• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a crosslinkable composition X comprising: at least one organopolysiloxane compound A comprising, per molecule, at least two C 2 -C 6 alkenyl radicals bonded to silicon atoms, at least one organohydrogenpolysiloxane compound B comprising, molecule, at least two hydrogen atoms bonded to an identical or different silicon atom, - at least one catalyst C which is a complex corresponding to the following formula: [M (L1) 2] in which: - the symbol M represents a metal with a degree of oxidation It is chosen from a group consisting of iron, cobalt and nickel; the symbols L1, which may be identical or different, represent a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound, optionally at least one adhesion promoter D and optionally at least one charge E The subject of the invention is also the use of the catalyst C previously described as a crosslinking catalyst for silicone compositions, as well as a process for crosslinking silicone compositions, characterized in that it consists in heating the composition X to a temperature ranging from 70 to 200 ° C, and the cross-linked silicone material Y thus obtained.
    公开号:FR3028258A1
    申请号:FR1460803
    申请日:2014-11-07
    公开日:2016-05-13
    发明作者:Vincent Monteil；Jean Raynaud；Delphine Crozet；Magali Bousquie；Sebastien Marrot
    申请人:Bluestar Silicones France SAS；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to the field of the crosslinking of silicone compositions in which are brought into contact reagents having at least two unsaturated bonds and organosilicon compounds having at least two hydrogenosilyl units (SiH ) in the presence of a catalyst C which is a complex corresponding to the following formula: p1 (L1) 2] in which: the symbol M represents a metal with an oxidation degree Il chosen from the group consisting of iron, cobalt and nickel, the symbols 12, which may be identical or different, represent a ligand which is a [3-dicarbonylato anion or the enolate anion of a [3-dicarbonyl] compound.
    [0002] BACKGROUND ART In the field of the crosslinking of silicone compositions, hydrosilylation, also called polyaddition, is a predominant reaction. In a hydrosilylation reaction, a compound comprising at least one unsaturation reacts with a compound comprising at least one hydrogen atom bonded to a silicon atom. This reaction may for example be described by the reaction equation (1) in the case of alkene unsaturation: ## STR1 ## Or by the reaction equation (2) in the case of alkyne unsaturation: II-Si-H + -CC- -Si-C = CH (2) IIII The hydrosilylation of unsaturated compounds is performed by catalysis, using organometallic catalyst. Currently, the appropriate organometallic catalyst for this reaction is a platinum catalyst. Thus, most of the industrial hydrosilylation reactions are catalyzed by the Karstedt platinum complex of the general formula Pt2 (divinyltetramethyldisiloxane) 3 (or abbreviated as Pt2 (DVTMS) 3): 1 F 1 Si / S (7 0 0 0 In the early 2000s, the preparation of platinum-carbene complexes of the general formula: n / Si Pt 0 - / provided access to more stable catalysts (see, for example, the application However, the use of organometallic platinum catalysts is still problematic, it is a toxic metal, expensive, in the process of becoming rare and whose cost fluctuates enormously. [..] It is therefore difficult to reduce the amount of catalyst required for the reaction as much as possible, without reducing the yield and the speed of the reaction. the reaction It has been found that during the catalyzed reaction platinum metal can precipitate, which results in the formation of insoluble colloids in the reaction medium. The catalyst is then less active. In addition, these colloids form a cloud in the reaction medium, and the products obtained are unsatisfactory aesthetically because they are colored. Finally, the platinum-based complexes catalyze the hydrosilylation reactions at room temperature with rapid kinetics, of the order of a few minutes. In order to have time to prepare, transport and implement the composition prior to curing, it is often necessary to temporarily inhibit the hydrosilylation reaction. For example, when it is desired to coat a paper or polymer substrate with a silicone release coating, the silicone composition is formulated to form a bath which must remain liquid at room temperature for several hours before being deposited on the substrate. It is only after this deposition that it is desired that the hardening by hydrosilylation occurs. The introduction of hydrosilylation inhibiting additives effectively prevents the reaction as long as necessary before activation. However, it is sometimes necessary to use large amounts of inhibiting agent, which causes a strong inhibition of the hydrosilylation catalyst. This has the consequence that the rate of hardening of the composition, even after activation, is slowed down, which is a major disadvantage from an industrial point of view since this notably obliges to reduce the coating speed and therefore the rate of production. . It would therefore be advantageous to propose alternative organometallic catalysts to platinum-based catalysts and to provide new curable and / or curable compositions by means of catalysts no longer having the problems described above, in particular not requiring the use of inhibitory agent. This objective is achieved by means of a catalyst which is a complex of iron, cobalt or nickel (II) having a specific structure. These catalysts, in particular, do not need to be handled in a protective atmosphere (for example under argon). The crosslinking reactions in which they are implemented can also be operated in air, without a protective atmosphere. The subject of the present invention is therefore, according to a first aspect, a crosslinkable composition X comprising: at least one organopolysiloxane compound A comprising, by molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms; an organohydrogenpolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom, - at least one catalyst C which is a complex corresponding to the following formula: [M (L 1) 2] in which: the symbol M represents a metal with an oxidation state It chosen from among a group consisting of iron, cobalt and nickel; the symbols L1, which may be identical or different, represent a ligand which is a [3-dicarbonylato anion or the enolate anion of an 8-dicarbonyl compound, optionally at least one adhesion promoter D and optionally at least one filler; E.
    [0003] The subject of the invention is also, according to a second aspect, the use of the catalyst C previously described as a crosslinking catalyst for silicone compositions. The subject of the invention is, according to a third aspect, a process for crosslinking silicone compositions, characterized in that it consists in heating the composition X described above at a temperature ranging from 70 to 200 ° C., preferably from 80 to 200 ° C. at 150 ° C., and more preferably from 80 to 130 ° C., as well as the crosslinked silicone material Y thus obtained.
    [0004] According to a particularly advantageous modality, the organopolysiloxane A comprising, per molecule, at least two alkenyl radicals at 02-06 bonded to silicon atoms, comprises: (i) at least two identical or different siloxyl units (A.1) of the following formula: VV, Z, SiO 44a + b) 2 (A.1) wherein: - a = 1 or 2, h = 0.1 or 2 and a + b = 1.2 or 3; the symbols W, which may be identical or different, represent a linear or branched alkenyl group at 02-06; and the symbols Z, which are identical or different, represent a monovalent hydrocarbon group having from 1 to 30 carbon atoms, and preferably chosen from the group consisting of alkyl groups having from 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferentially chosen from the group consisting of a methyl, ethyl, propyl radical, 3.3, 3-trifluoropropyl, xylyl, tolyl and phenyl, (ii) and optionally at least one siloxyl unit of the following formula: ZiaSiO4_, (A.2) 2 in which: - a = 0, 1, 2 or 3, - the symbols Z1 , identical or different, represent a monovalent hydrocarbon group having 1 to 30 carbon atoms and preferably selected from the group consisting of alkyl groups having 1 to 8 carbon atoms inclusive and the aryl groups containing between 6 and 12 carbon atoms, and even more preferably chosen from the group consisting of a methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl radical. Advantageously, the radicals Z and Z1 are chosen from the group consisting of a methyl and phenyl radical, and W is chosen from the following list: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10-undecenyl, , 9-decadienyl and 6-11-dodecadienyl, and preferably W is a vinyl.
    [0005] These organopolysiloxanes may have a linear, branched or cyclic structure. Their degree of polymerization is preferably between 2 and 5000. In the case of linear polymers, these consist essentially of "D" siloxyl units selected from the group consisting of siloxy units W 2 SiO 2, WZSiO2 / 2 and Z12SiO2 / 2, and siloxyl "M" units selected from the group consisting of siloxy units W3Si01 / 2, WZ2Si01 / 2, W2ZSi0112 and Z13Si01 / 2. The symbols W, Z and Z1 are as described above.
