JP5611849B2 - Ethylene / α-olefin / non-conjugated polyene copolymer and thermoplastic elastomer containing the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer, and more particularly to an ethylene / α-olefin / non-conjugated polyene copolymer that can be handled as pellets without impairing rubber properties and a thermoplastic elastomer containing the same. .

  Since the ethylene / α-olefin / non-conjugated polyene copolymer does not have an unsaturated bond in the main chain, it is superior in weather resistance, heat resistance, and ozone resistance as compared with a conjugated diene rubber. A rubber composition comprising an ethylene / α-olefin / non-conjugated polyene copolymer and an ethylene / α-olefin / non-conjugated polyene copolymer, and a crosslinked product of the rubber composition utilizing the above properties, It is widely used for rubber products such as rubber products, electrical insulation materials, civil engineering and building materials, and rubberized cloth.

  In recent years, thermoplastic elastomer compositions that do not require a vulcanization step have started to be used from the viewpoint of productivity, environmental friendliness, and weight reduction in place of the crosslinked rubber composition. Among them, the dynamically cross-linked olefin-based thermoplastic elastomer has many heat resistance and weather resistance, and is therefore widely used for automobile weather strip applications. Generally, a dynamically crosslinked olefin-based thermoplastic elastomer is produced by dynamically crosslinking a thermoplastic resin typified by polypropylene and an ethylene / α-olefin / nonconjugated polyene copolymer together with a crosslinking agent in an extruder. . Accordingly, the ethylene / α-olefin / non-conjugated polyene copolymer used as a raw material is generally in the form of a pellet having a high ethylene content.

  On the other hand, ethylene / α-olefin / non-conjugated polyene copolymers with high ethylene content are inferior in compression set at low temperatures, so ethylene / α-olefin / non-conjugated with low ethylene content is used for applications that require low-temperature properties. It is necessary to use a polyene copolymer. Since ethylene / α-olefin / non-conjugated polyene copolymer has a low ethylene content, it will block immediately even when pelletized, so as a measure to maintain the pellet shape, a crystalline resin such as polyethylene or polypropylene is mixed. Measures are known. In this case, since the crosslinking efficiency of the crystalline resin is lower than that of the ethylene / α-olefin / non-conjugated polyene copolymer, the problem that the physical properties of rubber such as compression set still deteriorate has not been solved.

  Therefore, there is a strong demand for a method of molding an ethylene / α-olefin / non-conjugated polyene copolymer having a low ethylene content into a pellet shape while maintaining rubber physical properties such as compression set.

Japanese Patent No. 3849340

  The present invention has been made to provide an ethylene / α-olefin / non-conjugated polyene copolymer having a low ethylene content that can be handled as pellets.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least one peak (melting point) of the endothermic curve (melting point) measured by a differential scanning calorimeter (DSC) is 40 ° C. or higher. The inventors have found that the object can be achieved by using a certain ethylene / α-olefin / non-conjugated polyene copolymer, and have reached the present invention.

  That is, in the present invention, the structural unit derived from ethylene is 40 to 85 mol% (provided that the total of structural units derived from ethylene and α-olefin is 100 mol%), and the iodine value is 0.5 to 40 g. / 100g ethylene / α-olefin / non-conjugated polyene copolymer, wherein at least one of the endothermic curve peaks (melting points) measured by a differential scanning calorimeter (DSC) is 40 ° C. or higher. It is a characteristic ethylene / α-olefin / non-conjugated polyene copolymer.

The above ethylene / α-olefin / non-conjugated polyene copolymer is polymerized by blending two or more types of ethylene / α-olefin / non-conjugated polyene copolymers or using two or more types of catalysts. Can be obtained.
The ethylene / α-olefin / non-conjugated polyene copolymer can be formed into a pellet shape.

  The thermoplastic elastomer containing the ethylene / α-olefin / non-conjugated polyene copolymer and the thermoplastic resin is a preferable embodiment in terms of low-temperature characteristics.

  In addition, a thermoplastic elastomer obtained by dynamically crosslinking a composition containing the above thermoplastic elastomer and a crosslinking agent is a preferred embodiment in terms of low temperature characteristics.

The ethylene / α-olefin / non-conjugated polyene of the present invention can be handled as pellets even if the ethylene content is low.
Further, by using the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention, a thermoplastic elastomer excellent in low temperature characteristics can be obtained.

  Hereinafter, the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention will be described in detail.

[Ethylene / α-olefin / non-conjugated polyene copolymer]
The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention includes a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms, and a non-conjugated polyene. Is a copolymer containing structural units derived from

The structural unit derived from ethylene is 40 to 85 mol%, preferably 40 to 80 mol%, particularly preferably 50 to 76 mol% (provided that the total of structural units derived from ethylene and α-olefin is 100 mol%). The iodine value is 0.5 to 40 g / 100 g, preferably 0.5 to 35 g / 100 g, more preferably 1 to 35 g / 100 g, still more preferably 3 to 35 g / 100 g, particularly preferably 5 to 5 g. 20g / 100g.
The content of each structural unit can be determined from ¹ H-NMR measurement.

