoethyl, ~-uya~ l or y-cyanopropyl radical, for example.
Using the nnm~n~l~fllre familiar to one skilled in the art:
, Le A 312~ srei~n Countrie8 . 21 8 ~ 4 41 .
~ 4 -M: (CH3)3SiOI/2 D: (CH3)2SiO22 T: (CH3)SiO3/2 MVi: (cH2=cH)(cH3)2siol/2 5 DVi: (CH2=CEI)(CH3)siO2/2~
the following examples of component a) can be cited:
M2DIooD
M ViD
MViMDIooD
I O T5Ds5OM7Vi T3DsooM2ViM3 T6D3OoDviM4vlM4 .
The molar proportion of unsaturated radicals of type R3 may be selected to have any desired value.
In component a), the molar proportion of unsaturated radicals of type R3 should preferably be between 0.01 and 10 mmole per gram, more preferably between 0.05 and I mmole per gram, and most preferably between 0.1 and 0.'.7 mmole per gram of component a). The viscosity of component a) is preferably between 0.01 and 100,000 Pa s, more preferably between 10 and 100,000 mPa s at 25C.
Component b) in the sense of the present invention is a polysilo~ane which is synthesized from units of general formula (III) HC(R4)dsio(4 -c d)/2 (III) where R4 has already been defined above and may optionally also have the meaning of R3. The si~ ,hir~me~ric suffices c and d are integers, where 0 < d < 3 and 0 c c < 2, and where 0 < c + d < 4. Preferably, 0 < c < 1.
.
Le A 31 ~8~-~oreign Countries 2 1 ~ 4 4 4 1 Using the nomenclature familiar to one skilled in the art:
Mll: H(CH3)2SiOI,2 Dl~: H(CH3)SiO2/2, the following examples of component b) can be cited:
M2 Dlo MDIoDIoH
M211DZoDIoH
M viD H
M2D3ViD8H
(where M, D, MVi and DVi are defined as for component a)).
The molar proportion of hydrogen atoms which are directly bonded to a silicon atom in component b) may be selected to have any desired value.
In component b), the molar proportion of hydrogen atoms which are directly bonded to a silicon atom is preferably between 0.01 and 17 mmole, more preferably between 0.1 and 1~ mmole, and most preferably between I and 17 mmole per gram of component b).
In the total mixture described above, r.nmrnnr-nt.i a) and b) should preferably be present in a quantitative ratio such that the molar ratio of hydrogen atoms which are directly bonded to silicon atoms (SiH) in component b) to the unsaturated radicals (Si-vinyl) in corr;ponent a) is between 0 05 and 20, more preferably between 0.5 and 10 and most preferably between 1 and 5.
Component c) in the sense of the invention preferably compnses the elements platinum, rhodium, iridium, nickel, ruthenium and/or palladium, in elemental form on a supporting substance or in the form of their compounds. Platinum compounds or platinum complexes are preferred, such as H2PtCI6, platinum-olefin complexes, platinum-alcohol complexes, platinum-vinylsiloxane complexes and ., . _, . .. , . .... ... ., ..... ..... .. . .. ... _ .. ......
Le A 31 2~5-~Qreign Co~ ries 2 1 8 4 4 4 1 also elemental platinum on a supporting substance, such as activated carbon7 Al2O3 or SiO2 for exampie. Component c) is most preferably a platinum-vinyl-siloxane complex. Platinum-vinylsiloxane complexes most preferably contain at least two olefinically unsaturated double bonds in the siloxane; see US 3 715 334 5 for example.
The term "siloxane" includes polysiloxanes, i.e. it includes vi~ylpoly~;loxanes also, for example. The proportion of component c) in the total mixture should -preferably be between I and 1000 ppm, more preferably between I and 500 ppm, and most preferably between 25 and 250 ppm.
10 Component d) in the sense of the invention comprises all the inhibitors which are known in the prior art, such as maleic acid and derivatives thereof, amines, alkyl isu~,y~lluldl~ and acetylenically unsaturated alcohols in which the OH group is bonded to a carbon atom adjacent to the C-C triple bond, such as those describedin detail in US 3 445 420, for example. Component d) is preferably 2-methyl-3-15 butyn-2-ol or l-ethynylcyclohexanol or (+) 3-phenyl-1-butyn-3-ol. Component d) is preferably added to the mixture in a quantitative proportion of 0.0001 % to S %
with respect to the total weight of mixture, more preferably 0.01 % to 2 %, and most preferably 0.1 to I %.
Component e) in the sense of the invention is an orgam",l~ ,llvlu~ compound of 20 type PR3. In this respect, R is a hydrogen atom or a monovalent hydrocarbon radical from the group comprising Cl-C~s alkyl, C6-C30 aryl and C7-C3l alkylaryl.
