COPOLYMER, RUBBER COMPOSITION, RECTICULAR RUBBER COMPOSITION, AND TIRE

专利摘要:
latex coating compositions including coalescent ketal carboxyester, manufacturing methods and uses thereof. a latex coating composition is disclosed, comprising a latex-binding polymer; Water; and a ketal adduct of formula (1), wherein r ^ 1 ^ is alkylac1-6, r ^ 2 ^ is hydrogen or alkylac1-3, er ^ 3 ^, r ^ 4 ^ and ^ 5 ^ are independently hydrogen or alkylac1 -6, r ^ 6 ^ and ^ 7 ^ are each independently hydrogen or alkyl-1-6, a is 0-3, and b is 0-1.
公开号:BR112013002291B1
申请号:R112013002291-4
申请日:2011-07-26
公开日:2020-03-24
发明作者:Yasuo Horikawa；Shojiro Kaita；Olivier Tardif；Junko Matsushita
申请人:Bridgestone Corporation；
IPC主号:

专利说明:

COPOLIMERO, RUBBER COMPOSITION, RECTICULAR RUBBER COMPOSITION, AND TIRE
Technical Field [001] The present invention relates to a copolymer of a conjugated diene compound and an unconjugated olefin, a rubber composition, a crosslinked rubber composition, and a tire, and more particularly to: a composite block copolymer of a conjugated diene compound and an unconjugated olefin, which is to be used for the production of a rubber having a high elastic modulus and being excellent in the property of low heat generation, in the resistance to the increase of cracks, and in the resistance to ozone ; a rubber composition including the block copolymer; a crosslinked rubber composition obtained by crosslinking the rubber composition; and a tire manufactured by using the rubber composition or the cross-linked rubber composition.
Background Art [002] At least two different monomers can be polymerized in the same polymerization system in order to generate a copolymer having those different units of monomers arranged as repeating units in a polymer chain, and the copolymer thus obtained, can be classified into a random copolymer, an alternative copolymer, a block copolymer, or a graft copolymer, depending on the arrangement of the monomer units. In any case, no reports have been made on the arrangement of the monomer units in the polymerization reaction of a conjugated diene compound and an unconjugated olefin.
[003] For example, JP 2000-154210 A (PTL 1) describes a catalyst for the polymerization of a conjugated diene, the catalyst including a metal compound of
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2/65 group IV transition which has a cyclopentadiene ring structure, in which an α-olefin, such as ethylene is exemplified as a copolymerizable monomer with the conjugated diene. In any case, no reference is made to the arrangement of the monomer units in the copolymer. In addition, JP 2006-249442 A (PTL 2) describes an α-olefin copolymer and a conjugated diene compound, but no reference is made to the arrangement of the monomer units in the copolymer. In addition, JP 2006-503141 A (PTL 3) describes a copolymer synthesized from ethylene / butadiene through the use of a catalytic system consisting of a specific organometallic complex, but simply describes that butadiene as a monomer is inserted in the form of trans1 , 2-cyclohexane in the copolymer, without making any reference to the arrangement of the monomer units in the copolymer, and no reference is made to a rubber manufactured using a block copolymer in which a cis bond content or a bond content vinyl (content of adducts
1,2 (including adducts 3,4)) is defined in order to obtain a module of high elasticity, an excellent low heat generation property, resistance to the increase of cracks, and resistance to ozone.
[004] In addition, JP 11-228743 A (PTL 4) describes an unsaturated elastomer composition composed of a copolymer based on unsaturated olefin and a rubber, but simply describes that the monomer units in the copolymer are randomly arranged and does not refer to a block copolymer in which a cis bond content or a vinyl bond content (adduct content
1.2 (including 3.4 adducts)) is defined in order to be able to produce a rubber that has a high elastic modulus, an excellent low heat generation property, an excellent resistance to cracking, and
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3/65 excellent ozone resistance.
[005] In addition, JP 2000-86857 A (PTL 5) describes a butadiene copolymer having: a vinyl content (vinyl bond content, 1.2 adducts (including 3.4 adducts content)) of 6% ; a cis content of 92%, and an ethylene content of 3% or 9%. In any case, JP 2000-86857 A (PTL 5) does not describe or suggest a block copolymer in which a cis bond content or a vinyl bond content (adduct content
1.2 (including adducts 3.4)) is defined in order to be able to produce a rubber that has a high elasticity modulus, an excellent low heat generation property, an excellent resistance to cracking, and an excellent resistance ozone.
Citation List
Patent Literature
PTL 1: JP 2000-154210 THE PTL 2: JP 2006-249442 THE PTL 3: JP 2006-503141 THE PTL 4: JP 11-228743 APTL 5: JP 2000-86857 A
Summary of the Invention
Technical Problem [006] In view of the above, an objective of the present invention is to provide: a block copolymer composed of a conjugated diene compound and an unconjugated olefin, which is to be used for the production of a rubber having a high elastic modulus and being excellent in the property of low heat generation, in the resistance to the increase of cracks, and in the resistance to ozone; a rubber composition including the block copolymer; a crosslinked rubber composition obtained by crosslinking the rubber composition; and a tire manufactured by using the rubber composition or the
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4/65 cross-linked rubber composition.
Solution to the Problem [007] As a result of the intense study to solve the problems mentioned above, the inventors of the present invention found the following, and obtained the present invention. That is, a copolymer of a conjugated diene compound and an unconjugated olefin can be obtained as a block copolymer (including a multi-block copolymer, hereinafter the same applies) through the polymerization of a conjugated diene compound and an unconjugated olefin in the presence of a specific catalyst, or by introducing, in the presence of an unconjugated olefin, a conjugated diene compound in a reaction polymerization system for the polymerization of a conjugated diene compound and an unconfined olefin. conjugated.
[008] That is to say, the copolymer according to the present invention is a copolymer of a conjugated diene compound and an unconjugated olefin in which: the copolymer being a block copolymer, and an adduct content of 1.2 (including adducts) 3.4) in the unit of the conjugated diene compound (a content of 1.2 unit adduct (including adduct unit 3.4) of the conjugated diene compound in a unit derived from the conjugated diene compound) is 5% or any less; or a cis-1,4 bond content in the conjugated diene compound unit (unit derived from the conjugated diene compound) is greater than 92%.
[009] According to the present invention, the block copolymer refers to a copolymer being composed of a block sequence of the monomer units of a conjugated diene compound and a block sequence of the monomer units of an unconjugated olefin .
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[0010] In another preferred example of the copolymer of the present invention, the unconjugated olefin (unit derived from the unconjugated olefin) is contained in 0 mol% to 100 mol% or less. Here, the unconjugated olefin (unit derived from the unconjugated olefin) is preferably contained in 0 mol% to 50 mol% or less.
[0011] In another preferred example of the copolymer according to the present invention, a content of 1,2 adducts (including adducts 3,4) in the conjugated diene compound unit is 5% or less; or a cis-1,4 bond content of the conjugated diene compound unit is greater than 92%.
[0012] In another preferred example of the block copolymer according to the present invention, the tapered copolymer has any of the structures of (AB) x, A- (BA) x and B- (AB) x (where A represents a block sequence including the unconjugated olefin monomer units, B represents one of a block sequence including the conjugated diene compound monomer units and a block sequence including the unconjugated olefin monomer units, ex represents a number at least 1). Here, the block copolymer including a plurality of (A-B) or (B-A) structures is referred to as a multi-block copolymer.
[0013] The copolymer according to the present invention preferably has an average molecular weight equivalent to that of polystyrene from 10,000 to 10,000,000.
[0014] The copolymer according to the present invention preferably has a molecular weight distribution (Mw / Mn) of 10 or less.
[0015] In a preferred example of the copolymer according to the present invention, the unconjugated olefin is an acyclic olefin.
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[0016] In other example favorite of copolymer of this invention, The olefin not conjugated have from 2 to 10 atoms of carbon. [0017] At the copolymer in wake up with this
invention, the unconjugated olefin is preferably at least one selected from a group consisting of ethylene, propylene, and 1-butene, and the unconjugated olefin is more preferably ethylene.
[0018] In another preferred example of the copolymer according to the present invention, the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.
[0019] A rubber composition according to the present invention includes the copolymer of the present invention.
[0020] The rubber composition according to the present invention preferably includes the copolymer in a component of the rubber.
[0021] The rubber composition according to the present invention preferably includes, with respect to the 100 parts by weight of the rubber component, a reinforcing charge of 5 parts by weight to 200 parts by weight, and a filler crosslinking by 0.1 parts by mass to 20 parts by mass.
[0022] A crosslinked rubber composition according to the present invention is obtained by crosslinking the rubber composition of the present invention.
[0023] A tire according to the present invention is manufactured using the rubber composition of the present invention or the crosslinked rubber composition of the present invention.
Advantageous Effect of the Invention [0024] The present invention is capable of
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7/65 supply: a block copolymer composed of a conjugated diene compound and an unconjugated olefin, which is used for the production of a rubber having a high elastic modulus and being excellent in the property of low heat generation, in resistance to increase cracking, and ozone resistance; a rubber composition including the block copolymer; a crosslinked rubber composition obtained by crosslinking the rubber composition; and a tire made using the rubber composition or the cross-linked rubber composition.
Brief Description of the Drawings [0025] The present invention should also be described below with reference to the drawings that follow, in which:
Figure 1 is a graph of the ¹³ C NMR spectrum of a copolymer A;
Figure 2 shows a DSC curve for copolymer A;
The figure 3 shows a curve of DSC on one copolymer C; andThe figure 4 shows a curve of DSC on one copolymer E.description of Modalities
Copolymer [0026] The present invention will be described in detail hereinafter. The present invention provides a copolymer of a conjugated diene compound and an unconjugated olefin wherein: the copolymer is a block copolymer, and an adduct content of 1.2 (including adducts 3.4) in the conjugated diene compound unit (a content of 1.2 adduct units (including adduct units 3.4) of the conjugated diene compound in a unit derived from the conjugated diene compound) is 5% or less; or a bond content of
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8/65 cis-1,4 in the conjugated diene compound unit (unit derived from the conjugated diene compound) is greater than
92%.
[0027] The content (including cis-1,4 adduct unit each corresponds to the 1.2 adduct unit
3.4) and the binding content of an amount in a unit derived from the conjugated diene compound, instead of the ratio to the entire copolymer.
[0028] The copolymer of the present invention, which includes a block sequence of the monomer units of an unconjugated olefin, exhibits static crystallinity, and thus is excellent in mechanical properties, such as resistance to breakage. In addition, the copolymer of the present invention includes a block sequence including the monomer units of a conjugated diene compound, which allows the copolymer to behave like an elastomer. In addition, in the copolymer of the present invention, a content of adducts 1,2 (including adducts 3,4) in the conjugated diene compound (a content of adduct unit 1,2 (including adduct unit 3,4) of the compound of conjugated diene in a unit derived from the conjugated diene compound) is preferably 5% or less. With the content of adducts 1,2 (including adducts 3,4) in the unit of the conjugated diene compound being 5% or less, the copolymer of the present invention can also be improved in ozone resistance and fatigue resistance. In addition, with the adduct content of 1.2 (including adducts 3.4) in the conjugated diene compound unit being 2.5% or less, the copolymer of the present invention can also be improved in ozone resistance and resistance fatigue. The content of adducts 1,2 (including adducts 3,4) in the conjugated diene compound unit is still preferably 2.0% or less.