Specific examples of the α-olefin include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-1, etc. Is mentioned. Of these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is particularly preferable.
These α-olefins are used alone or in combination of two or more.

Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4s-hexadiene, 4 , 5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene Diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2 -Norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2 Cyclic non-conjugated dienes such as norbornene, cyclopentadiene and norbornadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4- And triene such as ethylidene-8-methyl-1,7-nonadiene. Of these, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable.
These non-conjugated polyenes are used alone or in combination of two or more.

  The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention usually has an intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.5 to 5.0 dL / g, preferably 0. .5 to 4.0 dL / g.

  When the intrinsic viscosity [η] is within the above range, a pellet shape tends to be formed when the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is used.

  The molecular weight distribution (Mw / Mn) measured by GPC of the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention is not particularly limited, but is preferably 1.5 to 50, more preferably 1.5 to 30, more preferably 1.5 to 10, particularly preferably 2 to 5, and most preferably 2 to 4.

  When this molecular weight distribution (Mw / Mn) is within the above range, a pellet shape is likely to occur when the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is used.

  In the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention, at least one peak of the endothermic curve measured by a differential scanning calorimeter (DSC) is 40 ° C. or higher, preferably 50 It is 60 degreeC or more, More preferably, it is 60 degreeC or more.

  When at least one peak in the endothermic curve measured by a differential scanning calorimeter (DSC) is within the above range, the ethylene / α-olefin / non-conjugated polyene copolymer can be handled as a pellet. . In the present application, the peak value of the endothermic curve is defined as the melting point (Tm).

  The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention preferably has a heat of fusion (ΔH) of at least one of the peaks of the endothermic curve measured by a differential scanning calorimeter (DSC), preferably 20 J. / G or less, more preferably 15 J / g or less, still more preferably 10 J / g or less.

  When the heat of fusion (ΔH) of at least one of the peaks of the endothermic curve measured by a differential scanning calorimeter (DSC) is within the above range, the ethylene / α-olefin / nonconjugated polyene copolymer of the present invention is obtained. When used, it becomes easy to handle as a pellet shape while maintaining rubber properties such as compression set.

  Specific examples of the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention include ethylene / propylene / 5-ethylidene-2-norbornene random copolymer, ethylene / butene / 5-ethylidene-2-norbornene random Examples include copolymers, ethylene / propylene / 5-vinyl-2-norbornene random copolymers, ethylene / propylene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene random copolymers, and the like. .

[Method for preparing ethylene / α-olefin / non-conjugated polyene copolymer]
Although there is no restriction | limiting in particular in the preparation method of the ethylene-alpha-olefin-nonconjugated polyene copolymer based on this invention, It can manufacture by the following preparation methods.

(Method for preparing ethylene / α-olefin / non-conjugated polyene copolymer (1))
The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention can be obtained, for example, by blending two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymers. At least one of the ethylene / α-olefin / non-conjugated polyene copolymer to be blended has an endothermic curve peak measured by a differential scanning calorimeter (DSC) of 40 ° C. or higher.

  By satisfying this condition, since the high melting point component exists, even if the content of the structural unit derived from ethylene is within the scope of the present invention, an antiblocking effect due to the high melting point component appears, and the pellet shape It becomes a moldable ethylene / α-olefin / non-conjugated polyene copolymer.

When blending two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymer, at least one peak (melting point) of the endothermic curve peak (melting point) measured by a differential scanning calorimeter (DSC) is 40. The content of the structural unit derived from ethylene in the ethylene / α-olefin / non-conjugated polyene copolymer having a temperature of not lower than ° C. is preferably 75 to 95 mol%, more preferably 77 to 95 mol% (provided that ethylene and α -The total of the structural units derived from the olefin is 100 mol%). The content of the structural unit derived from ethylene in the ethylene / α-olefin / non-conjugated polyene copolymer having no peak of 40 ° C. or higher is preferably 45 to 75 mol%, more preferably 45 to 70 mol%. (However, the total of structural units derived from ethylene and α-olefin is 100 mol%).
When blending two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymer, the blend ratio is the total weight of the ethylene / α-olefin / non-conjugated polyene copolymer having at least one peak of 40 ° C. or more. The weight ratio [A / (A + B)] determined from the total weight B of the ethylene / α-olefin / non-conjugated polyene copolymer having no peak of A and 40 ° C. or higher is preferably 0.05 to 0.7. Preferably it is 0.05-0.5, More preferably, it is 0.1-0.5. The content of the structural unit derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention can be adjusted to 40 to 85 mol% by adjusting to this range. The ethylene / α-olefin / non-conjugated polyene copolymer of the invention can be formed into a pellet shape.

