Method for producing vulcanized rubber

Abstract

To provide a method for producing a vulcanized rubber which can be molded in a short time while maintaining physical properties when subjected to LIM molding.SOLUTION: The method for producing the vulcanized rubber includes a step of subjecting a resin composition containing a specific ethylene / α - olefin / 5-vinyl-2-norbornene copolymer (A), a hydrosilyl group-containing compound (Y) which is an organohydrogenpolysiloxane represented by a specific formula and having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule, and a platinum-based catalyst to LIM molding.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing vulcanized rubber. [Background technology]

[0002] In recent years, LIM (Liquid Injection Molding), or liquid rubber injection molding, has become widespread. It has recently become a popular molding method due to its advantages, such as the ability to quickly automate molding and to perform composite molding with plastics (insert molding). LIM's advantages include: (1) the ability to continuously automate processes such as material transfer, weighing, mixing, and injection, and to reduce the power required; (2) the ability to shorten molding cycles through rapid curing; (3) the absence of reaction by-products; (4) the lack of foreign matter contamination; and (5) the ability to perform insert molding and other composite molding due to the material's fluidity, low-pressure molding, and wide curing temperature range.

[0003] As compositions that can be used for LIM molding, for example, several compositions containing ethylene-α-olefin-non-conjugated polyene copolymers have been proposed (Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4343870 [Patent Document 2] Patent No. 3908001 [Patent Document 3] Patent No. 3901599 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the previously proposed ethylene-α-olefin-non-conjugated polyene copolymers have excellent fluidity and are applicable to LIM molding, the molding time is not satisfactory.

[0006] An object of the present invention is to provide a method for producing vulcanized rubber that maintains its physical properties when molded by LIM and that can be molded in a short time. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention.

[0008] [1] An ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A) that satisfies the following requirements (i) to (vi); a hydrosilyl group-containing compound (Y) which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule; Platinum-based catalysts A method for producing vulcanized rubber, comprising a step of LIM molding a resin composition comprising: (i) a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 1,000 to 50,000; (ii) the molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) is 2.7 or less; (iii) 13 The intensity ratio Tαβ / Tαα of the C-NMR spectrum is 0.0-0.1; (iv) the content of structural units derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0 mass%; (v) the structural units derived from 5-vinyl-2-norbornene contain an endo structure and an exo structure, and the ratio of the endo structure / exo structure is 2.5 or less; (vi) The intrinsic viscosity [η] measured in decahydronaphthalene at 135°C is in the range of 0.01 to 0.8 dl / g. [ka] [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and R a is an aralkyl group, and multiple R b and R c are each independently a monovalent alkyl group, and two R are each independently R a , R b , R c and a hydrogen atom, a )(R b )]-, -[O-Si(R b )H]- and -[O-Si(R b )(R c The structural units of n=1, n=2, and n=3 may be arranged in a block fashion or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms. [2] The method for producing a vulcanized rubber according to item [1], further comprising adding a reaction inhibitor to the resin composition. [3] The method for producing vulcanized rubber according to item [1] or [2], wherein the reaction inhibitor is 1-ethynyl-1-cyclohexanol. [4] The method for producing a vulcanized rubber according to any one of items [1] to [3], wherein the platinum catalyst is contained in an amount of 0.00005 to 1.0 part by mass per 100 parts by mass of the copolymer (A). [5] The method for producing a vulcanized rubber according to any one of items [1] to [4], wherein the resin composition further contains a filler, and the filler is contained in an amount of 1 to 200 parts by mass per 100 parts by mass of the copolymer (A). [6] A bridged metallocene compound (a) represented by the following general formula [I], and at least one compound (b) selected from the group consisting of an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and a compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair;

[0023] A method for producing a vulcanized rubber according to any one of [1] to [5], comprising a first step of producing an ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A) by copolymerizing ethylene, an α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst comprising: [ka] (In formula [I], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are atoms or substituents selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and may be the same or different; R 13 and R 14 one of the groups is an aryl group or a substituted aryl group, and the other is an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; R 1 From R 14 Adjacent substituents up to may be bonded to each other to form a ring, Y is selected from Group 14 atoms; M is a titanium atom, a zirconium atom, or a hafnium atom; Q is selected from the group consisting of halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands capable of coordinating with lone electron pairs, and may be the same or different in combination; n is an integer from 1 to 4, and j is an integer from 1 to 4. [7]R 13 and R 14 Item [6], the method for producing a vulcanized rubber according to item [6], wherein either one of the above is a hydrocarbon group having 1 to 20 carbon atoms. [8] The method for producing a vulcanized rubber according to any one of items [1] to [7], wherein the LIM molding temperature is 120 to 250°C. [9] The method for producing a vulcanized rubber according to any one of items [1] to [7], wherein the LIM molding time is 1 to 500 seconds. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing vulcanized rubber that maintains its physical properties when molded by LIM and can be molded in a short time. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below.

[0011] <Ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A)> The ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A) of the present invention (hereinafter also referred to as "copolymer (A)") is a copolymer that satisfies the following requirements (i) to (vi).

[0012] <Requirement (i)> The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 1,000 to 50,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000, even more preferably 2,300 to 5,000, and particularly preferably 2,500 to 4,000. When the weight average molecular weight is within this range, physical properties can be maintained during LIM molding, and the molding time for the vulcanized rubber can be shortened. The measurement method is as described below.

[0013] <Requirement (ii)> The molecular weight distribution (Mw / Mn, where Mw is weight average molecular weight and Mn is number average molecular weight) measured by gel permeation chromatography (GPC) is 2.7 or less, preferably 2.6 or less, and more preferably 2.5 or less.

[0014] When the molecular weight distribution of the copolymer (A) is within the above range, the physical properties can be maintained when LIM molding is performed, and the molding time for the vulcanized rubber can be shortened.

