WO2019239782A1 - Procédé de production d'organopolysiloxane à fonction éther vinylique, composition polymérisable et produit durci obtenu à partir de celle-ci - Google Patents

Procédé de production d'organopolysiloxane à fonction éther vinylique, composition polymérisable et produit durci obtenu à partir de celle-ci Download PDF

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WO2019239782A1
WO2019239782A1 PCT/JP2019/019454 JP2019019454W WO2019239782A1 WO 2019239782 A1 WO2019239782 A1 WO 2019239782A1 JP 2019019454 W JP2019019454 W JP 2019019454W WO 2019239782 A1 WO2019239782 A1 WO 2019239782A1
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vinyl ether
group
component
functional organopolysiloxane
compound
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PCT/JP2019/019454
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Japanese (ja)
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龍太 橋本
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信越化学工業株式会社
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Publication of WO2019239782A1 publication Critical patent/WO2019239782A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a vinyl ether functional organopolysiloxane, a polymerizable composition containing the same, and a cured product thereof.
  • Energy beam curable resin is used for ink, paint, adhesive, coating agent, resist and the like.
  • As the main agent radically polymerizable acrylic monomers are often used.
  • acrylic monomers are strong in skin irritation and odor and have problems in workability
  • vinyl ether compounds having low odor and less skin irritation have been attracting attention.
  • a vinyl ether compound is a polymerizable monomer having an electron-donating substituent and is not expected to be cured by oxygen due to cationic polymerizability. Therefore, the vinyl ether compound is expected as a material for improving the defects of the acrylic compound.
  • Silicone has properties such as heat resistance, weather resistance, electrical insulation, water repellency, and antifouling properties. For example, it modifies acrylic resin by copolymerizing acrylic functional siloxane with other acrylic monomers. be able to. Since the production method of acrylic functional siloxane has been established and can be easily obtained commercially, there are many applications of silicone graft type acrylic polymers. On the other hand, vinyl ether functional siloxanes have difficulty in production method and cost, are not on the market, and have little knowledge about silicone graft type vinyl ether polymers.
  • Patent Document 1 describes a method of obtaining a vinyl ether functional silicone by a hydrosilylation reaction between an excess amount of divinyl ether or trivinyl ether and hydrogen siloxane.
  • this method since the polyfunctional vinyl compound and polyhydrogensiloxane are reacted, the reaction of crosslinking between the siloxane chains with the vinyl compound cannot be avoided, and an unexpected high molecular weight product is formed. End up. Moreover, there is a possibility that non-functional silicone having no vinyl ether group in the molecule is generated.
  • Patent Document 2 describes a method of obtaining a vinyl ether functional silicone by hydrosilylation reaction between a compound having both allyl and vinyl ether functional groups in one molecule and hydrogen siloxane.
  • a vinyl ether functional compound is preferentially obtained by utilizing a difference in reaction rate between an allyl group and a vinyl ether group with respect to a hydrosilyl group.
  • Patent Document 3 describes a method of obtaining a vinyl ether functional siloxane by a condensation reaction of acetoxysilane and a hydroxy group-containing vinyl ether compound.
  • the vinyl ether groups in the polymer are linked by SiOC bonds, there is a risk of being easily hydrolyzed by moisture or the like, and there is a limit to the method of use.
  • JP-A-6-345872 Japanese Patent Publication No. 2-336134 JP 2000-159895 A
  • the present invention has been made in view of the above circumstances, and is a method for producing a vinyl ether functional organopolysiloxane useful as an energy ray curable material capable of quantitatively introducing a vinyl ether group from a hydrosilyl group. It is an object of the present invention to provide a polymerizable composition containing a vinyl ether functional organopolysiloxane and a cured product obtained by curing the composition.
  • the present inventor has obtained (a) an organopolysiloxane having a hydrosilyl group and (b) a specific vinyl ether compound having an allyl group and a vinyl ether group in one molecule.
