Classifications

• • 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
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0086—Platinum compounds
  • C07F15/0093—Platinum compounds without a metal-carbon linkage
• • 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
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/828—Platinum

Definitions

• the present invention includes a platinum-phosphite complex-containing hydrosilylation catalyst, a method for producing the hydrosilylation catalyst, a method for inhibiting crystallization of the platinum-phosphite complex-containing hydrosilylation catalyst, and the hydrosilylation catalyst.
• the present invention relates to a curable organopolysiloxane composition and an article having the cured product.
• Addition-curable silicone composition (addition-curable organopolysiloxane composition)
• the term "addition-curable silicone composition” used herein means that the cured product obtained by curing the composition is a cured product of rubber such as silicone rubber (elastomer elasticity body) or gel cured products such as silicone gel (low-stress non-elastic body that does not exhibit an effective rubber hardness value), which does not limit the hardness after curing) is the main agent Organopolysiloxane having an alkenyl group such as a vinyl group bonded to a silicon atom as a (base polymer), Organohydrogenpolysiloxane having a hydrogen atom (i.e., SiH group) bonded to a silicon atom as a curing agent (crosslinking agent), and a platinum-based catalyst as a curing catalyst, and a millable (raw rubber-like) or liquid addition reaction-curable organopolysiloxane composition, wherein a
• Cured products such as silicone rubbers and silicone gels, which are cured by heating this addition-curable silicone composition, are excellent in heat resistance, weather resistance, oil resistance, cold resistance, electrical insulation, etc. It is used in a wide range of applications, such as optical components, building materials, and automobile sealing materials.
• a mixed type silicone composition is prepared by dividing the components into two or more components and mixing them immediately before use, or a one-component silicone composition is refrigerated or frozen. The method of transporting is taken.
• Patent Document 1 proposes a method of adding an amine compound having an ethylenediamine skeleton.
• the addition of the amine compound may cause problems such as corrosion of the electronic substrate and deterioration of electrical properties.
• Patent No. 4530147 proposes a method of using a catalyst obtained by heating and aging a specific phosphite ester compound with a platinum catalyst.
• the activity of the catalyst obtained by heat aging is not stable, and the organic peroxide is used in combination. Therefore, low temperature conditions are essential for storage and transportation for performance stability.
• Patent Documents 3 and 4 European Patent Application Publication No. 2050768A1 and US Pat. No. 6,706,840
• Patent Document 5 proposes a method of using a platinum-phosphite complex and a tin salt.
• this publication uses a tin compound, there are concerns that it may be harmful to the human body, and if it is exposed to room temperature for a long time, it will thicken or gel, so it should be stored for performance stability. Low-temperature conditions are essential in the transportation of raw materials.
• Patent Document 6 proposes a method using a platinum catalyst, a phosphorus compound, and an organic peroxide containing no hydroperoxide group. Even in the compositions proposed in the above publications, when exposed to room temperature for a long time, thickening and gelation occur, so low temperature conditions are essential for storage and transportation for performance stability.
• German Patent Application Publication No. 60316102T2 Patent Document 7 describes a one-part organopolysiloxane gel composition made from a platinum catalyst, a phosphite triester, and an organic peroxide. ing.
• the phosphite triester is described as tris(2,4-di-tert-butylphenyl) phosphite and the amount of organic peroxide present is at least A method is proposed that is 2 equivalents.
• Japanese Patent Publication No. 2018-503709 Patent Document 8 proposes a method of using tris(2,4-di-tert-butylphenyl) phosphite.
• Patent Documents 9 and 10 a method for enhancing storage stability using a specific phosphite ester compound has been proposed. ing. Although the above proposal certainly improves storage stability dramatically, it is not possible to obtain a sufficiently cured silicone cured product unless it is exposed to a high temperature of about 150 ° C., and the hydrolysis performance of the phosphite compound Because of its high storability, the storage stability in the air was sometimes inferior.
• hydrosilylation catalyst containing a platinum-phosphite ester complex that does not contain a hydrocarbon-based organic solvent and is liquid at 23°C.
• a platinum-phosphite ester complex that does not contain a hydrocarbon-based organic solvent and is liquid at 23°C can be obtained because it is possible to obtain a one-liquid addition-curable silicone composition that does not contain an organic solvent and has stable physical properties.
• the present invention has been made in order to solve such problems.
• An object of the present invention is to provide a curable organopolysiloxane composition containing no hydrocarbon-based organic solvent, which is stable in properties and physical properties even in a cured state, and an article having the cured product.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• a solution is prepared by dissolving the phosphite ester compound represented by in a hydrocarbon-based organic solvent having a boiling point of 80 ° C. or less, and the solution is added with platinum chloride, chloroplatinic acid, and chloroplatinic acid or chloroplatinate.
• a platinum catalyst containing no hydrocarbon-based organic solvent selected from one or more platinum-alkenyl group-containing siloxane complexes formed from alkenyl group-containing siloxanes, is added, dispersed and dissolved, and platinum and A solution containing a platinum-phosphite ester complex composed of a phosphite ester compound represented by the above general formula (1) is prepared, and the solution is added with the following general formula (2) (wherein R 2 represents an alkenyl group having 2 to 10 carbon atoms, R 3 represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 200; is.) A solution containing at least part of the platinum-phosphite ester complex and the association of the siloxane compound represented by the above general formula (2) by adding an organopolysiloxane compound having a unit represented by and dispersing and dissolving After that, by removing the hydrocarbon-based organic solvent having a boiling point of 80° C.
• the solution remains stable even during long-term storage at 23° C. without containing the desired hydrocarbon-based organic solvent.
• platinum-phosphite ester complex-containing hydrosilylation catalysts are available.
• a one-component (one-liquid) curable organopolysiloxane composition containing no hydrocarbon-based organic solvent can be produced.
• the obtained one-component curable organopolysiloxane composition is a composition with stable properties and physical properties even when exposed to room temperature for a long time. I came up with the invention.
• the present invention provides the following hydrosilylation catalyst containing a platinum-phosphite complex, a method for producing the hydrosilylation catalyst, a method for suppressing crystallization of the hydrosilylation catalyst containing a platinum-phosphite complex, and the hydrosilyl A curable organopolysiloxane composition containing a curing catalyst and an article having the cured product are provided.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• a platinum-phosphite ester complex composed of a phosphite ester compound represented by, and the following general formula (2) (wherein R 2 represents an alkenyl group having 2 to 10 carbon atoms, R 3 represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 200; is.)