    [0006] As examples of terminal "M" units, mention may be made of trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups. As examples of "D" units, mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups. Said organopolysiloxanes A may be oils with a dynamic viscosity of the order of 10 to 100,000 mPa.s at 25 ° C., generally of the order of 10 to 70,000 mPa.s at 25 ° C., or gums having a molecular weight. of the order of 1,000,000 mPa.s or more at 20 ° C. All the viscosities referred to herein correspond to a dynamic viscosity value at 25 ° C. called "Newtonian", that is to say the dynamic viscosity which is measured, in a manner known per se, with a viscometer Brookfield has a shear rate gradient sufficiently low that the measured viscosity is independent of the velocity gradient. In the case of cyclic organopolysiloxanes, these consist of "D" siloxyl units of the following formulas: W 2 SiO 2/2, Z 2 SiO 2 or W 2 SiO 2/2, which may be of the dialkylsiloxy, alkylarylsiloxy or alkylvinylsiloxy or alkylsiloxy type. Examples of such siloxyl units have already been mentioned above. These cyclic organopolysiloxanes A have a viscosity of the order of 10 to 5000 mPa.s at 25 ° C. According to a preferred embodiment, the composition according to the invention comprises a second organopolysiloxane compound comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms, different from the organopolysiloxane A compound, said second organopolysiloxane compound. preferably being divinyltetramethylsiloxane (dvtms).
    [0007] Preferably, the organopolysiloxane compound A has a mass content of Si-vinyl unit of between 0.001 and 30%, preferably between 0.01 and 10%.
    [0008] According to a preferred embodiment, the organohydrogenpolysiloxane compound B is an organopolysiloxane having at least two hydrogen atoms, per molecule, bonded to an identical or different silicon atom and, preferably, having at least three hydrogen atoms per molecule. directly related to an identical or different silicon atom.
    [0009] Advantageously, the organohydrogenpolysiloxane compound B is an organopolysiloxane comprising: (i) at least two siloxyl units and, preferably, at least three siloxyl units of the following formula: HdZe3S iO4 (d + e) (B.1) 2 in which: d = 1 or 2, e = 0, 1 or 2 and d + e = 1, 2 or 3, the symbols Z3, which may be identical or different, represent a monovalent hydrocarbon group having 1 to 30 carbon atoms and preferably chosen from group consisting of alkyl groups having 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferably selected from the group consisting of a methyl, ethyl, propyl, 3,3,3 trifluoropropyl, xylyl, tolyl and phenyl, and (ii) optionally at least one siloxyl unit of the following formula: Zc2Si ° 4-c (B.2) 2 in which: - c = 0, 1, 2 or 3, - symbols Z2, which may be identical or different, represent a monovalent hydrocarbon group having from 1 to 30 carbon atoms and preferably selected from the group consisting of alkyl groups having 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferably selected from the group consisting of a methyl radical, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
    [0010] The organohydrogenpolysiloxane compound B may be formed solely of siloxyl units of formula (B.1) or may also comprise units of formula (B.2). It may have a linear, branched, or cyclic structure. The degree of polymerization is preferably greater than or equal to 2. More generally, it is less than 5000. Examples of siloxyl units of formula (B.1) are in particular the following units: H (CH 3) 2 SiO 1/2, HCH 3 SiO 2, and H (C6H5) SI02 / 2 - In the case of linear polymers, these consist essentially of: "D" siloxyl units chosen from the following formulas: Z22SiO212 or Z3HSiO2 / 2, and siloxyl units "M" Chosen from among the following formula units Z23Si01 / 2 OR Z32HSi01 / 2. These linear organopolysiloxanes can be oils with a dynamic viscosity of from 1 to 100,000 mPa.s at 25 ° C., generally of the order of 10 to 5000 mPa.s at 25 ° C., or gums having a molecular weight of the order of 1,000,000 mPa.s or more at 25 ° C. In the case of cyclic organopolysiloxanes, these consist of "D" siloxyl units of the following formulas: Z22SiO2 / 2 and Z3HSiO2 / 2, which may be of the dialkylsiloxy or alkylarylsiloxy type or of Z3HSiO212 units only. They then have a viscosity of the order of 1 to 5000 mPa.s. Examples of linear organohydrogenpolysiloxane compound B are: dimethylpolysiloxanes with hydrogenodimethylsilyl ends, trimethylsilyl-terminated dimethylhydrogenomethylpolysiloxanes, dimethylhydrogenomethylpolysiloxanes with hydrogenodimethylsilyl ends, trimethylsilyl-terminated hydrogenomethylpolysiloxanes, and cyclic hydrogenomethylpolysiloxanes. Particularly preferred as the organohydrogenpolysiloxane compound B are the oligomers and polymers of the general formula (B.3): ## STR1 ## wherein R 1 is SiO-R 1 R 1 -SiO SiO SiO R 1 SiO-R 1 3) in which: x and y are an integer ranging from 0 to 200, the symbols R 1, which are identical or different, represent, independently of one another: a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals being, preferably, methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl, - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms an aryl radical containing between 6 and 12 carbon atoms, or an aralkyl radical having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms. Particularly suitable for use in the invention as organohydrogenpolysiloxane compound B are the following compounds: ## STR1 ## ## STR2 ## where: ## STR2 ## with a, b, c , d and e defined below: in the polymer of formula Si: - 0 to 150, preferably 0 to 100, and more particularly 0 to 20, and - 1 b 90, preferably 10 to 80 and more particularly 30 b 70, in the polymer of formula S2: in the polymer of formula S3: 5 d 200, preferably 20 d 100, and 2 e 90, preferably 10 e 70. CH 3 O 3 Si 3 CH 3 O 1 Me 3 Si OSiMe 3 In particular, the organohydrogenpolysiloxane compound B suitable for the invention is the compound of formula Si, where a = 0.
    [0011] Preferably, the organohydrogenpolysiloxane compound B has an SiH mass content of between 0.2 and 91%, preferably between 0.2 and 50%. In the context of the invention, the proportions of the organopolysiloxane A and of the organohydrogenpolysiloxane B are such that the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane B on the bound alkenyl radicals to the silicon (Si-CH = CH 2) in the organopolysiloxane A is between 0.2 and 20, preferably between 0.5 and 15, more preferably between 0.5 and 10 and even more preferably between 0.5 and 5; .
    [0012] The composition according to the invention uses at least one catalyst C which is a complex corresponding to the following formula: [jvi (L1) 2] in which: the symbol M represents a metal with oxidation state II chosen from The group consisting of iron, cobalt and nickel, the symbols 12, which may be identical or different, represent a ligand which is a [3-dicarbonylato anion or the enolate anion of a 6-dicarbonyl compound. It should be noted that at least part of the inventive character of the invention is due to the judicious and advantageous selection of the catalyst structure C. In particular, the metal M of catalyst C is preferably chosen from the group consisting of cobalt at the oxidation state II and the nickel at the oxidation degree II.
    [0013] According to another preferred embodiment of the invention, ligand L'is an anion derived from a compound of formula (1): R1000HR200R3 (1) in which: R1 and R3, identical or different, represent a hydrocarbon radical in linear, cyclic or branched C1-C30, an aryl containing between 6 and 12 carbon atoms, or a radical -ORLI with R4 which represents a linear, cyclic or branched C1-C30 hydrocarbon radical, R2 is an atom of hydrogen or a hydrocarbon radical, preferably alkyl, comprising from 1 to 4 carbon atoms; with - R1 and R2 can be connected to form a 05-06 cycle, and - R2 and R4 can be connected to form a 05-06 cycle.
