method for producing a hydrogenated conjugated diene polymer, hydrogenated conjugated diene polymer,

专利摘要:
METHOD TO PRODUCE A HYDROGENATED CONJUNGED DIENO POLYMER, HYDROGENATED CONJUGATED DIENE POLYMER, AND, POLYMERIC COMPOSITION [Problem] Provide a method to produce a hydrogenated conjugated diene polymer that allows for the improvement in the dispersibility of a filler in the filler polymer combination , also makes it possible to reduce the hysteresis loss of a combined polymer product, and also enables the formation of a polymeric alloy that has excellent processability in combination with a thermoplastic resin or the like and of which a combined product can have excellent properties. [Solution] A method for producing a hydrogenated conjugated diene polymer, comprising the steps of: polymerizing a conjugated diene compound in the presence of a polymerization initiator comprising an amine compound having a structure represented by the formula (x) and / or a structure represented by the formula (y) and a metallic compound such as an alkali metal compound, thereby producing a conjugated diene polymer; and hydrogenating the conjugated diene polymer. [In formulas (x) and (y), R1 represents a hydrocarbilene group, where the hydrocarbilene group in R1 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom; (...).
公开号:BR112015019419B1
申请号:R112015019419-2
申请日:2014-02-14
公开日:2020-12-22
发明作者:Naoya Nosaka；Masahiro Shibata；Nobuyuki Toyoda；Shigeru Abe；Jirou Ueda
申请人:Jsr Corporation；
IPC主号:

专利说明:

Technical Field
[001] The present invention relates to a method for producing a hydrogenated conjugated diene polymer. More specifically, it relates to a method for producing a hydrogenated conjugated diene polymer using a modified polymerization initiator, a hydrogenated conjugated diene polymer obtained by the production method, and a polymeric composition containing the polymer. Fundamentals of Technique
[002] A hydrogenated block copolymer which is a product of the hydrogenation of a block copolymer formed from a conjugated diene compound and an aromatic vinyl compound has a relatively high compatibility with non-polar resins such as polyolefin resins and polystyrene and non-polar rubbers such as ethylene-propylene rubbers. Therefore, several compositions containing the hydrogenated block copolymer have been produced and widely used.
[003] Since the hydrogenated block copolymer has low compatibility with polar resins such as polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) copolymers, and nylon, it is necessary to communicate a polar group to the block copolymer hydrogenated to ensure durable physical properties in use. For example, Patent Document 1 shows a hydrogenated conjugated diene block copolymer modified with an amino group.
[004] However, the hydrogenated conjugated diene block copolymer modified with a conventional amino group involves problems of poor processability in combination with a thermoplastic resin or the similar and poor physical properties of a polymeric alloy after the combination.
[005] Furthermore, for example, Patent Document 2 proposes a modified diene-based polymer rubber obtained from step 1 of polymerizing a conjugated diene polymer or a conjugated diene polymer and an aromatic vinyl monomer in one hydrocarbon solvent in the presence of an alkali metal catalyst to obtain an active polymer having an alkali metal end and a step 2 of reacting the active polymer with a compound represented by a specific formula to obtain a modified polymeric rubber.
[006] In addition, for example, Patent Document 3 also proposes a method for producing a modified polymer that enhances interactions with silica and carbon black and that can improve rupture characteristics, abrasion resistance, and low properties heat generation.
[007] However, the above method for modifying the active polymerization end of the active polymer with a modifier involves a problem that there is a limitation in the case where the amount of modification is intended to increase since a modifier is reacted by a molecule of the polymer. Related Art Documents Patent Document Patent Document 1: JP-A-2005-298797 Patent Document 2: JP-A-2005-290355 Patent Document 3: WO2003 / 048216 pamphlet Summary of the Invention Problems to be solved by the invention
[008] An objective of the invention is to provide a method to produce a hydrogenated conjugated diene polymer that is excellent at improving dispersibility at the time of combination with a filler, is excellent at reducing hysteresis loss after the combination, and enables formation of a polymeric alloy that has excellent processability at the time of combination with a thermoplastic resin or the like and has excellent physical properties after the combination. In addition, another object of the invention is to provide a hydrogenated conjugated diene polymer obtained by the above production method, a polymeric composition containing the polymer, and a molded body composed of the polymeric composition. Means to Solve Problems
[009] In order to solve the problem mentioned above, the present inventors carried out intensive studies. As a result, they found that it is possible to solve the above problem by a production method having the following features, and thus they have accomplished the present invention. That is, the present invention relates, for example, to the following [1] to [7].
[0010] [1] A method for producing a hydrogenated conjugated diene polymer, the method comprising a step of polymerizing at least one conjugated diene compound in the presence of an amine compound polymerization initiator having at least one structure of the formulas (x) and (y) and at least one metallic compound selected from alkali metal compounds and alkaline earth metal compounds to obtain a conjugated diene polymer and a step of hydrogenating the conjugated diene polymer. [Chemical Substance 1]
where, in formula (x), R1 is a hydrocarbilene group, the hydrocarbilene group in R1 may contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A1 is a trihydrocarbylsilyl group; in formula (y), R2 and R3 are each independently a hydrocarbilene group, the hydrocarbilene group in each of R2 and R3 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A2 is a functional group which has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S, has a trihydrocarbylsilyl group, and does not have an active hydrogen atom and the atom that is attached to R3 is N, P or S; and the above R1 and A1 can be linked together to form a cyclic structure and a part of the R2, R3, and A2 above can be linked together to form a cyclic structure.
[0011] [2] The method for producing a hydrogenated conjugated diene polymer according to claim 1, wherein the amine compound having a structure represented by the formula (x) is at least one compound selected from a compound represented by the formula (x1) and a compound represented by the formula (x2): [Chemical Substance 2]
wherein, in formulas (x1) and (x2), R1bs u «q ecfc wo independently a hydrocarbilene group, and the hydrocarbilene group in R11 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom; the A ^ su «q ecfc wo kpfgrgpfgpVgogpVg a trihydrocarbylsilyl group; a plurality of R1bs and Abs rqfg ugt ecfc wo q the same or different; and the above R11 and A1 can be linked together to form a cyclic structure.
[0012] [3] The method for producing a hydrogenated conjugated diene polymer according to claim 1, wherein the amine compound having a structure represented by the formula (y) is at least one compound selected from a compound represented by the formula (y1) and a compound represented by the formula (y2): [Chemical Substance 3]
wherein, in formulas (y1) and (y2), the R2 ^ ug T3óu u «q ecfc wo independently a hydrocarbilene group, and the hydrocarbilene group in each of R21 and R3 may contain a heteroatom as long as the hydrocarbilene group has no an active hydrogen atom; A2 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S, has a trihydrocarbylsilyl group, and does not have an active hydrogen and in which the atom which is linked to R3 is N, P or S; a plurality of R2 ^ u. T3óu. and A2, u rqfg ugt ecfc the same or different; and a part of the above R21, R3, and A2 can be linked together to form a cyclic structure.
[0013] [4] A hydrogenated conjugated diene polymer obtained by the method for production according to any one of claims 1 to 3.
[0014] [5] A hydrogenated conjugated diene polymer having at least one structure of formulas (X) and (Y) at the end of the polymer: [Chemical Substance 4]
where, in formula (X), R1 is a hydrocarbilene group, and the hydrocarbilene group in R1 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A3 is a hydrogen atom or a triple group hydrocarbylsilyl; in formula (Y), R2 and R3 are each independently a hydrocarbilene group, the hydrocarbilene group in each of R2 and R3 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A4 is a functional group which has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S and where all or a part of the atoms can be protected with a trihydrocarbylsilyl group and the atom that is attached R3 is N, P or S; and the above R1 and A3 can be linked together to form a cyclic structure and a part of the above R2, R3, and A4 can be linked together to form a cyclic structure.
[0015] [6] A polymeric composition comprising the hydrogenated conjugated diene polymer according to claims 4 or 5 and at least one selected from carbon black and silica.
[0016] [7] A polymeric composition comprising the hydrogenated conjugated diene polymer according to claims 4 or 5 and at least one polymer selected from a non-polar polymer and a polar polymer. Effects of the invention
[0017] According to the invention, it is possible to provide a hydrogenated conjugated diene polymer which is excellent at improving dispersibility at the time of combination with a filler, is excellent at reducing the loss of hysteresis after the combination, and allows the formation of a polymeric alloy that has excellent processability at the time of combination with a thermoplastic resin or the like and has excellent physical properties after the combination.
[0018] For example, a crosslinked body formed from a polymeric composition containing the hydrogenated conjugated diene polymer is excellent in low hysteresis loss properties (70flQanf), wet slip resistance (0flCtanf), and abrasion resistance and so on. it can result in excellent low fuel consumption performance in the case where the body is used as a material for a car tire (especially tread) or the like. Modalities for Carrying Out the Invention
[0019] The following will describe the terms used in the invention.
