CA2185823A1 - Platinum complexes and light-activatable hydrosilylation catalysts containing same - Google Patents

Abstract

The present invention relates to new catalytic systems formed by photoactive organoplatinic complexes in the crosslinking by hydrosilylation of polyorganosiloxanes Si-H and Si-Vi or Si-epoxy. These platinum complexes correspond to the formula: (I) with L consisting of a ligand which is advantageously a chromophore and which can be of varied nature. These platinum complexes of degree of oxidation 0 can serve as a basis for the constitution of catalytic hydrosilylation systems which are photoactivable and possibly thermoactivable, stable and efficient. The present invention also relates to photocrosslinkable compositions containing the Si-H / Si-Vi or Si-epoxide polyorganosiloxanes, one of the catalytic systems referred to above and optionally various other additives such as thermal blockers and / or L ligand in excess. Application: Silicone composition photocrosslinkable by hydrosilylation and usable as non-stick coating, for example, for paper.

Description

~ W095/25734;2 1 ~5~23 P l/r~5~
I
PLATINUM COMPLEXES AND PHOTOACTIVATED HYDROSILILATION CATALYSTS
CONTAINING THEM
S TECHNICAL FIELD:
The present invention relates to the field of the catalysis of reactions of , UIaiiU .. between chains of polymers, eg silica, ~. All of the Radicals reagents capable of forming bridges, '^ so as to obtain a material 10 crosslinked having a certain hardness and a certain mechanical strength.
It is more ~, -ui "" question, in the present presentation, of substrates to pûlyvll type crosslink, 'A having, per molecule, at least one radical reactive Si-H, while being free of silicon atoms bonded to more than two atoms of l.~ lU2'~. These substrates A are intended to react with substrates. type B15 having, per molecule, at least one 2.uu ~, ~, L unsaturated aliphatic reagent and / or at least one reactive function eg epoxide, in the presence of a UUI ~ catalyst at least one platinum complex, such a reaction being initiated or activated by light rays, of wavelength, chosen, preferably, in the field of ultraviolet (UV).
More, u. ~ still, the present invention relates, first of all, to new uaLdl~L;~Iu_;~ systems formed by Ul~r' complexes.
photoactive in cross-linking by h~Jlu .;l~.aL;ul~ de polyu.~ A de tvpe Si—H and compounds B with aliphatic Al;ull and/or with a reactive function.
The present invention also relates to a method of lyJIu ~; lylaL; ul ~ in which the aforesaid CaLalyL;y--o systems are implemented, as well as r labl ~ by 1 ': ''va ~; ull and containing, among other things, the substrates A and B as well as the above catalyst.
ART Ar~ ;UK:
Among the ~ e, ~ E ". t ~ bl_ ~ in the context of the mvention include, for example: the coatings form a mixture of crosslinkable silicone oils between them and intended to form release layers on fibrous supports, such as paper, dental impressions, adhesives, d~rl~ materials for 35 jointing, etc.

W095/25734 2 1 ~8~3 Pl~r~'l ~

For the ~, aliu ~ anti-adhesion paper, among others, the in situ crosslinking by pllu ~ a ~, Li ~ n ~ l, eg by irradiation W, is umi "~ i..t ~ in the insofar as it allows high coating speeds. In addition, this crosslinking in situ can take place, easily, to, aLul ~; ambient. It also avoids 5 uses solvents, including r ~ ~ is expensive and difficult ~ here.
Finally, the ~ character of cross-linking reactions of this type is ~ali ~-` I;i..l~"lL a~ ~ , with regard to the activation energy savings that this generate.
One of the crucial elements in this cross-linking technique by lû 1' - `valiûl ~, is of course the catalyst l'', We thus seek to develop systems càl ~ lyt; uu ~ inactive until. . ' ~O upper or equal to the ~ ulllJ ~, .a ~ ul ~; ambient (3û ~0 C) and this, over the longest periods possible. It goes without saying that these catalytic systems are also required to have a very high reactivity to the light rays considered.
(~ these catalysts come in the form of complexes " . (platinum or analogs).
In this field, we can mention in particular FALTYNI~C, which mentions in ~Inorg. Chem., 20 (1981), 1357" of rhodium complexes active in the photocatalysis of ~rhJdluailyl~Lio~ reactions. appears only these complexes of the 20 rhodium has low CaLaly'Liu activities, u ~ .sl ~,] aii ~.
Ultimately, platme turned out to be the most suitable metal to fit in the ~ . of these complexes u.~, "", Thus, to date, most reactions i...l.~l.,.ll. of h.~iluailylaLiu~ are catalyzed by the KAI~SIEDT solution (~1S-A-3 775 4s2) which consists of platinum complexes at formal and real oxidation state = 0 with lé ~ 'J! ~ i ~ J! ~, oilu ~ n ~ lc (TMDVS), useful as a ligand. The average formula of these complexes can be expressed as follows: [Pt" (TMDVSh).
The source of platinum in this solution is formed by the SPED~R catalyst or acid l~ a~ 01~, '-, This catalyst of I ~ ARSTEDT has al '. ~ not to be part of the catalysts of ll ~ lluoll ~ ldtiu ~ plluluauli ~ n ~ l ~ o. The activation adapted to this catalyst of KARSTED~ is the Lh~.l.lu~Livdliu." which is, all the same, much more CO-I ~ l,, and expensive than a simple activation W, of the type of that referred to by the invention.

~w095/2s734? 18~23 r~llrlv~

Another major defect of the KARSTEDT solution catalyst is have a storage stability. ~ mediocre (gel time at 2 ~ C
less than or equal to I min).
In this state of affairs, one of the essential objectives of the present invention is to S provide new platinum complexes and systems, aLal ~ yLil ~ u., ~ based on these platinum complexes, preferably of degree J'u ~ yl '= O, said systems being useful, in particular in rl-yd ~ vDil ~ ldLiull of polyul3 'of Si-H type and of compounds to; ~. aliphatic (preferably ethylenic, eg Si-Vi) and/or reactive functions:
lo - which are IJh.~Lùa~Livd~1~3D and ~. " Ll~ a., LivdbL.3, - which are stable in aLIlluD ~ the and a L ~,, aLulc ambient on long durations, - and who are p. ~ without sacrificing the imperatives of feasibility and profitability;...1~
Another object of the invention is to provide a method of ll ~, D; l ~: aLiu, l parph ~ lLùà., LivaLiul ~ of reactive products, and in particular of silicones, in which one has use of the above systems ~, aLdl ~ Li ~ lu ~; "said process ~ to be implemented easy, fast, and inexpensive.
Another object of the invention is to provide oils ~
20 cross-linkable silicones by IJllvLuacLvaLi - .qui Cu~ c. .~.1. Ies aforesaid systems ~ .d ~ al ~ ',, - which are stable until t~,..ly;. aLul CD superior to the L~...";, aLul ,, ambient, preferably greater than or equal to 30 ~ 0 C, and this on long durations, - and which are very reactive to radiation I
Such c . stable in storage can be used, for example, for ranti ~ III;. cll,, e paper, dental impressions, materials of ~ ... or dejointing, adhesives, or for any other application in laqueDe it is interesting to 30 implement an in situ crosslinking of ~, the ~ you ~ silicones.
3~