R may have a different meaning within a molecule. In a preferred i-mhorlimPn~ ofthe present invention, component e) is a compound of formula P(ORI)3, where R~
= C~-CIs alkyl, C6-C30 aryl or C7-C3l alkylaryl, wherein the aryl radicals may 25 optionally be substituted with linear or branched alkyl radicals and Rl may have different meanings within the molecule. Examples of component e) include triphenylphosphine, triethylphosphine, tribu~ l.o~lli,.e, phosphoric acid trimethyl ester, phosphoric acid triisopropyl ester, phosphoric acid triphenyl ester or tris-(2,4-di-tert. butylphenyl)-phosphite. Component e) of the invention can also 30 include phosphite derivatives of pentaerythritol, such as, for example, bis (2,4-di-tert.butylphenyl)-~ .yLl..i~ol diphosphite (obtainable from the &reak Dakes Company under the trade name Alkanox P24(~). Component e) of the present invention is preferably added in a quantitative proportion of 0.0001 % to S % with Le A 31 ~-FQrei~n Countries 2 1 ~ 4 4 4 ~
. ~
respect to the total weight of the mixture, more preferably 0.001 % to 4 % and most preferably between 0.001 % and 2.~ %.
Examples of auxiliary materials (component f)) in the sense of the invention include polysiloxane resins which are synthesized from Culllpu~ of general formulae (II) and (111), filrers which have a positive effect on the mechanical and electrical properties of the cured mixture according to the invention, such as pyrogenic and ~ dte:l hydrated silicas having a BET specific surface of 5û to 50û m2/g, for example. The surfaces of fillers of this type may be modified, e g.
with organosilicon compounds. Modification may also be effected during tlleir incorporation into the polymer, by the addition of hexamethyldisilazane or 1,3-divinyl-1,1,3,3-tetramethyldisilazane with the addition of water, for example.
Substances such as ~ om~ oll~ earths, finely divided quartz flour, amorphous hydrated silicas or carbon blacks may also be used as fillers, for example.
In another embodiment the mixtures according to the invention additionally contain water or an orgMic solvent.
In a preferred embodiment of the invention, cul~ ullell~ a) and b) are present in a quantitative ratio such that the SiH:Si-vinyl ratio is between 0.1 and 10, the content of component c) is between 1 and 1000 ppm, the content of component d) is between 0.0001 and 5 %, and the content of component e) is between 0.0001 and 5 %, wherein the quantitative data are given with respect to the total weight of the mixture in each case.
This invention also relates to a method of preparing the crosslinkable mixtures according to the invention. In this process, ~ulllpu~ a), d) and e) are preferably mixed, and thereafter component b) and finally component c) are added.
This invention further relates to the use of the crosslinkable mixture according to the invention for the coating of substrates.
Le A 31 286-~orei~n Çountries 2 1 8 4 4 4 ~
. ~
The following examples serve to explain the invention. The invention is not restricted to these examples, however.
Exam~les of ~
In the following examples, all parts by weight and p~ CS are given with 5 respect to the weight of the total mixture unless defined otherwise.
General (-~1" ' ' procedure for Examples la ~o lj The quantitative data which do not appear in this description, as well as the type of ~ and the experimental results, are given in Table 1.
9.15 g of a branched polydimethylsiloxane with a viscosity of ~ = 250 mPa s and 10 a content of vinyl groups bonded directly to silicon of 0.32 mmole/g were mixed optionally with an cc-hyd~u~y~,c~ylene (see Table 1) and optionally with an or~n-~rh--~rh~lrus compound (see Table 1) 0~5 g of a pulyllydl~ cilo~r~ne having a content of hydrogen atoms bonded directly to silicon of 11~3 mmole/g were then added ~inally, a sufficient amount of a soluhon of a Pt-vinylsiloxane 15 complex were added to the vinyl-containing polymer described above in order to obtain a Pt content of 100 ppm. The meanings of the abbreviations in the following Table are as follows:
ECH: I-ethynylcyclohexanol PhB ~ 3-phenyl-1-butyn-3-ol PoVI: triphenyl phosphite PoVZ: triethyl phosphite PoV3: triisopropyl phosphite PoV4: tris-(2,4-di-tert butylphenyl)-phosphite PoV5: triphenylphosphine oxide (companson) PoV6: trimethyl phosphite . ` ~e A 31 286-FQrei~n Cr~llntrjP~ 2 7 ~ ~ 4 ~ 1 Table E~. a-hydrmcy- Amount Organo- Amount Workin~ Workin~
No. acctylcnc pho~phoru~ lifo a~ thin iirc in l~ulk compouml film lal) EC~ 27 mg - - 20 min 24 h S Ibl) - - PoV4 10 mg 5 s 5 s Ic ECI~ 27 mg PoV4 10 mg 22 h >10 days Id ECH 27 mg PoV3 10 mg 3 h 15 min >6 days le ECH 27 mg PoV2 10 mg 4 h 15 min >6 days If ECH 27 mg PoV6 10 mg 2 h 20 min >6 days 10 Igl) - PoVI 10 mg 1 h 40 min >6 days Ih ECH 27 mg PoVI 10 mg 22 h >10 days lil) PhB 10 mg - - 20 min 24 h Il rhB 10 mg PoVI 10 mg 26 h >10 days ~) comparative examples 15 The combination of 1.""l",.. ,l~ d) and e) is an essenùal part of this invention As can be seen from ~WII~ala~;V~ examples la, Ib7 Ig and li, the presence of only one of the two components does not result in a long working life.
