WO2016152711A1 - 熱可塑性エラストマー組成物、その用途、その製造方法、エチレン・α-オレフィン・非共役ポリエン共重合体およびその用途 - Google Patents
熱可塑性エラストマー組成物、その用途、その製造方法、エチレン・α-オレフィン・非共役ポリエン共重合体およびその用途 Download PDFInfo
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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Definitions
- the present invention (1) relates to a thermoplastic elastomer composition, and more particularly, to a thermoplastic elastomer composition that can provide a molded article that is lightweight, high in strength, and excellent in oil resistance and mechanical properties.
- the present invention (2) relates to an ethylene / ⁇ -olefin / non-conjugated polyene copolymer and its use.
- Olefin-based thermoplastic elastomers are lightweight and easy to recycle. As energy- and resource-saving thermoplastic elastomers, especially as an alternative to vulcanized rubber, hoses, pipes and boots (blow molded products) for automobiles, etc. Widely used in automobile parts and the like (for example, Patent Documents 1 and 2).
- thermoplastic elastomers used contain a large amount of filler, so the specific gravity tends to be large and hinders weight reduction of the parts.
- these automobile parts are used in places where they come into contact with lubricating oil or grease.
- olefin-based thermoplastic elastomers have low oil resistance against paraffin-based process oils, so Even in these automobile parts obtained by including a plastic elastomer, oil resistance is low, and further improvement has been demanded.
- ethylene / ⁇ -olefin rubbers such as ethylene / propylene copolymer rubber (EPR) and ethylene / propylene / diene copolymer rubber (EPDM) do not have an unsaturated bond in the main chain of the molecular structure.
- EPR ethylene / propylene copolymer rubber
- EPDM ethylene / propylene / diene copolymer rubber
- EPDM is known to use, for example, ethylene / propylene / diene copolymer rubber (EPDM) as a rubber component of a hose forming composition (Patent Document 3).
- EPDM ethylene / propylene / diene copolymer rubber
- Patent Document 3 ethylene / propylene / diene copolymer rubber
- Applications where hoses are used, such as automobiles, are also expected to be used in cold regions. Therefore, in addition to mechanical properties at room temperature (tensile strength, etc.), rubber properties at low temperatures (rubber elasticity, etc.) are also required. Is done.
- Patent Document 4 An ethylene / 1-butene / ENB copolymer having a maximum B value of 1.12 represented by the following formula, which is an index indicating the quality of randomness, was obtained. Is described.
- thermoplastic elastomers used contain a large amount of filler, so the specific gravity tends to be large and hinders weight reduction of the parts.
- these automobile parts are used in places where they come into contact with lubricating oil or grease.
- olefin-based thermoplastic elastomers have low oil resistance against paraffin-based process oils, so Even in these automobile parts obtained by including a plastic elastomer, oil resistance is low, and further improvement has been demanded.
- the present invention (1) has been made in order to solve the above-mentioned problems, is lightweight, has oil resistance superior to that of a conventional cross-linked thermoplastic elastomer, and has a conventional cross-link type heat. It is an object of the present invention to provide a thermoplastic elastomer composition that can be a molded product having hardness, mechanical properties such as tensile strength and tensile elongation equivalent to or higher than those of a plastic elastomer.
- An object of the present invention is to provide molded parts having a better oil resistance obtained by including the thermoplastic elastomer composition, in particular, automotive parts such as hoses, pipes and boots (blow molded articles) for automobiles.
- the problem of the present invention (2) is that, compared with the already proposed ethylene / ⁇ -olefin / non-conjugated polyene copolymer, the compression set at a low temperature is small and has flexibility,
- the object is to obtain an ethylene / ⁇ -olefin / non-conjugated polyene copolymer having an excellent balance between rubber elasticity at low temperature and tensile strength at room temperature.
- hoses that have both low temperature characteristics and mechanical properties are desired.
- hose-forming composition containing EPDM with a low ethylene content is used, the low-temperature characteristics of the resulting hose are improved, but the tensile strength is reduced.
- Another object of the present invention (2) is to provide a hose forming composition capable of forming a hose excellent in low temperature characteristics and mechanical properties, and a hose formed from the composition. .
- the present invention (2) is light in weight, has oil resistance superior to that of conventional cross-linked thermoplastic elastomers, and has hardness and tensile strength equal to or higher than those of conventional cross-linked thermoplastic elastomers.
- Another object of the present invention is to provide a thermoplastic elastomer composition that can be a molded article having mechanical properties such as tensile elongation. It is another object of the present invention to provide molded parts, particularly automobile parts such as hoses and boots (blow molded articles) for automobiles, which are obtained by including the thermoplastic elastomer composition and have better oil resistance.
- thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing a crystalline olefin polymer, a specific ethylene / ⁇ -olefin / non-conjugated polyene copolymer, and a phenol resin crosslinking agent is obtained.
- the present inventors have found that the above problems can be solved, and have completed the present invention (1).
- thermoplastic elastomer composition according to the present invention (1) (also referred to as composition (I) in the present invention) is a crystalline olefin polymer (A), which satisfies the following requirements (1) and (2): It is obtained by dynamically crosslinking a mixture containing an ⁇ -olefin (having 4 to 20 carbon atoms), a non-conjugated polyene copolymer (1B), and a phenol resin crosslinking agent (C).
- the B value represented by the following formula (i) is 1.20 to 1.80.
- [E], [X] and [Y] are, respectively, the mole fraction of structural units derived from ethylene, the mole fraction of structural units derived from ⁇ -olefins having 4 to 20 carbon atoms, and those derived from non-conjugated polyenes.
- the molar fraction of the structural unit is indicated, and [EX] indicates the dyad chain fraction of the structural unit derived from ethylene-the structural unit derived from ⁇ -olefin having 4 to 20 carbon atoms.
- the molar ratio of the structural unit derived from ethylene and the structural unit derived from ⁇ -olefin (having 4 to 20 carbon atoms) in the copolymer (1B) is 40/60 to 90/10.
- the ⁇ -olefin of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (1B) is preferably 1-butene.
- the mixture preferably further contains 2 to 100 parts by weight of the softening agent (D) with respect to 100 parts by weight in total of the crystalline olefin polymer (A) and the copolymer (1B). .
- the phenol resin-based crosslinking agent (C) is preferably a halogenated phenol resin-based crosslinking agent.
- the phenol resin-based crosslinking agent (C) is preferably contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (1B).
- the molded article of the present invention (1) is obtained by including the thermoplastic elastomer composition of the present invention (1).
- the automobile part of the present invention (1) is characterized by being obtained by including the thermoplastic elastomer composition of the present invention (1).
- the automobile hose of the present invention (1) is obtained by including the thermoplastic elastomer composition of the present invention (1).
- the boot for automobiles of the present invention (1) is characterized by being obtained by including the thermoplastic elastomer composition of the present invention (1).
- the method for producing the thermoplastic elastomer composition (I) of the present invention comprises a crystalline olefin polymer (A) and the ethylene / ⁇ -olefin (having 4 to 20 carbon atoms) / non-conjugated polyene copolymer (1B). And a step of dynamically crosslinking the mixture containing the phenol resin-based crosslinking agent (C).
- the present inventors have intensively studied to solve the above problems.
- the compression set at low temperature is small and flexible, and the rubber elasticity at low temperature and room temperature are low.
- a specific ethylene / ⁇ -olefin / non-conjugated polyene copolymer having an excellent balance with the tensile strength of the resin and a composition containing the copolymer (also referred to as composition (IIA) in the present invention) (2) has been completed.
- a hose-forming composition capable of forming a hose excellent in low-temperature characteristics and mechanical properties by using a specific ethylene / ⁇ -olefin / non-conjugated polyene copolymer (in the present invention, a composition (Also referred to as (IIB)) and a hose formed from the composition can be provided, and the present invention (2) has been completed.
- thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing a crystalline olefin polymer, a specific ethylene / ⁇ -olefin / non-conjugated polyene copolymer, and a phenol resin crosslinking agent (present)
- the composition also referred to as IIC
- the composition has oil resistance superior to that of a conventional cross-linked thermoplastic elastomer, and has a hardness, tensile strength and It has been found that a molded article having mechanical properties such as tensile elongation can be obtained, and the thermoplastic elastomer composition (IIC) is a molded article having better oil resistance, in particular, hoses and boots for automobiles ( The present inventors have found that automobile parts such as blow molded products can be provided, and have completed the present invention (2).
- the present invention (2) relates to the following [1] to [18], for example.
- the molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] and the structural unit derived from ⁇ -olefin [B] is 40/60 to 90/10
- the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%.
- the B value represented by the following formula (i) is 1.20 to 1.80.
- B value ([EX] +2 [Y]) / [2 ⁇ [E] ⁇ ([X] + [Y])] (i) [Where [E], [X] and [Y] are the mole fractions of ethylene [A], ⁇ -olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. [EX] represents ethylene [A] - ⁇ -olefin [B] dyad chain fraction having 4 to 20 carbon atoms. ]
- A a transition metal compound represented by the following general formula [VII];
- B (b-1) an organometallic compound, in the presence of an olefin polymerization catalyst comprising (b-2) an organoaluminum oxy compound, and (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair.
- An ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B) obtained by copolymerizing ethylene, an ⁇ -olefin having 4 to 20 carbon atoms, and a non-conjugated polyene, according to [1] or [2] .
- M is a titanium atom, a zirconium atom or a hafnium atom
- R 5 and R 6 are substituted aryl groups obtained by substituting one or more hydrogen atoms of an aryl group with an electron donating substituent having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less
- each of the electron donating substituents may be the same or different, and other than the electron donating substituent, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, nitrogen
- a substituted aryl which may have a substituent selected from a containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and when there are a plurality of such substituents, each substituent may be the same or different.
- Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordinating with a lone electron pair in the same or different combinations; j is an integer of 1 to 4.
- a composition comprising the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B) according to any one of [1] to [3].
- [6] [1] A composition for forming a hose comprising the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B) according to any one of [1] to [3].
- the mixture further contains 2 to 100 parts by weight of a softening agent (D) with respect to a total of 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (2B) [9 ].
- a softening agent (D) with respect to a total of 100 parts by weight of the crystalline olefin polymer (A) and the copolymer (2B) [9 ].
- thermoplastic elastomer composition according to [9] or [10], wherein the phenol resin crosslinking agent (C) is a halogenated phenol resin crosslinking agent.
- the phenol resin-based crosslinking agent (C) is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B).
- the thermoplastic elastomer composition according to any one of the above.
- thermoplastic elastomer composition obtained by including the thermoplastic elastomer composition according to any one of [12].
- thermoplastic elastomer composition obtained by including the thermoplastic elastomer composition according to any one of [12].
- thermoplastic elastomer composition obtained by including the thermoplastic elastomer composition according to any one of [9] to [12].
- thermoplastic elastomer composition obtained by including the thermoplastic elastomer composition according to any one of [12].
- B) (b-1) an organometallic compound, in the presence of an olefin polymerization catalyst comprising (b-2) an organoaluminum oxy compound, and (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair.
- a mixture comprising a crystalline olefin polymer (A), the ethylene / ⁇ -olefin (C4-20) / nonconjugated polyene copolymer (2B), and a phenol resin crosslinking agent (C),
- a method for producing a thermoplastic elastomer composition comprising a step of dynamically crosslinking.
- thermoplastic elastomer composition capable of forming a molded article having mechanical properties such as tensile elongation.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer of the present invention (2) has a small compression set at low temperature and has flexibility, and has a rubber elasticity at low temperature and a tensile strength at normal temperature. Since the balance is excellent, a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene copolymer can be suitably used for various applications by taking advantage of such properties.
- a composition for forming a hose capable of forming a hose excellent in low temperature characteristics such as rubber elasticity at low temperature and mechanical properties such as tensile strength at normal temperature, And a hose formed from the composition.
- thermoplastic elastomer composition capable of forming a molded article having mechanical properties such as tensile elongation.
- the crystalline olefin polymer (A) (also referred to as polymer (A) in the present invention) is not particularly limited as long as it is a crystalline polymer obtained from olefin, but one or more monoolefins are converted into a high pressure method.
- a polymer composed of a crystalline high molecular weight solid product obtained by polymerization by either low pressure method is preferred. Examples of such a polymer include an isotactic monoolefin polymer and a syndiotactic monoolefin polymer.
- the polymer (A) may be obtained by synthesis by a conventionally known method, or a commercially available product may be used.
- a polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- Monoolefins used as starting materials for the polymer (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl- 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like can be mentioned. These olefins may be used alone or in combination of two or more.
- a propylene homopolymer or a propylene-based (co) polymer that is a propylene copolymer obtained from a monoolefin mainly composed of propylene is preferable.
- the content of the structural unit derived from propylene is preferably 40 mol% or more, more preferably 50 mol% or more, and as a monoolefin that becomes a structural unit derived from a monomer other than propylene. Is preferably the above monoolefin other than propylene, more preferably ethylene or butene.
- the polymerization mode may be random type or block type, and any polymerization mode can be adopted as long as a crystalline resinous material can be obtained.
- the crystalline olefin polymer (A) has an MFR (ASTM D1238-65T, 230 ° C., 2.16 kg load), usually 0.01 to 100 (g / 10 min), preferably 0.05 to 50 ( g / 10 minutes).
- the polymer (A) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) of usually 100 ° C. or higher, preferably 105 ° C. or higher.
- the differential scanning calorimetry is performed, for example, as follows. About 5 mg of a sample is packed in a special aluminum pan, heated to 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer, Inc., held at 200 ° C. for 5 minutes, and then 200 ° C.
- the melting point is determined from the endothermic curve when the temperature is lowered from 10 to 30 ° C. at 10 ° C./min, held at 30 ° C. for 5 minutes, and then heated at 10 ° C./min.
- Tm melting point
- the polymer (A) plays a role of improving the fluidity and heat resistance of the thermoplastic elastomer composition.
- ⁇ Ethylene / ⁇ -Olefin / Nonconjugated Polyene Copolymer (1B)> The ethylene / ⁇ -olefin / non-conjugated polyene copolymer (1B) used in the present invention (1) (also referred to as copolymer (1B) in the present invention) is a structural unit derived from ethylene and contains at least one carbon number.
- An ethylene / ⁇ -olefin / non-conjugated polyene copolymer comprising 4 to 20 ⁇ -olefin-derived structural units and at least one structural unit derived from a non-conjugated polyene;
- [EX] represents the dyad chain fraction of the structural unit derived from ethylene-the structural unit derived from ⁇ -olefin having 4 to 20 carbon atoms), (2) The molar ratio of the structural unit derived from ethylene and the structural unit derived from ⁇ -olefin (having 4 to 20 carbon atoms) in the copolymer (1B) is 40/60 to 90/10.
- Examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-nonadecene (19 carbon atoms), 1- Linear ⁇ -olefin having no side chain such as eicosene (carbon number 20); 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene having a side chain, 12- And ⁇ -olefins having a side chain such as ethyl-1-tetradecene. These ⁇ -olefins may be used alone or in combination of two or more.
- ⁇ -olefins having 4 to 10 carbon atoms are preferable, 1-butene, 1-hexene and 1-octene are more preferable.
- 1-butene is particularly preferable in the obtained molding.
- the oil resistance of the body in particular, oil resistance at a relatively high temperature, flexibility and impact resistance can be improved, which is more preferable.
- Non-conjugated polyenes include chains such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, etc.
- non-conjugated polyenes may be used alone or in combination of two or more.
- mixtures of cyclic non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are included.
- 5-Ethylidene-2-norbornene and 5-vinyl-2-norbornene are more preferable.
- Examples of the copolymer (1B) include ethylene / 1-butene / 1,4-hexadiene copolymer, ethylene / 1-pentene / 1,4-hexadiene copolymer, ethylene / 1-hexene / 1,4-hexadiene.
- Copolymer ethylene / 1-heptene / 1,4-hexadiene copolymer, ethylene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-nonene / 1,4-hexadiene copolymer, Ethylene / 1-decene / 1,4-hexadiene copolymer, ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer Ethylene / 1-pentene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-hexene / 5-ethylidene-2-norbornene copolymer, ethylene 1-
- the copolymer (1B) may be used alone or in combination of two or more.
- the copolymer (1B) has (1) a B value represented by the above formula (i) of 1.20 or more, preferably 1.20 to 1.80, particularly preferably 1.22 to 1.40. is there.
- the copolymer (1B) having a B value of less than 1.20 has a large compression set, and there is a possibility that a thermoplastic elastomer composition having an excellent balance between rubber elasticity and tensile strength may not be obtained.
- the B value is an index indicating the randomness of the copolymer monomer chain distribution in the copolymer (1B), and [E], [X], [Y], [EX] in the above formula (i). measures the 13 C-NMR spectrum, J. C.Randall [Macromolecules, 15 , 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)] can be determined based on these reports.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (1B) comprises (2) a molar ratio [[A] of the structural unit [A] derived from ethylene and the structural unit [B] derived from ⁇ -olefin. / [B]] is in the range of 40/60 to 90/10.
- the lower limit of the molar ratio [A] / [B] is preferably 45/55, more preferably 50/50, and particularly preferably 55/45.
- the upper limit of the molar ratio [A] / [B] is preferably 80/20, more preferably 75/25, still more preferably 70/30, and particularly preferably 65/35.
- thermoplastic elastomer composition (I) excellent in balance with the tensile strength at room temperature can be obtained.
- the copolymer (1B) preferably satisfies at least one of the following requirements (3) and (4).
- the copolymer (1B) is obtained as long as the Mooney viscosity ML (1 + 4) (125 ° C.) at 125 ° C. obtained by measuring according to (3) JIS K6300 (1994) exhibits the effects of the present invention. Although not particularly limited, it is preferably in the range of 5 to 100, more preferably 20 to 95, and still more preferably 50 to 90.
- the content of structural units [C] derived from non-conjugated polyenes is such that the total of structural units of [A], [B] and [C] is 100 mol%. , Preferably 0.1 to 6.0 mol%, more preferably 0.5 to 4.0 mol%, still more preferably 0.5 to 3.5 mol%, particularly preferably 0.5 to 3.0 mol%. % Range.