The blending method is not particularly limited. For example, the copolymer of the present invention is obtained by kneading two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymer with a Banbury mixer, a kneader, an extruder, or the like. A method is mentioned.
As the Banbury mixer and kneader used in the preparation method, various conventionally known Banbury mixers and kneaders can be used.

  As a blending method, when kneading with an extruder, an aliphatic hydrocarbon solvent such as hexane may be present. In the case where an aliphatic hydrocarbon solvent is present, the solvent may be the solvent used in the polymerization of the copolymer, or a solvent may be added separately to the produced copolymer.

  In this preparation method, since the solvent is present, the copolymers can be uniformly mixed as compared with the case where the copolymers are alloyed in the absence of the solvent.

  When the copolymer is kneaded in the presence of a solvent by an extruder, the solvent is removed after kneading.

As the extruder used for the preparation method, various conventionally known extruders can be used.
The ethylene / α-olefin / non-conjugated polyene copolymer is produced by blending, for example, using two or more polymerizers to produce ethylene / α-olefin / non-conjugated polyene copolymers having different compositions in each polymerizer. A method is mentioned. In this case, the content of the structural unit derived from ethylene in the ethylene / α-olefin / non-conjugated polyene copolymer produced in each polymerizer is 5 mol% or more, preferably 7 mol% or more, more preferably 10 Combinations differing by mol% or more are preferred.

(Method for preparing ethylene / α-olefin / non-conjugated polyene copolymer (2))
The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention can be prepared, for example, using two or more kinds of main catalysts as shown below.
As the two or more kinds of main catalysts, for example, two or more kinds of metallocene catalysts can be used. In this case, it is preferable to select from the metallocene catalysts exemplified below and use as the main catalyst.
Examples of the metallocene catalyst include the following general formula [I] described in Japanese Patent No. 2535249.

(In the formula [I], M is titanium, zirconium or hafnium; C _p ^* is a cyclopentadienyl or substituted cyclopentadienyl group bonded to M in an η ⁵ bond mode; and X is 30 in each case. An anionic ligand group having up to 1 carbon atom; n is 1 or 2; Y is —O—, —S—, NR ^* — or —PR ^* —; Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ , GeR ^* ₂ , BR ^* or BR ^* ₂ ; R ^* in each case Is a moiety selected from hydrogen or an alkyl, aryl, silyl, halogenated alkyl, halogenated aryl group, and combinations thereof having up to 20 non-hydrogen atoms, or Z, The or two or more R ^* groups metal coordination complexes corresponding to form a fused ring system) from both the Y and Z, the following formula described in Japanese Patent No. 3407074 [II]

(In formula [II], M is Ti; j is 1 or 2, T is O when j is 1, T is N or P when j is 2, and R ^B is If independently of, 1-20 a hydrocarbyl group having carbon atoms, and j is two R ^B groups are N with covalently bonded to one another 5- or 6-membered heterocyclic ring in the case of 2 R ^A , R ^W , R ^X , R ^Y and R ^Z are independently hydrogen or a hydrocarbyl group having from 1 to 20 carbon atoms, and optionally with R ^X R ^Y may be covalently bonded to each other; Z is -SiR ^* ₂ NR ^* - nitrogen atom a is bonded to M, ^{R *} is a hydrocarbyl having 1 to 20 carbon atoms; X is a halogen or an anionic or dianionic ligand having up to 20 atoms X ′ is independently a neutral diene having no more than 20 atoms in each case; p is 0, 1 or 2, and formal oxidation of M when X is an anionic ligand 2 less than the state; when X is a dianionic ligand, p is 1; and q is 0, 1 or 2), a metal complex corresponding to the following general formula [III ] Or the following general formula [IV]

(In the formula [III], M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are each a hydrogen atom, a halogen atom, or a C 1-20 carbon atom that may be substituted with a halogen atom. A hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is 1 carbon atom. -20 divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, -O-, -CO-, -S _{-, - SO -, - SO} 2 -, - NR 7 -, ^{-P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ -. A [However, ^{R 7} is a hydrogen atom, a halogen atom, having 1 to 20 carbon atoms A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms.])

(In Formula [IV], M is a transition metal of Group IVB of the periodic table, and R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a halogenated carbon atom. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or —NR ₂ , —SR, —OSiR ₃ , —SiR _3, or —PR ₂ group (where R is a halogen atom, 1 to 10 carbon atoms) R ^{22 to} R ²⁸ are the same as R ²¹ described above, or adjacent R ^{22 to} R ²⁸ together with the atoms to which they are bonded, An aromatic ring or an aliphatic ring may be formed, and X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom -10 alkoxy groups, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, carbon atoms An alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,
Z is