Example 2 The following example demonstrates the effect of certain or~nr~rho~rhl~rus 20 compounds on the curing times at T = 180C. An o~-hydroxyacetylene and an organu~ho~ .us compound, of the type and in the amounts given in detail in Table 2, were added to 8 96 g of the vinyl-containing polymer described in Example 1. Thereafter, 0.21 g of the polyhydrogensiloxane described in Example I and a sufficient amount of the catalyst solution described in Example I were 25 added, in order to obtain a Pt content of 100 ppm. The results are given in Table Le A 31 2~6-Forei~n ~ountries 2 1 8 ~ 4 4 1 Table 2 a-hydro~y- Amount Or~ano- Amount Working lifc Curing timc at acotylcne pho~phoru~ a~ thin film T = 180C
compound ECI~ 27 mg 20 min 7 s S ECI~ 27 mg PoV4 10 mg 21 h 7 s ECI~ 27 mg PoVS 10 mg 50 min >60 s It will be understood that the specification and examples are illustrative but not limitabve of the present invention and that other ~ budi~ b within the spirit and scope of the invention will suggest themselves to those skilled in the art.
10 EYample 3 The following example is intended to demonstrate the synergistic effect of the inhibitory activity of a dicarboxylic acid ester and an organophosphorus compound.
9.15 g of a branched polydimethylsiloxane with a viscosity of ~ = 250 mPas and 15 a content of vinyl groups bonded directly to the silicon of 0.32 mmol g~l aremixed with an ul~lu~llo;,~)llul~ls compound and a dicarboxylic acid ester. Then 0.55 g of a polylly~lu~ siloxane which has a content of hydrogen atoms directly bonded to the silicon of 11.3 mmol g~l is added. Then a sufficient quantity of asolution of a Pt/vinylsiloxane complex is added in order to obtain a Pt content of 20 100 ppm. The exact quantities and the type of inhibitors used are shown in Table 3. The organophosphorus compound has the name given in Example 1.
I
Cl~ kq~ mixtures, a method of nre~arin~ them and their use The present invention relates to crosslinkable mixtures, to a method of preparing 5 them and to thei} use.
The use of silicones for the adhesive coating of substrates such as paper, plastics or metal foils, for example, i.e. for coatings which repel adhesive substances, has been hnown for some time. In this connection, a liquid mixture comprising a vinyl-containing polydiorganosiloxane, an Si-H-containing polydiorgqnr~eiloYqn~
10 (polyhydrogensiloxane) and a suitable catalyst is applied to the paper and is cured at elevated Lt~ rldLulu~ by what is termed a hydrosilylation reaction (addition-u~u~ hillg systems). A solid silicone layer which adheres to the substrate is formed in the course of this procedure. The silicone layer is applied to the substrate via rollers, which take up the liquid, reactive silicone mixture from a vat 15 and transfer it to the substrate. If a substrate coating machine such as this breaks down for an extended period of time for technical reasons, the silicone film is capable of crosslinhing on the rollers even at room Ltlllp~,.a~ul~. This results in silicone residues on the rollers which are extremely difficult to remove, and which make it impossible to achieve trouble-free operation again aRer the machine has 20 been re-started.
Since problems which are similar in principle also arise in other applications of addition-crosslinhing silicone systems (e.g. lLS~), numerous additives (inhibitors) have been developed in the past, the function of all of which is to keep the reactive mixtures liquid for longer at }oom ~tUll~ldLUlt:. Thus US-A-4 329 275, 25 for example, discloses the use of phosphorus compounds in combination with peroxides as worhing life extenders. However, the addition of peroxides is associated with safety risks during the production and processing of mixtures ofthis type. US-A-4 645 815 relates to the use of cyclometallized Pt phosphite complexes. In this disclosure the catalyst complex is produced in a separate step, 30 which is associated with additional costs. However, both of the aforementioned possible solutions have a further, very senous disadvantage. They were developedfor systems which employ relatively low concentrations of catalyst (10 ppm).
Silicone mixtures which have a considerably higher content of catalyst (100 ppm)are used for the coating of substrates, however. In systems with high catalyst 35 concentrations such as this, the aforementioned inhibitors do not fulfil the requirements which are desired by the market as regards room temperature .. . . ..... . . . . ..... ... .. .
Le A 31 28eS-Forei~n Countries 2 1 8 4 4 ~ 1 . ~
stability. US-A-4 851 452 ptoposes the use of Pt-vinylsiloxane complexes in eombination with Pt-phosphine complexes as catalysts which haYe a signifieantly decreased activity at room temperature. However, phosphines have the disadvantage that the activity of the catalyst is also decreased to an appreciable 5 extent at elevated ~l..p~ld~Ulc~ (T=180C), i.e. under curing eonditions. For this reason, they are only of very limited value for substrate coating applications.
a-hydroxyacetylenes, whieh are deseribed in detail in US-A-3 445 420, eonstitute -another group of inhibitors which can be used. These e~mro~m~i~ do in fact prolong the working life of the system "in bulk", but are extremely I '` y 10 as regards prolonging the working life of thin films such as those which are present on the rollers during the coating operation.
The object of this invention is therefore to provide suitable mixtures which decrease the aetivity of the catalyst at room Lclllpcld~UIc, even in rapid, addition-~,lu~lillkillg silicone systems, without prolonging the curing times under reaction 15 conditions. At the same time, an object is to be able to prepare the mixture in a simple manner and without safety risks.