• a hydrosilylation catalyst containing a platinum-phosphite ester complex which is liquid at 23° C. and is liquid at 23° C., and does not contain a hydrocarbon-based organic solvent.
• platinum-phosphite ester complex 0.01 to 100 mol% of the platinum-phosphite ester complex is associated with an organopolysiloxane compound having a unit represented by the general formula (2)
• the platinum-phosphorous acid according to [3] A hydrosilylation catalyst containing an acid ester complex.
• the alkenyl group-containing siloxane compound further contains 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and/or 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst according to any one of [1] to [4], which contains siloxane.
• the curable organopolysiloxane composition according to [6] which does not contain a hydrocarbon-based organic solvent.
• a method for producing a platinum-phosphite ester complex-containing hydrosilylation catalyst comprising the following steps (a) to (d).
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• a method for producing a hydrosilylation catalyst containing a platinum-phosphite ester complex comprising the following steps (a) to (d). (a) a step of preparing a solution in which a phosphite ester compound represented by the following general formula (1) is dissolved in a hydrocarbon-based organic solvent having a boiling point of 80° C.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• a platinum-phosphite ester complex composed of platinum and a phosphite ester compound represented by the above general formula (1) by adding a platinum catalyst that does not contain a hydrocarbon-based organic solvent, dispersing and dissolving it.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention is stably liquid even during long-term storage at 23° C. without containing a hydrocarbon-based organic solvent. Excellent for In addition, when the catalyst is incorporated into a one-component (one-liquid) curable organopolysiloxane composition, it can be easily and uniformly dispersed to obtain a curable organopolysiloxane composition containing no hydrocarbon-based organic solvent. be able to. The resulting one-component curable organopolysiloxane composition containing no hydrocarbon-based organic solvent has stable properties even when exposed to room temperature (23° C. ⁇ 15° C.) for a long period of time. It gives. Furthermore, since it does not contain a hydrocarbon-based organic solvent or the like, a very safe cured product can be obtained.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention comprises platinum and the following general formula (1) (In the formula, R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.) A platinum-phosphite ester complex composed of a phosphite ester compound represented by, and the following general formula (2) (wherein R 2 represents an alkenyl group having 2 to 10 carbon atoms, R 3 represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 200; is.) A platinum-phosphite ester complex-containing hydrosilylation catalyst that is liquid at 23 ° C.
• liquid alkenyl group-containing siloxane compound containing an organopolysiloxane compound having a unit represented by be refers to a state in which the platinum-phosphite ester complex in the platinum-phosphite ester complex-containing hydrosilylation catalyst is not crystallized.
• the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention at least part of the platinum-phosphite complex is associated with an organopolysiloxane compound having a unit represented by the general formula (2).
• an organopolysiloxane compound having a unit represented by the general formula (2) Preferably, 0.01 to 100 mol%, particularly 0.02 to 100 mol% of the platinum-phosphite complex is associated with an organopolysiloxane compound having a unit represented by the general formula (2) It is preferable that If it is less than 0.01 mol %, the platinum-phosphite ester complex in the platinum-phosphite ester complex-containing hydrosilylation catalyst may crystallize and become cloudy during long-term storage.
• the platinum-phosphite ester complex and the organopolysiloxane compound having the unit represented by the general formula (2) contain the platinum-phosphite ester complex in the organopolysiloxane compound in a free state (liquid state).
• a free state liquid state
• By dispersing and dissolving and contacting with the organopolysiloxane compound it is believed that an aggregate is formed quantitatively and easily according to the compounding ratio. It is believed that crystallization of the acid ester complex is suppressed (see Examples 1, 2, 3 and Comparative Example 2 described later).
• alkenyl group-containing siloxane compounds other than the organopolysiloxane compound having the unit represented by the general formula (2) are considered not to form effective aggregates even when in contact with the platinum-phosphite ester complex. (See Comparative Examples 1 and 2 to be described later).
• Platinum-phosphite ester complex contained in the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention is composed of platinum and a phosphite ester compound represented by the general formula (1) described later. is.
• the phosphite compound represented by the following general formula (1) contained as a platinum-phosphite complex is a complex with platinum (platinum-phosphite By forming a phosphate ester complex), the storage stability of the properties and physical properties of the curable organopolysiloxane composition containing the catalyst of the present invention can be significantly improved, and it is an essential component. is.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, preferably a monovalent aliphatic hydrocarbon group having 1 or 2 carbon atoms.
• phosphite compound represented by the above formula (1) examples include tris(2,4-dimethylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2 ,4-bis(3-ethylpentan-3-yl)phenyl)phosphite, tris(2,4-bis(4-propylheptan-4-yl)phenyl)phosphite, etc.
• R 1 has the same carbon number Phosphite compounds, also tris(4-(tert-butyl)-2-methylphenyl)phosphite, tris(4-(tert-butyl)-2-ethylphenyl)phosphite, tris(2-(tert- R 1 such as butyl)-4-(3-ethylpentan-3-yl)phenyl)phosphite, tris(2-(tert-butyl)-4-(3-methylhexan-3-yl)phenyl)phosphite and phosphite ester compounds having different carbon numbers.
• the phosphite ester compound represented by the general formula (1) is preferably more than 0.6 mol and 1.9 mol or less per 1 mol of platinum atoms. It is preferably 0.8 to 1.5 mol. If it is less than 0.6 mol, the resulting curable organopolysiloxane composition containing the platinum-phosphite complex-containing hydrosilylation catalyst may have poor storage stability or may gel.
• the resulting platinum-phosphite ester complex in the hydrosilylation catalyst containing the platinum-phosphite ester complex may crystallize at room temperature (23° C. ⁇ 15° C., hereinafter the same) and may not be able to retain liquid. be.
• alkenyl group-containing siloxane compound contained in the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention is liquid at 23° C. and is an organopolysiloxane having units represented by the general formula (2) described later. containing compounds.
• Organopolysiloxane compound The organopolysiloxane compound having a unit represented by the following general formula (2) contained in the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention is combined with at least a part of the platinum-phosphite complex described above.
• the association is an essential component for preventing the platinum-phosphite complex in the hydrosilylation catalyst containing the platinum-phosphite complex from crystallizing at room temperature.
• R 2 represents an alkenyl group having 2 to 10 carbon atoms
• R 3 represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms
• n is an integer of 2 to 200; is.
