• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method for Copolymer Production This invention relates to a method for producing a copolymer of a conjugated diene compound and an unconjugated olefin, rather than the conjugated diene compound, having a high cis-1.4 bonding content. portion of the conjugated diene compound. more particularly, the invention describes a method for producing a copolymer comprising a step of polymerizing a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, in the presence of a catalytic polymerization composition containing at least least one complex selected from a metallocene complex represented by the following general formula (i): wherein m is a lanthanide, scandium or yttrium element, and the groups cpr are independently an unsubstituted or substituted indenyl, and r a rf each one independently, are an alkyl group having from 1 to 3 carbon atoms or a hydrogen atom, and l is a neutral lewis base, and w is an integer from o to 3.
    公开号:BR112012002746B1
    申请号:R112012002746-8
    申请日:2010-07-30
    公开日:2019-06-11
    发明作者:Shojiro Kaita；Olivier Tardif；Yasuo Horikawa
    申请人:Bridgestone Corporation；
    IPC主号:
    专利说明:

    METHOD FOR PRODUCTION OF COPOLIMER
    Technique Field
    This invention relates to a method for the production of a copolymer, and more particularly, to a method for the production of a copolymer of a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, having a high content of cis-1,4 bond in the conjugated diene compound portion.
    Fundamentals of Technique
    In an anionic polymerization using, it is well known to use coordination a catalytic system classified as a ZieglerNatta catalyst, in which in the polymerization the olefin or a diene can be homo-polymerized. In such a catalytic system, however, it is difficult to copolymerize olefin and diene efficiently. For example, patent application JP-A2006-503141 (Patent Document 1) describes the copolymerization of olefin and diene, but there are problems with the method, as described in
    Document of
    Patent 1, since the resulting polymer has a restricted structure, the catalytic activity is low, and the molecular weight of the polymer is low, among others.
    Prior Art Document
    Patent Document
    Patent Document 1: JP-A-2006-503141
    Summary of the Invention
    Problems to be solved by the Invention
    It is, therefore, an object of the present invention to provide a method for the production of a copolymer of a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, having a high cis-1 bond content, 4 in the portion of the diene compound conjugated to a new metallocene complex.
    2/29
    Means to solve the Problem
    The inventors carried out several studies in order to achieve the above objective and found that a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, are polymerized in the presence of a catalytic polymerization composition including a metallocene complex. specific to obtain a copolymer comprised of these monomers, and as a result of these studies, the present invention has been achieved.
    That is, the method for producing the copolymer according to the invention is characterized by comprising a polymerization step of a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, in the presence of a catalytic composition polymerization process including at least one complex selected from the group consisting of a metallocene complex represented by the following general formula (I):
    (I)
    N —S i (R to R b R c ) /
    S i (R d R and R f ) where M is a lanthanide, scandium or yttrium element, and Cp R is, independently, a substituted or unsubstituted indenyl, and R a to R f are, independently, an alkyl group having a number of carbons from 1 to 3 or a hydrogen atom, and L is a neutral Lewis base, and w is an integer from 0 to 3, a metallocene complex represented by the following general formula (II):
    3/29
    Lw (Π) where M is a lanthanide, scandium or yttrium element, and Cp R is, independently, a substituted or unsubstituted indenyl, and X 'is a hydrogen atom, a halogen atom, amide, a neutral number, and cationic formula in which
    Cp R 'is, a group of carbon silyl alkoxide group, a thiolate group, or a group of 1 to 20, and L w is an integer of 0 a hydrocarbon group is a base of and a having
    Lewis general represented half-metallocene complex (III):
    EB] 0
    OH) for the following
    M is a lanthanide, scandium or independently element, a cyclopentadienyl, yttrium, and indenyl or fluorenyl substituted hydrogen atom, an alkoxide, one or a group of 1 to 20, and an integer of 0 thiolate group, of or unsubstituted, and atom of a hydrocarbon group having is a Lewis base
    3, and [B] is an anion
    The metallocene complex
    X is a halogen, an amide group, a silyl group a neutral carbon number, and w is a non-coordinating number.
    a complex compound in which one or more cyclopentadienyls or a derivative thereof is attached to a central metal. In particular, a metallocene complex having a cyclopentadienyl or derivative
    4/29 of it attached to the central metal can be referred to as a half-metallocene complex. Also, olefin is an aliphatic unsaturated hydrocarbon, which is a compound having one or more double carbon-carbon bonds.
    In a preferred embodiment of the method for producing the copolymer according to the invention, at least one of R a to R f is a hydrogen atom.
    In another preferred embodiment of the method for producing the copolymer according to the invention, at least one of R a to R c is a hydrogen atom and at least one of R d to R f is a hydrogen atom.
    In another preferred embodiment of the method for producing the copolymer according to the invention, the polymerization of the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, is an addition polymerization.
    In another preferred embodiment of the method for producing the copolymer according to the invention, the unconjugated olefin, instead of the conjugated diene compound, is an acyclic olefin. In yet another preferred preferred embodiment of the method for producing the copolymer according to the invention, the unconjugated olefin, instead of the conjugated diene compound, is an α-olefin that has a carbon number of 2 to 10. In this case, as unconjugated olefins, rather than the conjugated diene compound, ethylene and propylene are preferred.
    In another preferred embodiment of the method for producing the copolymer according to the invention, the conjugated diene compound has a carbon number of 4 to 8. In this case, as the conjugated diene compounds, 1,3-butadiene and isoprene.
    In another preferred embodiment of the method for producing the copolymer according to the invention, when the
    5/29 conjugated diene compound is polymerized with unconjugated olefin, the unconjugated olefin pressure is 0.1 MPa to 10 MPa.
    In another preferred embodiment of method a for producing the copolymer according to the invention, when the conjugated diene compound is polymerized with the unconjugated olefin, a concentration of the conjugated diene compound (mol / 1) and a concentration of the olefin non-conjugated (mol / 1) at the beginning of the polymerization satisfies the relationship of the following equation:
    concentration of unconjugated olefin / concentration of the conjugated diene compound is 1.0.
    Effects of the Invention
    According to the invention, the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, are polymerized in the presence of the catalytic polymerization composition including the specified metallocene complex, and thus a copolymer having a high content of cis-1,4 bond in the conjugated diene compound portion can be produced.
    Brief Description of Drawings
    THE Figure 1 it's a graph of a spectrum in infrared (IR) of a copolymer of butadiene-ethylene B. THE Figure 2 is a chart of an IR spectrum of one polybutadiene E. THE Figure 3 it's a graph of a spectrum in resonance magnetic nuclear 1 H-NMR of a copolymer in
    butadiene-ethylene B.
    THE Figure 4 it is a graphic in a spectrum in resonance magnetic nuclear 13 c-nmr in a copolymer in
    butadiene-ethylene B.
    Mode of Execution of the Invention
    The invention will be described in detail here below.