~ i 8~8~3 WO 9512!i734 r~ r~

BRIEF DESCRIPTION OF THE INVENT~ON:
These objectives, among others, are achieved by the present invention which relates new platinum complexes of formal and real oxidation state = 0 and 5 corresponding to the following formula:
R
Rl,",.. If/~
O Pt--L
If ~
"`' 1 \=
R _ n= l or 2 ~[) with L = L, when n = I
10 with L = L~ when n = 2, Rl, R2, R3, R4 are different or similar to each other and lqJl ~ '' a ~ uu ~ alkyl and / or acyl, preferably an alkyl having from 1 to 18 atoms carbon, the ~ I r 'methyl, ethyl, propyl, pentyl4 hexyl, allyl, acetyl, propionyl being preferred ~ Cll ~ and especially methyl, 15 ~ L, being a ligand of the following formula:
Y~zl (1) 20 in which:
î~ Z2 are identical or different and:
~ or are 5~ from the following list of radicals:

~ WO 9 ~ i / 25734 2 1 8 ~ 8 ~ ~ ~ ~JIr~

- OH, -O-alkyl, -o-alkenyl, -NR'R6 with identical or different R5, R6 and chosen from the ~- -r' below: hydrogen, alkyl, a'ikenyl, the alkyl and ai'kenyl residues considered above being linear or branched and ~, U ~ IIpUI Lalll of I to 6 carbon atoms, or form a single divalent radical of the type:
i' - NR7 - with R~ = X a'ikyl, aikenyl, phenyl, said ~uu~ being themselves ~,~ 1 substituted by alkyl, a'~kenyl, aryloxy, ai yla'ikyle residues, structures lû alu~ Li4u~,;. of these last two remains that can be carriers ~ UU~ amide chains, such as -7.~1H-CO-CH3, preferably alkenylene CU~ r ~ ' to: - R~ C = CR9, with R~, R9 identical or different and Cull~ Jùlld~ to ll~dlu~ ~..c or an aikyl, aikoxyl ha'iogenated radica'i.
either are two atoms i'iin each other and a~,~L~,.. G.. L has a cycle of aromatic preference.
i~i E" E2 are identical or different and, CiJI l,.~C..'.;: O, 71~R' with R~ = a'ikyle or alkenyl C ~ -C6, CRI ~ R ~ I with R ~, Rl2 identical or different and ..ul,. r 'aun alkyl in Cl-C6, an alkoxyl, a halogen..., the oxygen being more yal; ~ t 20 preferred.
o yi, y2 are identical or different and ,c~,, 6,...~ an alkyl, aryl radicai of preferably phenyl, alkyloxy, oryloxy, hydrogen or a halogen, Q L2 being an iigand consisting of one of the following two remainders (2,), (2):

y4~
E
(2,) in which the . .

2 1 85~3 wo ss/2s~ r~S;c Y3 a y6 on the one hand and E3, E4 on the other hand are identical or different and meet the same definition as that given above for yl, y2 d E', E2 ~c~,Li~ L, Y3 and Y4 and/or Y5 and y6 which can also together form a ~-uu~.,.-.~,.-L
5 cyclic, preferably a ~,.UUl.~..~,..t aromatic cv...~,.c one or more rings ~uUIIl~LiyucS having 6 to 8 links, occurring in ortho or ~6. ' and i~ -t ~ 1 substituted by radicals ~vr~vll ' corresponding to the definition given above for Y3 to Y6;
E5 E~
y7~y9 ~3--Z4--Z~y10 E6 Eg (21) in which * E5 to E~ and Y' to y'C are as defined above * Z3, Z~ are identical or different and CUllC_r~ ~'' to:
CR13 with R~3 = H or lower alkyl C~, C6, N;
* Z~ is a residue .,u~ of 2 to 5 phenylene radicals linked together by:
0 a valuable link 0 or by at least one of the following radicals 0, COO, linear or branched alkylene CO, CoNRI4 with R'4 = H or linear or branched alkyl in Cl - C6 ~ Excluding complexes for which L = Ll with Zl and Z2 form a single oxygen atom, E ~ = E2 = o, Y '= YZ = H and Rl = R2 = R3 = R ~ = CH3.

~2185823 W0 95/25734 P~,l/r ~_ DETAILED DESCRIPTION:
The ligamd L is av ,, a .,Iu~ rl 1;. n can be of varied nature This ligand L is also ~ 'with regard to the definition of two preferred species C, and C2 (~ f ~ 1 to the invention.
The first species C, is ceDe in laqueDe one finds only a ~ tome of platinum of degree of v~Jaiivll real and formal 0, complexed with the siloxane residue and the ligamd L~, by the i ''~; double bonds ~.
The deu ~ th species C2 has two ~ ~ tomes of platinum, also of degree 10 of real and formal oxidation 0 and each complexed with a siloxane residue and the ligand L2: (2,), (~2)~
These two preferred species according to the invention are not exclusive of other structures CVIIIIJVI kul~ more than two platinum atoms, associated with residues '-1'~`~'';'l''5 and to binding subunits, of the type of those presented above.
The invention also relates to a new catalytic system r vd~ h~,.-.lo~ iV~L, - platinum-based and useful 1u~mm~nt in the ly,l. u ~ aliull between, on the one hand, pvl) ~ A having, per molecule, at least one reactive radical Si-H and free of silicon atoms bonded to more than two atoms of l ~ Ju ~, _l. ~ and, on the other hand, compounds B having at least one reactive glVU ~ and / or at least one reactive polar function, characterized in that it comprises platinum complexes of formula (I) as described above, without excluding the complexes for which L = L, with Z, and Z2 form a single oxygen atom, E' = E2 = O, yl = yl = H and R~ = R2 = R3 = R4 = CH3.
11 is the merit of the D ~ ul ~ to have isolated these organo-complexes platinum (I) for having implemented them, in a completely new and unexpected way, as a catalyst of ~ lJJ ~ v: ~ ilylldlivll I ''-vdbl ~. Indeed, one could, a priori, ~1.11 ~.. 1.. ~1 s ~ expect that the general family of lylllv catalysts ~ '~' of the type I ' ~ .- .~ '' ~ can c, constitute an interesting deposit for the selection 30 new catalysts or catalytic system -,, complexes (1) ~ 'val ~ L..I - ~ v~ "L ~ l ~ .l..oa., ~ ivdl, l ~ s - ~ ..1 `.... ~ and stable at storage in ~ and at ~ Lul~; ambient.
Such systems l, aLal ~ 5 are l) a 1 ~ C; ll .., ~ t '~ in the context of m situ crosslinking techniques, for example of silicones, in which are used 35 c. ~l oC ~ "ready to use" and, . both polymers intended for W0 95125734 P_~lr~

react between them and a catalytic system ~J~ d~ , so that it simplifies . --- '''' Ieur ., ' These ~ are known by the man of the srt under the .' ~ . ".
The systems ~ I ~ Lyu ~ 'vdl, lcs, according to the invention, make it possible to 5 my ~ sort the crosslinking conditions and therefore the final ~ properties targeted for cross-linked "~ UJ....~.CDs. It is thus possible to adapt these last at 1', . " target (eg non-stick, paper).
Count-ter~u of the various identities r~ lf ' cO ~ ,.. for the complexes (I) according to the invention, it must be considered that the catalytic system of which it is 10 question in the present presentation, can be constituted by a mixture of complexes C "
C, with lines of formulas (1) and/or (21) and/or (21).
According to a preferred arrangement of the invention, the Cl complexes are chosen from the following compounds, taken alone or as a mixture:
Same Me/' ~ ~g~ ~0 M~ Me (a) (b) ~MI ~NH~
Me (c) (d) 2 1 ~5823 (e) (f) N~
fri (g) ~¢N~CH2~HAcH3 CH3~O
(h) ~ ~ B~823 wo95125734 r~ l/r~v.