  • (B) Allyl group in component / hydrosilyl group in component (a)) is a molar ratio of 3.0 or more, and is reacted quantitatively with component (a) by reacting with a hydrosilylation catalyst. It has been found that a vinyl ether functional organopolysiloxane in which a group is added and a hydrosilyl group is converted into a vinyl ether group is obtained, and the present invention has been made.
  • the present invention provides the following inventions.
  • One or more vinyl ether compounds selected from The molar ratio of (allylic group in component (b) / hydrosilyl group in component (a)) is 3.0 or more
  • the method for producing a vinyl ether functional organopolysiloxane according to 1, comprising a step of removing an excess of the (b) vinyl ether compound from the reaction solution after the reaction step.
  • (A) component is the following average composition formula (1) (R 2 3 SiO 1/2 ) a (R 2 2 SiO 2/2 ) b (R 2 SiO 3/2 ) c (SiO 4/2 ) d (1) (Wherein R 2 is the same or different hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and the hydrocarbon group may contain an oxygen atom.
  • a polymerizable composition comprising a vinyl ether functional organopolysiloxane obtained by the method for producing a vinyl ether functional organopolysiloxane according to any one of items 1 to 5, and a polymerization initiator.
  • the manufacturing method of the vinyl ether functional organopolysiloxane which can introduce
  • the production method of the present invention comprises: (A) an organopolysiloxane having one or more hydrosilyl groups; (B) H 2 C ⁇ CHOCH 2 CH ⁇ CH 2 and H 2 C ⁇ CHOR 1 CH 2 CH ⁇ CH 2 (R 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms and contains an oxygen atom.
  • One or more vinyl ether compounds selected from The molar ratio of (allylic group in component (b) / hydrosilyl group in component (a)) is 3.0 or more
  • the component (a) is an organopolysiloxane having a hydrosilyl group (a hydrogen atom directly bonded to a silicon atom) in the molecule, and the number of hydrosilyl groups may be one or more. 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the main chain skeleton may be linear or branched. Specific examples include one-end-modified polyorganosiloxane having a hydrosilyl group at one end, both-end-modified organopolysiloxane having hydrosilyl groups at both ends, and side-chain-modified polyorganosiloxane having hydrosilyl groups in the side chain. However, any polyorganosiloxane can be used in the present invention.
  • a component can be used individually by 1 type or in combination of 2 or more types as appropriate.
  • the following average composition formula (1) (R 2 3 SiO 1/2 ) a (R 2 2 SiO 2/2 ) b (R 2 SiO 3/2 ) c (SiO 4/2 ) d (1)
  • R 2 is the same or different hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and the hydrocarbon group may contain an oxygen atom.
  • R 2 is the same or different, a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms which may contain an oxygen atom, and having 1 to 4 carbon atoms.
  • the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group.
  • the hydrocarbon group may contain an oxygen atom.
  • R 2 is one or more, preferably 1 to 10, more preferably 1 to 3 hydrogen atoms per molecule.
  • A, b, c and d are 0 or a positive number, preferably a is 0 or a positive number of 1 to 30, b is 0 or a positive number of 1 to 70, and c is a positive number of 0 or 1 to 30.
  • component (a) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,1,3,5, 5,5-heptamethyltrisiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, both molecular chains Terminal dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane Dimethylsiloxane with dimethylhydrogensiloxy group blocked at both
  • the number average molecular weight of the component (a) is not particularly limited, but is preferably 100 to 50,000, more preferably 200 to 10,000. If the number average molecular weight is too low, the proportion of siloxane units in the resulting polymer is reduced, and the characteristics of siloxane may not be sufficient. On the other hand, if the number average molecular weight is too high, the modified vinyl ether functional organopolysiloxane has a high viscosity, which makes it difficult to mix the cationic polymerizable composition.
  • a number average molecular weight is a polystyrene conversion value by GPC (gel permeation chromatography) analysis.