    6/29
    The method for producing the copolymer according to the invention is characterized by comprising a polymerization step of a conjugated diene compound and an unconjugated olefin, instead of the conjugated diene compound, in the presence of a catalytic polymerization composition, including at least one complex selected from the group consisting of metallocene complexes represented by the general formulas above (I) and (II), and the cationic half-metallocene complex represented by the general formula above (III). As mentioned above, it is difficult to copolymerize olefin and diene effectively with the conventional coordinating polymerization catalyst. The inventors have found that by optimizing a central metal used in a main catalyst and a central metal ligand in a catalytic system used in anionic coordination polymerization, unconjugated olefin can be introduced effectively, rather than the conjugated diene compound. , in the polymerization reaction of the conjugated diene compound. Also, the copolymer of the conjugated diene compound and unconjugated olefin, instead of the conjugated diene compound, obtained using said catalytic system has a high content of cis-1,4 in the microstructure of the portion of the compound of conjugated diene. Therefore, the copolymer obtained by the production method according to the invention has a high crystallinity in the extension of the conjugated diene compound portion and maintains a glass transition temperature (Tg) in a lower state, so that it is able to improve wear resistance and is preferably used as a rubber component of a rubber composition.
    copolymer of the conjugated diene compound and the unconjugated olefin, instead of the diene compound
    7/29 conjugate, which is obtained by the method for producing the copolymer according to the invention, is not particularly limited, except to use a catalytic polymerization composition described in more detail below, and can be obtained, for example, by copolymerization of a mixture of a conjugated diene compound and an unconjugated olefin, rather than the conjugated diene compound, as a monomer, such as the method for producing a polymer with the common coordination ionic polymerization catalyst. Also, in the method for producing the copolymer according to the invention, the polymerization of the conjugated diene compound and the unconjugated olefin, rather than the conjugated diene compound, is preferably an addition polymerization. Furthermore, in the method for producing the copolymer according to the invention, the polymerization of the conjugated diene compound and the unconjugated olefin, rather than the conjugated diene compound, is preferably a random copolymerization. As a method of polymerization, any method can be used, such as the solution polymerization method, suspension polymerization method, liquid phase mass polymerization method, emulsion polymerization method, vapor phase polymerization method, solid phase and similar polymerization. When a solvent is used in the polymerization reaction, it is sufficient that the solvent used is inactive in the polymerization reaction, and the amount of the solvent used is optional, but it is preferable that it be an amount in which the concentration of the complex included in the catalytic composition of polymerization provide from 0.1 to 0.0001 mol / 1.
    The conjugated diene compound used as the monomer preferably has a carbon number of 4 to
    8/29
    8. As the conjugated diene compound, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-butadiene and the like are specifically mentioned. Among them, 1,3butadiene and isoprene are preferable. These conjugated diene compounds can be used alone or combined with two or more.
    On the other hand, the unconjugated olefin used as the monomer is an unconjugated olefin, instead of the conjugated diene compound, which has excellent heat resistance and it is possible to improve the degree of design freedom as an increasing elastomer a proportion of double bonds occupied in the copolymer backbone, but also controlling the crystallization capacity. As the unconjugated olefin, an acyclic olefin is preferable, as well as an α-olefin that has a carbon number from 2 to 10, with olefin being preferable as an unconjugated olefin. Since α-olefin has a double bond at the α position of the olefin, copolymerization with the conjugated diene compound can be conducted efficiently. Therefore, like unconjugated olefin, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1heptene, 1-octene and the like are preferable. Among them, ethylene, propylene and 1-butene are preferable. These non-conjugated olefins can be used alone or in a combination of two or more.
    The catalytic polymerization composition used in the method for producing the copolymer according to the invention is necessary to comprise at least one complex selected from the group consisting of metallocene complexes represented by the general formulas (I) and (II) and the cationic complex of half -metalocene represented by the general formula (III) and it is still preferable to include another
    9/29 component contained in the catalytic polymerization composition comprising the usual metallocene complex, for example, a co-catalyst or the like.
    In the metallocene complexes represented by the general formulas (I) and (II), the Cp R group is an unsubstituted indenyl or a substituted indenyl. The CP R group having an indenyl ring as a basic structure can be shown by C 9 H 7 - X R X or C 9 Hn_ x R x , where x is an integer from 0 to 7 or 0 to 11. Also , it is preferable that the group R is independently a hydrocarbyl group or a metalloid group. The number of carbons in the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and more preferably 1 to 8. Concretely, like the hydrocarbyl group, the methyl group, the ethyl group, the phenyl group are preferably mentioned, the benzyl group and the like. On the other hand, as an example of a metalloid in the metalloid group, Ge of germyl, Sn of stannyl and Si of silyl are mentioned, and the metalloid group is preferable to have a hydrocarbyl group, and the hydrocarbyl group included in the group of metalloid is the same as in the hydrocarbyl group mentioned above. As the metalloid group, the trimethylsilyl group is specifically mentioned, among others. As the substituted indenyl, 2-phenyl-indenyl, 2-methyl-indenyl and the like are specifically mentioned. In addition, the two Cp R s in the general formulas (I) and (II) can be the same or different from each other.
    In the half-metallocene complex represented by the general formula (III), the Cp R 'group is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, among which unsubstituted or substituted indenyl is preferable. The Cp R 'group having a cyclopentadienyl ring as a basic structure is shown by
    10/29
    C5H 5 - x R x . In this case, x is an integer from 0 to 5. Also, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbons in the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and more preferably 1 to 8. Concretely, like the hydrocarbyl group, the methyl group, ethyl group, phenyl group are preferably mentioned , benzyl group and the like. On the other hand, as an example of metalloid in the metalloid group, Ge of germyl, Sn of stannyl and Si of silyl are mentioned, and it is preferable that the metalloid group has a hydrocarbyl group, and that the hydrocarbyl group included in the group metalloid is the same as in the hydrocarbyl group mentioned above. Like the metalloid group, the trimethylsilyl group, among others, are specifically mentioned. As the group Cp R 'having the cyclopentadienyl ring as one of the following:
    and
    where R is a hydrogen atom, a methyl group or ethyl group.
    In the general formula (III), the Cp R 'group which has the indenyl ring as a basic structure is defined in the same way as in the Cp R group of the general formula (I) and also a preferable example of this is the same.
    In formula (III), Cp R 'group having fluorenila ring as a basic structure can be shown by Ci3H 9 _ x R x or C 3 Hi7- x R x. In this case, x is an integer
    11/29 from 0 to 9 or 0 to 17. Also, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbons in the hydrocarbyl group is preferably 1 to 20, more preferably 1 to
    10, and more preferably from 1 to 8. Concretely, as the hydrocarbyl group, the methyl group, ethyl group, phenyl group, benzyl group and the like are preferably mentioned. On the other hand, as an example of a metalloid in the metalloid group, Ge of germyl, Sn of stannyl and Si of silyl are mentioned, and the metalloid group is preferred to have a hydrocarbyl group, and the hydrocarbyl group included in the group of metalloid is the same as in the hydrocarbyl group mentioned above. Like the metalloid group, the trimethylsilyl group, among others, are specifically mentioned.
