Ethylene-α-olefin-5-vinyl-2-norbornene copolymer, composition containing the copolymer, and crosslinked body

Abstract

[Problem] The purpose of the present invention is to obtain an ethylene / α-olefin / non-conjugated polyene copolymer which can be applied to LIM molding or other wide range of molding methods, and is suitable for achievement of a molded body that has excellent mechanical strength. [Solution] The present invention relates to an ethylene / α-olefin / 5-vinyl-2-norbornene copolymer which is characterized by satisfying the requirements (i) to (vi) described below. (i) The weight average molecular weight is within 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) as determined by gel permeation chromatography (GPC) is 2.7 or less. (iii) The intensity ratio Tαβ / Tαα of 13C-NMR spectrum is 0.0 to 0.1. (iv) The content of a constituent unit derived from 5-vinyl-2-norbornene is within the range of 0.1% by mass to 20.0% by mass. (v) The constituent unit derived from 5-vinyl-2-norbornene comprises an endo structure and an exo structure; and the (endo structure) / (exo structure) ratio is 2.5 or less. (vi) The limiting viscosity (η) as measured in decahydronaphthalene at 135°C is within the range of 0.01 dl / g to 0.8 dl / g.

Description

[Technical Field]

[0001] The present invention relates to ethylene-α-olefin-5-vinyl-2-norbornene copolymer, compositions containing the copolymer, and crosslinked bodies. [Background technology]

[0002] In recent years, Liquid Injection Molding (LIM), or injection molding of liquid rubber, has become widely adopted. In particular, it has recently attracted attention as a molding method due to its advantages such as enabling rapid automated molding and composite molding with plastics (insert molding). The characteristics of LIM molding include: (1) continuous automation of processes such as material transfer, metering, mixing, and injection, and reduction of power requirements; (2) shortening of the molding cycle due to rapid curing; (3) no reaction by-products; (4) no contamination of foreign matter; and (5) material fluidity. 、 Advantages include low-pressure molding and a wide curing temperature range, which enables insert molding and other composite molding processes.

[0003] Several compositions have been proposed that are suitable for LIM molding, for example, those containing ethylene-α-olefin-non-conjugated polyene copolymers (Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 43433870 [Patent Document 2] Patent No. 3908001 [Patent Document 3] Patent No. 3901599 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, while conventionally proposed ethylene-α-olefin-non-conjugated polyene copolymers exhibit excellent fluidity and can be applied to LIM molding or a wide range of other molding methods, their mechanical strength has not been able to satisfy that of cured materials.

[0006] The object of the present invention is to obtain an ethylene-α-olefin-non-conjugated polyene copolymer that can be applied to LIM molding or a wide range of other molding methods and is suitable for obtaining molded articles with excellent mechanical strength. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of this invention have discovered that an ethylene-α-olefin-non-conjugated polyene copolymer having a specific structure can be applied to LIM molding or a wide range of other molding methods, and that molded articles with excellent mechanical strength can be obtained, thus completing the present invention.

[0008] In other words, the present invention relates to the following [1] to [6].

[0009] [1] Ethylene-α-olefin-5-vinyl-2-norbornene copolymer characterized by satisfying the following requirements (i) to (vi); (i) The weight-average molecular weight is 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 1C-NMR spectrum is between 0.0 and 0.1. (iv) The content of the constituent units derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass. (v) The constituent units derived from 5-vinyl-2-norbornene include endo and exo structures, and the ratio of endo to exo structures 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.

[0010] [2] The copolymer described in item [1], wherein the B value represented by the following formula (i) is 1.10 or greater.

[0011] B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) (Here, [E], [X], and [Y] represent the mole fractions of ethylene, α-olefin, and 5-vinyl-2-norbornene, respectively, and [EX] represents the ethylene-α-olefin dyad chain fraction.) [3] A copolymer composition comprising the ethylene-α-olefin-5-vinyl-2-norbornene copolymer described in item [1].

[0012] [4] term [3] A crosslinked body obtained by crosslinking the copolymer composition described above.

[0013] [5] (a) A crosslinked metallocene compound represented by the following general formula [I], and (b) At least one compound (b) selected from the group consisting of organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds (b-3) that react with the crosslinked metallocene compound (a) to form an ion pair. A method for producing an ethylene-α-olefin-5-vinyl-2-norbornene copolymer that satisfies the following requirements (i) to (vi), characterized by comprising the step of copolymerizing ethylene, α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst containing: (i) The weight-average molecular weight is 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) 13The intensity ratio Tαβ / Tαα of the 13C-NMR spectrum is 0.0 to 0.1. (iv) The content of the structural unit derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass. (v) The structural unit derived from 5-vinyl-2-norbornene includes an endo-form structure and an exo-form structure, and the ratio of the endo-form structure to the exo-form 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.

[0014] [Chemical formula] (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 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, and may be the same or different from each other, R 13 and R 14 either one of them 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 to R 14 adjacent substituents up to may be bonded to each other to form a ring, Y is selected from Group 14 atoms, and M is a titanium atom, a zirconium atom, or a hafnium atom, Q is selected from halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons, in identical or different combinations; n is an integer from 1 to 4; and j is an integer from 1 to 4. [6] R 13 and R 14 The other side is an alkyl group having 1 to 20 carbon atoms. Term [5] A method for producing the ethylene-α-olefin-5-vinyl-2-norbornene copolymer described above. [Effects of the Invention]

[0015] The ethylene-α-olefin-5-vinyl-2-norbornene copolymer of the present invention has a high crosslinking efficiency of the constituent units derived from 5-vinyl-2-norbornene (VNB). Therefore, even with a small amount of copolymerized VNB, the resulting molded article can achieve high strength and has a good balance between crosslinked properties and processability when not crosslinked. [Modes for carrying out the invention]

[0016] <Ethylene-α-olefin-5-vinyl-2-norbornene copolymer> The ethylene-α-olefin-5-vinyl-2-norbornene copolymer of the present invention (hereinafter sometimes referred to as "polymer") is a copolymer that satisfies the following requirements (i) to (vi).