[0020] In the present Description, a compound represented by the formula (i) (i is a formula number) Vcodfio fi cnwfkfq eqoq "eqopquVq * k +". woc wpkfcfg eqpuVkVwkntg fgtkxcfc fg wo eqorquVq * z + pq pqlímgrq Vcodfio fi clwfkfc eqoq woc “wpkfcfg fg eqopquVq z”. c rgc> «q fg jkfrqigpc>« q Vcodfio fi clwfkfc eqoq woc "rgc>" q fg jkfrqigpc> "q". w the hydroggpc catalyst> «q Vcodfio fi clwfkfq eqoq wo“ ecVclkucfqr fg jkfrqigpc> «q”. wo pqlíogrq fg fkgpq eqpjwicfq fgpqku fc jkfrqigpc> «q Vcodfio fi clwfkfq eqoq wo“ rqlíogrq fg fkgpq eqplwicfq jkfrqigpcfq ”. g Woc Vczc fg jkfrqigpc> «q Vcodfio fi clwfkfc eqoq woc“ Vczc fg hydrogen> «q”
[0021] Wo “Vgqt fg nkic>« q fg xkpüc ”fi woc taz« q VqVcn * go Vgtoqu of mol%) of the units incorporated by connection 1,2 and connection 3,4 between the units of the incorporated conjugated diene compound in connection ways of connection 1,2, connection 3,4, and connection 1,4. The vinyl bond content, the bond content 1,2, and the bond content 3,4 can be determined by an infrared absorption spectrum method (Morello method).
[0022] Q "jkftqiêpkq cVkxq" ug tgfetg cq áVqoq fg jkftqiêpkq nkicfq is an atom other than a carbon atom.
[0023] C “rqnkogtkzc>« q ”fi wucfc pq ugpVkfq fg kpenwkt homopolymerization and copolymerization.
[0024] The following will describe modalities for carrying out the invention including preferable modalities. [Method for Producing Hydrogenated Conjugated Diene Polymer]
[0025] The method for producing a hydrogenated conjugated diene polymer of the invention comprises: (1) a step of polymerizing at least one conjugated diene compound in the presence of a polymerization initiator compound (hereinafter also cnwfkfq eqoq “kpkekcfqt fg rqnkogtkzc > «Q oqfkhkecfq” + fg w the amine compound having at least one structure of the formulas (x) and (y) and at least one metal compound selected from alkali metal compounds and alkaline earth metal compounds to obtain a diene polymer conjugate and (2) a step of hydrogenating the conjugated diene polymer. [Step (1)] (Step of Producing Conjugated Diene Polymer Before Hydrogenation)
[0026] A modality of step (1) contains a step (1a) of carrying out a polymerization reaction. According to the need, it contains one or two or more steps selected from a step (1b) of carrying out a coupling reaction on the conjugated diene polymer having an active point obtained in the polymerization reaction or the like, a step (1c ) to react the conjugated diene polymer having an active point obtained in the polymerization reaction or the like with a modifier capable of reacting with the active point to further modify the polymer, and a step (1d) of carrying out a termination reaction polymerization in the conjugated diene polymer having an active point obtained in the polymerization reaction, in the coupling reaction, or in the modification reaction. << Step (1a) >> (Polymerization reaction)
[0027] In step (1a), a monomer such as a conjugated diene compound is polymerized in the presence of the modified polymerization initiator to obtain a conjugated diene polymer. As a mode of polymerization, it is preferable to adopt anionic polymerization (live anionic polymerization).
[0028] The "wo oqp" ogtq fi rqnkogtkzcfq pc rtgugp> c fq kpkekcfqt fg rqnkogtkzc> "q oqfkfiecfq" kpenwk woc method of feeding the amine compound and the metallic compound to a reaction vessel individually or feeding of the amine compound and the metallic compound to a reaction vessel and polymerize a monomer in the reaction vessel.
[0029] As the polymerization method, it is possible to use either a solution polymerization method, a batch polymerization method, and a gas phase polymerization method. Of these, the solution polymerization method is preferable. Like the polymerization mode, it is possible to use either batch or continuous.
[0030] The temperature of the liquid phase of the polymerization reaction in the solution polymerization method is preferably from -20 to 150 ° C, more preferably from 0 to 120 ° C, and particularly preferably from 20 to 100 ° C. The polymerization reaction is preferably carried out under a pressure sufficient to maintain the monomer substantially as a liquid phase. Such pressure can be obtained by a method of pressurizing the inside of the reaction vessel with a gas (example: nitrogen gas) inert to the polymerization reaction or the like.
[0031] Examples of specific polymerization methods when using the solution polymerization method include an anionic polymerization method of a monomer such as a conjugated diene compound in the presence of a polymerization initiator and a vinyl content regulator which is used as required, in a solvent composed of an inert organic solvent for the polymerization reaction.
[0032] In the case of using the solution polymerization method, the concentration of monomer in the solution is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass from the point of view of maintaining the balance between the productivity and ease of polymerization control.
[0033] The conjugated diene polymer obtained by the polymerization reaction can be a homopolymer compound of a conjugated diene compound, it can be a random copolymer compound of a conjugated diene compound and another monomer such as an aromatic vinyl compound, or it may be a block copolymer composed of conjugated diene compounds or a conjugated diene compound and another monomer such as an aromatic vinyl compound.
[0034] The conjugated diene block copolymer can be obtained by the block polymerization of conjugated diene compounds or block copolymerization of a conjugated diene compound and another monomer such as an aromatic vinyl compound. From the point of view of the physical properties and moldability of the polymeric composition to be mentioned later, the conjugated diene block copolymer is preferably a block copolymer containing two or more polymeric blocks selected from the following polymeric blocks (A) to (D). (A) A polymeric vinyl aromatic block in which the unit quantity of the vinyl aromatic compound is 80% by weight or more. (B) A polymeric conjugated diene block in which the unit amount of the conjugated diene compound is 80% by weight or more and the vinyl bond content is less than 30 mol%. (C) A polymeric block of conjugated diene in which the unit amount of the conjugated diene compound is 80% by weight or more and the vinyl bond content is 30 to 90 mol%. (D) A random copolymeric block of the conjugated diene compound and the aromatic vinyl compound in which the unit quantity of the conjugated diene compound is greater than 20% by weight and less than 80% by weight.
[0035] When the polymeric block is a copolymeric block formed of two or more compounds, it can be a random type or a so-called tapered type in which the content of the conjugated diene compound unit or the aromatic vinyl compound unit continuously changes in the polymeric block, depending on the purpose of the polymeric composition.
[0036] Examples of the “block copolymer containing two or more dnqequ rqnkofitkequ ugngekqpcfqu fqu ugiwkpVgu dnqequ rqnkofitkequ * C + c * F +” include (A) - (B), (A) - (C), (A) - (D ), (B) - (C), (B) - (D), [(A) - (B)] xY, [(A) - (C)] xY, [(A) - (D)] xY , [(B) - (C)] xY, [(B) - (D)] xY, [(B) - (A)] xY, [(C) - (A)] x- Y, [(D ) - (A)] xY, (A) - (B) - (D), (A) - (B) - (A), (A) - (C) - (A), (A) - (C ) - (B), (A) - (D) - (A), (A) - (D) - (B), (B) - (A) - (B), [(A) - (B) - (D)] xY, [(A) - (B) - (A)] xY, [(A) - (C) - (A)] xY, [(A) - (C) - (B)] xY, [(A) - (D) - (A)] xY, [(B) - (A) - (B)] xY, (A) - (B) - (A) - (B), (B ) - (A) - (B) - (A), [(A) - (B) - (A) - (B)] xY, (A) - (B) - (A) - (B) - ( A), [(A) - (B) - (A) - (B) - (A)] xY, (B) - (A) - (B) - (D), (B) - (A) - (B) - (A), (B) - (A) - (C) - (A), (B) - (A) - (C) - (B), (B) - (A) - (D ) - (A), [(C) - (A) - (B) - (D)] xY, [(C) - (A) - (B) - (A)] xY, [(C) - ( A) - (C) - (A)] xY, [(C) - (A) - (C) - (B)] xY, [(C) - (A) - (D) - (A)] xY , (C) - (A) - (B) - (A) - (B), (C) - (B) - (A) - (B) - (A), (C) - (A) - ( B) - (A) - (C), [(C) - (A) - (B) - (A) - (B)] xY, (C) - (A) - (B) - (A) - (B) - (A), [(C) - (A) - (B) - (A) - (B) - (A)] xY, and the like (and m that. z> 4. and Y is a residual group of a binding agent). Here, the copolymers obtained in the coupling reaction to be mentioned later are also exemplified. When the block copolymer is formed in a granular form, the block polymer preferably contains at least one polymer block (A) and / or at least one polymer block (B) as an external block component of the conjugated diene block copolymer. .
[0037] The following will describe each component to be used in the polymerization reaction. <Modified Polymerization Initiator>
[0038] In the invention, a modified polymerization initiator compound of an amine compound having at least one structure of the formulas (x) and (y) and at least one metal compound selected from the alkali metal compounds and alkaline earth metal compounds. The modified polymerization initiator can, for example, be obtained by reacting the amine compound with the metallic compound.
[0039] Using the modified polymerization initiator, a modification group derived from the amine compound can be introduced at the polymerization initiation end of the conjugated diene polymer. In this way, an N atom that becomes an interaction point to increase the dispersibility of various fillers or a reaction point to function as a compatibilizer with various polymers is introduced at the polymerization start end. In one embodiment, it is possible to convert the N atom into an active amino group through deprotection by hydrolysis, depending on the objective physical properties. [Chemical Substance 5]
wherein, in formula (x), R1 is a hydrocarbilene group, and the hydrocarbilene group in R1 may contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A1 is a trihydrocarbylsilyl group; in formula (y), R2 and R3 are each independently a hydrocarbilene group, the hydrocarbilene group in each of R2 and R3 may contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom; and A2 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S, has a trihydrocarbylsilyl group, and does not have an active hydrogen atom and that the atom that is attached to R3 is N, P or S.