    The central metal M in the general formulas (I), (II) and (III) is a lanthanide, scandium or iterium element. The element lanthanide includes fifteen elements of atomic numbers 57 to 71, any of which can be used. As the central metal M, Samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, Scandium Sc and itium Y are preferably mentioned.
    metallocene complex represented by the general formula (I) includes a silyl-amide binder [N (SiR 3 ) 2 ].
    Each of the groups R (R to R f in formula (I)) included in the silyl-amide binder is independently an alkyl group having a carbon number of 1 to 3 or a hydrogen atom. Also, at least one of R a to R f is preferably a hydrogen atom. When at least one of R a to R f is a hydrogen atom, the synthesis of the catalyst becomes easier, and the volume around the silicon becomes smaller, and thus the unconjugated olefin is introduced more easily. From the same point of view
    12/29 seen, it is more preferable than at least one among the groups
    R a to R c is a hydrogen atom and at least one of
    R d to R f is a hydrogen atom. In addition, as an alkyl group, a methyl group is preferable.
    formula included therein, from the group
    The complex in the ligand forms that of metallocene includes a silyl ligand [-SiX'3]
    X of the general formula and also a
    In the formula consisting of a general group, a preferable one is represented by is a defined group (III) described plus the same.
    (III), X is a group selected from a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group and a hydrocarbon group having a carbon number of 1 mentioned the group groups methoxy, ethoxy group, at 20. Like the alkoxide group, are aliphatic alkoxide, such as propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and the like; and aryloxy groups, such as phenoxy group,
    2,6-di-tert-butyl-phenoxy, 2,6-di-isopropyl-phenoxy group, 2,6-dineopentyl-phenoxy group, 2-tert-butyl-6 isopropyl-phenoxy group, 2-tert-butyl group -6-neopentyl-phenoxy, group 2-isopropyl-6-neopentyl-phenoxy, and the like, and among them, group 2, β-di-tert-butyl-phenoxy is preferred.
    As the thiolate group shown by X in general formula (III), aliphatic thiolate groups are mentioned, such as the thiomethoxy group, thioethoxy group, thiopropoxy group, thio-n-butoxy group, thioisobutoxy group, thio-sec-butoxy group, thio-tert-butoxy group and the like; aryl-thiolate groups, such as the thiophenoxy group, 2,6-ditherc-butyl-thiophenoxy group, 2,6-diisopropyl-thiophenoxy group, 2,6-dineopentyl-thiophenoxy group, 2-tert-butyl group 6 isopropyl-thiophenoxy, 2-tert-butyl-6-thioneopentyl phenoxy group, 2-isopropyl-6-thioneopentyl-phenoxy group, group
    13/29
    2,4,6-tri-isopropyl-thiophenoxy and the like, and among them, the 2,4,6-tri-isopropyl-thiophenoxy group is preferred.
    As the amide group shown by X in general formula (III), are the aliphatic amide groups mentioned above, such as the dimethyl-amide group, diethyl-amide group, diisopropyl-amide group, and the like; aryl-amide groups, such as the phenyl-amide group, the 2,6-di-tert-butylphenyl-amide group, 2,6-diisopropyl-phenyl-amide group, 2,6-dineopentyl-phenyl-amide group, the 2-tert-butyl-6-isopropylphenyl-amide, group 2-tert-butyl-6-neopentyl-phenyl-amide, group 2-isopropyl-6-neopentyl-phenyl-amide, group 2,4,6-
    tert-butyl-phenyl-amide and the like; and bisexual groups trialqui1-silyl-amide, such as the group bis-trimethyl- silyl-amide and the like, and they, the bis- group trimethyl-silyl-amide is preferred. As the group silyl shown by X in formula
    general (III), the trimethyl-silyl group, tris (trimethyl-silyl) group, bis (trimethylsilyl) methyl-silyl group, trimethyl-silyl (dimethyl) sily group, tri-isopropyl-silyl group (bis-trimethyl- silyl) silyl and the like, and among them, the tris (trimethylsilyl) silyl group is preferred.
    Like the halogen atom shown by X in general formula (III), it can be a fluorine atom, chlorine atom, bromine atom or iodine atom, with chlorine atom or bromine atom being preferable. As the hydrocarbon group having a carbon number from 1 to 20 shown by X, linear or branched aliphatic hydrocarbon groups are specifically mentioned, such as the methyl group, ethyl group, n-propyl group, isopropyl group, n- group butyl, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group, octyl group, and the like; groups of
    Aromatic hydrocarbons, such as the phenyl group, tolyl group, naphthyl group, and the like; an aralkyl group, such as the benzyl group or the like; a hydrocarbon group containing the silicon atom, such as the trimethylsilyl-methyl group, bis-trimethyl-silyl-methyl group or similar, among others, and among them the methyl group, ethyl group, isobutyl group and trimethyl-silyl group methyl among others are preferred.
    As X in general formula (III), a bis-trimethyl-silyl-amide group or a hydrocarbon group having a carbon number from 1 to 20 is preferred.
    As the non-coordinating anion shown by [B] in the general formula (III), for example, a tetravalent boron anion is mentioned.
    As the tetravalent boron anion, concrete tetraphenyl borate, tetrakis borate (monofluoro-phenyl), tetrakis borate (diflúor-phenyl), tetrakis borate (trifluorphenyl), tetrakis borate (tetrafluoro-phenyl) are specifically mentioned. , tetrakis (pentafluor-phenyl) borate, tetrakis (tetrafluoro-methyl-phenyl), tetra (tolyl) de, tetra borate (xylyl), (triphenyl-pentafluor-phenyl) borate, [tris (pentafluorfenila) borate phenyl], tridecahydride-7,8-dicarbaundecaborate and the like, and among them tetrakis borate (pentafluorfenil) is preferred.
    The metallocene complexes represented by the general formulas (I) and (II), as well as the cationic half-metallocene complex represented by the general formula (III) still contain 0 to 3, and preferably 0 to 1 neutral base Lewis L. As the neutral Lewis base L are mentioned, for example, tetrahydrofuran, diethyl ether, dimethylaniline, trimethyl phosphine, lithium chlorine, neutral olefins, neutral diolefins, among others.
    15/29
    In this case, when the complex contains a plurality of Lewis L neutral bases, the Lewis L neutral bases can be the same or different.
    Also, the metallocene complexes represented by the general formulas (I) and (II), as well as the cationic half-metallocene complex represented by the general formula (III) may be present as a monomer or may be present as a dimer or higher mere .