  • the vinyl ether compound of the present invention includes H 2 C ⁇ CHOCH 2 CH ⁇ CH 2 and H 2 C ⁇ CHOR 1 CH 2 CH ⁇ CH 2 (R 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, It may contain oxygen atoms.) It is 1 or more types chosen from these, 1 type can be used individually or in combination of 2 or more types as appropriate.
  • R 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain an oxygen atom.
  • R 1 is an alkylene group such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, octylene group, oxymethylene group, oxyethylene group, oxypropylene group, Examples thereof include oxyalkylene groups such as oxyisopropylene group, oxybutylene group, and oxyisobutylene group, and groups having a structure represented by the following formula.
  • H 2 C ⁇ CHOCH 2 CH ⁇ CH 2 H 2 C ⁇ CHOCH 2 CH 2 OCH 2 CH ⁇ CH 2 and H 2 C ⁇ CHOCH 2 CH 2 OC 6 H 4 CH 2 CH ⁇ CH
  • One or more selected from 2 are particularly preferred.
  • H 2 C ⁇ CHOCH 2 CH ⁇ CH 2 is commercially available.
  • H 2 C ⁇ CHOR 1 CH 2 CH ⁇ CH 2 can be obtained by reacting an appropriate hydroxy vinyl ether compound and an allyl halide compound, or a hydroxy allyl compound and a haloalkyl vinyl ether compound under basic conditions.
  • examples of the hydroxy vinyl ether compound include hydroxy vinyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, alkoxy vinyl ether such as dipropylene glycol monovinyl ether, and the like.
  • examples of the allyl halide compound include allyl chloride, allyl bromide, and allyl iodide.
  • hydroxyallyl compound 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, ethylene glycol monoallyl ether, propylene glycol monoallyl
  • examples include ether, 2-allylphenol, 3-allylphenol, 4-allylphenol, 4-allyl-2-methoxyphenol, and the like.
  • haloalkyl vinyl ether compounds include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 4-chlorobutyl vinyl ether, bromomethyl vinyl ether, 2-bromoethyl vinyl ether, 3-bromopropyl vinyl ether, 4-bromobutyl vinyl ether, Examples include iodomethyl vinyl ether, 2-iodoethyl vinyl ether, 3-iodopropyl vinyl ether, 4-iodobutyl vinyl ether and the like.
  • the amount of both compounds to be reacted (hydroxyvinyl ether compound and allyl halide compound, or hydroxyallyl compound and haloalkyl vinyl ether compound) is used based on 1.0 mole equivalent of OH group of the hydroxyvinyl ether compound or hydroxyallyl compound.
  • the haloalkyl vinyl ether compound is usually 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol.
  • Examples of the basic compound used for the basic conditions include potassium hydroxide, sodium hydroxide, sodium hydride and the like, and these can be used alone or in combination of two or more.
  • the amount used is usually 0.5 to 10 mol, preferably 1.0 to 3.0 mol, per 1.0 mol equivalent of OH groups of the hydroxyvinyl ether compound or hydroxyallyl compound.
  • phase transfer catalyst such as 400
  • the amount of the phase transfer catalyst used is usually 0.001 to 0.2 mol, preferably 0.005 to 0.1 mol, relative to 1.0 mol equivalent of OH groups in the hydroxyvinyl ether compound or hydroxyallyl compound.
  • the above reaction may be performed in a solvent as necessary.
  • the type of the solvent is not particularly limited, and specific examples include hydrocarbons such as toluene, xylene and cyclohexane, aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.
  • the reaction temperature is usually 30 to 150 ° C., preferably 60 to 100 ° C., and the reaction time is usually 3 to 48 hours, preferably 6 to 12 hours.
  • the reaction mixture is cooled to room temperature, the salt insoluble in the target product is removed by filtration, and then the target product can be obtained by distillation under reduced pressure.