- the content of the structural unit [C] derived from the non-conjugated polyene is in the above range, an ethylene copolymer having sufficient crosslinkability and flexibility tends to be obtained.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B) of the present invention (2) (also referred to as copolymer (2B) in the present invention) is a structural unit derived from ethylene [A], having 4 to 4 carbon atoms. 20 structural units derived from ⁇ -olefin [B] and structural units derived from non-conjugated polyene [C], which satisfy the following (1) to (4).
- Such a specific ethylene / ⁇ -olefin / non-conjugated polyene copolymer is also referred to as “ethylene-based copolymer 2A”.
- the ⁇ -olefin [B] having 4 to 20 carbon atoms and the non-conjugated polyene [C] may be used alone or in combination of two or more.
- the copolymer (1B) or (2B) comprises a structural unit derived from ethylene [A], at least one structural unit derived from ⁇ -olefin [B] having 4 to 20 carbon atoms, and at least one non-structural unit. It contains structural units derived from conjugated polyene [C].
- the molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] and the structural unit derived from ⁇ -olefin [B] is 40/60 to 90/10
- the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%.
- the B value represented by the above formula (i) is 1.20 or more.
- Formula (i) is the same as Formula (i) of copolymer (1B).
- Examples of the ⁇ -olefin [B] having 4 to 20 carbon atoms can refer to the examples of the ⁇ -olefin having 4 to 20 carbon atoms in the copolymer (1B).
- the ⁇ -olefin [B] is preferably an ⁇ -olefin having 4 to 10 carbon atoms, particularly 1-butene, 1-hexene, 1-octene, etc., and particularly 1-butene. Is preferred.
- the ethylene / propylene / non-conjugated polyene copolymer in which the ⁇ -olefin is propylene tends to have insufficient rubber elasticity at low temperatures, and its use may be limited.
- the copolymer (2B) since the copolymer (2B) has a structural unit derived from an ⁇ -olefin [B] having 4 to 20 carbon atoms, it has excellent rubber elasticity at low temperatures.
- non-conjugated polyene [C] examples of the non-conjugated polyene in the copolymer (1B) can be referred to.
- examples of the non-conjugated polyene [C] include linear non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl- Cyclic non-conjugated dienes such as 2-norbornene are preferred, among which cyclic non-conjugated dienes are preferred, and 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are particularly preferred.
- Examples of the copolymer (1B) can be referred to as the copolymer (2B).
- the copolymer (2B) one type or two or more types are used as necessary.
- the molar ratio [[A] / [B]] of (1) the structural unit derived from ethylene [A] and the structural unit derived from ⁇ -olefin [B] is The molar ratio [[A] / [B]] of requirement (2) in the polymer (1B) and the preferable range of the molar ratio are the same.
- the content of the structural unit derived from (2) non-conjugated polyene [C] in the copolymer (2B) is the same as the content of the requirement (4) in the copolymer (1B), including the preferred range. It is.
- the copolymer (2B) has (3) Mooney viscosity ML (1 + 4) at 125 ° C. of 125 ° C. exceeding 100 and not exceeding 200, preferably exceeding 100 and not exceeding 150, particularly preferably exceeding 100 and not exceeding 120 It is in the range.
- the composition (2) containing the copolymer (2B) is preferable because the sealing properties and low temperature characteristics are improved.
- the (4) B value of the copolymer (2B) is the same as the B value of requirement (1) in the copolymer (1B), including the preferred range.
- a copolymer having a B value of less than 1.20 has an increased compression set at low temperatures, and is an ethylene-based polymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at normal temperatures. There is a possibility that a copolymer cannot be obtained.
- B value is an parameter
- index index which shows the randomness of the copolymerization monomer chain distribution in a copolymer (2B) as detailed in the said copolymer (1B).
- the molar amount of the structural unit derived from ethylene [A], the structural unit derived from ⁇ -olefin [B], and the structural unit derived from non-conjugated polyene [C] is: It can be determined by intensity measurement with a 1 H-NMR spectrometer.
- Copolymers (1B) and (2B) can be obtained, for example, by the following production method.
- (a-3) a transition metal compound represented by the following general formula [VII] (may be abbreviated as “bridged metallocene compound” in the following description), and (b) (b- 1) at least one selected from the group consisting of an organic metal compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the transition metal compound (a-3) to form an ion pair.
- an olefin polymerization catalyst containing a compound it can be produced by copolymerizing ethylene, an ⁇ -olefin having 4 to 20 carbon atoms and a non-conjugated polyene.
- Y is an atom selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom, and is preferably a carbon atom.
- M is a titanium atom, a zirconium atom or a hafnium atom, preferably a hafnium atom.
- R 5 and R 6 are substituted aryl groups obtained by substituting one or more hydrogen atoms of an aryl group with an electron donating substituent having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less, In the case of having a plurality of electron-donating substituents, the electron-donating substituents may be the same or different.
- a hydrocarbon group having 1 to 20 carbon atoms, silicon-containing May have a substituent selected from the group consisting of a group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and when there are a plurality of such substituents, each substituent may be the same or different.
- a substituted aryl group hereinafter also referred to as “electron-donating group-containing substituted aryl group”).
- aryl group phenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group
- aryl group is preferably a phenyl group or a 2-naphthyl group.
- aromatic compounds examples include aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, and heterocyclic aromatic compounds. Is mentioned.
- Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but this is widely accepted today.
- Substituent constants obtained by Hammett's rule include ⁇ p when substituted at the para-position of the benzene ring and ⁇ m when substituted at the meta-position, and these values can be found in many general literatures. For example, the literature by Hansch and Taft [Chem.
- an electron donating group having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less means that ⁇ p is ⁇ 0 when the electron donating group is substituted at the para position (position 4) of the phenyl group. .2 or less electron-donating group, and when substituted at the meta position (3-position) of the phenyl group, ⁇ m is an electron-donating group of ⁇ 0.2 or less.
- ⁇ p is ⁇ 0.2 or less. Electron donating group.
- the electron donating substituents having Hammett's rule constant ⁇ p or ⁇ m of ⁇ 0.2 or less include p-amino group (4-amino group), p-dimethylamino group (4-dimethylamino group), p- Nitrogen-containing groups such as diethylamino group (4-diethylamino group) and m-diethylamino group (3-diethylamino group), oxygen-containing groups such as p-methoxy group (4-methoxy group) and p-ethoxy group (4-ethoxy group) Groups, tertiary hydrocarbon groups such as pt-butyl group (4-t-butyl group), silicon-containing groups such as p-trimethylsiloxy group (4-trimethylsiloxy group), and the like.
- the electron donating substituents having Hammett's rule constant ⁇ p or ⁇ m defined in the present invention of ⁇ 0.2 or less are those described in the literature by Hansch and Taft [Chem. Rev., 91, 165 (1991)].
- the substituents are not limited to those described in Table 1 (pages 168-175). Even if the substituent is not described in the document, the substituent constant ⁇ p or ⁇ m when measured based on Hammett's rule is within the range thereof is the Hammett's rule substituent defined in the present invention.
- the constant ⁇ p or ⁇ m is included in the electron donating group having ⁇ 0.2 or less. Examples of such a substituent include a pN-morpholinyl group (4-N-morpholinyl group) and an mN-morpholinyl group (3-N-morpholinyl group).
- each electron-donating substituent may be the same or different.
- a substituent selected from the group consisting of 1 to 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups may be substituted, and a plurality of the substituents may be substituted.
- Each substituent may be the same or different, but the sum of the electron donating substituent contained in one substituted aryl group and the Hammett's rule substituent constant ⁇ of each substituent is ⁇ 0. .15 or less is preferable.
- substituted aryl groups examples include m, p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p- (dimethylamino) -m-methoxyphenyl group (4- (dimethylamino) -3-methoxyphenyl. Group), p- (dimethylamino) -m-methylphenyl group (4- (dimethylamino) -3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group) And p-methoxy-m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms that the electron-donating group-containing substituted aryl group may have include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and 2 carbon atoms. And a chain unsaturated hydrocarbon group having 20 to 20 and a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms. In the case where a plurality of hydrocarbon groups having 1 to 20 carbon atoms are present and the hydrocarbon groups having 1 to 20 carbon atoms are adjacent to each other, they may be bonded to each other to form a ring. Examples of the group in this case include an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 20 carbon atoms.
- alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl.
- a straight-chain saturated hydrocarbon group such as n-decanyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3-methylpentyl group, 1,1- Diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl Examples thereof include branched saturated hydrocarbon groups such as a -2-methylpropyl group and a cyclopropylmethyl group.
- the alkyl group preferably has 1 to 6 carbon atoms.
- Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, and 2-adamantyl group.
- the cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
- Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), etc. , An alkynyl group such as ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), and the like.
- the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
- cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms examples include unsubstituted cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group.
- Hydrogen group 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group,
- a hydrogen atom of an unsubstituted cyclic unsaturated hydrocarbon group such as 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group (mesityl group),
- a group substituted by a hydrocarbon group; a hydrogen atom of a linear hydrocarbon group such as a benzyl group or a cumyl group or a branched saturated hydrocarbon group has 3 carbon atoms
- Such groups are replaced by cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group et 19 thereof.
- the number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6-10.
- alkylene group having 1 to 20 carbon atoms examples include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples include 1,2-dimethylethylene group and n-propylene group.
- the alkylene group preferably has 1 to 6 carbon atoms.
- Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4′-biphenylylene group.
- the arylene group preferably has 6 to 12 carbon atoms.
- Examples of the silicon-containing group that the electron-donating group-containing substituted aryl group may have include an alkylsilyl group such as a trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group; dimethylphenylsilyl group, methyl Arylsilyl groups such as diphenylsilyl group and t-butyldiphenylsilyl group; groups having 1 to 20 carbon atoms such as pentamethyldisiranyl group and trimethylsilylmethyl group, wherein carbon atoms are replaced by silicon atoms, etc. Is mentioned.
- the alkylsilyl group preferably has 1 to 10 carbon atoms
- the arylsilyl group preferably has 6 to 18 carbon atoms.
- Examples of the nitrogen-containing group that the electron-donating group-containing substituted aryl group may have include an amino group, a nitro group, an N-morpholinyl group, the above-described hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group.
- a group in which the CH— structural unit is replaced with a nitrogen atom a group in which the —CH 2 — structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a —CH 3 structural unit has 1 carbon atom Dimethylamino group, diethylamino group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, and the like, which are groups substituted by nitrogen atoms or nitrile groups to which 20 to 20 hydrocarbon groups are bonded.
- the nitrogen-containing group a dimethylamino group and an N-morpholinyl group are preferable.
- the oxygen-containing group that the electron-donating group-containing substituted aryl group may have includes a hydroxyl group, a —CH 2 — structural unit in the above-described hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group.
- Phenoxy group trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2- Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapenthi Group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamo
- halogen atom that the electron-donating group-containing substituted aryl group may have include fluorine, chlorine, bromine and iodine which are Group 17 elements.
- Examples of the halogen-containing group that the electron-donating group-containing substituted aryl group may have include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, or an oxygen-containing group, in which a hydrogen atom is a halogen atom.
- Examples thereof include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups substituted by atoms.
- Q is an atom, substituent or ligand selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, When there are a plurality of Qs, they may be the same or different.
- halogen atom to be Q and the hydrocarbon group having 1 to 20 carbon atoms are the same as the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms that the electron-donating group-containing substituted aryl group may have. It is.
- Q is a halogen atom
- a chlorine atom is preferable.
- Q is a hydrocarbon group having 1 to 20 carbon atoms
- the hydrocarbon group preferably has 1 to 7 carbon atoms.
- anionic ligand examples include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.
- Neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc. An ether compound etc. are mentioned.
- J is an integer from 1 to 4, preferably 2.
- the 2,3,6,7-tetramethylfluorenyl group contained in the bridged metallocene compound (a) represented by the general formula [VII] has four substituents at the 2, 3, 6 and 7 positions. Therefore, it is presumed that the electronic effect is large, and this produces a high polymerization activity and high molecular weight ethylene copolymer.
- the polymerization catalyst for polymerizing the non-conjugated polyenes should not be bulky in the vicinity of the central metal of the metallocene compound that is the polymerization active site. Presumed to lead to performance improvement.
- the crosslinked metallocene compound represented by the above general formula [VII] containing a 2,3,6,7-tetramethylfluorenyl group in particular has a high molecular weight and a high non-conjugation of the resulting ethylene copolymer. It is presumed that the polyene copolymerization performance and the high polymerization activity are simultaneously realized at a high level with a good balance.
- the bridged metallocene compound (a-3) can be synthesized by a simple method such as the following formula [VIII].
- R 5 and R 6 are as described above.
- Various ketones satisfying such a condition represented by the general formula R 5 —C ( ⁇ O) —R 6 are generally used. Since it is commercially available from reagent manufacturers, it is easy to obtain the raw material for the bridged metallocene compound (a-3). Even if such a ketone is not commercially available, it can be easily synthesized, for example, by the method of Olah et al. [Heterocycles, 40, 79 (1995)].
- the bridged metallocene compound (a-3) has a relatively simple and easy production process, further reducing the production cost.
- the production cost of the ethylene copolymer can be reduced.
- the advantage that is reduced is obtained.
- ethylene, an ⁇ -olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a-3), the copolymer to be produced is further increased. An advantage that molecular weight can be obtained is also obtained.
- R 5 and R 6 are preferably a group selected from the group consisting of an aryl group and a substituted aryl group.
- R 5 and R 6 are preferably a group selected from the group consisting of an aryl group and a substituted aryl group.
- the copolymerization performance of the nonconjugated polyene is improved (for example, the content of the nonconjugated polyene unit in the copolymer is increased, and the nonconjugated polyene unit is easily dispersed uniformly in the copolymer). can get.
- R 5 and R 6 are more preferably the same group.
- the synthesis process of the bridged metallocene compound is simplified, and the production cost is further reduced.
- the production cost of the copolymer is reduced.
- ethylene, an ⁇ -olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, the resulting copolymer can have a higher molecular weight. There is an advantage of being.
- the bridged metallocene compound (a-3) represented by the general formula [VII] has R 5 and R 6 as the above groups.
- the bridged metallocene compound (a-3) is contained by forming an electron donating group-containing substituted aryl group in which one or more electron donating substituents having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less are substituted.
- the molecular chain of the olefin polymer produced by the repeated polymerization of olefins on the central metal of the catalyst It is known to grow (growth reaction) and increase the molecular weight of the olefin polymer.
- a reaction called chain transfer the molecular chain of the olefin polymer is dissociated from the central metal of the catalyst, so that the growth reaction of the molecular chain is stopped, and therefore the increase in the molecular weight of the olefin polymer is also stopped.
- the molecular weight of the olefin polymer is characterized by the ratio between the frequency of the growth reaction and the frequency of the chain transfer reaction inherent to the organometallic complex catalyst that produces it. That is, the larger the ratio between the frequency of the growth reaction and the frequency of the chain transfer reaction, the higher the molecular weight of the olefin polymer produced, and vice versa.
- the frequency of each reaction can be estimated from the activation energy of each reaction. A reaction with a low activation energy is high in frequency, and conversely, a reaction with a high activation energy is low in frequency. It is thought that it can be done.
- the frequency of the growth reaction in olefin polymerization is sufficiently high compared to the frequency of the chain transfer reaction, that is, the activation energy of the growth reaction is sufficiently low compared to the activation energy of the chain transfer reaction.
- the value obtained by subtracting the activation energy of the growth reaction from the activation energy of the chain transfer reaction (hereinafter referred to as ⁇ Ec) is positive, and the larger the value, the greater the frequency of the growth reaction compared to the frequency of the chain transfer reaction. It is presumed that the molecular weight of the produced olefin polymer is high.
- R 5 and R 6 are preferably one electron donating substituent having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less.
- ⁇ Ec increases, and in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a-3), ⁇ and ⁇ having 4 or more carbon atoms are present.
- -It is presumed that when the olefin and the non-conjugated polyene are copolymerized, the molecular weight of the resulting copolymer increases.
- the electron donating substituent contained in R 5 and R 6 is a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group. More preferably it is.
- These substituents have a particularly low ⁇ in Hammett's rule, and the molecular weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is high, and in particular, the molecular weight can be increased even in high temperature polymerization that generally causes a decrease in molecular weight.
- R 5 and R 6 are a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent. More preferably, it is a substituted phenyl group.
- R 5 and R 6 are a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent. More preferably, it is a substituted phenyl group.
- examples of the substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent include o-aminophenyl group (2-aminophenyl group), p-aminophenyl Group (4-aminophenyl group), o- (dimethylamino) phenyl group (2- (dimethylamino) phenyl group), p- (dimethylamino) phenyl group (4- (dimethylamino) phenyl group), o- ( Diethylamino) phenyl group (2- (diethylamino) phenyl group), p- (diethylamino) phenyl group (4- (diethylamino) phenyl group), m- (diethylamino) phenyl group (3- (diethylamino) phenyl group), o- Methoxyphenyl group (2-
- R 5 and R 6 are substituted with the electron donating substituent at the meta position and / or the para position with respect to the bond with the carbon atom as Y. It is more preferably a substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as a group.
- a substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as a group for example, when synthesizing according to a method such as the above formula [VIII], the synthesis is facilitated compared to the case where the group is substituted at the ortho position, the production process is simplified, the production cost is further reduced, and this bridged metallocene is eventually produced.
- the advantage that the production cost of the ethylene copolymer is reduced is obtained by using the compound.
- R 5 and R 6 are substituted with the electron donating substitution at the meta position and / or the para position with respect to the bond with the carbon atom as Y.
- the nitrogen-containing group is more preferably a group represented by the following general formula [II].
- R 7 and R 8 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, an oxygen-containing group and a halogen-containing group; They may be the same or different, and may be bonded to each other to form a ring, and the line drawn to the right of N represents the bond with the phenyl group.
- Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the oxygen-containing group and the halogen-containing group as R 7 and R 8 are the same as those in the above formula [VII].
- Such a bridged metallocene compound (a-4) is represented by the following general formula [IX].
- R 7 , R 8 and R 10 are each a hydrogen atom having 1 to 20 carbon atoms.