[0040] The R1 and A1 above can be linked together to form a cyclic structure. That is, an atom in R1 and an atom in A1 can be linked to form a cyclic structure. A part of R2, R3, and A2 above can be linked together to form a cyclic structure. That is, an atom in R2 and an atom in R3 can be linked to form a cyclic structure, an atom in R2 and an atom in A2 can be linked to form a cyclic structure, or an atom in R3 and an atom in A2 can be linked to form a cyclic structure.
[0041] Examples of the hydrocarbilene group include a methylene group, an alkylene group, an arylene group, and an aralkylene group. The hydrocarbilene group usually has 1 to 10 carbon atoms, and preferably 1 to 3.
[0042] In the present Description, the hydrocarbilene group having no active hydrogen and containing a heteroatom is a group in which one or two or more atoms or groups contained in the hydrocarbilene group are replaced with the heteroatom and which does not have an active hydrogen. However, it is preferable that the carbon atom attached to the nitrogen atom described in formulas (x) and (y) or the carbon atom attached to the N, P, or S terminal in A2 is not replaced with the hetero atom.
[0043] Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and a halogen atom. However, a nitrogen atom attached to -A1 or -R3- A2 is excluded. A1, R3, and A2 in the formulas above have the same meanings as those of the same symbols in formulas (x) and (y), respectively. Examples of substituents containing a nitrogen atom include imino groups and amino groups (-NR-, -NR2 * OR "u« q "ecfc" wo independently a hydrocarbon group)).
[0044] The trihydrocarbilsilila group means a group represented by -SiR3 * go "swg" TÓu "u« q "ecfc" wo "kpfgrgpfgpvgogpvg" wo "itwrq" fg "hydrocarbon). Examples of the hydrocarbyl group, i.e., a hydrocarbon group, of the trihydrocarbylsilyl group include alkyl groups, aryl groups, and aralkyl groups. The hydrocarbyl group usually has 1 to 10 carbon atoms, and preferably 1 to 4. The trihydrocarbylsilyl group is preferably a trialkylsilyl group, and particularly preferably a trimethylsilyl group or a t-butyldimethylsilyl group.
[0045] The trihydrocarbylsilyl group at A2 is preferably attached to at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S. A2 is preferably a group represented by -XRn * go "swg" Z "fi" P0 "R." qw "U =" TÓu "u« q "independently of a trihydrocarbylsilyl group; n is 2 when X is N, is 2 when X is P, and is 1 when X is S).
[0046] Examples of the amine compound having a structure represented by formula (x) include at least one compound selected from a compound represented by formula (x1) and a compound represented by formula (x2) and specifically include compounds represented by formula (x) x1-1), the formula (x1-2), and the formula (x2-1). [Chemical Substance 6]
in which, in formulas (x1) and (x2), Rπ's are each independently a hydrocarbilene group, and the hydrocarbilene group in R11 may contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, it is preferably a methylene group or an alkylene group having from 2 to 10 carbon atoms, and is more preferably a methylene group or an ethylene group; the A1's u'q ecfc wo independently a trihydrocarbylsilyl group, preferably a trialkylsilyl group, and more preferably a trimethylsilyl group or a t-butyldimethylsilyl group; and a plurality of R11's and A1's rqfgo sgt ecfc wo q the same or different.
[0047] The R11 and A1 above can be linked together to form a cyclic structure. That is, an atom in R11 and an atom in A1 can be linked to form a cyclic structure. [Chemical Substance 7]

[0048] Examples of the amine compound having a structure represented by the formula (y) are at least one compound selected from a compound represented by the formula (y1) and a compound represented by the formula (y2) and specifically include compounds represented by the formula ( y1-1), the formula (y1-2), and the formula (y2-1). [Chemical Substance 8]
where, in formulas (y1) and (y2), R2 ^ ug T ^ uu «q ecfc wo independently a hydrocarbilene group, and the hydrocarbilene group in each of R21 and R3 may contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, is preferably a methylene group or an alkylene group having from 2 to 10 carbon atoms, and is more preferably a methylene group or an ethylene group; A2 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S, has a trihydrocarbylsilyl group, and does not have an active hydrogen and in which the atom that is connected to R3 is N, P or S.
[0049] A2 is preferably a group represented by -XRn (where Z "fi" P0 "R." qw "U =" TÓu "u« q "ecfc" wo "kpfgrgpfgpvgogpvg" wo "itwrq" trihydrocarbilsilila; n is 2 when X is N, is 2 when X is P, and is 1 when X is S).
[0050] A plurality of R ^ s, T3óu. and A2, u rqfgo ugt ecfc wo same or different.
[0051] In addition, a part of the R21, R3, and A2 above can be linked together to form a cyclic structure. That is, an atom in R21 and an atom in R3 can be linked to form a cyclic structure, an atom in R21 and an atom in A2 can be linked to form a cyclic structure, or an atom in R3 and an atom in A2 can be linked to form a cyclic structure. [Chemical Substance 9]

[0052] The modified polymerization initiator can be prepared by adding the above amine compound and the above metallic compound to the polymerization system (in situ). Alternatively, the modified polymerization initiator can be added to the polymerization system after being prepared from the above amine compound and the above metallic compound beforehand.
[0053] For example, the modified polymerization initiator can be obtained by feeding the above amine compound and the above metallic compound in a polymerization solution containing a monomer, a solvent, and the like and mixing and reacting these two compounds. Alternatively, the modified polymerization initiator can also be obtained by mixing and reacting the above amine compound and the above metal compound beforehand before feeding into the polymerization solution.
[0054] Examples of the alkali metal in the alkali metal compound include lithium, sodium and potassium. Examples of the alkaline earth metal in the alkaline earth metal compound include calcium and magnesium.
[0055] Of these, the alkali metal compound is preferable and lithium is particularly preferable as the alkali metal. In the present Description, hereinafter, explanation is conducted using lithium as an example, but a modality in which another alkali metal or an alkaline earth metal is used instead of lithium is also possible.
[0056] The alkali metal compound is preferably an alkylithium and examples thereof include alkylates having 1 to 4 carbon atoms. Examples of alkyls having 1 to 4 carbon atoms include methyl lithium, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyllith, and sec-butyl lithium.
[0057] The amount of the amine compound to be used is preferably 0.2 to 20 mmoles, more preferably 0.3 to 10 mmoles, and more preferably 0.5 to 3 mmoles per 100 g of the monomer. In the case where a reaction product of the above amine compound and the above metallic compound is added to the polymerization system, the amount is the amount of the amine compound used to form the reaction product. In the case of block polymerization, the amount of the amine compound to be used is an amount per 100 g of the monomers as a whole.
[0058] The amount of the metallic compound to be used is preferably 10 to 1 mol, more preferably 5 to 1 mol, and more preferably 2 to 1 mol based on 1 mol of the active hydrogen in the nitrogen atom of the compound of the mine. <Conjugated diene compound>
[0059] Examples of the conjugated diene compound (conjugated diene monomer) to be used in the invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1, 3-hexadiene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. Of these, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene are preferable.
[0060] The conjugated diene compounds can be used alone or two or more of them can be used in combination. <Other Monomers>
[0061] In the invention, a monomer (hereinafter also referred to as "qwVtq oqp» ogtq "+ qwVtq swg p" qq eqorquVq of conjugated diene can be used as a monomer and an aromatic vinyl compound (aromatic vinyl monomer) may preferably be used.
[0062] Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-ogvknguvktgpq. g-methylstyrene, 2,4-dimethyl-styrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzildren dimethylaminoethyl ether (4-vinylbenzyl), N, N-dimethylaminoethylstyrene, N, N-dimethylaminomethylstyrene, 2-ethyl styrene, 3-ethyl styrene, 4-ethyl styrene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-t- butylstyrene, vinylxylene, vinylnaphthalene, vinyliltoluene, vinylpyridine, diphenylethylene, diphenylethylene containing tertiary amino group. Of these, styrene is preferable.
[0063] The vinyl aromatic compounds can be used alone or two or more of them can be used in combination.
[0064] In the case where copolymerization is carried out in combination of the conjugated diene compound and the aromatic vinyl compound, it is preferable to use 1,3-butadiene and styrene. These compounds are excellent in view of easy availability and high life-giving character in anionic polymerization.
[0065] In the case where copolymerization is carried out in combination of the conjugated diene compound and the aromatic vinyl compound, the weight ratio of the aromatic vinyl compound to the conjugated diene compound is preferably 0.5 / 99.5 to 55 / 45, and more preferably from 5/95 to 50/50 from the point of view of the balance between the low loss properties of hysteresis and wet slip resistance of the resulting crosslinked polymer.
[0066] As a monomer other than the vinyl aromatic compound, a monomer containing functional group can be mentioned. When the monomer containing functional group is polymerized to introduce a functional group into a copolymer, the functional group in the copolymer can be activated by the polymerization initiator. For example, it is also effective to lithium the functional group part of a copolymer containing an isobutylene unit, a p-methylstyrene unit, and a halogenated p-methylstyrene unit to form an active site. As the other monomer, for example, 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene can be mentioned. <Solvent>
[0067] As the solvent in the solution polymerization method, for example, an inert organic solvent for the polymerization, such as a hydrocarbon solvent, can be used. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents, and hydrocarbon solvents having 3 to 8 carbon atoms are preferable.