• the organopolysiloxane compound having a bifunctional siloxane unit represented by the general formula (2) has n of 2 or more (i.e., 2 represented by [(R 2 )(R 3 )SiO 2/2 ]). have two or more functional siloxane units), the molecular chain non-terminal (molecular chain in the middle) of the silicon atom (hereinafter, in the present invention, may be referred to as an adjacent silicon atom) alkenyl group such as a vinyl group (hereinafter, in the present invention, when referred to as an adjacent vinyl group or adjacent alkenyl group ) in the molecule.
• the organopolysiloxane compound having units represented by the above general formula (2) has only the units represented by the above formula (2) other than the molecular chain ends (i.e., triorganosiloxy units or diorganohydroxysiloxy units). preferably configured.
• R 2 is an alkenyl group having 2 to 10 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms (vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group , isobutenyl group, etc.), and more preferably an alkenyl group having 2 carbon atoms, that is, a vinyl group.
• R 3 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), more preferably a monovalent saturated aliphatic hydrocarbon group having 1 carbon atom, that is, a methyl group.
• n is an integer of 2 to 200, preferably an integer of 3 to 100, more preferably an integer of 4 to 40, still more preferably an integer of 4 to 10. .
• the terminal of the organopolysiloxane compound having a bifunctional siloxane unit represented by the general formula (2) is not particularly limited, but when the organopolysiloxane compound is linear or branched, the molecular chain
• the terminal may be a silanol group-containing siloxy group (diorganohydroxysiloxy group) or a triorganosiloxy group such as a trimethylsiloxy group or a dimethylvinylsiloxy group.
• the organopolysiloxane compound is a cyclic organopolysiloxane compound (organocyclopolysiloxane compound), there are no molecular chain terminals.
• the organopolysiloxane compound having two or more adjacent alkenyl groups having a unit represented by the above general formula (2) associates with the platinum-phosphite ester complex to produce crystals of the platinum-phosphite ester complex. Since it is a component for preventing quenching, when it is dispersed and mixed with a platinum-phosphite ester complex and brought into contact with the platinum-phosphite ester complex, the molecules are in a liquid state in which they are individually liberated. is required.
• organopolysiloxane compound examples include organoalkenylcyclopolysiloxanes such as 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (here, the organo group is an alkyl group), cyclic polysiloxanes containing adjacent alkenyl groups such as organoalkenylsiloxane-diorganosiloxane cyclic copolymers (same as above), 1,3,5,7-tetravinyl-1,3,5,7-tetra Adjacent alkenyl group-containing siloxane polymer (adjacent alkenyl group-containing linear methylvinylpolysiloxane) obtained by linear ring-opening polymerization of methylcyclotetrasiloxane by equilibration reaction.
• organoalkenylcyclopolysiloxanes such as 1,3,5,7-tetravinyl-1,3,
• the terminal of the adjacent alkenyl group-containing siloxane polymer (adjacent alkenyl group-containing linear methylvinylpolysiloxane) linearly ring-opening polymerized by the equilibration reaction is not limited as described above, but a trimethylsiloxy group, Polymers with silanol group-containing siloxy groups (dimethylhydroxysiloxy groups) and dimethylvinylsiloxy groups are preferably used.
• the organopolysiloxane compound having a unit represented by the general formula (2) among these, a cyclic organopolysiloxane compound (organocyclo polysiloxane compound).
• the amount of the organopolysiloxane compound having the unit represented by the general formula (2) is preferably 0.01 to 500 mol, preferably 0.02 to 0.02, per 1 mol of the platinum atom in the platinum-phosphite ester complex. It is more preferably 200 mol, still more preferably 0.03 to 100 mol, and most preferably 0.05 to 50 mol. If it is less than 0.01 mol, the platinum-phosphite ester complex in the platinum-phosphite ester complex-containing hydrosilylation catalyst will crystallize at room temperature, making it impossible to retain a liquid, or the catalyst will be damaged.
• the alkenyl group-containing siloxane compound includes, in addition to the organopolysiloxane compound (adjacent alkenyl group-containing organopolysiloxane compound) having a unit represented by the general formula (2) described above, 1,3-divinyl-1,1,3, 3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3- Alkenyl group-containing disiloxane compounds such as divinyl-1,1,3,3-tetraphenyldisiloxane, terminal alkenyl groups such as 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane containing trisiloxane compounds and the like can be included.
• organopolysiloxane compound adjacent alkenyl group-containing organopolysi
• This alkenyl group-containing disiloxane compound or terminal alkenyl group-containing trisiloxane compound can be used, for example, as an intermediate material when preparing a platinum-phosphite complex in the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention.
• Alkenyl group-containing siloxane compounds contained as ligands for platinum atoms in the platinum catalyst used.
• a platinum catalyst for example, a platinum-alkenyl group-containing siloxane complex such as a Karstedt complex
• a catalyst solution such as a silicone solution.
• Siloxy groups containing terminal alkenyl groups that do not have alkenyl groups in the middle of the molecular chain such as straight-chain dimethylpolysiloxanes capped with vinyldimethylsiloxy groups at both ends of the molecular chain, which are used as simple silicone-based diluents (solvents) when used in the form of
• the end-blocked linear diorganopolysiloxane particularly the terminal alkenyl group-containing siloxy group-blocked linear diorganopolysiloxane having a degree of polymerization of 14 or more and having no alkenyl group in the middle of the molecular chain (terminal alkenyl group-containing silicone oil) is described above.
• an alkenyl group-containing siloxane compound other than an organopolysiloxane compound having a unit represented by the general formula (2) that is, it is excluded from the constituent components of the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention ) may be included in the curable organopolysiloxane composition as a silicone solution of the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention because it does not adversely affect the present invention.
• the content of the alkenyl group-containing siloxane compound other than the organopolysiloxane compound having the unit represented by the general formula (2) is preferably 0 to 99.5% by mass in the alkenyl group-containing siloxane compound, and 0.5 More preferably, it is up to 98% by mass. If the content of this compound is too high, the concentration of the organopolysiloxane compound having the unit represented by the general formula (2) in the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention will decrease.
• the formation of an association between the phosphite complex and the organopolysiloxane compound having the unit represented by the general formula (2) is not effectively promoted, and the hydrosilylation catalyst containing the platinum-phosphite complex during long-term storage
• the platinum-phosphite ester complex may crystallize and become cloudy.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst described above can be stably produced by performing the following four steps. (a) preparing a solution in which the phosphite ester compound represented by the general formula (1) is dissolved in a hydrocarbon organic solvent having a boiling point of 80° C.