Me M~
Me~o Me~o Same (i)~j) (CH~CH
(k) cl~cl ~G ~e O Me Me O
(m) (n) As~. " t, the C complexes are ~1 . 1,.. ,'~ among the compounds following, taken alone or in combination -2 1 8~82~
~ W0 95125734 ~ /r~
~ I
O
Me Me N~
(O) N~2 ~ 2 o~ ~o~
Me Nk Me (P) All of these complexes (a) to (p) come within the scope of the invention as photo (thermo)activatable catalysts of lydluDilyl~i;ù
In addition, they ~ r, nctihlPnt excluding (a), new products objects delû the invention.
C. '` to a (, ala ~ of the invention, the system catalyst contains, in the free state, at least one stabilizing agent formed by at least one ligand Ls of formula L1 or L2 as defined above.
In the same catalytic system, the ligand Ls forming the stabilizing agent can êhre identical or different to the ligands (L "L2) of the complexes a): Cl, C2.
Among the preferred Ls radical ligands, mention may be made of those of formula (I) with yl = y2 = H and Zl, Z2 forming a carbon-carbon double bond or a bridge oxygen, the latter case fl ~ mt ~ .t preferred.
VS. . ~/. ., . - 'In the invention, it is advantageous to use the compound Ls in the catalytic system in an excess of 1 to 30, preferably 10 to 20 equivalents - molars compared to the platinum present.
This Ls compound can in fact be considered as an inhibitor of the catalyst. D
is also possible to employ in I or in .- t, ~ of Ls other inhibitors ~. 'catalysts I ~ I.uD; lyldtiu ... C ~ are also inhibitors , WO 9 ~ 125734 r ~, l / rlv ~

known as thermal blockers help increase the "pot life" of , (stabilities greater than 3-5 d) without affecting the kinetics ~'1 ~.1 ""' As examples of such compounds, certain siloxanes can be 5 pGl ~ u ~, s, pyridine, phosphines and organic phosphites, amides msaturated, alkylated maleates and a. alcohols, et ~ D,. i4u., ~ (See FR-Bl 528 464 and FR-A-2 372,874).
These alcohols ac ~. which form part of the reaction thermal blockers preferred llydl ~ laiiùll, have the formula:
R-(R)C(OH)-C=CH
formula in laqueFrom, . R is a linear or branched aDcyle radical, or a phenyl radical;
. R' is H or a linear or branched alkyl radical, or a phenyl radical;
the radicals R, R 'and the carbon atom located in a of the triple bond can ~ .. 1 form a cycle;
the total number of carbon atoms contained in R and R1 being at least 5, of preference from 9 to 20.
Said alcohols are preferably chosen from those having a point boiling point greater than 250 C. Examples include:
. I'ethynyl-l-;
. 3-methyl-3-dodecyne-1-ol;
. 3,7,11-trimethyl-1-dodecyne-3-ol;
. 1-diphenyl, 2-propyneol-1;
. 3-ethyl-6-ethyl-3-nonyne-1-ol;
. Ie methyl-3 ~ -1 ol-3.
These alcohols a-ac ~ t ~ '. are commercial products.
The synthesis of platinum (I) complexes, according to the invention, consists in making reacting a ligand L with products of average formula [Pt2j [ViMe, Si - O - Si Me2 Vi]3. These products are preferably formed by a catalyst solution of 30 KARST~T.
This reaction can be carried out in bulk or in a solvent, such as toluene, I'ethanol or i ~ uylu ~ Jall ~ l.
This syynthese is simple and involves products that are neither toxic, nor expensive. A priori, eDe satisfies all the criteria required to be considered as 35 '" feasible, especially since eDe is L~ by good ~1 ' .

WO 95/25734 2 1 8 ~ 8 2 3 P~ r~

.
isolated values which can be values as high as cdles greater than or equal to 50%.
According to a variant of the invention, the catalytic system can cu ~ c ~ d ~ o a precursor of compiexes (I), eg C~ or C2. One such precursor is, ~17'~
5 consisting of a c.. ~.., - starting products of the synthesis of the complexes (I), namely: KARSTEDT catalyst and excess iigand.
In this sense, the formation of platinic complexes takes place m situ, before and / or during the use of the crosslinkable ~ containing the precursor. This simplifies, ~ 'I' the ~ JIc ~ a ~ iOt ~.
Although the catalytic system according to the invention is ~.. 11--,.. 1 reactive and powerful to overcome the use of I ''', it is quite g ~ dL, I ~, for the sake of ~ -J ~ to implement such products.
Thus, '` to a variant of the invention, there is provided at least one I ''' possessing a triplet energy greater than or equal to 31 Kcai/mole and selected from products (poly) ~uul~la~ u~s (~
" . ) and l.~,~olu~,~iuu~, preferably from the following list of products:
toluene, pyridine, ferrocene, benzene, II~ A~ antnracene, ~ -~1 '"", this selection being made in such a way that the triplet state lifetimes of the complexes platinum and the j'''(s) are preferably of the same order.
A~ vt, these, ''' ~ are employed at the rate of 5 x 10 3 to 5, preferably er ~ about 1% by weight relative to the weight of compounds A and B put implemented.
For more details on these I ''" we refer to the request for European Patent No. 3s8 4s2.
The catalytic system l,l,,.l,, . .. he l. according to the invention is non-reducible, so that it does not tend to react with the reactive Si-H of the puly, vl( of type A.
According to another of these aspects, the present invention relates to a process dhrllu~ la~ iull between, on the one hand, p~l~u-~ A having, per molecule, at 30 moirts a reactive Si-H radical and free of silicon atoms bonded to more than two atoms of i. ~ uv_..4 and on the other hand, compounds B chosen preferably from pGl~v~v~ .-:I -- ~ and presenting, per molecule, at least um v uu~ reactive unsaturated aliphatic and/or at least one reactive function, process in which one puts employs at least one platinum complex as a catalyst.