    [0014] Advantageously, the compound of formula (1) is chosen from the group consisting of [3-diketones: 2,4-pentanedione (acac); the 2,4-hexanedione; 2,4-heptanedione; heptanedione3,5; ethyl-3-pentanedione-2,4; methy1-5-hexanedione-2,4; 2,4-octanedione; octanedione3,5; dimethyl-5.5 hexanedione-2,4; methyl-heptanedione-2,4; dimethyl-2,2,2-nonanedione-3,5; dimethyl-2,6-heptanedione-3,5; 2-acetylcyclohexanone (Cyacac); 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD); 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (F-acac)]; benzoyl acetone; dibenzoyl-methane; 3-méthy1-2,4-pentanedione; 3-acetyl-pentane-2-one; 3- acetyl-2-hexanone; 3-acéty1-2-heptanone; 3-acéty1-5-méthy1-2-hexanone; stearoylbenzoylmethane; octanoylbenzoylmethane; 4 Does buty1-4'-methoxy-dibenzoylmethane; 4,4'-dimethoxy-dibenzoylmethane and 4,4'-di-tert-butyl-dibenzoylmethane, and preferably from [3-diketones 2,4-pentanedione (acac) and 2,2,6,6-tetramethyl); 3,5-heptanedione (TMHD). According to another preferred embodiment of the invention, the ligand F3-dicarbonylato L1 is a [3-ketoesterat anion chosen from the group consisting of anions derived from the following compounds: methyl, ethyl, n-propyl, isopropyl, n-Butyl, sec-butyl, isobutyl, tert-butyl, isopentyl, n-hexyl, nicotyl, 1-methylheptyl, n-nonyl, n-decyl and n-dodecyl acetylacetic acid or those described in the FR patent application -A-1435882.
    [0015] According to a particularly preferred embodiment, the catalyst C is chosen from the [Ni (acac) 2], [Ni (TMHD) 2], [Co (acac) 2] and [Co (TMHD) 2] complexes. It is understood that in the above formulas "acac" means the anion derived from the compound 2,4-pentanedione and "THMD" signifies the anion derived from the compound 2,2,6,6-tetramethyl-3,5,5- heptanedione. The catalyst C can in particular be present in the composition according to the invention in a content ranging from 0.001 to 10 mol% of metal M per number of moles of alkenyl radicals at 02-06 bonded to silicon atoms of the organopolysiloxane compound A, from preferably from 0.01 to 7%, and more preferably from 0.1 to 5%. The composition according to the invention is preferably free of platinum, palladium, ruthenium or rhodium catalyst. By "free" of catalyst other than catalyst C is meant that composition X according to the invention comprises less than 0.1% by weight of catalyst other than catalyst C, preferably less than 0.01% by weight, and more preferably less than 0.001% by weight, relative to the total weight of the composition.
    [0016] The composition X may advantageously comprise at least one adhesion promoter D. Without being limiting, it can be considered that the adhesion promoter D comprises: - (D.1) at least one alkoxylated organosilane containing, per molecule at least one C 2 -C 6 alkenyl group, or - (D.2) at least one organosilicon compound comprising at least one epoxy radical, or - (D.3) at least one M metal chelate and / or a metal alkoxide of general formula: M (OJ) n, with n = valence of M and J = linear or branched C1-C8 alkyl, M being chosen from the group formed by: Ti, Zr, Ge, Li, Mn, Fe, Al and Mg or mixtures thereof According to a preferred embodiment of the invention, the alkoxylated organosilane (D.1) of the adhesion promoter D is selected from the products of the following general formula: R1R2C / (4 c R i R3 I x Si (OR5) 3-x (D.1) in which formula: R1, R2 and R3 are identical or different hydrogenated or hydrocarbon radicals; and they represent a hydrogen atom, a linear or branched C1-C4 alkyl or a phenyl optionally substituted by at least one C1-C3 alkyl, - U is a linear or branched C1-C4 alkylene, - W is a valence bond, - R4 and R5 are the same or different radicals and represent a linear or branched C1-C4 alkyl, - x '= 0 or 1, and - x = 0 to 2. Without this being limiting, it can be considered that vinyltrimethoxysilane is a particularly suitable compound (D.1). With regard to the organosilicon compound (D.2), it is intended according to the invention to choose it: a) or from the products (D.2a) corresponding to the following general formula: ## STR2 ## in which: R 6 is a linear or branched C1-C4 alkyl radical, R7 is a linear or branched alkyl radical, y is 0, 1, 2 or 3, and X being defined by the following formula: x = - 0 .-- - .------. CR 8 CR9R "with: E and D which are identical or different radicals chosen from linear or branched C1-4 alkyls, z which is equal to 0 or 1, R9, R9, R19 which are identical or different radicals representing a hydrogen atom or a linear or branched C1-C4 alkyl, and R8 and R9 or R19 may alternatively constitute together with the two epoxy-bearing carbons an alkyl ring having from 5 to 7 members, or b) or among the products (D.2b) consisting of epoxyfunctional polydiorganosiloxanes comprising: (i) at least one siloxyl unit of formula: XPGci SiO 2 (D.2 bi) in which: - X is the radical as defined above; above for the formula (D.2 a) 4- (p + q) G is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from among alkyl groups having from 1 to 8 carbon atoms inclusive , optionally substituted by at least one halogen atom, and as aryl groups containing between 6 and 12 carbon atoms, p = 1 or 2, q = 0, 1 or 2, p + q = 1, 2 or 3. and (ii) optionally at least one siloxyl unit of formula: 4 - r Gr SiO (D.2 bii) formula wherein G has the same meaning as above and r is 0, 1,2 or 3.
    [0017] With regard to the last compound (D.3) of the adhesion promoter D, the preferred products are those whose metal M of the chelate and / or the alkoxide (D.3) is chosen from the following list: Ti , Zr, Ge, Li or Mn. It should be emphasized that titanium is more particularly preferred. It may be associated, for example, an alkoxy radical of butoxy type. The adhesion promoter D may be formed of: (D.1) alone (D.2) alone (D.1) + (D.2) Or according to two preferred methods of: (D.1) + (D. 3) (D.2) + (D.3) and finally according to the most preferred modality: (D.1) + (D.2) + (D.3). According to the invention, an advantageous combination for forming the adhesion promoter is as follows: vinyltrimethoxysilane (VTMO), 3-glycidoxypropyltrimethoxysilane (GLYMO) and butyl titanate. From a quantitative point of view, it may be stated that the weight proportions between (D.1), (D.2) and (D.3), expressed in percentages by weight relative to the total of the three, are the following: (D.1) 10, preferably between 15 and 70 and still more preferably between 25 to 65, - (D.2) 90, preferably between 70 and 15 and even more preferably between 65 to 25, and - ( D.3) 1, preferably between 5 and 25 and even more preferably between 8 to 18, it being understood that the sum of these proportions in (D.1), (D.2) and (D.3) is equal to 100%. For better adhesion properties, the weight ratio (D.2): (D.1) is preferably between 2: 1 and 0.5: 1, the ratio 1: 1 being more particularly preferred. Advantageously, the adhesion promoter D is present in a proportion of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and more preferably 1 to 3% by weight, relative to total weight of all the constituents of composition X.