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = NR ²⁹ , = CO, = PR ²⁹ or = P (O) R ²⁹ is there. [However, R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. C-10 aryl group, C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, carbon atom or arylalkenyl group or an alkylaryl group having 7 to 40 carbon atoms having 8 to 40, or the R ²⁹ and R ^30, may form a ring together with the atoms connecting them, respectively, M ² is , Silicon, germanium or tin atoms. ], Metallocene compounds represented by the following general formula [V] and general formula [VI] described in JP2011-001497A

(In Formula [V] and Formula [VI], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group of carbon atoms, which may be substituted by a halogen atom is 1 to 20, and are selected from silicon-containing group, each may be the same or different, from R ¹ Adjacent substituents up to R ¹⁴ may combine with each other to form a ring, Y is a silicon atom or a carbon atom, and M is selected from a titanium atom, a zirconium atom, and a hafnium atom, provided that the formula [ in V], Y is a silicon atom, ^{R 5} to ^{R 12} are all hydrogen ^{atoms, R 13} and ^{R 14} are methyl group, butyl group, a phenyl group, silicon-substituted phenyl group, a cyclohexyl group, Ben Selected from groups other than Le group; Y is a silicon atom, a and ^{R 6} and ^{R 11} are both t- butyl ^{group, R 5, R 7, R} 8, R 9, R 10, R 12 is t- When it is not a butyl group, R ¹³ and R ¹⁴ are selected from groups other than benzyl and silicon-substituted phenyl groups; when Y is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ , R ¹⁴ is a methyl group, isopropyl group, t-butyl group, isobutyl group, phenyl group, pt-butylphenyl group, pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, A group other than a naphthyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, and a xylyl group; Y is a carbon atom, and R ⁶ and R ¹¹ are a common group selected from a t-butyl group, a methyl group, and a phenyl group. Yes ^{R 5, R 7, R 8} , R 9, when it is ^{R 10} and ^{R 12} is different group or ^atom, R ^{13, R 14} is a methyl group, a phenyl group, p-t-butylphenyl group, p-n - butylphenyl group, silicon-substituted phenyl group, selected from the group other than a benzyl group; Y is a carbon atom, R ⁶ is dimethylamino group, a methoxy group or a methyl ^{group, R 5, R 7, R} 8, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are groups or atoms different from R ⁶ , R ¹³ and R ¹⁴ are selected from groups other than methyl and phenyl; Y is a carbon atom, fluorenyl group And R ^{5 to} R ¹² are b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are from groups other than methyl and phenyl groups. To be elected. A in the formula [VI] represents a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A represents two or more including a ring formed with Y It may contain a ring structure. However, the ring formed by Y and A is selected from groups other than cyclobutylidene, cyclopentylidene and cyclohexylidene when R ⁵ to R ¹² are simultaneously hydrogen atoms.

  Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, neutral having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and neutral coordination capable of coordination with a lone electron pair. Chosen from a child. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different. The transition metal compound represented by this can be illustrated.

  For the production of an ethylene / α-olefin / non-conjugated polyene copolymer (A) having a high ethylene content, it is particularly preferable to use a catalyst having a low α-olefin copolymerizability, and an ethylene / α-olefin / non-conjugated material having a low ethylene content. For the production of the polyene copolymer (B), it is particularly preferable to use a catalyst having a high α-olefin copolymerizability.

As a combination of catalysts having different α-olefin copolymerizability, each of them contains a structural unit derived from ethylene of an ethylene / α-olefin / non-conjugated polyene copolymer produced under the same polymerization conditions by using the catalyst alone. Preference is given to combinations which yield copolymers with an amount of 5 mol% or more, preferably 7 mol% or more, more preferably 10 mol% or more.
For the production of an ethylene / α-olefin / nonconjugated polyene copolymer (A) having a high ethylene content, a catalyst in which M is a zirconium atom among the transition metal compounds represented by the formulas [V] and [VI] In the production of the ethylene / α-olefin / non-conjugated polyene copolymer (B) having a low ethylene content, M of the transition metal compounds represented by the formulas [V] and [VI] is particularly preferred. The use of a catalyst that is a hafnium atom is preferred.

  For the production of an ethylene / α-olefin / nonconjugated polyene copolymer (A) having a high ethylene content, a catalyst in which Y is a silicon atom among the transition metal compounds represented by the formulas [V] and [VI]. In the production of the ethylene / α-olefin / non-conjugated polyene copolymer (B) having a low ethylene content, among the transition metal compounds represented by the formulas [V] and [VI], Y is The use of a catalyst that is a carbon atom is preferred.

  Although there is no other restriction | limiting in particular, For example, when using a metallocene catalyst as a main catalyst, a cocatalyst can be used. Examples of cocatalysts include aluminum compounds containing an Al-O bond exemplified in Japanese Patent No. 2535249, ion-forming compounds composed of proton-donating cations exemplified in Japanese Patent No. 3407704, and Japanese Patent No. 3486005. , Compounds that react with metallocene compounds to form ion pairs, organoaluminum compounds, organometallic compounds, organoaluminum oxy compounds, and transition metals exemplified in Japanese Patent Application No. 2009-146896 Examples include compounds that react with compounds to form ion pairs and mixtures thereof.