    The metallocene complex represented by the general formula (I) can be obtained by reacting a lanthanide trishalide, scandium trishalide or yttrium trishalide with a salt (for example, potassium salt or lithium salt) of indene and a salt (for example, potassium salt or lithium salt) of amide bis (trialkylsilyl) in a solvent. In addition, the reaction temperature is sufficient to be almost at room temperature, so that the complex can be produced under moderate conditions. In addition, the reaction time is optional, but it can be from several hours to a few hours, such as ten hours. The reaction solvent is not particularly limited, but it should preferably be a solvent that dissolves a raw material and a product, and toluene can be used, for example. An example of the reaction to obtain the metallocene complex represented by the general formula (I) is shown below:
    KN
    M - N6R 3 ^
    (I) where X is a halide.
    The metallocene complex represented by
    16/29 general formula (II) can be obtained, for example, by reacting a lanthanide tris-halide, scandium tris-halide or yttrium tris-halide with a salt (for example, potassium salt or lithium salt) of indenyl and a silyl salt (eg potassium salt or lithium salt) in a solvent. In addition, the reaction temperature is sufficient to be almost at room temperature, so that the complex can be produced under moderate conditions. Also, the reaction time is optional, but it is about several hours to a few hours, such as ten hours. The reaction solvent is not particularly limited, but it should preferably be a solvent that dissolves a raw material and a product, and toluene can be used, for example. An example of the reaction to obtain the metallocene complex represented by the general formula (II) is shown below:
    MK 3 + 2Dp R Li + KS X 3
    where X is a halide.
    The half-metallocene cation complex represented by the general formula (III) can be obtained, by
    Cp ^
    ® Θ
    UV + AI] [B] αν)
    an) example, by the following reaction.
    17/29
    In the compound represented by the general formula (IV), M is an element of lanthanide, scandium or itium, and Cp R 'is independently a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, and X is a hydrogen atom, an atom of halogen, an alkoxide group, a thiolate group, an amide group, a silyl group or a hydrocarbon group, having a number of carbon atoms of a 2 0, and L is a neutral Lewis base, and w is an integer of 0 to 3.
    In an ionic compound represented by a general formula [A] + is a cation and [B] “is a non-coordinating anion.
    As the cation shown by [A] + are mentioned, for example, the carbon cation, oxon cation, amine cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation containing a metal
    Like the carbon cation, tri-substituted carbon cations are mentioned, such as triphenyl-carbonium cation, tri (phenyl-substituted) carbon cation and the like, among others. As the tri (substituted phenyl) carbon cation, the tri (methylphenyl) carbon cation and the like are specifically mentioned. As the amine cation, trialqui-ammonium cations are mentioned, such as the trimethyl-ammonium cation, triethyl-ammonium cation, tripropyl-ammonium cation, tributyl-ammonium cation or the like; N, N-dialkyl-anilinium cations, such as the N, N-dimethyl-anilinium cation, N, N-diethyl-anilinium cation, N, N-2,4,6-pentamethyl-anilinium cation or the like; dialkylammonium cations, such as diisopropylammonium cation, dicyclohexylammonium cation; among others. Like the phosphonium cation, triaryl-phosphonium cations, such as triphenyl-phosphonium cation, tri (methylphenyl) -phosphonium cation, tri (dimethyl-phenyl) -phosphonium cation, or
    Similar 18/29; among others. Among these cations, the N, N-dialkyl-anilinium or carbonium cation is preferable, and the N, N-dialkyl-anilinium cation is particularly preferable.
    ionic compound of the general formula [A] + [B] ~ used in the above reaction is a compound, composed of a combination of the anion and the selected non-coordination cation and is preferably the N, N-dimethylanilinium-tetrakis borate (pentafluor -phenyl), triphenylcarbonium borate tetrakis (pentafluorophenyl) or similar. In addition, the ionic compound of the general formula [A] + [B] is added to the metallocene complex in a molar amount, preferably 0.1 to 10 times, and more preferably about 1 time. In addition, when the cationic half-metallocene complex represented by the general formula (III) is used in the polymerization reaction, the cationic half-metallocene complex represented by the general formula (III) can be provided for the polymerization reaction system such as it is, or the compound of the general formula (IV) and the ionic compound of the general formula [A] + [B] “used in the above reaction can be provided separately for the polymerization reaction system to form the cationic complex of metademetalocene of the general formula (III) in the reaction system. Also, using a combination of the metallocene complex of the general formula (I) or (II) and the ionic compound of the general formula [A] + [B] _ , the cationic half-metallocene complex of the general formula (III ) in the reaction system.
    It is preferable to determine the structures of the metallocene complexes represented by the general formulas (I) and (II) and the cationic half-metallocene complex represented by the general formula (III) using a
    19/29 X-ray structure analysis.
    A promoter usable in the composition of the polymerization catalyst can optionally be selected from components used as a promoter in the composition of the polymerization catalyst containing the usual metallocene complex. As the promoter, preferably, for example, aluminoxane, an organoaluminium compound, the ionic compounds mentioned above and the like are mentioned. These promoters can be used alone or combined with two or more.
    Like aluminoxane, an alkylaluminoxane, which includes, for example, methylaluminoxane (MAO), a modified methylaluminoxane and the like, is preferable. Like the modified methyl aluminoxane, MMAO-3A (manufactured by Toso Finechem Co., Ltd.) and the like are preferable. In addition, the content of aluminoxane in the composition of the polymerization catalyst is preferable in such a way that an elemental ratio Al / M of the aluminum element Al in the aluminoxane to the central metal M in the metallocene complex is about 10 to 1000, and preferably about of 100.
    As the organoaluminium compound, an organic aluminum compound represented by the general formula is preferred: A1RR'R, where R and R 'are independently a C1-C10 hydrocarbon group or a hydrogen atom, and R is a C1 hydrocarbon group. -Cio). As the concrete example of the organoaluminium compound, for example, a trialkyl aluminum, a chloro dialkyl aluminum, an alkyl aluminum dichloride, a hydride and the like are mentioned. Among them, trialkyl aluminum is preferable. As trialkyl aluminum, mention is made, for example, of triethyl aluminum, triisobutyl aluminum and the like. Furthermore, the content of the organoaluminium compound in the composition
    20/29 of the polymerization catalyst is preferably 1 to 50 times, and more preferably about 10 times per 1 mol of the metallocene complex.
    In the composition of the polymerization catalyst, each of the metallocene complexes of the general formulas (I) and (II), as well as the cationic half-metallocene complex of the general formula (III), are combined with a suitable promoter, in which the cis-1,4 bond content or the molecular weight of the resulting copolymer can be increased.
    The method for producing the copolymer according to the invention can be carried out in the same way as in a method for polymerizing through the polymerization reaction using the conventional coordinating ion polymerization catalyst except to use the above mentioned polymerization catalyst composition, as a polymerization catalyst, as mentioned above. In the method for producing the copolymer according to the present invention, for example, (1) components that make up the polymerization catalyst composition can be supplied separately for a polymerization reaction system containing the conjugated diene compound and the non-olefin. -conjugated, instead of the conjugated diene compound, as a monomer to form the polymerization catalyst composition in said reaction system, or (2) the previously prepared polymerization catalyst composition can be supplied to the reaction system of polymerization. Also, item (2) includes the provision of a metallocene complex activated by the promoter (active species). In addition, the amount of metallocene complex included in the composition of the polymerization catalyst used should preferably be in the range of 0.0001 to 0.01 times greater than the molar amount in the total of the conjugated diene compound and the non-olefin21 / 29 conjugated, rather than the conjugated diene compound.