[0015] The Mw, Mn, and Mw / Mn (molecular weight distribution) were determined using a gel permeation chromatograph HLC-8321 GPC / HT model (manufactured by Tosoh Corporation). The main measurement conditions were as follows:

[0016] Detector: differential refractometer Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 1 (each with an inner diameter of 7.8 mm and a length of 300 mm) Temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Injection volume: 400μL Sample concentration: ca 0.15% (w / v) Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm Column calibration: Monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: EPR conversion / calibration method taking viscosity into account A universal calibration curve of third-order polynomial was constructed by measuring 16 monodisperse standard polystyrenes (molecular weights: 20.6 million to 580) manufactured by Tosoh Corporation. EPR conversion parameters K: 0.000403, α: 0.700

[0017] <Requirement (iii)> 13 The intensity ratio Tαβ / Tαα in the C-NMR spectrum is 0.0 to 0.1, preferably 0 to 0.05, more preferably 0 to 0.01, and even more preferably 0 to 0.005. Here, as shown below, Tαβ is 13 indicates the peak intensity of carbon atoms having branches at the α- and β-positions in a C-NMR spectrum, and Tαα indicates the peak intensity of carbon atoms having branches at both α-positions.

[0018] [ka] When the strength ratio Tαβ / Tαα is within the above range, the physical properties can be maintained when LIM molding is performed, and the molding time for vulcanized rubber can be shortened.

[0019] <Requirement (iv)> The content of structural units derived from 5-vinyl-2-norbornene (hereinafter also referred to as "VNB") is in the range of 0.1 to 20.0 mass%, preferably 0.5 to 15.0 mass%, more preferably 1.0 to 14.0 mass%, even more preferably 1.5 to 13.0 mass%, and particularly preferably 2.0 to 12.0 mass%.

[0020] When the content of structural units derived from VNB is within the above range, rapid curing can be achieved, shortening the molding cycle, and when LIM molding is performed, the physical properties can be maintained and the molding time of the vulcanized rubber can be shortened. The mass fraction of the structural unit derived from VNB was determined using the apparatus and conditions described in the Examples section below. 13 It can be calculated by measuring the C-NMR spectrum.

[0021] <Requirement (v)> The structural units derived from VNB contain an endo structure and an exo structure, and the ratio of the endo structure / exo structure is 2.5 or less, preferably 2.4 or less, and more preferably 2.3 or less. There is no particular lower limit, but it is, for example, 0.1 or more.

[0022] When the endo / exo structure ratio is within this range, the physical properties can be maintained during LIM molding, and the molding time for vulcanized rubber can be shortened.

[0023] The endobody 13 The C-NMR spectrum shows a peak intensity of carbon atoms (9n) at around 114 ppm, and the exo-isomer 13 The peak intensity (9x) of the carbon atom at around 111.5 ppm in the C-NMR spectrum is shown.

[0024] [ka]

[0025] <Measurement of the intensity ratio Tαβ / Tαα and the endo / exo structure ratio> The intensity ratio Tαβ / Tαα and the endo structure / exo structure ratio can be determined as follows. Copolymer (A) 13 The C-NMR spectrum is measured using, for example, a 400 MHz NMR measuring device manufactured by JEOL Ltd. The measurement is carried out at 67.8 MHz, 25°C, and d6-benzene (128 ppm) as the standard using a mixed solution of hexachlorobutadiene / d6-benzene = 2 / 1 (volume ratio) prepared so that the sample concentration is 5 wt%. 13 C-NMR spectra are analyzed according to the suggestions of Lindeman Adams (Analysis Chemistry 43, p. 1245 (1971)) and J.C.Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)).

[0026] <Requirement (vi)> The intrinsic viscosity [η] measured in decahydronaphthalene at 135°C is in the range of 0.01 to 0.8 dl / g, preferably 0.02 to 0.6 dl / g, more preferably 0.03 to 0.4 dl / g, still more preferably 0.04 to 0.20 dl / g, and particularly preferably 0.05 to 0.15 dl / g.

[0027] When the intrinsic viscosity [η] is within the above range, the physical properties can be maintained when LIM molding is performed, and the molding time for the vulcanized rubber can be shortened.

[0028] In the copolymer (A) of the present invention, the molar ratio of structural units derived from ethylene (a1) to structural units derived from α-olefin (a2) [(a1) / (a2)] is usually 40 / 60 to 99.9 / 0.1, preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, and even more preferably 55 / 45 to 78 / 22.

[0029] By using the copolymer (A) that satisfies these requirements, a molded article excellent in rubber elasticity, mechanical strength and flexibility can be obtained.

[0030] The ethylene content (content of structural units derived from ethylene (a1)) and the α-olefin content (content of structural units derived from α-olefin (a2)) in copolymer (A) are 13 It can be determined by C-NMR.

[0031] α-olefin (a2) The α-olefin (a2) is preferably an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin (a2) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as 1-butene, 1-hexene, and 1-octene are preferred, with propylene being particularly preferred. Such α-olefins are preferred because they are relatively inexpensive in terms of raw material cost, the resulting copolymer (A) exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained.

[0032] The α-olefin (a2) may be used alone or in combination of two or more kinds.

[0033] The copolymer (A) may contain structural units derived from at least one biomass-derived monomer. The biomass-derived monomer used as the raw material for the copolymer (A) may be biomass-derived ethylene, biomass-derived α-olefin, or biomass-derived 5-vinyl-2-norbornene. An example of a biomass-derived α-olefin is biomass-derived propylene. The monomers used as the raw material for the copolymer (A) may contain only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers such as biomass-derived ethylene, biomass-derived α-olefins, and biomass-derived 5-vinyl-2-norbornene can be obtained by known methods. It is preferable that the copolymer (A) contain structural units derived from biomass-derived monomers from the viewpoint of reducing the environmental impact.

[0034] The copolymer (A) may contain at least one structural unit derived from a chemically recycled monomer. The chemically recycled monomer used as the raw material for the copolymer (A) may be ethylene derived from chemical recycling, an α-olefin derived from chemical recycling, or 5-vinyl-2-norbornene derived from chemical recycling. Furthermore, the monomer used as the raw material for the copolymer (A) may contain only a chemically recycled monomer, or may contain both a chemically recycled monomer and a fossil fuel-derived monomer. Chemically recycled monomers such as ethylene derived from chemical recycling, an α-olefin derived from chemical recycling, and 5-vinyl-2-norbornene derived from chemical recycling can be obtained by known methods. It is preferable that the copolymer (A) contains a structural unit derived from a chemically recycled monomer from the viewpoint of reducing the environmental load (mainly reducing waste).