It llas now been found that these problems can be solved with addition-erosslinking polysiloxane mixtures which contain Pt compounds or elemental Pt, an a-hydlu~yacc~ylene or an ester of a dicarboxy acid and at least one 20 organophosphorus eompound of the type speeified in detail below.
The present invention therefore relates to ulu~ kal)le mixtures eûntaining a) at least one polysiloxane which contains at least two olefinically or acetylenically unsaturated multiple bonds, b) at least ore polyll~.llu~;c..siloxane which eontains at least two hydrogen atoms direetly bonded to silieon, e) at least one substanee which eatalyzes hydrosilylation, d) at least one inhibitor, and e) at least one phosphorus eompound of formula (1) Le A 31 ~ oreign Countrie3 2 1 8 4 4 4 1 ' ~
PR3 (1) wherein R each independently is H, Cl-CI8-alkyl, C6-C30-aryl, C7-C3l-alkylaryl, or ORI
S Rl each in~ r~n~ is Cl-C18-alkyl, C6-C30-aryl, C7-C3l-alkylaryl, and wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals and R and Rl may have a different meaning within the molecule, and f) optionally other auxiliary materials.
Component a) in the sense of the invention is preferably a cyclic, linear or branched polysiloxane which is synthesized from units of tlle general formula (II) (R3)a(R4)bsio(4 -a-b) 2 (Il) Here, R3 represents a C2-C8 alkenyl radical, e.g. vinyl, allyl, I-butenyl, I-hexenyl, etc. The alkenyl radicals may be bonded to silicon atoms within the chain or at the end of the chain. R4 is a ~ luv 1~..., saturated lly~l~JuallJwl radical containing up to 10 carbon atoms, from the group comprising substituted and .~
alkyl, aryl and arylalkyl radicals. Examples of monovalent radicals R4 include methyl, ethyl, propyl, isopropyl, butyl, octyl, etc., cyclobutyl, cyclopentyl, 20 cyclohexyl, etc., phenyl, tolyl, xylyl, naphthyl, etc., and benzyl, phenylethyl or phenylpropyl. The relationships 0 < a < 3, 0 < b < 3 and 0 < a + b < 4 apply to the integers a and b. . a is preferably equal to 0 or 1. In radicals R4 of the present invention, some or all of the hydrogen atoms may be substituted by fluorine and / or chlorine, bromine, or iodine atoms or cyano radicals This means 25 that R4 may also be a chloromethyl, trinu~"o~",yl, chlorophenyl, dibromophenyl, ~3-cyanoethyl, ~-uya~ l or y-cyanopropyl radical, for example.
Using the nnm~n~l~fllre familiar to one skilled in the art:
, Le A 312~ srei~n Countrie8 . 21 8 ~ 4 41 .
~ 4 -M: (CH3)3SiOI/2 D: (CH3)2SiO22 T: (CH3)SiO3/2 MVi: (cH2=cH)(cH3)2siol/2 5 DVi: (CH2=CEI)(CH3)siO2/2~
the following examples of component a) can be cited:
M2DIooD
M ViD
MViMDIooD
I O T5Ds5OM7Vi T3DsooM2ViM3 T6D3OoDviM4vlM4 .
The molar proportion of unsaturated radicals of type R3 may be selected to have any desired value.
In component a), the molar proportion of unsaturated radicals of type R3 should preferably be between 0.01 and 10 mmole per gram, more preferably between 0.05 and I mmole per gram, and most preferably between 0.1 and 0.'.7 mmole per gram of component a). The viscosity of component a) is preferably between 0.01 and 100,000 Pa s, more preferably between 10 and 100,000 mPa s at 25C.
Component b) in the sense of the present invention is a polysilo~ane which is synthesized from units of general formula (III) HC(R4)dsio(4 -c d)/2 (III) where R4 has already been defined above and may optionally also have the meaning of R3. The si~ ,hir~me~ric suffices c and d are integers, where 0 < d < 3 and 0 c c < 2, and where 0 < c + d < 4. Preferably, 0 < c < 1.
.
Le A 31 ~8~-~oreign Countries 2 1 ~ 4 4 4 1 Using the nomenclature familiar to one skilled in the art:
Mll: H(CH3)2SiOI,2 Dl~: H(CH3)SiO2/2, the following examples of component b) can be cited:
M2 Dlo MDIoDIoH
M211DZoDIoH
M viD H
M2D3ViD8H
(where M, D, MVi and DVi are defined as for component a)).
The molar proportion of hydrogen atoms which are directly bonded to a silicon atom in component b) may be selected to have any desired value.
In component b), the molar proportion of hydrogen atoms which are directly bonded to a silicon atom is preferably between 0.01 and 17 mmole, more preferably between 0.1 and 1~ mmole, and most preferably between I and 17 mmole per gram of component b).
In the total mixture described above, r.nmrnnr-nt.i a) and b) should preferably be present in a quantitative ratio such that the molar ratio of hydrogen atoms which are directly bonded to silicon atoms (SiH) in component b) to the unsaturated radicals (Si-vinyl) in corr;ponent a) is between 0 05 and 20, more preferably between 0.5 and 10 and most preferably between 1 and 5.
Component c) in the sense of the invention preferably compnses the elements platinum, rhodium, iridium, nickel, ruthenium and/or palladium, in elemental form on a supporting substance or in the form of their compounds. Platinum compounds or platinum complexes are preferred, such as H2PtCI6, platinum-olefin complexes, platinum-alcohol complexes, platinum-vinylsiloxane complexes and ., . _, . .. , . .... ... ., ..... ..... .. . .. ... _ .. ......