[0017] <Requirement (i)> The weight-average molecular weight is in the range of 1,000 to 50,000, preferably 1,500 to 35,000, more preferably 2,000 to 30,000, and most preferably 2,300 to 10,000.

[0018] The copolymer of the present invention has a molecular weight within the specified range. 、 It has good fluidity, can be molded at low pressure, and the resulting molded product has high mechanical strength.

[0019] <Requirement (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, preferably 2.6 or less.

[0020] The copolymer of the present invention, when having such a molecular weight distribution, yields a molded article with high mechanical strength.

[0021] Mw, Mn, and Mw / Mn (molecular weight distribution) were determined using a gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation). The main measurement conditions were as follows.

[0022] Detector: Differential refractometer Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 1 (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Injection volume: 400 μL Sample concentration: Ca 0.15% (w / v) Sample filtration: Filtered using a 1.0 μm pore size sintered filter. Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation) Molecular weight conversion: EPR conversion / Calibration method considering viscosity Sixteen monodisperse standard polystyrene samples (molecular weights ranging from 20.6 million to 5.8 million) manufactured by Tosoh Corporation were measured, and a universal calibration curve for cubic polynomials was created.

[0023] EPR conversion parameters: K: 0.000403, α: 0.700 <Requirement (iii)> 13 The intensity ratio Tαβ / Tαα of the 1C-NMR spectrum is 0.0 to 0.1, preferably 0 to 0.05, and more preferably 0 to 0.01. Here, as shown below, Tαβ is 13The peak intensities for carbon atoms with branching at the α and β positions in the 1C-NMR spectrum are shown, with Tαα indicating the peak intensity for carbon atoms with branching at both α positions.

[0024] [ka] When the strength ratio Tαβ / Tαα is within this range, molded articles obtained from ethylene-α-olefin-5-vinyl-2-norbornene copolymers are superior in terms of strength.

[0025] <Requirement (iv)> The content of constituent units derived from 5-vinyl-2-norbornene (hereinafter sometimes referred to as "VNB") is in the range of 0.1 to 20.0% by mass, preferably 0.5 to 15.0% by mass, and more preferably 1.0 to 10.0% by mass.

[0026] When the content of the constituent units derived from VNB falls within the above range, rapid curing shortens the molding cycle, resulting in a molded product with high mechanical strength.

[0027] <Requirement (v)> The constituent units derived from VNB include endo and exo structures, and the ratio of endo to exo structures is 2.5 or less, preferably 2.4 or less, and more preferably 2.3 or less.

[0028] When the ratio of endo-form to exo-form is within this range, the mechanical strength of molded articles obtained from ethylene-α-olefin-VNB copolymer is high.

[0029] endo body 13 The C-NMR spectrum shows a peak intensity of carbon atoms (9n) around 114 ppm, and the exo form is shown. 13 C-NMR spectrum, peak intensity of carbon atoms around 111.5 ppm (9x) of show.

[0030] [ka] <Measurement of intensity ratio Tαβ / Tαα and endo-body structure / exo-body structure ratio> The intensity ratio Tαβ / Tαα and the endo-body structure / exo-body structure ratio can be determined as follows.

[0031] copolymer 13 The 13C-NMR spectrum is measured using, for example, a 400MHz NMR spectrometer manufactured by JEOL Ltd. The measurement is performed using a mixed solution of hexachlorobutadiene / d6-benzene = 2 / 1 (volume ratio) prepared to a sample concentration of 5% by weight, at 67.8MHz, 25°C, and d6-benzene (128 ppm) as the reference. 13 The 1C-NMR spectrum will be analyzed according to the methods proposed by Lindemann-Adams (Analysis Chemistry 43, p 1245 (1971)) and JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)).

[0032] <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 0.03 to 0.6 dl / g, more preferably 0.05 to 0.5 dl / g, and most preferably 0.05 to 0.4 dl / g.

[0033] When the intrinsic viscosity [η] is within the above range, the copolymer has good fluidity, can be molded at low pressure, and the resulting molded product has high mechanical strength.

[0034] The ethylene-α-olefin-VNB copolymer of the present invention preferably has the following requirements in addition to the above requirements (i) to (vi) (vii) It satisfies the condition.

[0035] <Requirements> (vii) > The B value represented by the following formula (i) is 1.10 or greater, more preferably 1.10 to 1.40, and most preferably in the range of 1.14 to 1.37.

[0036] B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) Here, [E], [X], and [Y] represent the mole fractions of ethylene (a1), α-olefins with 3 to 20 carbon atoms (a2), and VNB(c), respectively, and [EX] represents the ethylene (a1)-α-olefin (a2) dyad chain fraction.

[0037] Ethylene-α-olefin-VNB copolymers that satisfy the above range for B value exhibit excellent low-temperature properties.