- the bridged metallocene compound (transition metal compound) represented by the general formula [IX] has a particularly low ⁇ in the Hammett rule of the NR 7 R 8 represented by the general formula [II], so that ethylene, ⁇ -olefin, non-
- the molecular weight of the conjugated polyene copolymer can be increased, and in particular, the molecular weight can be increased even in high temperature polymerization that generally causes a decrease in molecular weight.
- R 5 and R 6 are substituted with the electron donating substitution at the meta position and / or the para position with respect to the bond with the carbon atom as Y.
- the oxygen-containing group is more preferably a group represented by the following general formula [III].
- R 9 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 and a halogen-containing group;
- the line drawn in Fig. 1 represents the bond with the phenyl group.
- Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group and the halogen-containing group as R 9 are the same as those in the formula [VII].
- Such a bridged metallocene compound (a-5) is represented by the following general formula [X].
- R 9 and R 10 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms. , a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from the group consisting of halogen atoms and halogen-containing groups, which may be the same as or different from each other, adjacent substituents of R 10 are each OR 9 may be bonded to form a ring, and OR 9 is an oxygen-containing group having a Hammett's rule substituent constant ⁇ of ⁇ 0.2 or less, and when there are a plurality of such oxygen-containing groups, The containing groups may be the same or different from each other, n is an integer of 1 to 3, and m is an integer of 0 to 4.) Specific examples of these substituents can be given as examples of the hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, oxygen
- the bridged metallocene compound (transition metal compound) represented by the general formula [X] has a lower ⁇ in the Hammett rule of OR 9 represented by the general formula [III], and therefore, ethylene / ⁇ -olefin / nonconjugated polyene
- the molecular weight of the copolymer can be increased, and in particular, the molecular weight can be increased even in high temperature polymerization that generally causes a decrease in molecular weight.
- M is more preferably a hafnium atom.
- the crosslinked metallocene compound used for the production of the copolymer (1B) or (2B) can be produced by a known method, and the production method is not particularly limited.
- a manufacturing method for example, J. et al. Organomet. Chem. , 63, 509 (1996), WO2006 / 123759, WO01 / 27124, JP2004-168744, JP2004-175759, and JP2000-, which are publications relating to applications by the present applicant. And the production method described in Japanese Patent No. 212194.
- the catalyst is (A) a bridged metallocene compound represented by the above general formula [VII], (b) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a bridged metallocene compound ( It comprises at least one compound selected from the group consisting of a compound that reacts with a) to form an ion pair, and (c) a particulate carrier, if necessary.
- a bridged metallocene compound represented by the above general formula [VII] (b) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a bridged metallocene compound ( It comprises at least one compound selected from the group consisting of a compound that reacts with a) to form an ion pair, and (c) a particulate carrier, if necessary.
- Examples of the compound represented by the general formula [X] include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride. , Ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, diisobutylaluminum hydride and the like.
- Examples of the compound represented by the general formula [XI] include LiAl (C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
- R a and R b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 represents Mg, Zn or A dialkyl compound having a metal of Group 2 or Group 12 of the periodic table represented by Cd.
- organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferable.
- organometallic compounds (b-1) may be used alone or in combination of two or more.
- the (b-2) organoaluminum oxy compound used in the production of the copolymer (1B) or (2B) may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. Such a benzene-insoluble organoaluminum oxy compound may be used.
- the organoaluminum oxy compound may be used alone or in combination of two or more.
- the conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbon solvent.
- Compounds containing adsorbed water or salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc.
- a method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
- the aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
- organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-1a).
- trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.
- organoaluminum compounds are used singly or in combination of two or more.
- (b-2) benzene-insoluble organoaluminum oxycompound which is one embodiment of organoaluminum oxycompound, has an Al component dissolved in benzene at 60 ° C., usually 10% by weight or less with respect to 100% by weight of benzene in terms of Al atom. It is preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, one that is insoluble or hardly soluble in benzene.
- the organoaluminum oxy compound includes an organoaluminum oxy compound containing boron represented by the following general formula [X].
- R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 2 to R 5 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a carbon number of 1 to 10 hydrocarbon groups are shown.
- the organoaluminumoxy compound containing boron represented by the general formula [X] includes an alkyl boronic acid represented by the following general formula [XI], R 1 -B (OH) 2 ...
- R 1 represents the same group as R 1 in the general formula [X]. It can be produced by reacting an organoaluminum compound 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.
- alkyl boronic acid represented by the general formula [XI] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron.
- Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like.
- methyl boronic acid n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.
- organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a).
- trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
- the (b-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.
- ⁇ (B-3) Compound that reacts with transition metal compound (a) to form an ion pair>
- a compound (b-3) (hereinafter referred to as “ionized ionic compound”) that reacts with the bridged metallocene compound (a) used in the production of the copolymer (1B) or (2B) to form an ion pair.
- ionized ionic compound that reacts with the bridged metallocene compound (a) used in the production of the copolymer (1B) or (2B) to form an ion pair.
- Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in USP-5321106.
- heteropoly compounds and isopoly compounds can also be mentioned.
- Such ionized ionic compounds (b-3) are used singly or in combination of two or more.
- a compound represented by BR 3 (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned.
- R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group
- trifluoroboron triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( and p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
- Examples of the ionic compound include compounds represented by the following general formula [XII].
- examples of R 1+ include H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
- 2 to R 5 may be the same or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
- Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
- ammonium cation examples 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, N, N, 2,4,6-pentamethylanilinium cation; Examples thereof include dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.
- phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
- R 1+ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.
- Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
- trialkyl-substituted ammonium salts include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl).
- N, N-dialkylanilinium salt examples include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6. -Pentamethylanilinium tetra (phenyl) boron and the like.
- dialkylammonium salt examples include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.
- triphenylcarbenium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl
- Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XIII] or [XIV].
- the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Metal borane anion salts such as -butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.
- carborane compound examples include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonarborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carba Badodecaborate, tri (n-butyl) ammonium-1-trimethyl
- the heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
- (B-3) Among the ionized ionic compounds, the above ionic compounds are preferable, and among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable. More preferred.
- transition metal compound (a) represented by the general formula [VII] is used as a catalyst, an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, or the like
- an ionized ionic compound (b-3) such as triphenylcarbenium tetrakis (pentafluorophenyl) borate is used in combination, it is very difficult to produce an ethylene / ⁇ -olefin / nonconjugated polyene copolymer (1B) or (2B). High polymerization activity.
- the olefin polymerization catalyst used for the production of the copolymer (1B) or (2B) includes the transition metal compound (a), (b-1) an organometallic compound, and (b-2) an organoaluminum oxy
- a carrier (c) can be used as necessary together with the compound and (b-3) at least one compound (b) selected from the group consisting of ionized ionic compounds.
- the carrier (c) is an inorganic compound or an organic compound and is a granular or particulate solid.
- porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable.
- porous oxide examples include inorganic oxides such as SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, and ThO 2 , or composites containing these inorganic oxides. Or, a porous material mainly composed of a mixture can be mentioned. Specific examples of the porous oxide include natural or synthetic zeolites; SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , Examples thereof include porous oxides mainly composed of SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , SiO 2 —TiO 2 —MgO.
- porous oxides mainly composed of SiO 2 and / or Al 2 O 3 are preferred.
- the carrier preferably used in the present invention has a particle size of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, and a specific surface area of usually 50 to It is desirable that it is in the range of 1000 m 2 / g, preferably 100 to 700 m 2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g.
- Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
- the inorganic halide examples include MgCl 2 , MgBr 2 , MnCl 2 , and MnBr 2 .
- the inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.
- the clay used as the carrier (c) is usually composed mainly of a clay mineral.
- the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. .
- Most clay minerals are ion-exchangeable layered compounds.
- these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.
- clay, clay mineral, or ion-exchangeable layered compound clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl 2 type, CdI 2 type, etc. Can be mentioned.
- clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Is mentioned.
- Examples of the ion-exchange layered compound include ⁇ -Zr (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2 ⁇ 3H 2 O, ⁇ -Ti (HPO 4 ). 2 , ⁇ -Ti (HAsO 4 ) 2 .H 2 O, ⁇ -Sn (HPO 4 ) 2 .H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Ti (HPO 4 ) 2 , ⁇ -Ti ( Examples thereof include crystalline acidic salts of polyvalent metals such as NH 4 PO 4 ) 2 .H 2 O.
- Such a clay, clay mineral or ion exchange layered compound preferably has a pore volume of not less than 0.1 cc / g having a radius of 20 mm or more as measured by a mercury intrusion method, and is preferably from 0.3 to 5 cc / g. Particularly preferred.
- the pore volume is measured in a pore radius range of 20 to 30000 mm by a mercury intrusion method using a mercury porosimeter.
- the clay and clay mineral used as the carrier (c) is also preferable to subject the clay and clay mineral used as the carrier (c) to chemical treatment.
- the chemical treatment any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used.
- Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.
- the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure.
- Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
- an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.
- the ion-exchangeable layered compound used as the carrier (c) is a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. May be.
- Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars.
- introducing another substance between the layers of the layered compound in this way is called intercalation.
- guest compounds to be intercalated include cationic inorganic compounds such as TiCl 4 and ZrCl 4 ; metal alkoxides such as Ti (OR) 4 , Zr (OR) 4 , PO (OR) 3 , and B (OR) 3 ( R is a hydrocarbon group), metal hydroxides such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ , and [Fe 3 O (OCOCH 3 ) 6 ] + And ions. These compounds can be used alone or in combination of two or more.
- these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) 4 , Al (OR) 3 , Ge (OR) 4 (R is a hydrocarbon group, etc.).
- metal alkoxides such as Si (OR) 4 , Al (OR) 3 , Ge (OR) 4 (R is a hydrocarbon group, etc.
- Polymers, colloidal inorganic compounds such as SiO 2, and the like can also coexist.
- the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
- the above clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment.
- These substances to be the carrier (c) may be used alone or in combination of two or more.
- clay or clay mineral is preferable, and montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica are particularly preferable.
- Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 ⁇ m.
- a (co) polymer produced mainly from an ⁇ -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.
- the olefin polymerization catalyst used in the production of the copolymers (1B) and (2B) includes a crosslinked metallocene compound (a), (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, And (b-3) at least one compound (b) selected from the group consisting of ionized ionic compounds and a carrier (c) used as necessary.
- At least two of the compound (a), the compound (b) and the carrier (c) may be contacted in advance.
- the unsupported compound (b) may be added in any order as necessary.
- the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).
- the solid catalyst component in which the compound (a) is supported on the carrier (c) and the solid catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c) are prepolymerized with olefin.
- a catalyst component may be further supported on the prepolymerized solid catalyst component.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (1B) or (2B) is prepared in the presence of the above-mentioned catalyst for ethylene / ⁇ -olefin / non-conjugated polyene copolymer. And can be prepared by copolymerizing non-conjugated polyenes.
- the above copolymer (1B) or (2B) can be produced by either a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization, or a gas phase polymerization method.
- Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; fats such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.
- the said inert hydrocarbon medium may be used individually by 1 type, and may be used in combination of 2 or more type.
- olefin itself can also be used as a solvent.
- the crosslinked metallocene compound (a) is usually 10 ⁇ 12 to 10 ⁇ 2 mol, preferably 10 ⁇ 10 mol per liter of reaction volume. It is used in an amount of ⁇ 10 ⁇ 8 mol.
- the molar ratio [(b-1) / M] of the compound (b-1) to all transition metal atoms (M) in the bridged metallocene compound (a) is usually 0. It is used in an amount of 0.01 to 50000, preferably 0.05 to 10000.
- the organoaluminum oxy compound (b-2) has a molar ratio [(b-2) / M] of the aluminum atoms in the compound (b-2) and the total transition metals (M) in the compound (a).
- the amount is usually 10 to 50000, preferably 20 to 10000.
- the molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atom (M) in the compound (a) is usually 1-20.
- the amount is preferably 1 to 15.
- the polymerization temperature of the copolymer (1B) or (2B) is usually ⁇ 50 to + 200 ° C., preferably 0 to + 200 ° C., more preferably +80 to + 200 ° C. Depending on the target molecular weight to be reached and the polymerization activity of the catalyst used, the polymerization temperature is preferably higher (+ 80 ° C. or higher) from the viewpoint of productivity.
- the polymerization pressure of the copolymer (1B) or (2B) is usually in the range of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure.
- the polymerization reaction mode of the copolymer (1B) or (2B) may be any of batch, semi-continuous and continuous.
- the polymerization can be performed in two or more stages having different reaction conditions.
- the molecular weight of the obtained copolymer (1B) or (2B) can be adjusted, for example, by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.
- the amount of hydrogen added is suitably about 0.001 to 100 NL per kg of olefin.
- a compound (b) for example, triisobutylaluminum, methylaluminoxane, diethylzinc etc.
- the molecular weight of a copolymer can be adjusted with the usage-amount of a compound (b).
- phenol resin-based crosslinking agent (C) also referred to as a crosslinking agent (C) in the present invention
- examples of the phenol resin-based crosslinking agent (C) include halogenated phenol resin-based crosslinking agents.
- the crosslinking agent (C) is a resole resin, which is produced by condensation of an alkyl-substituted phenol or unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde, or with a bifunctional phenol dialcohol. It is also preferable.
- the alkyl-substituted phenol is preferably an alkyl group-substituted product having 1 to 10 carbon atoms. Furthermore, dimethylolphenols or phenol resins substituted with an alkyl group having 1 to 10 carbon atoms in the p-position are preferred.
- the phenolic resin-based cured resin is typically a heat-crosslinkable resin and is also called a phenolic resin-based crosslinking agent or a phenol resin.
- phenol resin-based cured resin examples include the following general formula (I).
- Q is a divalent group selected from the group consisting of —CH 2 — and —CH 2 —O—CH 2 —, m is 0 or a positive integer of 1 to 20, and R ′ Is an organic group).
- Q is a divalent group —CH 2 —O—CH 2 —
- m is 0 or a positive integer from 1 to 10
- R ′ is an organic group having less than 20 carbon atoms. More preferably, m is 0 or a positive integer of 1 to 5, and R ′ is an organic group having 4 to 12 carbon atoms.
- Specific examples include alkylphenol formaldehyde resins, methylolated alkylphenol resins, halogenated alkylphenol resins, and the like, preferably halogenated alkylphenol resins, and more preferably brominated terminal hydroxyl groups. In the phenol resin-based cured resin, an example in which the terminal is brominated is shown in the following general formula (II).
- n is an integer of 0 to 10
- R is a saturated hydrocarbon group having 1 to 15 carbon atoms.
- Examples of products of the above-mentioned phenolic resin-based cured resins include tackolol (registered trademark) 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), tackirol (registered trademark) 250-I (bromination with a bromination rate of 4%) Alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), Tactrol (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) Vulkaresat 510E (manufactured by Hoechst), Vulcaresat 532E (manufactured by Hoechst), Vulkaresen® E (manufactured by Hoechst), Vulkaresen 105E (manufactured by Hoechst), Vulkarensen 130E (Hoech)
- Symform-C-1001 manufactured by Anchor Chem.
- Tamanol registered trademark
- Scientady® SP1059 manufactured by Schentechdy® Chem.
- Scientadey® SP1045 manufactured by Schemedy Chem.
- CRR-0803 manufactured by U.C.C.
- Sectectady® SP1055F Schominated alkylphenol Formaldehyde resin
- Schenectady SP1056 manufactured by Schenectady Chem.
- halogenated phenol resin-based crosslinking agent is preferable, and brominated alkylphenol / formaldehyde resins such as Tactrol (registered trademark) 250-I, Taccolol (registered trademark) 250-III, and Schenectady SP1055F can be more preferably used.
- thermoplastic vulcanizates with phenolic resins include US Pat. No. 4,311,628, US Pat. No. 2,972,600 and US Pat. No. 3,287,440. These techniques are also described and can be used in the present invention.
- U.S. Pat. No. 4,311,628 discloses a phenolic curative system composed of a phenolic curing resin and a cure activator.
- the basic component of the system is the condensation of substituted phenols (eg halogen-substituted phenols, C 1 -C 2 alkyl-substituted phenols) or unsubstituted phenols with aldehydes, preferably formaldehyde, in an alkaline medium, or bifunctional phenols
- aldehydes preferably formaldehyde
- bifunctional phenols A phenol resin-based crosslinking agent produced by condensation of dialcohols (preferably, dimethylolphenols substituted at the para position with a C 5 -C 10 alkyl group).
- halogenated alkyl-substituted phenolic resin crosslinking agents prepared by halogenation of alkyl-substituted phenolic resin crosslinking agents.
- a phenolic resin-based crosslinking agent comprising a methylolphenol curable resin, a halogen donor and a metal compound can be particularly recommended, and details thereof are described in US Pat. Nos. 3,287,440 and 3,709,840. Has been.
- Non-halogenated phenolic resin-based crosslinkers are used simultaneously with the halogen donor, preferably with a hydrogen halide scavenger.
- halogenated phenolic resin-based crosslinking agents preferably brominated phenolic resin-based crosslinking agents containing 2 to 10% by weight of bromine
- a halogen donor but for example iron oxide, titanium oxide, oxidation
- a hydrogen halide scavenger such as a metal oxide such as magnesium, magnesium silicate, silicon dioxide and zinc oxide, preferably zinc oxide.
- hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by weight per 100 parts by weight of the phenol resin-based crosslinking agent.
- Suitable halogen donors include stannous chloride, ferric chloride, or halogen donating heavys such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Coalescence is mentioned.
- vulcanization accelerator refers to any substance that substantially increases the crosslinking efficiency of a phenolic resin-based crosslinking agent, and includes metal oxides and halogen donors, which are Used alone or in combination. For more details on phenolic vulcanizing systems, see “Vulcanization and Vulcanizing Agents” (W. Hoffman, Palmerton Publishing Company).
- Suitable phenolic resin-based crosslinkers and brominated phenolic resin-based crosslinkers are commercially available, for example such crosslinkers from Schenectady Chemicals, Inc. under the trade names “SP-1045”, “CRJ-352”, It can be purchased as “SP-1055F” and “SP-1056”. Similar functionally equivalent phenolic resin crosslinkers can also be obtained from other suppliers.