    In addition, it is preferable to carry out the polymerization reaction in an atmosphere of an inert gas, and preferably in nitrogen gas or argon gas.
    The polymerization temperature in the polymerization reaction is not particularly limited, but is preferably in the range, for example, -100 ° C to 200 ° C and can also be almost at room temperature. If the polymerization temperature is high, the selectivity of cis-1,4 in the polymerization reaction can be reduced. On the other hand, the reaction time in the polymerization reaction is not particularly limited and is preferably in a range, for example, from 1 second to 10 days, but it can be appropriately selected according to the type of monomer to be polymerized, the type of catalyst, and conditions, such as polymerization temperature and the like.
    In the method for producing the copolymer according to the invention, when the conjugated diene compound is polymerized with the unconjugated olefin, instead of the conjugated diene compound, the pressure of the unconjugated olefin should preferably be 0.1 MPa to 10 MPa. When the pressure of the unconjugated olefin is not less than 0.1 MPa, the unconjugated olefin can be introduced effectively into the reaction mixture.
    When the pressure of the unconjugated olefin is too high, the effect of efficiently introducing the saturated unconjugated olefin, so that the pressure of the unconjugated olefin is preferably not greater than 10 MPa.
    In the method for producing the copolymer according to the invention, when the conjugated diene compound is polymerized with the unconjugated olefin, instead of the conjugated diene compound, the concentration of the
    22/29 conjugated diene (mol / 1) and the concentration of the unconjugated olefin (mol / 1) at the beginning of the polymerization should preferably satisfy the relationship of the following equation:
    concentration of unconjugated olefin / concentration of conjugated diene compound 1.0, and more preferably the ratio of the following equation:
    concentration of unconjugated olefin / concentration of conjugated diene compound ^ 1.3, and more preferably the ratio of the following equation:
    concentration of unconjugated olefin / concentration of conjugated diene compound is 1.7. When having the value of the unconjugated olefin concentration / conjugated diene compound concentration in no more than 1, the unconjugated olefin can be efficiently introduced into the reaction mixture.
    In the method for producing the copolymer according to the invention, the reaction mixture includes the composition of the polymerization catalyst, the solvent, among others, in addition to the conjugated diene compound and the unconjugated olefin.
    Also, in the copolymer of the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, obtained by the method for producing the copolymer according to the invention, the average molecular weight in number (Mn) of the copolymer is not particularly limited, and there are also no molecular weight reduction problems. From the point of view of an application for materials of macromolecular structure, the numerical average molecular weight (Mn) is preferably less than 50,000, and more preferably 100,000. In addition, the molecular weight distribution (Mw / Mn) represented by an average molecular weight to weight (Mw) to numerical average molecular weight (Mn) ratio is preferably not more than 4, and
    23/29 more preferably not more than 2.5. In this case, the average molecular weight and molecular weight distribution can be determined by gel permeation chromatography (GPC), using polystyrene as a standard substance.
    The copolymer of the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, obtained by the method for producing the copolymer according to the invention, has a high content of cis1,4 of the portion of the compound of conjugated diene. The cis-1,4 bond content of the conjugated diene compound is preferably
    When the cis-1,4 bond content of the conjugated diene compound portion is less than 85%, a high extent crystallinity and a low glass transition temperature (Tg) can be maintained, with properties such as strength wear and the like, are perfected.
    When the cis-1,4 bond content of the conjugated diene compound portion is less than 85%, the extent crystallinity is deteriorated surprisingly, but also the glass transition temperature (Tg) is high, such that durability, such as wear resistance or the like, may be impaired.
    The copolymer of the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, obtained by the method for producing the copolymer according to the invention, preferably has a content of no more than 20%, and most preferably of not more than 15%, vinyl bond in the conjugated diene compound portion. When the vinyl bond content of the conjugated diene compound portion exceeds 20%, the cis-1,4 bond content is reduced and the effect of improving wear resistance may not be achieved
    Satisfactory 24/29.
    In the copolymer of the conjugated diene compound and the unconjugated olefin, instead of the conjugated diene compound, obtained by the method for the production of the copolymer according to the invention, a content of the unconjugated olefin, instead of the diene compound conjugate, it is preferably in a range of 3 to 98 mol%, and more preferably in a range of 10 to 50 mol%. When the content of the unconjugated olefin, instead of the conjugated diene compound, is in the specified range, the advantage of introducing the unconjugated olefin to have the effect of improving the heat resistance in the main chain, being composed of the same homogeneously as an elastomer, is retained. When the content of unconjugated olefin, instead of the conjugated diene compound, is less than 3 mol%, the advantage of introducing unconjugated olefin into the main chain may be lost, whereas when it exceeds 98 mol% , the advantage of introducing the conjugated diene compound into the main chain (e.g., a cross-linked facility or the like) may be lost.
    unconjugated olefin copolymer, conjugated, obtained by that of the conjugated diene compound and instead of the method compound for producing the copolymer diene according to the invention, it is advantageously cross-linked, while maintaining the crystallization capacity , so that it can be used in elastomeric products as a whole, and more particularly as tire components.
    Examples
    The following examples are given as an illustration of the invention and are not to be construed as limitations of the invention.
    25/29
    Example 1
    In a pressure glass reactor, having 400 ml and being sufficiently dry, 325 ml of a solution containing 13.58 g (0.25 mol) of 1,3-butadiene in toluene are added, and then ethylene is added. introduced into it at a pressure of 0.4 MPa for 30 minutes. After introducing ethylene, the weight of the polymerization reaction system gains 7.00 g, from which it is confirmed that 0.25 mol of ethylene is introduced in the polymerization reaction system. Thus, the ratio of the concentration of ethylene E to the concentration of butadiene Bd at the beginning of the polymerization (E / Bd) is 1.00. On the other hand, in a glass container in a glove compartment under an atmosphere of nitrogen 18 pmol of bis (2-phenyl-indenyl) gadolinium bis (dimethyl-silyl-amide) [(2PhCgHê) 2 GdN (SiHMe 2 ) 2 are loaded 2 ], tetraquispentafluoro-phenyl borate jumol) of dimethyl-anilinium [Me 2 NHPhB (CgFs) 4] and
    0.90 mmol of diisobutyl aluminum hydride are dissolved in 10 ml of toluene to form a catalytic solution.
    Then, the catalytic solution is removed from the glove compartment and added to the monomer solution in an amount of 17.5 pmol by gadolinium conversion and the polymerization is carried out at temperature, for 180 minutes. After polymerization, 1 ml of a 5% by mass solution of 2,2'-methylene-bis (4-ethyl-6-t-butyl-phenol) (NS-5) in isopropanol is added to complete the reaction, and the resulting copolymer is separated with a large amount of methanol and dried under vacuum at 70 ° C to obtain a copolymer A. The yield of the resulting copolymer A is 12.00 g.