Le A 31 2~5-~Qreign Co~ ries 2 1 8 4 4 4 1 also elemental platinum on a supporting substance, such as activated carbon7 Al2O3 or SiO2 for exampie. Component c) is most preferably a platinum-vinyl-siloxane complex. Platinum-vinylsiloxane complexes most preferably contain at least two olefinically unsaturated double bonds in the siloxane; see US 3 715 334 5 for example.
The term "siloxane" includes polysiloxanes, i.e. it includes vi~ylpoly~;loxanes also, for example. The proportion of component c) in the total mixture should -preferably be between I and 1000 ppm, more preferably between I and 500 ppm, and most preferably between 25 and 250 ppm.
10 Component d) in the sense of the invention comprises all the inhibitors which are known in the prior art, such as maleic acid and derivatives thereof, amines, alkyl isu~,y~lluldl~ and acetylenically unsaturated alcohols in which the OH group is bonded to a carbon atom adjacent to the C-C triple bond, such as those describedin detail in US 3 445 420, for example. Component d) is preferably 2-methyl-3-15 butyn-2-ol or l-ethynylcyclohexanol or (+) 3-phenyl-1-butyn-3-ol. Component d) is preferably added to the mixture in a quantitative proportion of 0.0001 % to S %
with respect to the total weight of mixture, more preferably 0.01 % to 2 %, and most preferably 0.1 to I %.
Component e) in the sense of the invention is an orgam",l~ ,llvlu~ compound of 20 type PR3. In this respect, R is a hydrogen atom or a monovalent hydrocarbon radical from the group comprising Cl-C~s alkyl, C6-C30 aryl and C7-C3l alkylaryl.
R may have a different meaning within a molecule. In a preferred i-mhorlimPn~ ofthe present invention, component e) is a compound of formula P(ORI)3, where R~
= C~-CIs alkyl, C6-C30 aryl or C7-C3l alkylaryl, wherein the aryl radicals may 25 optionally be substituted with linear or branched alkyl radicals and Rl may have different meanings within the molecule. Examples of component e) include triphenylphosphine, triethylphosphine, tribu~ l.o~lli,.e, phosphoric acid trimethyl ester, phosphoric acid triisopropyl ester, phosphoric acid triphenyl ester or tris-(2,4-di-tert. butylphenyl)-phosphite. Component e) of the invention can also 30 include phosphite derivatives of pentaerythritol, such as, for example, bis (2,4-di-tert.butylphenyl)-~ .yLl..i~ol diphosphite (obtainable from the &reak Dakes Company under the trade name Alkanox P24(~). Component e) of the present invention is preferably added in a quantitative proportion of 0.0001 % to S % with Le A 31 ~-FQrei~n Countries 2 1 ~ 4 4 4 ~
. ~
respect to the total weight of the mixture, more preferably 0.001 % to 4 % and most preferably between 0.001 % and 2.~ %.
Examples of auxiliary materials (component f)) in the sense of the invention include polysiloxane resins which are synthesized from Culllpu~ of general formulae (II) and (111), filrers which have a positive effect on the mechanical and electrical properties of the cured mixture according to the invention, such as pyrogenic and ~ dte:l hydrated silicas having a BET specific surface of 5û to 50û m2/g, for example. The surfaces of fillers of this type may be modified, e g.
with organosilicon compounds. Modification may also be effected during tlleir incorporation into the polymer, by the addition of hexamethyldisilazane or 1,3-divinyl-1,1,3,3-tetramethyldisilazane with the addition of water, for example.
Substances such as ~ om~ oll~ earths, finely divided quartz flour, amorphous hydrated silicas or carbon blacks may also be used as fillers, for example.
In another embodiment the mixtures according to the invention additionally contain water or an orgMic solvent.
In a preferred embodiment of the invention, cul~ ullell~ a) and b) are present in a quantitative ratio such that the SiH:Si-vinyl ratio is between 0.1 and 10, the content of component c) is between 1 and 1000 ppm, the content of component d) is between 0.0001 and 5 %, and the content of component e) is between 0.0001 and 5 %, wherein the quantitative data are given with respect to the total weight of the mixture in each case.
This invention also relates to a method of preparing the crosslinkable mixtures according to the invention. In this process, ~ulllpu~ a), d) and e) are preferably mixed, and thereafter component b) and finally component c) are added.
This invention further relates to the use of the crosslinkable mixture according to the invention for the coating of substrates.
Le A 31 286-~orei~n Çountries 2 1 8 4 4 4 ~
. ~
The following examples serve to explain the invention. The invention is not restricted to these examples, however.
Exam~les of ~
In the following examples, all parts by weight and p~ CS are given with 5 respect to the weight of the total mixture unless defined otherwise.
General (-~1" ' ' procedure for Examples la ~o lj The quantitative data which do not appear in this description, as well as the type of ~ and the experimental results, are given in Table 1.