- the crosslinking agent (C) is a suitable vulcanizing agent from the viewpoint of preventing fogging because it is less likely to generate decomposition products.
- Crosslinker (C) is used in an amount sufficient to achieve essentially complete vulcanization of the rubber.
- auxiliary agent Uniform and gentle crosslinking reaction can be expected by using the above auxiliary agent.
- divinylbenzene is preferable. Divinylbenzene is easy to handle and has good compatibility with the polymer (A) and the copolymer (1B) or copolymer (2B) contained as the main component in the composition (I) or (IIC). And a thermoplastic elastomer having a function of solubilizing the cross-linking agent (C) and acting as a dispersant for the cross-linking agent (C), so that the cross-linking effect by heat treatment is uniform and the fluidity and physical properties are balanced. Composition (I) or (IIC) is obtained.
- the above auxiliary agent is usually used in an amount of 2 parts by weight or less, preferably 0.3 to 1 part by weight based on 100 parts by weight of the copolymer (1B) or (2B).
- Decomposition accelerators include tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol; Naphthenic acid and various metals (for example, Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, rare earth) such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury Examples thereof include naphthenate.
- composition (I) or (IIC) of the present invention has the effects of the present invention. You may mix
- the additive examples include rubbers other than the copolymer (1B) or the copolymer (2B) (for example, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, propylene / butene copolymer rubber, and propylene / butene).
- Propylene elastomers such as ethylene copolymer rubber, ethylene elastomers such as ethylene / propylene copolymer rubber, styrene / butadiene / styrene block polymers, styrene / isoprene / styrene block polymers, styrene / isobutylene / styrene block polymers and these Styrene-based elastomers such as hydrogenated products); resins other than crystalline olefin polymers (A) such as thermosetting resins and thermoplastic resins such as polyolefins; UV absorbers; antioxidants
- additives may be used alone or in combination of two or more.
- the amount of additives other than those specifically mentioned in the present specification is not particularly limited as long as the effects of the present invention are exhibited, but the polymer (A) and the copolymer (1B) or (2B) ) To 100 parts by weight in total, usually 0.0001 to 10 parts by weight, preferably about 0.01 to 5 parts by weight.
- the softener (D) a softener usually used for rubber can be used.
- the softening agent (D) petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt and petroleum jelly; coal tar-based softening agents such as coal tar and coal tar pitch; castor oil and linseed oil
- Oil oil softeners such as rapeseed oil, soybean oil, coconut oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, stear Fatty acids or fatty acid salts such as calcium phosphate and zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, atactic polypropylene, coumarone indene resin; dioctyl phthalate, dio
- softeners (D) are not particularly limited as long as the effects of the present invention are exhibited, but usually 2 parts per 100 parts by weight of the total amount of the polymer (A) and the copolymer (1B) or (2B). It is used in an amount of ⁇ 100 parts by weight, preferably 5 to 80 parts by weight.
- the softening agent (D) is used in such an amount, the composition (I) or (IIC) has excellent fluidity at the time of preparation and molding, improves the dispersibility of carbon black, etc. It is difficult to lower the mechanical properties, and the obtained molded article is excellent in heat resistance and heat aging resistance.
- inorganic filler (E) calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, disulfide
- examples include molybdenum, graphite, carbon black, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.
- These inorganic fillers (E) are usually 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymer (A) and the copolymer (1B) or (2B). Used in parts quantity.
- anti-aging agent can refer to the composition (2B) described below.
- the rubber is used in a total amount of 100 parts by weight of the polymer (A) and the copolymer (1B) or (2B).
- the amount is usually 2 to 200 parts by weight, preferably 5 to 150 parts by weight.
- thermoplastic elastomer composition (I) or thermoplastic elastomer composition (IIC) The thermoplastic elastomer composition (I) of the present invention (1) is obtained by dynamically crosslinking a mixture containing the polymer (A), the copolymer (1B), and the crosslinking agent (C). The composition (I) is obtained by dynamically crosslinking at least the polymer (A), the copolymer (1B), and the crosslinking agent (C).
- composition (I) is crosslinked by dynamically heat-treating a mixture containing the polymer (A), the copolymer (1B), and additives that are blended as necessary in the presence of the crosslinking agent (C). It can be obtained by (dynamic crosslinking).
- composition (I) is obtained.
- thermoplastic elastomer composition (IIC) of the present invention (2) is obtained by dynamically crosslinking a mixture containing the polymer (A), the copolymer (2B), and the crosslinking agent (C).
- the composition (IIC) is obtained by dynamically crosslinking at least the polymer (A), the copolymer (2B), and the crosslinking agent (C).
- composition (IIC) is crosslinked by dynamically heat-treating a mixture containing the polymer (A), the copolymer (2B), and additives that are blended as necessary in the presence of the crosslinking agent (C). It can be obtained by (dynamic crosslinking).
- dynamically heat-treating refers to kneading the mixture in a molten state in the presence of the crosslinking agent (C).
- Dynamic crosslinking refers to crosslinking while applying a shearing force to the mixture.
- composition (I) or (IIC) may be a composition in which a polymer component containing the polymer (A) and the copolymer (1B) or (2B) is partially cross-linked. It may be a crosslinked composition.
- the weight ratio (A) / (1B) or the weight ratio (A) / (2B) of the polymer (A) and the copolymer (1B) or (2B) is , Preferably 90/10 to 10/90, more preferably 60/40 to 20/80.
- the weight ratio (A) / (1B) or the weight ratio (A) / (2B) is in the above range, a molded article having excellent mechanical properties and moldability can be obtained.
- the crosslinking agent (C) is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the copolymer (1B) or (2B). It is used in such an amount that it becomes a part.
- the blending amount of the crosslinking agent (C) within the above range, a composition having excellent moldability can be obtained, and the obtained molded body has high strength, excellent oil resistance, and sufficient Has heat resistance and mechanical properties.
- the dynamic heat treatment is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide.
- the temperature of the heat treatment is usually in the range from the melting point of the polymer (A) to 300 ° C., preferably 150 to 280 ° C., more preferably 170 to 270 ° C.
- the kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes.
- the applied shear force is usually 10 to 100,000 sec ⁇ 1 at the maximum shear rate, preferably 100 to 50,000 sec ⁇ 1 , more preferably 1,000 to 10,000 sec ⁇ 1 , and still more preferably 2,000. It is in the range of ⁇ 7,000 sec ⁇ 1 .
- Examples of the kneading apparatus used for kneading include a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw extruder, a twin screw extruder, and the like. These kneading devices are preferably non-open type devices.
- Composition (I) or (IIC), and a molded product obtained by molding the composition (I) or (IIC) by a conventionally known method are lighter in weight than conventional cross-linked thermoplastic elastomers. It has excellent oil resistance and mechanical properties such as hardness, tensile strength and tensile elongation equivalent to or higher than those of conventional cross-linked thermoplastic elastomers.
- the molded body of the present invention (1) or the molded body of the present invention (2) The shaped product of the present invention (1) is obtained containing the composition (I) of the present invention (1).
- the molded product of the present invention (2) is obtained containing the composition (IIC) of the present invention (2).
- compositions (I) and (IIC) have hardness and mechanical properties (tensile strength, elongation, etc.) equal to or higher than those of conventional cross-linked thermoplastic elastomers, and therefore can be used for various applications.
- the compositions (I) and (IIC) have excellent oil resistance compared to conventional cross-linked thermoplastic elastomers, it is particularly difficult to use conventional cross-linked thermoplastic elastomers.
- it can be suitably used for automobile parts such as hoses, pipes and boots (blow-molded products) for automobiles that require superior oil resistance because they come into contact with grease or lubricating oil.
- Compositions (I) and (IIC) are excellent in lightness, heat resistance, flexibility, rubber elasticity, molding processability, weather resistance, and compatibility.
- Compositions (I) and (IIC) are excellent in molding processability and can be molded by various molding methods.
- the molding include extrusion molding, injection molding, compression molding, calendar molding, vacuum molding, press molding, stamping molding, and blow molding.
- blow molding include breath blow molding, direct blow molding, injection blow molding, and the like.
- the molded product of the present invention (1) or (2) can be obtained by molding the composition (I) or (IIC).
- it can be obtained by molding the composition (I) or (IIC) by a conventional plastic molding method such as extrusion molding, injection molding or compression molding.
- scraps and burrs generated by such a molding method can be recovered and reused.
- Examples of the molded body of the present invention (1) or (2) include bumper parts, body panels, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, weather strip materials, hoses, steering wheels, boots, Automotive parts such as wire harness covers and seat adjuster covers; electrical parts such as wire covering materials, connectors and cap plugs; footwear such as shoe soles and sandals; leisure for swimming fins, underwater glasses, golf club grips, baseball bat grips, etc. Goods, gaskets, waterproof cloth, belts, garden hoses; various civil engineering and architectural gaskets and sheets.
- the molded body is particularly suitable for applications requiring oil resistance, and automotive parts such as automobile hoses, boots, wire harness covers, and sheet adjuster covers are particularly preferred applications.
- the molded body is preferably an automobile part as described above, and more detailed examples of the automobile part include a mechanism member, an interior member, an exterior member, and other members.
- Mechanical members include CVJ boots, suspension boots, rack and pinion boots, steering rod covers, AT cushions, AT slide covers, leaf spring bushes, ball joint retainers, timing belts, V belts, engine room hoses, air ducts, air Examples include a bag cover and a propeller shaft cover material.
- Interior materials include various skin materials (instrumental panel, door trim, ceiling, rear pillar), console box, armrest, airbag case lid, shift knob, assist grip, side step mat, reclining cover, trunk seat, seat belt buckle, Examples include lever slide plates, door latch strikers, seat belt parts, and switches.
- various molding materials inner / outer window moldings, roof moldings, belt moldings, side trim moldings
- door seals body seals
- glass run channels glass run channels
- mudguards kicking plates
- step mats number plate housings
- silencer gears Control cable covers and emblems.
- Other members include air duct packing, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, opening seal / trunk seal member, bonnet cushion, fuel tank band, cable and the like.
- the molded product of the present invention (1) or (2) may be a miscellaneous goods, daily necessities or these members.
- Miscellaneous goods, daily necessities or these components include grips (eg, ballpoint pens, mechanical pencils, toothbrushes, cups, disposable razors, handrails, cutters, power tools, screwdrivers, power cables, door grips), assist grips, shift knobs, toys , Notebook skins, gaskets (for example, gaskets for tableware, tappers, etc.), various rubber feet, sports equipment (for example, sheathed soles, ski boots, skis, ski bindings, ski soles, golf balls, goggles members, snowboard members, snowboard shoes) , Snowboard bindings, surfboard members, body boards, banana boats, kiteboards, snorkeling members, water ski members, parasailing members, wakeboard members and other sports equipment), belts (examples) If, belts and watches belt, fashion belt), hairbrush, bath panel button sheet, cap, shoes of the inner sole, and the like health equipment member.
- composition (IIA) containing ethylene / ⁇ -olefin / non-conjugated polyene copolymer (2B) of the present invention (2) is generally used as a composition containing components other than the copolymer, and a desired molded product can be obtained by molding and crosslinking.
- Components other than the copolymer (2B) contained in the composition (IIA) are not particularly limited, and the copolymer (2B) may be selected depending on the use and purpose of the composition and a molded body formed from the composition. Ingredients other than) can be appropriately blended.
- Components other than the copolymer (2B) include softeners, inorganic fillers, crosslinking agents, processing aids, activators, hygroscopic agents, heat stabilizers, weathering stabilizers, antistatic agents, colorants, lubricants and additives. A sticky agent etc. are mentioned.
- the blending amount is generally 100 parts by weight in total of the copolymer (2B) and other polymers (elastomer, rubber, etc.) blended as necessary.
- the softening agent is 0.1 to 200 parts by weight, and the filler is 1 to 300 parts by weight.
- composition (IIA) When the composition (IIA) is used as a rubber composition, other elastomers, rubber and the like can be blended as necessary.
- the proportion of the copolymer (2B) in the rubber composition is generally 20% by weight or more, preferably 30 to 90% by weight.
- the composition (IIA) is prepared by kneading the copolymer (2B) and other components blended as necessary at a desired temperature using a kneader such as a mixer, kneader, or roll. can do. Since the copolymer (2B) is excellent in kneadability, the composition can be prepared satisfactorily.
- a softening agent such as a softening agent, an inorganic filler, a crosslinking agent, a processing aid, an activator, and a hygroscopic agent, for example, those exemplified in the description of the hose forming composition described below are used in the exemplified amounts. be able to.
- the copolymer (2B) of the present invention (2) is a molded product formed from the copolymer, a molded product formed by crosslinking the copolymer (2B), and a crosslinked copolymer (2B). Molded article formed from a composition containing the copolymer (2B), a molded article formed by crosslinking a composition containing the copolymer (2B), or a copolymer As a molded product obtained by crosslinking the composition containing (2B), it can be used for various applications.
- the molded body is preferably a molded body formed by crosslinking the composition (IIA) containing the copolymer (2B). Moreover, as a molded object, a crosslinked molded object and a crosslinked foamed body (crosslinked foamed molded object) are preferable.
- the molded body include tire rubber, O-ring, industrial roll, packing (for example, capacitor packing), gasket, belt (for example, heat insulation belt, copying machine belt), hose (for example, water hose, brake) Reservoir hose, radiator hose), prevention rubber, sponge (for example, weatherstrip sponge, heat insulation sponge, protection sponge, fine foam sponge), cable (ignition cable, cabtire cable, high tension cable), wire covering material (high voltage wire covering) Materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, color skin materials, paper feed rolls, roofing sheets, and the like.
- packing for example, capacitor packing
- gasket for example, heat insulation belt, copying machine belt
- hose for example, water hose, brake
- prevention rubber for example, weatherstrip sponge, heat insulation sponge, protection sponge, fine foam sponge
- cable ignition cable, cabtire cable, high tension cable
- wire covering material high voltage wire covering
- Materials low-voltage wire covering materials, marine wire covering materials
- glass run channels color skin materials, paper feed rolls, roofing sheets
- the copolymer (2B) is a moving hose-forming composition (IIB) containing the copolymer (2B) and a mixture containing the copolymer (2B), the polymer (A) and the crosslinking agent (C). It can be suitably used as a thermoplastic elastomer composition (IIC) obtained by mechanical crosslinking.
- composition (IIB) for forming hose of the present invention contains a copolymer (2B).
- the hose-forming composition containing the copolymer (2B) is also referred to as a hose-forming composition.
- the copolymer (2B) has a low compression set at low temperature and good results of a torsion test at low temperature, so that it has flexibility at low temperature, rubber elasticity at low temperature and normal temperature at room temperature. Excellent balance with tensile strength.
- the composition for hose formation containing a copolymer (2B) can be used suitably for uses, such as a motor vehicle, a motorbike, an industrial machine, a construction machine, an agricultural machine, which can be used in a cold region.
- the content ratio of the copolymer (2B) in the composition is usually 20% by mass or more, preferably 20 to 50% by mass, more preferably 25 to 40% by mass.
- composition (IIB) of the present invention preferably contains a crosslinking agent in addition to the copolymer (2B).
- Composition (IIB) may contain other polymers in addition to copolymer (2B).
- examples of other polymers that require crosslinking include cross-linkable rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, acrylic rubber, silicone rubber, fluorine rubber, and urethane rubber. Is mentioned.
- polymers that do not require crosslinking include, for example, block copolymers of styrene and butadiene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-poly (ethylene-propylene) -polystyrene ( SEPS) styrene thermoplastic elastomer (TPS), olefin thermoplastic elastomer (TPO), vinyl chloride elastomer (TPVC), ester thermoplastic elastomer (TPC), amide thermoplastic elastomer (TPA), urethane heat Examples include elastomers such as a plastic elastomer (TPU) and other thermoplastic elastomers (TPZ).
- the other polymer can be blended in an amount of usually 100 parts by mass or less, preferably 80 parts by mass or less with respect to 100 parts by mass of the copolymer (2B).
- the composition (IIB) may contain other additives such as crosslinking aids, vulcanization accelerators, vulcanization aids, softeners, inorganic fillers, reinforcing agents, anti-aging agents, processing aids, You may contain at least 1 sort (s) chosen from an activator, a hygroscopic agent, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a coloring agent, a lubricant, a thickener, and a foaming agent. Also. Each additive may be used individually by 1 type, and may use 2 or more types together.
- the composition (IIB) is obtained by kneading the copolymer (2B) and other components blended as necessary at a desired temperature using a kneader such as a mixer, a kneader, or a roll. Can be prepared. Since the copolymer (2B) is excellent in kneadability, the composition (IIB) can be prepared favorably.
- the copolymer (2B) and, if necessary, the other component 1 are added at a predetermined temperature and time, for example, 80 to 200 ° C. for 3 to 30.
- other components 2 such as a crosslinking agent are added to the obtained kneaded material as necessary, and using a roll at a predetermined temperature and time, for example, 1-30 at a roll temperature of 30-80 ° C.
- the composition (IIB) can be prepared by kneading for a minute.
- Examples of other components 1 include other polymers, crosslinking aids, vulcanization accelerators, vulcanization aids, softeners, inorganic fillers, reinforcing agents, anti-aging agents, processing aids, activators, and hygroscopic agents. And at least one selected from a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener.
- Other components 2 include, for example, a crosslinking agent (vulcanizing agent), a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a softening agent, an inorganic filler, a reinforcing agent, an antiaging agent, a processing aid, And at least one selected from activators, hygroscopic agents, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, thickeners and foaming agents.
- crosslinking agent examples include organic peroxides, phenol resins, sulfur compounds, hydrosilicon compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanates.
- the crosslinking agent generally used when bridge
- organic peroxides examples include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butyl).
- the amount of the organic peroxide in the composition (IIB) is determined depending on the copolymer (2B) and other polymers that need to be crosslinked (crosslinking). 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 with respect to a total of 100 parts by mass of the conductive rubber. When the blending amount of the organic peroxide is within the above range, the composition (IIB) exhibits excellent crosslinking characteristics without blooming to the surface of the hose obtained.