  • the (c) hydrosilylation catalyst used in the present invention may be any catalyst that promotes the reaction between the hydrosilyl group in the component (a) and the allyl group in the component (b), and platinum containing a platinum group metal.
  • Group metal-based catalysts The platinum group metal means iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Among these, a platinum-containing catalyst is preferable.
  • the platinum-containing catalyst optionally includes platinum metal, platinum-containing compounds or complexes deposited on a support such as silica gel or powdered charcoal.
  • Preferred platinum-containing catalysts are preferably in the form of chloroplatinic acid in the generally available hexahydrate or anhydrous form, as disclosed in US Pat. No. 2,823,218.
  • chloroplatinic acid an organic compound having an aliphatic unsaturated group as disclosed in US Pat. No. 3,419,593 is disclosed because it has a property of being easily dispersed in an organosilicon system. The composition obtained by making it react with a silicon compound is mentioned.
  • the amount of the component (c) catalyst is not particularly limited as long as there is an amount sufficient to promote the reaction of the hydrosilyl group in the component (a) and the allyl group in the component (b) at room temperature.
  • the amount of the active component of the catalyst for example, platinum is as low as 1 to 10 parts by mass per 1 million parts by mass of the total of the components (a) and (b). .
  • an organopolysiloxane having a hydrosilyl group and (b) a vinyl ether compound have a molar ratio of (allyl group in component (b) / hydrosilyl group in component (a)) of 3.0.
  • the above includes (c) the step of reacting with the hydrosilylation catalyst.
  • the ratio is not particularly limited as long as it is 3.0 or more, but it is preferably 3.0 to 7.0, more preferably 4.0 to 5.0.
  • the allyl group in the component (b) is preferentially organolated.
  • the reaction temperature of (a) an organopolysiloxane having a hydrosilyl group and (b) a vinyl ether compound is not particularly limited, but is preferably 25 to 150 ° C, more preferably 70 to 100 ° C.
  • the time is not particularly limited, but is appropriately selected from 1 to 24 hours, for example.
  • a step of removing excess (b) vinyl ether compound from the reaction solution may be included.
  • Stripping is an example of a method for removing excess (b) vinyl ether compound.
  • a method of removing volatile components by stripping a method well known in the art can be employed.
  • the excess vinyl ether compound removed by stripping can be recovered and reused in the hydrosilylation reaction with the component (a), the cost is excellent.
  • vinyl ether functional organopolysiloxane means that only the allyl group portion of component (b) is added to the hydrosilyl group of (a) the organopolysiloxane component having a hydrosilyl group. And an organopolysiloxane having a vinyl ether group.
  • the vinyl ether functional organopolysiloxane may be polymerized with a vinyl ether functional organopolysiloxane alone, or another compound having a group capable of polymerizing with the above compound such as a vinyl group (hereinafter, polymerizable). Monomer).
  • the compound of the present invention can give a copolymer having further improved heat resistance, weather resistance, water repellency and the like.
  • the polymerizable composition of the present invention contains the vinyl ether functional organopolysiloxane of the present invention, and if necessary, other polymerizable monomers, and a polymerization initiator.
  • polymerizable monomers include, in particular, compounds having a vinyl group.
  • ethylene glycol divinyl ether diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether, etc. Is mentioned.
  • the ratio of the vinyl ether functional organopolysiloxane of the present invention to other polymerizable monomers used as required is not particularly limited, but the total of 100 masses of the vinyl ether functional organopolysiloxane of the present invention and other polymerizable monomers.
  • the vinyl ether functional organopolysiloxane of the present invention is preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight, based on parts.
  • the other polymerizable monomer is preferably 20 to 99 parts by mass, and more preferably 50 to 95 parts by mass.
  • the polymerization initiator is not particularly limited as long as it can cause cationic polymerization.
  • a photocleavable acid is used.
  • the photocleavable acid there is a photocationic polymerization initiator having an onium salt structure.
  • an onium salt represented by the following general formula (2) is preferable.