  For example, when a metallocene catalyst is used as the main catalyst, the reaction temperature is usually in the range of −20 to 200 ° C., preferably 0 to 150 ° C., more preferably 0 to 100 ° C., and the pressure exceeds 0. -8 MPa (gauge pressure), preferably in the range of more than 0 to -5 MPa (gauge pressure). Within the above range, the ethylene / α-olefin / non-conjugated polyene copolymer rubber can be suitably produced with excellent catalyst activity.

  The amount ratio of the raw materials used for the reaction is usually 0.2 to 1.0 mol of α-olefin, 0.01 to 0.10 mol of non-conjugated polyene, preferably 0.4 to α-olefin per 1 mol of ethylene. -0.8 mol, non-conjugated polyene is 0.04-0.08 mol.

  Also, depending on the amount of raw material supplied, for example, when supplying ethylene at 4.6 kg / h, the amount of main catalyst used is 0.03 mmol / h to 0.11 mmol / h, and the amount of cocatalyst used Is 0.10 mmol / h to 0.46 mmol / h, and the amount of the organoaluminum compound used is 0.6 mmol / h to 3.0 mmol / h.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. Further, in the copolymerization, a molecular weight regulator such as hydrogen can be used.

[Pelletization of ethylene / α-olefin / non-conjugated polyene copolymer]
The pellets of the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention are obtained by kneading and granulating using an extruder equipped with a pelletizer.

[Thermoplastic elastomer]
The thermoplastic elastomer of the present invention is a thermoplastic elastomer containing the above-mentioned ethylene / α-olefin / non-conjugated polyene and a thermoplastic resin.
Further, the thermoplastic elastomer according to the present invention is prepared by dynamically heat-treating a blend comprising the ethylene / α-olefin / non-conjugated polyene copolymer and the thermoplastic resin in the presence of a crosslinking agent. May be.

  The thermoplastic resin is preferably an olefin resin from the viewpoint of processability. The olefin resin is a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. Examples of such olefin-based resins include isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

  Specific examples of suitable raw material olefins for the olefin resins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3- Examples thereof include α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms such as methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These α-olefins are used alone or in combination of two or more. The polymerization mode may be random type or block type, and any polymerization mode can be adopted as long as a resinous material is obtained.

The olefin-based resin is preferably a propylene-based polymer, and specifically, a propylene homopolymer, a propylene / ethylene block copolymer, propylene / ethylene, and a propylene / ethylene / butene random copolymer are preferable.
The olefin resin has a melt flow rate (MFR: ASTM D1238-65T, 230 ° C., 2.16 kg load) usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes. It is desirable.
The olefin resin has a role of improving the fluidity and heat resistance of the thermoplastic elastomer. Olefin resins may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as said olefin resin, A polypropylene etc. can be illustrated and a polypropylene is especially preferable.

  The use ratio of the thermoplastic resin and the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is thermoplastic relative to the total of the thermoplastic resin and the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention. The resin is 10 to 80% by weight, preferably 15 to 60% by weight, and the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is 90 to 20% by weight, preferably 85 to 40% by weight. Desirable in terms of sex.

(Crosslinking agent)
Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds, phenolic vulcanizing agents such as phenol resins, etc. Among them, organic peroxides are preferably used.

  Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-Di (tert-butylperoxy) hexyne-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, tert-butylperbenzoate, tert-butylperoxyisopropyl Carbonate Diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 in terms of odor and scorch stability 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) ) Valerate is preferred.

  The crosslinking agent is used in a proportion of 0.01 to 15 parts by weight, preferably 0.03 to 12 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer. When the crosslinking agent is used in the above ratio, a thermoplastic elastomer in which the ethylene / α-olefin / non-conjugated polyene copolymer is crosslinked is obtained, and a molded article having sufficient heat resistance, tensile properties and rubber elasticity is obtained. Moreover, this thermoplastic elastomer is excellent in moldability.

(Crosslinking aid)
In the present invention, during the crosslinking treatment with the crosslinking agent, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, tri Cross-linking aids such as methylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl A polyfunctional methacrylate monomer such as methacrylate and a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be blended. By such a compound, a uniform and mild crosslinking reaction can be expected. In particular, when divinylbenzene is used in the present invention, it is easy to handle, has good compatibility with the ethylene / α-olefin / non-conjugated polyene copolymer as the main component of the object to be treated, and is an organic peroxide. Because it has an organic peroxide solubilizing action and works as a dispersion aid for organic peroxides, it can provide a thermoplastic elastomer with a uniform cross-linking effect by heat treatment and a balance between fluidity and physical properties. Most preferred.

