Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

• the catalyst is based on platinum and can be in different forms: on a support, in the pure phase (liquid or solid) or in a solvent.
• the invention aims to propose the use of new catalytic systems based on a platinum group metal and a heterocyclic organic compound for hydrosilylation in particular between unsaturated reagents and polyorganosiioxanes carrying at least a s ⁇ SiH motif, this catalytic system substantially accelerating said reaction without loss of selectivity and by inhibiting gelation phenomena.
• the first object of the present invention is the use as catalyst, in particular heat-activated, for the hydrosilylation of at least one unsaturated reagent (A) with at least one monomer, oligomer and / or silicone polymer (B) having, per molecule, at least one reactive unit - ⁇ SiH, in the presence of a homogeneous catalytic system comprising (i) a metal, preferably complexed, chosen from the group consisting of rhodium, ruthenium, platinum, palladium, iridium and / or nickel and (ii) a heterocyclic organic compound of the lactone type.
• a homogeneous catalytic system comprising (i) a metal, preferably complexed, chosen from the group consisting of rhodium, ruthenium, platinum, palladium, iridium and / or nickel and (ii) a heterocyclic organic compound of the lactone type.
• catalytic systems are particularly advantageous in terms of reactivity insofar as they are active at low concentrations and advantageously require only small amounts of energy to carry out the hydrosilylation.
• the claimed catalytic systems therefore prove to be particularly advantageous in terms of profitability and cost for industrial processes.
• the groups R 3 , R 5 , R 7 identical or different, represent (i) a free valence, (ii) a linear or branched, saturated or unsaturated and possibly substituted alkyl radical, (iii) a radical linear or branched, saturated or unsaturated and which may be substituted alkylene - the groups R 4 and R 6 , which are identical or different, represent (i) a hydrogen atom, (ii) a linear or branched radical, saturated or unsaturated and which may be substituted, (iii) a linear or branched, saturated or unsaturated and which may be substituted alkylene radical, or (iv) form a saturated or unsaturated, linear or branched hydrocarbon ring which may be substituted.
• heterocyclic lactone compounds can be chosen from those of formulas below:
• the molar ratio of the heterocyclic compound to the platinum group metal is between 10 and 10,000, preferably between 100 and 1000.
• the metal within the catalytic system is preferably platinum , in particular of zero oxidation state.
• any type of heating source can be used.
• unsaturated reactant (A) means that the compound contains at least one unsaturated bond, and is chosen from the group consisting of:
• the unsaturated reagents (A1) are chosen from the following:
• alkenes can be, for example, 1-hexene, 1, 5-he> .adiene, 1-octene and / or 1-dodecene.
• the alkynes can be, for example, 1-hexyne, and / or
• silicone reagents (A2) they are preferably selected from polyorganosiioxanes comprising:
• an aryl radical containing between 6 and 12 carbon atoms which may be substituted possibly on the aryl part by halogens, alkyls and / or alkoxys containing 1 to 3 carbon atoms, preferably phenyl or dichlorophenyl,
• an arylalkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms,
• * the symbols Y similar or different, represent a linear or branched C 2 -C 12 alkenyl residue, and having at least one ethylenic unsaturation at the chain end and optionally at least one heteroatom; * e is equal to 1 or 2, d is equal to 0, 1 or 2 with the sum (d + e) having a value between 1 and 3;
• the polyorganosiloxane (A2) can be formed solely of unit of formula (1) or additionally comprise units of formula (2).
• the radicals Y are chosen from the following list: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10-undecenyl, 5.9-decadienyl, and
• These polyorganosiioxanes can have a linear structure (branched or not) cyclic or network. Their degree of polymerization is preferably between 2 and 5000.
• terminal "M” units examples include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy, dimethylhexenylsiloxy, dimethylethoxysiloxy, dimethylethyltriethoxysiloxy groups.
• units "D” mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy, methyldecadienylsiloxy, methyl-3-hydropropylsiloxy, methylethyliloxy-methyloxyoxy.
• Said linear polyorganosiioxanes (A2) can be oils of dynamic viscosity at 25 ° C of the order of 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 mass of the order of 1,000,000.
• cyclic polyorganosiioxanes consist of “D” units W 2 SiO 2/2 , Y 2 SiO 2/2 , WYSiO 2/2 , which can be of the dialkylsiloxy, alkylarylsiloxy, alkylvinylsiloxy type, alkylsiloxy; examples of such patterns have already been cited above.
• Said cyclic polyorganosiioxanes (A2) have a viscosity of the order of 1 to 5000 mPa.s.