9.15 g of a branched polydimethylsiloxane with a viscosity of ~ = 250 mPa s and 10 a content of vinyl groups bonded directly to silicon of 0.32 mmole/g were mixed optionally with an cc-hyd~u~y~,c~ylene (see Table 1) and optionally with an or~n-~rh--~rh~lrus compound (see Table 1) 0~5 g of a pulyllydl~ cilo~r~ne having a content of hydrogen atoms bonded directly to silicon of 11~3 mmole/g were then added ~inally, a sufficient amount of a soluhon of a Pt-vinylsiloxane 15 complex were added to the vinyl-containing polymer described above in order to obtain a Pt content of 100 ppm. The meanings of the abbreviations in the following Table are as follows:
ECH: I-ethynylcyclohexanol PhB ~ 3-phenyl-1-butyn-3-ol PoVI: triphenyl phosphite PoVZ: triethyl phosphite PoV3: triisopropyl phosphite PoV4: tris-(2,4-di-tert butylphenyl)-phosphite PoV5: triphenylphosphine oxide (companson) PoV6: trimethyl phosphite . ` ~e A 31 286-FQrei~n Cr~llntrjP~ 2 7 ~ ~ 4 ~ 1 Table E~. a-hydrmcy- Amount Organo- Amount Workin~ Workin~
No. acctylcnc pho~phoru~ lifo a~ thin iirc in l~ulk compouml film lal) EC~ 27 mg - - 20 min 24 h S Ibl) - - PoV4 10 mg 5 s 5 s Ic ECI~ 27 mg PoV4 10 mg 22 h >10 days Id ECH 27 mg PoV3 10 mg 3 h 15 min >6 days le ECH 27 mg PoV2 10 mg 4 h 15 min >6 days If ECH 27 mg PoV6 10 mg 2 h 20 min >6 days 10 Igl) - PoVI 10 mg 1 h 40 min >6 days Ih ECH 27 mg PoVI 10 mg 22 h >10 days lil) PhB 10 mg - - 20 min 24 h Il rhB 10 mg PoVI 10 mg 26 h >10 days ~) comparative examples 15 The combination of 1.""l",.. ,l~ d) and e) is an essenùal part of this invention As can be seen from ~WII~ala~;V~ examples la, Ib7 Ig and li, the presence of only one of the two components does not result in a long working life.
Example 2 The following example demonstrates the effect of certain or~nr~rho~rhl~rus 20 compounds on the curing times at T = 180C. An o~-hydroxyacetylene and an organu~ho~ .us compound, of the type and in the amounts given in detail in Table 2, were added to 8 96 g of the vinyl-containing polymer described in Example 1. Thereafter, 0.21 g of the polyhydrogensiloxane described in Example I and a sufficient amount of the catalyst solution described in Example I were 25 added, in order to obtain a Pt content of 100 ppm. The results are given in Table Le A 31 2~6-Forei~n ~ountries 2 1 8 ~ 4 4 1 Table 2 a-hydro~y- Amount Or~ano- Amount Working lifc Curing timc at acotylcne pho~phoru~ a~ thin film T = 180C
compound ECI~ 27 mg 20 min 7 s S ECI~ 27 mg PoV4 10 mg 21 h 7 s ECI~ 27 mg PoVS 10 mg 50 min >60 s It will be understood that the specification and examples are illustrative but not limitabve of the present invention and that other ~ budi~ b within the spirit and scope of the invention will suggest themselves to those skilled in the art.
10 EYample 3 The following example is intended to demonstrate the synergistic effect of the inhibitory activity of a dicarboxylic acid ester and an organophosphorus compound.
9.15 g of a branched polydimethylsiloxane with a viscosity of ~ = 250 mPas and 15 a content of vinyl groups bonded directly to the silicon of 0.32 mmol g~l aremixed with an ul~lu~llo;,~)llul~ls compound and a dicarboxylic acid ester. Then 0.55 g of a polylly~lu~ siloxane which has a content of hydrogen atoms directly bonded to the silicon of 11.3 mmol g~l is added. Then a sufficient quantity of asolution of a Pt/vinylsiloxane complex is added in order to obtain a Pt content of 20 100 ppm. The exact quantities and the type of inhibitors used are shown in Table 3. The organophosphorus compound has the name given in Example 1.
2 ~ 8~44 1 Le A 31 28G-ForeiPn Collntries . ~
I I
T,tble 3 Ex. No. Dicarho~ylic Quantity Organo- Quantity Worldng life as acid cstcr ,oh~Jphorus thin rllm compounll 3al dimethyl 0 mg PoV4 10 mg 5 sZ
maleate 3bl dimethyl 32 mg PoV4 O mg 25 min maleate 5 3c dimethyl 32 mg PoV4 ~0 mg 12 h maleate I U~ Ja~ iV~ example 2The whole mixture gelated immediately after the introduction of the Pt catalyst solution
I I
T,tble 3 Ex. No. Dicarho~ylic Quantity Organo- Quantity Worldng life as acid cstcr ,oh~Jphorus thin rllm compounll 3al dimethyl 0 mg PoV4 10 mg 5 sZ
maleate 3bl dimethyl 32 mg PoV4 O mg 25 min maleate 5 3c dimethyl 32 mg PoV4 ~0 mg 12 h maleate I U~ Ja~ iV~ example 2The whole mixture gelated immediately after the introduction of the Pt catalyst solution
Claims (11)
1. A crosslinkable mixture, containing a) at least one polysiloxane which contains at least two olefinically or acetylenically unsaturated multiple bonds, b) at least one polyhydrogensiloxane which contains at least two hydrogen atoms directly bonded to silicon, c) at least one substance which catalyzes hydrosilylation, d) at least one inhibitor, and e) at least one phosphorus compound of general formula (1):
PR3 (I) wherein R each independently is H, C1-C18-alkyl, C6-C30-aryl, C7-C31 alkylaryl, or OR1, R1 each independently is C1-C18-alkyl, C6-C30-aryl or C7-C31-alkylaryl, and wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals f) optionally other auxiliary materials.