[0038] The above B value was measured using o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) as the measurement solvent at a measurement temperature of 120°C. 13 The 13C-NMR spectrum (100 MHz, JEOL ECX400P) was measured and calculated based on the above formula (i).

[0039] The ethylene-α-olefin-VNB copolymer of the present invention is typically 、 The molar ratio [(a1) / (a2)] of structural units derived from ethylene (a1) and structural units derived from α-olefins (a2) having 3 to 20 carbon atoms is 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.

[0040] By using copolymers that satisfy these requirements, molded articles with excellent rubber elasticity, mechanical strength, and flexibility can be obtained.

[0041] Furthermore, the amount of ethylene in the copolymer (content of constituent units derived from ethylene (a1)) and the amount of α-olefin (content of constituent units derived from α-olefin (a2)) are as follows: 13 This can be determined by 13C-NMR.

[0042] <α-olefin (a2)> Examples of the above α-olefins (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. Of these, α-olefins having 3 to 8 carbon atoms, such as 1-butene, 1-hexene, and 1-octene, are preferred, with propylene and 1-butene being particularly preferred. Such α-olefins are preferred because their raw material costs are relatively low, the resulting copolymers exhibit excellent mechanical properties, and molded articles with rubber elasticity can be obtained.

[0043] The above α-olefin (a2) may be used alone or in combination of two or more types.

[0044] Ethylene (a1), α-olefin (a2), and 5-vinyl-2-norbornene may each be derived from biomass.

[0045] <Method for producing ethylene-α-olefin-VNB copolymer> Ethylene-α-olefin-5-vinyl-2-norbornene copolymer (hereinafter sometimes abbreviated as "polymer") can be produced by the following manufacturing method. (a) A crosslinked metallocene compound represented by the following general formula [I], and (b) At least one compound (b) selected from the group consisting of organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds (b-3) that react with the crosslinked metallocene compound (a) to form an ion pair. It can be produced by a manufacturing method characterized by comprising the step of copolymerizing ethylene, α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst containing the above.

[0046] By this manufacturing method, an ethylene-α-olefin-5-vinyl-2-norbornene copolymer that satisfies the following requirements (i) to (vi) can be produced. (i) The weight-average molecular weight is 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 1C-NMR spectrum is between 0.0 and 0.1. (iv) The content of the constituent units derived from 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass. (v) The constituent units derived from 5-vinyl-2-norbornene include endo and exo structures, The ratio of endo structure to 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.

[0047] [ka] (In equation [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 These 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 Either one of them is an aryl group or a substituted aryl group, and the other is an atom or 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 The adjacent substituents up to this point may be bonded to each other to form a ring. Y is selected from Group 14 atoms, and M is a titanium atom, zirconium atom, or hafnium atom. Q is selected from halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons, in identical or different combinations; n is an integer from 1 to 4; and j is an integer from 1 to 4. The crosslinked metallocene compound (a) represented by the above general formula [I] is R 13 and R 14 Preferably, one of them is an aryl group or a substituted aryl group, and the other is a hydrocarbon group having 1 to 20 carbon atoms. Here, one and the other are R 13 and R 14 In relation to R 13 If so, the other party is R 14 And either one is R 14 If so, the other party is R 13 This refers to the fact that...

[0048] ≪Compound (b)≫ The compound (b) is at least one compound selected from (b-1) organometallic compounds, (b-2) organoaluminum oxy compounds, and (b-3) ionized ionic compounds, and preferably includes at least the organometallic compound (b-1).

[0049] (b-1) Organometallic compound As the organometallic compound (b-1), for example, organometallic compounds of groups 1, 2 and 12, and 13 of the periodic table, such as those shown in the following general formulas [VII] to [IX], can be used.

[0050] (b-1a) General formula: R a m Al(OR b ) n H p X q ...[VII] (In formula [VII], R a and R bmay be the same or different from each other, and represents 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 ).

[0051] 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, diisobutylaluminum hydride.

[0052] (b-1b) General formula: M 2 AlR a 4···[VIII] (In formula [VIII], M 2 represents Li, Na or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkyl compound of a Group 1 metal of the periodic table and aluminum.

[0053] Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4, etc.

[0054] (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 from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M 3 is Mg, Zn or Cd.) A dialkyl compound having a Group 2 or Group 12 metal of the periodic table.

[0055] Among the organometallic compounds (b-1) listed above, triethylaluminum, triisobutylaluminum, and tri - Organoaluminum compounds such as n-octylaluminum are preferred. Furthermore, such organometallic compounds (b-1) may be used individually or in combination of two or more.

[0056] (b-2) Organoaluminum oxy compounds The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or it may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687.

[0057] Conventionally known aluminoxanes can be produced by, for example, the following methods, and are usually obtained as solutions in a hydrocarbon solvent: (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate, and the adsorbed water or crystal water is reacted with the organoaluminum compound. (2) A method in which an organoaluminum compound such as trialkylaluminum is reacted directly with water, ice, or water vapor 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.

[0058] The aluminoxane may contain small amounts of organometallic components. Alternatively, the recovered aluminoxane solution may be distilled to remove the solvent or unreacted organoaluminum compounds, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0059] Examples of organoaluminum compounds used in preparing aluminoxanes include those similar to those exemplified as organoaluminum compounds belonging to (b-1a) above.

[0060] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among them, trimethylaluminum and triisobutylaluminum are particularly preferred.

[0061] The organoaluminum compounds described above can be used individually or in combination of two or more.