[0035] <Method for producing ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A)> The copolymer (A) can be produced by the following production method. A bridged metallocene compound (a) represented by the following general formula [I], and at least one compound (b) selected from the group consisting of an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and a compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair; The copolymer can be produced by a production process comprising a step of copolymerizing ethylene, an α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst containing

[0036] This production method makes it possible to produce an ethylene-α-olefin-5-vinyl-2-norbornene copolymer (A) that satisfies the following requirements (i) to (vi): (i) The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 1,000 to 50,000. (ii) The molecular weight distribution (Mw / Mn, where Mw is the weight average molecular weight and Mn is the number average molecular weight) measured by gel permeation chromatography (GPC) is 2.7 or less. (iii) 13 The intensity ratio Tαβ / Tαα of the C-NMR spectrum is 0.0 to 0.1. (iv) The content of structural units derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0 mass %. (v) The structural units derived from 5-vinyl-2-norbornene contain an endo structure and an exo structure, and the ratio of the endo structure / exo structure is 2.5 or less. (vi) The intrinsic viscosity [η] measured in decahydronaphthalene at 135°C is in the range of 0.01 to 0.8 dl / g.

[0037] [ka] (In formula [I], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, R 9 , R 10 , R 11 and R 12 are atoms or substituents selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and may be the same or different; R 13 and R 14 one of the groups is an aryl group or a substituted aryl group, and the other is an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; R 1 From R 14 Adjacent substituents up to may be bonded to each other to form a ring, Y is selected from Group 14 atoms; M is a titanium atom, a zirconium atom, or a hafnium atom; Q is selected from the group consisting of halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands capable of coordinating with lone electron pairs, and may be the same or different in combination; n is an integer of 1 to 4; and j is an integer of 1 to 4. The bridged metallocene compound (a) represented by the general formula [I] is R 13 and R 14 Preferably, one of R is an aryl group or a substituted aryl group, and the other is a hydrocarbon group having 1 to 20 carbon atoms. 13 and R 14 In the relationship between 13 If so, the other is R 14 or one is R 14 If so, the other is R 13 This refers to the fact that...

[0038] ≪Compound (b)≫ The compound (b) is at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the crosslinked metallocene compound (a) to form an ion pair (hereinafter also referred to as an "ionizable ionic compound"), and preferably contains at least the organometallic compound (b-1).

[0039] (b-1) Organometallic compound As the organometallic compound (b-1), for example, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table represented by the following general formulas [VII] to [IX] are used.

[0040] (b-1a) General formula: R a m Al(OR b ) n H p X q ···[VII] (In formula [VII], R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.) An organoaluminum compound represented by.

[0041] Examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0042] (b-1b) General formula: M 2 AlR a 4···[VIII] (In formula [VIII], M2 indicates Li, Na, or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4. A complex alkylation product of aluminum and a metal of Group 1 of the periodic table, represented by:

[0043] Such compounds include LiAl(C2H5)4, LiAl(C7H 15 ) 4 can be exemplified.

[0044] (b-1c) General formula: R a R b M 3 [IX] (In formula [IX], R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M 3 is Mg, Zn or Cd. Dialkyl compounds containing a metal of Group 2 or 12 of the periodic table represented by

[0045] Among the organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, etc. are preferred. These organometallic compounds (b-1) may be used singly or in combination of two or more.

[0046] (b-2) Organoaluminum oxy compounds The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A No. 2-78687.

[0047] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0048] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0049] Examples of organoaluminum compounds used in preparing aluminoxane include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to the above (b-1a).

[0050] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among these, trimethylaluminum and triisobutylaluminum are particularly preferred.

[0051] The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0052] The benzene-insoluble organoaluminum oxy-compound (b-2) used in the present invention is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably 2% by weight or less, calculated as Al atoms, relative to 100% by weight of benzene. In other words, the benzene-insoluble organoaluminum oxy-compound is preferably one which is insoluble or poorly soluble in benzene.

[0053] The organoaluminum oxy compound (b-2) used in the present invention may also include boron-containing organoaluminum oxy compounds represented by the following general formula [X].

[0054] [ka] (In formula [X], R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, and R 2 ~R 5 may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.) The boron-containing organoaluminum oxy compound represented by the general formula [X] is General formula: R 1 -B(OH)2 [XI] (In formula [XI], R 1 is R in the general formula [X] 1 The alkylboronic acid represented by the formula (I) is the same group as that represented by the formula (I). The alkylboronic acid can be produced by reacting an alkylboronic acid represented by the formula (I) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

[0055] Examples of the alkylboronic acid represented by the general formula [XI] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid.

[0056] Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred, and these may be used singly or in combination of two or more.

[0057] Examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above (b-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred.

[0058] The organoaluminum oxy compounds (b-2) may be used singly or in combination of two or more.

[0059] (b-3) Ionized ionic compounds Examples of the ionizable ionic compound (b-3) include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. Such ionizable ionic compounds (b-3) can be used singly or in combination of two or more.

[0060] Specific examples of Lewis acids include compounds represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0061] The ionic compound may, for example, be a compound represented by the following general formula [XII].

[0062] [ka] (In formula [XII], R 1+ As for H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation containing a transition metal, etc. 2 ~R 5 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0063] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; Examples include dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0064] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0065] R 1+ As the cation, a carbonium cation, an ammonium cation, etc. are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are particularly preferred.

[0066] Examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0067] Specific examples of trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0068] Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0069] Specific examples of dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0070] Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula [XIII] or [XIV]: In the following formulas, Et represents an ethyl group.

[0071] [ka]

[0072] [ka] Specific examples of the borane compound include decaborane; salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0073] Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-7,8 -Dicarbaundecaborane, Dodecahydride-11-methyl-2,7-dicarbaundecaborane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium-1-carbaundecaborate, Tri(n-butyl)ammonium-1-carbadodecaborate, Tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium ) ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8-dicarbaundecaborate, tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate salts of anions such as tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxundecaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxundecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate(IV).