PR3 (I) wherein R each independently is H, C1-C18-alkyl, C6-C30-aryl, C7-C31 alkylaryl, or OR1, R1 each independently is C1-C18-alkyl, C6-C30-aryl or C7-C31-alkylaryl, and wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals f) optionally other auxiliary materials.
2. A crosslinkable mixture according to claim 1, wherein c) is a Pt compound,platinum complex, or elemental platinum on a supporting substance.
3. A crosslinkable mixture according to claim 1, wherein c) is a platinum-vinylsiloxane complex in which the siloxane contains at least two olef inically unsaturated double bonds.
4. A crosslinkable mixture according to claim 1, wherein d) is 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol or (+)-3-phenyl-1-butyn-3-ol.
5. A crosslinkable mixture according to claim 1, wherein e) is a compound of the formula P (OR1) 3, wherein R each in r independently is C1-C18-alkyl, C6 30-aryl or C7-C31-alkylaryl, wherein the aryl radicals may optionally be substituted with linear or branched alkyl radicals.
6. A crosslikable mixture according to any one of claims 1 to 5, containing water.
7. A crosslinkable mixture according to any one of claims 1 to 5, additionally containing an organic solvent.
8. A crosslinkable mixture according to any one of claims 1 to 5, wherein a) and b) are present in a quantitive ratio such that the SiH:Si-vinyl ratio is between 0.01 and 300, the content of component c) is between 1 and 1,000 ppm, the content of component a) is between 0.0001% and 5%, and the content of component e) is between 0.0001 and 5%, wherein the quantitive data in each instance are with respect to the total weight of the mixture.
9. A process for preparing a crosslinkable mixture according to claim 1, which process comprises mixing a), d) and e), and subsequently adding b) and finally adding c), each of a), b), c), d) and e) being as defined in claim 1.
10. A crosslinkable mixture according to claim 8, wherein c) is a platinum-vinylsiloxane complex in which the siloxane contains at least two olefinically unsaturated double bonds, d) is 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol or (+)-3-phenyl-1-butyn-3-ol, e) is a compound of the formula P(OR1)3, wherein R1 each independently is C1-C18-alkyl, C6-C30-aryl, C7-C31-alkylaryl, and additionally containing at least one of water and an organic solvent.
11. In the coating of a substrate by applying thereto a silicone composition, the improvement wherein said composition comprises a mixture according to any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19532316.5 | 1995-09-01 | ||
| DE19532316A DE19532316C1 (en) | 1995-09-01 | 1995-09-01 | Crosslinkable polysiloxane mixtures, a process for their preparation and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2184441A1 true CA2184441A1 (en) | 1997-03-02 |
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ID=7771034
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002184441A Abandoned CA2184441A1 (en) | 1995-09-01 | 1996-08-29 | Crosslinkable mixtures, a method of preparing them and their use |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0761759B1 (en) |
| JP (1) | JP4211951B2 (en) |
| KR (1) | KR970015668A (en) |
| AT (1) | ATE236221T1 (en) |
| AU (1) | AU716990B2 (en) |
| CA (1) | CA2184441A1 (en) |
| DE (2) | DE19532316C1 (en) |
| ES (1) | ES2196110T3 (en) |
| NO (1) | NO311139B1 (en) |
| PL (1) | PL315870A1 (en) |
| TW (1) | TW343992B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
| CN115340570A (en) * | 2022-06-17 | 2022-11-15 | 华南理工大学 | Alkynyl phosphite ligand, preparation method thereof and application thereof in hydrosilylation platinum catalyst |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59710143D1 (en) * | 1996-12-30 | 2003-06-26 | Ge Bayer Silicones Gmbh & Co | CROSSLINKABLE MIXTURES AND A METHOD FOR THE PRODUCTION THEREOF |
| DE19757222A1 (en) * | 1997-12-22 | 1999-06-24 | Ge Bayer Silicones Gmbh & Co | Polysiloxane mixture stabilized at room temperature without inhibiting vulcanization on heating based on addition vulcanizable silicon rubber with (het)aryl sulfide or selenide |
| DE19757221A1 (en) * | 1997-12-22 | 1999-06-24 | Ge Bayer Silicones Gmbh & Co | Polysiloxane mixture stabilized at room temperature without inhibiting vulcanization on heating |
| FR2847900B1 (en) * | 2002-12-02 | 2006-06-09 | Rhodia Chimie Sa | CATALYTIC ASSEMBLY FOR HYDROSILYLATION, PROCESS FOR PREPARING THE SAME, AND SILICONE COMPOSITION INCORPORATING SAME |