  • R 3 is independently of each other a substituted or unsubstituted monovalent group selected from an aromatic group in which an aromatic ring carbon atom is directly bonded to E and an aromatic heterocyclic group;
  • Y ⁇ is BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , ClO 4 ⁇ , HSO 4 ⁇ , B (C 6 F 5 ) 4 , which is a central element selected from I, S, Se and P.
  • a non-basic and non-nucleophilic anion selected from, X is, E is 2 when I, E is 3 when S or Se, a 4 when E is P.
  • R 3 is a monovalent group independently selected from a substituted or unsubstituted aromatic group and aromatic heterocyclic group in which an aromatic ring carbon atom is directly bonded to E.
  • the aromatic group include monovalent aromatic groups such as phenyl and naphthyl groups, and a part of hydrogen atoms bonded to carbon atoms of the monovalent aromatic group is methyl, ethyl, propyl, butyl, octyl, Groups selected from alkyl groups such as decyl and dodecyl groups, alkoxy groups such as methoxy, ethoxy and propoxy groups, halogen atoms such as chlorine and bromine atoms, sulfur-containing groups such as cyano groups, mercapto and thiophenyl groups And a group substituted by.
  • examples of the aromatic heterocyclic group include a pyrrole ring, a pyridine ring, and an imidazole ring, and a part of hydrogen atoms bonded to the carbon atom of the monovalent aromatic heterocyclic group is the same as the above aromatic group. May be substituted.
  • R 3 is preferably an aromatic group substituted with an alkyl group having 8 to 20 carbon atoms or an alkoxy group having 1 to 10 carbon atoms from the viewpoint of excellent solubility in silicone.
  • E is a central element selected from I, S, Se, and P, and is preferably I or S because of its high reactivity.
  • Y ⁇ is BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ .
  • the onium salt represented by the formula (2) is selected from a combination of the above R 3 , E, and Y ⁇ , and from the viewpoint of solubility and curability, bis [4-n-alkyl (C10 to C13) phenyl ] Iodonium hexafluorophosphate, bis [4-n-alkyl (C10-C13) phenyl] iodonium hexafluoroantimonate, bis [4-n-alkyl (C10-C13) phenyl] iodonium tetrakispentafluorophenylboric acid Salts are preferred.
  • the blending amount of the polymerization initiator is not particularly limited as long as an effective amount as a photocationic polymerization initiator is added.
  • 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass in total of the vinyl ether functional organopolysiloxane of the present invention and other polymerizable monomers, and 0.3 to 5 parts by mass. Part is more preferred.
  • the polymerizable composition it can be prepared by mixing the vinyl ether functional organopolysiloxane obtained by the above production method, if necessary, another polymerizable monomer, and a polymerization initiator.
  • the polymerizable composition is cured, for example, after applying the composition of the present invention to various substrates by various coating methods, it is copolymerized by irradiation with energy rays or irradiation with energy rays and heating. By doing so, a cured product (coating film) can be obtained.
  • energy rays used for cationic polymerization include active energy rays such as light, electron beam, and X-ray.
  • the substrate include, for example, plastics such as paper, polycarbonate, acrylic, ABS, polyester, and polypropylene, metals such as iron, copper, aluminum, zinc, chromium, and tin, glass, wood, rubber, stone, Concrete etc. are mentioned.
  • Specific examples of the application method include spin coating, spraying, electrostatic coating, roll coating, curtain flow coating, brush coating, bar coating, gravure printing, screen printing, offset printing, and the like. Can be mentioned.
  • the exposure time to the energy rays depends on the strength of the energy rays, the thickness of the coating film and the cationic polymerizable substance, but usually about 0.1 to 10 seconds is sufficient.
  • most of the composition is dry to the touch by cationic polymerization.
  • heat energy such as heating or a thermal head may be used in combination.
  • the heating condition may be 50 to 150 ° C. and 0.1 to 600 seconds.