[0074] The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, usable examples include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids, such as salts with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0075] Among the ionizing ionic compounds (b-3), the above-mentioned ionic compounds are preferred, and among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are more preferred.

[0076] In the present invention, when a metallocene catalyst containing the bridged metallocene compound (a), an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, and an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used as the polymerization catalyst, extremely high polymerization activity can be exhibited in the production of the copolymer (A).

[0077] <Granular carrier (c)> In the present invention, the particulate carrier (c) (hereinafter also referred to as "carrier (c)") used as needed is an inorganic compound or an organic compound, and is a granular or fine particle solid.

[0078] The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound, specific examples of which include those described in WO2015 / 122495.

[0079] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

[0080] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica are particularly preferred.

[0081] Examples of organic compounds include granular or particulate solids with particle sizes in the range of 10 to 300 μm. Specific examples include (co)polymers mainly composed of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and (co)polymers mainly composed of vinylcyclohexane and styrene, and modified products thereof.

[0082] The polymerization catalyst used in the present invention comprises a metallocene compound (a), at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and an ionizing ionic compound (b-3), a carrier (c) used as needed, and may further contain a specific organic compound component (d) as needed.

[0083] ≪Organic compound component (d)≫ In the present invention, the organic compound component (d) is used as needed to improve the polymerization performance and the physical properties of the resulting polymer. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0084] The copolymer (A) of the present invention is produced by copolymerizing ethylene, an α-olefin, and VNB. When copolymerizing these monomers, the use method and addition order of the components constituting the polymerization catalyst described above can be selected arbitrarily, and examples thereof include the following methods (1) to (5). (1) A method in which the bridged metallocene compound (a) is added alone to a polymerization reactor. (2) A method in which the bridged metallocene compound (a) and the compound (b) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which a bridged metallocene compound (a) is supported on a carrier (c) and a compound (b) are added to a polymerization reactor in any order. (4) A method in which the catalyst component in which the compound (b) is supported on the carrier (c) and the bridged metallocene compound (a) are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which a bridged metallocene compound (a) and a compound (b) are supported on a carrier (c) is added to a polymerization reactor.

[0085] In each of the above methods (2) to (5), at least two of the bridged metallocene compound (a), the compound (b) and the support (c) may be contacted in advance.

[0086] In the above methods (4) and (5) in which the compound (b) is supported, an unsupported compound (b) may be added in any order, if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the support (c).

[0087] In addition, the solid catalyst component in which the bridged metallocene compound (a) is supported on the support (c) and the solid catalyst component in which the bridged metallocene compound (a) and the compound (b) are supported on the support (c) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may further have a catalyst component supported thereon.

[0088] The copolymer of the present invention can be suitably obtained by copolymerizing ethylene, an α-olefin, and VNB in ​​the presence of the above-mentioned polymerization catalyst.

[0089] When ethylene, α-olefins, and VNB are polymerized using the above-mentioned polymerization catalyst, the bridged metallocene compound (a) is usually used in an amount of 1×10 per liter of reaction volume. -12 ~1×10 -2 mol, preferably 1 x 10 -10 ~1×10 -5 It is used in molar amounts.

[0090] Compound (b-1) is used in an amount such that the molar ratio of compound (b-1) to the total transition metal atoms (M) in bridged metallocene compound (a) [(b-1) / M] is usually 0.01 to 50,000, preferably 0.05 to 10,000. Compound (b-2) is used in an amount such that the molar ratio of aluminum atoms in compound (b-2) to the total transition metal atoms (M) in bridged metallocene compound (a) [(b-2) / M] is usually 10 to 50,000, preferably 20 to 10,000. Compound (b-3) is used in an amount such that the molar ratio of compound (b-3) to the transition metal atoms (M) in bridged metallocene compound (a) [(b-3) / M] is usually 1 to 20, preferably 1 to 15.

[0091] In the present invention, the method for producing the copolymer can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization, and is not particularly limited, but preferably includes a step of obtaining the following polymerization reaction liquid.

[0092] The step of obtaining a polymerization reaction liquid is a step of copolymerizing ethylene, an α-olefin, and VNB in ​​the presence of the bridged metallocene compound (a) using an aliphatic hydrocarbon as a polymerization solvent to obtain a polymerization reaction liquid of a copolymer.

[0093] Examples of polymerization solvents include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These solvents can be used alone or in combination of two or more. Furthermore, olefins themselves can also be used as solvents. Among these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer.

[0094] The polymerization temperature is usually −50 to +200° C., preferably in the range of 0 to +150° C., and more preferably in the range of +70 to +130° C. Although it depends on the attainable molecular weight and polymerization activity of the metallocene catalyst system used, a higher temperature (+70° C. or higher) is desirable from the viewpoints of catalytic activity, copolymerizability, and productivity.

[0095] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, more preferably 1.2 to 4.0 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. Among these, in the present invention, it is preferable to adopt a method in which ethylene and a non-conjugated polyene are continuously supplied to a reactor to carry out copolymerization.

[0096] The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours, and more preferably 10 minutes to 2 hours.

[0097] The molecular weight of the resulting copolymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount is preferably about 0.001 to 100 nL per kg of olefin.

[0098] The present invention preferably comprises, after the step (1) of copolymerizing in the presence of the polymerization catalyst, a step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator.

[0099] As the catalyst deactivator, alcohols can be used, and methanol or ethanol is preferred, with ethanol being particularly preferred.

[0100] In step (2), the catalyst deactivator is preferably added in an amount of 0.05 to 3.0 mol, more preferably 0.06 to 2.5 mol, and even more preferably 0.08 to 2.0 mol relative to the organometallic compound (b-1). This allows for the generation of a small amount of catalyst denatured by the catalyst deactivator, such as ethanol, and moderate polymerization of low molecular weight components, resulting in a copolymer with a moderately broad molecular weight distribution. On the other hand, if too much catalyst deactivator is added, almost no denatured catalyst is generated, and almost no polymerization of low molecular weight components occurs, resulting in a narrow molecular weight distribution of the resulting copolymer. Furthermore, if no catalyst deactivator is added, or if the amount added is too small, a large amount of denatured catalyst is generated, resulting in the polymerization of a large amount of low molecular weight components, and the resulting copolymer tends to have an excessively high content of low molecular weight components.