[0029] Here, the copolymer is a copolymer of
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9/65 a conjugated diene compound and an unconjugated olefin, which is a block copolymer, where the content of adducts 1,2 (including adducts 3,4) in the unit of the conjugated diene compound is 5% or less (vinyl bond content is 5 mol% or less) while the cis-1,4 bond content in the conjugated diene unit (unit derived from the conjugated diene compound) is greater than 92%, so that the high elastic modulus, the low heat generation property, and the resistance to cracking can all be achieved at high levels.
[0030] Here, the content of adduct unit 1,2 (including adduct unit 3,4) in the unit of the conjugated diene compound (content of adduct unit 1,2 (including
unity adduct 3.4) of a diene compound together in a unit derived from the diene compound joint) is equal to a content vinyl bonding in 1.2 when The compound of diene conjugate is butadiene. [0031] 0 block copolymer to be formed in wake up with the present invention is identified
mainly by means of differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). Here, differential scanning calorimetry (DSC) is an evaluation method according to JIS K 7121-1987. Specifically, when the DSC observes a glass transition temperature derived from a block sequence of the monomer units of the conjugated diene compound, a crystallization temperature derived from the block sequence, and a crystallization temperature derived from a block sequence including the unconjugated olefin monomer units means that the copolymer has a block sequence including the conjugated diene compound monomer units and a block sequence including the unconjugated olefin monomer units
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10/65 formed in this.
[0032] In the copolymer of the present invention, the cis-1,4 bond content in the conjugated diene compound unit (unit derived from the conjugated diene compound) is preferably more than 92%, also preferably 95 % or more, and yet preferably still 97% or more. With the cis-1,4 bond content in the conjugated diene compound unit (derived unit from the conjugated diene compound) being more than 92%, the block sequence including the monomer units of the conjugated diene compound has high stress-induced crystallinity, and thus the copolymer of the present invention can also be improved in ozone resistance and fatigue resistance.
[0033] The copolymer of the present invention is free from a problem of reducing the molecular weight, and its average weight molecular weight (Mw) is not specifically limited. In any case, in view of the application to the polymer materials, an average molecular weight equivalent to the polystyrene (Mw) of the copolymer is preferably from 10,000 to 10,000,000, more preferably from 10,000 to 1,000,000, and also preferably from 50,000 to 600,000. In addition, the molecular weight distribution (Mw / Mn) obtained as a ratio of the average weight molecular weight (Mw) to the average numerical molecular weight (Mn) is preferably 10 or less, and more preferably 5 or less . Here, the average molecular weight and molecular weight distribution can be determined by means of gel permeation chromatography (GPC) employing polystyrene as a standard reference material.
[0034] According to the copolymer of the present invention, the content of the unconjugated olefin (unit derived from the unconjugated olefin) is preferably more than
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0 mol% to less than 100 mol%. With the content of the unconjugated olefin (unit derived from the unconjugated olefin) falling within the range specified above, the copolymer can be reliably improved in mechanical properties, such as fracture resistance. In addition, in view of the improvement of mechanical properties, such as fracture strength without causing phase separation in the copolymer, the content of unconjugated olefin (unit derived from unconjugated olefin) is also preferred to be more than 0 mol% to 50 mol% or less.
[0035] On the other hand, according to the copolymer of the present invention, the content of the conjugated diene compound (unit derived from the conjugated diene compound) is preferably from more than 0 mol% to less than 100% mol. mol, and also preferably from 50 mol% or more to less than 100 mol%. With the content of a conjugated diene compound (unit derived from the conjugated diene compound) falling within the ranges specified above, the copolymer of the present invention is allowed to uniformly behave like an elastomer.
[0036] According to the copolymer of the present invention, examples of the structure of the block copolymer include (A-B) x, A- (B-A) x, and B- (A-B) x. Here, A represents a random unit including the unconjugated olefin monomer units; B represents a block sequence including the monomer units of the conjugated diene compound; ex represents an integer of at least 1, and preferably an integer from 1 to 5. Here, there is no need to clearly define the boundaries between the block portions, and a so-called tapered structure, in other words, a unit composed of a mixture of the conjugated diene compound and the unconjugated olefin can
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12/65 be formed, for example, between the block sequence represented by A and the block sequence represented by B. Furthermore, when the copolymer includes a plurality of the same block portions, the types and compositions of monomers forming the Block portions should not be uniform.
[0037] A conjugated diene compound to be used as a monomer preferably has 4 to 12 carbon atoms. Specific examples of such conjugated diene compounds include: 1,3-butadiene; isoprene; 1,3-pentadiene; and 2,3-dimethyl butadiene, with 1,3-butadiene and isoprene being preferred. These conjugated diene compounds can be used alone or in combination of two or more.
Any of the specific examples mentioned above of the conjugated diene compounds can be used for the preparation of the copolymer of the present invention in the same mechanism.
[0039] In the meantime, an unconjugated olefin to be employed as a monomer is an unconjugated olefin other than the conjugated diene compound, and preferably an acyclic olefin. The unconjugated olefin preferably has 2 to 10 carbon atoms. For this reason, preferred examples of the aforementioned unconjugated olefin include α-olefins, such as: ethylene; propylene; 1-butene; 1-pentene; 1-hexene; 1 heptene; and 1-octene. Of these, ethylene, propylene, 1-butene are more preferred, and ethylene is particularly preferred. These unconjugated olefin compounds can be used alone or in combination with two or more. Here, an olefin refers to unsaturated aliphatic hydrocarbon, which is a compound containing at least one carbon-carbon covalent double bond.
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13/65 [0040] In the following, a method of producing the copolymer according to the present invention will be described in detail. In any case, the production method described in detail below is simply an example.
[0041] According to a first production method the copolymer of the present invention, a conjugated diene compound and an unconjugated olefin are polymerized in the presence of a polymerization catalyst composition illustrated below. An arbitrary method can be employed as the polymerization method including, for example, solution polymerization, suspension polymerization, liquid phase polymerization, emulsion polymerization, vapor phase polymerization, and solid state polymerization. In the case of using a solvent for polymerization, any solvent that is inactive in the polymerization can be employed, including, for example, toluene, hexane, cyclohexane, and a mixture of these.
First Polymerization Catalyst Composition [0042] An example of the aforementioned polymerization catalyst composition includes a polymerization catalyst composition (hereinafter, also referred to as the first polymerization catalyst composition) including at least one complex selected from a group consisting of : a metallocene complex represented by the general formula that follows (I); a metallocene complex represented by the general formula that follows (II); and a semi-metallocene cation complex represented by the following general formula (III):
Formula 1
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Cp ^R
L _w r ^{R P} N — Si (R ^a R ^b R ^c ) • · · (I)
Si (R ^d R ^and R ^f ) [0043] In formula (I), M represents a lanthanoid, scandium, or iterium element; CpR each independently represents a substituted or unsubstituted indenyl group; Ra to Rf each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; L represents a neutral Lewis base; ew represents an integer from 0 to 3;
Formula 2
Cp ^R
[0044] In formula (II), M represents a lanthanoid, scandium, or iterium element; CpR each independently represents a substituted or unsubstituted indenyl group; X 'represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having from 1 to 20 carbon atoms; L represents a base of
Lewis neutral; and w represents an integer from 0 to 3; and
Formula 3
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Cp ^{R /}
[0045] In formula (III), M represents a lanthanoid, scandium, or iterium element; CpR 'each independently represents a substituted or unsubstituted fluorenyl, indenyl, cyclopentadienyl group; X represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms; L represents a neutral Lewis base; w represents an integer from 0 to 3; and [B] - represents a non-coordinating anion.). The first polymerization catalyst composition can also include another component, such as a co-catalyst, which is included in a general polymerization catalyst composition containing a metallocene complex. Here, the metallocene complex is a complex compound having one or more cyclopentadienyl groups or derived from cyclopentadienyl groups attached to the central metal. In particular, a metallocene complex can be referred to as a semimetalocene complex when the number of cyclopentadienyl group or its derivative attached to the central metal is one. In the polymerization system, the concentration of the complex included in the first polymerization catalyst composition is preferably defined to be within a range of 0.1 mol / L to 0.0001 mol / L.
[0046] In the metallocene complex represented by the general formulas (I) and (II) above, CpR in the formulas
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16/65 represents a substituted or unsubstituted indenyl group. CpR having an indenyl ring as a basic skeleton can be represented by C9H7-XRX or C9H11-XRX. Here, X represents an integer from 0 to 7 or from 0 to 11. Each R independently preferably represents a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms. Preferred specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid in the metalloid group include germyl (Ge), stanyl (Sn), and silyl (Si). In addition, the metalloid group preferably has a hydrocarbyl group that is similar to the hydrocarbyl group described above. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl group include 2-phenyl indenyl, 2-methyl indenyl, and 1methyl-2-phenyl indenyl group. Two CpRs in the general formulas (I) and (II) can be the same as or different from each other.
[0047] In the semimetalocene cation complex represented by the general formula (III), CpR 'in the formula represents a substituted or unsubstituted fluorenyl, indenyl, or cyclopentadienyl group, with the substituted or unsubstituted indenyl group being preferred. CpR 'having a cyclopentadienyl ring as a basic skeleton is represented by C5H5-XRX. Here, X represents an integer from 0 to 5. In addition, each R independently preferably represents a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has from 1 to 20 atoms of
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17/65 carbon, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms. Preferred specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a benzyl group. Examples of metalloid in the metalloid group include germyl (Ge), stannyl (Sn), and silyl (Si). In addition, the metalloid group preferably has a hydrocarbyl group that is similar to the hydrocarbyl group described above. Specific examples of the metalloid group include a trimethylsilyl group. CpR 'having a cyclopentadienyl ring as a basic skeleton is specifically exemplified as follows.
Formula 4
Me
Me
Me [0048] In the formula, R represents a hydrogen atom, a methyl group, or an ethyl group.
[0049] In the general formula (III), CpR 'having an indenyl ring as a basic skeleton is defined as the same as CpR in the general formula (I), and its preferred examples are also the same as those of CpR in the formula general (I).
[0050]
In the general formula (III), CpR 'having the fluorenyl ring above as a basic skeleton, can be represented by C13H9-XRX or C13H17-XRX. Here, X represents an integer from 0 to 9 or from 0 to 17. R independently preferably represents a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 atoms of
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18/65 carbon, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms. Preferred specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid in the metalloid group include germyl (Ge), stanyl (Sn), and silyl (Si). In addition, the metalloid group preferably has a hydrocarbyl group that is similar to the hydrocarbyl group described above. A specific example of the metalloid group includes a trimethylsilyl group.