woss/2s734 r~llr This process differs from its similar in that it consists of ~
make react compounds A and B in the presence of a catalytic system of the type decelui in accordance with the invention described above, and / or by implementing ' a synthesis of complexes (I) in which one makes interYenir, as 5 described above, a precursor formed by a ~. starting products (Ligand in excess + cata! yseur of KARSTEDT) and ayamt C ~ ~ t. -11` ~ 'recourse to at least the ~ of the aforementioned catalytic system, the initiation of the reaction being at less in part performed by PIIU~OC~1;VaL;UII.
AVY I:.r. ~-~ l 1, Ies compounds A are chosen from 10 PCll.rulL ~ -uc~ co---lu~ ' * reasons of the following formula:
HaWbSiO4 - a + b (1) ( ) 15 in which:
- the symbols W are similar or different and l~l~ one group h.~.Lu~,~ubùl~cn~ù~ t, exempt from the action of~avulal~l~
on the activity of the catalyst and chosen, preferably, from (cyclo)alkyl groups having from 1 to 18 carbon atoms inclusive and, ~ t, from methyl, ethyl, propyl, octyl and 3,3,3-II~UUIU~IUIJYI~ and as well as among the groups a~ the or araDcyles in C6-C~1 and, ~v~ among the xylyl and totyl and phenyl radicals, all these groups being ~v...1... ll .... l halogenated (fiuor eg) and/or hydroxylated andlor alkoxylated.
- a is 1 or 2, b is û, I or 2, the sum (a + b) has a value between I and 3, and ~" other medium formula patterns:
WcSiO4 - c (2) in which W has the same "r- as above and ca a value between Oet3.
The ~.L r ~ ~ A can be, I form of units of formula (I) or additionally comprise units of formula (2).
_ 2 1 ~8~3 WO g5~25734 r~

The o. ~, opoly '- A can have a linear structure, branched or not, cyclic or in network. The degree of pul ~ is greater than or equal to 2. More ~, '' t, it is less than 5000.
- Examples of patterns of formula (I) are:
H(CH,)SiO,n, ~ "" H(CoHs)Si2~2~
When it comes to linear polymers, these are . . .. ;~11 . ,1 consisting of motrfs "D" WzSiO~Q~ WHSiO2,2, and "M" W3SiO~n or W2HSiOl~1,WH2SiO~n; the motr~s "M" blocking terminals can be groups L.;~L~''y, ~''y.
By way of example of terminal "M" units, mention may be made of the groups 10 Ilu~ hJ'-' y, L.,~ ,'*I-~...,'-' y, ~... LI-.~!~.LIlu~ 'y, ~Iu~.LIlJ! ~, LllylLli;
silylsilo~y...
By way of example of "D" units, mention may be made of the groups ''.yl~lu.sy, yl~ 'y.
Said linear p ~ lyul ~ r ~ c A can be oils of viscosity dynamic at 25C of the order of 1 to 100,000 mPa s at 25C, b.''.hl. l.. ,1 of the order of 10 to 5000 mPa.sa 25C, or gums having a mass ~, ul ~ u ~ of the order of 1000,000.
When it comes to PUIJVIL' cyclics, these consist of patterns "D" W, SiO2, ~, and WHSiO22, which can be of the type ""yl~; lu~y OR
20 L..y~ y.
Said ~ GI ~, IT 'cyclic have a viscosity of the order of I to 5000 mPa.s.
The dynamic viscosity at 25 C all the silicone polymers considered in the present presentation can be measured using a ~; i.~, c.~u.. ~.t.~; BROOKFIELD, according to AFNOR NFT 76 102 standard of February 1972.
The viscosity referred to herein is the viscosity dynamic at 25 C called "~ ..; ", that is to say the dynamic viscosity which is measured, in a manner known per se, at a speed gradient of "
~ low so that the measured viscosity is "r I 'of the gradient of 30 speed.
Examples J~UI~Srll~UI.~oilW~ A are:
- - the !'- '' ~!yOI~ ' with extremities l~,J.~ ~, '',''~I~,s, - cul.ul.~ ;. '' yl! ~ .UL ~ u ~ Lh ~! y ~ ' with trimethyl- ends silyls, WO 95125734 1 ~ I / r ~ C 't - the CU ~ JUIY ~ di ~ u ~ l .; hr'pul ~ 'with hydrogeno- ends Jl.l~ .yl~
-les~,Jlu~e~lùlll;~ ul)~" at the endstl-..;~
- the !~IIu~;.lu.~ h~Gl~ 'cyclics With regard to compounds B, they are ~ 'among the p ~ l ~ ul -' cu.,,~,~ similar or different patterns of formula:
W'dXeYfSiO4 - (d + e + fl (3) in lacquerFrom:
The W' symbols respond to the same definition as that given above for 'lu W, ~ The symbols X are similar or different and .c~ .h~ an atom dl.~.llu~,_..or a reactive function, pr ~ sfcsrence é ~ u~ yr "9, linked to silicon by a divalent radical e g. in C,-C20 comprising .,. t, 1l, ~ at least one heteroatom, the radicals X plus IJalL; ~, uL8.~ .l.._llt preferred being: 3-~ v ~ "u ~ jl , 4-ethanediyl 15 (1.2~}.w.yl), ~ The symbols Y are similar or different and It ~ ., 6 ~ .h ~." a linear or branched alkenyl residue in C, -C, 2, and having at least one; ~ I taiu ~ iull ethylenic in extr8mite chain etlou in the chain and ~ at least one; ~ t ~ udtu ~ C;
~d, eetfsodegauxaO, 1.2OU3;
20 ~d+e+f=0,1,20u3;
Ie rate of SiO ~ 2 units being less than 30% by moles;
As for the remainders Y, they are ..~B chosen from the following list:
vinyl, propenyl, 3-butenyl, S-hcxenyl, 9-decenyl, 10-undecenyl, 5,9 -d~GJ;;..,/l~ 6-11-dOd6~,ad;;~/D,.
The u ~ `' B can present a linear structure (branched or no) cyclic or in network. Their degree of PUIJ..I;.;~a~;U.. is preferably understood between 2 and 5000.
When it comes to linear polymers, these are ` " made up of patterns "D" W2SiO2,2, XSiO2,D YSiO2,2, and "M" W3SiO,n, W2YSiO,n, W2XSiO,n, the 30 patterns "M" ter ~ ninals blockers can 8tre groups i "yl: lv,, ~, '- 'I ~la~ ilu~y~ ~liaD~
.

w0 95125734 CA 2 1 ~ 5 8 2.32 ~ ~ 5 ~ 2 3 P~llr~ s , By way of example of terminal "M" units, mention may be made of the groups L~U~ .. ;lUAy, ~IUI.. LI.~ f Y, fJ~ ~,llylYul~ y, ! ~i l.~AGII~ y, IUA f:I;IUA~Y~li~..~II~l~.~hJ;l;~ IUA~.~y. ., As examples of 'D' units, mention may be made of the groups d;...~,LI,~'y, 5 ,1,.,.1l,;"1l."l~ y, ~ L}IJI~ ~ y, ..,~h~:.,u~ y, ~ I.,A~ y, Il.~.llyldc~''y,~Lh~'y, methyl-3 }If.LuAy~Jlup~''y, methyl-