[0101] <Hydrosilyl Group-Containing Compound (Y)> The hydrosilyl group-containing compound (Y) (hereinafter also referred to as "compound (Y)") is an organohydrogenpolysiloxane represented by the following formula (Y1): Compound (Y) has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in one molecule.

[0102] [ka]

[0103] The meanings of the symbols in formula (Y1) are as follows: n and p are each independently 0 or a positive number. m is 1 to 20. The sum of n, m, and p is 5 to 50. R a is an aralkyl group. Multiple R b and R c are each independently a monovalent alkyl group. b are each independently an alkyl group. c are each independently an alkyl group. b is R c In the alkyl group, some of the carbon atom-bonded hydrogen atoms may be substituted with halogen atoms. The two R are independently R a , R b , R c and a hydrogen atom, provided that when n=1, at least one of the two Rs is a hydrogen atom, and when n=0, both of the two Rs are hydrogen atoms. R is selected from the group consisting of R b or R c It is preferable that:

[0104] The crosslinked product obtained by crosslinking a composition containing the copolymer (A) and the compound (Y) as a crosslinking agent tends to have little odor and excellent heat aging resistance. In addition, the composition can be handled in air.

[0105] Compound (Y) is an organohydrogenpolysiloxane with a linear structure that has a relatively low degree of siloxane polymerization and has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule.

[0106] In formula (Y1), m is the number of diorganosiloxy units having silicon-bonded aralkyl groups, and is 1 to 20, preferably 2 to 10, more preferably 2 to 8, and even more preferably 3 to 6.

[0107] In formula (Y1), n ​​is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms. n can be 0 or 1, but when n=1, at least one of the two Rs is a hydrogen atom, and when n=0, both Rs are hydrogen atoms. In other words, the organohydrogenpolysiloxane represented by formula (Y1) has a structure containing at least two silicon-bonded hydrogen atoms per molecule. Note that even if n is a number other than 0 or 1, one or both of the Rs at both ends of the molecular chain can be silicon-bonded hydrogen atoms.

[0108] n is preferably a number other than 0 or 1, and more preferably a number satisfying n≧m. n is preferably 3-10, more preferably 3-9, and even more preferably 5-9.

[0109] In formula (Y1), p is the number of diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms. p may be 0, or may be the number obtained by subtracting the values ​​of n and m from the total degree of polymerization of siloxy units, which is represented by the sum of n, m, and p, as described below. p is preferably 0 to 12, more preferably 0 to 10, even more preferably 0 to 5, and particularly preferably 0 to 2.

[0110] In the organohydrogenpolysiloxane represented by formula (Y1), the diorganosiloxy unit (-[O-Si(R a )(R b)]-), organohydrogensiloxy units having silicon-bonded hydrogen atoms (-[O-Si(R b )H]-), and diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms (-[O-Si(R b )(R c The siloxy units such as (Y1)-) may be arranged in a block form or randomly, that is, the order of arrangement of the siloxy units in formula (Y1) is not particularly limited.

[0111] The compound (Y) has a relatively low degree of siloxane polymerization. In formula (Y1), the sum of the values ​​of n, m, and p is 5 to 50, preferably 5 to 20, and more preferably 5 to 15. In formula (Y1), it is preferable that m is 3 to 6, n is 5 to 9, and p is 0 to 2.

[0112] In formula (Y1), R a The number of carbon atoms in the aralkyl group in R is preferably 7 to 20, more preferably 7 to 15. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. a As R, an aralkyl group containing at least one branching unit represented by -CH(CH3)- in the alkanediyl group between the aryl group such as a phenyl group and the silicon atom is preferred. a As the alkyl group, an aralkyl group represented by —CH2—CH(CH3)—C6H5 is particularly preferred.

[0113] In formula (Y1), R b and R c The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, with a methyl group being particularly preferred.

[0114] The aralkyl group is a characteristic functional group that confers usefulness as a crosslinking agent to the hydrosilyl group-containing compound (Y). In particular, the presence of an aralkyl group together with a silicon-bonded hydrogen atom in the compound (Y) having n, m, and p within the above ranges tends to significantly improve the physical properties of the resulting crosslinked product.

[0115] The compound (Y) may be used alone or in combination of two or more. In the composition of the present disclosure, the content of compound (Y) is preferably 0.1 to 100 parts by mass, more preferably 0.3 to 75 parts by mass, even more preferably 0.5 to 50 parts by mass, still more preferably 0.8 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, relative to 100 parts by mass of copolymer (A).

[0116] <Platinum-based catalyst> Platinum catalysts for hydrosilyl crosslinking are widely used in hydrosilylation crosslinking reactions involving the addition of silicon-bonded hydrogen atoms to carbon-carbon double bonds. Platinum catalysts for hydrosilyl crosslinking are addition reaction catalysts, and any catalyst can be used without particular limitation as long as it promotes the addition reaction (hydrosilylation reaction of an alkene) between, for example, an alkenyl group contained in the copolymer (A) and a hydrosilyl group contained in the hydrosilyl group-containing compound (Y).

[0117] Examples of platinum-based catalysts include the fine powder metal platinum catalysts described in U.S. Pat. No. 2,970,150 and the like, the chloroplatinic acid catalysts described in U.S. Pat. No. 2,823,218 and the like, the complex compounds of platinum and hydrocarbons described in U.S. Pat. Nos. 3,159,601 and 159,662 and the like, the complex compounds of chloroplatinic acid and olefins described in U.S. Pat. No. 3,516,946 and the like, and the complex compounds of platinum and vinylsiloxanes described in U.S. Pat. Nos. 3,775,452 and 3,814,780 and the like.