[0068] Examples of hydrocarbon solvents having 3 to 8 carbon atoms include propane, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, propene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and cyclohexene.
[0069] Solvents can be used alone or two or more of them can be used in combination. <Vinyl content regulator>
[0070] The vinyl content regulator (hereinafter also referred to as "tcpfqokzcfqt" + rode is used to regulate the vinyl bond content derived from the conjugated diene compound. For example, the microstructure of the conjugated diene block copolymer , that is, the 1,2 bond content and the 3,4 bond content can be controlled using the randomizer together with the hydrocarbon solvent.
[0071] As the randomizer, Lewis bases such as ethers and amines can be mentioned, and specifically ethers such as tetrahydrofuran, 1,4-dioxane, diethyl ether, propyl ether, butyl ether, higher ethers can be mentioned, 2 , 2-di (tetrahydrofuryl) propane, tetrahydrofurfuryl methyl ether, ethyl tetrahydrofurfuryl ether, bis (tetrahydrofurfuryl) formal, dimethoxybenzene, 2- (2-ethoxyethoxy) -2-methylpropane, and ether derivatives polyalkylene glycols such as ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol diethyl ether, and propylene glycol ethyl propyl ether; tertiary amines such as tetramethylethylenediamine, pyridine, triethylamine, tributylamine, and N-methylmorpholine.
[0072] Randomizers can be used alone or two or more of them can be used in combination. << Step (1b) >> (Coupling Reaction)
[0073] The production method of the invention may comprise a step (1b) of reacting the conjugated diene polymer having an active point such as an active lithium end with a linker capable of reacting with the active point. <Liaison officer>
[0074] In the case where the conjugated diene polymer has the active point such as the active lithium end, the Mooney viscosity of the conjugated diene polymer can be regulated and a branched structure can be introduced into the polymer, by the coupling reaction.
[0075] Examples of the coupling agent include N, N-bis (trimethylsilyl) aminopropyltrichlorosilane, N, N-bis (trimethylsilyl) aminopropyl-methyldichlorosilane, 1- (3-trichlorosilylpropyl) -2,2,5,5-tetramethyl- 1-aza-2,5-disylacyclopentane, and 1- (3-methyldichlorosilylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disylacyclopentane.
[0076] In addition, as the coupling agent, halogen compounds other than those above, epoxy compounds, carbonyl compounds, and polyvinyl compounds can also be mentioned. Specifically, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, epoxidized soybean oil, tetraglycidyl-1,3-bisaminomethylcyclohexane, divinylbenzene, tetrachloroethane, butyltrichloroethane, butyltrichloroethane, butyltrichloroethane dimethyl, dimethyl terephthalate, diethyl terephthalate, and polyisocyanates.
[0077] Coupling agents can be used alone or two or more of them can be used in combination.
[0078] The amount of the coupling agent to be used is usually 0.1 to 1.2 mol, and preferably 0.5 to 1.0 mol as a reaction point of the coupling agent based on 1 mol of the active point of the polymerization end.
[0079] The coupling reaction can be carried out, for example, as a reaction in solution. In the coupling reaction, the reaction temperature is usually 0 to 120 ° C, and preferably 50 to 100 ° C and the reaction time is usually 1 to 30 minutes, and preferably 5 to 20 minutes. << Step (1c) >> Modification Reaction
[0080] The production method of the invention can comprise a step (1c) of reacting the conjugated diene polymer having an active point such as an active lithium end with a modifier capable of reacting with the active point.
[0081] By the modification reaction, in addition to the introduction of a modifying group at the polymerization initiation end of the conjugated diene polymer by the action of the modified polymerization initiator, a modifying group is introduced further at the polymer end of the conjugated diene polymer for obtaining a modified conjugated diene polymer. In this way, an excellent hysteresis loss property can be imparted to a cross-linked body formed from a composition containing the polymer.
[0082] As the modifier, for example, a silane compound capable of reacting with the active point of the conjugated diene polymer can be mentioned and, from the point of view of reactivity with the conjugated diene polymer having the active point, a compound silane represented by formula (z) is preferable. [Chemical Substance 10]
wherein, in formula (z), R 3 is independently a hydrocarbyl group, and preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R33 is a hydrocarbilene group and preferably a methylene group, an alkylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. A plurality of R31óu g T32óu. rqfgo ugt ecfc wo same or different. n is an integer from 0 to 2 and, from the point of view of increasing the reactivity with the conjugated diene polymer having the active point, n is preferably 0 or 1.
[0083] A31 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S and does not have an active hydrogen and where the atom attached to R33 is N , P, or S. In A31, a part or all of at least one atom selected from N, P, and S can be protected with a trihydrocarbylsilyl group.
[0084] A31 is preferably a group represented by -XRn (where X is N, P or S = ALL u «q ecfc wo kpfgrgpfgpvgogpvg wo itwrq trihydrocarbylsilyl; n is 2 when X is N, is 2 when X is P , and is 1 when X is S.
[0085] Pq eqorquVq * z +. q "jkftqiêpkq cVkxq" ukinifies a hydrogen atom bonded to an atom other than a carbon atom and preferably means a hydrogen atom having a lower bonding energy than that of the polymethylene carbon-hydrogen bond.
[0086] In addition, as the silane compound capable of reacting with the active point such as the active lithium end or the like of the conjugated diene polymer, in addition to the group capable of reacting with the active point, a compound having a group capable of becoming an onyx by the action of an onyx-forming agent can also be used. When the compound has the group capable of becoming an onyx by the action of an onion-forming agent, an excellent shape retention property can be communicated to the polymer before crosslinking.
[0087] A31 in formula (z) is a group capable of becoming an onyx by the action of an onyx-forming agent. By reacting the conjugated diene polymer having the hotspot with such a silane compound (z), the hotspot is reacted with a Si-OR32 site to obtain a modified conjugated diene polymer having a group capable of becoming a onium.
[0088] Examples of the group capable of becoming an onyx by the action of an onion-forming agent include nitrogen-containing groups in which two hydrogen atoms of a primary amino group are replaced with two protective groups, groups containing nitrogen in which an atom hydrogen from a secondary amino group is replaced with a protecting group, tertiary amino groups, imino groups, pyridyl groups, phosphorus-containing groups in which two hydrogen atoms in a primary phosphine group are replaced with two protective groups, phosphorus-containing groups in which a hydrogen atom of a secondary phosphine group is replaced with a protective group, tertiary phosphine groups, and sulfur-containing groups in which a hydrogen atom in a thiol is replaced by one of the protective groups.
[0089] Examples of a compound having a nitrogen-containing group in which two hydrogen atoms from a primary amino group are replaced with two protective groups, a nitrogen-containing group in which a hydrogen atom from a secondary amino group is replaced with a protective group, or a tertiary amino group and an alkoxysilyl group include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N- dku * vtkogvknuknkn + cokpqrtqrknogvknfkgvqzkuukncpq. "P.PÓ.PÓ-tris (trimyl) amino-ethyl) -3-aminopropyltriethoxysilane, 1- (3-triethoxysilylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disylacyclopentane, 1-trimethylsilyl-2,2-dimethoxy-1-aza -2-silacyclo-pentane, N- [3- (trimethoxysilyl) -propyl] -P.PÓ-diethyl-PÓ-trimethylsilyl-ethane-1,2-diamine, N- [3- (methyldimethoxysilyl) -propyl] -P .PÓ-diethyl-PÓ-trimethylsilyl-p-phenylenediamine, 3- [3- (trimethylsilylethylamino) -1-pyrrolidinyl] - propyl-methyl-diethoxysilane, N- [3- (dietoxymethylsilil) -propyl] -N-ethyl-PÓ - (2-ethoxyethyl) -POW-trimethylsilyl-ethane- 1,2-diamine, 3- (4-trimethylsilyl-1-piperazine) - propylmethyl-dimethoxysilane, N-trimethylsilyl-N-methylaminopropylmethyldietoxy silane, 3- (4-trimethylsilyl-1-piperazine) propyltriethoxysilane, N- [2- (trimethoxy-silyl) -ethyl] -P.PÓ.PÓ-trimethylethane-1,2-diamine, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) -propyl] -3-methylimidazolidine, 2- (3-tri-methoxy-silyl-propyl) -1,3-dimethyl-imidazolidine, 1- [3- (triethoxy-silyl) -propyl] -3-methyl-hydroxy-pyrimidine, 3- [3- (tributoxy-silyl) -propyl] -1-methyl-1,2,3,4-tetrahydro-pyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) -propyl] -imidazolidine, 2- {3- [3- ( trimethoxysilyl) -propyl] -tetrahydropyrimidin-1-yl} -ethyldimethylamine, 2- (tri-methoxysilyl) -1,3-dimethylimidazolidine, 2- (triethoxysilyl) -1,4-diethyl-piperazine, 5- (triethoxysilyl) -1,3-dipropylexahydropyrimidine, 5- (diethoxyethylsilyl) - 1,3-diethylhexahydropyrimidine, 2- [3- (2-dimethylaminoethyl) -2- (3-ethyldimethoxysilyl-propyl) -imidazolidin-l-yl] -ethyl -dimethylamine, 5- (3-trimethoxysilyl-propyl) l) -1,3-bis- (2-methoxyethyl) -hexahydropyrimidine, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-morpholinopropylmethyldimethoxysilane, 3-piperidinopropyltrimethoxyethyl, 3-piperidinopropylmethyl-3-piperidinopropylmethyl triethoxysilyl) propyl] trimethylsilylamine, bis [3- (trimethoxysilyl) propyl] trimethylsilylamine, 3- (4-methyl-1-piperazine) propyltriethoxysilane, and compounds in which the alkyl groups or alkylene groups in the above compounds are replaced with alkyl groups or alkylene groups having 1 to 6 carbon atoms.