| FR2848215B1 (en) * | 2002-12-04 | 2006-08-04 | Rhodia Chimie Sa | SILICONE ELASTOMER COMPOSITION, ADHESIVE, MONOCOMPONENT AND CROSS-LINKABLE BY POLYADDITION |
| US7067570B2 (en) * | 2002-12-10 | 2006-06-27 | Shin-Etsu Chemical Co., Ltd. | One-part organopolysiloxane gel composition |
| JP5123177B2 (en) | 2005-06-22 | 2013-01-16 | スリーエム イノベイティブ プロパティズ カンパニー | Hydrophilized curable silicone impression material with improved storage properties |
| JP2007131750A (en) * | 2005-11-11 | 2007-05-31 | Shin Etsu Chem Co Ltd | Addition curing type organopolysiloxane composition and method for promoting curing thereof |
| DE102006016753A1 (en) | 2006-04-10 | 2007-10-11 | Wacker Chemie Ag | Crosslinkable compositions based on organosilicon compounds |
| JP2007308581A (en) * | 2006-05-18 | 2007-11-29 | Shin Etsu Chem Co Ltd | Curing method of addition cure silicone rubber composition, and addition cure silicone rubber composition |
| DE102007047212A1 (en) | 2007-10-02 | 2009-04-09 | Wacker Chemie Ag | Curable silicone compositions |
| JP2009091403A (en) * | 2007-10-04 | 2009-04-30 | Shin Etsu Chem Co Ltd | Addition-curable type silicone rubber composition and method for curing the same |
| JP2009220384A (en) * | 2008-03-17 | 2009-10-01 | Shin Etsu Chem Co Ltd | Method of forming silicone rubber thin film coating layer and silicone rubber thin film coated article |
| DE102009027847A1 (en) | 2009-07-20 | 2011-01-27 | Wacker Chemie Ag | Curable silicone compositions |
| KR20140144750A (en) * | 2009-12-23 | 2014-12-19 | 블루스타 실리콘즈 프랑스 에스에이에스 | Hydrosilylation reaction inhibitors, and use thereof in a coating method |
| JP5792800B2 (en) * | 2010-05-14 | 2015-10-14 | ネクサム ケミカル エイビー | Cross-linking catalysis |
| WO2019025002A1 (en) | 2017-08-04 | 2019-02-07 | Wacker Chemie Ag | Stabilization of noble metal catalysts |
| WO2023136259A1 (en) * | 2022-01-13 | 2023-07-20 | 信越化学工業株式会社 | Platinum-phosphite complex-containing hydrosilylation catalyst, method for producing same, curable organopolysiloxane composition, and article |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4329275A (en) * | 1979-07-27 | 1982-05-11 | Toshiba Silicone Co., Ltd. | Heat-curable polysiloxane composition |
| US5334687A (en) * | 1989-09-08 | 1994-08-02 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane composition |
| DE4336703A1 (en) * | 1993-10-27 | 1995-05-04 | Wacker Chemie Gmbh | Crosslinkable compositions and their use for the production of coatings which repel tacky substances |
-
1995
- 1995-09-01 DE DE19532316A patent/DE19532316C1/en not_active Expired - Fee Related
-
1996
- 1996-08-20 AT AT96113292T patent/ATE236221T1/en not_active IP Right Cessation
- 1996-08-20 EP EP96113292A patent/EP0761759B1/en not_active Expired - Lifetime
- 1996-08-20 DE DE59610291T patent/DE59610291D1/en not_active Expired - Lifetime
- 1996-08-20 ES ES96113292T patent/ES2196110T3/en not_active Expired - Lifetime
- 1996-08-26 TW TW085110348A patent/TW343992B/en not_active IP Right Cessation
- 1996-08-27 AU AU64302/96A patent/AU716990B2/en not_active Ceased
- 1996-08-27 JP JP24251296A patent/JP4211951B2/en not_active Expired - Lifetime
- 1996-08-29 NO NO19963609A patent/NO311139B1/en not_active IP Right Cessation
- 1996-08-29 CA CA002184441A patent/CA2184441A1/en not_active Abandoned
- 1996-08-29 PL PL96315870A patent/PL315870A1/en unknown
- 1996-08-31 KR KR1019960037665A patent/KR970015668A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
| CN115340570A (en) * | 2022-06-17 | 2022-11-15 | 华南理工大学 | Alkynyl phosphite ligand, preparation method thereof and application thereof in hydrosilylation platinum catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4211951B2 (en) | 2009-01-21 |
| NO311139B1 (en) | 2001-10-15 |
| NO963609L (en) | 1997-03-03 |
| TW343992B (en) | 1998-11-01 |
| AU716990B2 (en) | 2000-03-16 |
| ATE236221T1 (en) | 2003-04-15 |
| NO963609D0 (en) | 1996-08-29 |
| EP0761759B1 (en) | 2003-04-02 |
| EP0761759A3 (en) | 1997-09-17 |
| DE59610291D1 (en) | 2003-05-08 |
| EP0761759A2 (en) | 1997-03-12 |
| AU6430296A (en) | 1997-03-06 |
| KR970015668A (en) | 1997-04-28 |
| ES2196110T3 (en) | 2003-12-16 |
| PL315870A1 (en) | 1997-03-03 |
| DE19532316C1 (en) | 1997-05-22 |
| JPH09183906A (en) | 1997-07-15 |
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