[0118] Specific examples of platinum catalysts include platinum itself (platinum black); platinum complexes such as chloroplatinic acid, platinum-hydrocarbon complexes, platinum-vinylsiloxane complexes, platinum-alcohol complexes, chloroplatinic acid-olefin complexes, and chloroplatinic acid-vinylsiloxane complexes. Among these, platinum-vinylsiloxane complexes are preferred due to their high catalytic activity. Examples of platinum-vinylsiloxane complexes include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complexes. The platinum-based catalyst may be supported on a carrier such as alumina or silica.

[0119] The platinum catalyst may be used alone or in combination of two or more. In the composition of the present disclosure, the content of the platinum-based catalyst (e.g., platinum complex) is preferably 0.00005 to 1.0 part by mass, more preferably 0.0001 to 0.10 part by mass, even more preferably 0.0005 to 0.050 part by mass, and particularly preferably 0.001 to 0.010 part by mass, relative to 100 parts by mass of the copolymer (A). The composition having a platinum-based catalyst content equal to or greater than the lower limit exhibits excellent room-temperature curing properties. The coating layer obtained from the composition having a platinum-based catalyst content equal to or less than the upper limit exhibits excellent physical properties, such as mechanical properties.

[0120] <Reaction inhibitor> The copolymer composition of the present invention preferably contains a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation addition reaction to alkene) between the alkenyl group of the copolymer (A) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). The addition of a reaction inhibitor is preferred in that it stabilizes the processability of the composition during kneading and molding.

[0121] Examples of reaction inhibitors include benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-ethynyl-1-cyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; acrylonitrile; amide compounds such as N,N-diallylacetamide, N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalic acid diamide, and N,N,N',N'-tetraallyl-p-phthalic acid diamide; and others, such as sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, 1-ethynyl-1-cyclohexanol is particularly preferred. The reaction inhibitor may be used alone or in combination of two or more.

[0122] The reaction inhibitor is contained in an amount of preferably 0.001 to 5 parts by mass, more preferably 0.005 to 1 part by mass, still more preferably 0.01 to 0.8 parts by mass, and particularly preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the copolymer (A).

[0123] <Filler> The copolymer composition of the present invention preferably contains a filler, such as light calcium carbonate, heavy calcium carbonate, carbon black, silica, talc, clay, etc., with carbon black being preferred. The filler may be used alone or in combination of two or more. The resin composition contains the filler in an amount of preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, even more preferably 30 to 100 parts by mass, and particularly preferably 50 to 80 parts by mass, per 100 parts by mass of copolymer (A).

[0124] <Other ingredients> The present composition may contain other components depending on the purpose, for example, at least one selected from the group consisting of a polymer crosslinking aid other than the copolymer (A), a vulcanization accelerator, a vulcanization aid, a softener, a processing aid, an activator, a moisture absorbent, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, a thickener, a foaming agent, and a foaming aid. Each additive may be used alone or in combination of two or more.

[0125] <Method of manufacturing resin composition> The present composition can be prepared by kneading the copolymer (A), the compound (Y), the platinum-based catalyst, and other components that are blended as needed, at a desired temperature using a kneading machine such as a mixer, kneader, or roll.

[0126] Specifically, the present composition can be prepared by kneading the components using a conventional kneading machine such as a mixer or kneader at a predetermined temperature for a period of time, for example, at 80 to 200°C for 3 to 30 minutes, adding other components to the resulting kneaded mixture as needed, and kneading the mixture using a roll at a predetermined temperature for a period of time, for example, at a roll temperature of 30 to 80°C for 1 to 30 minutes.

[0127] <Manufacturing method of vulcanized rubber> The vulcanized rubber of the present invention can be prepared, for example, by mixing the copolymer (A), the hydrosilyl group-containing compound (Y), and the platinum catalyst, and, if necessary, the other components described above.

[0128] The composition of the present invention can be produced, for example, by a method comprising the steps of: a first step of producing a copolymer (A) in the presence of an olefin polymerization catalyst containing a bridged metallocene compound (a) and a compound (b); a second step of kneading the copolymer (A) with a hydrosilyl group-containing compound (Y); a third step of kneading the copolymer (A) with a platinum-based catalyst to obtain a resin composition; and a fourth step of performing LIM molding.

[0129] In the second step, the hydrosilyl group-containing compound (Y) is added to the copolymer (A) obtained in the first step. In the second step, the above-mentioned other components may be added as necessary. In the second step, the components may be kneaded using a kneading device such as a Banbury mixer, a kneader, or an internal mixer. The kneading temperature in the second step is preferably 10 to 170° C. The kneading time in the second step is preferably 1 to 20 minutes, more preferably 2 to 12 minutes.

[0130] In the third step, a platinum catalyst is added to the composition obtained in the second step. In the third step, the above-mentioned other components may be added as necessary. The preparation temperature in the third step is preferably 0 to 100°C, more preferably 5 to 50°C, and even more preferably 10 to 40°C, and may be, for example, 40°C or lower, or 30°C or lower. It is preferable to carry out the third step while maintaining the solution temperature within the above range. The kneading time in the third step is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes.

[0131] In the fourth step, the resin composition obtained in the third step is molded by LIM. LIM molding can be performed using a LIM molding machine. The molding temperature for LIM molding is preferably 120 to 250°C, more preferably 130 to 200°C, and even more preferably 150 to 185°C, and the molding time is preferably 1 to 500 seconds, more preferably 8 to 400 seconds, and even more preferably 10 to 350 seconds. [Example]

[0132] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0133] [Manufacturing Example 1] Dehydrated and purified n-hexane was fed at a rate of 47.7 L / h into one feed port of a 136 L continuous polymerization reactor, and [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5A hexane solution of 0.55 mmol / L (2,7-di-t-butylfluorenyl)zirconium dichloride was continuously fed at a rate of 0.27 L / h, a hexane solution of triisobutylaluminum (5.0 mmol / L) was continuously fed at a rate of 1.2 L / h, a hexane slurry of 0.15 mmol / L N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (CB-4) was continuously fed at a rate of 4.0 L / h, and 5-vinyl-2-norbornene (VNB) was continuously fed at a rate of 1430 g / h (total hexane: 53.2 L / h). Simultaneously, ethylene (2.1 kg / h), propylene (3.5 kg / h), and hydrogen (1000 nL / h) were continuously fed to another feed port of the polymerization reactor. Continuous solution polymerization was carried out under the conditions of a polymerization temperature of 115 °C, a total pressure of 3.3 MPaG, and a residence time of 23 minutes.