[0062] Furthermore, a benzene-insoluble organoaluminum oxy compound (b-2) used in the present invention is preferably one in which the Al component that dissolves 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, based on Al atoms relative to 100% by weight of benzene; in other words, it is preferably insoluble or sparingly soluble in benzene.

[0063] Examples of organoaluminum oxy compounds (b-2) used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula [X].

[0064] [ka] (In formula [X], R 1 R represents a hydrocarbon group with 1 to 10 carbon atoms. 2 ~R 5 These may be identical or different from each other, and represent hydrogen atoms, halogen atoms, or hydrocarbon groups with 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 R in the above general formula [X] is 1It can be produced by reacting an alkylboronic acid (which shows the same group as ) 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.

[0065] Examples of alkylboronic acids 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.

[0066] Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually or in combination of two or more.

[0067] Examples of organoaluminum compounds to be reacted with such alkylboronic acids include those similar to those exemplified as organoaluminum compounds belonging to (b-1a) above. Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred.

[0068] The organoaluminum oxy compounds (b-2) described above can be used individually or in combination of two or more.

[0069] (b-3) Ionized ionic compounds Examples of the ionized ionic compound (b-3) include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, and USP No. 5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (b-3) can be used individually or in combination of two or more.

[0070] Specifically, examples of Lewis acids include compounds represented by BR3 (where R is a phenyl group or fluorine, which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0071] Examples of ionic compounds include those represented by the following general formula [XII].

[0072] [ka] (In formula [XII], R 1+ H + Examples include carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals. 2 ~R 5 These may be the same or different groups, and are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0073] Specifically, the ammonium cations mentioned above 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 di(isopropyl)ammonium cations and dialkylammonium cations such as dicyclohexylammonium cations.

[0074] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0075] R 1+ Preferred cations include carbonium cations and ammonium cations, with triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations being particularly preferred.

[0076] Other examples of ionic compounds include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0077] 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.

[0078] 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.

[0079] Examples of dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0080] Furthermore, as ionic compounds, examples 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 formulas [XIII] or [XIV]. In the following formulas, Et represents an ethyl group.

[0081] [ka]

[0082] [ka] Examples of borane compounds 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(dodecahydridodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridodecaborate)nickelate(III).

[0083] Specifically, examples of carborane compounds 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-dicarbowndecaborane, 2,7-dicarbowndecaborane, undecahydride-7,8-dimethyl-7,8-dicarbowndecaborane, dodecahydride-11-methyl-2,7-dicarbowndecaborane, and tri(n-butyl)ammonium -1-Carbadecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, 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-6-carbadecaborate, tri(n-butyl)ammonium-7-carbadodecaborate, tri(n-butyl)ammonium-7,8-dicarbadodecaborate, tri(n-butyl)ammonium-2,9-dicarbadodecaborate, tri(n-butyl)ammonium dodecahydrate Salts of anions such as dipropyl-8-methyl-7,9-diculfound decaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-diculfound decaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-diculfound decaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-diculfound decaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-diculfound decaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-diculfound decaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)niclate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)ferric acid Examples include salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0084] Heteropoly compounds consist of atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstovanadic 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 can be used, but are not limited to these.

[0085] Among the ionized 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.

[0086] In the present invention, when a metallocene catalyst is used as a polymerization catalyst, comprising the above-mentioned crosslinked metallocene compound (a), an organometallic compound such as triisobutylaluminum (b-1), an organoaluminum oxy compound such as methylaluminoxane (b-2), and an ionized ionic compound such as triphenylcarbenium tetrakis(pentafluorophenyl)borate (b-3), extremely high polymerization activity can be achieved during the production of copolymers.

[0087] (c) Particulate carrier In the present invention, (c) particulate carriers used as needed are inorganic compounds or organic compounds, and are solid in the form of granules or fine particles.

[0088] Preferred inorganic compounds include porous oxides, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds. Specific examples of these are those described in Publication No. WO2015 / 122495.

[0089] The clay, clay minerals, and ion-exchangeable layered compounds used in this invention may be used as is, or after being subjected to treatments such as ball milling or sieving. They may also be used after being newly treated with water adsorption or heat dehydration. Furthermore, they may be used individually or in combination of two or more.

[0090] Of these, clay or clay minerals are preferred, with montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica being particularly preferred.

[0091] Examples of organic compounds include granular or particulate solids with particle sizes ranging from 10 to 300 μm. Specifically, examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and their modified products.

[0092] The polymerization catalyst used in the present invention comprises a metallocene compound (a), at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and ionized ionic compounds (b-3), and a support (c) as needed, and may further optionally include a specific organic compound component (d).

[0093] (d) Organic compound component In the present invention, the organic compound component (d) is used as needed to improve 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.

[0094] <<Method and conditions for manufacturing copolymers>> The copolymer of the present invention is produced by copolymerizing ethylene, α-olefin, and VNB.

[0095] When copolymerizing such monomers, the method of use and the order of addition of each component constituting the polymerization catalyst described above can be arbitrarily selected, but the following methods (1) to (5) are examples: (1) Adding the crosslinked metallocene compound (a) alone to the polymerizer. (2) Adding the crosslinked metallocene compound (a) and compound (b) to the polymerizer in any order. (3) Adding the catalyst component, in which the crosslinked metallocene compound (a) is supported on a support (c), and compound (b) to the polymerizer in any order. (4) Adding the catalyst component, in which compound (b) is supported on a support (c), and crosslinked metallocene compound (a) to the polymerizer in any order. (5) Adding the catalyst component, in which the crosslinked metallocene compound (a) and compound (b) are supported on a support (c), to the polymerizer.