[0090] Of these compounds, examples of preferred compounds include N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (tri-methylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropyl-methyldiethoxysilane, N, N- bis (trimethylsilyl) aminopropyltriethoxysilane, 1- (3-tri-ethoxysilylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disilaekenqrgpvcpq. "P.PÓ.PÓ- tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, diethyl-POW-trimethylsilyl-ethane-1,2-diamine, diethyl-POW-trimethylsilyl-ethane- 1,2-diamine, methyldiethoxysilane, 3- (4-trimethylsilyl-1-piperazine) propyltriethoxysilane, N- [2- (trimethoxysilyl) -ethyl] -P.PPO.POW-trimethylethane-1,2-diamine, 1- [ 3- (triethoxysilyl) - propyl] -4-methylpiperazine, 2- (trimethoxysilyl) -1,3-dimethylimidazolidine, 2- (3-trimethoxysilyl-propyl) -1,3-dimethylimidazolidine, 3-dimethylaminopropyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane , 3-dimethylaminopropyltriethoxysilane, 3-diethyl laminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl] - trimethylsilylamine, bis [3- (trimethoxysilyl) propyl] trimethylsilylamine, and 3- (4-methyl-1-piperazine) propyltriethoxysilane.
[0091] Examples of a compound having an imino group, a pyridyl group, or an imidazole group and an alkoxysilyl group include N- (1,3-dimethylbutylene) -3- (triethoxysilyl) -1-propanamine, N- (1 -methylpropylidene) -3- (triethoxysilyl) -1-propanamine, (triethoxysilyl) -1-propanamine, propanamine, and methyl-methoxysilyl compounds, and compounds of triethoxysilyl, N- (3-trimethoxysilyl-propyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole, N- (3-triethoxysilylpropyl) -4,5-imidazole, 3-hexamethyleniminopropyl-trimethoxysilane, 3-hexamethyleniminopropylmethylimethoxy and compounds in which the alkyl groups or alkylene groups in the above compounds are replaced with alkyl groups or alkylene groups having from 1 to 6 carbon atoms.
[0092] Of these, examples of preferred compounds include N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N - (3-trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole, and N- (3-triethoxysilylpropyl) - 4,5-imidazole.
[0093] Examples of a compound having a phosphorus-containing group in which two hydrogen atoms in a primary phosphine group are replaced with two protective groups, a phosphorus-containing group in which a hydrogen atom in a secondary phosphine group is replaced with a protective group, a tertiary phosphine group, or a sulfur-containing group in which a thiol hydrogen atom is replaced with a protective group and an alkoxysilyl group includes P, P-bis (trimethylsilyl) phosphinopropylmethyldimethoxysilane, P, P-bis (trimethylsilyl) fosfinopropiltrimetoxissilano, dimetilfosfinopropiltrimetoxissilano-3, 3-dimetilfosfinopropilmetildimetoxi- silane, 3-difenilfosfinopropiltrimetoxissilano, 3-difenilfosfinopropiltrietoxi- silane, 3-diphenylphosphino-propilmerildimetoxissilano, trimetilsililmercapto- propilmetildimetoxissilano S-S-trimetilsililmercaptopropiltrimetoxissilano, trimetilsililmercaptopropiltrietoxissilano S, S-trimetilsililmercaptopropilmetil- dietoxissilano , and compounds in that the alkyl groups or alkylene groups in the above compounds are substituted with alkyl groups or alkylene groups having from 1 to 6 carbon atoms.
[0094] Of these, examples of preferred compounds include 3-diphenylphosphinopropyltrimethoxysilane, 3-diphenylphosphinopropyltriethoxysilane, S-trimethylsilylmercaptopropylmethyldimethoxysilane, S-trimethylsilylmercaptopropyl-trimethoxyethyl, and trimethylethylethylethylethylethylethylethylethylethylethylethylethylethylethylethylethylmethyl.
[0095] The modification reaction can be carried out, for example, as a reaction in solution. The solution reaction can be carried out using a solution containing an unreacted monomer after completion of the polymerization reaction or the like. In addition, the modification reaction is preferably carried out after completion of the polymerization or the like and before carrying out a solvent removal treatment, a water treatment, a thermal treatment, and various operations necessary for the polymer insulation. In addition, the modification reaction can be carried out by batch using a batch-type reaction vessel or can be carried out continuously using an apparatus such as a continuous multi-stage reaction vessel.
[0096] In the modification reaction, the reaction temperature can be around the same temperature as the polymerization temperature mentioned above and is preferably from -20 to 150 ° C, more preferably from 0 to 120 ° C, and particularly preferably from 20 to 100 ° C. When the reaction temperature is low, there is a tendency for the viscosity of the modified conjugated diene polymer to increase. When the reaction temperature is high, the active point of the modified conjugated diene polymer is likely to be deactivated. The reaction time of the modification reaction is preferably 1 minute to 5 hours, and more preferably 2 minutes to 1 hour.
[0097] The amount of the modifier to be used in the modification reaction is preferably 0.1 molar equivalent or more, and more preferably 0.3 molar equivalent or more with respect to the active point of the conjugated diene polymer. When the amount is above or above, the modification reaction proceeds sufficiently, the dispersibility of a reinforcing agent such as carbon black or silica is improved, and the properties of abrasion resistance, wet skid resistance, and loss of low hysteresis of the reticulated body are improved. In addition, compatibility with a polar resin tends to be improved.
[0098] The method of adding the modifier is not particularly limited and there may be mentioned a method of adding the same at once, a method of adding the same to the portions, and a method of adding the same continuously. Of these, the method of adding it at once is preferable. << Step (1d) >> (Polymerization termination reaction)
[0099] The production method of the invention may comprise a step (1d) of reacting the conjugated diene polymer having an active point on such an active lithium end with a polymerization terminator capable of reacting with the active point. <Polymerization Terminator>
[00100] In the aforementioned polymerization reaction, the coupling reaction, or modification reaction, in the case where the resulting conjugated diene polymer has an active point such as the active lithium end, it is possible to disable the active point using a polymerization terminator.
[00101] Examples of the polymerization terminator include hydrogen; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol and octanol; alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride, benzyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, methyl iodide, ethyl iodide, iodide propyl, and butyl iodide. Of these, hydrogen is preferable.
[00102] The polymerization terminators can be used alone or two or more of them can be used in combination. [Stage (2)] (Stage of Hydrogenation)
[00103] In step (2), the conjugated diene polymer obtained in step (1) is hydrogenated. The hydrogenation reaction method and conditions are not particularly limited and the hydrogenation is carried out, for example, at 20 ~ 150 ° C, under pressurization with 0.1 ~ 10 MPa hydrogen in the presence of a hydrogenation catalyst.
[00104] The hydrogenation rate of the hydrogenated conjugated diene polymer obtained can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure or the reaction time at the time of the hydrogenation reaction, or the like. From the point of view of improving weather resistance, the rate of hydrogenation is usually 10% or more, preferably 50% or more, more preferably 80% or more, and particularly preferably 95% or more of the aliphatic derivatives derived of the conjugated diene compound. Details of the hydrogenation rate measurement conditions are as described in the Examples.
[00105] As described above, it is possible to obtain a polymer having excellent thermal resistance and weather resistance by carrying out the hydrogenation reaction of the conjugated diene polymer obtained using a modified polymerization initiator.
[00106] As the hydrogenation catalyst, typically a compound containing any of the elements in groups 4, 5, 6, 7, 8, 9, and 10 in the periodic table, for example, a compound containing the elements Ti, V, Co , Ni, Zr, Ru, Rh, Pd, Hf, Re, or Pt can be used.
[00107] Examples of the hydrogenation catalyst include metallocene compounds containing Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, or the like; heterogeneous sustained catalysts in which a metal such as Pd, Ni, Pt, Ph, or Ru is supported in a carrier such as carbon, silica, alumina, or diatomaceous earth; homogeneous Ziegler-type catalysts in which an organic salt or acetylacetone salt of Ni, Co, or the like is combined with a reducing agent such as an organoaluminium; organometallic compounds or Ru, Rh complexes, or the like; and fullerenes and carbon nanotubes in which hydrogen is absorbed.
[00108] Of these, the metallocene compounds containing any of Ti, Zr, Hf, Co, and Ni are preferable since the hydrogenation reaction can be carried out in a homogeneous system in an inert organic solvent. In addition, metallocene compounds containing any of Ti, Zr, and Hf are preferable. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with an alkylithium is preferable, since it is inexpensive and is a particularly useful catalyst in the industry.