3--~}ly.,;~uAy~Jlu~ fy, methyl--2 (3, 4--él, uAy~,yl, lùll.,Ayl) ethylsiloAy, methyl--'ULUA~I'y,methyl-d-Ll~.~;LlluA~ilyl~l}lr~'y,methyl-~3-Ll~LlluAy:ily~h~'y.
Said pfjl ~ vL 'B iinéaires can be viscosite oils dynamic at 25C of the order of I at 100,000 mPa s at 25 C, g' of the order of 10 to 5000 mPa.s at 25C, or gums having a mass '~'; of the order of 1,000,000.
When it comes to pGI ~ UII, 'B cyclic, these are made up of patterns "D"W~SiO"" WSiO~,2, ~'YSiO2,~, which can be of the type '"~'' y, 15 &Ii~YIf1I~;IUAY~aliylv~''y, allAylYsiloxy, aikyiXsiloxy; examples of such orlt reasons already mentioned above.
Said pul, u-., ~ 'B cyclic have a viscosity of the order of I
at 5000 rnPa.s.
Having this great variety of pfjl ,u.~..f .~ - B, he is p~. r~.,rl,.....
20 ~ .dl, lc to implement a mixture of different products of formula (3), as defined above.
Compounds B to ~ Liull aliphatic utiies as part of the seion process the invention are, for example, those with; II ~ LulflLiu .. olefinic or a ,, ~ i.yk..u ~ uf well known in the technical field considered. In this regard, one can refer to the US patents ~ os 3,159,662, 3,220,272 and 3,410,886, which describe the above compounds.
According to a modality ~ of the invention the reaction mixture comprises compounds A and compounds B in such quantity as the molar ratio Si-H / g ~ uu ~ l., .lls unsaturated andlor reactive function eg epoxy, is between 0.4 and 10 preferably between I and 4 and, even more ~ r ~ rt, or of the order of 1.7.
the catalyst being present at a rate of 1 to 400, preferably 10 to 300 and, more ". ~ r ~ from 20 to 200 ppm of platinum metal, eAprimés by weight per with respect to compounds A and B present.

WO 95/2 ~ V734 2 1 ~ 5 ~ 2 ~. .

The technical literature of the field considered covers all the others ;"r."", ~;....~ useful, as to the conditions .~'" of }~ us;1.~ ;u~l by I '''-vai; ul ~ (mixture A / B and irradiation W at 25 C).
The crosslinking reactions of silicone oils, in particular lly-lluD; l ~ Liù.
5 (e. g: Si-H/Si-VI), catalyzed by 1~ platinum complexes, such as eyes in accordance with the invention, go through the formation of coDoidal particles, useful as platinum support, sdon a process of heterogeneous catalysis~
According to a modality c .. ~. ~ u., bl ~ of the invention, it is expected to ill ~ l. 'vs;oxygen""' ~, in the reaction medium before I ' vaLiull ~ which has 0 I~J~..UUD~; UIIS positive on the kinetics of crosslinking before or during the L;u~l.
As already indicated above, the pl ~ uLùa ~, Livd ~ iu ~ operates preferably in the ultra-violet domain.
The fact of coupling this ~ uLuau ~; v ~ iiu ~ l to a Lh ~ ù ~ iv ~ iiUI ~ can constitute another factor further improving the ~ r of the method according to the invention.
This Lll ~ ù ~ u ~ ivd ~ iu ~ is preferably carried out using a l ~ yu, ~,, l."
irlfrarouge and it comes after the ~, 'vd ~ i ~ n.
A final aspect of the invention, which is mentioned in a non-limiting way in the present presentation, concerns a -, crosslinkable and in particular 20 ~ D, uldDe, ~ in ow that eDe comprises compounds A and B, and a catalyst as defined above.
The amounts by weight of compounds A and B as well as of the catalyst are also given above.
As can be deduced from the above, the aforesaid c ~,. may 25 .,c,..,ut,d.~i also at least one . ': '' possessing an energy of triplet greater than or equal to 3l KcaUmule and product selection (poly) ~u..~ u~ . "metallic) and the k ~ t ~ "u ~ and, preferably, in the following product list: toluene, pyridine, ferrocene, benzene, 11.;.,.~.~ll..~~, anthracene; ~ . , this selection being made so that the lifetimes in the triplet state of the platinum complexes and of the 1 ''"(s) are, t, of the same order.
Those C . ~ confommes the irlvention are prepared i., .li ~ before (or even a long time before) or even '" before the implementation of the lydl process ~

~3 WO 95125734 - P ~ 5 /.

It should be noted that these ~ are ~ t stable in storage and that erles offer "- r ~ to the process of the invention, rapid crosslinking kinetics. In addition, their uncrosslinked state, before exposure to light layl of activation, offers great facilities of , ' di, . ' or setting 5 place on different supports or other shaping moulds.
t, the ~ - and / or the method according to the invention can incorporate dif ~ erent additives, chosen according to the -rr ~ - 'targeted final. he can be, for example, mineral or non-mineral fillers and/or pigments such as fibers ~yllLll.,t;y~l. s Or natural ground (polymers) of calcium carbonate, talc, 10 clay titanium dioxide or fumed silica. This can improve eg Ies ~ c .... ~ of the final materials.
Soluble color~mts, oxidation inhibitors and/or any other material "~..rt.~ not with platinum complex catalytic activity and not absorbing in the range of wavelengths chosen for the 1' -- VdtiUI~ can be 15 also added to the c.-....l...- ~ i., or implemented in the context of the method according to the invention Once prepared by mixing all the compounds referred to above, the ~.~.,..1..,~ 1...-- can be applied, for various purposes, to the surface of any substrate solid. These solid supports can be paper, cardboard, wood, plastic (eg 20 polyester, nylon, pcl~), woven or non-woven fibrous supports in cotton, polyester, nylon etc, or metal, glass or ceramic.
DDSTRIAL APPLICATION:
The . r ~ '', more ~ al L; uul; `~ lt, covered by the catalyst, the process and lesc. ~;.- - according to the invention are, t, those of crosslinkable silicone oils "in situ", useful for the ~ aLiull of the ~, ~. t~ lt~ anti-adherent on supports fibrous of any kind and especially on paper. In this ,,' the aforesaid. ~ make it possible to reach very high coating speeds, because of their very fast crosslinking kinetics.
The other ,, '~v;..~ are, for example, the materials ~ .l .. ~ JI ~ dental, adhesives, products; '' of jomtage, the adhesion primers.
The examples which follow, of the systems ~,aL~.;uu~s, of ----T " and of 35 implementations of the method according to the invention, ~. u..L a better A~~85~23 WO 9.5 / ~ 5734 ~ - P ~ .l / r resume. ll,.él.~;v.. of the latter and will provide an illustration of its many advantages and its variants.
EXAMPLES

EXAMPLE 1: PREPARATION OF ORGAN-I COMPLEXES ~ ~ TA1.T TQUES OF
PLATE(0) ENTERING THE SYSTEM C~ UI~
CATALYTIC VE ACCORDING TO IUI. ~.
10 The procedure used consists in reacting a ligand of type 7~ (anhydride rmaleic, E, maleimide, ....) on the KARSIEDT complex of formula ideal: Pt2 (V~e2Si-O-SiMel~l)3. This reaction can be carried out in bulk or in a solvent such as toluene, ethanol or i ~ v ~ .." ~, according to the sequences following:
New P~iSiMe2~5iN~2~)3 +2~Z > 2 ~ e2Si~SiNb2\
me~
EU
U~ hle U~
1.1. MODE OF OPERATION:
Slowly introduced into a toluene solution of the catalyst of ~ STEDT
(~ 10 % rnassique of Pt), the ligand in a Ligand / platinum molar ratio equal to 1 or 112 depending on the desired complex. After complete addition, the mixture is heated to 60° C. for 30 n~in. Allowed to cool, filtered through cellulose and the solvent evaporated. We obtain .. ... . _ . . .. . . .