(Softener)
In the present invention, a softener may be added as a fluidity or hardness adjusting agent.
Specifically, process oil, lubricant oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, petroleum softener such as petroleum jelly, coal tar softener such as coal tar and coal tar pitch, castor oil, Fat oil softeners such as linseed oil, rapeseed oil, soybean oil, coconut oil, waxes such as tall oil, sub (factis), beeswax, carnauba wax, lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate Fatty acids and fatty acid salts such as calcium stearate and zinc laurate, naphthenic acid, pine oil, rosin or derivatives thereof, terpene resin, petroleum resin, coumarone indene resin, synthetic polymer substances such as atactic polypropylene, dioctyl phthalate, dioctyl Adipate, Dioc Ester softeners such Rusebaketo, microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, end modified polyisoprene, water 添末 end modified polyisoprene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. Among these, petroleum softeners, particularly process oils are preferably used.

(Additive)
In the thermoplastic elastomer composition according to the present invention, additives such as a slip agent, a nucleating agent, a filler, an antioxidant, a weathering stabilizer, a colorant, and the like, as long as necessary, do not impair the purpose of the present invention. Can be blended.

  Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents, and these can be used alone or in combination of two or more. Non-melting crystallization nucleating agents include inorganic substances such as talc, mica, silica, aluminum, brominated biphenyl ether, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), organophosphate, rosin crystallization Nucleating agents, substituted triethylene glycol terephthalate and Terylene & Nylon fibers, etc., especially hydroxy-di-p-tert-butylbenzoic acid aluminum salt, methylenebis (2,4-di-tert-butylphenyl) phosphoric acid sodium salt, 2, 2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, rosin-based crystallization nucleating agent is desirable. Examples of the melting crystallization nucleating agent include sorbitol-based compounds such as dibenzylidene sorbitol (DBS), substituted DBS, and lower alkyl dibenzylidene sorbitol (PDTS).

  Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.

  Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber and the like.

  Examples of the carbon black include SRF (Semi Reinforcing Furnace), GPF (General Purpose Furnace), FEF (Fast Extracting Furnance), MAF (Medium Absuring Furnace), and AF (Him (Abduction Furnace), HAF (Him (Abduction)). Carbon black such as (Super Abrasion Furnace), FT (Fine Thermal), MT (Medium Thermal) and the like can be used. Commercially available carbon blacks include “Asahi # 50”, “Asahi # 55”, “Asahi # 60”, “Asahi # 60H”, “Asahi # 70”, “Asahi # 80”, “Asahi # 90”. , “Asahi # 15” (trade name; manufactured by Asahi Carbon Co., Ltd.), “Seast SO”, “Seast 116”, “Seast 3”, “Seast 6”, “Seast 7HM”, “Seast 9” (trade name; Tokai Carbon Co., Ltd.).

〔Example〕
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, the evaluation method of each characteristic in an Example and a comparative example is as follows.

(1) Composition of ethylene / α-olefin / non-conjugated polyene copolymer Using an ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL at a measurement temperature of 120 ° C., a measurement solvent ODCB-d ₄ , and an integration count of 512 times, ¹ By measuring the spectrum of H, the compositions of ethylene and α-olefin were calculated.
(2) Mooney viscosity ML _{1 + 4 of} an ethylene / α-olefin / nonconjugated diene copolymer _{1 + 4} 125 ° C.
Measurements were made at a temperature of 125 ° C. according to ASTM D1646.
(3) Measuring method of iodine value (g / 100g) It measured according to JISK0070.
(4) Melting point (Tm) and heat of fusion (ΔH) measurement Using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments), about 10 mg of a sample was packed in an aluminum pan for measurement, and the temperature was raised to 200 ° C. at 50 ° C./min. Then, after maintaining at 200 ° C. for 10 minutes, the temperature was lowered to −100 ° C. at 10 ° C./min, and then obtained from an endothermic curve heated to 200 ° C. at 10 ° C./min. When there is one peak, the peak is Tm1 and the corresponding heat of fusion is ΔH1. When there are two or more peaks, the lowest temperature peak is Tm1, the corresponding heat of fusion is ΔH1, the highest temperature peak is Tm2, and the corresponding heat of fusion is ΔH2.
(5) Blocking property 50 g of ethylene / α-olefin / non-conjugated polyene copolymer pellets coated with 0.1% by weight of calcium stearate are prepared and placed in a cylinder having a diameter of 5 cm. A 4 kg load is applied to the pellets in the cylinder, and the state of the pellets after observing 48 hours at 40 ° C. is observed. The blocking score is determined from the observation results according to the following criteria. The larger the value of the blocking property, the easier it can be handled as a pellet. In order to handle it as a pellet, it is preferably 3 or more, more preferably 4 or more, and most preferably 5.
1: Completely fixed.
2: Although it can be loosened by hand, a small lump remains.
3: Loosen to pellet shape.
4: Easy to loosen by hand.
5: Not blocked at all (6) Melt flow rate (MFR)
The melt flow rate of the thermoplastic elastomer was measured at 230 ° C. and a 2.16 kg load according to ASTM D 1238-65T.
(7) Tensile test The molded body was subjected to a tensile test in accordance with JIS K6251 under conditions of a measurement temperature of 23 ° C and a tensile speed of 500 mm / min, and the strength at break (TB) and elongation at break (EB) were measured.
(8) Hardness test The flat part of the molded body was overlapped to 12 mm, and the Shore A hardness was measured according to JIS K6253.
(9) Compression set (CS)
According to JIS K6262, the compression set of the molded bodies obtained in the examples and comparative examples was measured. The flat part of the molded body is overlapped to 12 mm, attached to a compression set measuring mold, compressed so that the height of the test piece becomes 3/4 of the height before applying the load, and the predetermined temperature together with the mold And then heat-treated for 22 hours. Next, the test piece was taken out, allowed to cool for 30 minutes, the height of the test piece was measured, and the compression set (%) was calculated by the following formula.
Compression set (%) = {(t0−t1) / (t0−t2)} × 100
t0: Height of the test piece before the test.
t1: Height after heat-treating the specimen and allowing it to cool for 30 minutes.
t2: Height of the test piece attached to the measurement mold.