[0051] The central metal represented by M in the general formulas (I), (II), and (III) represents a lanthanoid, scandium, or yttrium element. The lanthanoid elements include 15 elements with atomic numbers from 57 to 71, and can be any one of them. Preferred examples of the central metal represented by M include samarium (Sm), neodymium (Nd), prasiodimium (Pr), gadolinium (Gd), cerium (Ce), holmium (Ho), scandium (Sc), and yttrium (Y) .
[0052] The metallocene complex represented by the general formula (I) includes a silyl amide ligand represented by [-N (SiR3) 2]. The groups represented by R (from Ra to Rf in the general formula (I)) in the silyl amide binder, each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and it is preferred that at minus one of Ra to Rf represents a hydrogen atom. With at least one of Ra to Rf representing a hydrogen atom, the catalyst can be synthesized with ease, and the height around the silicon can be reduced, to thereby allow the unconjugated olefin to be easily introduced. Based on the same objective, it is also preferred that at least one of Ra to Rc represents a hydrogen atom, and at least one
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19/65 Rd to Rf represents a hydrogen atom. A methyl group is preferred as the alkyl group.
[0053] The metallocene complex represented by the general formula (II) includes a silyl binder represented by [-SiX'3], X 'in the silyl binder represented by [-SiX'3] is a group defined as the same as X in the general formula (III) described below, and its preferred examples are also the same as those of X in the general formula (III).
[0054] In the general formula (III), X represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amide group, a silyl group, and a group hydrocarbon having 1 to 20 carbon atoms. In the general formula (III), the alkoxy group represented by X can be any of the aliphatic alkoxy groups, such as, a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, an sec-butoxy, and a tert-butoxy group; and aryl oxide groups (aromatic alkoxy groups), such as, a phenoxy group, a 2,6-ditherc-butylphenoxy group, a 2,6-diisopropylphenoxy group, a group
2,6-dineopentylphenoxy, a 2-tert-butyl-6dineopentylphenoxy group, a 2-tert-butyl-6-neopentylphenoxy group, and a 2-isopropyl-6-neopentylphenoxy group, with the 2,6di-tert-butylphenoxy group being preferred.
[0055] In the general formula (III), the thiolate group represented by X can be any of: aliphatic thiol groups, such as, a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio-n-butoxy group, a thioisobutoxy group, a thio-sec-butoxy group, and a thio-tert-butoxy group; and aryl thiolate groups, such as, a thiophenoxy group, a 2,6-di-tert-butylthiophenoxy group, a 2,6-diisopropylthiophenoxy group, a 2,6 group Petition 870190112324, of 11/4/2019, p. 24/79
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dineopentylthiophenoxy, one group 2-tert-butyl-6- isopropylthiophenoxy, one group 2-tert-butyl-6- thioneopentylphenoxy, one group 2-isopropyl-6- thioneopentylphenoxy, and a group 2,4,6-triisopropylthiophenoxy,
with the 2,4,6-triisopropylthiophenoxy group being preferred.
[0056] In the general formula (III), the amide group represented by X can be any of: aliphatic amide groups, such as, dimethyl amide group, a diethyl amide group, and a diisopropyl amide group; arylamide groups, such as, a phenyl amide group, a 2,6-ditherc-butylphenyl amide group, a 2,6-diisopropylphenyl amide group, a 2,6-dineopentylphenyl amide group, a 2-tert amide group -butyl-6-isopropylphenyl, an amide group of 2-tertbutyl-6-neopentylphenyl, an amide group of 2-isopropyl-6neopentylphenyl, and an amide group of 2,4,6-tri-tertbutylphenyl; and bistrialkylsilyl amide groups, such as, a bistrimethylsilyl amide group, with bistrimethylsilyl amide group being preferred.
[0057] In the general formula (III), the silyl group represented by X can be any one of a trimethylsilyl group, a tris (trimethylsilyl) silyl group, a bis (trimethylsilyl) methylsilyl group, a trimethylsilyl (dimethyl) silyl group, and a triisopropylsilyl (bistrimethylsilyl) silyl group, with the tris (trimethylsilyl) silyl group being preferred.
[0058] In the general formula (III), the halogen atom represented by X can be any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with the chlorine atom and the iodine atom being preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include: linear or branched aliphatic hydrocarbon groups, such as, a methyl group, an ethyl group, an n-propyl group,
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21/65 an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, and an octyl group; aromatic hydrocarbon groups, such as, a phenyl group, a tolyl group, and a naphthyl group; aralkyl groups, such as a benzyl group; and hydrocarbon groups, such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group, each containing a silicon atom, with the methyl group, the ethyl group, the isobutyl group, the trimethylsilylmethyl group, and the like being preferred.
[0059] In the general formula (III), the bistrimethylsilyl amide group and the hydrocarbon group having from 1 to 20 carbon atoms are preferred as X.
[0060] In the general formula (III), the examples of the non-coordinating anion represented by [B] - include the tetravalent boron anions. Examples of a tetravalent boron anion include tetrafenyl borate, tetracis (monofluorophenyl) borate, tetracis (difluorophenyl) borate, tetracis (trifluorophenyl) borate, tetracis (tetrafluorophenyl) borate, tetracis (tenta) ) borate, tetra (xylyl) borate, (trifnill, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8dicarbaundecaborate, with tetracis (pentafluorophenyl) borate being preferred.
[0061] The metallocene complexes represented by the general formulas (I) and (II) and the semi-metallocene cation complex represented by the general formula (III) can include 0 to 3, preferably 0 or 1 Lewis bases neutrals represented by L. Examples
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22/65 of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, and neutral diolefins. When a plurality of neutral Lewis bases represented by L are incorporated, the respective L can be the same as or different from each other.
[0062] The metallocene complexes represented by the general formulas (I) to (II), and the semi-metallocene cation complex represented by the general formula (III) can each be present as a monomer or as a dimer or a multimer having more monomers.
[0063] The metallocene complex represented by the general formula (I) can be obtained by, for example, subjecting a lanthanoid trisalide, a scandium trisalide, or an yttrium trisalide to reaction in a solvent with an indenyl salt (eg for example, a potassium salt or a lithium salt) and a bis (trialkylsilyl) amide salt (for example, a potassium salt or a lithium salt). The reaction temperature only needs to be adjusted to around room temperature, and thus the complex can be manufactured under mild conditions. In addition, reaction time is arbitrary, but about several hours to several tens of hours. A reaction solvent is not particularly limited, with a solvent that dissolves a raw material and a product being preferred, and, for example, toluene can be employed. Below, an example of the reaction to obtain the complex represented by the general formula (I) is described.
Formula 5
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23/65
Cp ^R MX3 + 2Cp ^R Li + KN — Si (R ^a R ^b R ^c ) ----- m * --- L _ff
I Cd ^r s ''''
Si (R ^d R ^and R ^f ) N — Si (R ^a R ^b R ^c ) Si (R ^d R ^and R ^f ) (I) [0064] In the formula, X '' represents a halide.
[0065] The metallocene complex represented by the general formula (II) can be obtained by, for example, subjecting a lanthanoid trishalide, a scandium trishalide, or an yttrium trisalide to reaction in a solvent with an indenyl salt (eg example, a potassium salt or a lithium salt) and a silyl salt (for example, a potassium salt or a lithium salt). The reaction temperature only needs to be adjusted to around room temperature, and thus the complex can be manufactured under mild conditions. In addition, the reaction time is arbitrary, but about several hours to several tens of hours. A reaction solvent is not particularly limited, with a solvent that dissolves a raw material and a product being preferred, and, for example, toluene can be employed. Below, an example of the reaction to obtain the complex represented by the general formula (II) is described.
Formula 6
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24/65
MX ₃ + 2Cp ^R Li + KSiX ' ₃
(Π) [0066] In the formula, X ' ¹ represents a halide.
[0067] The semimetalocene cation complex represented by the general formula (III) can be obtained by, for example, the following reaction:
Formula 7
[0068] In the general formula (IV) representing a compound: M represents a lanthanoid, scandium, or itiary element; CpR 'independently represents an unsubstituted or substituted fluorenyl, indenyl, or cyclopentadienyl; X represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having from 1 to 20 carbon atoms; L represents a neutral Lewis base; and w represents an integer from 0 to 3. In addition, in the general formula [A] + [B] - representing an ionic compound, [A] + represents a cation; and [B] - represents a non-coordinating anion.
[0069] Examples of the cation represented by [A] + include a carbon cation, an oxon cation, an amine cation, a phosphonium cation, a
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25/65 cycloheptatrienyl, and a ferrocene cation containing a transition metal. Examples of the carbonic cation include the tri-substituted carbonic cations, such as triphenylcarbonium cation and a tri (substituted phenyl) carbonic cation. Specific examples of the tri (substituted phenyl) carbon dioxide include a tri (methylphenyl) carbon dioxide. Examples of the amine cation include: trialkylammonium cations, such as, a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, and a tributylammonium cation; N, N-dialkylanilinium cations, such as, an N, N-dimethylanilinium cation, an N, N-diethylanilinium cation, and an N, N-2,4,6-pentamotylanilinium cation; and dialkylammonium cations, such as a diisopropylammonium cation and a dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations, such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation. Of these cations, N, N-dialkylanilinium cations or carbonium cations are preferred, and N, Ndialkylanilinium cations are particularly preferred.
[0070] In the general formula [A] + [B] - representing the ionic compound to be used in the above reaction is a compound obtained by combining any one selected from the non-coordination anions described above and any one selected a from the cations described above. Its preferred examples include N, N-dimethylanilinium tetracis (pentafluorophenyl) borate and triphenylcarbonium tetracis (pentafluorophenyl) borate. The ionic compound represented by the general formula [A] + [B] - is added in an amount preferably from 0.1 times in mol to 10 times in mol and more preferably from about 1 time in mol, in the
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26/65 that concerns the metallocene complex. When the semi-metallocene cation complex represented by the general formula (III) is used in the polymerization reaction, the semi-metallocene cation complex represented by the general formula (III) can be supplied directly to the polymerization system, or alternatively , the compound represented by the general formula (IV) and the ionic compound represented by the general formula [A] + [B] - can be separately supplied to the polymerization system, to thereby form the complex of semimetalocene cations represented by the general formula (III) in the reaction system. In addition, the semimetalocene cation complex represented by the general formula (III) can be formed in the reaction system through the use of the metallocene complex represented by the general formula (I) or (II) and the ionic compound represented by the general formula [A] + [B] - in combination.
[0071] The structures of the metallocene complex represented by the general formula (I) or (II) and the semi-metallocene cation complex represented by the general formula (III) are preferably determined by X-ray crystallography.