- crosslinking agent When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination.
- crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinonedioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl isocyanurate. Allyl-based crosslinking aids such as maleimide-based crosslinking aids; divinylbenzene; zinc oxide (for example, ZnO # 1 and two types of zinc oxide, manufactured by Hakusuitec Co., Ltd.), magnesium oxide, zinc white (for example, “META-Z102”) (Zinc oxide such as “trade name; manufactured by Inoue Lime Industry Co., Ltd.”).
- the blending amount of the crosslinking aid in the composition (IIB) is usually 0.5 to 10 moles, preferably 0.5 to 7 moles per mole of the organic peroxide.
- the amount is preferably 1 to 5 mol.
- sulfur compounds examples include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.
- the compounding amount of the sulfur compound in the composition (IIB) is the copolymer (2B) and other polymers (crosslinkable rubbers) that need to be blended as required.
- Etc. is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, and more preferably 0.7 to 5.0 parts by weight.
- a sulfur compound is used as the crosslinking agent, it is preferable to use a vulcanization accelerator in combination.
- vulcanization accelerator examples include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide, 2 -Mercaptobenzothiazole (for example, Sunseller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2- (4-morpholinodithio) penzothiazole (for example, Noxeller MDB-P (trade name; Ouchi Shinsei Chemical Industry Co., Ltd.) )), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide (eg Sunceller DM (trade name; three New chemical industry))) and other thiazole vulcanization accelerators; diphenylgu
- the blending amount of the vulcanization accelerator in the composition (IIB) is the copolymer (2B) and other polymers that need to be blended and blended as necessary (crosslinkable rubber, etc.) ) Is usually 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.
- the composition (IIB) exhibits excellent crosslinking characteristics without blooming on the surface of the hose obtained.
- a vulcanization aid can be used in combination.
- vulcanization aid examples include zinc oxide (for example, ZnO # 1 and two types of zinc oxide, manufactured by Hux Itec Co., Ltd.), magnesium oxide, zinc white (for example, “META-Z102” (trade name; Inoue Lime Industry). Zinc oxide) such as manufactured by Co., Ltd.).
- zinc oxide for example, ZnO # 1 and two types of zinc oxide, manufactured by Hux Itec Co., Ltd.
- magnesium oxide for example, “META-Z102” (trade name; Inoue Lime Industry).
- Zinc oxide such as manufactured by Co., Ltd.
- the blending amount of the vulcanization aid in the composition (IIB) is determined depending on the copolymer (2B) and other polymers that need to be blended (crosslinkable rubber, etc.). ) Is usually 1 to 20 parts by mass per 100 parts by mass in total.
- the softener As a softener, the illustration of the said softener (D) is mentioned, for example.
- the softener is preferably a petroleum softener, and particularly preferably process oil.
- the amount of the softening agent is 100 in total of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is usually 2 to 100 parts by mass, preferably 10 to 100 parts by mass with respect to parts by mass.
- Inorganic filler examples include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. Among these, heavy calcium carbonate such as “Whiteon SB” (trade name: Shiraishi Calcium Co., Ltd.) is preferable. .
- the blending amount of the inorganic filler is that of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is usually 2 to 100 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass in total.
- the blending amount of the inorganic filler is within the above range, the kneadability of the composition (IIB) is excellent, and a hose excellent in mechanical properties can be obtained.
- the reinforcing agent examples include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid.
- the total amount of the reinforcing agent is 100 in total of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) compounded as necessary.
- the amount is usually 30 to 200 parts by mass, preferably 50 to 180 parts by mass with respect to parts by mass.
- Anti-aging agent (stabilizer) By mix
- anti-aging agents include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.
- the antiaging agent examples include aromatic secondary amine type antiaging agents such as phenylbutylamine and N, N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5-di- -T-butyl-4-hydroxy) hydrocinnamate] phenolic antioxidants such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide and the like Thioether-based antioxidants; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc.
- sulfur-based anti-aging agent There is a sulfur-based anti-aging agent.
- the blending amount of the antioxidant is that of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass with respect to 100 parts by mass in total.
- processing aids those generally blended into rubber as processing aids can be widely used.
- processing aids for example, fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid, fatty acid salts such as barium stearate, zinc stearate, calcium stearate, ricinoleic acid ester, stearic acid ester, palmitic acid ester, Examples include fatty acid esters such as lauric acid esters, and fatty acid derivatives such as N-substituted fatty acid amides. Of these, stearic acid is preferred.
- the blending amount of the processing aid is that of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is usually 10 parts by mass or less, preferably 8.0 parts by mass or less with respect to 100 parts by mass in total.
- Activator examples include amines such as di-n-butylamine, dicyclohexylamine, and monoelaanolamine; diethylene glycol, polyethylene glycol, lecithin, triarylate melylate, aliphatic carboxylic acid, and aromatic carboxylic acid zinc compound. Activators; zinc peroxide preparations; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds.
- amines such as di-n-butylamine, dicyclohexylamine, and monoelaanolamine
- diethylene glycol polyethylene glycol, lecithin, triarylate melylate, aliphatic carboxylic acid, and aromatic carboxylic acid zinc compound.
- Activators zinc peroxide preparations
- kutadecyltrimethylammonium bromide synthetic hydrotalcite, special quaternary ammonium compounds.
- the amount of the active agent is a total of 100 of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) to be blended as necessary.
- the amount is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to parts by mass.
- hygroscopic agent examples include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.
- the amount of the hygroscopic agent is 100 in total of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass with respect to parts by mass.
- the hose made of the composition (IIB) may be a non-foamed material or a foamed material.
- a foaming agent can be used in forming the foam.
- an inorganic foaming agent such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N, N′-dinitroterephthalamide, N, N Nitroso compounds such as'-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p , P′-oxybis (benzenesulfonylhydrazide) diphenylsulfone-3,3′-disul
- the blending amount of the foaming agent is appropriately selected so that the specific gravity of the foamed product after crosslinking foaming is usually 0.01 to 0.9.
- the blending amount of the foaming agent is usually 0.5 to 30 parts by mass with respect to 100 parts by mass in total of the copolymer (2B) and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary.
- the amount is preferably 1 to 20 parts by mass.
- composition (IIB) By using the composition (IIB), it is possible to form a hose excellent in mechanical properties at room temperature and low temperature properties. For example, it is possible to obtain a hose that is excellent in tensile strength at room temperature, has a low compression set at low temperature, and has a good result of a torsion test at low temperature.
- the hose of the present invention (2) has a layer formed from the composition (IIB).
- the hose may be one layer or two or more layers consisting of only the layer formed from the composition (IIB), and other layers such as a layer composed of natural rubber, a fabric layer, a thermoplastic resin layer, and a thermosetting resin. You may have one layer chosen from a layer, or two or more layers.
- the composition (uncrosslinked composition) is formed into a desired hose shape, and the composition is subjected to a crosslinking treatment simultaneously with or after the forming.
- a crosslinking treatment simultaneously with or after the forming.
- (I) a method of forming a desired shape using the composition (IIB) containing a crosslinking agent, and crosslinking by heat treatment, (II) molding the composition (IIB) into a desired shape, and electronic There is a method of crosslinking by irradiating a line.
- the hose forming composition of the present invention is molded into a hose shape having a hollow portion using an extrusion molding machine, a calender roll, a press molding machine, an injection molding machine, a transfer molding machine or the like.
- the molded body is heated at 50 to 200 ° C. for 1 to 120 minutes, for example, simultaneously with molding or after molding.
- a crosslinking process is performed, or a foaming process is performed together with the crosslinking process.
- the crosslinking tank include a steam vulcanizing can, a hot air vulcanizing tank, a glass bead fluidized bed, a molten salt vulcanizing tank, and a microwave tank. These crosslinking tanks can be used singly or in combination of two or more.
- an electron beam having an energy of 0.1 to 10 MeV is applied to the molded article simultaneously with or after molding, and the absorbed dose is usually 0.5 to 35 Mrad, preferably 0.5. Irradiate to ⁇ 20 Mrad.
- the hose of the present invention (2) can be suitably used as a hose used for automobiles, motorbikes, industrial machines, construction machines, agricultural machines and the like. Specifically, radiator hose for cooling the engine, drain hose for radiator overflow, heater hose for indoor heating, air conditioner drain hose, wiper water supply hose, roof drain hose, protract hose, etc. can do.
- parts means “parts by weight” or “parts by mass” unless otherwise specified.
- parts by weight and parts by mass are treated synonymously.
- Mooney viscosity Mooney viscosity ML (1 + 4) 125 ° C. and Mooney viscosity ML (1 + 4) 150 ° C. were measured according to JIS K6300 (1994) using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation). .
- the iodine value of the copolymer obtained in the following synthesis example is a value determined by a titration method. Specifically, the following method was used.
- B value ([EX] +2 [Y]) / [2 ⁇ [E] ⁇ ([X] + [Y])] (i)
- [E], [X] and [Y] represent the molar fractions of ethylene [A], ⁇ -olefin [B] having 4 to 20 carbon atoms and non-conjugated polyene [C], respectively
- [EX ] Represents ethylene [A] - ⁇ -olefin [B] dyad chain fraction having 4 to 20 carbon atoms.
- the intrinsic viscosity [ ⁇ ] of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is a value measured at 135 ° C. using a decalin solvent.
- thermoplastic elastomer compositions (I) and (IIC) in the following examples and comparative examples and methods for evaluating the physical properties of the molded products are as follows.
- thermoplastic elastomer composition (I) pellets were press-molded at 230 ° C. for 6 minutes and then cooled and pressed at room temperature for 5 minutes to give a thickness of 3 mm.
- a press sheet was produced. Using this sheet, the value after 5 seconds was measured with a Shore D hardness meter according to JIS K6253.
- thermoplastic elastomer composition (IIC) pellets were press-molded at 230 ° C. for 6 minutes and then cooled and pressed at room temperature for 5 minutes to give a thickness of 3 mm.
- a press sheet was produced. Using this sheet, the scale was read immediately after contact with the pressing needle using an A-type measuring instrument in accordance with JIS K6253.
- thermoplastic elastomer composition (I) or (IIC) pellets were press-molded at 230 ° C. for 6 minutes using a 100-ton automatic heat press (manufactured by Shoji), and then cold-pressed at room temperature for 5 minutes. A press sheet having a thickness of 2 mm was produced.
- a press sheet having a thickness of 2 mm produced as described above was laminated according to JIS K6250, and a compression set test was performed according to JIS K6262.
- test conditions were 12 mm thick (4 mm stack of 3 mm pieces) laminated sheets, compressed at 25% compression, -30 ° C, 23 ° C, or 70 ° C for 22 hours each.
- the sample was compressed under the conditions of 125 ° C. and 72 hours and measured after 30 minutes from the removal of the strain (compression).
- test piece used was a No. 3 dumbbell piece punched out of a 2 mm thick press sheet.
- ⁇ Measurement of filler ratio Set the sample (sample weight: about 5 mg) using an alumina pan in order to fully replace the inside of the TGA device (TGA Q50001R, manufactured by T.A. Instruments Japan Co., Ltd.) with a nitrogen atmosphere. Hold at 40 ° C. for 20 minutes. Then, it heated up to 1000 degreeC on the following measurement conditions, and made the remainder at that time into the filler rate with respect to object sample amount (about 5 mg).
- the heating rate was 10 ° C./min, and the cooling rate was 10 ° C./min.
- the sample purge gas was nitrogen at 25 ml / min and Air at 25 ml / min.
- the balance balance purge gas was nitrogen at 10 ml / min.
- the amount of purge gas into the furnace was 35 ml / min for the sample and balance balance.
- the specific gravity of the examples was calculated using the specific gravity of each resin component and softener and the number of blended parts thereof.
- the specific gravity of the comparative example is a catalog value.
- Unvulcanized physical property test 1 minimum viscosity (Vm) and scorch time (min)
- the physical property test of the unvulcanized composition was performed according to JIS K6300. Specifically, using a Mooney viscometer (SMV202 type, manufactured by Shimadzu Corporation), the change in Mooney viscosity at 125 ° C. of Formulation 2 obtained in Examples and Comparative Examples was measured. Viscosity (Vm) was determined, and the time required to rise 5 points or 35 points from the minimum viscosity Vm was determined, and this was defined as scorch time (t5, min) and scorch time (t35, min).
- Vulcanization rate (TC90) was measured as follows using a vulcanization measuring apparatus: MDR2000 (manufactured by ALPHA TECHNOLOGIES) using the formulation 2 obtained in Examples and Comparative Examples.
- the torque change obtained under the condition of constant temperature and constant shear rate was measured.
- the time required to reach 90% of the difference between the maximum torque value (S′Max) and the minimum torque value (S′Min) was defined as TC90 (min).
- the measurement conditions were a temperature of 160 ° C. and a time of 50 minutes. A smaller TC90 indicates a faster vulcanization rate.
- Strength at break (TB) and elongation at break (EB) was measured.
- compression set test With respect to the test piece for measuring compression set (CS), the compression set after treatment at 70 ° C., 0 ° C., ⁇ 20 ° C., or ⁇ 40 ° C. ⁇ 22 hours was measured according to JIS K6262 (1997).
- the solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and extracted with dichloromethane.
- the solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane, hexane was added, and recrystallization was performed at ⁇ 20 ° C.
- ethylene feed amount is 3.2 kg / h
- 1-butene feed amount is 12 kg / h
- ENB feed amount is 520 g / h and hydrogen.
- the polymerizer was continuously fed so that the feed amount was 0.0 NL (normal liter) / h.
- the catalyst-a1 was used as the main catalyst, and continuously fed to the polymerization vessel so that the feed amount was 0.030 mmol / h. Further, (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) is fed as a cocatalyst at a feed rate of 0.15 mmol / h, and triorganobutylaluminum (TIBA) is fed as an organoaluminum compound at a rate of 10 mmol / h. Then, each was continuously fed to the polymerization vessel.
- TIBA triorganobutylaluminum
- an ethylene / 1-butene / ENB copolymer (EBDM-1 (1B)) formed from ethylene, 1-butene and ENB was obtained at a rate of 5.4 kg / hour.
- Thermoplastic elastomer composition (I) and molded article >> [Example 1] 100 parts by weight of EBDM-1 (1B) obtained in Synthesis Example 1 and polypropylene having a melt flow rate (ASTM-D-1238-65T; 230 ° C., 2.16 kg load) of 2.0 g / 10 min.
- brominated alkylphenol / formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) as a phenolic resin-based crosslinking agent
- phenolic antioxidant Irganox 1010, BASF Japan Ltd.
- Example 3 the polypropylene blended in the masterbatch preparation process is a polypropylene having a melt flow rate (ASTM-D-1238-65T; 230 ° C., 2.16 kg load) of 2.0 g / 10 min from E-200GP (product)
- a pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the name was changed to Prime Polypro (trademark) B241 (manufactured by Prime Polymer Co., Ltd.).
- thermoplastic elastomer composition Santoprene (trademark) 103-40 (manufactured by ExxonMobil, specific gravity: 0.95 g / cm 3 (catalog value)), a crosslinked thermoplastic elastomer obtained by dynamically crosslinking EPDM and PP (polypropylene) ) was used to evaluate the physical properties. The results are shown in Table 3.
- the ethylene feed amount is 4.7 kg / h
- the 1-butene feed amount is 4.3 kg / h
- the ENB feed amount is 530 g / h.
- the hydrogenation amount was continuously supplied to the polymerization reactor so that the hydrogen feed amount was 5.5 NL / h.
- the catalyst-a1 was used as the main catalyst, and continuously fed to the polymerization vessel so that the feed amount was 0.018 mmol / h. Further, (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) is fed as a cocatalyst at a feed rate of 0.09 mmol / h, and triorganobutylaluminum (TIBA) is fed as an organoaluminum compound at a rate of 5 mmol / h. Then, each was continuously fed to the polymerization vessel.
- TIBA triorganobutylaluminum
- an ethylene / 1-butene / ENB copolymer (EBDM-1 (2B)) formed from ethylene, 1-butene and ENB was obtained at a rate of 5.3 kg / hour.
- Example 5 The ethylene / 1-butene / ENB copolymer (EBDM-2 (2B)) of Example 5 and Example 6 were used in the same manner as in Example 4 except that the polymerization conditions were changed as shown in Table 4. An ethylene / 1-butene / ENB copolymer (EBDM-3 (2B)) was obtained. The results are shown in Table 4.
- Comparative Example 2 An ethylene / 1-butene / ENB copolymer (EBDM-4) of Comparative Example 2 was obtained in the same manner as in Example 4 except that the polymerization conditions were changed as shown in Table 4. The results are shown in Table 4.
- Hose Forming Composition (IIB) >> [Example 7] The ethylene / 1-butene / ENB copolymer (EBDM-3 (2B) obtained in Example 6 using MIXRON BB MIXER (manufactured by Kobe Steel, BB-2, volume 1.7 L, rotor 2WH).
- the kneading conditions were a rotor speed of 40 rpm, a floating weight pressure of 3 kg / cm 2 , a kneading time of 5 minutes, and a kneading discharge temperature of 144 ° C.
- the compound 2 was vulcanized at 160 ° C. for 20 minutes using a press molding machine to obtain a vulcanized rubber sheet having a thickness of 2 mm.
- a straight cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm was prepared from the compound 2 using a cylindrical mold, and vulcanized at 160 ° C. for 25 minutes to obtain compression set (CS). A test specimen was obtained.
- the obtained unvulcanized product (unvulcanized rubber) was subjected to an unvulcanized physical property test by the above method. Further, the obtained vulcanizate (vulcanized rubber) was subjected to a hardness test, a tensile test, a low-temperature twist test, and a compression set test by the above methods. The results are shown in Table 5.
- the low temperature characteristics of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer are largely affected by the crystallization rate of the copolymer due to the ethylene content. That is, Example 7 and Comparative Example 5 were compared, Example 8 and Comparative Example 3 were compared, and Example 9 and Comparative Example 4 were compared. From the results shown in Tables 4 and 5, the use of a polymer having a high ML (1 + 4) 125 ° C. as the ethylene / ⁇ -olefin / non-conjugated polyene copolymer results in a balance between sealing properties and low temperature characteristics. It turns out that it is excellent. Sealability can be evaluated from compression set at high temperature (70 ° C.