[Example A-1]
[Preparation of ethylene / α-olefin / non-conjugated polyene copolymer (A-1)]
Using a reactor with a stirrer made of SUS with a volume of 130 L, the temperature was kept at 110 ° C., the liquid level was 28 L, hexane was 12 kg / h, ethylene was 2 kg / h, propylene was 2.4 kg / h, 5-ethylidene- 2-norbornene (ENB) at a rate of 0.3 kg / h and hydrogen at a rate of 0.2 NL / h as di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-) as the main catalyst. t-butylfluorenyl) hafnium dichloride 0.0495 mmol / h and di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride 0.0005 mmol / h h, and TIBA as cocatalyst _{(C 6 H 5) 3 CB} (C 6 F 5) 4 0.25mmol / h, as the organoaluminum compound Supplied to the reactor continuously at a rate of 0 mmol / h, to obtain a polymer liquid terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene.
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride and di (p-tolyl) silylene (cyclopentadienyl) (2,7-di- (t-Butylfluorenyl) zirconium dichloride was synthesized by the method described in WO2004 / 029062.
The solvent of the polymerization solution thus obtained was removed to obtain an ethylene / α-olefin / non-conjugated polyene copolymer (A-1). The obtained copolymer had an ethylene content of 62.9 mol% (the content of ethylene and α-olefin was 100 mol%) and an iodine value of 16.8 g / 100 g.
The obtained ethylene / α-olefin / non-conjugated polyene copolymer was subjected to an extruder [model: VG-50-30 extruder] equipped with a pelletizer [model: PASC214-HS type, manufactured by Tanabe Plastics Co., Ltd.] Tanabe Plastics Co., Ltd., cylinder temperature: D / C4 / C3 / C2 / C1 / F = 260/260/230/200/140/50 ° C., screw rotation speed: 50 rpm, resin pressure: 47 kgf / cm ² , The mixture was kneaded and granulated using a cutter rotation speed of 1200 rpm to obtain ethylene / α-olefin / non-conjugated polyene copolymer pellets.
Table 1 shows the physical properties of the obtained copolymer and pellets.

[Example A-2]
Ethylene / propylene / 5-ethylidene-2-norbornene copolymer [ethylene content: 66.1 mol% (content of ethylene and α-olefin is 100 mol%), iodine value: 16.0 g / 100 g, Mooney Viscosity [ML _{1 + 4} 100 ° C .: 45], product name Mitsui EPT 4045M, Tm not measured] 84 parts by weight, ethylene / butene / 5-ethylidene-2-norbornene copolymer [ethylene content: 90.1 mol % (Content of ethylene and α-olefin is 100 mol%), iodine value: 20.3 g / 100 g, Mooney viscosity [ML _{1 + 4} 100 ° C .: 22], Tm: 69 ° C., product name Mitsui EPT K-9720 ] 16 parts by weight was mixed with a 3 L kneader for 4 minutes to obtain an ethylene / α-olefin / non-conjugated polyene copolymer (A-2). .

  The ethylene / α-olefin / non-conjugated polyene copolymer is produced by the method shown in Example A-1, except that the ethylene / α-olefin / non-conjugated polyene copolymer (A-2) obtained as a rubber component is used. Combined pellets were obtained. Table 1 shows the physical properties of the obtained copolymer and pellets.