[0072] The co-catalyst that may be included in the first polymerization catalyst composition can be arbitrarily selected from the components employed as the co-catalyst for the general polymerization catalyst composition containing a metallocene complex. Preferred examples of the cocatalyst include aluminoxanes, aluminum compounds
organic, and the compounds ionic above. These co- catalysts can be included alone or in combination of two or more. [0073] 0 aluminoxane is preferably one
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27/65 alkyl aluminum oxane. Examples of alkyl aluminoxane include methylaluminoxane (MAO) and modified methylaluminoxanes. In addition, preferred examples of modified methyl aluminoxane include MMA0-3A (manufactured by Tosoh Finechem Corporation). An aluminoxane content in the first polymerization catalyst composition is preferably about 10 to 1,000, more preferably about 100, in an element ratio (Al / M) of the aluminum element Al of the aluminoxane to the metal element central M in the metallocene complex.
[0074] On the other hand, a preferred example of organic aluminum compounds may include an organic aluminum compound represented by a general formula AIRR'R '' (where R and R 'each independently represents a hydrocarbon group from Cl to C10 or a hydrogen atom, and R '' is a hydrocarbon group from Cl to C10). Specific examples of the organic aluminum compound include a trialkyl aluminum, a dialkyl aluminum chloride, an alkyl aluminum dichloride, and a dialkyl aluminum hydride, with trialkyl aluminum being preferred. In addition, examples of trialkyl aluminum include triethyl aluminum and triisobutyl aluminum. A content of the organic aluminum compound in the first polymerization catalyst composition is preferably from 1 mole to 50 mole times and more preferably from about 10 mole times with respect to the metallocene complex.
[0075] In the first polymerization catalyst composition, the metallocene complex represented by the general formulas (I) and (II) and the semi-metallocene complex represented by the general formula (III) can be combined with an appropriate co-catalyst, for thereby increasing the cis-1,4 bond content and the molecular weight of
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28/65 is a copolymer to be obtained.
Second Polymerization Catalyst Composition [0076] A preferred example of the aforementioned polymerization catalyst composition may include:
a polymerization catalyst composition (hereinafter, also referred to as a second polymerization catalyst composition) containing:
component (A): a compound of the rare earth element or a reagent of a compound of the rare earth element and a Lewis base, without the bond formed between the rare earth element and carbon;
component (B): at least one selected from a group consisting of: an ionic compound (B-1) composed of a non-coordinating anion and a cation; an aluminoxane (B-2); and at least one kind of halogen compound (B-3) out of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing active halogen. In addition, if the polymerization catalyst composition contains at least one species of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition also contains:
component (C): an organic metal compound represented by the following general formula (i):
YRi _a R2 _b R3 _c ··· (i) where Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the periodic table; R ¹ and R ² are the same or different hydrocarbon groups each having from 1 to 10 carbon atoms or a hydrogen atom; and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, where R ³ can be the same as or different from R ¹ or R ² above, with 1 being ebec both
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29/65 being 0 when Y is a metal selected from Group 1 of the periodic table, a and b being 1 and c being 0 when Y is a metal selected from Group 2 and Group 12 of the periodic table, a, b, and c are all 1 when Y is a metal selected from Group 13 of the periodic table). The ionic compound (Bl) and the halogen compound (B-3) do not have carbon atoms to be fed by component (A), and therefore, component (C) becomes necessary as a power source for carbon for component (A). Here, the polymerization catalyst composition can still include component (0) even if the polymerization catalyst composition includes aluminoxane (B-2). In addition, the second polymerization catalyst composition can also include another component, such as a co-catalyst, which is included in a polymerization catalyst composition based on the compound of the general rare earth element. In the polymerization system, the concentration of component (A) contained in the second polymerization catalyst composition is preferably defined to be within a range of 0.1 mol / L to 0.0001 mol / L.
[0077] Component (A) included in the second
composition i catalyst in polymerization is a compound of element rare earthy or one reagent of compound of element rare earthy and an basis of Lewis. On here, one compound of the element earthy rare or one reagent of
compound of the rare earth element and a Lewis base does not have a direct bond formed between the rare earth element and carbon. When the compound of the rare earth element or a reagent thereof does not have a direct bond formed between a rare earth element and carbon, the resulting compound is stable and easy to handle. Here, the compound of the rare earth element refers to a compound containing
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30/65 a lanthanoid, scandium, or yttrium element. The lanthanoid elements include the elements with the atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanum, cerium, prasiodimium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. These components (A) can be included alone or in combination of two or more.
[0078] The compound of the rare earth element is preferably composed of a rare earth metal of a bivalent or trivalent salt or a complex compound, and also preferably of a compound of the rare earth element containing at least one binder selected from a residue of the organic compound, a hydrogen atom, and a halogen atom. In addition, the rare earth element compound or the rare earth element compound reagent and the Lewis base is represented by the following general formula (XI) or (XII):
M11X112-Lllw ··· (XI)
M11X113-L11W ··· (XII) where: Mil represents a lanthanoid, scandium, or yttrium element; X11 each independently represents a hydrogen atom, a halogen atom, an alkoxy group, a thiol group, an amide group, a silyl group, an aldehyde residue, a ketone residue, a carboxylic acid residue, a carboxylic acid residue ticarboxylic acid, or a phosphorous compound residue; Lll represents a Lewis base; and w represents 0 to 3).
[0079] Specific examples of a group (linker) to form a bond to the rare earth element of the compound of the rare earth element include: a hydrogen atom; aliphatic alkoxy groups, such as, a methoxy group, an ethoxy group, a propoxy group, an n group
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Butoxy, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; aromatic alkoxy groups, such as a phenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,6-diisopropylphenoxy group, a 2,6-dineopentylphenoxy group, a 2-tert-butyl-6-dineopentylphenoxy group, a 2-tert-butyl-6neopentylphenoxy group, and a 2-isopropyl-6-neopentylphenoxy group; aliphatic thiol groups, such as, thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio-n-butoxy group, a thioisobutoxy group, a thio-sec-butoxy group, and a thio-tert-butoxy group; aryl thiolate groups, such as, a thiophenoxy group, a 2,6-di-tert-butylthiophenoxy group, a 2,6-diisopropylthiophenoxy group, a 2,6-dineopentylthiophenoxy group, a 2-tert-butyl-6isopropylthiophenoxy group, a group 2-tert-butyl-6thionopentylphenoxy, a 2-isopropyl-6thioneopentylphenoxy group, and a 2,4,6-triisopropylthiophenoxy group; aliphatic amide groups, such as, a dimethyl amide group, a diethyl amide group, a diisopropyl amide group; arylamide groups such as a phenyl amide group, a 2,6-di-tert-butylphenyl amide group, a 2,6-diisopropylphenyl amide group, a 2,6-dineopentylphenyl amide group, a 2-tert amide group -butyl-6-isopropylphenyl, an amide group of 2-tert-butyl-6-neopentylphenyl, an amide group of 2-isopropyl-6-neopentylphenyl, and an amide group of 2,4,6 tert-butylphenyl; bistrialkylsilyl amide groups, such as a bistrimethylsilyl amide group; silyl groups, such as a trimethylsilyl group, a tris (trimethylsilyl) silyl group, a bis (trimethylsilyl) methylsilyl group, a trimethylsilyl (dimethyl) silyl group, and a triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms, such as, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Another examples
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32/65 may include: aldehyde residues, such as, salicylaldehyde, 2-hydroxy-1-naphthaldehyde, and 2-hydroxy-3 naphthaldehyde; hydroxyphenone residues, such as, 2'hydroxyacetophenone, 2'-hydroxybutyrophenone, and 2'hydroxypropiophenone; diketone residues, such as acetylacetone, benzoylacetone, propionylacetone, isobutyl acetone, valerylacetone, and ethylacetylacetone; residues of a carboxylic acid, such as, isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isesteric acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, a naphthenic acid, an ethylhexanoic acid, a pivalic acid, a versatile acid (trade name for a product manufactured by Shell Chemicals Japan Ltd., a synthetic acid composed of a mixture of isomers of CIO monocarboxylic acid), a phenylacetic acid , a benzoic acid, 2-naphthoate acid, a maleic acid, and a succinic acid; residues of ticarboxylic acid, such as, a hexanothioic acid, 2,2-dimethylbutanothioic acid, a decanothioic acid, and a thiobenzoic acid; phosphoric acid ester residues, such as a phosphoric acid dibutyl, a phosphoric acid dipentyl, a phosphoric acid dihexyl, a phosphoric acid dieptyl, a phosphoric acid dioctyl, bis (2-ethylhexyl) phosphoric acid, a bis (1-methylheptyl) phosphoric acid, a phosphoric acid dilauryl, a phosphoric acid dioleyl, a phosphoric acid diphenyl, a bis (p-nonylphenyl) phosphoric acid, a bis (polyethylene glycol-p) phosphoric acid -nonylphenyl), a phosphoric acid (butyl) (2-ethylhexyl), a phosphoric acid (1-methylheptyl) (2-ethylhexyl), and a phosphoric acid (2-ethylhexyl) (p-nonylphenyl); phosphonic acid ester residues, such as an acid monobutyl 2
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33/65 ethylhexyl phosphonic, a mono-2-ethylhexyl of 2ethylhexyl phosphonic acid, a mono-2-ethylhexyl of phenylphosphonic acid, a mono-p-nonylphenyl of 2-ethylhexyl phosphonic acid, a mono-2-ethylhexyl of phosphonic acid, a phosphonic acid mono-1-methylheptyl, and a phosphonic acid mono-pnonylphenyl; phosphonic acid residues, such as a dibutylphosphine acid, a bis (2-ethylhexyl) phosphinic acid, a bis (lmethylheptyl) phosphinic acid, a dilauryl phosphinic acid, a dioleyl phosphinic acid, a diphenyl phosphinic acid (p-nonylphenyl) phosphine, a butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (2-methylhexyl) (1-methylheptyl) phosphinic acid, a (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, a butyl phosphinic acid , 2-ethylhexyl phosphonic acid, a 1-methylheptyl phosphinic acid, an oleyl phosphinic acid, a lauryl phosphinic acid, a phenyl phosphinic acid, and a pnonylphenyl phosphinic acid. These binders can be used alone or in combination of two or more. Of these, amide groups, which easily form the active species through reaction with the co-catalyst, are preferred.
[0080] According to component (A) employed in the second polymerization catalyst composition, examples of the Lewis base for reacting with the rare earth element compound may include: tetrahydrofuran; diethyl ether; dimethylaniline; trimethylphosphine; lithium chloride, neutral olefins, and neutral diolefins. Here, in the case where the compound of the rare earth element reacts with a plurality of Lewis bases (in the case where w is 2 or 3 in Formulas (XI) and (XII)), and the Lewis base Lll in each Formula it can be the same or different from each other.
[0081] Component (B) included in the second
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34/65 polymerization catalyst composition is at least one compound selected from a group consisting of: an ionic compound (B-1); an aluminoxane (B-2); and a halogen compound (B-3). The total content of component (B) included in the second polymerization catalyst composition is preferably defined to be within a range of 0.1 mol to 50 mol in respect to component (A).