- Thermoplastic elastomer composition (IIC) and molded article >> Example 10 100 parts by weight of EBDM-1 (2B) obtained in Example 4 and polypropylene having a melt flow rate (ASTM-D-1238-65T; 230 ° C., 2.16 kg load) of 2.0 g / 10 min ( Trade name: Prime Polypro (trademark) B241, manufactured by Prime Polymer Co., Ltd.) 40 parts by weight, softener (Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) 40 parts by weight, fully mixed with a Banbury mixer Pellets were obtained.
- the obtained master batch pellets 8.0 parts by weight of brominated alkylphenol / formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) as a phenolic resin-based crosslinking agent, and phenolic antioxidant (IRGANOX 1010 as an antioxidant) , Manufactured by BASF Japan Ltd.) 0.16 parts by weight, benzotriazole ultraviolet absorber (trade name: Tinuvin 326FL, manufactured by BASF Japan Ltd.) 0.16 parts by weight, hindered amine (HALS) weathering stabilizer (Product name: Sanol LS-770, manufactured by Sankyo Lifetech Co., Ltd.) 0.08 parts by weight, zinc oxide (two types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.) 0.80 parts by weight, carbon black masterbatch (PE4993, manufactured by Cabot) 4.0 parts by weight, softener (Diana Process PW-100, paraffin oil) 75 parts by weight, melt flow rate (ASTM-D-1238-
- Example 11 The amount of softener (Diana Process PW-100, paraffin oil) mixed with the masterbatch was changed from 75 parts by weight to 73 parts by weight, and the amount of EL-Pro TM P440J was changed from 18 parts by weight to 23 parts by weight. Except that, pellets of the thermoplastic elastomer composition (IIC) were produced in the same manner as in Example 10.
- softener Diana Process PW-100, paraffin oil
- Example 12 A pellet of the thermoplastic elastomer composition (IIC) was produced in the same manner as in Example 10, except that EBDM-1 (2B) was changed to EBDM-2 (2B).
- Table 7 shows the physical property evaluation results.
- thermoplastic elastomer composition Santoprene TM 121-73W175 (manufactured by ExxonMobil, specific gravity: 0.97 g / cm 3 (catalog value)), a crosslinked thermoplastic elastomer obtained by dynamically crosslinking EPDM and PP (polypropylene) ) was used to evaluate the physical properties.
- Table 7 shows the physical property evaluation results.
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Abstract
Description
(式(i)中、[E]および[X]は、エチレン・α―オレフィン・非共役ポリエン共重合体中のエチレンおよび炭素数4~20のα-オレフィンのモル分率をそれぞれ表し、[EX]は、エチレン・炭素数4~20のα-オレフィンのダイアッド連鎖分率を表す。)
一方、特許文献5の実施例には、特定の遷移金属化合物(架橋メタロセン化合物)を用いて、ランダム性を示すB値(但し、特許文献2に記載のB値とは、幾分定義が異なる)が、1.11~1.24のエチレン・プロピレン・ENB共重合体を得たことが開示されている。なお、特許文献5には、当該エチレン・プロピレン・ENB共重合体の機械的物性は記載されていない。
(式[IV]中、a、eおよびfはそれぞれ前記エチレン/α-オレフィン/非共役ポリエン共重合体中のエチレンモル分率、α-オレフィンモル分率および非共役ポリエンモル分率であり、cはエチレン-α-オレフィンダイアッドモル分率、dはエチレン-非共役ポリエンダイアッドモル分率である。)
また、オレフィン系熱可塑性エラストマーは、軽量でリサイクルが容易なことから、省エネルギー、省資源タイプの熱可塑性エラストマーとして、特に加硫ゴムの代替として、自動車用のホース、パイプおよびブーツ(ブロー成形品)などの自動車部品等に広く使用されている(例えば、特許文献6および7)。
ここで[E]、[X]および[Y]は、それぞれ、エチレン由来の構造単位のモル分率、炭素数4~20のα-オレフィン由来の構造単位のモル分率、非共役ポリエン由来の構造単位のモル分率を示し、[EX]はエチレン由来の構造単位-炭素数4~20のα-オレフィン由来の構造単位のダイアッド連鎖分率を示す。
エチレン[A]に由来する構造単位、炭素数4~20のα-オレフィン[B]に由来する構造単位、および非共役ポリエン[C]に由来する構造単位を含み、下記(1)~(4)を満たすエチレン・α―オレフィン・非共役ポリエン共重合体(2B)。
(2)非共役ポリエン[C]に由来する構造単位の含有量が、[A]、[B]および[C]の構造単位の合計を100モル%として、0.1~6.0モル%であり、
(3)125℃におけるムーニー粘度ML(1+4)125℃が、100を超えて200以下であり、
(4)下記式(i)で表されるB値が1.20~1.80である。
[ここで[E]、[X]および[Y]は、それぞれ、エチレン[A]、炭素数4~20のα-オレフィン[B]、および非共役ポリエン[C]のモル分率を示し、[EX]はエチレン[A]-炭素数4~20のα-オレフィン[B]ダイアッド連鎖分率を示す。]
炭素数4~20のα-オレフィン[B]が、1-ブテンであることを特徴とする[1]に記載のエチレン・α―オレフィン・非共役ポリエン共重合体(2B)。
(a)下記一般式[VII]で表される遷移金属化合物と、
(b)(b-1)有機金属化合物、
(b-2)有機アルミニウムオキシ化合物、および
(b-3)遷移金属化合物(a)と反応してイオン対を形成する化合物から選ばれる少なくとも1種の化合物とを含むオレフィン重合触媒の存在下において、エチレン、炭素数4~20のα-オレフィンおよび非共役ポリエンを共重合することにより得られる、[1]または[2]に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)。
Mはチタン原子、ジルコニウム原子またはハフニウム原子であり、
R5およびR6が、アリール基の水素原子の一つ以上をハメット則の置換基定数σが-0.2以下の電子供与性置換基で置換してなる置換アリール基であって、該電子供与性置換基を複数個有する場合にはそれぞれの該電子供与性置換基は同一でも異なっていてもよく、該電子供与性置換基以外の、炭素数1~20の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基を有していてもよく、該置換基を複数個有する場合にはそれぞれの置換基は同一でも異なっていてもよい置換アリール基であり、
Qはハロゲン原子、炭素数1~20の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
jは1~4の整数である。)
[1]~[3]のいずれか一項に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)を含有する組成物。
[4]に記載の組成物を架橋処理して形成された成形体。
[1]~[3]のいずれか一項に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)を含有するホース形成用組成物。
[6]に記載のホース形成用組成物を架橋処理して形成された層を有するホース。
自動車用、モーターバイク用、工業機械用、建設機械用または農業機械用のいずれかの用途に用いられる、[7]に記載のホース。
結晶性オレフィン系重合体(A)、
エチレン・α―オレフィン・非共役ポリエン共重合体(2B)、および
フェノール樹脂系架橋剤(C)を含む混合物を
動的架橋して得られ、
エチレン・α―オレフィン・非共役ポリエン共重合体(2B)が、[1]~[3]のいずれか一項に記載のエチレン・α―オレフィン・非共役ポリエン共重合体である熱可塑性エラストマー組成物。
前記混合物には、さらに、軟化剤(D)を、前記結晶性オレフィン系重合体(A)および前記共重合体(2B)の合計100重量部に対して、2~100重量部含む、[9]に記載の熱可塑性エラストマー組成物。
フェノール樹脂系架橋剤(C)が、ハロゲン化フェノール樹脂系架橋剤である、[9]または[10]に記載の熱可塑性エラストマー組成物。
結晶性オレフィン系重合体(A)とエチレン・α-オレフィン・非共役ポリエン共重合体(2B)とを、(A)/(2B)=90/10~10/90の質量比で含有し、
フェノール樹脂系架橋剤(C)を、エチレン・α-オレフィン・非共役ポリエン共重合体(2B)100重量部に対して、0.1~20重量部含有する、[9]~[11]のいずれか一項に記載の熱可塑性エラストマー組成物。
[9]~[12]のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、成形体。
[9]~[12]のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車部品。
[9]~[12]のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ホース。
[9]~[12]のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ブーツ。
(a)前記一般式[VII]で表される遷移金属化合物と、
(b)(b-1)有機金属化合物、
(b-2)有機アルミニウムオキシ化合物、および
(b-3)遷移金属化合物(a)と反応してイオン対を形成する化合物から選ばれる少なくとも1種の化合物と
を含むオレフィン重合触媒の存在下において、エチレン、炭素数4~20のα-オレフィンおよび非共役ポリエンを共重合する工程を含むことにより得られる、エチレン・α-オレフィン・非共役ポリエン共重合体(2B)の製造方法。
結晶性オレフィン系重合体(A)と、前記エチレン・α-オレフィン(炭素数4~20)・非共役ポリエン共重合体(2B)と、フェノール樹脂系架橋剤(C)とを含む混合物を、動的架橋する工程を含むことを特徴とする、熱可塑性エラストマー組成物の製造方法。
結晶性オレフィン系重合体(A)(本発明において重合体(A)とも称す)は、オレフィンから得られる結晶性の重合体であれば特に制限されないが、1種以上のモノオレフィンを、高圧法または低圧法の何れかにより重合して得られる結晶性の高分子量固体生成物からなる重合体であることが好ましい。このような重合体としては、アイソタクチックモノオレフィン重合体、シンジオタクチックモノオレフィン重合体等が挙げられる。
本発明(1)で用いるエチレン・α-オレフィン・非共役ポリエン共重合体(1B)(本発明において共重合体(1B)とも称す)は、エチレンに由来する構造単位、少なくとも1種の炭素数4~20のα-オレフィンに由来する構造単位、および少なくとも一種の非共役ポリエンに由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体であり、
(1)下記式(i)で表されるB値が1.20~1.80であり、
B値=([EX]+2[Y])/〔2×[E]×([X]+[Y])〕・・・(i)
(ここで[E]、[X]および[Y]は、それぞれ、エチレン由来の構造単位のモル分率、炭素数4~20のα-オレフィン由来の構造単位のモル分率、非共役ポリエン由来の構造単位のモル分率を示し、[EX]はエチレン由来の構造単位-炭素数4~20のα-オレフィン由来の構造単位のダイアッド連鎖分率を示す)、
(2)共重合体(1B)の、エチレンに由来する構造単位とα-オレフィン(炭素数4~20)に由来する構造単位とのモル比、40/60~90/10である。
本発明(2)のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)(本発明において共重合体(2B)とも称す)は、エチレン[A]に由来する構造単位、炭素数4~20のα-オレフィン[B]に由来する構造単位、および非共役ポリエン[C]に由来する構造単位を含み、下記(1)~(4)を満たす。なお、このような特定のエチレン・α-オレフィン・非共役ポリエン共重合体を「エチレン系共重合体2A」ともいう。
(2)非共役ポリエン[C]に由来する構造単位の含有量が、[A]、[B]および[C]の構造単位の合計を100モル%として、0.1~6.0モル%であり、
(3)125℃におけるムーニー粘度ML(1+4)125℃が、100を超えて200以下であり、
(4)上記式(i)で表されるB値が1.20以上である。
共重合体(1B)および(2B)は、例えば、以下の製造方法により得ることができる。
上記式[VIII]において、R5およびR6は上記のとおりであるが、一般式R5-C(=O)-R6で表される、このような条件を満たす種々のケトンが一般の試薬メーカーより市販されているため、該架橋メタロセン化合物(a-3)の原料の入手が容易である。また、仮にこのようなケトンが市販されていない場合でも、例えばOlahらによる方法[Heterocycles, 40, 79 (1995)]などにより、該ケトンは容易に合成することが可能である。このように、該架橋メタロセン化合物(a-3)は、比較的製造工程が簡素かつ容易であり、製造コストがさらに低減され、ひいてはこの架橋メタロセン化合物を用いることでエチレン系共重合体の製造コストが低減されるという利点が得られる。さらに、該架橋メタロセン化合物(a-3)を含むオレフィン重合触媒の存在下でエチレンと炭素数が4以上のα-オレフィンと非共役ポリエンとを共重合する場合、生成する共重合体のさらなる高分子量化が可能であるという利点も得られる。
R7およびR8としての炭素数1から20の炭化水素基、ケイ素含有基、酸素含有基およびハロゲン含有基の具体例および好適例は、上記式[VII]の場合と同様である。
R10としての炭素数1~20の炭化水素基、ケイ素含有基、酸素含有基およびハロゲン含有基としては、上述したこれらの置換基の具体例を挙げることができる。
R9としての炭素数1から20の炭化水素基、ケイ素含有基、窒素含有基およびハロゲン含有基の具体例および好適例は、式[VII]の場合と同様である。
このような架橋メタロセン化合物(a-5)は、下記一般式[X]で表される。
R10としての炭素数1~20の炭化水素基、ケイ素含有基、酸素含有基およびハロゲン含有基としては、上述したこれらの置換基の具体例を挙げることができる。
[ジメチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジエチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジ-n-ブチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、 [ジシクロペンチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジシクロヘキシルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[シクロペンチリデン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[シクロヘキシリデン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ジフェニルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジ-1-ナフチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジ-2-ナフチルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ビス(3-メチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-メチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(3,4-ジメチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-n-ヘキシルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-シクロヘキシルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-t-ブチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ビス(3-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(3,4-ジメトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-メトキシ-3-メチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-メトキシ-3,4-ジメチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-エトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-フェノキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス{4-(トリメチルシロキシ)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ビス{3-(ジメチルアミノ)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス{4-(ジメチルアミノ)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-N-モルフォリニルフェニル)(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ビス{4-(トリメチルシリル)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ビス(3-クロロフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-クロロフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(3-フルオロフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス(4-フルオロフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス{3-(トリフルオロメチル)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ビス{4-(トリフルオロメチル)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[メチルフェニルメチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[メチル(4-メチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[メチル(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[メチル{4-(ジメチルアミノ)フェニル}メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[メチル(4-N-モルフォリニルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ジメチルシリレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジエチルシリレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジシクロヘキシルシリレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジフェニルシリレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジ(4-メチルフェニル)シリレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[ジメチルゲルミレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、[ジフェニルゲルミレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド、