Example A-3
Using a reactor with a stirrer made of SUS with a volume of 310 L, the temperature was kept at (90 ° C.), the liquid level was 100 L, hexane was 28 kg / h, ethylene was 4 kg / h, propylene was 3 kg / h, 5-ethylidene- 2-norbornene (ENB) at a rate of 200 kg / h, hydrogen at a rate of 0.2 NL / h, di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-) as the main catalyst Butylfluorenyl) hafnium dichloride 0.0198 mmol / h and di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride 0.0002 mmol / h, as cocatalyst _{(C 6 H 5) 3 CB} (C 6 F 5) 4 0.1mmol / h, the TIBA as an organoaluminum compound 2 It was fed at a rate of mmol / h to the reactor continuously to obtain a polymer solution of a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene. The solvent of the polymerization solution thus obtained was removed to obtain an ethylene / α-olefin / non-conjugated polyene copolymer (A-3). The obtained copolymer had an ethylene content of 69.1 mol% (the content of ethylene and α-olefin was 100 mol%) and an iodine value of 11.7 g / 100 g.

  The ethylene / α-olefin / non-conjugated polyene copolymer was prepared by the method shown in Example A-1, except that the ethylene / α-olefin / non-conjugated polyene copolymer (A-3) obtained as a rubber component was used. Combined pellets were obtained. Table 1 shows the physical properties of the obtained copolymer and pellets.

[Comparative Example AC-1]
Ethylene / propylene / 5-ethylidene-2-norbornene copolymer [ethylene content: 66.1 mol% (content of ethylene and α-olefin is 100 mol%), iodine value: 16.0 g / 100 g, Mooney viscosity [ML _{1 + 4} 100 ° C .: 45], product name Mitsui EPT 4045M, Tm1 was not measured], and ethylene / α-olefin / non-conjugated polyene copolymer in the same manner as in Example A-1. Combined pellets were obtained. The physical properties of the copolymer and pellets are shown in Table 1. The obtained pellets were extremely poor in blocking properties and could not be handled as pellets because the pellets were completely fixed together.

[Comparative Example AC-2]
Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (AC-2) [ethylene content: 66.4 mol%, iodine value: 10.5 g / 100 g, Mooney viscosity [ML _{1 + 4} 150 ° C .: 56] ], Tm1: -1.9 ° C.], an ethylene / α-olefin / non-conjugated polyene copolymer pellet was obtained in the same manner as in Example A-1. The physical properties of the copolymer and pellets are shown in Table 1.

[Example B-1]
(Preparation of thermoplastic elastomer composition)
100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (A-1) as a rubber component and 100 parts by weight of paraffinic process oil (trade name PW-100, manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer Propylene homopolymer as polypropylene [MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 0.5 g / 10 min, melting point (Tm): 165 ° C .; trade name E111G] with 82 parts by weight in a 3 L kneader After mixing for 4 minutes, 0.73 parts by weight of an organic peroxide [manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhexa 25B] as a crosslinking agent and 0.68 weight of divinylbenzene 81% masterbatch (DVB) as a crosslinking aid The thermoplastic elastomer composition was obtained by kneading at 120 ° C for 2 minutes and kneading at 190 ° C for 1 minute.

  (B-1) is molded in a mold at 190 ° C. for 10 minutes using a press molding machine, and a 2 mm (thickness) × 20 cm (length) × 20 cm (width) thermoplastic elastomer composition A molded body is obtained. About the obtained thermoplastic elastomer molded object, MFR and compression set (CS) were measured.

[Example B-2]
A thermoplastic elastomer composition was obtained by the method shown in Example B-1, except that the ethylene / α-olefin / non-conjugated polyene copolymer (A-2) obtained as the rubber component was used.

[Example B-3]
A thermoplastic elastomer composition was obtained by the method shown in Example B-1, except that the ethylene / α-olefin / non-conjugated polyene copolymer (A-3) obtained as the rubber component was used.

[Comparative Example BC-1]
As a rubber component, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer [ethylene content: 77 mol%, iodine value: 9.8, Mooney viscosity [ML _{1 + 4} 125 ° C .: 61, melting point: 20.8 ° C.], A thermoplastic elastomer composition was obtained by the method shown in Example B-1, except that the product name Mitsui EPT 3092PM was used.

  The ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is capable of pellet handling. Therefore, it can be used as a thermoplastic elastomer raw material, and can be used for various applications including automobile parts, industrial machine parts, electrical and electronic parts, civil engineering and building parts, and medical parts.

Claims (6)

Ethylene / α-olefin having a structural unit derived from ethylene of 50 to 76 mol% (provided that the total of structural units of ethylene and α-olefin is 100 mol%) and iodine value of 0.5 to 40 g / 100 g (C3 or more) non-conjugated polyene copolymer,
An ethylene / α-olefin / non-conjugated polyene copolymer, wherein at least one peak of an endothermic curve measured by a differential scanning calorimeter (DSC) is at 60 ° C. or higher.   The ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1, which is obtained by blending two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymers.   The ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1, which is polymerized using two or more kinds of catalysts.   A pellet containing the ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1.   A thermoplastic elastomer comprising the ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 3 and a thermoplastic resin.   A thermoplastic elastomer obtained by dynamically crosslinking a composition comprising the thermoplastic elastomer according to claim 5 and a crosslinking agent.