[0082] The ionic compound represented by (B1) is formed of non-coordinating cation and anion, and an example thereof includes: an ionic compound that reacts with the compound of the rare earth element as component (A) or with the resulting reagent of the base of Lewis and the compound of the rare earth element, in order to form a cationic transition metal compound. Here, examples of the non-coordinating anion include: tetrafenyl borate, tetrads (monofluorophenyl) borate, tetrads (difluorophenyl) borate, tetrads (trifluorophenyl) borate, tetrads (tetrafluorophenyl) borate, tetrads (pentafluorethyl, tetrafluorohydrate) tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8dicarbaundecaborate.
[0083] In the meantime, examples of the cation may include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocene cation containing a transition metal. Specific examples of the carbon dioxide include trisubstituted carbon dioxide, such as a triphenylcarbonium cation and a tri (substituted phenyl) carbon dioxide, plus the examples
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35/65 specific for the tri (substituted phenyl) carbon dioxide cation include a tri (methylphenyl) carbon dioxide cation and a tri (dimethylphenyl) carbon dioxide cation. Examples of the ammonium cation include: trialkylammonium cations, such as, a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, and a tributylammonium cation (such as, a tri (n-butyl) ammonium cation) ; N, N-dialkylanilinium cations, such as, an N, N-dimethylanilinium cation, N, N-diethylanilinium cation, and an N, N-2,4,6-pentamotylanilinium cation; and dialkylammonium cations, such as a diisopropylammonium cation and a dicyclohexylammonium cation. Specific examples of the phosphonium cation include triarylphosphonium cations, such as, a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation. For this reason, the ionic compound can preferably be a compound obtained by combining any one selected from the non-coordination anions described above and any one selected from the cations described above. Their specific examples of preference include an N, N-dimethylanilinium tetracis (pentafluorophenyl) borate and a triphenylcarbonium tetracis (pentafluorophenyl) borate. These ionic compounds can be included alone or in a combination of two or more. The content of the ionic compound in the second polymerization catalyst composition is preferably 0.1 times mol to 10 times mol, and more preferably about 1 mol time, with respect to component (A).
[0084] The aluminoxane represented by (B-2) is a compound obtained by contacting an organic aluminum compound with a condensing agent, and its examples include: a chain-type aluminoxane or a cyclic aluminoxane, both having a unit repetition
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36/65 represented by the general formula (-Al (R ') O-) (where R' is a hydrocarbon group having 1 to 10 carbon atoms and can be partially substituted by halogen atom and / or alkoxy group, and the degree of polymerization of the repeating unit is preferably at least 5, more preferably at least 10). Here, specific examples of R 'include a methyl group, an ethyl group, a propyl group, and an isobutyl group, with the methyl group being preferred. In addition, examples of the organic aluminum compound used as a raw material for aluminoxane may include: trialkylaluminiums, such as, trimethylaluminum, triethylalumin, triisobutylalumin and so on; and mixtures thereof, with trimethylalumin being particularly preferred. For example, an aluminoxane obtained using, as a raw material, a mixture of trimethylaluminum and tributylalumin can be suitably employed. The aluminoxane content in the second polymerization catalyst composition is preferably about 10 to 1,000 in an element ratio (Al / M) of the aluminum element Al of the aluminoxane with the rare earth element M forming the component (A).
[0085] The halogen compound represented by (B-3) includes at least one of: a Lewis acid; a complex compound of a metal halide and a Lewis base; and an organic compound containing active halogen, and is capable of reacting with, for example, the compound of the rare earth element as component (A) or with the resulting reagent from the Lewis base and the compound of the rare earth element in order to form a cationic transition metal compound. The content of the halogen compound in the second polymerization catalyst composition is preferably 1 mol to 5 mol, with respect to component (A).
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37/65 [0086]
Examples of Lewis acid may include: a boron-containing halogen compound such as B (C6F5) 3 and an aluminum-containing halogen compound such as A1 (C6F5) 3, and may also include a halogen compound containing an element of the Group III, Group IV, Group V, Group VI, and Group VIII of the periodic table. Its preferred examples include an aluminum halide or an organometallic halide. Preferred examples of the halogen element include chlorine and bromine. Specific examples of Lewis acid include: a methyl aluminum dibromide; a methyl aluminum dichloride; an ethyl aluminum dibromide; an ethyl aluminum dichloride; a butylaluminum dibromide; a butylaluminum dichloride; a dimethyl aluminum bromide; a dimethyl aluminum chloride; a diethyl aluminum bromide; a diethyl aluminum chloride; a dibutyl aluminum bromide; a dibutyl aluminum chloride; a methyl aluminum sesquibromide; a methyl aluminum sesquichloride; an ethyl aluminum sesquibromide; an ethyl aluminum sesquichloride; a dibutyltin dichloride; an aluminum tribromide; an antimony trichloride; an antimony pentachloride; a phosphorus trichloride; a phosphorus pentachloride; a tin tetrachloride; a titanium tetrachloride; and tungsten hexachloride, such as diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide, and ethyl aluminum dibromide being particularly preferred.
[0087]
Preferred examples of the metal halide forming a complex metal halide compound and a Lewis base include: a beryllium chloride, a beryllium bromide; a beryllium iodide; a magnesium chloride; a magnesium bromide; a magnesium iodide; one
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38/65 calcium chloride; a calcium bromide; a calcium iodide; a barium chloride; a barium bromide; a barium iodide; a zinc chloride; a zinc bromide; a zinc iodide; a cadmium chloride; a cadmium chloride; a cadmium bromide; a cadmium iodide; a mercury chloride; a mercury bromide; a mercury iodide; a manganese chloride; a manganese bromide; a manganese iodide; a rhenium chloride; a rhenium bromide; a rhenium iodide; a copper chloride; a copper bromide; a copper iodide; a silver chloride; a silver bromide; a silver iodide; a gold chloride; an iodide of
gold; it is a bromide in gold, with The chloride in magnesium, the chloride calcium, The chloride in barium, The chloride manganese, the chloride in zinc and The chloride in copper being
It is preferred, and magnesium chloride, manganese chloride, zinc chloride, and copper chloride being particularly preferred.
[0088] Preferred examples of the Lewis base forming a complex metal halide compound and the Lewis base include: a phosphorus compound; a carbonyl compound; a nitrogen compound; an ether compound; and an alcohol. Its specific examples include: a tributyl phosphate; a tri-2-ethylhexyl phosphate; a triphenyl phosphate; a tricresyl phosphate; a triethylphosphine; a tributylphosphine; a triphenylphosphine; a diethylphosphinoethane; an acetylacetone; a benzoylacetone; a propionitrileacetone; a valerylacetone; an ethylacetylacetone; a methyl acetoacetate; an ethyl acetoacetate; a phenyl acetoacetate; a dimethyl malonate; a diphenyl malonate; an acetic acid; an octanoic acid; a 2-ethylhexanoic acid; an oleic acid; a stearic acid; a benzoic acid; a naphthenic acid; a versatile acid; an
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39/65 triethylamine; an N, N-dimethylacetamide; a tetrahydrofuran; a diphenyl ether; a 2-ethylhexyl alcohol; an oleyl alcohol; stearyl alcohol; a phenol; a benzyl alcohol; a 1-decanol; and a lauryl alcohol, with tri-2-ethylhexyl phosphate, tricresyl phosphate; acetylacetone, 2-ethylhexylic acid, versatic acid, 2-ethylhexylic alcohol; 1-decanol; and lauryl alcohol being preferred.
[0089] The Lewis base is subjected to reaction with the metal halide in the proportion of 0.01 mol to 30 mol, preferably from 0.5 mol to 10 mol, per 1 mol of the metal halide. The use of the reagent obtained from the Lewis base reaction can reduce the residual metal in the polymer.
[0090] An example of the organic compound containing active halogen includes benzyl chloride.
[0091] The component (C) included in the second polymerization catalyst composition is an organic compound represented by the general formula (i):
YRlaR2bR3c ··· (i) where Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the periodic table; RI and R2 are the same or different hydrocarbon groups each having from 1 to 10 carbon atoms or a hydrogen atom; and R3 is a hydrocarbon group having from 1 to 10 carbon atoms, where R3 can be the same as or different from RI or R2 above, being 1 ebec both being 0 when Y is a metal selected from Group 1 of periodic table, a and b being 1 and c being 0 when Y is a metal selected from Group 2 and Group 12 of the periodic table, a, b, and c are all 1 when Y is a metal selected from Group 13 of the periodic table ), and is preferably an organic aluminum compound represented by the general formula (X):
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A1R11R12R13 ··· (X) where R11 and R12 are the same or different hydrocarbon groups each having from 1 to 10 carbon atoms or a hydrogen atom; and R13 is a hydrocarbon group having 1 to 10 carbon atoms, where R13 can be the same as or different from R11 or R12 above). Examples of the organic aluminum compound in formula (X) include: a trimethyl aluminum, a triethyl aluminum, a tri-npropyl aluminum, a tri-npropyl aluminum, a tri-n-butyl aluminum, a tri-butyl aluminum, a tri-t-butyl aluminum, a tripentyl aluminum, a tri-aluminum aluminum, a tri-aluminum aluminum, a trioctyl aluminum; a diethyl aluminum hydride, a di-n-propyl aluminum hydride, a di-n-butyl aluminum hydride, a diisobutyl aluminum hydride, a dihexyl aluminum hydride; a diisohexylaluminum hydride, a dioctyl aluminum hydride, a diisooctylaluminum hydride; an ethyl aluminum dihydride, an n-propyl aluminum dihydride, and an isobutyl aluminum dihydride, with triethyl aluminum, triisobutyl aluminum, diethyl aluminum hydride, and diisobutyl aluminum hydride being preferred. Organic metal compounds like component (C) can be included alone or in a combination of two or more. The content of the organic aluminum compound in the second polymerization catalyst composition is preferably 1 mol to 50 mol, and most preferably about 10 mol, with respect to component (A).
[0092] In the first method of producing the copolymer according to the present invention, polymerization can be carried out similarly to a conventional method of producing a copolymer through the polymerization reaction employing the coordination of the ion polymerization catalyst, unless by the fact that
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41/65 above mentioned polymerization catalyst composition is employed as described above. Here, in the case of carrying out the production method of the copolymer of the present invention using the polymerization catalyst composition, the method can be performed in any of the following ways. That is, for example, (1) the components forming the polymerization catalyst composition can be separately supplied in the polymerization reaction system including, as monomers, a conjugated diene compound and a conjugated olefin different from the conjugated diene compound, for, thus, preparing the polymerization catalyst composition in the reaction system, or (2) the polymerization catalyst composition prepared in advance can be provided in the polymerization reaction system. In addition, the method of (2) also includes the supply of the metallocene complex (active species) activated by the co-catalyst. The amount of the metallocene complex to be contained in the polymerization catalyst composition is preferably adjusted to be within a range of 0.0001 mol in 0.01 mol in respect to the total amount of the conjugated diene compound and unconjugated olefin other than the conjugated diene compound.
[0093] In addition, in the first method of producing the copolymer according to the present invention, a terminator, such as ethanol and isopropanol, can be employed to interrupt the polymerization.