    [0018] According to a particular embodiment, the composition X according to the invention also comprises at least one charge E. The charges E that may be present in the compositions according to the invention are preferably mineral. They can be especially siliceous. As for siliceous materials, they can act as reinforcing or semi-reinforcing filler. The reinforcing siliceous fillers are chosen from colloidal silicas, silica powders for combustion and precipitation, or mixtures thereof. These powders have an average particle size generally less than 0.1 μm (micrometers) and a BET specific surface area greater than 30 m 2 / g, preferably between 30 and 350 m 2 / g. Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used. In the case of non-siliceous mineral materials, they can be used as semi-reinforcing mineral filler or stuffing. Examples of these non-siliceous fillers that can be used alone or in a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, unexpanded vermiculite, and optionally treated calcium carbonate. on the surface with fatty acids, zinc oxide, mica, talc, iron oxide, barium sulphate and slaked lime. These fillers have a particle size generally of between 0.001 and 300 μm (micrometers) and a BET surface area of less than 100 m 2 / g. In a practical but nonlimiting manner, the fillers used may be a mixture of quartz and silica. Charges can be processed by any suitable product. In terms of weight, it is preferred to use a filler quantity of between 1% and 50% by weight, preferably between 1% and 40% by weight relative to all the constituents of the composition. The composition according to the invention may further comprise one or more usual functional additives. As families of usual functional additives, mention may be made of: silicone resins, adhesion modulators, additives for increasing the consistency, pigments, and additives for heat resistance, resistance to oils or fire resistance, by for example, metal oxides. Silicone resins are well known and commercially available branched organopolysiloxane oligomers or polymers. They have, in their structure, at least two different units chosen from those of formula R 3 SiO 11 2 (unit M), R2 SiO 2 (unit D), RSiO 3 12 (unit T) and SiO 4 12 (unit Q), at least one of these units being a T or Q unit. The radicals R are identical or different and are chosen from linear or branched C1-C6 alkyl, hydroxyl, phenyl and 3,3,3-trifluoropropyl radicals. Mention may be made, for example, as alkyl radicals, methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals. Examples of oligomers or branched organopolysiloxane polymers that may be mentioned are MQ resins, MDQ resins, ID resins and MDT resins, the hydroxyl functions that may be borne by the M, D and / or T units. Resins which are particularly suitable include hydroxylated MDQ resins having a hydroxyl content by weight of between 0.2 and 10% by weight, the compositions X according to the invention can in particular be obtained by firstly introducing Instead, the organopolysiloxane compound B is introduced and the temperature of the mixture is increased to reach the crosslinking temperature. crosslinking until the stirring stops due to an increase in the viscosity of the mixture The present invention also relates to a process for crosslinking silicone compositions, characterized in that it consists in heating the composition X as defined above at a temperature ranging from 70 to 200 ° C., preferably from 80 to 150 ° C., and more preferably from 80 to 150 ° C. at 130 ° C.
    [0019] The composition according to the invention has the advantage of not being sensitive to air and can thus be used and in particular crosslink in a non-inert atmosphere, and in particular in air. The present invention is illustrated in more detail in the nonlimiting exemplary embodiments. EXAMPLE 1: Nickel-based catalysts for the crosslinking of divinyltetramethylsiloxane (dvtms) with MD'5011 / 1 I) Components 1) Organopolysiloxane A: divinyltetramethylsiloxane (dvtms) (1.073 mol of silicon-bonded vinyl radicals per 100g of oil) 2 ) Organohydrogenpolysiloxane B of formula: MD'50M (1.58 mol of silicon-bonded hydrogen atoms per 100 g of oil), with: M: (CH 3) 3 SiO 2, and D ': (CH 3) HSiO 2 2 ) Catalysts (A), (B), (C) and (D): (A) = [Ni (TMHD) 2] when R = t-Butyl (B) = [Ni (acac) 2] when R = methyl (C) = [Ni (COD) 2] oo (Cl-12) 15C1-13 H3c (H2c), z (D) = Ni (II) Stearate II) Formulations and Results: For each formulation tested, the catalyst is weighed and introduced into a Schlenk at room temperature and under an inert atmosphere when the complex is sensitive to air (especially Ni (0)), or in a glass flask when the complexes are stable in air. Then 1.87 g of divinyltetramethylsiloxane (dvtms) and then 1.27 g of MD'50M oil were introduced. The flask (or Schlenk) is stirred in an oil bath which will be heated to the desired reaction temperature. The ratio R corresponding to the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl (here vinyl) radicals bonded to silicon (Si-CH = CH 2) in the organopolysiloxane (dvtms) being 1: 1. The beginning of crosslinking is measured. The beginning of crosslinking is defined as the cessation of stirring due to an increase in the viscosity of the medium.
    [0020] Table 1: Catalyst Temperature% mol of Atmosphere Start of reaction 1, catalyst crosslinking "Formulation 1 (comparative) [Ni (COD) 2] 110 ° C 0.25% Inert (under 3h20 argon) Formulation 2 (Invention) [Ni (TMHD) 2] 110 ° C 0.25% Non-inert 1h Formulation 3 (Comparative) Ni (II) Stearate 110 ° C 0.25% Non-Inert 45h Formulation 4 (Invention) [Ni (acac) 2] 110 ° C 0.25% Non-inert 2h (1) Expressed in mol% nickel by number of moles of silicon-bonded vinyl radicals (SiCH = CH 2) in dvtms Comparative formulation 1 comprising a complex of Ni (0) cross-links after 3h20 but it must be maintained under an inert atmosphere because, under a non-inert atmosphere, the complex degrades very rapidly, even before the start of the reaction, during the temperature rise, and formulations 2 and 4 according to the invention, in which the catalyst is a Ni (II) complex having two 8-dicarbonyl ligands crosslinking in 1 to 2 hours.
    [0021] The comparative formulation 3, using a Ni (II) complex having stearate ligands, does not crosslink until after 45h.
    [0022] The nickel catalysts according to the invention were furthermore tested under the following different operating conditions: Table 2: Catalyst Temperature Atmospheric% mole Start of reaction, catalyst crosslinking (1) Formulation 5 (invention) [Ni (TMHD) 2 ] 90 ° C 0.25% Not inert Less than 15h Formulation 6 (invention) [Ni (acac) 2] 90 ° C 0.25% Non-inert Less than 15h Formulation 7 (Invention) [Ni (TMHD) 2] 110 ° C 0.125% Not inert Less than 15h Formulation 8 (invention) [Ni (acac) 2] 110 ° C 0.125% Not inert Less than 15h (1) Expressed in mol% nickel by number of moles of silicon-bonded vinyl radicals (SiCH = CH 2) in dvtms The formulations 5 and 6 according to the invention show that a crosslinking is obtained at 90 ° C., even if this crosslinking is slower than that observed for the formulations 2 and 4 operated at 110 ° C. Formulations 7 and 8 according to the invention show that a crosslinking is obtained from 0.25 mol% of catalyst, even if this crosslinking is slower than that observed for formulations 2 and 4 comprising 0.5 mol% of catalyst.