[0096] In each of the methods described in (2) to (5) above, at least two of the crosslinked metallocene compound (a), compound (b), and carrier (c) may be in contact with each other beforehand.

[0097] In the methods described in (4) and (5) above, in which compound (b) is supported, unsupported compound (b) may be added in any order as needed. In this case, compound (b) may be the same as or different from compound (b) supported on the carrier (c).

[0098] Furthermore, the solid catalyst component in which a crosslinked metallocene compound (a) is supported on the above-mentioned support (c), and the solid catalyst component in which both the crosslinked metallocene compound (a) and compound (b) are supported on the support (c), may have the olefin prepolymerized, and the catalyst component may be further supported on the prepolymerized solid catalyst component.

[0099] The copolymer of the present invention can be suitably obtained by copolymerizing ethylene, α-olefin, and VNB in ​​the presence of the polymerization catalyst described above.

[0100] When polymerizing ethylene, α-olefin, and VNB using the polymerization catalyst described above, the amount of crosslinked metallocene compound (a) is typically 10 per liter of reaction volume. -12 ~10 -2 moles, preferably 10 -10 ~10 -8 It is used in quantities that equal moles.

[0101] Compound (b-1) is used in an amount such that the molar ratio [(b-1) / M] of compound (b-1) to the total transition metal atoms (M) in the cross-linked metallocene compound (a) is usually 0.01 to 50000, preferably 0.05 to 10000. Compound (b-2) consists of aluminum atoms in compound (b-2) and the total transition metal atoms in the cross-linked metallocene compound (a). atom Compound (b-3) is used in an amount such that the molar ratio of compound (b-3) to the transition metal atom (M) in the cross-linked metallocene compound (a) [(b-3) / M] is usually 1 to 20, preferably 1 to 15.

[0102] In the present invention, the method for producing the copolymer can be carried out by either a liquid-phase polymerization method such as solution polymerization or suspension polymerization, or a gas-phase polymerization method, and is not particularly limited, but it is preferable to have a step of obtaining the polymerization reaction solution described below.

[0103] The step of obtaining the polymerization reaction solution involves using an aliphatic hydrocarbon as the polymerization solvent and copolymerizing ethylene, α-olefin, and VNB in ​​the presence of the crosslinked metallocene compound (a) to obtain a polymerization reaction solution of the copolymer.

[0104] Examples of polymerization solvents include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, these 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 can be used individually or in combination of two or more. Olefins themselves can also be used as solvents. Of these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer.

[0105] Furthermore, the polymerization temperature is typically in the range of -50 to +200°C, preferably 0 to +150°C, and more preferably in the range of +70 to +110°C, depending on the attainable molecular weight and polymerization activity of the metallocene catalyst system used. However, a higher temperature (above +70°C) is desirable from the viewpoint of catalytic activity, copolymerizability, and productivity.

[0106] The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, and more preferably 1.2 to 2.0 MPa gauge pressure. The polymerization reaction can be carried out in batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. In this invention, it is preferable to employ a method in which ethylene and unconjugated polyene are continuously supplied to the reactor to carry out copolymerization.

[0107] The reaction time (or average residence time if copolymerization is carried out by a continuous process) 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.

[0108] The molecular weight of the resulting copolymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specifically, examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, an appropriate amount is approximately 0.001 to 100 NL per kg of olefin.

[0109] In the present invention, it is preferable to include a step (2) in which a catalyst deactivator is added after a step (1) in which copolymerization is carried out in the presence of the polymerization catalyst.

[0110] Alcohols can be used as the catalyst deactivator, with methanol or ethanol being preferred, and ethanol being particularly preferred.

[0111] In step (2) above, by adding the catalyst deactivator in an amount preferably 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times, and even more preferably 0.08 to 2.0 mol times, relative to the organometallic compound (b-1), a small amount of catalyst modified by the catalyst deactivator such as ethanol is generated, and low molecular weight components are polymerized appropriately, resulting in a copolymer with a moderately broad molecular weight distribution. On the other hand, if too much catalyst deactivator is added, almost no modified catalyst is generated, and polymerization of low molecular weight components hardly occurs, so the molecular weight distribution of the resulting copolymer tends to be narrow. Also, if no catalyst deactivator is added, or if too little is added, a large amount of modified catalyst is generated and a large amount of low molecular weight components are polymerized, so the content of low molecular weight components in the resulting copolymer tends to be too high.

[0112] <Uses of ethylene-α-olefin-5-vinyl-2-norbornene copolymer> When applying the copolymer of the present invention to LIM molding or other broad molding methods, it may contain at least one selected from crosslinking agents, crosslinking aids, vulcanization aids, fillers, softeners, anti-aging agents, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. 、 Each additive may be used individually or in combination of two or more.

[0113] <Crosslinking agents, crosslinking aids, and vulcanization aids> Examples of crosslinking agents commonly used when crosslinking rubber include organic peroxides, phenolic resins, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. Of these, organic peroxides are preferred.

[0114] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, t Examples include ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0115] When using an organic peroxide as a crosslinking agent, the amount used is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of copolymer. When the amount of organic peroxide is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article, making it preferable.