• platinum-phosphite ester complex composed of platinum and a phosphite ester compound represented by the above general formula (1) by adding a platinum catalyst that does not contain a hydrocarbon-based organic solvent, dispersing and dissolving it.
• step (c) preparing a solution containing (c) adding an organopolysiloxane compound having a unit represented by the general formula (2) to the solution obtained in step (b), dispersing and dissolving at least a portion of the platinum-phosphite ester complex; and a step of preparing a solution containing an aggregate of an organopolysiloxane compound having a unit represented by the general formula (2), and (d) removing the hydrocarbon-based organic solvent from the solution obtained in step (c);
• the first step is a step of dissolving a phosphite ester compound represented by the following general formula (1) in a hydrocarbon organic solvent having a boiling point of 80° C. or less to prepare a solution.
• R 1 is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• phosphite compound The phosphite ester compound represented by the general formula (1) is as described above. Among them, tris(2,4-di-tert-butylphenyl) phosphite, which is easily available and highly effective in storage stability, is used. preferably.
• the phosphite ester compound represented by the general formula (1) is often solid at room temperature, and the phosphite ester compound was dissolved in a hydrocarbon-based organic solvent having a boiling point of 80° C. or less to form a solution. After that, in the second step, it is necessary to form a platinum-phosphite ester complex by mixing with a platinum catalyst, which will be described later.
• the hydrocarbon-based organic solvent is a hydrocarbon that may contain a heteroatom (oxygen atom, nitrogen atom, sulfur atom) in the molecule and is liquid at room temperature (23°C ⁇ 15°C). It means an organic compound as a basic skeleton, and excludes organosilicon compounds such as organosilane compounds and organopolysiloxane compounds.
• the boiling point here is a boiling point in atmospheric pressure.
• the hydrocarbon-based organic solvent having a boiling point of 80°C or lower may be linear or branched.
• hydrocarbon-based organic solvents having a boiling point of 80° C. or lower include n-pentane (boiling point: 36° C.), n-hexane (boiling point: 68° C.), 2-methylbutane (boiling point: 30° C.), 2, 2-dimethylbutane (boiling point: 50°C), 2,3-dimethylbutane (boiling point: 58°C), 2-methylpentane (boiling point: 62°C), 3-methylpentane (boiling point: 63°C), and the like.
• n-hexane (boiling point: 68° C.) is particularly suitable because it is relatively easy to handle for industrial use and easy to remove in the subsequent removal step.
• a boiling point of 80° C. or lower is necessary is that it is preferable to distill off the hydrocarbon-based organic solvent under reduced pressure in the step of removing the hydrocarbon-based organic solvent from the prepared platinum-phosphite ester complex-containing hydrosilylation catalyst.
• the hydrocarbon-based organic solvent can be removed even at a vacuum distillation temperature of 40° C. or less, and a stable platinum-phosphite ester complex-containing hydrosilylation catalyst can be obtained.
• the hydrocarbon-based organic solvent with a boiling point exceeding 80 ° C. the hydrocarbon-based organic solvent used cannot be completely removed unless the vacuum distillation temperature exceeds 40 ° C., so the platinum-phosphite ester complex is contained.
• a hydrocarbon-based organic solvent may remain in the hydrosilylation catalyst, or the platinum-phosphite ester complex-containing hydrosilylation catalyst may be decomposed depending on the temperature of the solvent removal step, resulting in precipitation of crystals.
• the amount of the hydrocarbon-based organic solvent having a boiling point of 80° C. or lower is not particularly limited, but 100 to 10,000 parts by mass, particularly 1 ,000 to 5,000 parts by mass.
• the temperature at which the phosphite ester compound represented by the general formula (1) is dissolved in the hydrocarbon-based organic solvent is preferably 40°C or less, more preferably within the range of 0 to 35°C.
• the phosphite ester compound represented by the general formula (1) is easily hydrolyzed by the water contained in the hydrocarbon-based organic solvent, so the compound represented by the general formula (1)
• the phosphite ester compound is likely to change to a phosphate ester compound, and the stability of the resulting platinum-phosphite ester complex-containing hydrosilylation catalyst is reduced.
• the dissolution time is not particularly limited, and the phosphite ester compound represented by the general formula (1) may be dissolved in the hydrocarbon-based organic solvent, and is about 10 minutes to 24 hours.
• the dissolution vessel it is preferable to choose a vessel that is oxygen-tight.
• Second step (b) In the second step, the solution obtained in step (a) is added with platinum chloride, chloroplatinic acid, and platinum-platinum formed from chloroplatinic acid or chloroplatinate and alkenyl group-containing siloxane such as vinyl group-containing siloxane.
• a platinum catalyst that does not contain a hydrocarbon-based organic solvent, selected from one or more alkenyl group-containing siloxane complexes, is added, dispersed and dissolved, and platinum and the phosphorus compound represented by the above general formula (1) are added. It is a step of preparing a solution containing a platinum-phosphite ester complex composed of an acid ester compound.
• the intermediate platinum catalyst used in the preparation of the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention includes platinum chloride, chloroplatinic acid, and alkenyl catalyst such as chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane.
• a platinum catalyst containing no hydrocarbon-based organic solvent which is selected from one or more of platinum-alkenyl group-containing siloxane complexes formed from a group-containing siloxane, wherein the platinum catalyst is usually itself Contributes to the hydrosilylation addition reaction between the alkenyl group in the base polymer (alkenyl group-containing organopolysiloxane) and the SiH group in the crosslinker (organohydrogenpolysiloxane) contained in the addition-curable silicone composition. It is a curing catalyst (hydrosilylation addition reaction catalyst).
• the platinum catalyst is further dispersed and dissolved in a solution containing the phosphite ester compound represented by the above-described general formula (1), and the platinum and the sub-substance represented by the above general formula (1) are obtained.
• a platinum-phosphite ester complex-containing hydrosilylation catalyst containing a platinum-phosphite ester complex composed of a phosphate ester compound is used as a curing catalyst for an addition-curable silicone composition (addition-curable organopolysiloxane composition). can dramatically improve the storage stability of the properties and physical properties of the target curable organopolysiloxane composition.
• the alkenyl group-containing siloxane in the platinum-alkenyl group-containing siloxane complex includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3 - diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3- tetraphenyldisiloxane, 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1, 3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and the like.
• 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and 1,3,5,7-tetramethyl The structure of -1,3,5,7-tetravinylcyclotetrasiloxane is illustrated below.