[0094] Furthermore, in the first production method of the copolymer according to the present invention, the polymerization reaction of the conjugated diene compound and the unconjugated olefin can preferably be performed in an atmosphere of inert gas, and of preferably in an atmosphere of nitrogen or argon. THE
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The polymerization temperature of the polymerization reaction is not particularly limited, and preferably in a range of, for example, -100 ° C to 200 ° C, and can also be adjusted to temperatures around room temperature. An increase in the polymerization temperature can reduce the selectivity of cis-1,4- in the polymerization reaction. The polymerization reaction is preferably carried out under pressure in a range of 0.1 MPa to 10 MPa in order to allow a conjugated diene compound and an unconjugated olefin to be sufficiently introduced into the polymerization system. In addition, the reaction time of the polymerization reaction is not particularly limited, and can preferably be in a range of, for example, 1 second to 10 days, which can be selected when appropriate depending on conditions, such as the type of the monomers to be polymerized, of the catalyst type, and of the polymerization temperature.
[0095] In addition, according to the first production method of the copolymer of the present invention, in the polymerization of a conjugated diene compound and an unconjugated olefin, the concentration of the conjugated diene compound (mol / L) and the concentration of unconjugated olefin
(mol / L) at the beginning of copolymerization in preference satisfies the following list: olefin concentration no conjugated concentration of the conjugated diene compound h 1.0; also preferably satisfies the relationship that Follow: olefin concentration no conjugated concentration of the conjugated diene compound h 1.3; and
however still preferably it satisfies the following relation:
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43/65 the concentration of the unconjugated olefin / the concentration of the conjugated diene compound Y 1.7.
The ratio of the concentration of the unconjugated olefin to the concentration of the conjugated diene compound is defined to be at least 1, to thereby efficiently introduce the unconjugated olefin into the reaction mixture.
[0097] In addition, the copolymer of the present invention can be manufactured by controlling the introduction of monomers into a polymerization system, even without the use of the first polymerization catalyst composition or the second polymerization catalyst composition, that is, even in a use case of a coordination of the general ion polymerization catalyst. Specifically, a second copolymer production method according to the present invention has an aspect in which the introduction of a conjugated diene compound is controlled in the presence of an unconjugated olefin in order to control the structure of the copolymer chain, thereby how to control the arrangement of the monomer units in the copolymer. In accordance with the present invention, the term polymerization system here refers to a location where a conjugated diene compound and an unconjugated olefin are copolymerized, and a specific example thereof includes a reaction vessel or others.
[0098] Here, the introduction of a conjugated diene compound can either be continuous introduction or divisional introduction. In addition, continuous introduction and divisional introduction can be used in combination. The continuous introduction here refers, for example, to adding a conjugated diene compound at a certain rate of addition over a certain period.
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44/65 [0099] Specifically, the introduction of a conjugated diene compound in a polymerization system for the copolymerization of the conjugated diene compound and an unconjugated olefin allows the control of the relationship of the concentration of monomers in the polymerization system, with the The result is that the structure of the chain (that is, the arrangement of the monomer units) in the copolymer to be obtained can be defined. In addition, a conjugated diene compound is introduced in the presence of an unconjugated olefin in the polymerization system, to thereby suppress the homopolymer generation of a conjugated diene compound. The polymerization of an unconjugated olefin can be initiated prior to the introduction of a conjugated diene compound.
[00100] For example, in the case of the production of a block copolymer by the second method mentioned above, it is effective to introduce, in the presence of an unconjugated olefin, a conjugated diene compound to a polymerization system in which the polymerization of an olefin unconjugated is started in advance. In particular, in the case of producing a multi-block copolymer by the second method mentioned above, it is effective to repeat the operation of subjecting an unconjugated olefin to a polymerization system at least twice, and then continuously introducing a diene compound. conjugated in the polymerization system in the presence of an unconjugated olefin.
[00101] The second production method mentioned above is not specifically limited since the introduction of monomers into a polymerization system is specified as described above, and can employ any method of polymerization including, for example, solution polymerization, polymerization of the suspension,
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45/65 bulk polymerization in liquid phase, emulsion polymerization, vapor phase polymerization, and solid state polymerization. In addition, the aforementioned second production method is capable of polymerizing the monomers, in other words, a conjugated diene compound and an unconjugated olefin, similarly to the first production method mentioned above, except for the fact that the of introduction of the monomers into the polymerization system is specified as described above.
[00102] In the second production method mentioned above, the introduction of a conjugated diene compound needs to be controlled. Specifically, it is preferred to control the amount of a conjugated diene compound to be introduced and the number of times to introduce the conjugated diene compound. Examples of a method of controlling the introduction of a conjugated diene compound can include, but is not limited to: a method of control based on a computer program or more; and a similar control method using a stopwatch or more. In addition, as described above, the method of introducing a conjugated diene compound is not specifically limited, and can be exemplified by continuous introduction or divisional introduction. Here, in divisionally introducing a conjugated diene compound, the number of times to introduce the conjugated diene can preferably be defined to be within a range of once to five times, although not specifically limited. Also often introducing the conjugated diene can make it difficult to differentiate the resulting copolymer from a random copolymer.
[00103] Furthermore, the second production method mentioned above requires the presence of an unconjugated olefin in the introduction of a diene compound
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46/65 conjugate, and thus it is preferred to continuously feed an olefin unconjugated to the polymerization system. Here, how to feed the unconjugated olefin is not specifically limited.
Rubber Composition [00104] The rubber composition of the present invention is not particularly limited, since the block copolymer of the present invention is included, and can be selected when appropriate depending on its application. The rubber composition preferably contains rubber components other than the block copolymer of the present invention, such as an inorganic filler, carbon black, and a crosslinking agent.
Copolymer [00105] The content of the copolymer of the present invention in the rubber components is not particularly limited, and can be selected when appropriate depending on your application. The preferred content of the copolymer is at least 3% by weight.
[00106] The content of the copolymer in the rubber components below 3% by mass, can diminish the effect of the present invention or develop any effect.
Rubber Components [00107] Rubber components are not particularly limited and can be selected when appropriate depending on your application. Examples include: the block copolymer of the present invention, natural rubber, various types of butadiene rubber, various types of styrene butadiene copolymer rubber, isoprene rubber, butyl rubber, an isobutylene copolymer bromide and p- methylstyrene, halogenated butyl rubber, acrylonitrile-butadiene rubber, chloroprene rubber, copolymer rubber
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47/65 ethylene-propylene, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene rubber, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluoroborch, and urethane rubber. These rubber components can be used alone or in combination with two or more.
[00108] The rubber composition can be mixed with a reinforcement charge when necessary. Examples of the reinforcement filler include a carbon black and an inorganic filler, and preferably at least one selected from carbon black and the inorganic filler.
Inorganic Load [00109] Inorganic load is not particularly limited and can be selected when appropriate depending on your application. Examples include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass flask, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, titanate potassium, and barium sulfate. These rubber components can be used alone or in combination of two or more. When using an inorganic filler, a silane coupling agent can also be used when appropriate.
[00110] The reinforcement load content is not particularly limited and any one can be selected as appropriate depending on its application. Its preferred content is 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the
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[00111] The reinforcement filler added in less than 5 parts by weight of content, may show little effect of its addition, while the content exceeding 200 parts by mass tends to prevent the reinforcement filler from being mixed in the component of the rubber, which can impair the performance of the rubber composition.
Crosslinking Agent [00112] The crosslinking agent is not particularly limited and can be selected when appropriate depending on your application. Examples include a sulfur-containing cross-linking agent, an organic peroxide-containing cross-linking agent, an inorganic cross-linking agent, a polyamine cross-linking agent, a resin cross-linking agent, a cross-linking agent based on the sulfur compound, a cross-linking agent based on oxime-nitrosamine, and sulfur, with the cross-linking agent containing sulfur being more preferred as the rubber composition for a tire.
[00113] The content of the crosslinking agent is not particularly limited and can be selected when appropriate depending on its application. Its preferred content is 0.1 parts by weight to 20 parts by weight with respect to 100 parts by weight of the rubber component.
[00114] The crosslinking agent added in less than 0.1 part by weight in the content can hardly develop the crosslinking, while the content exceeding 20 parts by weight tends to develop the crosslinking in part of the crosslinking agent during mixing , or impair the physical property of the vulcanized.
Other Components [00115] Unlike the above, an accelerator of
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49/65 vulcanization may also be included. Examples of compounds that can be used as the vulcanization accelerator include: guanidine-based compounds, aldehyde-amine-based compounds, aldehyde-ammonium-based compounds, thiazole-based compounds, sulfenamide-based compounds, compounds based on thiourea, compounds based on thiuram, compounds based on detiocarbamate, and compounds based on xanthate.
[00116] Furthermore, if necessary, any known agent, such as a reinforcing agent, a softening agent, a co-agent, a dye, a flame retardant, a lubricant, a defoaming agent, a plasticizer, a processing aid, an antioxidant, an age resistor, a surface anti-scald agent, an ultraviolet protection agent, an antistatic agent, a color protection agent, and another composition agent can be employed according to the purpose of its use.
Crosslinked Rubber Composition [00117] The crosslinked rubber composition according to the present invention is not particularly limited since it is obtained by crosslinking the rubber composition of the present invention, and can be selected when appropriate depending on its application.
[00118] The crosslinking conditions are not particularly limited and can be selected when appropriate depending on your application. Preferred temperature conditions and heating time for crosslinking can preferably be in the range of 120 ° C to 200 ° C for 1 minute to 900 minutes.
Tire [00119] A tire of the present invention is not particularly limited since it is manufactured using
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50/65 of the use of the rubber composition of the present invention or the crosslinked rubber composition of the present invention, and can be selected when appropriate depending on its application.
[00120] The rubber composition of the present invention or the crosslinked rubber composition of the present invention can be applied, for example, to a tread, a base tread, a side wall, a side reinforcement rubber, and a tire bead filling, without being limited to this.
[00121] The tire can be manufactured using a conventional method. For example, a carcass layer, a belt layer, a tread layer, which are composed of non-vulcanized rubber, and other members used to produce the usual tires are successively laminated in a tire molding drum, and then the drum is removed to obtain a raw tire. After that, the raw tire is heated and vulcanized according to an ordinary method, to thereby obtain a desired tire.
Applications other than Tires [00122] The rubber composition of the present invention or the crosslinked rubber composition of the present invention can be used for applications other than tires, such as anti-vibration rubber, seismic isolation rubber, a mat carrier), a rubber tracker, various types of hoses, and moran.
Examples [00123] In the following, the invention of the present invention is described with reference to the Examples. In any event, the present invention is in no way limited to the Examples which follow.