[0116] When using organic peroxides as crosslinking agents, it is preferable to use crosslinking aids in combination. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; zinc oxide (e.g., ZnO#1, zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.); magnesium oxide; activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0117] When a crosslinking aid is used, the amount of the crosslinking aid in the copolymer composition is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 6 moles, per mole of organic peroxide.

[0118] Examples of vulcanization aids include zinc oxide (e.g., ZnO#1, two types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0119] When using a vulcanization aid, the amount of the vulcanization aid added is usually 1 to 20 parts by mass per 100 parts by mass of copolymer.

[0120] <Filler> The filler according to the present invention is a known rubber reinforcing agent that is compounded in rubber compositions, and is an inorganic substance that is usually referred to as carbon black or an inorganic reinforcing agent.

[0121] The fillers related to this invention include, specifically, Asahi #55G, Asahi #60UG (both manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) carbon black (manufactured by Tokai Carbon Co., Ltd.), and these carbon blacks are surface-treated with a silane coupling agent or the like. Ta Examples include materials such as silica, activated calcium carbonate, fine talc, fine silicic acid, light calcium carbonate, heavy calcium carbonate, talc, and clay.

[0122] These fillers may be used individually or as a mixture of two or more.

[0123] Preferably, the fillers used in this invention are carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

[0124] If a filler is included, it should typically be added in an amount of 50 to 300 parts by mass, preferably 80 to 250 parts by mass, per 100 parts by mass of copolymer.

[0125] <Softener> Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softening agents such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factis). Of these, petroleum-based softening agents are preferred, and process oil is particularly preferred.

[0126] If a softening agent is included, the amount of softening agent is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of ethylene copolymer.

[0127] <Anti-aging agent (stabilizer)> By incorporating an antioxidant (stabilizer) into the copolymer composition of the present invention, the lifespan of the seal packing formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0128] Examples of anti-aging agents include aromatic 2-amine anti-aging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether anti-aging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate anti-aging agents such as dibutyldithiocarbamate nickel; and sulfur-based anti-aging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0129] When an antioxidant is included, the amount of the antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of copolymer. When the amount of the antioxidant is within the above range, there is no bloom on the surface of the resulting molded article, and the occurrence of vulcanization inhibition can be suppressed.

[0130] <Processing aids> As processing aids, those commonly used in rubber processing can be widely used. Specifically, examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. Of these, stearic acid is preferred.

[0131] If a processing aid is included, it can be appropriately added in an amount of typically 1 to 3 parts by mass per 100 parts by mass of copolymer. When the amount of processing aid is within the above range, it is preferable because it provides excellent processability such as kneadability, extrusionability, and injection moldability.

[0132] The processing aid may be a single type or two or more types.

[0133] <Activating agent> Examples of activators include di-n-butylamine, dicyclohexylamine, and monoethylamine. Ta Amines such as nolamines; diethylene glycol, polyethylene glycol, lecithin, trialyl Bird Meri Te Activators such as zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide compounds Made thing; O Examples include kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0134] If an activator is included, the amount of activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of copolymer.

[0135] <Copolymer composition containing ethylene-α-olefin-5-vinyl-2-norbornene copolymer> The copolymer composition containing the ethylene-α-olefin-5-vinyl-2-norbornene copolymer of the present invention (hereinafter sometimes referred to as the "polymer composition"), and in particular the copolymer composition containing the above-mentioned crosslinking agent, can be suitably used for applications such as sealing materials, coating materials, potting materials, and adhesives. Here, "sealing material" refers to a material used for sealing. Therefore, materials used in various industries such as mechanical, electrical, and chemical industries for the purpose of watertight and airtight joints and contact points are also considered sealing materials in a broad sense. The sealing material may be in paste form or mold form. If necessary, you can refer to "Building Sealing Materials - Basics and Correct Usage -" (1st edition, Japan Sealing Material Manufacturers Association, Kobunsha Co., Ltd.) p141 for more information on sealing materials. Here, sealing materials that are filled into gaps and then hardened, or sealing materials that are applied between objects and then hardened, can be particularly preferably exemplified.

[0136] The following explains specific uses.

[0137] The copolymer composition of the present invention can be used in applications such as electrical and electronic components, transportation equipment, civil engineering and construction, medical or leisure.

[0138] Specific applications of electrical and electronic components include heavy electrical components, light electrical components, sealing materials, potting materials, coating materials or adhesives for circuits and circuit boards of electrical and electronic equipment; repair materials for wire insulation; insulating sealants for wire joint components; rolls for office automation equipment; vibration absorbers; or gels or capacitor encapsulants.

[0139] The above-mentioned sealing material is suitably used as a sealant for refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, and circuit breakers.

[0140] The above potting material is suitably used for potting, for example, high-voltage transformer circuits, printed circuit boards, high-voltage transformers with variable resistors, electrical insulating components, semiconducting components, conductive components, solar cells, or flyback transformers for televisions.

[0141] The above-mentioned coating material is suitably used to coat various circuit elements such as high-voltage thick-film resistors or hybrid ICs; HICs, electrical insulating components; semiconducting components; conductive components; modules; printed circuits; ceramic substrates; buffer materials such as diodes, transistors or bonding wires; semiconducting elements; or optical fibers for optical communication.

[0142] The above adhesive is suitably used, for example, to bond cathode ray tube wedges, necks, electrical insulating components, semiconducting components, or conductive components.

[0143] The above-mentioned transport equipment can be used for automobiles, ships, aircraft, or railway vehicles.