    [0023] EXAMPLE 2: Cobalt catalysts for crosslinking dvtms with MD'50M I) Components 1) Organopolysiloxane A: divinyltetramethylsiloxane (dvtms) (1.073 mol of silicon-bonded vinyl radicals per 100 g of oil) 2) Organohydrogenpolysiloxane B: de formula: MD'50M (1.58 mol of silicon-bonded hydrogen atoms per 100g of oil), with: M: (CH 3) 3 SiO 2, and D ': (CH 3) HSiO 2 O 3) Catalysts (E ), (F), (G) and (H) (E) = [Co (TMHD) 2] when R = t-Butyl (F) = [Co (acac) 2] when R = Methyl (G) = [ Co (TMHD) 3] when R = t-Butyl (H) = [Co (acac) 3] when R = Methyl II) Formulations and Results: For each formulation tested, the catalyst is weighed and introduced at room temperature into a flask. of glass. Then 1.87 g of divinyltetramethylsiloxane (dvtms) and then 1.27 g of MD'50M oil were introduced. The flask is stirred in an oil bath which will be heated to the desired reaction temperature. The ratio R corresponding to the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl (here vinyl) radicals bonded to silicon (Si-CH = CH 2) in the organopolysiloxane (dvtms) being 1: 1. The beginning of crosslinking is measured. Table 3: Catalyst Temperature% mole of Atmosphere Start of reaction 1, crosslinking catalyst "Formulation 9 (comparative) [Co (acac) 3] 110 ° C 0.25% Not inert No crosslinking Formulation 10 (Comparative) [Co (TMHD) 3] 110 ° C 0.25% Not inert No crosslinking Formulation 11 (invention) [Co (acac) 2] 110 ° C 0.25% Non-inert 15min Formulation 12 (invention ) [Co (TMHD) 2] 110 ° C 0.25% Non-inert 15min (1) Expressed in mol% cobalt by number of moles of silicon-bonded vinyl radicals (SiCH = CH2) in dvtms The results show that the formulations 9 and 10 comparative where the catalyst is a complex of Co (III) does not crosslink while formulations 11 and 12 according to the invention where the catalyst is a complex of Co (II) having two p-dicarbonyl ligands crosslink in 15min .
    [0024] The cobalt catalysts according to the invention were furthermore tested under the following different operating conditions: Table 4: Catalyst Atmospheric% mole Temperature Start of catalyst reaction (1) crosslinking Formulation 13 (invention) [Co (acac) 2] 90 ° C 0.25% Not inert Less than 25min Formulation 14 (Invention) [Co (TMHD) 2] 110 ° C 0.125% Non-inert 25min Formulation 15 (Invention) [Co (acac) 2] 130 ° C 0.125% No inert Instant crosslinking (1) Expressed in mol% cobalt by number of moles of silicon-bonded vinyl radicals (Si-CH = CH 2) in dvtms Formulation 13 according to the invention shows that a crosslinking is obtained at 90 ° C., even if this crosslinking is slower than that observed for the formulation 11 operated at 110 ° C. Formulations 14 and 15 according to the invention show that a crosslinking is obtained from 0.125 mol% of catalyst. It should also be noted that the increase in temperature makes it possible to significantly reduce the crosslinking time (formulations 14 and 15). EXAMPLE 3: Nickel-Based Catalysts for Crosslinking Mvi D70 Mvi with MD'5011 / 1 I) Constituents 1) Organopolysiloxane A of formula MviD70Mvi (0.038 mol of silicon-bonded vinyl radicals per 100 g of oil), with: Vi = Vinyl; Mvi: (CH3) 2ViSiO1 / 2 and D: (CH3) 2SiO2 / 2 2) Organohydrogenpolysiloxane B of formula: MD'50M (1.58 mol of silicon-bonded hydrogen atoms per 100g of oil), with: M: (CH3) 3Si01,2; and D ': (CH3) HSiO212 3) Catalysts (A), (B), (C) and (D) as defined in Example 1. II) Formulations and Results: For each formulation tested, the catalyst is weighed and introduced into a Schlenk at room temperature and under an inert atmosphere when the complex is sensitive to air (case of Ni (0)), or in a glass flask when the complexes are stable in air. MviD70Mvi oil was then introduced, followed by MD'50M oil. For a ratio R corresponding to the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl (here vinyl) radicals bonded to silicon (Si-CH = CH 2) in the organopolysiloxane (MviD70Mvi) of 1: 1, 4.39 g of MviD70Mvi oil and then 0.105 g of MD'50M oil are introduced. The contents of MviD70Mvi oil and MD'50M oil are adjusted according to the desired R ratio.
    [0025] The flask (or Schlenk) is stirred in an oil bath which will be heated to the desired reaction temperature. For the formulations 16 to 23, the ratio R corresponding to the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl (here vinyl) radicals bonded to silicon (Si- CH = CH2) in the organopolysiloxane (Mvi D70 Mvi) being 1: 1. The beginning of crosslinking is measured.
    [0026] Table 5: Catalyst Temperature% mol of catalyst (1 Start of reaction, Atmosphere crosslinking Formulation 16 (comparative) [Ni (COD) 2] 110 ° C 4% Inert (under 2h50 argon) Formulation 17 (invention) [Ni ( TMHD) 2] 110 ° C 4% Non-inert 1h50 Formulation 18 Ni (II) 110 ° C 4% Non-inert No (comparative) stearate crosslinking at 48h Formulation 19 (invention) [Ni (acac) 2] 110 ° C 4 % Not inert 2h20 (1) Expressed in mol% nickel by number of moles of silicon-bonded vinyl radicals (SiCH-CH2) in organopolysiloxane (MviD701V1vi) Formulation 16 comprising a Ni (0) complex cross-links after However, as already indicated in Example 1, the complex degrades very rapidly under a non-inert atmosphere, even before the start of the reaction.
    [0027] Formulations 17 and 19 according to the invention in which the catalyst is a Ni (II) complex having two 8-dicarbonyl ligands crosslink after 1 h 50 at 2 h 20. The comparative formulation, employing a Ni (II) complex having stearate ligands, still does not crosslink after 48h. The nickel catalysts according to the invention were furthermore tested under the following different operating conditions: Table 6: Effect of the temperature increase Catalyst Temperature Atm.% Mole Atmosphere Start of reaction (1, catalyst cross-linking "Formulation 20 (invention ) [Ni (TMHD) 2] 90 ° C 2% Non-inert 17h Formulation 21 (Invention) [Ni (TMHD) 2] 110 ° C 2% Non-inert 2h20 Formulation 22 (Invention) [Ni (TMHD) 2] 130 ° C 2% Non-inert 10min (1) Expressed in mol% nickel by number of moles of silicon-bonded vinyl radicals (Si-CHCH 2) in the organopolysiloxane (MvID 7oMvi) Formulations 20 to 22 according to the invention show that the Increasing the temperature significantly reduces the crosslinking time Table 7: Effect of increasing catalyst concentration Catalyst Temperature Atmospheric% mole Start of reaction (1, catalyst crosslinking "Formulation 23 (Invention) [Ni ( TMHD) 2] 110 ° C 1% Non-inert 26h F ormulation 21 (invention) [Ni (TMHD) 2] 110 ° C 2% Non-inert 2h20 Formulation 17 (invention) [Ni (TMHD) 2] 110 ° C 4% Non-inert 1h50 (1) Expressed as mol% of nickel per number of moles of silicon-bonded vinyl radicals (Si-CH-CH 2) in the organopolysiloxane (MviD70Mvi) The formulations 17, 21 and 23 according to the invention show that the increase in the catalyst concentration makes it possible to significantly reduce the time Table 8: Effect of R ratio (Yomol Si-H /% mol Si-CH = CH 2) Catalyst Temperature% mol of catalyst Ratio R Start of crosslinking crosslinking reaction Formulation 19 (invention) [Ni (acac) 2] 110 ° C 4% 1: 1 2h20 Formulation 19A (Invention) [Ni (acac) 2] 110 ° C 4% 2: 1 1h50 (1) Expressed in ° A> molar cobalt by number of moles of vinyl radicals related to silicon (SiCH = CH2) in the organopolysiloxane (MviD7oMv) The crosslinking is carried out under a non-inert atmosphere. Formulations 19 and 19A show that increasing the R ratio (`Yomol Si-H /% mol Si-CH = CH2) makes it possible to reduce the crosslinking time.