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Example 1 [00124] A 160 ml toluene solution was added to a 400 ml pressure resistant glass reactor that was sufficiently dry, and then ethylene was introduced in 0.8 MPa. In the meantime, in a glove box under a nitrogen atmosphere, 28.5 μιηοΐ of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2PhC9H6) 2GdN (SiHMe2) 2], 34.2 pmol of dimethylanilinium tetracis ( pentafluorophenyl) borate [Me2NHPhB (C6F5) 4], and 1.43 mmol of diisobutyl aluminum hydride were supplied in a glass container, which was dissolved in 8 ml of toluene, to thereby obtain a catalyst solution. After that, the catalyst solution was removed from the glove box and added 28.2 pmol of gadolinium equivalent to the monomer solution, which was then subjected to polymerization at room temperature for 5 minutes. Thereafter, 100 mL of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added at the same time that the pressure of introducing ethylene was reduced at a rate of 2 MPa / min , and then the polymerization was carried out for another 90 minutes. After polymerization, 1 ml of an isopropanol solution containing 5% by mass, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS5), was added to stop the reaction. Then, a large amount of methanol was added to isolate the copolymer, and the copolymer was vacuum dried at 70 ° C to obtain copolymer A (block copolymer). The yield of copolymer A thus obtained was 12.50 g.
Example 2 [00125] A 100 ml toluene solution was added to a 400 ml pressure resistant glass reactor that was sufficiently dry, and then ethylene
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52/65 was introduced to this at 0.8 MPa. In the meantime, in a glove box under a nitrogen atmosphere, 28.5 μτηοΐ of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2— PhC9H6) 2GdN (SiHMe2) 2], 34.2 pmol of dimethylaniline tetracis (pentafluorophenyl) borate [Me2NHPhB (C6F5) 4], and 1.43 mmol of diisobutylaluminum hydride were supplied in a glass container, and dissolved in 8 mL of toluene, to thereby obtain a catalyst solution. After that, the catalyst solution was removed from the glove box, and added to 28.2 pmol of gadolinium equivalent to the monomer solution, which was then subjected to polymerization at room temperature for 5 minutes. Thereafter, 30 mL of a toluene solution containing 4.57 g (0.085 mol) of 1,3-butadiene was added at the same time as reducing the pressure of ethylene introduction at a rate of 0.2 MPa / min, and then the polymerization was carried out for another 60 minutes. Then, the operation of restoring the pressure of introduction of ethylene to 0.8 MPa and carrying out the polymerization for 5 minutes, and then adding 30 mL of a solution of toluene containing 4.57 g (0.085 mol) of 1.3 -butadiene while reducing the pressure of introducing ethylene at a rate of 0.2 MPa / min, and carrying out the polymerization for another 60 minutes was repeated three times. After polymerization, 1 ml of an isopropanol solution containing 5% by mass 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS5) was added to stop the reaction. Then, a large amount of methanol was added to isolate the copolymer, and the copolymer was vacuum dried at 70 ° C to obtain copolymer B (multiple block copolymer). The yield of copolymer B thus obtained was 14.00 g.
Example 3
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Multiple Block Copolymer [00126] A 150 mL toluene solution was added to a 2L stainless reactor that was sufficiently dry, and then ethylene was introduced at 0.8 MPa. In the meantime, in a glove box under a nitrogen atmosphere, 14.5 pmol of bis (2phenylindenyl) gadolinium bis (dimethylsilylamide) [(2PhC9H6) 2GdN (SiHMe2) 2], 14,1 pmol of triphenylcarbonium tetracis (pentafluorophenyl) borate [Ph3CB (C6F5) 4], and 0.87 mmol of diisobutylaluminum hydride were supplied in a glass container, which was dissolved in 5 ml of toluene, to thereby obtain a catalyst solution. After that, the catalyst solution was removed from the glove box and added 14.1 μιηοΐ of gadolinium equivalent to the monomer solution, which was then subjected to polymerization at 50 ° C for 5 minutes. Thereafter, 20 ml of a toluene solution containing 3.05 g (0.056 mol) of 1,3-butadiene was added at the same time as reducing the pressure of ethylene introduction at a rate of 0.2 MPa / min, and then the polymerization was carried out for another 15 minutes. Then, the operation of restoring the introduction pressure of ethylene to 0.8 MPa and carrying out the polymerization for 5 minutes, and then adding 40 mL of a solution of toluene containing 6.09 g (0.113 mol) of 1.3 -butadiene while reducing the pressure of introducing ethylene at a rate of 0.2 MPa / min, and carrying out the polymerization for another 30 minutes was repeated three times. After polymerization, 1 ml of an isopropanol solution containing 5% by mass, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS5), was added to stop the reaction. Then, a large amount of methanol was added to isolate the copolymer, and the copolymer was vacuum dried at 70 ° C
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54/65 to obtain a copolymer C (multiple block copolymer). The yield of copolymer C thus obtained was 24.50 g.
Example 4 [00127] An experiment was carried out similarly to Example 3 except that bis (2-phenyl-1-methylindenyl) gadolinium bis (dimethylsilylamide) [(2Ph-1-MeC9H5) 2GdN (SiHMe2) 2] was added in place of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2PhC9H6) 2GdN (SiHMe2) 2], in order to obtain a copolymer D (multiple block copolymer). The yield of copolymer D was 28.55g.
Comparative Example 1 [00128] Butadiene rubber (BR01, manufactured by JSR) was prepared as a sample of the Comparative Example.
Comparative Example 2 [00129] A mixture of butadiene rubber (BR01, manufactured by JSR) and polyethylene (trade name: Polyethylene, manufactured by Aldrich) (in a mass ratio of 85:15) was prepared as a sample of the Comparative Example .
Comparative Example 3 [00130] A 300 ml toluene solution containing 19.2 g (0.36 mol) of 1,3-butadiene was added to a 400 ml pressure resistant glass reactor that was sufficiently dry, and in then ethylene was introduced at 0.8 MPa. In the meantime, in a glove box under a nitrogen atmosphere, 50.0 pmol of bis (2phenylindenyl) neodymium bis (dimethylsilylamide) [(2PhC9H6) 2NdN (SiHMe2) 2], 14.0 pmol of triphenylcarbonium tetracis (pentafluorophenyl) borate [Ph3CB (C6F5) 4], and 0.20 mmol of triethyl aluminum were supplied in a container
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55/65 glass, and dissolved in 8 mL of toluene, to thereby obtain a catalyst solution. After that, the catalyst solution was removed from the glove box, and the catalyst solution was added with 49.0 pmol of gadolinium equivalent to the monomer solution, which was then subjected to polymerization at 80 ° C for 300 minutes. After polymerization, 1 ml of an isopropanol solution containing 5% by mass 2,2'-methylene-bis (4-ethyl-6-tbutylphenol) (NS-5) was added to stop the reaction. Then, a large amount of methanol was added to isolate the copolymer, and the copolymer was vacuum dried at 70 ° C to obtain a copolymer E (random copolymer). The yield of copolymer D thus obtained was 19.00 g.
Comparative Example 4 [00131] As illustrated in Preparation 2 of JP 2000-86857 A (PTL 5), a toluene solution (manufactured by Tosoh Akzo Corporation) containing 26.0 g of toluene and 6.7 mmol of methylaluminoxane were supplied in a tight, pressure-sealed glass ampoule having an internal capacity of 150 mL in a nitrogen atmosphere. A toluene solution containing 0.0067 mmol of 2-methoxycarbonyl methylcyclopentadienyl trichlorotitanium (MeO (CO) CH2CpTiC13) (TiES) was released in drops in the ampoule which was maintained at an aging temperature (25 ° C) for an aging time of 5 minutes. After that, the temperature was reduced to -25 ° C, and a solution containing 2.0 g of butadiene and 6.0 g of toluene was added, to which it was subjected to polymerization at this temperature for 0.05 hours (3 minutes) (in the proportion of 500 g of butadiene to 1 mole of titanium). Subsequently, the ethylene was filled into the vessel to obtain a pressure of 5 kgf / cm2, and the reaction was carried out for about 1 hour.
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After polymerization, the container was immediately filled with ethylene at a pressure of 3 kgf / cm2, and 30 minutes later, the polymerization was stopped by the addition of methanol containing hydrochloric acid. Then, the polymerization solution was poured into a large amount of acidic methanol, so that a precipitated white solid was collected by filtration and dried to obtain an ethylene-butadiene copolymer F. The yield was 37% and the polymerization activity was 3,500.
[00132] Copolymers A to D of Examples 1 to 4, the butadiene rubber of Comparative Example 1, the mixture of butadiene rubber and metallocene polyethylene of Comparative Example 2, and copolymers E and F of Comparative Examples 3 and 4 were each subjected to measurement and evaluation by the method that follows in order to investigate the microstructure, the ethylene content, the average weight molecular weight (Mw), the molecular weight distribution (Mw / Mn), and the curve of DSC. Figure 1 is a graph of the 13C NMR spectrum of copolymer A; Figure 2 shows a DSC curve of copolymer A; Figure 3 shows a DSC curve of copolymer C; and Figure 4 shows a DSC curve of copolymer E.
[00133] Here, the ordinate of the DSC curve is the thermal flow.
(1) Microstructure (vinyl bond content 1,2 (Vi (%)), cis-1,4 bond content) [00134] The microstructure (vinyl bond content 1,2) of the butadiene unit in copolymer is determined from an integral ratio of 1,2-vinyl binding component (5.0 ppm to 5.1 ppm) to a butadiene binding component (5 ppm to 5.6 ppm) of the general, with based on the 1H NMR spectrum (100 ° C, d
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57/65 standard tetrachloroethane: 6 ppm), and the microstructure (cis-1,4 bond content) of the butadiene unit in the copolymer is determined from an integral ratio of cis-1,4 bond bond component ( 26.5 ppm at 27.5 ppm) for a butadiene binding component (26.5 ppm at 27.5 ppm + 31.5 ppm at 32.5 ppm) of the general, based on the 13C NMR spectrum (100 ° C, standard d-tetrachloroethane: 73.8 ppm). The calculated values of the vinyl binding content 1,2 (Vi (%)) and the cis-1,4 binding content (%) are shown in Table 1A and Table 1B.
(2) Ethylene content [00135] The content (mol%) of the ethylene unit in the copolymer is determined from an integral ratio of an ethylene-binding component (28.5 ppm to 30.0 ppm) of the general for a butadiene binding component (26.5 ppm to 27.5 ppm + 31.5 ppm to 32.5 ppm) of the general, based on 13C NMR spectrum (100 ° C, standard dtetrachloroethane: 7.38 ppm ). The content (mol%) of the ethylene unit is shown in Table 1.
(3) Average Weight Molecular Weight (Mw) and Molecular Weight Distribution (Mw / Mn) [00136] An equivalent average weight molecular weight (MW) polystyrene and a molecular weight distribution (Mw / Mn) of each copolymer were obtained through gel permeation chromatography [GPC: HLC-8121GPC / HT (manufactured by Tosoh Corporation), column: two from GMHHRH (S) HT (manufactured by Tosoh Corporation), detector: a differential refractometer (IR)], using polystyrene monodispersed as a reference. The measurement temperature was 140 ° C.