[0144] Automotive applications include, for example, gaskets for automotive engines, sealing materials for electrical components or oil filters; and igniter HICs or automotive hybrid ICs. Po Examples include adhesives for coatings on automobile bodies, automobile windows, and engine control boards; or gaskets for oil pans or timing belt covers, moldings, headlamp lenses, sunroof seals, and mirrors.

[0145] Applications for marine applications include, for example, wiring junction boxes, sealing materials for electrical system components or wires; and adhesives for wires or glass.

[0146] Examples of the above-mentioned civil engineering and construction applications include glass screen construction methods for commercial buildings. butt jointExamples include building sealants used for joints, glass joints between sashes, interior joints in toilets, washrooms or showcases, bathtub joints, exterior wall expansion joints for prefabricated houses, and joints for siding boards; sealants for double-glazed windows; civil engineering sealants used for road repair; paints and adhesives for metals, glass, stone, slate, concrete or tiles; or adhesive sheets, waterproof sheets or vibration-damping sheets.

[0147] Examples of the medical applications mentioned above include medical rubber stoppers, syringe gaskets, and rubber stoppers for decompression vessels.

[0148] Examples of the above-mentioned leisure applications include swimming accessories such as swimming caps, diving masks, and earplugs; and gel cushioning materials for sports shoes, baseball gloves, etc.

[0149] The copolymer composition of the present invention can be suitably used as a sealing material, potting material, coating material, and adhesive in applications such as electrical and electronic components, transportation equipment, civil engineering and construction, and leisure. [Examples]

[0150] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0151] The copolymers used in the examples and comparative examples were produced by the following manufacturing method.

[0152] The metallocene catalyst used in the polymerization example of the example is [methylphenylmethylene(η)]. 5 -cyclopentadienyl)(η 5 (-2,7-di-t-butylfluorenyl)zirconium dichloride was synthesized by the method described in WO2015 / 147215.

[0153] The symbols (a) to (t) shown in Examples 1 to 4 represent the quantities of each unit shown in Table 1 below.

[0154] [Examples 1 to 4] Dehydrated and purified n-hexane was supplied at a rate of (a) liters / h to one feed port of a continuous polymerization reactor with a volume of 136 liters, and [methylphenylmethylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride (ZD) hexane solution ( (b) mmol / liter) at a rate of (c) liters / h, a hexane solution of triisobutylaluminum (5 mmol / liter) at a rate of (d) liters / h, a hexane slurry of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ( (e) mmol-B / liter) at a rate of (f) liters / h, and 5-vinyl-2-norbornene (VNB) was continuously supplied at a rate of (g) g / h (total hexane (h) liters / hr). At the same time, ethylene (i) kg / h, 1-butene (j) kg / h, and hydrogen were continuously supplied at a rate of (k) NL / h to another feed port of the polymerization reactor, and continuous solution polymerization was carried out under the conditions of a polymerization temperature of (l) °C, a total pressure of (m) MPaG, and a residence time of (n) minutes.

[0155] The hexane solution of the ethylene·1-butene·VNB copolymer produced in the polymerization reactor was continuously discharged through a discharge port provided in the side wall of the polymerization reactor and led to a connecting pipe heated by 8 kg / cm 2 steam. The hexane solution of the ethylene·1-butene·VNB copolymer heated to about 170 °C in the connecting pipe with a steam jacket was adjusted by the opening degree of a liquid level control valve provided at the end of the connecting pipe so as to maintain the amount of the solution in the polymerization tank at about 28 liters, and 10 kg / cm 2The liquid was continuously supplied to the flash tank through a double-walled pipe heated by steam. Immediately after the liquid level control valve, a supply port for injecting methanol, a catalyst deactivator, was provided. Methanol was injected at a rate of 12 liters / hour as a 1.0 vol% hexane dilution solution and merged with the hexane solution. During transfer into the flash tank, the solution temperature and pressure adjustment valve opening were set to maintain a pressure of 0.05 MPaG in the flash tank and a vapor temperature of 180°C in the flash tank.

[0156] As a result, ethylene-1-butene-VNB copolymer was obtained at a production rate of (p) kg / h. The polymerization mileage of the ethylene-diene copolymer was (q) kg / mmol-Zr, the intrinsic viscosity [η] of the ethylene-1-butene-VNB copolymer was (r) dl / g, the ethylene content was (s) mass%, and the VNB content was (t) mass%.

[0157] [Table 1] [Comparative Examples 1 and 2] The ethylene-propylene-5-vinyl-2-norbornene copolymers shown in Comparative Example 1 and Comparative Example 2 were produced by the following manufacturing method.

[0158] [Manufacturing Example 1] A stainless steel polymerizer with a substantial internal volume of 100 L and equipped with stirring blades (stirring speed = 250 rpm) was used to continuously perform ternary copolymerization of ethylene, propylene, and 5-vinyl-2-norbornene. Hexane was added to the liquid phase from the side of the polymerizer at a rate of 45.5 L per hour, ethylene at 1.4 kg per hour, propylene at 6.8 kg per hour, and 5-vinyl-norbornene at 70 g per hour. Hydrogen was added at a rate of 500 NL per hour, along with 16 mmol of the catalyst VO(OEt)Cl2 and Al(Et) 1.5 Cl 1.5 It was continuously supplied at a rate of 112 mmol.