[0134] The hexane solution of ethylene-propylene-VNB copolymer produced in the polymerization reactor was continuously discharged through an outlet on the side wall of the polymerization reactor, and the pressure in the jacket was 10 kg / cm. 2 The hexane solution of ethylene-propylene-VNB copolymer heated to about 115°C in the steam-jacketed connecting pipe was maintained at a constant pressure of 10 kg / cm by adjusting the opening of the liquid level control valve at the end of the connecting pipe so that the solution volume in the polymerization vessel was maintained at about 28 L. 2 The liquid was continuously fed to the flash tank through the inner pipe of a double pipe heated with steam. A supply port for injecting methanol, a catalyst deactivator, was attached immediately after the liquid level control valve, and methanol was injected as a 0.5 vol% diluted hexane solution at a rate of 1.0 L / h to join the hexane solution. During transfer to the flash tank, the solution temperature and the pressure control valve opening were set so that the pressure inside the flash tank was maintained at 0.03 MPaG and the temperature of the vapor in the flash tank was maintained at 210°C. As a result, ethylene-propylene-VNB copolymer (A-1) was obtained at a production rate of 4.0 kg / h. The polymerization mileage of the ethylene-diene copolymer was 22 kg / mmol-Zr, and the intrinsic viscosity [η] of the ethylene-propylene-VNB copolymer (A-1) was 0.08 dl / g. The ethylene content was 45% by mass, and the VNB content was 11% by mass. The physical properties of the obtained ethylene-propylene-VNB copolymer (A-1) are shown in Table 1.

[0135] [Method for measuring physical properties of copolymer (A-1)] The physical properties of the copolymer (A-1) were measured as follows.

[0136] <Composition of copolymer (A-1), Tαβ / Tαα, endo structure / exo structure ratio> The content of each structural unit in the copolymer (A-1) is: 13 The C-NMR spectrum of copolymer (A) was calculated using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.) under the conditions of a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000. 13 C-NMR spectra were measured. The Tαβ / Tαα and endo / exo structure ratios were determined according to the proposals of Lindeman Adams (Analysis Chemistry 43, p. 1245 (1971)) and JC Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)).

[0137] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn> The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the copolymer (A) are values ​​measured by gel permeation chromatography (GPC) in terms of polystyrene. The measuring apparatus and conditions are as follows. The molecular weight was calculated based on a calibration curve prepared using commercially available monodisperse polystyrene and converted into a polystyrene equivalent. Apparatus: Gel permeation chromatograph HLC-8321 GPC / HT type (Tosoh Corporation) Detector: differential refractometer Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 1 (each with an inner diameter of 7.8 mm and a length of 300 mm) Temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Injection volume: 400μL Sample concentration: ca 0.15% (w / v) Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm Column calibration: Monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: EPR conversion / calibration method taking viscosity into account A universal calibration curve of third-order polynomial was constructed by measuring 16 monodisperse standard polystyrenes (molecular weights: 20.6 million to 580) manufactured by Tosoh Corporation. EPR conversion parameters K: 0.000403, α: 0.700

[0138] [Table 1]

[0139] <Crosslinking agent (Y-1)> The crosslinking agents used in the examples are as follows: 536 g of methylhydrogenpolysiloxane represented by the following formula (a-1-1) was placed in a reactor and heated to 40°C while stirring under a nitrogen stream. 0.4 g of a toluene solution of platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex (Pt concentration 0.3 wt %) was added, and 265 g of α-methylstyrene was added dropwise while maintaining the reaction temperature at 40 to 90°C.

[0140] [ka]

[0141] After the dropwise addition was completed, stirring was continued for 2 hours at 85°C, and then 0.5 g of the reaction solution was sampled, and the reaction rate of the Si-H group was confirmed to be about 36% by the alkali decomposition gas generation method (the remaining Si-H group was decomposed with an ethanol / aqueous solution of KOH, and the reaction rate of the Si-H group was calculated from the volume of the generated hydrogen gas). The reaction solution was then heated to 135°C under reduced pressure for 2 hours to distill off low boiling points, and 673 g of crosslinking agent (Y-1) was obtained.

[0142] The resulting crosslinking agent (Y-1) was 29 It was confirmed by Si-NMR that the compound was the compound represented by the following formula (a-1). The viscosity of the obtained crosslinking agent (Y-1) was measured at 25°C using an Ubbelohde viscometer according to JIS Z 8803. 2 / s.

[0143] [ka]

[0144] <Other ingredients> Other components used in the examples and comparative examples are as follows: Carbon black: Asahi #50HG manufactured by Asahi Carbon Co., Ltd. Reaction inhibitor: 1-ethynyl-1-cyclohexanol, manufactured by Nissin Chemical Industry Co., Ltd. Platinum catalyst: SRX212 Catalyst manufactured by Dow Toray Industries, Inc., a catalyst solution containing 1% by mass or more but less than 3% by mass of a complex salt of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane

[0145] [Example 1] In the first step, 100 parts by mass of the ethylene-propylene-VNB copolymer (A-1) obtained in Production Example 1 above was mixed with 60 parts by mass of carbon black and 17.4 parts by mass of the crosslinking agent (Y-1) using a degassing conditioning mixer, Awatori Neritarou (Thinky Corporation, AR-250, rotation / revolution propellerless mixing method), and 0.3 parts by mass of a reaction inhibitor was added. The mixture was kneaded for 10 minutes to obtain Compound 1. Next, in the second step, 0.2 parts by mass of a platinum catalyst was added to the mixture 1 obtained in the first step, and the mixture was stirred for 1 minute using a defoaming conditioning mixer, Awatori Neritaro, to obtain the mixture 2. Next, in the third step, the compound obtained in the second step was wound around a three-roll mill (BR-230BV, manufactured by Imex Co., Ltd., roll dimensions: φ86.5 × 230 mmL) and kneaded at room temperature for 10 minutes to obtain an uncrosslinked composition. The compound obtained in the second step was placed in a mold (40 mm × 40 mm × 2 mm thick) in a liquid injection molding machine (LIM molding machine: VS-200-75-L) manufactured by Yamashiro Seiki Seisakusho Co., Ltd. The prepared composition was then injected into the mold and crosslinked for 300 seconds to obtain a crosslinked molded product. Molding was performed under the following conditions: mold temperature: 170°C, injection speed: 4.5 mm / sec, injection time: 10 seconds, and holding pressure: 1 MPa.