  • the cured product of the above composition is a vinyl ether (co) polymer having siloxane characteristics. That is, the polymer is excellent in heat resistance, weather resistance, antifouling property and the like in addition to low skin irritation and low odor.
  • the polymer is useful in various fields such as inks, paints, adhesives, coating agents and resists.
  • the polymerizable composition of the present invention has the advantage that the cationic polymerization curing rate is high and the polymerization inhibition by oxygen is small.
  • Example 1 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 86 g (molecular weight 128, 0.67 mol) of the vinyl ether compound (b-1) of Synthesis Example 1 and platinum catalyst (0.5 mass of platinum) % -Containing toluene solution) 0.14 g was charged. The flask containing the mixture was purged with nitrogen, heated to 100 ° C., and (a-1) 1,1,1,3,5,5,5-hepta which was liquid at 25 ° C. using a dropping funnel.
  • Example 2 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 144 g of vinyl ether compound (b-1) of Synthesis Example 1 (molecular weight 128, 1.11 mol), platinum catalyst (platinum 0.5 mass) % -Containing toluene solution) 0.19 g was charged. The inside of the flask containing this mixture was purged with nitrogen, then heated to 100 ° C., and (a-1) 1,1,1,3,5,5,5-hepta which was liquid at 25 ° C. using a dropping funnel.
  • Example 3 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 89 g (molecular weight 128, 0.69 mol) of vinyl ether compound (b-1) of Synthesis Example 1 and platinum catalyst (0.5 mass of platinum) % -Containing toluene solution) 0.14 g was charged. The flask containing the mixture was purged with nitrogen, then heated to 100 ° C., and a liquid at 25 ° C.
  • silicone F was a colorless transparent liquid.
  • GPC the formation of a high molecular weight product due to crosslinking was not confirmed.
  • Example 4 To a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 40 g (molecular weight 128, 0.31 mol) of vinyl ether compound (b-1) of Synthesis Example 1 and platinum catalyst (0.5 mass of platinum). % -Containing toluene solution) 0.09 g was charged. The flask containing the mixture was purged with nitrogen, heated to 100 ° C., and a liquid at 25 ° C.
  • each siloxane unit is not limited to the following: 50 g (SiH: 0.06 mol) was added dropwise over 10 minutes (allyl group in component (b) / hydrosilyl in component (a)) Group) molar ratio: 5.0). After completion of dropping, the mixture was stirred at 100 ° C. for 4 hours. Here, by 1 H-NMR, the hydrosilyl group peak (4.6 to 4.8 ppm) disappeared, and a new silethylene peak (0.5 to 0.7 ppm) was generated, which caused the reaction to proceed. confirmed.
  • Example 5 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 142 g (molecular weight 204, 0.69 mol) of vinyl ether compound (b-2) of Synthesis Example 2 and platinum catalyst (0.5 mass of platinum) % -Containing toluene solution) 0.19 g was charged. The flask containing the mixture was purged with nitrogen, then heated to 100 ° C., and a liquid at 25 ° C.
  • a-2 50 g of organopolysiloxane represented by the following formula (4) (SiH : 0.14 mol) was added dropwise over 10 minutes (molar ratio of allyl group in component (b) / hydrosilyl group in component (a): 5.0). After completion of dropping, the mixture was stirred at 100 ° C. for 4 hours. Here, by 1 H-NMR, the hydrosilyl group peak (4.6 to 4.8 ppm) disappeared, and a new silethylene peak (0.5 to 0.7 ppm) was formed, which caused the reaction to proceed. confirmed. Thereafter, the reaction solution was cooled to room temperature, and excess vinyl ether compound (b-2) was distilled off and recovered by stripping.
  • a-2 50 g of organopolysiloxane represented by the following formula (4) (SiH : 0.14 mol) was added dropwise over 10 minutes (molar ratio of allyl group in component (b) / hydrosilyl group in component (a): 5.0
  • silicone H was a colorless transparent liquid.