[00109] As specific examples, for example, the hydrogenation catalysts described in JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5 can be mentioned -222115, JP-A-11-292924, JP-A- 2000-37632, JP-A-59-133203, JP-A-63-5401, JP-A-62-218403, JP-A-7- 90017 , JP-B-43-19960, and JP-B-47-40473.
[00110] Hydrogenation catalysts can be used alone or two or more of them can be used in combination. [Stage (3)] (Stage of Onion Formation)
[00111] The production method of the invention can comprise a step (3) of mixing and reacting the aforementioned hydrogenated modified conjugated diene polymer having a group capable of forming an onium with an onium forming agent. By this step, a structure can be introduced into the modified hydrogenated conjugated diene polymer to enhance its shape retention property. The group capable of forming an onium by the action of an onion-forming agent is a group that corresponds to A31 in formula (z).
[00112] Examples of the onion forming agent include metal halides such as silicon halide compounds, tin halide compounds, aluminum halide compounds, titanium halide compounds, zirconium halide compounds, germanium halide compounds , gallium halide compounds, and zinc halide compounds; esters of inorganic acids such as sulfate esters, phosphate esters, carbonate esters, and nitrate esters; inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid; inorganic acid salts such as potassium fluoride, tetramethylammonium fluoride, and tetra-n-butylammonium fluoride; and organic acids such as carboxylic acids (example: maleic acid), and sulfonic acid (example: benzenesulfonic acid).
[00113] Of these, due to the easy availability and easy handling of the compounds, the silicon halide compound, tin halide compounds, aluminum halide compound, titanium halide compounds, zirconium halide compounds, halide compounds are preferred of germanium, gallium halide compounds, zinc halide compounds, sulfate esters, phosphate esters, carboxylic acids and sulfonic acid.
[00114] Specific examples of the onion forming agent include silicon tetrachloride, tin tetrachloride, trimethylsilyl chloride, dimethyldichlorosilane, diethyl aluminum chloride, zinc chloride, titanium tetrachloride, zirconium tetrachloride, geranium tetrachloride, trichloride, trichloride, trichloride, trichloride, trichloride, trichloride, trichloride, trichloride. diethyl sulfate, trimethyl phosphate, dimethyl carbonate, maleic acid, and benzenesulfonic acid.
[00115] The mixture of the modified hydrogenated conjugated diene polymer with the onion forming agent can, for example, be carried out in the form of a solution. The mixing can be carried out by batch using a batch type mixer or can be carried out continuously using an apparatus such as a continuous multi-stage mixer or an in-line mixer.
[00116] The amount of the onion-forming agent to be added is preferably 0.5 molar equivalent or more, and more preferably 1.0 molar equivalent or more with respect to the group capable of forming an onion of the hydrogenated modified conjugated diene polymer. . When the amount is above or above, the formation of onium is sufficiently processed and there is a tendency to improve the shape retention property of the hydrogenated modified conjugated diene polymer.
[00117] The method of adding the onion forming agent is not particularly limited and there may be mentioned a method of adding it at once, a method of adding it to the portions, and a method of adding it continuously. Of these, the method of adding it at once is preferable.
[00118] The mixing temperature of the hydrogenated modified conjugated diene polymer with the onion forming agents is about the same as the polymerization temperature in the aforementioned polymerization reaction and is preferably from -20 to 150 ° C, more preferably from 0 to 120 ° C, and particularly preferably 20 to 100 ° C. When the temperature is low, the viscosity of the hydrogenated modified conjugated diene polymer tends to increase. When the temperature is high, the hotspot such as the active lithium tip is prone to deteriorate.
[00119] The formation of the onium structure in the hydrogenated modified conjugated diene polymer is conducted in the presence of water. As methods for forming the onium structure, for example, mention may be made of (i) a method of adding water directly to a solution of the hydrogenated modified conjugated diene polymer and mixing them, (ii) a method of adding one obtained by dissolving it whether water in an organic solvent such as an alcohol capable of dissolving in both water and an organic solvent, in a solution of the hydrogenated modified conjugated diene polymer and mixing them, and (iii) a mixture of a solution of the diene polymer modified conjugate hydrogenated with water simultaneously with the removal of the solvent by stripping with steam in the recovery step.
[00120] In this case, the polymer solution obtained in the preparation of the hydrogenated modified conjugated diene polymer can be used in the form of the polymer solution without removing the solvent or the polymer solution can be subjected to solvent removal by steam stripping or the like and further dried and the resulting hydrogenated modified conjugated diene polymer can be used after dissolving again in an organic solvent such as cyclohexane. [Step (4)] (Recovery Step)
[00121] The conjugated diene polymer can be recovered from the solution containing the hydrogenated conjugated diene polymer obtained as described above, for example, by a solvent removal method known in the production of the conjugated diene polymer and drying operations. As the known solvent removal methods, a steam stripping method, a drum dryer method, and an instant evaporation (flash) solvent removal method can be mentioned.
[00122] It is possible to adjust the Mooney viscosity by adding extender oil to the hydrogenated conjugated diene polymer according to the need to improve workability. Examples of extender oil include aromatic oil, naphthene oil, and paraffin oil. The amount of the extender oil is, for example, usually 10 to 50 parts by weight based on 100 parts by weight of the hydrogenated conjugated diene polymer. [Hydrogenated conjugated diene polymer]
The hydrogenated conjugated diene polymer of the invention has at least one structure of formulas (X) and (Y) at the end of the polymer. Also, the hydrogenated conjugated diene polymer of the invention can have a structure represented by formula (Z). [Chemical Substance 11]

[00124] In formula (X), R1 is a hydrocarbilene group, and the hydrocarbilene group in R1 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom, and A3 is a hydrogen atom or a triple group hydrocarbylsilyl. In the formula (Y), R2 and R3 are each independently a hydrocarbilene group, the hydrocarbilene group in each of R2 and R3 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom; and A4 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S and in which all or part of the atoms can be protected with a trihydrocarbylsilyl group and the atom that is attached to R3 is N, P or S.
[00125] The R1 and A3 above can be linked together to form a cyclic structure. That is, an atom in R1 and an atom in A3 can be linked to form a cyclic structure. A portion of R2, R3, and A4 above can be linked together to form a cyclic structure. That is, an atom in R2 and an atom in R3 can be linked to form a cyclic structure, an atom in R2 and an atom in A4 can be linked to form a cyclic structure, or an atom in R3 and an atom in A4 can be linked to form a cyclic structure. [Chemical Substance 12]

[00126] In formula (Z), R3μu u «q ecfc wo kpfgrgpfgpVgogpVg wo hydrocarbyl group. R3 ^ u are each independently a hydrogen atom or a hydrocarbyl group. R33 is a hydrocarbilene group. A32 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S and in which some or all of the atoms can be protected with a trihydrocarbylsilyl group and the atom that is attached to R33 is N, P or S. A32 can be a group that results from the formation of the onium of A31 in formula (z). n is an integer from 0 to 2. A plurality of R3nu g T32óu rqfg ugt ecfc wo q oguoq or different.
[00127] As the hydrogenated conjugated diene polymer having a structure represented by formula (X), for example, a hydrogenated conjugated diene polymer having at least one group selected from a group represented by formula (X1) and a group represented by the formula (X2) at the end of the polymer. [Chemical Substance 13]

[00128] In the formulas (X1) and (X2), R ^ u uq qw independently a hydrocarbilene group, and the hydrocarbilene group in R11 can contain a heteroatom as long as the hydrocarbilene group does not have an active hydrogen atom; A3’s u «q ecfc wo kpfgrgpfgpVgogpVg w the hydrogen atom or a trihydrocarbylsilyl group. A plurality of Rn’s and A3ós rqfgo sgt ecfc wo qs ogsoqs qw fkfetepVes.
[00129] The above R11 and A3 can be linked together to form a cyclic structure. That is, an atom in R11 and an atom in A3 can be linked to form a cyclic structure.
[00130] As the hydrogenated conjugated diene polymer having a structure represented by the formula (Y), for example, a modified hydrogenated conjugated diene polymer having at least one group selected from a group represented by the formula (Y1) and one group represented by the formula (Y2) at the end of the polymer. [Chemical Substance 14]

[00131] In formulas (Y1) and (Y2), R21's and T3's are independent of a hydrocarbilene group, and the hydrocarbilene group in each of R21 and R3 may contain a heteroatom as long as the hydrocarbilene group does not have an atom active hydrogen; A4 is a functional group that has at least one atom selected from a nitrogen atom N, a phosphorus atom P, and a sulfur atom S and in which all or part of the atoms can be protected with a trihydrocarbylsilyl group and the atom that is attached to R3 is N, P or S. A plurality of R21os, T3ós. and A4’s rqfeo set ecfc wo qs oesoqs qw fkhetepVeso
[00132] A part of the above R21, R3, and A4 can be linked together to form a cyclic structure. That is, an atom in R21 and an atom in R3 can be linked to form a cyclic structure, an atom in R21 and an atom in A4 can be linked to form a cyclic structure, or an atom in R3 and an atom in A4 can be linked to form a cyclic structure.
[00133] The conjugated diene polymer of the invention may be a homopolymer composed of a conjugated diene compound, it may be a random copolymer compound of a conjugated diene compound and another monomer such as an aromatic vinyl compound, or it may be a block copolymer composed of conjugated diene compounds or a conjugated diene compound and anther monomer such as an aromatic vinyl compound.