[1-(η5-シクロペンタジエニル)-2-(η5-2,3,6,7-テトラメチルフルオレニル)エチレン]ハフニウムジクロリド、[1-(η5-シクロペンタジエニル)-3-(η5-2,3,6,7-テトラメチルフルオレニル)プロピレン]ハフニウムジクロリド、[1-(η5-シクロペンタジエニル)-2-(η5-2,3,6,7-テトラメチルフルオレニル)-1,1,2,2-テトラメチルシリレン]ハフニウムジクロリド、[1-(η5-シクロペンタジエニル)-2-(η5-2,3,6,7-テトラメチルフルオレニル)フェニレン]ハフニウムジクロリド、および、これらの化合物のハフニウム原子をジルコニウム原子に置き換えた化合物またはクロロ配位子をメチル基に置き換えた化合物等が挙げられる。これら触媒の中でも、[ビス(4-メチルフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリドが好ましい。
(a)上記一般式[VII]で表される架橋メタロセン化合物と、(b)(b-1)有機金属化合物、(b-2)有機アルミニウムオキシ化合物、および(b-3)架橋メタロセン化合物(a)と反応してイオン対を形成する化合物、からなる群より選ばれる少なくとも1種の化合物と、さらに必要に応じて、(c)粒子状担体とから構成される。
以下、各成分について具体的に説明する。
上記共重合体(1B)または(2B)の製造に用いられる(b-1)有機金属化合物として、具体的には下記一般式[X]~[XII]のような周期律表第1、2族および第12、13族の有機金属化合物が用いられる。
(式[X]中、RaおよびRbは、互いに同一でも異なっていてもよく、炭素原子数が1~15、好ましくは1~4の炭化水素基を示し、Xはハロゲン原子を示し、mは0<m≦3、nは0≦n<3、pは0≦p<3、qは0≦q<3の数であり、かつm+n+p+q=3である。)で表される有機アルミニウム化合物。
(式[XI]中、M2はLi、NaまたはKを示し、Raは炭素原子数が1~15、好ましくは1~4の炭化水素基である。)で表される周期律表第1族金属とアルミニウムとの錯アルキル化物。
(式[XII]中、RaおよびRbは、互いに同一でも異なっていてもよく、炭素原子数が1~15、好ましくは1~4の炭化水素基を示し、M3はMg、ZnまたはCdである。)で表される周期律表第2族または第12族金属を有するジアルキル化合物。
上記共重合体(1B)または(2B)の製造に用いられる(b-2)有機アルミニウムオキシ化合物は、従来公知のアルミノキサンであってもよく、また特開平2-78687号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物であってもよい。(b-2)有機アルミニウムオキシ化合物は、1種単独で用いてもよいし2種以上組み合せて用いてもよい。
前記一般式[X]で表されるボロンを含んだ有機アルミニウムオキシ化合物は、下記一般式[XI]で表されるアルキルボロン酸と、
R1-B(OH)2 …[XI]
(式[XI]中、R1は前記一般式[X]におけるR1と同じ基を示す。)
有機アルミニウム化合物とを、不活性ガス雰囲気下に不活性溶媒中で、-80℃~室温の温度で1分~24時間反応させることにより製造できる。
上記共重合体(1B)または(2B)の製造に用いられる架橋メタロセン化合物(a)と反応してイオン対を形成する化合物(b-3)(以下、「イオン化イオン性化合物」という。)としては、特開平1-501950号公報、特開平1-502036号公報、特開平3-179005号公報、特開平3-179006号公報、特開平3-207703号公報、特開平3-207704号公報、USP-5321106号などに記載されたルイス酸、イオン性化合物、ボラン化合物およびカルボラン化合物などを挙げることができる。さらに、ヘテロポリ化合物およびイソポリ化合物も挙げることができる。このようなイオン化イオン性化合物(b-3)は、1種単独でまたは2種以上組み合せて用いられる。
前記カルボニウムカチオンとして具体的には、トリフェニルカルボニウムカチオン、トリ(メチルフェニル)カルボニウムカチオン、トリ(ジメチルフェニル)カルボニウムカチオンなどの三置換カルボニウムカチオンなどが挙げられる。
N,N-ジメチルアニリニウムカチオン、N,N-ジエチルアニリニウムカチオン、N,N,2,4,6-ペンタメチルアニリニウムカチオンなどのN,N-ジアルキルアニリニウムカチオン;
ジ(イソプロピル)アンモニウムカチオン、ジシクロヘキシルアンモニウムカチオンなどのジアルキルアンモニウムカチオンなどが挙げられる。
ボラン化合物として具体的には、たとえばデカボラン;ビス〔トリ(n-ブチル)アンモニウム〕ノナボレート、ビス〔トリ(n-ブチル)アンモニウム〕デカボレート、ビス〔トリ(n-ブチル)アンモニウム〕ウンデカボレート、ビス〔トリ(n-ブチル)アンモニウム〕ドデカボレート、ビス〔トリ(n-ブチル)アンモニウム〕デカクロロデカボレート、ビス〔トリ(n-ブチル)アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩;トリ(n-ブチル)アンモニウムビス(ドデカハイドライドドデカボレート)コバルト酸塩(III)、ビス〔トリ(n-ブチル)アンモニウム〕ビス(ドデカハイドライドドデカボレート)ニッケル酸塩(III)などの金属ボランアニオンの塩などが挙げられる。
上記担体(c)は、無機化合物または有機化合物であって、顆粒状ないしは微粒子状の固体である。
エチレン、α-オレフィン、及び非共役ポリエンを共重合させる際、重合触媒を構成する各成分の使用法、添加順序は任意に選ばれるが、以下のような方法が例示される。
フェノール樹脂系架橋剤(C)(本発明において架橋剤(C)とも称す)としては、ハロゲン化フェノール樹脂系架橋剤が挙げられる。
アルミニウム、コバルト、バナジウム、銅、カルシウム、ジルコニウム、マンガン、マグネシウム、鉛、水銀等、ナフテン酸と種々の金属(たとえば、Pb、Co、Mn、Ca、Cu、Ni、Fe、Zn、希土類)とのナフテン酸塩等が挙げられる。
本発明の組成物(I)または(IIC)には、重合体(A)、共重合体(1B)または共重合体(2B)、および架橋剤(C)の他に、本発明の効果を損なわない範囲において、添加剤を配合してもよい。添加剤としては、特に限定されないが、軟化剤(D)、無機充填剤(E)等が挙げられる。また、添加剤としては、共重合体(1B)または共重合体(2B)以外のゴム(たとえば、ポリイソブチレン、ブチルゴム、プロピレン・エチレン共重合体ゴム、プロピレン・ブテン共重合体ゴムおよびプロピレン・ブテン・エチレン共重合体ゴムなどのプロピレン系エラストマー、エチレン・プロピレン共重合体ゴムなどのエチレン系エラストマー、スチレン・ブタジエン・スチレンブロックポリマー、スチレン・イソプレン・スチレンブロックポリマー、スチレン・イソブチレン・スチレンブロックポリマーおよびこれらの水素添加物などのスチレン系エラストマー);熱硬化性樹脂、ポリオレフィンなどの熱可塑性樹脂等の結晶性オレフィン系重合体(A)以外の樹脂;紫外線吸収剤;酸化防止剤;耐熱安定剤;老化防止剤;耐光安定剤、耐候安定剤;帯電防止剤;金属セッケン;脂肪族アミド;ワックスなどの滑剤等、ポリオレフィンの分野で用いられている公知の添加剤が挙げられる。
〔熱可塑性エラストマー組成物(I)または熱可塑性エラストマー組成物(IIC)〕
本発明(1)の熱可塑性エラストマー組成物(I)は、重合体(A)、共重合体(1B)、および架橋剤(C)を含む混合物を動的架橋することによって得られる。組成物(I)は、少なくとも重合体(A)、共重合体(1B)、および架橋剤(C)が動的架橋されてなる。
本発明(1)の成形体は、本発明(1)の組成物(I)を含んで得られる。
本発明(2)の共重合体(2B)は、一般に該共重合体以外の成分を含有する組成物として用いられ、成形し、架橋されることにより所望の成形体を得ることができる。
本発明(2)の共重合体(2B)は、該共重合体から形成された成形体、共重合体(2B)を架橋処理して形成された成形体、共重合体(2B)を架橋してなる成形体、共重合体(2B)を含有する組成物から形成された成形体、共重合体(2B)を含有する組成物を架橋処理して形成された成形体、または共重合体(2B)を含む組成物を架橋してなる成形体として、様々の用途に用いることができる。
本発明のホース形成用組成物(IIB)は、共重合体(2B)を含有する。共重合体(2B)を含有するホース形成用組成物を、ホース形成用組成物とも記す。
本発明の組成物(IIB)は、共重合体(2B)に加えて、架橋剤を含有することが好ましい。
組成物(IIB)において、架橋剤としては、有機過酸化物、フェノール樹脂、硫黄系化合物、ヒドロシリコーン系化合物、アミノ樹脂、キノンまたはその誘導体、アミン系化合物、アゾ系化合物、エポキシ系化合物、イソシアネート系化合物等の、ゴムを架橋する際に一般に使用される架橋剤が挙げられる。これらのうちでは、有機過酸化物、硫黄系化合物(以下「加硫剤」ともいう)が好適である。
軟化剤としては、例えば、前記軟化剤(D)の例示が挙げられる。組成物(IIB)において、軟化剤は、石油系軟化剤が好ましく、プロセスオイルが特に好ましい。
無機充填剤としては、軽質炭酸カルシウム、重質炭酸カルシウム、タルク、クレーなどが挙げられ、これらのうちでは、「ホワイトンSB」(商品名;白石カルシウム株式会社)等の重質炭酸カルシウムが好ましい。
補強剤としては、カーボンブラック、シランカップリング剤で表面処理したカーボンブラック、シリカ、炭酸カルシウム、活性化炭酸カルシウム、微粉タルク、微分ケイ酸などが挙げられる。
組成物(IIB)に、老化防止剤(安定剤)を配合することにより、これから形成されるホースの寿命を長くすることができる。このような老化防止剤として、従来公知の老化防止剤、例えば、アミン系老化防止剤、フェノール系老化防止剤、イオウ系老化防止剤などがある。
加工助剤としては、一般に加工助剤としてゴムに配合されるものを広く用いることができる。加工助剤としては、例えば、リシノール酸、ステアリン酸、パルミチン酸、ラウリン酸等の脂肪酸、ステアリン酸バリウム、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸塩、リシノール酸エステル、ステアリン酸エステル、パルチミン酸エステル、ラウリン酸エステル類等の脂肪酸エステル類、N-置換脂肪酸アミドなどの脂肪酸誘導体が挙げられる。これらのうちでは、ステアリン酸が好ましい。
活性剤としては、例えば、ジ-n-ブチルアミン、ジシクロヘキシルアミン、モノエラノールアミン等のアミン類;ジエチレングリコール、ポリエチレングリコール、レシチン、トリアリルートメリレート、脂肪族カルボン酸または芳香族カルボン酸の亜鉛化合物等の活性剤;過酸化亜鉛調整物;クタデシルトリメチルアンモニウムブロミド、合成ハイドロタルサイト、特殊四級アンモニウム化合物が挙げられる。
吸湿剤としては、例えば、酸化カルシウム、シリカゲル、硫酸ナトリウム、モレキュラーシーブ、ゼオライト、ホワイトカーボンが挙げられる。
組成物(IIB)からなるホースは、非発泡体であってもよいし、発泡体であってもよい。発泡体形成に際して発泡剤を使用することができ、例えば、重炭酸ナトリウム、炭酸ナトリウム、重炭酸アンモニウム、炭酸アンモニウム、亜硝酸アンモニウム等の無機系発泡剤;N,N'-ジニトロテレフタルアミド、N,N'-ジニトロソペンタメチレンテトラミン等のニトロソ化合物;アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾシクロヘキシルニトリル、アゾジアミノベンゼン、バリウムアゾジカルボキシレート等のアゾ化合物;ベンゼンスルフォニルヒドラジド、トルエンスルフォニルヒドラジド、p,p'-オキシビス(ベンゼンスルフォニルヒドラジド)ジフェニルスルフォン-3,3'-ジスルフェニルヒドラジド等のスルフォニルヒドラジド化合物;カルシウムアジド、4,4'-ジフェニルスルホニルアジド、パラトルエンスルホニルアジド等のアジド化合物が挙げられる。
組成物(IIB)を用いることにより、常温での機械的特性および低温特性に優れるホースを形成することができる。例えば、常温での引張強度にも優れるとともに、低温での圧縮永久ひずみが小さく、また低温での捻り試験の結果が良好であるホースを得ることができる。
本発明(2)のホースは、組成物(IIB)から形成された層を有する。ホースは、組成物(IIB)から形成された層のみからなる1層または2層以上のホースでもよく、他の層、例えば天然ゴムからなる層、布帛層、熱可塑性樹脂層および熱硬化性樹脂層から選ばれる1層または2層以上の層、を有してもよい。
[エチレン・α-オレフィン・非共役ポリエン共重合体]
〔各構造単位のモル量および質量〕
エチレン[A]に由来する構造単位、α-オレフィン[B]に由来する構造単位および非共役ポリエン[C]に由来する構造単位のモル量および質量は、1H-NMRスペクトルメーターによる強度測定によって求めた。
ムーニー粘度ML(1+4)125℃およびムーニー粘度ML(1+4)150℃は、ムーニー粘度計((株)島津製作所製SMV202型)を用いて、JIS K6300(1994)に準じて測定した。
下記合成例で得られた共重合体のヨウ素価は、滴定法により求めた値である。具体的には、以下の方法で行った。
o-ジクロロベンゼン-d4/ベンゼン-d6(4/1[v/v])を測定溶媒とし、測定温度120℃にて、13C-NMRスペクトル(100MHz、日本電子製ECX400P)を測定し、下記式(i)に基づき、B値を算出した。
ここで[E]、[X]および[Y]は、それぞれ、エチレン[A]、炭素数4~20のα-オレフィン[B]および非共役ポリエン[C]のモル分率を示し、[EX]はエチレン[A]-炭素数4~20のα-オレフィン[B]ダイアッド連鎖分率を示す。
エチレン・α-オレフィン・非共役ポリエン共重合体の極限粘度[η]は、デカリン溶媒を用いて、135℃で測定した値である。
[熱可塑性エラストマー組成物(I)、(IIC)、および成形体の物性]
下記実施例および比較例における熱可塑性エラストマー組成物(I)、(IIC)、および成形体の物性の評価方法は次の通りである。
100t電熱自動プレス(ショージ社製)を用いて、得られた熱可塑性エラストマー組成物(I)のペレットを230℃で6分間プレス成形し、その後、室温で5分間冷却プレスして厚さ3mmのプレスシートを作製した。該シートを用いて、JIS K6253に準拠して、ショアーD硬度計により5秒後の値を測定した。
100t電熱自動プレス(ショージ社製)を用いて、得られた熱可塑性エラストマー組成物(IIC)のペレットを230℃で6分間プレス成形し、その後、室温で5分間冷却プレスして厚さ3mmのプレスシートを作製した。該シートを用いて、JIS K6253に準拠して、A型測定器を用い、押針接触後直ちに目盛りを読み取った。
JIS K6721に準拠して、230℃で10kgfの荷重にて測定した。
100t電熱自動プレス(ショージ社製)を用いて、得られた熱可塑性エラストマー組成物(I)または(IIC)のペレットを230℃で6分間プレス成形し、その後、室温で5分間冷却プレスして厚さ2mmのプレスシートを作製した。
JIS K6301の方法に従って測定した。
M25:25%伸び時の応力(MPa)
M50:50%伸び時の応力(MPa)
M100:100%伸び時の応力(MPa)
M200:200%伸び時の応力(MPa)
M300:300%伸び時の応力(MPa)
TB:引張破断強度(MPa)
EB:引張破断点伸び(%)
[重量変化率]
試験油として流動パラフィン(軟質)(ナカライテスク社製コード番号:26132-35)を使用し、2mmプレスシートを80℃×24時間浸漬した。その後サンプル表面をふき取り、n数=2にて重量変化率を測定した。
TGA装置(ティー・エイ・インスツルメント・ジャパン(株)社製TGA Q50001R)の系内を窒素雰囲気に十分置換するため、アルミナパンを用いてサンプル(サンプル重量:約5mg)をセットしてから40℃で20分間保持した。その後、次の測定条件にて1000℃まで昇温し、その時の残分を対象サンプル量(約5mg)に対するフィラー率とした。
・40℃(20分)→600℃→400℃[窒素雰囲気]
→400℃(20分)→1000℃[Air雰囲気]
・かっこ内は保持時間を表す。
実施例の比重は、各樹脂分および軟化剤の比重と、これらの配合部数を用いて算出した。比較例の比重は、カタログ値である。
下記比較例で用いたゴムの詳細、実施例および比較例におけるホース形成用組成物(IIB)および加硫物の物性の評価方法は次の通りである。
3072EM:三井化学(株)製、EPDM、エチレン含量=64wt%、ジエン含量=5.4wt%、ムーニー粘度ML(1+4)125℃=51、油展量=40(PHR)
上記製品の物性値はカタログ値である。
未加硫組成物の物性試験は、JIS K6300に準拠して行った。具体的には、ムーニー粘度計((株)島津製作所製SMV202型)を用いて、実施例・比較例で得られた配合物2の125℃におけるムーニー粘度の変化を測定し、測定開始から最低粘度(Vm)を求め、さらにその最低粘度Vmより5ポイントまたは35ポイント上昇するまでの時間を求め、これをスコーチ時間(t5、min)およびスコーチ時間(t35、min)とした。
実施例・比較例で得られた配合物2を用いて、加硫測定装置:MDR2000(ALPHA TECHNOLOGIES社製)により、加硫速度(TC90)を以下のとおり測定した。
実施例・比較例で得られた厚さ2mmの加硫ゴムシートの平らな部分を重ねて厚さ12mmのシートとし、JIS K6253に従い、硬度(JIS-A)を測定した。
実施例・比較例で得られた厚さ2mmの加硫ゴムシートについて、JIS K6251に従い、測定温度23℃、引張速度500mm/分の条件で引張試験を行い、伸び率が25%であるときの引張応力(25%モジュラス(M25))、伸び率が50%であるときの引張応力(50%モジュラス(M50))、伸び率が100%であるときの引張応力(100%モジュラス(M100))、伸び率が200%であるときの引張応力(200%モジュラス(M200))、伸び率が300%であるときの引張応力(300%モジュラス(M300))、破断時強度(TB)および破断伸び(EB)を測定した。
圧縮永久歪(CS)測定用試験片について、JIS K6262(1997)に従って、70℃、0℃、-20℃、または-40℃×22時間処理後の圧縮永久歪みを測定した。
低温捻り試験は、JIS K6261(1993)に従って、ゲーマン捻り試験機を用いて、実施例・比較例で得られた厚さ2mmの加硫ゴムシートについて、T2(℃)、T5(℃)、T10(℃)およびTg(℃)を測定した。これらの温度は、加硫ゴムの低温での柔軟性の指標となる。例えばT2が低いほど、低温での柔軟性は良好である。
〔遷移金属化合物の合成〕
[ビス(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド(触媒-a1)の合成
(i)6,6-ビス(4-メトキシフェニル)フルベンの合成
窒素雰囲気下、500 ml三口フラスコにリチウムシクロペンタジエニド8.28 g(115mmol)および脱水THF(テトラヒドロフラン)200 mlを加えた。氷浴で冷却しながらDMI(1,3-ジメチル-2-イミダゾリジノン)13.6 g (119 mmol)を添加し、室温で30分間攪拌した。その後4,4'-ジメトキシベンゾフェノン 25.3 g (105 mol)を加え、加熱還流下で1週間攪拌した。氷浴で冷却しながら水 100 mlを徐々に添加し、更にジクロロメタン 200 mlを加えて室温で30分間攪拌した。得られた二層の溶液を500 ml分液漏斗に移し、有機層を水 200 mlで3回洗った。無水硫酸マグネシウムで30分間乾燥した後、減圧下で溶媒を留去して橙褐色固体を得た。シリカゲルクロマトグラフ(700 g、ヘキサン:酢酸エチル = 4:1)による分離を行い、赤色溶液を得た。減圧下で溶媒を留去し、橙色固体として6,6-ビス(4-メトキシフェニル)フルベン 9.32 g (32.1 mmol、30.7%)を得た。6,6-ビス(4-メトキシフェニル)フルベンの同定は1H NMRスペクトルにて行った。以下にその測定値を示す。