    [0028] EXAMPLE 4: Cobalt catalysts for the crosslinking of Mvi D70 Mvi with MD'50M I) Components 1) Organopolysiloxane A of formula MviD70Mvi (0.038 mol of silicon-bonded vinyl radicals per 100 g of oil), with: Vi = Vinyl ; Mvi: (CH3) 2ViSiO1 / 2 and D: (CH3) 25iO2 / 2 2) Organohydrogenpolysiloxane B of formula: MD'50M (1.58 mol of silicon-bonded hydrogen atoms per 100g of oil), with: M: (CH3) 35i0112; and D ': (CH3) H5i0212 3) Catalysts (E) and (F) as described in Example 2.
    [0029] II) Formulations and Results: For each test formulation, the catalyst is weighed and introduced at room temperature into a glass vial. MviD70Mvi oil was then introduced, followed by MD'50M oil. For a ratio R corresponding to the molar ratio of the silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl (here vinyl) radicals bonded to silicon (Si-CH = CH 2) in the organopolysiloxane (MviD70Mvi) of 1: 1, 4.39 g of MviD70Mvi oil and then 0.105 g of MD'50M oil are introduced. The contents of MviD70Mvi oil and MD'50M oil are adjusted according to the desired R ratio.
    [0030] The flask is stirred in an oil bath which will be heated to the desired reaction temperature. The beginning of crosslinking is measured.
    [0031] The cobalt catalysts according to the invention were tested under the following different operating conditions: Table 8: Effect of the Increase in the Catalyst Concentration Catalyst Temperature Atm.% Mole Start of reaction, catalyst crosslinking (1) Formulation 24 ( invention) [Co (TMHD) 2] 110 ° C 2% Non-inert 2h15 Formulation 25 (invention) [Co (TMHD) 2] 110 ° C 4% Non-inert Less than 1h15 (1) Expressed in `/ molar of cobalt by number of moles of silicon-bonded vinyl radicals (Si-CH = CH 2) in the organopolysiloxane (MviD70Mvi) The ratio R corresponding to the molar ratio of silicon-bonded hydrogen atoms (Si-H) in the organohydrogenpolysiloxane (MD'50M) on the alkenyl radicals (here vinyl) bound to silicon (Si-CH = CH2) in the organopolysiloxane (MviD70Mvi) is 2: 1 for the formulations 24 and 25. The formulations 24 and 25 according to the The invention shows that the increase in the catalyst concentration makes it possible to decrease significantly t the time of crosslinking.
    [0032] Table 9: Effect of ratio R (`Yomol Si-H /% mol Si-CH = CH2) Catalyst Temperature% mol of catalyst Ratio R Start of reaction crosslinking crosslinking Formulation 26 (invention) [Co (acac) 2] 110 ° C 2% 2: 1 Less than 17h Formulation 27 (invention) [Co (acac) 2] 110 ° C 2% 4: 1 1h20 (2) Expressed in mol% cobalt by number of moles of silicon-bonded vinyl radicals ( SiCH = CH2) in the organopolysiloxane (MviD70Mvi) The crosslinking is carried out under a non-inert atmosphere. Formulations 26 and 27 show that increasing the R ratio (`Yomol Si-H /% mol Si-CH = CH2) makes it possible to significantly reduce the crosslinking time.
    [0033] The tests shown in Table 9 show the impact of the addition of a few molar equivalents of dvtms in the reaction medium. In these tests, the dvtms was introduced after the catalyst, and before the MviD70Mvi and MD'50M oils.
    [0034] Table 9: Effect of addition of dvtms Catalyst Temperature Ratio Ratio% mol dvtms (2) Start of catalyst reaction (1) crosslinking Formulation [Co (acac) 2] 110 ° C 2% 2: 1 _ Less than 26 (invention) 17h Formulation [Co (acac) 2] 110 ° C 2% 2: 1 10 eq / Co 45min 28 (invention) Formulation [Co (acac) 2] 110 ° C 2% 4: 1 1:20 27 (invention) Formulation [Co (acac) 2] 110 ° C 2% 4: 1 10 eq / Co 30min 29 (invention) (1) Expressed in mol% cobalt by number of moles of silicon-bonded vinyl radicals (SiCH = CH 2) in organopolysiloxane (MvID7oMvi) (2) Expressed in molar equivalents relative to cobalt The crosslinking is carried out under a non-inert atmosphere. The results in Table 9 show that the addition of dvtms makes it possible to significantly reduce the crosslinking time.
    权利要求:
    Claims (16)
    [0001]
    CLAIMS1 - Crosslinkable composition X comprising: - at least one organopolysiloxane compound A comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms, - at least one organohydrogenpolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom, - at least one catalyst C which is a complex corresponding to the following formula: pi (L1) 2] in which: the symbol M represents a metal at the degree of oxidation II selected from the group consisting of iron, cobalt and nickel; the symbols 12, which are identical or different, represent a ligand which is a [3-dicarbonylato anion or the enolate anion of a 6-dicarbonyl compound, optionally at least one adhesion promoter D and optionally at least one filler; E.
    [0002]
    2 - Composition X according to claim 1, characterized in that the metal M of catalyst C is selected from the group consisting of cobalt oxidation state II and nickel oxidation state II.
    [0003]
    3 - Composition X according to claim 1, characterized in that the catalyst C is present in a content ranging from 0.001 to 10 mol% of metal M by number of moles of C2-C6 alkenyl radicals bonded to silicon atoms of the compound organopolysiloxane A, preferably from 0.01 to 7%, and more preferably from 0.1 to 5%.
    [0004]
    4 - Composition X according to any one of the preceding claims, characterized in that it is free of platinum catalyst, palladium, ruthenium or rhodium.
    [0005]
    5 - Composition X according to claim 1, characterized in that the ligand L1 is an anion derived from a compound of formula (1): R1COCHR2COR3 (1) in which: - R1 and R3, identical or different, represent a hydrocarbon radical linear, cyclic or branched C1-C30, an aryl containing between 6 and 12 carbon atoms, or a radical -ORLI with R4 which represents a linear, cyclic or branched C1-C30 hydrocarbon radical, R2 is an atom of hydrogen or a hydrocarbon radical, preferably alkyl, comprising from 1 to 4 carbon atoms; with - R1 and R2 can be connected to form a 05-06 cycle, and - R2 and R4 can be connected to form a 05-06 cycle. 5
    [0006]
    6 - Composition X according to the preceding claim, wherein the compound of formula (1) is selected from the group consisting of [3-diketones: 2,4-pentanedione (acac); the 2,4-hexanedione; 2,4-heptanedione; heptanedione-3,5; ethyl-3-pentanedione-2,4; methyl hexanedione-2,4; 2,4-octanedione; octanedione-3,5; dimethyl-5.5 hexanedione-2,4; Methyl-heptanedione-2,4; dimethyl-2, 2 nonanedione-3,5; dimethyl-2,6-heptanedione-3,5; 2-acetylcyclohexanone (Cyacac); 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD); 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (F-acac)]; benzoyl acetone; dibenzoyl-methane; méthy1-2,4-pentanedione; 3-acetyl-pentane-2-one; 3-acéty1-2-hexanone; 3-acéty1-2-heptanone; 3-acéty1-5-méthy1-2-hexanone; stearoylbenzoylmethane; octanoylbenzoylmethane; 4-t-butyl-4'-methoxy-dibenzoylmethane; 4,4'-dimethoxy-dibenzoylmethane and 4,4'-di-tert-butyl-dibenzoylmethane, and preferably from [3-diketones 2,4-pentanedione (acac) and 2,2,6,6-tetramethyl); 3,5-heptanedione (TMHD).