[00134] The hydrogenated conjugated diene polymer having the above configuration can be synthesized, for example, by the production method of the invention mentioned above. The specific examples and preferable examples of each group in the formulas above are the same as described in the paragraphs of the production method of the invention.
[00135] The molecular weight of the hydrogenated conjugated diene polymer of the invention is usually from 30,000 to 2,000,000, preferably from 40,000 to 1,000,000, and more preferably from 50,000 to 500,000 as the weighted average molecular weight in terms of polystyrene in the method gel permeation chromatography (GPC). Details of the weighted average molecular weight measurement conditions are as described in the Examples.
[00136] The hydrogenation rate of the hydrogenated conjugated diene polymer of the invention is usually 10% or more, preferably 50% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably at minus 95% of the aliphatic double bond derived from the conjugated diene compound, as weather resistance is improved. Details of the hydrogenation rate measurement conditions are as described in the Examples.
[00137] In the following, the hydrogenated conjugated diene polymer of the aforementioned invention and the hydrogenated conjugated diene polymer obtained by the production method of the invention are also eqngVkxcogpVg cnwfkfqu eqoq "polyπigto fg fkgpq eqpjwicfq jkftqigpcfq fc invepic.
[00138] The hydrogenated conjugated diene polymer of the invention has an N atom that becomes an interaction point to increase the dispersibility of fillers such as carbon black and silica or a reaction point to function as a compatibilizer for various polymers at the end beginning of polymerization. Therefore, the polymer can increase the dispersibility of fillers such as carbon black and silica and is excellent in processability when combined with a thermoplastic resin or the like, so that a polymeric alloy having excellent physical properties can be formed after the combination .
[00139] In one embodiment, the N atom can be protected with a trihydrocarbylsilyl group and, depending on the objective physical properties, it is possible to convert it into an active amino group through deprotection by hydrolysis. [First Polymeric Composition and Reticulated Body thereof]
[00140] The first polymeric composition of the invention contains the hydrogenated conjugated diene polymer of the invention and may also contain a polymeric component other than the polymer (hereinafter Vcodfio clwfkfq eqoq q "qwVtq eqorqpgpVg rqlkofitkeq '^. polymeric composition of the invention may contain at least one selected from carbon black and silica. <Hydrogenated conjugated diene polymer>
[00141] In the first polymeric composition of the invention, the hydrogenated conjugated diene polymer of the invention can be incorporated without any particular limitation, but from the point of view of the balance between wet skid resistance, low hysteresis loss properties, and abrasion resistance, the previously mentioned conjugated diene homopolymer and random copolymer are preferable.
[00142] In the first polymeric composition of the invention, the content of the hydrogenated conjugated diene polymer of the invention is preferably 30% by weight or more, more preferably from 50 to 100% by weight, and particularly preferably from 70 to 100% by weight. mass based on the total amount of polymeric components. When the content resides within the above range, mechanical properties such as tensile strength and tensile strength, crack development resistance, and abrasion resistance of the reticulated body can be made more satisfactory. <Other Polymeric Components>
[00143] Examples of other polymeric components include natural rubber, isoprene synthetic rubber, butadiene rubber, modified butadiene rubber, styrene-butadiene rubber, modified styrene-butadiene rubber, ethylene-g-olefin copolymer rubber, rubber copolymeric ethylene-olefin-g-diene, copolymeric acrylonitrile-butadiene rubber, chloroprene rubber, halogenated butyl rubber, copolymeric styrene-isoprene rubber, copolymeric butadiene-isoprene rubber, random copolymeric rubber of styrene-butadiene-isoprene, rubber copolymeric styrene-acrylonitrile-butadiene, copolymeric acrylonitrile-butadiene rubber, and copolymeric polystyrene-polybutadiene-polystyrene rubber.
[00144] The other polymeric components can be used alone or two or more of them can be used in combination. <Carbon Black, Silica>
[00145] Examples of carbon black include varying degrees of carbon black, such as oven black typified by SRF, GPF, FEF, HAF, ISAF, SAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF- HS, and HAF-LS, acetylene black, thermal black, channel black, graphite, in addition, graphite fibers, and fullerenes. In addition, carbon black having an iodine (IA) absorption amount of 60 mg / g or more and an dibutyl phthalate (DBP) absorption amount of 80 ml / 100 g or more is preferable. Using carbon black, the effect of improving skidding performance and fracture resistance of the reticulated body is enhanced. From the point of view of improving the abrasion resistance of the reticulated body, SRF, HAF, ISAF, and SAF are particularly preferable.
[00146] Carbon black can be used alone or two or more of them can be used in combination.
[00147] Examples of silica include wet silica (hydrated silicic acid), dry silica anhydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. Of these, wet silica is preferable, which shows more sharply the effect of improving fracture resistance and the effect of obtaining both wet skidding performance and low rolling resistance. In addition, it is also preferable to use high dispersible type silica (High Dispersible Type) from the point of view of increasing dispersibility within the polymer composition and improving physical properties and processability.
[00148] Silica can be used alone or two or more of them can be used in combination.
[00149] In the first polymeric composition of the invention, the content of carbon black and / or silica (total amount they, if they contain both) is preferably 20 to 130 parts by weight, and more preferably 25 to 110 parts by weight based on 100 parts by weight of the polymeric components (total of the hydrogenated conjugated diene polymer and the other polymers) from the point of view of the effect of improving the reinforcing properties and various physical properties in this way. The carbon black and / or silica content is preferably the lower or more limit value from the point of view of obtaining the effect of improving fracture strength and the like, and is preferably the upper or less limit value from the point of view. to maintain the processability of the polymeric composition.
[00150] Furthermore, by mixing a carbon-silica dual phase filler (Dual Phase Filler) in the first polymeric composition of the invention, it is possible to obtain the same advantages as in the case where carbon black and silica are used in combination . The double-phase carbon-silica filler is called silica-coated carbon black in which the silica is chemically bonded to the surface of the carbon black, and is sold under the trade name CRX2000, CRX2002, or CRX2006 from Cabot Corporation. The content of the carbon-silica dual phase filler is preferably from 1 to 100 parts by weight, and more preferably from 5 to 95 parts by weight based on 100 parts by weight of the polymeric components (total of the hydrogenated conjugated diene polymer and other polymeric components). <Silane Coupling Agent>
[00151] In the case where the silica is mixed as a reinforcing agent to the first polymeric composition of the invention, in order to further improve the reinforcing effect, it is preferable to mix a silane coupling agent. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) bis tetrasulfide, bis (3-triethoxysilylpropyl) bis disulfide, bis (2-triethoxysilylethyl) bis disulfide, bis (3) tetrasulfide -trimethoxysilylpropyl), bis (2-trimethoxy-silylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilethylethylethylethylethylethylsethoxy-trimethoxy-trimethoxy-trimethoxy-3-trimethoxy N, N-dimetiltiocarbamoíla, tetrassulfeto trietoxissililetil 2-N, N dimetiltiocarbamoíla, 3-trimetoxissililpropilbenzotiazolila of tetrassulfeto, 3-trietoxissililpropilbenzolila of tetrassulfeto, monossulfeto 3-trietoxissililpropila methacrylate, 3-monossulfeto trimetoxissililpropila methacrylate, bis tetrassulfeto (3-dietoxymethylsilylpropyl), 3-mercaptopropyldimethoxy-methylsilane, dimethoxymethyl tetrasulfide lilpropyl-N, N-dimethylthio-carbamoyl, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, 3-methacryloxypropyltrimethoxysilane, and mercapto silane compounds exemplified in JP-A-2006-249069.
[00152] Examples of commercially available products include qu pqogu eqogtekcku "PZV uklcnq", "PZV ¥ uklcnq", "PZV-Low-V uklcnq", and "PZV WlVtc Dckzq-X uücnq" manufactured by Momentive Performance OcVgq. NVfo, nqog eqogtekcl “VR Uk585” manufactured by Degussa Eqtrqtcvkqn. nqog eqogtekcl “33-MERCAPTOUNDECILTRIMETOXI- UKNCPQ” manufactured by Gelest Co., comerekcl name “Uk97” manufactured by Evonik Degussa Japan Co., Ltd., and nqog eqogtekcl “VUN: 592” manufactured by GE Toshiba Silicone Co., Ltd.
[00153] From the silane coupling agents, from the point of view of improving the reinforcing properties and the like, bis (3-triethoxysilylpropyl) bisulfide, 3-trimethoxysilylpropylbenzothiazila tetrasulfide, 3-methacryloxypropyltrimethoxysilane, and the mercaptossilane compounds exemplified in JP-A- 2006-249069 are suitable.
[00154] Silane coupling agents can be used alone or two or more of them can be used in combination.
[00155] In the first polymeric composition of the invention, the content of the silane coupling agent is preferably 1 to 20 parts by weight, and more preferably 3 to 15 parts by weight based on 100 parts by weight of silica. When the content is less than the above value, there is a tendency that the effect as the coupling agent is less likely to be sufficiently exhibited. When the content exceeds the above value, there is a tendency that the polymeric components are likely to be turned into a gel. <Compatibility>
[00156] In the preparation of the first polymeric composition of the invention, for the purpose of improving workability when mixing or further improving the balance between wet skid resistance, low hysteresis loss properties, and abrasion resistance, a compatibilizer can be added at the time of mixing.