• polyorganosiioxane derivatives (B) are chosen from polyorganohydrogensiloxanes comprising:
• the polyorganosiloxane (B) can be formed solely of unit of formula (3) or additionally comprise units of formula (2). It can have a linear structure, branched or not, cyclic or networked. The degree of polymerization is greater than or equal to 2. More generally, it is less than 5000.
• units of formula (3) are: H (CH 3 ) 2 SiO 1/2 , HCH 3 SiO 2/2 , H (C 6 H 5 ) SiO 2/2 ,
• linear polyorganosiioxanes can be oils of dynamic viscosity at 25 ° C of the order of 1 to 100,000 mPa.s at 25 ° C, generally of the order of 10 to 5,000 mPa.s at 25 ° C, or gums with a molecular weight of the order of 1,000,000.
• cyclic polyorganosiioxanes consist of "D" units W 2 SiO 22 and WHSiO 22 , which can be of the dialkylsiloxy or alkylarylsiloxy type. They have a viscosity of the order of 1 to 5000 mPa.s.
• the dynamic viscosity at 25 ° C of all the polymers considered in this presentation can be measured using a BROOKFIELD viscometer, according to AFNOR NFT 76 102 standard of February 1972.
• polyorganosiioxanes (B) are: dimethylpolysiloxanes with hydrogenodimethylsilyl ends, dimethylhydrogenomethylpolysiloxanes with trimethylsilyl ends, dimethylhydrogenomethylpolysiloxanes with hydrogenodimethylsilyl ends, hydrogenomethylpolysiloxanes and trimethylsoloxyl ends.
• oligomers and polymers corresponding to the general formula (4) are especially preferred as derivatives (B):
• - x and y are an integer varying between 0 and 200,
• the monomers, oligomers, polyorganosiioxane polymers (B) with a reactive SiH unit comprise from 1 to 50 active SiH units per molecule.
• the quantity of silicone (B) and of reagent (A) within the reaction medium is chosen such that the ratio number of SiH units of silicone (B) with respect to the number of bonds unsaturated reagent (A) is between 0.01 and 100, preferably between 0.1 and 10.
• a second aspect of the present invention relates to a catalytic system making it possible to accelerate the reaction without loss of selectivity and by inhibiting the phenomena of gelation.
• This homogeneous catalytic system comprises (i) a metal, preferably complexed, chosen from the group consisting of cobalt, rhodium, ruthenium, platinum and nickel and (ii) a heterocyclic organic compound of lactone type.
• This catalytic system according to the invention can be implemented according to various variants; it can be prepared before use or prepared in the reaction medium.
• it is possible to use an implementation in which all of the reactants and the catalytic system are mixed in the reaction medium ("batch" type).
• the Applicant has developed an advantageous process for the preparation of functional silicone oils in accordance with this implementation.
• This hydrosilylation process between at least one monomer, oligomer and / or silicone polymer (B) and an unsaturated reagent (A) comprises the following steps:
• the ratio of the number of SiH units to the number of hydrosilylatable units being between 0.1 and 10.
• step (a) is carried out before step (b). More particularly, the heterocyclic compound can be mixed with the reagent (A) before adding the platinum group metal.
• the process preferably implemented comprises the following steps:
• the hydrosilylation processes in the context of the invention can be carried out in bulk, which means that the reaction between the silicone (B) and the unsaturated reagent (A) takes place in the absence of solvent.
• many solvents such as toluene, xylene, octamethyltetrasiloxane, cyclohexane or hexane can be used. If necessary, the reaction product obtained is finally devolatilized. Examples.
• the platinum catalyst used is a platinum complex (O) in solution at 10% by weight of platinum in ⁇ , ⁇ -divinylated silicone oils.
• the platinum concentration is calculated relative to the total mass of the alkene + stoichiometric silicone oil SiH.
• Examples 1 to 4 demonstrate the advantage of using a catalytic system according to the invention of lactone during hydrosilylation reactions of type 1, 2-epoxy-4-vinyl-cyclohexane monomers.
• the amount of organic compound added is expressed by weight, calculated relative to the VCMX introduced (i.e. 1000 ppm means 1 g per 1 kg of VCMX).
• the time required to reach full conversion of the SiH units is measured. The origin of the times is taken at the start of the pouring of the SiH fluid.

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• Chemical Kinetics & Catalysis (AREA)
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• 2001
  • 2001-10-30 FR FR0114040A patent/FR2831543B1/fr not_active Expired - Fee Related
• 2002
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  • 2002-10-29 WO PCT/FR2002/003716 patent/WO2003037962A1/fr not_active Application Discontinuation
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