• platinum-alkenyl group-containing siloxane complexes selected from one or more platinum-alkenyl group-containing siloxane complexes, platinum catalysts containing no hydrocarbon-based organic solvents
• platinum-alkenyl group-containing siloxane complexes include platinum-1, 3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt complex), platinum-1,3-diallyl-1,1,3,3-tetramethyldisiloxane complex, platinum-1,3- divinyl-1,3-dimethyl-1,3-diphenyldisiloxane complex, platinum-1,3,5-trimethyl-1,3,5-
• the platinum-alkenyl group-containing siloxane complex is preferably at least one selected from these groups, and it is also essential that it does not contain a hydrocarbon-based organic solvent.
• platinum catalysts it is particularly preferable to use a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt complex).
• basic hydrocarbon organic solvents such as aromatic organic solvents such as toluene and xylene, alcoholic organic solvents such as ethanol, n-butanol and 2-ethylhexyl alcohol
• oligosiloxanes having low molecular weight and vinyl groups such as tetramethyldivinyldisiloxane, trimethyltrivinylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane
• Linear organopolysiloxanes such as linear dimethylpolysiloxane with both molecular chain ends blocked with trimethylsiloxy groups and linear methylphenylpolysiloxane with both molecular chain ends blocked with trimethylsiloxy groups (so-called silicone oils) are excluded.
• silicone oils such as linear dimethylpolysiloxane with both molecular chain ends blocked with trimethylsiloxy groups and linear methylphenylpolysiloxane with both mole
• Hydrocarbon organic selected from one or more of platinum chloride, chloroplatinic acid, and platinum-alkenyl group-containing siloxane complex formed from chloroplatinic acid or chloroplatinate and alkenyl group-containing siloxane
• a platinum catalyst that does not contain a solvent is an alkenyl group-containing organopolysiloxane that is the same as or different from the alkenyl group-containing siloxane that forms the ligand of the platinum-alkenyl group-containing siloxane complex (generally, a dimethylvinylsiloxy It is in the form of a silicone solution with a diluent (solvent), such as linear dimethylpolysiloxane, which is a vinyldiorganosiloxy group-blocked linear organopolysiloxane at both ends of the molecular chain that does not have adjacent alkenyl groups in the molecule.
• solvent such as linear dimethylpolysiloxane, which is a vinyld
• This silicone solution is usually prepared so that the platinum atom content is about 0.001 to 0.010 mol %. This is for enhancing the stability and handleability (workability) of the platinum-alkenyl group-containing siloxane complex.
• the amount (mass concentration) of platinum contained in the silicone solution is about 0.2 to 2.0% by mass.
• the addition ratio of the platinum catalyst and the phosphite compound is such that the amount of the phosphite compound exceeds 0.6 molecules and is within the range of 1.9 molecules or less per 1 atom of platinum in the platinum catalyst. Optimally, more preferably, it is desirable to add 0.8 molecules or more and 1.5 molecules or less per platinum atom in the platinum catalyst.
• the platinum-phosphite ester complex obtained in the second step is converted to the above-mentioned general formula Even when associated with an organopolysiloxane compound having a unit represented by (2), the platinum-phosphite ester complex in the obtained platinum-phosphite ester complex-containing hydrosilylation catalyst crystallizes and precipitates at room temperature.
• the platinum-phosphite complex-containing hydrosilylation catalyst cannot be kept liquid at 23° C., or the platinum-phosphite complex-containing hydrosilylation catalyst cannot be used as a curable organopolysiloxane.
• problems such as deterioration of dispersibility and deterioration of blending workability may occur.
• the method of adding the platinum catalyst is not particularly limited. good.
• the dispersion/dissolution of the platinum catalyst is preferably carried out at a temperature of 40°C or less, particularly 0 to 35°C for 30 minutes or more, particularly 30 minutes to 4 hours.
• a container that can block oxygen it is preferable to select a container that can block oxygen, and the container used in the first step can be used as it is.
• step (c) In the third step, an organopolysiloxane compound having a unit represented by the following general formula (2) (organopolysiloxane compound having two or more adjacent alkenyl groups) is added to the solution obtained in step (b), Aggregate of dispersed/dissolved platinum-phosphite ester complex and organopolysiloxane compound having units represented by the following general formula (2) (organopolysiloxane compound having two or more adjacent alkenyl groups) is a step of preparing a solution containing (wherein R 2 represents an alkenyl group having 2 to 10 carbon atoms, R 3 represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 200; is.)
• a platinum-phosphite ester complex-containing hydrosilylation catalyst excellent in dispersibility and property stability can be obtained. Furthermore, when the platinum-phosphite ester complex-containing hydrosilylation catalyst is used as a curing catalyst in an addition-curable silicone composition (curable organopolysiloxane composition), even when exposed to room temperature for a long time, the properties It is possible to provide a composition having stable properties and a composition free from hydrocarbon organic solvents.
• the organopolysiloxane compound having the unit represented by general formula (2) (organopolysiloxane compound having two or more adjacent alkenyl groups) is as described above.
• the organopolysiloxane compound having the unit represented by the general formula (2) is a component for preventing crystallization of the platinum-phosphite ester complex by associating with the platinum-phosphite ester complex.
• the platinum-alkenyl group in that when dispersed and mixed with the platinum-phosphite complex and brought into contact with the platinum-phosphite complex, the molecules are in a liquid state in which the molecules are individually liberated. It differs from alkenyl group-containing siloxanes such as vinyl group-containing siloxanes as ligands that form complexes with platinum atoms in the siloxane complexes contained.
• the alkenyl group-containing siloxane as a ligand forming a complex with the platinum atom in the platinum-alkenyl group-containing siloxane complex as an intermediate material is platinum.
• the liberated alkenyl group-containing siloxane is an organopolysiloxane compound having a unit represented by the general formula (2) (organopolysiloxane having two or more adjacent alkenyl groups compound) other than the alkenyl group-containing siloxane (for example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, which is a ligand of the Karstedt complex), the alkenyl group-containing siloxane is not believed to associate with the platinum-phosphite complex as described above.