wo 9s~25734 ~ 2 ~ A 2 1 8 ~ 8 23 a solid which is washed twice with petroleum ether (50 ml) The solid is dried recovered under pump vacuum at 25° C. for 4 h.
1.2. WEIGHTS:

TABLE I below summarizes the results obtained. All the complexes of prepared platinum were ~ by lR, NMR and IlliUI U ~ lllalJ i ......
EXLMPLE2: C ~ ETIQI3ES OF .YLATION OF ~ nTHE SILICONES A
PATTERNS Si-H/Si-Vi.
fig. 1 attached represents the kinetics dllJJl ~;, ilyldLi ~, l. silicone oils Si-H and Si-Vi motifs. The silicone oils used have the following structures:
- Si-H pattern oils: Me3SiO-(-SiMe2O)" 6(-SiMeHO),,-SiMe3 15 - Si-Vi patterned oils: ViSiMe2O-(-SiMe2O)9,-SiMe2Vi 2.1. OPERATING MODE:
The ~L~.i4u.,s systems to be tested are introduced into the Si-Vi pattern buile as well as a 20 excess ligand. Then this mixture is added to the oil with Si-H units. The platinum rate is 200 ~ pm relative to the total mass. The Si-H/Si-Vi molar ratio is of 1.7. 20 molar equivalents of ligand are used. Irradiation is carried out using of an HPK 125 lamp with power: 120 mJ/cm2.min. The thickness of the film studied is 24 μm. The kinetics of disappearance of the Si-H units is carried out by FT~ in 25 measuring the dc ~ l ~ fi ~ t of the vibration band v Si-H. The tests are carried out at 25 C. TABLE 2 below lists the main systems used.
2.2. FREEZING TIMES:
TABLE 3 below summarizes the freezing times for some of the systems 30 ~, aL ~ Li ~ lu ~ .il implemented, ~. ~ or not ligands. This ~' - was carried out in the dark by mixing the catalyst (200 ppm of Pt/total mass) with a mixture of silicone oils with Si-H and Si-Vi units described in example 2 (Si-H/Si-Vi molar ratio = 1.7). The ligand is introduced with an excess of 20 elected;~. ' molars relative to the platinum complex.

' ` '' J 2185823 W095125734 CA 21 8 5 8 2 3 P_l/rn7~,'C

EXE~LE 3: SYSTEM ~XTE:.
fig. 2 cijomte represents the kinetics ~ dlus; lylai; ol ~ of a mixture of silicone oils with Si-EI/Si-Vi units described in Example 2, catalyzed by the complex 5 next:
M~
Pt~+(O)~) M~
(200 ppm of Pt / total mass) in the presence of 20 molar equivai'ents of ~ dlidi, May'eic. The ~ operating conditions are identical to ceres described in example 2.
EXAMPLE 4: CO~RATIVE Essays fig. 3 attached represents the ~ ", of the kinetics observed for the hyllu~;lylaiiull of the sii`es huii`es icons with Si-H/Si-Vi patterns (identical to those of example 2) with the two systems ~, a ~ dlyl;
Me ~PI~ + (o) +
~ Me 2û a) (200 ppm I mssse tot ~ le) (20 ~ ' molar I Pt) . , 2 i &~?
w095~5734 ~A2 18~823 ~3 r~llr)-- -KARSTEDT (200 ppm / ma~s~ total) + ~3 O
(2~ equals~ moldres / Pt) 5 The operating conditions are identical to those described in Example 2. These tests show that the system studied has no induction period and is more efficient than the catalyst of KARSTEDT + B, ~ I -EXAMPLE 5: ADDITlo;~ FROM: BLOQIIEUR10 5. 1 CLINICS:
fig. 4 represents the various kinetics observed using the system catalyst of the following formula:
Me Me has) (200 ppm of Pt/total mass) and various ligands and blockers.
The three systems ~ J, K, L are tested:

21 8~23 WO 95/2573

4~llrh.~
~h~ 5823 24 ~ ;
I
Hb J) N~
a) (10 molar equivalents / Pt) (200 ppm / total mass) (10% é~il~ivaient molai~es / Pt) Me We// ~ ~ H
~If/~Pt~ ()+ ~
M~~O
K) Me a) (20% e~uivaient molaues / Pt) (200 ppm / total mass 3+(o)+ ~
L) Don't has) (200 ppm / total mass) (20% e ~ iu were moldy / Pt) The operating conditions are identical to those described in Example 2.

5.2 TE~iPS OF GEL: -20 In absence Jil~llJi~lu.. W, we observe the time of gels given in the TABLE IV below, at 25 C.

21~.5~3 wo ss/2s7s4 C ~ 2 i 8 5 8 2 3 ` 25 !! ~ ~ r~,l/r~5 The C4 ~ dSVI ~ of the gel times of one of the systems ~ J ~; qU ~ i of the invention and of a known KARSTEDT catalyst makes it possible to show the thermal stability of systems ~ lyt; yu ~, ~ according to the invention. The silicone oils used are identical to ceDes described in Example 2 (Molar ratio Si-H / Si-Vi = 1.7). These measures are 5 performed away from light.
EXAMPLE 6: CATALYTIC SYSTEMS WITH THERMAL BLOCKERS:
COMPARISON BETWEEN D~l'~MF~FS:DE
PREPARATION

6.1 CATALYTIC SYSTEMS:
(0): obtained by simultaneous mixing of the KARSTEDT catalyst of 10 equivalents molars / Pt of ethynyl ~.I~ ~.ol = thermal blocker and 10 equivalents molars / Pt of ~ _ . (=ligand L).
15 (P): obtained by mixing the KARSTEDT catalyst of 1 molar equivalent / Pt of b ~ (= L) for 2h at 25 C, 20 molar equivalents / Pt of ethynyl ~. ''- being then added.
(0~): We mix the catalyst below:

i~e ~s~ 13 ire has) and 20 molar equivalents / Pt of ethynyl ~ lol. ~ .ol.
6.2 OPERATING MODE:
The catalytic mixture is introduced into an oil with Si—Vi units (idem for example NO 2 ) then into a silicone oil with Si—H units. The Si-H / Si-~'i molar ratio =
1.7. A film with a thickness of 24 μm is produced. The platinum is 30,200ppm.

2 1 ~5~23 WO 95/25734 C 1 ~ 2 1 ~ 5 8 2 3; r~llr 6.3 nFrF~r ~ noN OF FREEZING TIME AT 250C:
Systems ~lal~tiuu~D ~el time (O) 3.5 hours (P) ~ 24 hrs (Q). )6d 6.4. C~ErlQUES:
5 Figure 5 attached shows the kinetics of ~ lJd ~ U jlYI ~; UII observed for O, P and Q.
EXAMPLE 7: COMPARISON OF THE NATURE OF BENZOQUINONE LIGANDEE
TO PLATINUM
10 7.1 COMFLEXESEIUDES:
Mel".. 5d-- ~Me~
R)Me Me ~1) If~=~
15 7.2 OPERATING MODE:
1 molar equivalent of the R and S complexes is mixed with 20 molar equivalents /
Pt of ethynyl ~, ''' in an oil with Si-Vi motifs (idem example N. 2) then one add the oil with Si-H units (idem example N. 2). The Si-H I Si-Vi molar ratio is of 1.7. The film thickness is 24 μm.