    Example 2
    Polymerization is carried out in the same way as in Example 1 except that ethylene is introduced into it at
    26/29 a pressure of 0.8 Mpa, for 30 minutes, and 12.5 g (0.45 mol) of ethylene are loaded (E / Bd = 1.80), with a copolymer B being obtained in a yield of 10.30 g.
    Example 3
    A polymerization is carried out in the same manner as in Example 1, except that the amount of diisobutyl aluminum hydride is charged to 1.35 mmol, with a copolymer C being obtained in a yield of 13.65 g.
    Example 4
    In a pressure glass reactor, having 200 ml and being sufficiently dry, 20 ml of a solution containing 3.38 g (0.063 mol) of 1,3-butadiene in toluene, ethylene are added to it (E / Bd side , in a glass container having a glove compartment under a nitrogen atmosphere, 5.5 pmol of gadolinium bis (2-phenyl-indenyl) bis (dimethyl-silyl-amide) is loaded
    11.0 pmol of tetrakis borate (pentafluorophenyl) [Me 2 NHPhB (C 6 F 5 ) 4 ], and 0.41 mmol of tri-isobutyl aluminum dimethylaniline, and are dissolved in 10 ml of toluene to form a catalytic solution. Then, the solution is removed from the glove compartment, and added to the monomer solution in an amount of 5.0 pmol by gadolinium conversion and the polymerization is carried out at room temperature for 240 minutes. After polymerization, 1 ml of a 5% by mass solution of 2,2'-methylene-bis (4-ethyl-6-t-butyl-phenol) (NS-5) in isopropanol is added to complete the reaction, and then the resulting copolymer is separated with a large amount of methanol and dried under vacuum at 70 ° C to obtain a copolymer D. The yield of the resulting copolymer D is 4.15 g.
    Reference Example 1
    27/29
    In a 1 L glass flask fitted with a rubber plug and dried and replaced with nitrogen, it is loaded with 450 g of a solution containing 54 g (1 mol) of 1,3-butadiene in toluene to form a monomer solution. On the other hand, in a glass container having a glove compartment, under a nitrogen atmosphere, 3 pmol of gadolinium bis (2-phenyl-indenyl) bis (dimethyl-silyl-amide) [(2-PhC 9 H 6 ) 2 GdN (SiHMe 2 ) 2], 4,5 pmol of dimethylaniline borate tetrakis (pentafluorophenyl) [Me 2 NHPhB (C 6 F 5 ) 4 ] and dissolved in 5 ml of toluene to form a solution catalytic. Then, the catalytic solution is removed from the glove compartment, and added to the monomer solution in an amount of 2 pmol by gadolinium conversion and the polymerization is carried out at room temperature for 180 minutes. After polymerization, 2 ml of a 5% by mass solution of 2,2'-methylene-bis (4-ethyl-6-tbutyl-phenol) (NS-5) in isopropanol are added to complete the reaction, plus , the resulting copolymer is separated with a large amount of methanol and dried under vacuum at 70 ° C to obtain a polybutadiene E in a yield of 54 g.
    With respect to the copolymers thus produced in Examples 1 to 4 and the polymer of Reference Example 1, the microstructure, the ethylene content, the numerical average molecular weight (Mn), the molecular weight distribution (Mw / Mn) and the characterization of the chain in the copolymer are measured and evaluated according to the following methods.
    (1) Microstructure
    The microstructure is determined by an infrared method (Morello method). The results are shown in Table 1. Figure 1 is a graph of the infrared (IR) spectrum of the butadiene-ethylene copolymer B. Figure 2 is a graph of the IR spectrum of polybutadiene E.
    28/29 (2) Ethylene content content of the ethylene portion in the copolymer (mol%) is determined by the integral ratio of the spectrum 1 H-NMR. In addition, measurement using 1 H-NMR is performed at 100 ° C using a deuterated 1,1,2,2-tetrachloroethane as the solvent. The results are shown in Table 1. Figure 3 is a graph of the H-NMR spectrum 1 of the butadiene-ethylene copolymer B.
    (3) Characterization of the chain in the copolymer
    The characterization of the chain in the ethylene portion and the butadiene portion in the copolymer is performed using the 13 C-NMR spectrum (methylene region from 22 to 36 ppm). In addition, measurement using 13 C-NMR is performed at 100 ° C, using deuterated 1,1,2,2-tetrachloroethane as a solvent. Figure 4 is a graph of the 13 C-NMR spectrum of the butadiene-ethylene B copolymer B.
    (4) Average molecular weight by weight (Mw) and molecular weight distribution (Mw / Mn)
    The average molecular weight by weight (Mw) and the molecular weight distribution (Mw / Mn) of each polymer as converted to polystyrene are measured using gel permeation chromatography [GPC: HLC-8121 GPC / HT made with TOSOH, column : GMH hr -H (S) HT x two columns made with TOSOH, detector: differential refractometer (IR)] as a monodisperse polystyrene standard. In addition, the measuring temperature is 140 ° C.
    Table 1
    Example1 Example2 Example3 Example4 Example ofReference1 Mn (xlO 3 ) 174 158 100 134 316 Mw / Mn 1.94 1.94 2.45 2.42 1.58 Binding content 98, 1 97.4 97.2 97.0 99, 0
    29/29
    cis-1.4 (%)Binding contentvinyl (%) 0, 6 0.7 0, 6 0.7 0.1 Ethylene content(mol%) 11 18 19 36 -
    As can be seen in Table 1, all polymers A to D of Examples 1 to 4 have a numerical average molecular weight (Mn) of not less than 100,000, and thus, high molecular weight copolymers are obtained. Also, it can be seen that the proportion of the cis-1,4 bond content of the butadiene portion in each of these copolymers is high and the same degrees of value are shown even if they are compared with the result in the butadiene homopolymer shown in Reference Example 1. Also, the ethylene content in each of the copolymers is not less than 10 mol%, from which it was found that the proportion of unconjugated olefin, instead of the conjugated diene compound, in the copolymer can be optionally controlled. Yet, additionally, the various peaks instead of a peak showing polyethylene (29.4 ppm) and a peak showing a cis-1,4-polybutadiene (27.3 ppm) are observed by characterizing the chain across the spectrum of 13 C-NMR, from which it was found that ethylene and butadiene are copolymerized randomly.