• the liberated alkenyl group-containing siloxane corresponds to an organopolysiloxane compound having a unit represented by the general formula (2) (organopolysiloxane compound having two or more adjacent alkenyl groups)
• the liberated although it is thought that the alkenyl group-containing siloxane can also form an association with a platinum-phosphite ester complex, an organopolysiloxane compound having a platinum-phosphite ester complex and a unit represented by the general formula (2)
• an organopolysiloxane compound having a unit represented by general formula (2) organopolysiloxane compound having a unit represented by general formula (2) (organopolysiloxane compound having two or more adjacent alkenyl groups)
• the amount of the organopolysiloxane compound having a unit represented by the general formula (2) is determined by the general formula ( 2) is preferably added in an amount of 0.01 to 500 mol, more preferably 0.02 to 200 mol, and 0.03 to 100 mol of the organopolysiloxane compound having the unit represented by is more preferred, and 0.05 to 50 mol is most preferred.
• the organopolysiloxane compound having the unit represented by the general formula (2) is more than 500 mol per 1 mol of the platinum atom in the platinum-phosphite complex, the resulting platinum-phosphite complex containing
• the influence on the viscosity of the hydrosilylation catalyst increases, and problems such as deterioration of workability when blending the catalyst may occur.
• the addition method of the organopolysiloxane compound having the unit represented by the general formula (2) is not particularly limited, and it may be added all at once to the solution containing the platinum-phosphite ester complex. , It may be added in divided portions or added dropwise over a predetermined period of time.
• the dispersion/dissolution is preferably carried out at a temperature of 40°C or less, particularly 0 to 35°C for 60 minutes or more, particularly 60 minutes to 24 hours.
• a temperature of 40°C or less particularly 0 to 35°C for 60 minutes or more, particularly 60 minutes to 24 hours.
• the fourth step is to remove the hydrocarbon-based organic solvent from the solution obtained in step (c).
• the hydrocarbon-based organic solvent is removed from the solution obtained in steps (a) to (c) to obtain a platinum-phosphite ester complex-containing hydrosilylation catalyst containing no hydrocarbon-based organic solvent. This is an essential step.
• the solvent removal method used here is preferably a vacuum distillation method in which the solvent is distilled off under reduced pressure using a vacuum pump or the like. This is because a stable platinum-phosphite ester complex-containing hydrosilylation catalyst can be obtained by setting the vacuum distillation temperature to 40° C. or less, preferably 0 to 35° C.
• the vacuum distillation time is not particularly limited, but is preferably 30 minutes to 4 hours. Although the degree of pressure reduction varies depending on the boiling point of the hydrocarbon-based organic solvent used, the used hydrocarbon-based organic solvent can be completely removed by setting the condition to 50 hPa or less, preferably 1 to 35 hPa.
• the method for confirming whether the used hydrocarbon-based organic solvent has been completely removed is the total mass of the used phosphite ester compound, platinum catalyst, and siloxane compound, and the platinum-sulfite obtained after the fourth step. It can be confirmed by the mass ratio of the phosphate ester complex-containing hydrosilylation catalyst. If the mass of the obtained platinum-phosphite complex-containing hydrosilylation catalyst is greater than the total mass of the phosphite ester compound, platinum catalyst, and siloxane compound used, the hydrocarbon-based organic solvent remains. Furthermore, by adding this process time to remove the hydrocarbon organic solvent, it can be completely removed.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst described above can be inhibited from crystallization by performing the following four steps. (a) preparing a solution in which the phosphite ester compound represented by the general formula (1) is dissolved in a hydrocarbon organic solvent having a boiling point of 80° C.
• platinum-phosphite ester complex composed of platinum and a phosphite ester compound represented by the above general formula (1) by adding a platinum catalyst that does not contain a hydrocarbon-based organic solvent, dispersing and dissolving it.
• step (c) preparing a solution containing (c) adding an organopolysiloxane compound having a unit represented by the general formula (2) to the solution obtained in step (b), dispersing and dissolving at least a portion of the platinum-phosphite ester complex; and a step of preparing a solution containing an aggregate of an organopolysiloxane compound having a unit represented by the general formula (2), and (d) removing the hydrocarbon-based organic solvent from the solution obtained in step (c);
• the four steps for suppressing crystallization are the same as the four steps shown in the method for producing the platinum-phosphite ester complex-containing hydrosilylation catalyst. Crystallization of the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention can be suppressed by the above steps.
• the above-mentioned platinum-phosphite complex-containing hydrosilylation catalyst can be used as a catalyst for curing various resins and as a purification catalyst. or silicone gel, etc.) curable organopolysiloxane composition that is a one-component (one-liquid) addition reaction curing type (for example, a millable type (raw rubber-like) or liquid addition-curable silicone rubber composition and addition-curable silicone gel compositions, etc.), the characteristics can be exhibited. Also, the curable organopolysiloxane composition preferably does not contain a hydrocarbon-based organic solvent.
• the curable organopolysiloxane composition (for example, an addition-curable silicone rubber composition, an addition-curable silicone gel composition, etc.) includes, as a basic constituent component, a linear compound capped with vinyldimethylsiloxy groups at both ends of the molecular chain.
• Silicon-bonded hydrogen atoms present in alkenyl groups and organohydrogenpolysiloxanes (crosslinking agents) in alkenyl group-containing organopolysiloxanes (base polymers) containing genepolysiloxanes and hydrosilylation addition reaction catalysts
• SiH groups present in alkenyl groups and organohydrogenpolysiloxanes (crosslinking agents) in alkenyl group-containing organopolysiloxanes (base polymers) containing genepolysiloxanes and hydrosilylation addition reaction catalysts
• a millable type (raw rubber-like) or liquid (one-liquid type) addition reaction type organopolysiloxane composition that cures by a hydrosilylation reaction to give a silicone rubber elastic body (rubber cured product) or a silicone gel cured product is particularly preferable.
• the amount of platinum in the platinum-phosphite complex-containing hydrosilylation catalyst relative to the entire composition is In terms of atomic mass, it is preferably about 0.1 to 1,000 ppm, more preferably 1 to 500 ppm, and even more preferably about 5 to 300 ppm.
• a catalyst solution such as a silicone solution in which a solvent other than a hydrocarbon-based organic solvent such as an alkenyl group-containing organopolysiloxane (terminal alkenyl group-containing silicone oil) is used as a solvent
• a solvent other than a hydrocarbon-based organic solvent such as an alkenyl group-containing organopolysiloxane (terminal alkenyl group-containing silicone oil) is used as a solvent
• the platinum When used in the form of a catalyst solution such as a silicone solution in which a solvent other than a hydrocarbon-based organic solvent such as an alkenyl group-containing organopolysiloxane (terminal alkenyl group-containing silicone oil) is used as a solvent, for example, the platinum -
• the amount of the catalyst solution is 100% of the organopolysiloxane (base polymer) containing an alkenyl group. It is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by
• the amount of the platinum-phosphite complex-containing hydrosilylation catalyst solution (1% by mass of platinum atoms) is less than 0.001 parts by mass (or the mass of platinum atoms relative to the entire composition is less than 0.1 ppm)
• the strength of the cured product of the curable organopolysiloxane composition may be lowered or the curing may be poor. exceeds 10 parts by mass (or the mass of platinum atoms is 1,000 ppm)
• the resulting curable organopolysiloxane composition will be colored, the time required for curing will be shortened, and the price will be reduced. is also disadvantageous.