[0146] [Example 2] An uncrosslinked composition of Example 2 was produced in the same manner as in Example 1, except that the crosslinking time was set to 150 seconds, and then a crosslinked molded article was produced.

[0147] [Example 3] An uncrosslinked composition of Example 3 was produced in the same manner as in Example 1, except that the crosslinking time was set to 60 seconds, and then a crosslinked molded article was produced.

[0148] [Example 4] An uncrosslinked composition of Example 3 was produced in the same manner as in Example 1, except that the crosslinking time was set to 15 seconds, and then a crosslinked molded article was produced.

[0149] [Comparative Example 1] The same procedure as in Example 1 was carried out using the ethylene-propylene-5-vinyl-norbornene copolymer (A-1) obtained in Production Example 1 to obtain a second-stage compound. The compound was then pressed in a mold at 170°C for 900 seconds using a press molding machine to obtain a crosslinked molded sheet having a thickness of 2 mm.

[0150] Comparative Example 2 An uncrosslinked composition of Comparative Example 2 was produced in the same manner as in Comparative Example 1, except that the crosslinking time was set to 300 seconds, and then a crosslinked molded article was produced.

[0151] [Hardness test (Durometer-A)] Six 2 mm thick sheet-like crosslinked molded articles obtained in the Examples and the like were stacked together to form a 12 mm thick test piece, and the hardness (Duro-A) was measured in accordance with JIS K 6253-3. The test piece was sized so that the measurement surface could be measured with the tip of an indenter positioned at least 12 mm away from the end of the test piece.

[0152] [Tensile test: tensile stress at break, tensile elongation at break, modulus] The crosslinked sheets prepared in the examples and the like were punched out to prepare No. 3 dumbbell test pieces described in JIS K 6251 (1993). Using these test pieces, a tensile test was carried out in accordance with the method specified in JIS K 6251, paragraph 3, at a measurement temperature of 25°C and a tensile speed of 500 mm / min, and the tensile stress at break (TB), tensile elongation at break (EB), tensile stress at an elongation rate of 25% (25% modulus (M25)), and tensile stress at an elongation rate of 50% (50% modulus (M50)) were measured.

[0153] [Method for evaluating scratch resistance] The surface of the crosslinked molded article obtained in each example was scratched with a brass rod having a circular, flat tip with a diameter of 3 mm, and evaluated according to the following criteria. The evaluation was carried out by three panelists, and the average of the results was calculated. 5: No scratches. 4: Very slight scratches. 3: Slight scratches. 2: Scratches. 1: Clear scratches.

[0154] [Table 2]

Claims

1. an ethylene / α-olefin / 5-vinyl-2-norbornene copolymer (A) that satisfies the following requirements (i) to (vi); a hydrosilyl group-containing compound (Y) which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule; Platinum-based catalysts A method for producing vulcanized rubber, comprising a step of LIM molding a resin composition comprising: (i) a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 1,000 to 50,000; (ii) the molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) is 2.7 or less; (iii) 13 The intensity ratio Tαβ / Tαα in the C-NMR spectrum is 0.0 to 0.1; (iv) the content of structural units derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass; (v) the structural units derived from 5-vinyl-2-norbornene contain an endo structure and an exo structure, and the ratio of the endo structure / exo structure is 2.5 or less; (vi) The intrinsic viscosity [η] measured in decahydronaphthalene at 135° C. is in the range of 0.01 to 0.8 dl / g. 【Chemistry 1】 [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and R a is an aralkyl group, and multiple R b and R c are each independently a monovalent alkyl group, and two R are each independently R a , R b , R c and a hydrogen atom, a ) (R b )]-,-[O-Si(R b )H]- and -[O-Si(R b ) (R c ) )]- may be arranged in a block form or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

2. The method for producing a vulcanized rubber according to claim 1 , wherein the resin composition further contains a reaction inhibitor.

3. The method for producing vulcanized rubber according to claim 1, wherein the reaction inhibitor is 1-ethynyl-1-cyclohexanol.

4. The method for producing a vulcanized rubber according to claim 1, wherein the platinum catalyst is contained in an amount of 0.00005 to 1.0 part by mass per 100 parts by mass of the copolymer (A).

5. The method for producing a vulcanized rubber according to claim 1, wherein the resin composition further contains a filler in an amount of 1 to 200 parts by mass per 100 parts by mass of the copolymer (A).

6. A bridged metallocene compound (a) represented by the following general formula [I], and at least one compound (b) selected from the group consisting of an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and a compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair; 2. A method for producing a vulcanized rubber according to claim 1, comprising a first step of copolymerizing ethylene, an α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst comprising: 【Chemistry 2】 (In formula [I], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are atoms or substituents selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and may be the same or different; R 13 and R 14 one of the groups is an aryl group or a substituted aryl group, and the other is an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; R 1 From R 14 Adjacent substituents up to may be bonded to each other to form a ring, Y is selected from Group 14 atoms; M is a titanium atom, a zirconium atom, or a hafnium atom; Q is selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and may be the same or different in combination; n is an integer from 1 to 4, and j is an integer from 1 to 4.

7. R 13 and R 14 The method for producing vulcanized rubber according to claim 6, wherein either one of the above is a hydrocarbon group having 1 to 20 carbon atoms.

8. The method for producing vulcanized rubber according to claim 1, wherein the molding temperature for LIM molding is 120 to 250°C.

9. The method for producing vulcanized rubber according to claim 1, wherein the molding time of the LIM molding is 1 to 500 seconds.

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