  • GPC the formation of a high molecular weight product due to crosslinking was not confirmed.
  • Example 6 3 g of silicone D obtained in Example 1, 7 g of diethylene glycol divinyl ether, and 0.1 g of bis [4-n-alkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate were mixed, and the resulting polymerizability was obtained. The composition was subjected to a curing test. The results are shown in Table 1.
  • Example 7 10 g of the silicone F obtained in Example 3 and 0.1 g of bis [4-n-alkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate were mixed, and a curing test of the resulting polymerizable composition was conducted. went. The results are shown in Table 1.
  • Example 8 10 g of the silicone G obtained in Example 4 and 0.1 g of bis [4-n-alkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate were mixed, and a curing test of the resulting polymerizable composition was conducted. went. The results are shown in Table 1.
  • Example 9 10 g of the silicone H obtained in Example 5 and 0.1 g of bis [4-n-alkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate were mixed, and a curing test of the resulting polymerizable composition was conducted. went. The results are shown in Table 1.
  • silicone I ′ in which the vinyl ether group in the vinyl ether compound (b-1) was added to 1,1,1,3,5,5,5-heptamethyltrisiloxane.
  • 1,1,1,3,5,5,5-heptamethyltrisiloxane was found to produce silicone I ′′ in which both allyl group and vinyl ether group in vinyl ether compound (b-1) were added.
  • silicone I / I ′ / I ′′ 68/8/24 was formed, and the ratio of siloxane chains cross-linked with a vinyl compound was extremely high.
  • 1,1,1,3,5,5,5-heptamethyltrisiloxane was found to produce a silicone J ′′ in which both the allyl group and the vinyl ether group in the vinyl ether compound (b-1) were added.
  • silicone J ′ / J ′′ 86/4/10, and the ratio of those obtained by crosslinking between siloxane chains with a vinyl compound was increased.
  • silicone K was a colorless transparent liquid.
  • GPC GPC
  • silicone L was a colorless transparent liquid.

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Abstract

L'invention concerne une réaction, utilisant un catalyseur d'hydrosilylation, entre (a) un organopolysiloxane portant un groupe hydrosilyle et (b) un composé d'éther vinylique prescrit comportant le groupe allyle et le groupe éther vinylique dans chaque molécule, en quantités telles que le rapport molaire (groupe allyle dans le constituant (b)/groupe hydrosilyle dans le constituant (a)) devrait être supérieur ou égal à 3,0, qui peut permettre d'obtenir un organopolysiloxane à fonction éther vinylique dans lequel le groupe allyle a été ajouté quantitativement au constituant (a) et le groupe hydrosilyle a été converti en un groupe éther vinylique.
PCT/JP2019/019454 2018-06-14 2019-05-16 Procédé de production d'organopolysiloxane à fonction éther vinylique, composition polymérisable et produit durci obtenu à partir de celle-ci WO2019239782A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59500522A (ja) * 1982-04-01 1984-03-29 ゼネラル・エレクトリック・カンパニイ ビニルオキシ官能性オルガノポリシロキサン組成物
JPS6281391A (ja) * 1985-10-04 1987-04-14 Asahi Glass Co Ltd ビニロキシプロピルトリメチルシロキシシラン化合物
JP2017014409A (ja) * 2015-07-02 2017-01-19 信越化学工業株式会社 重合性モノマー、およびその重合体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59500522A (ja) * 1982-04-01 1984-03-29 ゼネラル・エレクトリック・カンパニイ ビニルオキシ官能性オルガノポリシロキサン組成物
JPS6281391A (ja) * 1985-10-04 1987-04-14 Asahi Glass Co Ltd ビニロキシプロピルトリメチルシロキシシラン化合物
JP2017014409A (ja) * 2015-07-02 2017-01-19 信越化学工業株式会社 重合性モノマー、およびその重合体

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