• the activity of the catalyst that is, the curability can be controlled by increasing or decreasing the concentration of the hydrosilylation catalyst containing the platinum-phosphite complex.
• the addition reaction type organopolysiloxane composition containing the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention may further contain fumed silica (dry silica), precipitated silica (wet silica), if necessary.
• silica sol-gel silica, fused silica, crushed silica, crystalline silica (micronized silica) and other silica-based fillers, calcium carbonate, reinforcing inorganic fillers such as fumed titanium dioxide, calcium silicate, titanium dioxide, oxide
• Non-reinforcing inorganic fillers such as ferric iron and carbon black, surface-hydrophobicized or untreated inorganic fillers, various fillers such as organic resin balloons, silane coupling agents (e.g., oxygen atoms, nitrogen atoms , a hydrolyzable organosilane compound such as an alkoxysilane containing a monovalent hydrocarbon group having a functional group containing a heteroatom selected from sulfur atoms (epoxy group, (meth)acryloxy group, mercapto group, etc.) and / or partial hydrolysis condensate thereof), trimethylsilyl groups at both ends of the molecular chain that do not contain functional groups involved in hydrosilylation addition
• the curing conditions for the curable organopolysiloxane composition containing the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention it is preferable to accelerate the curing by heating.
• a heating temperature of about 90 to 150° C. is preferred.
• the curing time is not particularly limited, but is preferably 5 to 240 minutes, particularly preferably 10 to 120 minutes.
• the curable organopolysiloxane composition containing the platinum-phosphite complex-containing hydrosilylation catalyst of the present invention is used in articles used as potting materials such as electric and electronic devices and IGBTs, various electronic substrates, resin cases, and the like.
• Example 1 In a transparent glass container, weigh 0.3311 parts of tris(2,4-di-tert-butylphenyl) phosphite, add 9.6689 parts of n-hexane (boiling point: 68 ° C.), seal, and then return to room temperature ( 23° C.) for about 1 hour. After visually confirming that the tris(2,4-di-tert-butylphenyl)phosphite crystals were dissolved, platinum-1,3-divinyl-1,1,3 having 1% by mass of Pt atoms was added.
• 3-tetramethyldisiloxane complex (Karstedt complex) silicone solution (solvent: vinyldimethylsiloxy group-blocked dimethylpolysiloxane at both ends with a degree of polymerization of 180) was added, and after sealing, 30 minutes until uniform. Stirred. After that, 0.0088 part of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was sealed and stirred for 60 minutes until uniform.
• the compounding amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounding amount of the adjacent alkenyl group-containing organopolysiloxane compound is 0 per 1 mol of the platinum atom in the platinum catalyst. .05 mol.
• Example 2 0.3311 parts of tris(2,4-di-tert-butylphenyl)phosphite was weighed into a transparent glass container, 9.6689 parts of n-hexane was added, and the container was sealed and dissolved at room temperature for about 1 hour. rice field. After visually confirming that the tris(2,4-di-tert-butylphenyl)phosphite crystals were dissolved, platinum-1,3-divinyl-1,1,3 having 1% by mass of Pt atoms was added.
• 3-tetramethyldisiloxane complex (Karstedt complex) silicone solution (solvent: vinyldimethylsiloxy group-blocked dimethylpolysiloxane at both ends with a degree of polymerization of 180) was added, and after sealing, 30 minutes until uniform. Stirred. After that, 0.1765 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was sealed and stirred for 60 minutes until uniform.
• the compounded amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounded amount of the adjacent alkenyl group-containing organopolysiloxane compound is 1 mol per 1 mol of the platinum atom in the platinum catalyst. .0 mol.
• Example 3 0.3311 parts of tris(2,4-di-tert-butylphenyl)phosphite was weighed into a transparent glass container, 9.6689 parts of n-hexane was added, and the container was sealed and dissolved at room temperature for about 1 hour. rice field. After visually confirming that the tris(2,4-di-tert-butylphenyl)phosphite crystals were dissolved, platinum-1,3-divinyl-1,1,3 having 1% by mass of Pt atoms was added.
• 3-tetramethyldisiloxane complex (Karstedt complex) silicone solution (solvent: vinyldimethylsiloxy group-blocked dimethylpolysiloxane at both ends with a degree of polymerization of 180) was added, and after sealing, 30 minutes until uniform. Stirred. After that, 2.50 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was sealed and stirred for 60 minutes until uniform.
• the compounded amount of the phosphite compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounded amount of the adjacent alkenyl group-containing organopolysiloxane compound is 14 per 1 mol of the platinum atom in the platinum catalyst. .2 mol.
• Example 1 In Example 1, instead of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octa The same operation as in Example 1 was performed except that 0.0088 parts of methylcyclotetrasiloxane was used. As a result, 10.33 g of a colorless transparent liquid was obtained in a 100 ml eggplant-shaped flask (yield: 99.9%). This silicone solution of the platinum-phosphite ester complex-containing hydrosilylation catalyst is referred to as "catalyst IV".
• the compounding amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounding amount of the adjacent alkenyl group-containing organopolysiloxane compound is 0 per 1 mol of the platinum atom in the platinum catalyst. becomes a mole.
• Example 2 The same procedure as in Example 1 was carried out, except that 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was not added. As a result, 10.33 g of a colorless transparent liquid was obtained in a 100 ml eggplant-shaped flask (yield: 99.9%).
• This silicone solution of the platinum-phosphite ester complex-containing hydrosilylation catalyst is referred to as "catalyst V".
• the compounding amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounding amount of the adjacent alkenyl group-containing organopolysiloxane compound is 0 per 1 mol of the platinum atom in the platinum catalyst. becomes a mole.
• 3-tetramethyldisiloxane complex (Karstedt complex) silicone solution (solvent: vinyldimethylsiloxy group-blocked dimethylpolysiloxane at both ends with a degree of polymerization of 180) was added, and after sealing, 30 minutes until uniform. Stirred. After that, 0.0088 part of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was sealed and stirred for 60 minutes until uniform.