(4) DSC curve [00137] A DSC curve was obtained by means of differential scanning calorimetry (DSC) according to
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JIS K7121-1987, and a block polyethylene melting point (DSC peak temperature) was measured. In the measurement, using as measurement samples were the rubber components obtained by immersing each copolymer in a large amount of tetrahydrofuran for 48 hours in order to remove all components dissolved in the tetrahydrofuran and then by drying the copolymer, in order to circumvent the effect to be produced by impurities, such as, unique polymers and catalyst residues.
Table IA
Example 1 Example 2 Example 3 Example 4 Copolymer THE B Ç D Mw (x 10 ³ ) 350 283 205 221 Mw / Mn 2.20 2.80 9.15 3.13 Cis-1,4 binding content (%) 98 97 97 97 Ethylene Content(mol%) 7 13 34 45 Block polyethylene melting point(peak temperature ofDSC) 121 121 121 122
Table 1B
ExampleComparative1 ExampleComparative2 ExampleComparative3 ExampleComparativo 4 Copolyme ro rubberbutadiene butadiene rubber + AND F
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polyethylene Mw (x 10 ³ ) 454 - 219 450 Mw / Mn 3.45 - 1.68 1, 32 Saw (%) 1.8 - 2.6 6, 0 Cis bond content1.4 (%) 97 - 50 92 EthyleneContent (%in mol) 0 13 10 6 Melting point of polyethyl ene block (DSC peak temperature) - 121 none 127
[00138] The 13C NMR spectrum graph of copolymer A of Figure 1 shows the peaks derived from the ethylene block sequence at 29.4 ppm. The DSC curves of copolymers A, C of Figures 2, 3 each show a crystallization temperature derived from a block sequence including cis 1,3-butadiene monomer units in the vicinity of -10 ° C and a crystallization temperature derived from a block sequence including units of ethylene monomers in the vicinity of 120 ° C, crystallization temperatures being observed through DSC.
[00139] The measurement results above
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60/65 mentioned revealed that copolymers A and C each were the high cis-1,3-butadiene and ethylene block copolymers.
[00140] In addition, the sequence distribution of copolymer A was analyzed using ozonolysis-GPC measurements disclosed in a document (Polymer Preprints, Japan, Vol. 42, No. 4, pp. 1347). An equivalent weight average molecular weight (MW) polystyrene and molecular weight distribution (Mw / Mn) of each copolymer was obtained by gel permeation chromatography [GPC: HLC-8121GPC / HT (manufactured by Tosoh Corporation), column: two from GPC HT-803 (manufactured by Showa Denko KK), detector: differential refractometer (RI)], using monodisperse polystyrene as a reference, at a measurement temperature of 140 ° C]. The result showed that the total ethylene component included at least 80% by mass of a block ethylene component, that is, a polyethylene component having an average numerical molecular weight (Mn) of 1,000 or more, and thus it was confirmed that copolymer A was a block copolymer.
[00141] In addition, copolymer A can also be identified as a block copolymer when a peak area of 80 ° C or more, indicating a quantity of polyethylene block components is responsible for at least 80% of a total area of endothermic peaks in a temperature range of 40 ° C to 140 ° C. A copolymer that is randomly elevated to failure to obtain excellent performance of the present invention.
[00142] Copolymers B, C, D, and F were similarly confirmed to be block copolymers of 1,3-butadiene and ethylene by 13C NMR, DSC, and ozonolysis oz-GPC measurements. According to copolymer E, DSC
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61/65 could not identify the light peak derived from an ethylene block sequence as shown in Figure 4, and HT-GPC ozonolysis measurements could hardly find any polyethylene content having an average numerical molecular weight (Mn) of 1,000 or more, and thus it was confirmed that copolymer E was a random copolymer.
[00143] Like Examples 1 to 4 and Comparative Examples 1 to 4, rubber compositions formulated as shown in Table 2 were prepared, which were vulcanized at 160 ° C for 20 minutes. The vulcanized rubber compositions thus obtained were subjected to measurements of elastic modulus, low heat generation property, resistance to cracking (constant tension), and ozone resistance, according to the method that follows.
Table 2
bulk parts copolymer 100 stearic acid 2 carbon black (gradeFEF) 50 old resistor * 1 1 zinc oxide 3 CZ-G * 2 co-agent 0.4 DM-P * 3 co-agent 0.2 sulfur 1.4
* 1: N- (1,3-dimethylbutyl) -N'-p-phenylenediamine (NOCRAC 6C), manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.
* 2: N-cyclohexyl-2-benzothiazolsulfenamide (NOCCELER CZ-G), manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.
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62/65 * 3: dibenzothiazil disulfide (NOCCELER DM-P), manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.
Elastic Module, Low Heat Generation Property (index) [00144] The Dynamic Spectrometer (manufactured by Rheometrics Inc. in US) was used to measure the storage module (G *) during a frequency of 15 Hz and a tensile voltage dynamic of 10% at a temperature of 50 ° C, and a loss tangent (3% tan δ) at a dynamic tensile stress of 3%. The results are shown in Table 3A and Table 3B. The values under Elastic Module G 'in Tables 3A and 3B are indexed with a score of 100 representing Comparative Example 1, and a lower index value shows more excellent storage module. In the meantime, the values under Property
low heat generation i (index) of Tables 3A and 3B are each represented c orno Low Heat Generation (index) = Tangent of loss / (Tangent in loss of Example Comparative 1) χ 100. 0 highest value of the index showed excellent property in generation in low heat (low loss of property).Resistance to increase in cracks (index) (Constant tension)[00145] One fissure 0.5 mm was produced in test piece center JIS No. 3, < s the piece of test
was repeatedly subjected to fatigue under a constant stress of Md 100% (measured value obtained in a stress test according to JIS K6251) at room temperature, in order to count the number of times the sample was subjected to fatigue until fracture . The results are shown in Table 3A and Table 3B. The highest index value showed the most excellent resistance to crack growth. In Tables,> 200 means that the sample that did not suffer
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63/65 fracture despite repetitive fatigue applied twice as many as those applied to Comparative Example 1.
[00146] Ozone Resistance Property (dynamic)
[00147] THE resistance ozone was measure of according to JIS K 6259 . One piece test on an form of strip was exposed ozone in a concentration in 50 pphm a 40 ° C to same time that being submitted The distension
dynamic of 30%. The condition (according to whether or not a crack occurred) of the sample after a 24-hour lapse was visually identified. The results are shown in Table 3A and Table 3B.
Table 3A
Example1 Example 2 Example 3 Example4 Copolymer THE B Ç D Mw (x 10 ³ ) 350 283 205 221 Mw / Mn 2.20 2.80 9.15 3.13 Saw (%) 1,, 2 1.2 1.4 1.8 Cis-1,4 binding content (%) 98 97 97 97 Ethylene Content (% by mol) 7 13 34 45 Block polyethylene melting point(DSC peak temperature) 121 121 121 122 Elastic ModuleG ' 120 158 185 275 Property oflow generation 105 121 108 146
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heat (index) Resistance to cracking (index) Constant Stress > 200 > 200 > 200 162 Resistance toOzone(dynamics) no crack no crack no crack no crack
Table 3B
ExampleComparative1 ExampleComparative2 ExampleComparativthe 3 ExampleComparativo 4 Copolyme ro Rubberbutadiene Butadiene rubber + Polyethylene AND F Mw (x 10 ³ ) 454 - 219 450 Mw / Mn 3.45 - 1.68 1.32 Saw (%) 1.8 - 2.6 6, 0 Cis bond content1.4 (%) 97 - 50 92 EthyleneContent (% in mol) 0 13 10 6 Melting point of polyethyl and non-block (tempera - 121 none 127
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tura ofpeak ofDSC) ModuleElasticG ' 100 131 104 117 Low heat generation property (index) 100 85 103 97 Resistance to cracking (index)Constant voltage and 100 86 100 125 Ozone Resistance (Dynamic) large cracks in thesampleentire fine cracks in the entire sample fine cracks in the extremity and the sample fine cracks at the end of the sample
Industrial Applicability [00148] The copolymer of the present invention can be used in general for elastomer products, in particular, the tire members.

权利要求:
Claims (12)
[1]
1. Copolymer of a conjugated diene compound and an unconjugated olefin characterized by the fact that the
copolymer it is a copolymer in block, and The unity of composed of diene conjugate has a content in adduct 1.2 (including adduct 3.4) 5% or less, and The unity of
The conjugated diene compound has a cis-1,4 bond content of more than 92% and the block copolymer has any of the structures of (AB) x, A- (BA) x, and B- (AB) x , where A represents a block sequence including the units of unconjugated olefin monomers, B represents a block sequence including the units of monomers of the conjugated diene compound, and x represents an integer of at least 1.
[2]
2. Copolymer, according to claim 1, characterized by the fact that the copolymer contains unconjugated olefin in more than 0 mol% and less than 100 mol%.
[3]
3. Copolymer, according to claim 2, characterized by the fact that the copolymer contains unconjugated olefin in more than 0 mol% and less than 50 mol%.
[4]
4. Copolymer according to claim 1, characterized in that it comprises a copolymer having an average molecular weight of the polystyrene equivalent of 10,000 to 10,000,000.
[5]
Copolymer according to claim 1, characterized in that it comprises a copolymer having a molecular weight distribution (Mw / Mn) of 10 or less.
[6]
6. Copolymer according to claim 1, characterized by the fact that the unconjugated olefin is an acyclic olefin.
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2/3
7. Copolymer, in wake up with the claim 1, characterized by the fact in that unconjugated olefin has from 2 to 10 carbon atoms. 8. Copolymer, in wake up with the claim 1, characterized by the fact in that olefin not conjugated is at least one selected in a group consisting of ethylene, propylene, and 1-butene. 9. Copolymer, in wake up with the claim 8, characterized by the fact in that olefin not conjugated is ethylene. 10. Copolymer, in wake up with the claim 1,
characterized by the fact that the conjugated diene compound is at least one selected from a group consisting of 1,3butadiene and isoprene.
[7]
11. Rubber composition characterized by comprising the copolymer, as defined in the claim
1.
[8]
Rubber composition according to claim 11, characterized in that it comprises the copolymer in a rubber component.
[9]
Rubber composition according to claim 12, characterized in that, with respect to 100 parts by mass of the rubber component, 5 parts by mass to 200 parts by mass of a reinforcement load and 0.1 parts by mass to 20 parts by mass of a crosslinking agent.
[10]
14. Cross-linked rubber composition characterized by being obtained by cross-linking the rubber composition, as defined in claim 11.
[11]
15. Tire characterized in that it is manufactured using the rubber composition, as defined in claim 11.
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3/3
[12]
16. Tire characterized in that it is manufactured using the cross-linked rubber composition, as defined in claim 14.

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RU2013108954A|2014-09-10|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-02-04| B09A| Decision: intention to grant|

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2020-03-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010-173126|2010-07-30|

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JP2010173126|2010-07-30|

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JP2011023400|2011-02-04|

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JP2011-023400|2011-02-04|

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PCT/JP2011/004227|WO2012014457A1|2010-07-30|2011-07-26|Copolymer, rubber composition, cross-linked rubber composition, and tire|

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