    权利要求:
    Claims (10)
    [1]
    1. A method for the production of a copolymer comprising a polymerisation step of a conjugated diene compound and an unconjugated olefin other than the conjugated diene compound in the presence of a catalytic polymerization composition, including at least one complex selected from the group consisting of in a metallocene complex represented by the following general formula (I):
    Cp R L w
    Cp R b cx
    NS i (R a R b R c ) /
    S i (R d R and R f ) - (I) where M is an element of lanthanide, scandium or itium, and Cp R is independently an unsubstituted or substituted indenyl, and R a to R f are, independently, an alkyl group having a carbon number of 1 to 3 or a hydrogen atom, and L is a Lewis-base , neutral, and w is an integer from 0 to 3, wherein at least one of R a to R f is a hydrogen atom, a metallocene complex represented by the following general formula (II):
    Cp R
    Cp R
    X '(Π) where M is an element of lanthanide, scandium or iterium,
    Cp R is, independently, a substituted or unsubstituted indenyl, and X 'is a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, a group
    Petition 870190031898, of 03/03/2019, p. 6/10
    [2]
    2/3 amide, a silyl group or a hydrocarbon group, having a number of carbon atoms from 1 to 20, and L is a neutral Lewis base, and w is an integer from 0 to 3, and a half cationic complex -metalocene represented by the following general formula (III):
    Cp R
    M® [bP Lv . . (π) where M is an element of lanthanide, scandium or yttrium, Cp R 'is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, and X is a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group or a hydrocarbon group having a carbon number from 1 to 20, and L is a neutral Lewis base, and w is an integer from 0 to 3, and [B] - it is an anion of non-coordination.
    2. Method for the production of a copolymer, according to claim 1, characterized in that at least one of R a to R c is a hydrogen atom and at least one of R d to R f is a hydrogen atom.
    [3]
    Method for the production of a copolymer according to claim 1, characterized in that the polymerization of the conjugated diene compound and the unconjugated olefin, other than the conjugated diene compound, is an addition polymerization.
    [4]
    Method for the production of a copolymer according to claim 1, characterized in that the unconjugated olefin, unlike the conjugated diene compound, is an acyclic olefin.
    [5]
    5. Method for the production of a copolymer according to claim 1, characterized by olefin
    Petition 870190031898, of 03/03/2019, p. 7/10
    3/3 unconjugated, unlike the conjugated diene compound, is an α-olefin that has a carbon number from 2 to 10.
    [6]
    Method for the production of a copolymer according to any one of claims 4 and 5, characterized in that the unconjugated olefin, different from the conjugated diene compound, is at least one of ethylene and propylene.
    [7]
    Method for the production of a copolymer according to claim 1, characterized in that the conjugated diene compound has a carbon number of 4 to 8.
    [8]
    Method for the production of a copolymer according to claim 7, characterized in that the conjugated diene compound is at least one of 1,3-butadiene and isoprene.
    [9]
    Method for the production of a copolymer according to claim 1, characterized in that the conjugated diene compound is polymerized with the unconjugated olefin, wherein the pressure of the unconjugated olefin is from 0.1 MPa to 10 MPa.
    [10]
    10. Method for the production of a copolymer according to claim 1, characterized in that the conjugated diene compound is polymerized with the unconjugated olefin, in which the concentration of the conjugated diene compound (mol / l) and the concentration of the olefin are not -conjugate (mol / l) at the beginning of the polymerization satisfies a relationship of the following equation:
    concentration of unconjugated olefin / concentration of conjugated diene compound> 1.0.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012002746B1|2019-06-11|METHOD FOR COPOLYMER PRODUCTION
    RU2663660C2|2018-08-08|Method for producing multicomponent copolymer
    BR112013002290B1|2020-02-04|method for controlling copolymer chain structure
    JP5083870B2|2012-11-28|Method for producing copolymer
    RU2537385C2|2015-01-10|Copolymer, rubber composition, cross-linked rubber composition and tyre
    RU2528410C1|2014-09-20|Copolymer, rubber composition, cross-linked rubber composition and tyre
    WO2012014455A1|2012-02-02|Copolymer of conjugated diene compounds and non-conjugated olefins, rubber composition, cross-linked rubber composition, and tyre
    JP5909121B2|2016-04-26|Rubber composition for tire
    BR112013019681B1|2020-03-24|COPOLYMER OF CONJUGATED DIENOUS AND UNCONJUGATED OLEFINE, RUBBER COMPOSITION, RUBBER COMPOSITION FOR TIRE Tread, Reticulated and TIRE RUBBER COMPOSITION
    CN108137766B|2020-09-04|Multipolymer, rubber composition, crosslinked rubber composition and rubber product
    JP5902587B2|2016-04-13|Method for producing copolymer
    JP2013155257A|2013-08-15|Rubber composition and tire
    CN108137758B|2020-10-23|Multipolymer, rubber composition, crosslinked rubber composition and rubber product
    JP5823674B2|2015-11-25|Copolymer of conjugated diene compound and non-conjugated olefin
    JP2013155259A|2013-08-15|Rubber composition and tire
    JP2017101150A|2017-06-08|Manufacturing method of copolymer, copolymer, rubber composition and rubber product
    CN108137767B|2021-03-09|Multipolymer, rubber composition, crosslinked rubber composition and rubber product
    CN108350129B|2021-03-09|Multipolymer, rubber composition, crosslinked rubber composition and rubber product
    JP5557642B2|2014-07-23|Copolymer of conjugated diene compound and non-conjugated olefin
    JP5898975B2|2016-04-06|Method for controlling content ratio of monomer unit in copolymer
    JP5917808B2|2016-05-18|Copolymer, rubber composition, crosslinked rubber composition, and tire
    JP2013159637A|2013-08-19|Rubber composition and tire
    同族专利:
    公开号 | 公开日
    WO2011016210A1|2011-02-10|
    JP5702286B2|2015-04-15|
    CN102549024A|2012-07-04|
    KR20120052385A|2012-05-23|
    JP5918345B2|2016-05-18|
    US20140371408A1|2014-12-18|
    EP2463313A1|2012-06-13|
    BR112012002746A2|2018-03-13|
    RU2012108638A|2013-09-20|
    US9346907B2|2016-05-24|
    US8853339B2|2014-10-07|
    JP2015078380A|2015-04-23|
    JPWO2011016210A1|2013-01-10|
    EP2463313B1|2015-04-15|
    US20120196993A1|2012-08-02|
    EP2463313A4|2014-03-12|
    RU2500691C2|2013-12-10|