[0159] When the copolymerization reaction was carried out under the above conditions, a random copolymer, ethylene-propylene-5-vinyl-norbornene copolymer (A-1), was obtained in a homogeneous solution state.

[0160] Subsequently, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization reactor to terminate the polymerization reaction. After separating the copolymer from the solvent by steam stripping treatment, vacuum drying was performed at 55°C for 48 hours.

[0161] The physical properties of the obtained ethylene·propylene·5-vinyl-norbornene copolymer (A-1) are shown in Table 2.

[0162] 〔Production Example 2〕 Using a stainless steel polymerization reactor with a substantial internal volume of 100 L equipped with stirring blades (stirring rotation speed = 250 rpm), copolymerization of ethylene, propylene, and 5-vinyl-2-norbornene was continuously carried out. From the side of the polymerization reactor, hexane was supplied to the liquid phase at a rate of 45.5 L per hour, ethylene at a rate of 1.4 kg, propylene at a rate of 6.8 kg, 5-vinyl-norbornene at a rate of 400 g, and hydrogen at a rate of 1000 NL, catalyst VO(OEt)Cl2 at 16 mmol, and Al(Et) 1.5 Cl 1.5 was continuously supplied at a rate of 112 mmol.

[0163] When the copolymerization reaction was carried out under the above conditions, an ethylene·propylene·5-vinyl-norbornene copolymer (A-2) was obtained in a uniform solution state.

[0164] Subsequently, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization reactor to terminate the polymerization reaction. After separating the copolymer from the solvent by steam stripping treatment, vacuum drying was performed at 55°C for 48 hours.

[0165] The physical properties of the obtained ethylene·propylene·5-vinyl-norbornene copolymer (A-2) are shown in Table 2.

[0166]

Table 2

[0167] For the obtained uncrosslinked compositions, the following values ​​were determined from the crosslinking curves measured at the crosslinking temperatures and crosslinking times shown in each table, in accordance with JIS K6300-2. An RPA2000P (manufactured by Alpha Technologies) was used for the measurements.

[0168] "S' max (dNm): Maximum torque value S' max That is the case.

[0169] "S' min (dNm): Minimum torque value S' min That is the case.

[0170] "tcx1" (min): Minimum torque value S' min From, "S' max -S' min The torque value equivalent to 1% of the above, and the maximum small Torque value S' min The time it takes to reach a torque value equivalent to the sum of the two. For example, "tc10" is the minimum torque value S'. min From, "S' max -S'min A torque value equivalent to 10% of " and the maximum small Torque value S' min This is the time it takes to reach a torque value equivalent to the sum of the two.

[0171] "Peak Rate" (dNm / min): This is the maximum rate of change of torque in the bridge bridging curve.

[0172] Next, the uncrosslinked compositions of each example were pressed in a mold at 170°C for 20 minutes using a press molding machine to obtain a sheet-like crosslinked molded body with a thickness of 2 mm.

[0173] Tensile tests were performed on the obtained crosslinked sheets according to the following method.

[0174] Tensile Test: Tensile tests were conducted in accordance with JIS K-6251, under conditions of a measurement temperature of 23°C and a tensile speed of 500 mm / min, and the tensile strength TB and tensile elongation EB of the crosslinked sheet at fracture were measured.

[0175] The results are shown in Table 3.

[0176] [Table 3]

Claims

1. Ethylene-α-olefin-5-vinyl-2-norbornene copolymer characterized by satisfying the following requirements (i) to (vi); (i) The weight-average molecular weight is 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 between 0.0 and 0.

1. The content of the constituent units derived from (iv) 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass. (v) The constituent units derived from 5-vinyl-2-norbornene include endo and exo structures, and the ratio of endo structure to 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.

2. The copolymer according to claim 1, wherein the intrinsic viscosity [η] measured in decahydronaphthalene at 135°C is in the range of 0.01 to 0.4 dl / g.

3. A copolymer composition comprising the ethylene-α-olefin-5-vinyl-2-norbornene copolymer described in claim 1.

4. A crosslinked body obtained by crosslinking the copolymer composition described in claim 3.

5. (a) Crosslinked metallocene compounds represented by the following general formula [I], and (b) At least one compound (b) selected from the group consisting of organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds (b-3) that react with the crosslinked metallocene compound (a) to form an ion pair. A method for producing an ethylene-α-olefin-5-vinyl-2-norbornene copolymer that satisfies the following requirements (i) to (vi), characterized by comprising the step of copolymerizing ethylene, α-olefin, and 5-vinyl-2-norbornene in the presence of an olefin polymerization catalyst containing: (i) The weight-average molecular weight is 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 between 0.0 and 0.

1. The content of the constituent units derived from (iv) 5-vinyl-2-norbornene is in the range of 0.1 to 20.0% by mass. (v) The constituent units derived from 5-vinyl-2-norbornene include endo and exo structures, The ratio of endo structure to 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 [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 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, and they may be the same or different from each other. R 13 and R 14 Either one of them is an aryl group or a substituted aryl group, and the other is an atom or 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 The adjacent substituents up to this point may be bonded to each other to form a ring. Y is selected from group 14 atoms, and M is a titanium atom, zirconium atom, or hafnium atom. Q is selected from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons, in the same or different combinations; n is an integer from 1 to 4; and j is an integer from 1 to 4.

6. R 13 and R 14 A method for producing an ethylene-α-olefin-5-vinyl-2-norbornene copolymer according to claim 5, wherein the other is an alkyl group having 1 to 20 carbon atoms.

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