    [0007]
    7 - Composition X according to any preceding claim, wherein the catalyst C is selected from the complexes [Ni (acac) 2], [Ni (TMHD) 2], [Co (acac) 2] and [Co (TMHD) 2].
    [0008]
    8 - Composition X according to the preceding claim, characterized in that the organopolysiloxane A comprises: (i) at least two siloxyl units (A.1), identical or different, of the following formula: VV Z, SiO (A.1 ) - wherein: - a = 1 or 2, h = 0, 1 or 2 and a + b = 1, 2 or 3; the symbols W, identical or different, represent a linear or branched C2-C6 alkenyl group, and the symbols Z, which are identical or different, represent a monovalent hydrocarbon group having from 1 to 30 carbon atoms, and preferably chosen from the group consisting of alkyl groups having from 1 to 8 carbon atoms and aryl groups containing from 6 to 12 carbon atoms, and still more preferably selected from the group consisting of methyl, ethyl, propyl, 3,3, 3-trifluoropropyl, xylyl, tolyl and phenyl, (ii) and optionally at least one siloxyl unit of the following formula: ZiaSiO4_, (A.2) 2 in which: - a = 0, 1, 2 or 3, - the symbols Z1 , identical or different, represent a monovalent hydrocarbon group having 1 to 30 carbon atoms and preferably selected from the group consisting of alkyl groups having 1 to 8 carbon atoms inclusive and aryl groups containing ent 6 and 12 carbon atoms, and even more preferably selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
    [0009]
    9 - Composition X according to any one of the preceding claims, wherein the organohydrogenpolysiloxane compound B comprises at least three hydrogen atoms per molecule directly bonded to an identical or different silicon atom.
    [0010]
    Composition X according to any one of the preceding claims, wherein the organohydrogenpolysiloxane compound B is an organopolysiloxane comprising: (i) at least two siloxyl units and, preferably, at least three siloxyl units of the following formula: HdZe3S iO4_ (d + e) (B.1) 2 in which: d = 1 or 2, e = 0, 1 or 2 and d + e = 1, 2 or 3, the symbols Z3, which may be identical or different, represent a monovalent hydrocarbon group having from 1 to 30 carbon atoms and preferably selected from the group consisting of alkyl groups having 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferably selected from the group consisting of a methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl radical, and (ii) optionally at least one siloxyl unit of the following formula: zc2sio4_c (B.2) 2 in which: - c = 0 , 1, 2 or 3, the symbols Z2, identical or different nts, represent a monovalent hydrocarbon group having 1 to 30 carbon atoms and preferably selected from the group consisting of alkyl groups having 1 to 8 carbon atoms and aryl groups containing 6 to 12 carbon atoms, and further more preferably selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
    [0011]
    11 - Composition X according to any one of the preceding claims, characterized in that it comprises a second organopolysiloxane compound comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms, different from the organopolysiloxane compound A said second organopolysiloxane compound being preferably divinyltetramethylsiloxane.
    [0012]
    12 - Composition X according to any one of the preceding claims, characterized in that the proportions of organopolysiloxane A and organohydrogenpolysiloxane B are such that the molar ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane B on the alkenyl radicals bonded to silicon in the organopolysiloxane A is between 0.2 and 20, preferably between 0.5 and 15, more preferably between 0.5 and 10 and even more preferably between 0.5 and 5.
    [0013]
    13 - Composition X according to any one of the preceding claims, characterized in that it comprises one or more functional additives chosen from: silicone resins, adhesion modulators, additives to increase the consistency, pigments, and additives for thermal resistance, resistance to oils or fire resistance, for example metal oxides.
    [0014]
    14 - Use of the catalyst C as described according to any one of claims 1 to 13 as a crosslinking catalyst of silicone compositions.
    [0015]
    15 - Process for crosslinking silicone compositions, characterized in that it consists in heating a composition X according to any one of claims 1 to 13 at a temperature ranging from 70 to 200 ° C, preferably from 80 to 150 ° C and more preferably from 80 to 130 ° C.
    [0016]
    Cross-linked silicone material Y obtained by heating at a temperature ranging from 70 to 200 ° C., preferably from 80 to 150 ° C., and more preferably from 80 to 130 ° C., a composition X according to any one of Claims 1 to 13.10
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3215556B1|2018-10-17|Novel silicone composition crosslinking catalysts
    EP3385304B1|2020-07-15|Organopolysiloxane composition which can be vulcanised at ambient temperature in elastomer
    EP2268743B1|2015-04-22|Compounds having a guanidine structure and use of same as organopolysiloxane polycondensation catalysts
    EP2222756B1|2018-10-17|Room-temperature vulcanisable organopolysiloxane compound to give an elastomer and novel organopolysiloxane polycondensation catalysts
    EP1641871B1|2014-08-27|Single-component polyorganosiloxane | compositions which crosslink to form elastomers by means of polycondensation reactions at ambient temperature and in the presence of water, and elastomers thus obtained
    CA2744667C|2014-07-08|Compounds with guanidine structure and uses thereof as organopolysiloxane polycondensation catalysts
    EP2443180B1|2014-04-09|Silicone composition for cross-linking by dehydrocondensation in the presence of a metal catalyst
    FR2575085A1|1986-06-27|PLATIN-TRIENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PROCESS FOR PREPARING THE SAME
    EP2443177B1|2014-04-02|Silicone composition which is cross-linkable by dehydrogenative condensation in the presence of a metal catalyst
    EP1641870B2|2017-08-09|Single-component polyorganosiloxane composition which crosslinks into a silicon elastomer
    FR2831548A1|2003-05-02|CROSS-LINKABLE ADHESIVE SILICONE COMPOSITION COMPRISING AS A THIXOTROPING AGENT A COMPOUND WITH CYCLIC AMINE FUNCTION CARRIED BY A SILOXANIC CHAIN
    WO2014096567A1|2014-06-26|Organopolysiloxane composition suitable for vulcanisation into an elastomer at room temperature and new organopolysiloxane polycondensation catalysts
    FR2597876A1|1987-10-30|ISOCYANATE-STABILIZED DIORGANOPOLYSILOXANE COMPOSITION
    EP2081943B1|2018-02-07|Thermally-stable hot cross-linking elastomer silicone composition
    FR3068699A1|2019-01-11|USEFUL IRON COMPOUND AS A CATALYST FOR HYDROSILYLATION, DEHYDROGENANT SILYLATION AND CROSSLINKING OF SILICONE COMPOSITIONS
    EP3559088B1|2020-11-18|Cobalt compound useful as catalyst for hydrosilylation, dehydrogenative silylation and crosslinking of silicone compositions
    同族专利:
    公开号 | 公开日
    EP3215556A1|2017-09-13|
    JP6400198B2|2018-10-03|
    US20180273690A1|2018-09-27|
    EP3215555A1|2017-09-13|
    EP3215555B1|2018-08-22|
    EP3215557A1|2017-09-13|
    FR3028258B1|2017-01-13|