7.3. C~EIICS:
Figure 6 attached shows the kinetics of ~ .J d. uD;l~ld~iu, observed for R and S.
EXAMPLE 8: ~ 1J~DD~Y~ T--~ OF SILICONE OILS A
MOT3FS Si-H / Si-Vi, S;_ALKYLENYL OR S;-EPOXY
The SiH and SiVI silicone oils are the same as those of example 2 The Si-alkenyl patterned silicone oil is as follows:

~ W095/25734 ~ 3 r~l,Y~
27: , ! . . ~
Me3SiO--(SiMe20~l~0 (SiMeO)8.6 SiMe3 (EC~2)4 The Si-Epoxy patterned silicone oil is as follows:
Me3Si --(SiMe20~40 (SiMeO)4 SiMe3 ~o ~.1 OPERATING MODE:
200 ppd Me H
M
. si~ (0) + 20 molar equivalents of U
Si-H / Si-Vi (or Si-Al~cenyl or Si Epoxy) molar ratio = 1.7 The conditions are the same as in example 2.
1~A test is carried out for each ~. silicone:
-Si-H/Si-V (T) -Si-H/Si-alkenyl (U) - Si - H / Si - epoxy (V) ~.2. C~NET~QUES:
20 fgure 7 shows the kinetics of ~, ~ Lu ~ 'obtained.

2l 85~i23 ~21 85823 28 TABLE I:
98% 155C(DC) 231(4.38) o par. (has) ~86% 165C (DC) 290 (4.0) o~u- (c) oh ~N~ ~ ~4.~ 76.5% 150C (DC) 279 (4.9) o~ L (b) [[~N~ 230 (4.6d ~Y~-1¢~ 96% 147 ~C) 260 (3.8) I~UY~ ~ (d~
nl~ '~
79% 146C (DC) 249 (4.3) -~(k) 44% 146 (DC) 225 (3.5) 73% 150C(DC) 270(4.3) O

WO 95/25734 ~ L i ~ j 5 ~ 3 P ~ l / r ~
2185~23 29 TABLE I CONTINUED:
~ (o) 138 C(DC) 265(4.2);
Om~
5.~~3 87% 384(2.6;
O~o 318 (2.8) '-32% 137~C (DC) 249 (4.2) 62% 147C~C) 228(35) I(~(m) 53% 142C (I)C) 230 (3.6) O 284 (3.2) 380 (0.6) CI~CI ~ a~a 52% 166 C (DC) 224 (sh) (3.1) ,.~. oo 30a(~h) 3,~) 2 1 &5~23 wo 95/25~4 ~ 2 1 8~5 8 2:3 TABLE II:
~a .
~0 O~' (C) C~N~
o ~ (b) D¦~N~ (e) E
oh F~$~
G
(P) wogsns734 ~ A 2 1 8 5 8 23 ~ i P, 5 3~ ~ r~l~r~
,, TABLE~UI~:
~r ~l~
~ M~,~o 3.5n~n 2.5h o M~ ~ (a) E~ M~ ~ O 3.5 mins 40 mins M~~ (C) ~N~ ~ ~ 4~5 ~ 2 hrs O _ (b~ 2 hours 9 min I hr ~ r lO min 2,sh or ".
10 min I hr o".o 21~35~,23.
wo gs/25734 CQ 2 1 8 5 8 2 3 32 ' r~llr~
TABLE: TO IV:
KARSTEDT
M (200 ppm Pt I mass ~ ~I HJTI -3 5 h total) ~ ~
oh ( 10 molar equivalents / Pt) (10 equivalents molai-~s I Pt) N ~~ <~ b ~5days (200 ppm I mass (lo equivalents total) (10 molar equivalents I Pt) molar equivalents I Pt)

Claims (21)

CLAIMS: 1 - Platinum complexes of Formula:
(I) with L = L1 when n = 1 with L = L2 when n = 2, .DELTA. R1, R2, R3, R4 are different or similar to each other and represent a alkyl and/or acyl group, preferably an alkyl having from 1 to 18 atoms carbon, methyl, ethyl, propyl, pentyl, hexyl, allyl, acetyl, propionyl being particularly preferred and especially methyl, .DELTA. L1 being a ligand of the following formula:
(1) in which:
? Z1, Z2 are identical or different and:
? or are selected from the following list of radicals:
-OH, -O-alkyl, -o-alkenyl, -NR5R6 with identical or different R5, R6 and chosen from the following groups: hydrogen, alkyl, alkenyl, the alkyl and alkenyl residues considered above being linear or branched and containing from 1 to 6 carbon atoms, ? or form a single divalent radical of the type:
*-O-, * -NR7- with R7 = H, alkyl, alkenyl, phenyl, said groups being themselves optionally substituted by alkyl, alkenyl, aryloxy, arylalkyl residues, structures aromatics of these last two remains that can be carriers chains with an amide group, such as -NH-CO-CH3, * alkenylene preferably corresponding to: -R8C=CR9, with R8, R9 identical or different and corresponding to hydrogen or a halogenated alkyl or alkoxyl radical.
? either are two atoms bonded to each other and belonging to a cycle of aromatic preference.
? E1, E2 are the same or different and represent: O, NR10 with R10 =
C1-C6 alkyl or alkenyl, CR11R12 with identical or different R11, R12 and corresponding to a C1-C6 alkyl, an alkoxyl, a halogen..., the oxygen being more particularly preferred.
? Y1, Y are identical or different and represent an alkyl radical, aryl preferably phenyl, alkyloxy, oryloxy, hydrogen or halogen, .DELTA. L2 being a ligand consisting of one of the following two residues (21), (22):
(21) in which Y3 to Y6 on the one hand and E3, E4 on the other hand, are identical or different and meet the same definition as given above for Y1, Y and E1, E
respectively, Y3 and Y4 and/or Y5 and Y6 which can also form together a group cyclic, preferably an aromatic group comprising one or more aromatic rings with 6 to 8 members, in ortho or pericondensed, and optionally substituted by monovalent radicals corresponding to the definition given above for Y3 to Y6;

(22) in which * E5 to E8 and Y7 to Y10 are as defined above, * Z3, Z5 are identical or different and correspond to:
CR13 with R13 = H or C1, C6, N lower alkyl;
* Z4 is a residue comprising from 2 to 5 phenylene radicals linked together by:
? a valentine link ? or by at least one of the following radicals:
O, COO, linear or branched alkylene CO, CONR14 with R14 = H or linear or branched C1 - C6 alkyl .DELTA. excluding complexes for which L = L1 with Z1 and Z2 form a single oxygen atom, E1 = E2 = O, Y1 = Y2 = H and R1 = R2 = R3 = R4= CH3. 2 - Use as a photo(thermo)activatable catalyst, based on platinum and useful in particular in the hydrosilylation between, on the one hand, polyorganosiloxanes A
having, per molecule, at least one reactive radical Si-H and free of silicon atoms bonded to more than two hydrogen atoms and, on the other hand, compounds B having at least at least one reactive group and/or at least one reactive function, platinum complexes of formula (I) according to claim 1 in which L = L1 with Z1 and Z2 form a single oxygen atom, E1 = E2 = O, Y1 = Y2 = H and R1 = R2 = R3 = R4 = CH3.
ie of the following formula (a):
(has) 36a 3 - Photo(thermo)activatable catalytic system, based on platinum, useful in particular in the hydrosilylation between, on the one hand, polyorganosiloxanes A having, per molecule, at least one reactive radical Si-H and free of silicon atoms bonded to more than two hydrogen atoms and, on the other hand, compounds B having at least at least one reactive group and/or at least one reactive function, characterized in that it comprises platinum complexes of formula (I) according to claim 1, preferably chosen from the following C1 compounds, taken together alone in mixture:

(b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) 4 - catalytic system according to claim 2 or claim 3, characterized in that it comprises complexes of formula (I2), chosen from following compounds C, taken alone or as a mixture:
(o) (p) 5 - catalytic system according to any one of claims 2 to 4, characterized in that it comprises a mixture of C1 and/or C2 complexes. 6 - catalytic system according to any one of claims 2 to 5, characterized in that it contains, in the free state, at least one stabilizing agent formed by at least one Ls ligand of formula L1 or L2 as defined in claim 1. 7 - catalytic system according to claim 6, characterized in that the agent stabilizer is present in an excess of 1 to 30, preferably 10 to 20, equivalents molars compared to Pt. 8 - Catalytic system according to any one of claims 2 to 7, characterized in that it comprises at least one thermal blocker present, preferably, chosen from acetylenic alcohols of formula:
R-(R')C(OH)-CCH
formula in which, . R is a linear or branched alkyl radical, or a phenyl radical;

. R' is H or a linear or branched alkyl radical, or a phenyl radical;
the radicals R, R1 and the carbon atom located at .alpha. of the triple bond that can optionally forming a cycle;
the total number of carbon atoms contained in R and R1 being at least 5, preferably from 9 to 20.
Said alcohols being more preferably selected from those having a boiling point above 250° C., such as:
. ethynyl-1-cyclohexanol 1:
. 3-methyl-1-dodecyne-3-ol;
. trimethyl-3,7,11-dodecyne-1-ol-3:
. 1,1-diphenyl-2-propyneol-1;
. 3-ethyl-6-ethyl-1-nonyne-3-ol;
. methyl-3-pentadecyne-1-ol-3. 9 - Process for synthesizing the complexes according to claim 1 characterized in that it consists in reacting at least one ligand L as defined in claim 1 with medium formula products:
[Pt°]2 [ViMe2Si-O-Si-Me2-Vi]3. 10 - Hydrosilylation process between. on the one hand, polyoganosilixanes A
having, per molecule, at least one reactive radical Si-H and free of silicon atoms bonded to more than two hydrogen atoms, and on the other hand. compounds B exhibiting, for molecule, at least one reactive unsaturated aliphatic group and/or at least one reactive polar function, in which at least one complex of the platinum as a catalyst, characterized in that it relies at least in part on photoactivation and in that that it essentially consists in reacting the compounds A and B in the presence of the catalytic system according to any one of claims 1 to 8 and/or by placing implements the synthetic process according to claim 9. 11 - Process according to claim 10, characterized in that the compounds A
are chosen from polyorganohydrogensiloxanes comprising:
*reasons of the following formula:
(?) in which:
- the W symbols are the same or different and represent groups monovalent hydrocarbons free of adverse action on the activity of the catalyst and preferably chosen from (cyclo)alkyl groups having from 1 to 18 carbon atoms inclusive and, advantageously, from methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl groups as well as from C6-C12 aryl or aralkyl groups and, advantageously, from xylyl and totyl and phenyl radicals, all these groups possibly being halogenated (eg fluorine) and/or hydroxylated and/or alkoxylated.
- a is 1 or 2, b is 0, 1 or 2, the sum (a + b) has a value between 1 and 3, * and, optionally, other medium-formula patterns:
(2) where W has the same meaning as above and c has a value between 0 and 3. 12 - Process according to claim 10, characterized in that the compounds B, are selected from polyorganosiloxanes comprising similar units or different formula:
(3) in which:
.DELTA. The W' symbols are the same or different and represent monovalent hydrocarbon groups, devoid of action unfavorable on the activity of the catalyst and chosen, preferably, from (cyclo)alkyl groups having from 1 to 18 carbon atoms carbon included and, advantageously, from methyl groups, ethyl, propyl, octyl and 3,3,3-trifluoropropyl as well as among the C6-C12 alkyl or aralkyl groups and, advantageously, from xylyl and totyl and phenyl radicals, all these groups possibly being halogenated (eg fluorine) and/or hydroxylated and/or alkoxylated, .DELTA. The X symbols are the same or different and represent a hydrogen atom or a reactive function, preferably, epoxyfunctional, linked to silicon by a divalent radical eg C1-C20 optionally comprising at least one heteroatom, the more particularly preferred X radicals being:
3-glycidoxypropyl, 4-ethanediyl, (1,2-epoxycylohexyl)...
.DELTA. The Y symbols are the same or different and represent a linear or branched C1-C12 alkenyl residue, alkenyl residue having at least one ethylenic unsaturation at the end of string and/or in the string and optionally at least one heteroatom;
.DELTA. d, e and f are 0, 1, 2 or 3;
.DELTA. d+e+f=0, 1,2 or 3;
the proportion of SiO4/2 units being less than 30 mol%. 13 - Process according to claim 12, characterized in that the residues Y are selected from the following list: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10-undecenyl, 5,9-decadienyl, 6-11-dodecadienyl. 14 - Process according to claim 12 or 13, characterized in that the compounds B consist of a mixture of the products of formula (3). 15 - Process according to any one of claims 10 to 14, characterized in that the reaction mixture comprises compounds A, and compounds B in quantity such that the SiH/unsaturated group and/or reactive function molar ratio is between 0.4 and 10, preferably between 1 and 4 and, even more preferably, is of the order of 2.5 0.5, the catalyst being present in a proportion of 1 to 400, of preferably from 10 to 300 and, more preferably, from 20 to 200 ppm of platinum metal, expressed by weight relative to the compounds A and B present. 16 - Process according to any one of claims 10 to 15, characterized in what oxygen is introduced into the reaction medium before photoactivation. 17 - Process according to any one of claims 10 to 16, characterized in that photoactivation takes place in the ultraviolet range. 18 - Process according to any one of claims 10 to 17 characterized in that the photoactivation is coupled with a thermoactivation, advantageously with using infrared radiation and preferably occurring after said photoactivation. 19 - Crosslinkable composition characterized in that it comprises:
- compounds A according to claim 10 or 11, - compounds B according to any one of claims 10 and 12 to 14, - And a catalytic system according to any one of claims 2 to 8. 20 - Crosslinkable composition characterized in that it comprises:
- compounds A according to claim 10 or 11, - compounds B according to any one of claims 10 and 12 to 14, - and a catalytic system precursor composition according to one any of claims 2 to 8. 21- Composition according to claim 20, characterized in that it comprises compounds A and B in quantity such as the SiH/unsaturated group molar ratio and/or reactive function is between 0.4 and 10, preferably between 1 and 4 and, more more preferably still, i.e. of the order of 2.5 to 0.5, the catalyst being present at ratio of 1 to 400, preferably 10 to 300 and more preferably 20 to 200 ppm of platinum metal, expressed by weight relative to the compounds A and B present.