    CN102549024B|2015-04-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5066741A|1990-03-22|1991-11-19|The Dow Chemical Company|Process for preparation of syndiotactic vinyl aromatic polymers|
    BE1006438A3|1992-12-17|1994-08-30|Solvay|Catalyst system, use of this system catalyst for the polymerization of olefins, method of preparation of this system and method for catalyst polymerization of olefins.|
    FR2799468B1|1999-10-12|2006-04-28|Michelin Soc Tech|CATALYTIC SYSTEM USABLE FOR THE COPOLYMERIZATION OF ETHYLENE AND A CONJUGATE DIENE, PROCESS FOR THE PREPARATION OF THIS CATALYTIC SYSTEM AND OF A COPOLYMER OF ETHYLENE AND A CONJUGATE DIENE|
    EP1101777A1|1999-11-22|2001-05-23|UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION |Mixed metal catalysts|
    DE10022497A1|2000-05-09|2001-11-15|Bayer Ag|Copolymerization of conjugated dienes with nonconjugated olefins in the presence of a catalyst comprising a rare earth metal allyl compound|
    EP1367069A1|2002-05-28|2003-12-03|Dow Global Technologies Inc.|Process for homo-or copolymerization of conjugated diens|
    CN100523023C|2002-10-16|2009-08-05|米其林技术公司|Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof|
    EP1764375B1|2004-07-02|2015-03-04|Riken|Polymerization catalyst compositions containing metallocene complexes and polymerisation processes using them|
    JP5035864B2|2005-09-02|2012-09-26|独立行政法人理化学研究所|Metallocene complex and polymerization catalyst composition containing the same|
    MX2008011531A|2006-03-15|2008-09-18|Basf Se|Quinoline derivatives and their use as pesticides.|
    US8653290B2|2006-05-09|2014-02-18|Riken|Metallocene complex and polymerization catalyst composition containing the same|
    JP5083870B2|2007-05-08|2012-11-28|株式会社ブリヂストン|Method for producing copolymer|
    JP2008291096A|2007-05-23|2008-12-04|Bridgestone Corp|Polybutadiene, and rubber composition and tire using the same|
    US8507627B2|2008-06-04|2013-08-13|Bridgestone Corporation|Aromatic vinyl compound-conjugated diene compound copolymer and method of producing the same as well as rubber composition and tire|
    US8853339B2|2009-08-07|2014-10-07|Bridgestone Corporation|Method for producing copolymer|
    WO2012014463A1|2010-07-30|2012-02-02|株式会社ブリヂストン|Copolymer of conjugated diene compounds and non-conjugated olefins, rubber composition, and tyre|US8853339B2|2009-08-07|2014-10-07|Bridgestone Corporation|Method for producing copolymer|
    RU2528410C1|2010-07-30|2014-09-20|Бриджстоун Корпорейшн|Copolymer, rubber composition, cross-linked rubber composition and tyre|
    JP5775872B2|2010-07-30|2015-09-09|株式会社ブリヂストン|Method for controlling the chain structure of a copolymer|
    US9056936B2|2010-07-30|2015-06-16|Bridgestone Corporation|Copolymer of a conjugated diene compound and a non-conjugated olefin, rubber composition, crosslinked rubber composition, and tire|
    JP5557710B2|2010-11-30|2014-07-23|株式会社ブリヂストン|Copolymer|
    JP5731217B2|2011-02-04|2015-06-10|株式会社ブリヂストン|Copolymer, rubber composition, crosslinked rubber composition, and tire|
    BR112013019682A2|2011-02-04|2016-10-11|Bridgestone Corp|copolymer, rubber composition, tire side rubber composition, cross-linked rubber composition and tire|
    JP5917810B2|2011-02-04|2016-05-18|株式会社ブリヂストン|Copolymer of conjugated diene compound and non-conjugated olefin, rubber composition, crosslinked rubber composition, and tire|
    WO2012105258A1|2011-02-04|2012-08-09|株式会社ブリヂストン|Copolymer of conjugated diene compound and non-conjugated olefin, rubber composition, rubber composition for tire tread use, crosslinked rubber composition, and tire|
    JP5675434B2|2011-02-28|2015-02-25|株式会社ブリヂストン|Rubber composition, crosslinked rubber composition, and tire|
    JP5639506B2|2011-02-28|2014-12-10|株式会社ブリヂストン|Rubber composition, crosslinked rubber composition, and tire|
    JP5917813B2|2011-03-01|2016-05-18|株式会社ブリヂストン|Rubber composition, tire tread rubber composition, crosslinked rubber composition, and tire|
    WO2012121216A1|2011-03-05|2012-09-13|株式会社ブリヂストン|Elastomer composition|
    EP2716670B1|2011-06-02|2017-01-18|Bridgestone Corporation|Copolymer, rubber composition, crosslinked rubber composition, and tire|
    JP5735886B2|2011-08-08|2015-06-17|株式会社ブリヂストン|Rubber composition for rubber bearing coating and rubber for rubber bearing coating using the same|
    JP5769563B2|2011-09-20|2015-08-26|株式会社ブリヂストン|Rubber crawler composition and rubber crawler using the same|
    JP5769577B2|2011-10-04|2015-08-26|株式会社ブリヂストン|Rubber composition for crawler and rubber crawler using the same|
    JP5735897B2|2011-10-11|2015-06-17|株式会社ブリヂストン|Anti-vibration rubber composition, crosslinked anti-vibration rubber composition and anti-vibration rubber|
    JP5917886B2|2011-11-04|2016-05-18|株式会社ブリヂストン|Conjugated diene polymers|
    JP5840481B2|2011-12-26|2016-01-06|株式会社ブリヂストン|Pneumatic tire|
    BR112014015983B1|2011-12-27|2021-01-12|Bridgestone Corporation|process for preparing a polydiene|
    JP5973736B2|2012-01-26|2016-08-23|株式会社ブリヂストン|Rubber composition for tire, crosslinked rubber composition for tire, and tire|
    JP5973735B2|2012-01-26|2016-08-23|株式会社ブリヂストン|Rubber composition for tire and tire comprising the rubber composition for tire|
    JP5973737B2|2012-01-26|2016-08-23|株式会社ブリヂストン|Rubber composition for tire, crosslinked rubber composition for tire, and tire|
    JP5898975B2|2012-01-27|2016-04-06|株式会社ブリヂストン|Method for controlling content ratio of monomer unit in copolymer|
    JP5898978B2|2012-01-30|2016-04-06|株式会社ブリヂストン|Rubber composition for air spring and air spring using the same|
    WO2014055868A1|2012-10-04|2014-04-10|Bridgestone Corporation|Organometallic complex catalyst and polymerization method employing same|
    EP3148937B1|2014-05-30|2019-09-18|Bridgestone Corporation|Metallic complex catalyst and polymerization methods employing same|
    RU2690373C2|2014-05-31|2019-06-03|Бриджстоун Корпорейшн|Metal complex catalyst, polymerisation methods using same and obtained polymer products|
    RU2663660C2|2014-06-12|2018-08-08|Бриджстоун Корпорейшн|Method for producing multicomponent copolymer|
    EP3344667B1|2015-08-31|2020-12-30|Bridgestone Corporation|Copolymerization of polyenes and alkenes|
    JPWO2017203830A1|2016-05-24|2019-03-22|株式会社ブリヂストン|Terminal-modified conjugated diene polymer, rubber composition, rubber product, and method for producing terminal-modified conjugated diene polymer|
    CN112250783B|2020-10-23|2021-11-05|中国科学院长春应用化学研究所|Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-05| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-04-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-06-11| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2009184643|2009-08-07|
    JP2009-184643|2009-08-07|
    PCT/JP2010/004847|WO2011016210A1|2009-08-07|2010-07-30|Method for producing copolymer|
    [返回顶部]