(ii)ビス(4-メトキシフェニル)(シクロペンタジエニル)(2,3,6,7-テトラメチルフルオレニル)メタンの合成
窒素雰囲気下、100 ml三口フラスコに2,3,6,7-テトラメチルフルオレン 500 mg (2.25 mmol)および脱水t-ブチルメチルエーテル 40 mlを添加した。氷浴で冷却しながらn-ブチルリチウム/ヘキサン溶液 (1.63 M) 1.45 ml (2.36 mmol)を徐々に添加し、室温で18時間攪拌した。6,6-ビス(4-メトキシフェニル)フルベン 591 mg (2.03 mmol)を添加した後、3日間加熱還流を行った。氷浴で冷却しながら水 50 mlを徐々に添加し、得られた溶液を300 ml分液漏斗に移した。ジクロロメタン 50 mlを加えて数回振った後水層を分離し、有機層を水 50 mlで3回洗った。無水硫酸マグネシウムで30分間乾燥した後、減圧下で溶媒を留去した。得られた固体を少量のジエチルエーテルで洗浄し、白色固体を得た。更に、洗浄液の溶媒を減圧下で留去し、得られた固体を少量のジエチルエーテルで洗浄して白色固体を採取し、先に得た白色固体と合わせた。この固体を減圧下で乾燥し、ビス(4-メトキシフェニル)(シクロペンタジエニル)(2,3,6,7-テトラメチルフルオレニル)メタン 793 mg (1.55 mmol、76.0%)を得た。ビス(4-メトキシフェニル)(シクロペンタジエニル)(2,3,6,7-テトラメチルフルオレニル)メタンの同定はFD-MSスペクトルにて行った。以下にその測定値を示す。
(iii)[ビス(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリドの合成
窒素雰囲気下、100 mlシュレンク管にビス(4-メトキシフェニル)(シクロペンタジエニル)(2,3,6,7-テトラメチルフルオレニル)メタン 272 mg (0.531 mmol)、脱水トルエン 20 mlおよびTHF90μl (1.1 mmol)を順次添加した。氷浴で冷却しながらn-ブチルリチウム/ヘキサン溶液 (1.63 M) 0.68 ml (1.1 mmol)を徐々に添加し、45℃で5時間攪拌したところ赤色溶液が得られた。減圧下で溶媒を留去し、脱水ジエチルエーテル 20 mlを添加して再び赤色溶液とした。メタノール/ドライアイス浴で冷却しながら四塩化ハフニウム 164 mg (0.511 mmol)を添加し、室温まで徐々に昇温しながら16時間攪拌したところ、黄色スラリーが得られた。減圧下で溶媒を留去して得られた固体をグローブボックス内に持ち込み、ヘキサンで洗浄した後ジクロロメタンで抽出した。減圧下で溶媒を留去して得られた固体を少量のジクロロメタンに溶解し、ヘキサンを加えて-20℃で再結晶した。析出した固体を採取し、ヘキサンで洗浄した後減圧下で乾燥することにより、黄色固体として[ビス(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリド 275 mg (0.362 mmol、70.8%)(触媒-a1)を得た。[ビス(4-メトキシフェニル)メチレン(η5-シクロペンタジエニル)(η5-2,3,6,7-テトラメチルフルオレニル)]ハフニウムジクロリドの同定は1H NMRスペクトルおよびFD-MSスペクトルにて行った。以下にその測定値を示す。
1H NMRスペクトル(270 MHz, CDCl3): δ/ppm 7.87 (s, 2H), 7.80-7.66 (m, 4H), 6.94-6.83 (m, 4H), 6.24 (t, J = 2.6 Hz, 2H), 6.15 (s, 2H), 5.65 (t, J = 2.6 Hz, 2H), 3.80 (s, 6H), 2.47 (s, 6H), 2.05 (s, 6H)
FD-MSスペクトル: M/z 760 (M+)
得られた触媒-a1の化学式を以下に示す。
〔合成例1〕
攪拌翼を備えた容積300Lの重合器を用いて、連続的に、エチレン、1-ブテン、5-エチリデン-2-ノルボルネン(ENB)の重合反応を95℃にて行った。
〔実施例1〕
合成例1で得られたEBDM-1(1B)を100重量部と、メルトフローレート(ASTM-D-1238-65T;230℃、2.16kg荷重)が2.0g/10分であるポリプロピレン(商品名:プライムポリプロ(商標)E-200GP、プライムポリマー社製)40重量部、軟化剤(ダイアナプロセスPW-100、パラフィンオイル、出光興産社製)10部を、バンバリーミキサーで十分に混合したマスターバッチペレットを得た。
実施例1において、軟化剤(ダイアナプロセスPW-100、パラフィンオイル)の配合比率をマスターバッチ作成工程と動的架橋工程で変えた以外は、実施例1と同様にして熱可塑性エラストマー組成物のペレットを製造した。
実施例1において、マスターバッチ作成工程で配合するポリプロピレンをE-200GPからメルトフローレート(ASTM-D-1238-65T;230℃、2.16kg荷重)が2.0g/10分であるポリプロピレン(商品名:プライムポリプロ(商標)B241、プライムポリマー社製)に変えた以外は、実施例1と同様にして熱可塑性エラストマー組成物のペレットを製造した。
熱可塑性エラストマー組成物として、Santoprene(商標)103-40(ExxonMobil社製、比重:0.95g/cm3(カタログ値)、EPDMとPP(ポリプロピレン)を動的架橋してなる架橋型熱可塑性エラストマー)を使用して物性評価を行った。結果を表3に示す。
〔実施例4〕
攪拌翼を備えた容積300Lの重合器を用いて、連続的に、エチレン、1-ブテン、5-エチリデン-2-ノルボルネン(ENB)の重合反応を95℃にて行った。
重合条件を表4に記載したとおりに変更したこと以外は実施例4と同様にして、実施例5のエチレン・1-ブテン・ENB共重合体(EBDM-2(2B))、実施例6のエチレン・1-ブテン・ENB共重合体(EBDM-3(2B))を得た。結果を表4に示す。
重合条件を表4に記載したとおりに変更したこと以外は実施例4と同様にして、比較例2のエチレン・1-ブテン・ENB共重合体(EBDM-4)を得た。結果を表4に示す。
[実施例7]
MIXTRON BB MIXER(神戸製鋼所社製、BB-2型、容積1.7L、ローター2WH)を用いて、実施例6で得られたエチレン・1-ブテン・ENB共重合体(EBDM-3(2B))100部に対して、架橋助剤として酸化亜鉛(ZnO#1・酸化亜鉛2種(JIS規格(K-1410))、ハクスイテック(株)製)を5部、加工助剤としてステアリン酸を1部、補強剤としてカーボンブラック(FEFカーボン)「旭#60G」(商品名;旭カーボン(株)製)を80部、軟化剤としてパラフィン系プロセスオイル「ダイアナプロセスオイルPS-430」(商品名;出光興産株式会社製)を50部の配合量で配合した後に混練し、配合物1を得た。
配合組成を表5に記載したとおりに変更したこと以外は実施例7と同様にして、実施例8、9、および比較例3~5それぞれについて、配合物1~配合物2を得た。実施例7と同様にしてシート、試験片を作成し、各種評価を行った。結果を表5に示す。
〔実施例10〕
実施例4で得られたEBDM-1(2B)を100重量部と、メルトフローレート(ASTM-D-1238-65T;230℃、2.16kg荷重)が2.0g/10分であるポリプロピレン(商品名:プライムポリプロ(商標)B241、プライムポリマー社製)40重量部、軟化剤(ダイアナプロセスPW-100、パラフィンオイル、出光興産社製)40重量部を、バンバリーミキサーで充分に混合したマスターバッチペレットを得た。
マスターバッチと混合される軟化剤(ダイアナプロセスPW-100、パラフィンオイル)の量を75重量部から、73重量部に変更し、EL-ProTM P440Jの量を18重量部から23重量部に変更した以外は、実施例10と同様にして熱可塑性エラストマー組成物(IIC)のペレットを製造した。
EBDM-1(2B)を、EBDM-2(2B)に変更した以外は、実施例10と同様にして熱可塑性エラストマー組成物(IIC)のペレットを製造した。
熱可塑性エラストマー組成物として、Sarlink(商標)4175(Teknor Apex社製、比重:0.96g/cm3(カタログ値)、EPDMを含んでなる架橋型熱可塑性エラストマー)を使用して物性評価を行った。
熱可塑性エラストマー組成物として、Santoprene(商標)121-73W175(ExxonMobil社製、比重:0.97g/cm3(カタログ値)、EPDMとPP(ポリプロピレン)を動的架橋してなる架橋型熱可塑性エラストマー)を使用して物性評価を行った。
Claims (28)
- 結晶性オレフィン系重合体(A)、
下記要件(1)と(2)とを満たすエチレン・α-オレフィン(炭素数4~20)・非共役ポリエン共重合体(1B)、および
フェノール樹脂系架橋剤(C)を含む混合物を
動的架橋して得られる熱可塑性エラストマー組成物。
(1)下記式(i)で表されるB値が1.20~1.80である。
B値=([EX]+2[Y])/〔2×[E]×([X]+[Y])〕・・・(i)
ここで[E]、[X]および[Y]は、それぞれ、エチレン由来の構造単位のモル分率、炭素数4~20のα-オレフィン由来の構造単位のモル分率、非共役ポリエン由来の構造単位のモル分率を示し、[EX]はエチレン由来の構造単位-炭素数4~20のα-オレフィン由来の構造単位のダイアッド連鎖分率を示す。
(2)共重合体(1B)の、エチレンに由来する構造単位とα-オレフィン(炭素数4~20)に由来する構造単位とのモル比が、40/60~90/10である。 - エチレン・α-オレフィン・非共役ポリエン共重合体(1B)のα-オレフィンが、1-ブテンである、請求項1に記載の熱可塑性エラストマー組成物。
- 前記混合物には、さらに、軟化剤(D)を、前記結晶性オレフィン系重合体(A)および前記共重合体(1B)の合計100重量部に対して、2~100重量部含む、請求項1または2に記載の熱可塑性エラストマー組成物。
- フェノール樹脂系架橋剤(C)が、ハロゲン化フェノール樹脂系架橋剤である、請求項1~3のいずれか一項に記載の熱可塑性エラストマー組成物。
- 結晶性オレフィン系重合体(A)とエチレン・α-オレフィン・非共役ポリエン共重合体(1B)とを、(A)/(1B)=90/10~10/90の重量比で含有し、
フェノール樹脂系架橋剤(C)が、エチレン・α-オレフィン・非共役ポリエン共重合体(1B)100重量部に対して、0.1~20重量部含有する、請求項1~4のいずれかに記載の熱可塑性エラストマー組成物。 - 請求項1~5のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、成形体。
- 請求項1~5のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車部品。
- 請求項1~5のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ホース。
- 請求項1~5のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ブーツ。
- 結晶性オレフィン系重合体(A)と、下記要件(1)と(2)とを満たすエチレン・α-オレフィン(炭素数4~20)・非共役ポリエン共重合体(1B)と、フェノール樹脂系架橋剤(C)とを含む混合物を、動的架橋する工程を含むことを特徴とする、熱可塑性エラストマー組成物の製造方法。
(1)下記式(i)で表されるB値が1.20~1.80である。
B値=([EX]+2[Y])/〔2×[E]×([X]+[Y])〕・・・(i)
ここで[E]、[X]および[Y]は、それぞれ、エチレン由来の構造単位のモル分率、炭素数4~20のα-オレフィン由来の構造単位のモル分率、非共役ポリエン由来の構造単位のモル分率を示し、[EX]はエチレン由来の構造単位-炭素数4~20のα-オレフィン由来の構造単位のダイアッド連鎖分率を示す。
(2)共重合体(1B)の、エチレンに由来する構造単位とα-オレフィン(炭素数4~20)に由来する構造単位とのモル比が、40/60~90/10である。 - エチレン[A]に由来する構造単位、炭素数4~20のα-オレフィン[B]に由来する構造単位、および非共役ポリエン[C]に由来する構造単位を含み、下記(1)~(4)を満たすエチレン・α―オレフィン・非共役ポリエン共重合体(2B)。
(1)エチレン[A]に由来する構造単位と、α-オレフィン[B]に由来する構造単位とのモル比〔[A]/[B]〕が、40/60~90/10であり、
(2)非共役ポリエン[C]に由来する構造単位の含有量が、[A]、[B]および[C]の構造単位の合計を100モル%として、0.1~6.0モル%であり、
(3)125℃におけるムーニー粘度ML(1+4)125℃が、100を超えて200以下であり、
(4)下記式(i)で表されるB値が1.20~1.80である。
B値=([EX]+2[Y])/〔2×[E]×([X]+[Y])〕・・(i)
[ここで[E]、[X]および[Y]は、それぞれ、エチレン[A]、炭素数4~20のα-オレフィン[B]、および非共役ポリエン[C]のモル分率を示し、[EX]はエチレン[A]-炭素数4~20のα-オレフィン[B]ダイアッド連鎖分率を示す。] - 炭素数4~20のα-オレフィン[B]が、1-ブテンであることを特徴とする請求項11に記載のエチレン・α―オレフィン・非共役ポリエン共重合体(2B)。
- (a)下記一般式[VII]で表される遷移金属化合物と、
(b)(b-1)有機金属化合物、
(b-2)有機アルミニウムオキシ化合物、および
(b-3)遷移金属化合物(a)と反応してイオン対を形成する化合物から選ばれる少なくとも1種の化合物と
を含むオレフィン重合触媒の存在下において、エチレン、炭素数4~20のα-オレフィンおよび非共役ポリエンを共重合することにより得られる、請求項11または12に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)。
Mはチタン原子、ジルコニウム原子またはハフニウム原子であり、
R5およびR6が、アリール基の水素原子の一つ以上をハメット則の置換基定数σが-0.2以下の電子供与性置換基で置換してなる置換アリール基であって、該電子供与性置換基を複数個有する場合にはそれぞれの該電子供与性置換基は同一でも異なっていてもよく、該電子供与性置換基以外の、炭素数1~20の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基を有していてもよく、該置換基を複数個有する場合にはそれぞれの置換基は同一でも異なっていてもよい置換アリール基であり、
Qはハロゲン原子、炭素数1~20の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
jは1~4の整数である。) - 請求項11~13のいずれか一項に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)を含有する組成物。
- 請求項14に記載の組成物を架橋処理して形成された成形体。
- 請求項11~13のいずれか一項に記載のエチレン・α-オレフィン・非共役ポリエン共重合体(2B)を含有するホース形成用組成物。
- 請求項16に記載のホース形成用組成物を架橋処理して形成された層を有するホース。
- 自動車用、モーターバイク用、工業機械用、建設機械用または農業機械用のいずれかの用途に用いられる、請求項17に記載のホース。
- 結晶性オレフィン系重合体(A)、
エチレン・α―オレフィン・非共役ポリエン共重合体(2B)、および
フェノール樹脂系架橋剤(C)を含む混合物を
動的架橋して得られ、
エチレン・α―オレフィン・非共役ポリエン共重合体(2B)が、請求項11~13のいずれか一項に記載のエチレン・α―オレフィン・非共役ポリエン共重合体(2B)である熱可塑性エラストマー組成物。 - 前記混合物には、さらに、軟化剤(D)を、前記結晶性オレフィン系重合体(A)および前記共重合体(2B)の合計100重量部に対して、2~100重量部含む、請求項19に記載の熱可塑性エラストマー組成物。
- フェノール樹脂系架橋剤(C)が、ハロゲン化フェノール樹脂系架橋剤である、請求項19または20に記載の熱可塑性エラストマー組成物。
- 結晶性オレフィン系重合体(A)とエチレン・α-オレフィン・非共役ポリエン共重合体(2B)とを、(A)/(2B)=90/10~10/90の質量比で含有し、
フェノール樹脂系架橋剤(C)を、エチレン・α-オレフィン・非共役ポリエン共重合体(2B)100重量部に対して、0.1~20重量部含有する、請求項19~21のいずれか一項に記載の熱可塑性エラストマー組成物。 - 請求項19~22のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、成形体。
- 請求項19~22のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車部品。
- 請求項19~22のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ホース。
- 請求項19~22のいずれか一項に記載の熱可塑性エラストマー組成物を含んで得られる、自動車用ブーツ。
- (a)下記一般式[VII]で表される遷移金属化合物と、
(b)(b-1)有機金属化合物、
(b-2)有機アルミニウムオキシ化合物、および
(b-3)遷移金属化合物(a)と反応してイオン対を形成する化合物から選ばれる少なくとも1種の化合物と
を含むオレフィン重合触媒の存在下において、エチレン、炭素数4~20のα-オレフィンおよび非共役ポリエンを共重合する工程を含むことにより得られる、エチレン・α-オレフィン・非共役ポリエン共重合体の製造方法。
Mはチタン原子、ジルコニウム原子またはハフニウム原子であり、
R5およびR6が、アリール基の水素原子の一つ以上をハメット則の置換基定数σが-0.2以下の電子供与性置換基で置換してなる置換アリール基であって、該電子供与性置換基を複数個有する場合にはそれぞれの該電子供与性置換基は同一でも異なっていてもよく、該電子供与性置換基以外の、炭素数1~20の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基を有していてもよく、該置換基を複数個有する場合にはそれぞれの置換基は同一でも異なっていてもよい置換アリール基であり、
Qはハロゲン原子、炭素数1~20の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
jは1~4の整数である。) - 結晶性オレフィン系重合体(A)と、エチレン[A]に由来する構造単位、炭素数4~20のα-オレフィン[B]に由来する構造単位、および非共役ポリエン[C]に由来する構造単位を含み、下記(1)~(4)を満たすエチレン・α-オレフィン(炭素数4~20)・非共役ポリエン共重合体(2B)と、フェノール樹脂系架橋剤(C)とを含む混合物を、動的架橋する工程を含むことを特徴とする、熱可塑性エラストマー組成物の製造方法。
(1)エチレン[A]に由来する構造単位と、α-オレフィン[B]に由来する構造単位とのモル比〔[A]/[B]〕が、40/60~90/10であり、
(2)非共役ポリエン[C]に由来する構造単位の含有量が、[A]、[B]および[C]の構造単位の合計を100モル%として、0.1~6.0モル%であり、
(3)125℃におけるムーニー粘度ML(1+4)125℃が、100を超えて200以下であり、
(4)下記式(i)で表されるB値が1.20~1.80である。
B値=([EX]+2[Y])/〔2×[E]×([X]+[Y])〕・・(i)
[ここで[E]、[X]および[Y]は、それぞれ、エチレン[A]、炭素数4~20のα-オレフィン[B]、および非共役ポリエン[C]のモル分率を示し、[EX]はエチレン[A]-炭素数4~20のα-オレフィン[B]ダイアッド連鎖分率を示す。]
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US20180072877A1 (en) | 2018-03-15 |
US11078352B2 (en) | 2021-08-03 |
CN107428956A (zh) | 2017-12-01 |
TW201641563A (zh) | 2016-12-01 |
KR20170118196A (ko) | 2017-10-24 |
KR101840993B1 (ko) | 2018-03-21 |
EP3272790A1 (en) | 2018-01-24 |
BR112017020142B1 (pt) | 2022-04-12 |
BR112017020142A2 (ja) | 2018-07-03 |
EP3272790A4 (en) | 2018-10-24 |
JPWO2016152711A1 (ja) | 2017-12-21 |
JP6439039B2 (ja) | 2018-12-19 |
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