• the compounding amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom in the platinum catalyst, and the compounding amount of the adjacent alkenyl group-containing organopolysiloxane compound is 0 per 1 mol of the platinum atom in the platinum catalyst. .05 mol.
• Example 4 In Example 1, the same operation as in Example 1 was performed except that n-hexane was not added. As a result, a colorless transparent liquid in which white crystals were dispersed (yield: 10.33 g) was obtained in a 100 ml eggplant-shaped flask, and a colorless transparent liquid in which no crystals were precipitated could not be obtained (yield: 99 .9%).
• This silicone solution of the platinum-phosphite ester complex-containing hydrosilylation catalyst is referred to as "catalyst VII".
• the compounding amount of the phosphite ester compound is 1.0 mol per 1 mol of the platinum atom of the platinum catalyst, and the compounding amount of the adjacent alkenyl group-containing organopolysiloxane compound is 0.05 per 1 mol of the platinum atom of the platinum catalyst. becomes a mole.
• the platinum-phosphite ester complex-containing hydrosilylation catalysts obtained in Examples 1-3 satisfy the requirements of the present invention.
• the compounding amount of the phosphite compound was 1.0 mol per 1 mol of platinum atoms in the platinum catalyst.
• the platinum-phosphite ester complex-containing hydrosilylation catalysts obtained in Examples 1 to 3 have suppressed crystal precipitation even after being left at 23 ° C. for 3 months under sealed conditions. Platinum with high property stability.
• a hydrosilylation catalyst containing a phosphite ester complex was obtained.
• the amount of the phosphite compound compounded was changed from 1.0 mol to 1.9 mol in increments of 0.1 mol per 1 mol of the platinum atom in the platinum catalyst, and the rest was the same as in Example 1.
• hydrosilylation catalysts containing a platinum-phosphite ester complex were prepared by the operation, all of them were colorless and transparent liquids were obtained at 23°C, and it was confirmed that they remained colorless and transparent liquids even after 3 months at 23°C. .
• the present invention provides a hydrosilylation catalyst containing a stable liquid platinum-phosphite ester complex.
• composition Example 1 100 parts by mass of dimethylpolysiloxane raw rubber composed of 99.85 mol% of dimethylsiloxane units, 0.125 mol% of methylvinylsiloxane units, and 0.025 mol% of dimethylvinylsiloxy units and having an average degree of polymerization of 6,000, BET method 55 parts by mass of fumed silica having a specific surface area of 200 m 2 /g (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.), 12 parts by mass of dimethyldimethoxysilane (surface treatment agent), 0.2 parts by mass of vinyltrimethoxysilane (surface treatment agent) 12 parts by weight of dimethylpolysiloxane (dispersant) having an average degree of polymerization of 4 and a viscosity of 15 mPa s at 23° C., and 0.15 parts by weight of 3% by weight potassium siliconate are added. and heated under mixing with a kneader at
• a type-curable organopolysiloxane composition I was prepared.
• composition Example 2 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst II" prepared in Example 2 was used instead of "Catalyst I”. II was produced.
• composition Example 3 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst III" prepared in Example 3 was used instead of "Catalyst I”. III was prepared.
• composition Comparative Example 1 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst IV" prepared in Comparative Example 1 was used instead of "Catalyst I”. IV was prepared.
• composition Comparative Example 2 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst V" prepared in Comparative Example 2 was used instead of "Catalyst I”. I made V.
• composition Comparative Example 3 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst VI" prepared in Comparative Example 3 was used instead of "Catalyst I”. VI was produced.
• composition Comparative Example 4 A one-component millable type curable organopolysiloxane composition was prepared in the same manner as in Composition Example 1, except that 0.05 parts by mass of "Catalyst VII" prepared in Comparative Example 4 was used instead of "Catalyst I”. VII was produced.
• composition Comparative Example 5 In Composition Example 1, a solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt complex) having 1 wt. A one-component millable type curable organopolysiloxane composition VIII was produced in the same manner except that 0.05 parts by mass of solvent: vinyldimethylsiloxy group-blocked dimethylpolysiloxane having a degree of polymerization of 180 at both ends was used.
• the curing torque of the one-component millable type curable organopolysiloxane composition was measured over time, and the time (T50) when the torque value reached 50% of the maximum torque value from the start of measurement was confirmed and compared. bottom. Also, at this time, those that could be evaluated at 23° C. for 6 months were judged to be acceptable.
• the catalyst when the catalyst is added to the composition, the precipitated crystal component (solid) is removed, and only the liquid component of the platinum-phosphite complex-containing hydrosilylation catalyst is added in the required amount. Since it was necessary to blend the composition, the workability was also unsatisfactory.
• the one-component millable type curable organopolysiloxane compositions of Composition Comparative Examples 1 to 3 using these catalysts (liquid components only) exhibited good storage stability (curability after storage).
• the platinum-phosphite complex-containing hydrosilylation catalyst of Comparative Example 4 was produced without using a hydrocarbon-based organic solvent, resulting in poor complex formation between the phosphite compound and platinum.
• Comparative Composition Example 5 without forming a complex with a phosphite ester and without association with a siloxane compound, platinum chloride, chloroplatinic acid, and chloroplatinic acid or chloroplatinate and alkenyl group-containing siloxane
• the one-component millable type curable organopolysiloxane composition produced using this catalyst had good workability when the catalyst was added, but resulted in poor storage stability (curability after storage). . From the above results, the one-component millable type curable organopolysiloxane composition using the platinum-phosphite complex-containing hydrosilylation catalyst obtained in the present invention is excellent in terms of workability improvement and storage stability. was found to exhibit excellent performance.
• the platinum-phosphite ester complex-containing hydrosilylation catalyst of the present invention does not use a hydrocarbon-based organic solvent, even in conventional platinum-phosphite complex-containing hydrosilylation catalysts that cause crystal formation. It can retain liquid properties at 23°C. Therefore, it is possible to improve the property stability of the hydrosilylation catalyst itself, improve the workability when producing a curable organopolysiloxane composition using this catalyst, and achieve highly safe curing that does not contain a hydrocarbon organic solvent. A polyorganopolysiloxane composition can be obtained. Therefore, there is very little adverse effect on the human body.
• the resulting curable organopolysiloxane composition containing no hydrocarbon-based organic solvent can be a composition with stable properties even when exposed to room temperature for a long time.
• a wide range of applications can be expected in the construction, medical, and food fields.

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• 2022
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