    KR20170101906A|2017-09-06|
    EP3215557B1|2018-09-26|
    CN107207733A|2017-09-26|
    WO2016071651A1|2016-05-12|
    CN107001634A|2017-08-01|
    KR102225423B1|2021-03-08|
    US10308770B2|2019-06-04|
    US20180016398A1|2018-01-18|
    JP2017533335A|2017-11-09|
    JP6533588B2|2019-06-19|
    JP2018500406A|2018-01-11|
    JP2017538849A|2017-12-28|
    WO2016071654A1|2016-05-12|
    US10196488B2|2019-02-05|
    US20170313823A1|2017-11-02|
    KR20170118033A|2017-10-24|
    CN107075120B|2021-02-26|
    KR20170102222A|2017-09-08|
    KR101944204B1|2019-01-30|
    KR101877192B1|2018-07-10|
    EP3215556B1|2018-10-17|
    WO2016071652A1|2016-05-12|
    JP6499757B2|2019-04-10|
    CN107075120A|2017-08-18|
    CN107207733B|2020-07-14|
    CN107001634B|2020-04-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2207924A1|1972-11-23|1974-06-21|Ceskoslovenska Akademie Ved|
    EP0604104A2|1992-12-14|1994-06-29|Shin-Etsu Chemical Co., Ltd.|Hydrosilylative compositions and hydrosilylation reaction processes|
    WO2013052838A1|2011-10-06|2013-04-11|Dow Corning Corporation|Method of forming a gel having improved thermal stability|
    FR1435882A|1964-01-22|1966-04-22|Argus Chem|Stabilization of Polyvinyl Chloride Resins Using Ketoacetic Acid Derivatives|
    US4803244A|1987-11-16|1989-02-07|Union Carbide Corporation|Process for the preparation of thermoplastic elastomers|
    EP0688564B1|1994-06-20|1999-08-04|Dow Corning Corporation|Method of controlling release of an active substance or drug from a silicone rubber matrix|
    DE19521757A1|1995-06-14|1996-12-19|Wacker Chemie Gmbh|Porphyrin-containing silicones with increased temperature resistance|
    JPH0934131A|1995-07-25|1997-02-07|Toray Ind Inc|Correcting method of waterless planographic printing plate|
    FR2801887B1|1999-12-07|2002-10-11|Rhodia Chimie Sa|METAL COMPLEXES SUITABLE FOR THE CATALYSIS OF HYDROSILYLATION REACTIONS, CATALYTIC COMPOSITION CONTAINING THEM AND THEIR USE|
    US6573328B2|2001-01-03|2003-06-03|Loctite Corporation|Low temperature, fast curing silicone compositions|
    JP2006131813A|2004-11-09|2006-05-25|Shin Etsu Chem Co Ltd|Self adhesive thermosetting-accelerating-type liquid silicone rubber composition|
    JP2007106905A|2005-10-14|2007-04-26|Shin Etsu Chem Co Ltd|Heat curing type liquid silicone rubber composition|
    DE102006017588A1|2006-04-13|2007-10-18|Wacker Chemie Ag|Hydrosilylation process in the presence of ruthenium catalysts|
    JP5288872B2|2008-04-28|2013-09-11|信越化学工業株式会社|Heat-curing silicone composition|
    EP2427333A2|2009-05-06|2012-03-14|Dow Corning Corporation|Vinylhydrogenpolysiloxane adhesive composition|
    FR2946981A1|2009-06-19|2010-12-24|Bluestar Silicones France|SILICONE COMPOSITION RETICULABLE BY DEHYDROGENOCONDENSATION IN THE PRESENCE OF A METAL CATALYST|
    WO2010146253A1|2009-06-19|2010-12-23|Bluestar Silicones France|Silicone composition which is cross-linkable by dehydrogenative condensation in the presence of a metal catalyst|
    JP5522111B2|2011-04-08|2014-06-18|信越化学工業株式会社|Silicone resin composition and optical semiconductor device using the composition|
    US8273914B1|2011-06-27|2012-09-25|Bausch & Lomb Incorporated|Process for preparing vinyl chloroformate|
    JP5922463B2|2012-03-30|2016-05-24|東レ・ダウコーニング株式会社|Curable silicone composition, cured product thereof, and optical semiconductor device|
    CN102977374B|2012-12-07|2015-01-07|中国科学院化学研究所|Cyclodisilazane-siloxane copolymer, preparation method and application thereof|FR3052784A1|2016-06-21|2017-12-22|Bluestar Silicones France|METHOD FOR FIGHTING THE FOG IN A CYLINDERS DEVICE WHEN COATING FLEXIBLE CARRIERS WITH A CROSS-LINKABLE LIQUID SILICONE COMPOSITION|
    FR3061183B1|2016-12-23|2020-09-11|Bluestar Silicones France|COBALT COMPOUNDS USEFUL AS A CATALYST FOR HYDROSILYLATION, DEHYDROGENANT SILYLATION AND CROSS-LINKING OF SILICON COMPOSITIONS|
    WO2018178319A1|2017-03-29|2018-10-04|Elkem Silicones France Sas|Polyaddition-crosslinkable silicone composition useful for overmolding parts|
    KR20210104854A|2018-12-20|2021-08-25|엘켐 실리콘즈 프랑스 에스에이에스|Method for Prevention of Mist Formation in Devices including Rolls During Coating of Flexible Supports with Crosslinkable Liquid Silicone Compositions|
    FR3099165A1|2019-07-25|2021-01-29|Elkem Silicones France Sas|SILICONE COMPOSITION FOR ELASTOMERIC FOAM.|
    WO2021134193A1|2019-12-30|2021-07-08|Elkem Silicones Shanghai Co., Ltd.|An abrasion resistant multi-layered composite|
    US20210324194A1|2020-04-15|2021-10-21|Elkem Silicones USA Corp.|Use of aryl group containing organopolysiloxane gums as additives to increase rheological behavior|
    WO2021260279A1|2020-06-25|2021-12-30|Elkem Silicones France Sas|Thermally conductive silicone compositions|
    法律状态:
    2015-10-08| PLFP| Fee payment|Year of fee payment: 2 |
    2016-05-13| PLSC| Search report ready|Effective date: 20160513 |
    2016-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-12| PLFP| Fee payment|Year of fee payment: 4 |
    2018-10-11| PLFP| Fee payment|Year of fee payment: 5 |
    2019-10-14| PLFP| Fee payment|Year of fee payment: 6 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 7 |
    2021-09-30| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1460803A|FR3028258B1|2014-11-07|2014-11-07|NEW CATALYSTS FOR CROSSLINKING SILICONE COMPOSITIONS|FR1460803A| FR3028258B1|2014-11-07|2014-11-07|NEW CATALYSTS FOR CROSSLINKING SILICONE COMPOSITIONS|
    PCT/FR2015/053012| WO2016071651A1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    PCT/FR2015/053017| WO2016071654A1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    JP2017525122A| JP6400198B2|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalyst|
    KR1020177014990A| KR102225423B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    US15/523,494| US10308770B2|2014-11-07|2015-11-06|Silicone composition crosslinking catalysts|
    US15/524,683| US20170313823A1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    US15/523,503| US10196488B2|2014-11-07|2015-11-06|Silicone composition crosslinking catalysts|
    EP15801906.7A| EP3215556B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    JP2017525121A| JP6499757B2|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalyst|
    KR1020177015223A| KR101944204B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    JP2017542350A| JP6533588B2|2014-11-07|2015-11-06|Novel catalyst for crosslinking silicone compositions|
    EP15801905.9A| EP3215555B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    CN201580068323.7A| CN107207733B|2014-11-07|2015-11-06|Novel crosslinking catalysts for silicone compositions|
    PCT/FR2015/053014| WO2016071652A1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    CN201580068317.1A| CN107001634B|2014-11-07|2015-11-06|Crosslinking catalysts for silicone compositions|
    EP15801908.3A| EP3215557B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    KR1020177015205A| KR101877192B1|2014-11-07|2015-11-06|Novel silicone composition crosslinking catalysts|
    CN201580060289.9A| CN107075120B|2014-11-07|2015-11-06|Silicone composition crosslinking catalyst|
    [返回顶部]