Preferred examples of the compatibilizer include organic compounds selected from compounds containing epoxy group, carboxylic acid compounds, carboxylate ester compounds, ketone compounds, ether compounds, aldehyde compounds, compounds containing hydroxyl group, and group containing compound amino; silicone compounds selected from alkoxysilane compounds, siloxane compounds, and aminosilanes compound.
[00158] Examples of the organic compound that is a compatibilizer include the following compounds. * Compounds containing epoxy group: ethylene glycidyl methacrylate, butyl glycidyl ether, diglycidyl ether, propylene oxide, neopentyl glycol diglycidyl ether, epoxy resins, epoxidized soybean oil, epoxidated fatty acid esters, and the like. * Carboxylic acid compounds: adipic acid, octylic acid, methacrylic acid, and the like. * Carboxylate ester compounds: acrylate esters, diethyl acrylate, ethyl methacrylate, orthoacetate esters, ethyl acetoacetate, butyl acetate, isopropyl acetate, dimethyl carbonate, p-hydroxyphenyl acetate, plasticizers based on polyester , plasticizers based on stearic acid, and the like. * Ketone compounds: methylcyclohexanone, acetylacetone, and the like. * Ether compounds: isopropyl ether, dibutyl ether, and the like. * Aldehyde compounds: undecylenic aldehyde, decyl aldehyde, vanillin, 3,4-dimethoxybenzaldehyde, cuminaldehyde, and the like. * Compounds containing an amino group: isopropylamine, diisopropylamine, triethylamine, 3-ethoxypropylamine, 2-ethylhexylamine, isopropanolamine, N-ethylethylenediamine, ethyleneimine, hexamethylenediamine, 3-lauryloxypropylamine, aminophenol, aniline, amine, aniline, amine, aniline, aniline, amine, aniline, amine, aniline, aniline, aniline, aniline, aniline, aniline, aniline, amine, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline. methyldiethanolamine, N-methylethylamine, 3-amino-1-propanol, ethylamine hydrochloride, n-butylamine hydrochloride, and the like. * Compounds containing hydroxyl group: isopropyl alcohol, butanol, octanol, octanediol, ethylene glycol, methylcyclohexanol, 2-mercaptoethanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-1,5-pentanediol, 1- octadecanol, diethylene glycol, butylene glycol, dibutylene glycol, triethylene glycol, and the like.
[00159] Examples of the silicone compound that is a compatibilizer include the following compounds. * Alkoxysilane compounds: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, tetraethoxy silane, methylldiethoxysilane, vinyltrimethoxysilane, and the like. * Siloxane compounds: dimethylsiloxane oligomers, silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, higher fatty acid ester-modified silicone, higher alkoxy-modified silicone oil, silicone oil containing higher fatty acid, and the like. * Aminosilane compounds: hexamethyldisilazane, nonamethyltrisilazane, anilitrimethylsilane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, triethylaminosilane, and the like.
[00160] Of organic compounds, compounds containing epoxy, compound containing amino group, and compounds containing hydroxyl group are preferable; and, of the silicone compounds, silazane and bis (dimethylamino) dimethylsilane compounds are preferable.
[00161] In the first polymeric composition of the invention, the content of the compatibilizer is preferably from 0.1 to 20 parts by weight, and more preferably from 0.5 to 10 parts by weight based on 100 parts by weight of silica. When the content lies within the above range, the balance between wet skid resistance, low hysteresis loss properties, and abrasion resistance tends to be improved. <Various Additives>
[00162] The first polymeric composition of the invention can optionally contain various chemicals, additives, and the like that are commonly used in the rubber industry. Examples of chemicals or additives include crosslinking agents (examples: vulcanizing agents), crosslinking aids (examples: vulcanizing aids), processing aids, crosslinking accelerators, process oils, antioxidants, surface burn prevention agents , and zinc white.
[00163] Examples of cross-linking agents include sulfur, sulfur halides, organic peroxides, quinone dioximes, polyvalent organic amine compounds, and alkyl phenol resins having a methylol group. Of these, sulfur is preferable. The amount of sulfur is preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight based on 100 parts by weight of the polymeric component (total of the hydrogenated conjugated diene polymer and the other components polymeric).
[00164] As the vulcanization aid and processing aid, stearic acid is preferable. The content of the vulcanization aid and processing aid is usually 0.5 to 5 parts by weight based on 100 parts by weight of the polymeric components (total of the hydrogenated conjugated diene polymer and the other polymeric components).
[00165] Examples of the crosslinking accelerator include compounds based on sulfenamide, based on guanidine, based on thiuram, based on thiourea, based on thiazole, based on dithiocarbamate, and based on xanthate and preferably include 2 -mercaptobenzothiazole, dibenzothiazila disulfide, N-cyclohexyl-2-benzothiazilsulfenamide, Nt-butyl-2-benzo-thiazolsulfenamide, N-oxyethylene-2-benzothiazolsulfenamide, N-oxyethylene-2-benzotiazolf-pn-di-p. isopropyl-2-benzothiazolsulfenamide, diphenylguanidine, di-o-tolylguanidine, and o-tolylbisguanidine.The amount of the crosslinker is preferably 0.1 to 5 parts by mass, and more preferably 0.4 to 4 parts by weight mass based on 100 parts by weight of the polymeric components (total of the hydrogenated conjugated diene polymer and the other polymeric components). <Method for Preparing Polymeric Composition>
[00166] The first polymeric composition of the invention can be produced by mixing the components using a mixer such as an open mixer (example: roller) or a closed type mixer (example: Banbury mixer). <Reticulated Body Formed from the First Polymer Composition>
[00167] The first polymeric composition of the invention can be applied to the various rubber products as a cross-linked body by cross-linking (vulcanization) after molding. Examples of uses of the reticulated body include uses in tires such as in the tread, sub-tread, casing, side, and tire bead parts; uses such as anti-vibration rubber, split, belt, hose, and other industrial products. The cross-linked body of the invention is, in particular, suitably used as a tire for tire tread from the point of view of providing low fuel consumption performance. [Second Polymeric Composition and Molded Body thereof]
[00168] The second polymeric composition of the invention contains the hydrogenated conjugated diene polymer of the invention (hereinafter also referred to as "eqorqpgpVg * K +" +) and at least one polymer selected from a non-polar polymer (hereinafter also referred to as " eqorqpgpVg * KK-3 + ”+ qwVtq swg p« qq eqorqpgpVg * K + g a polar polymer (hereinafter also referred to as “component (II-4 +” + o
[00169] The hydrogenated conjugated diene polymer of the invention is excellent in the effect of polar polymer modification and also excellent in the effect of compatibilizing a conventional heterogeneous polymer mixture. Therefore, using the above polymer as a contained component of the polymeric composition containing another polymer, it is possible to give an excellent molded body in the balance between processability properties, thermal resistance, rigidity, impact resistance, resistance to surface impact, tensile elongation at break, specular reflection, and delamination or the like.
[00170] The non-polar polymer and the polar polymer can be a resin or a rubber. <Component (I)>
[00171] In the second polymeric composition of the invention, the hydrogenated conjugated diene polymer of the invention can be incorporated without any particular limitation, but, from the point of view of improving compatibility with polar resins, the aforementioned conjugated diene block copolymer is preferable. <Component (II-1)>
[00172] As component (II-1), an olefin polymer and an aromatic vinyl polymer are preferable.
[00173] Examples of the olefin polymer include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE); polypropylene (PP) resins such as random type, block type or homo type; copolymers of ethylene and a -olefin having 3 to 20 carbon atoms, such as ethylene-propylene copolymer (EPM), ethylene-1-butene copolymer (EBM), ethylene-hexene copolymer (EHM), and copolymer ethylene-octene (EOM); copolymers of propylene and a -olefin having from 4 to 20 carbon atoms, such as propylene-1-butene copolymer (PBM); ternary ethylene-based copolymers such as ethylene-propylene-1-butene copolymer (EPBM), ethylene-propylene-diene copolymer (EPDM), and ethylene-1-butene-diene copolymer (EBDM); poly-1-butene (PB), polymethylpentene (PMP), and polybutadiene (PBD). These can be used alone or two or more of them can be used in combination.
[00174] Examples of aromatic vinyl polymer include polystyrene based resins such as general purpose polystyrene (GPPS), high impact polystyrene (HIPS), isotactic polystyrene (iPS), syndiotatic polystyrene (sPS), and polymethyl styrene (P MS). These can be used alone or two or more of them can be used in combination. <Component (II-2)>
[00175] As component (II-2), for example, a polymer having at least one functional group selected from a carboxyl group (including the carboxyl group that constitutes an acid anhydride or a metal salt), a hydroxyl group, a halogen group, an epoxy group, an oxazoline group, a sulfonic acid group, an isocyanate group, a thiol group, an ester bond, a carbonate bond, an amide bond, an ether bond, an urethane, and a urea bond.
[00176] Examples of the polymer having the functional group include: polymers containing carboxyl group such as ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid (EMA) copolymer, ethylene-maleic acid (meth) acrylic copolymer , ethylene- (meth) acrylate-maleic anhydride copolymer, an ionomer (IO) which is a copolymer of ethylene and (meth) acrylic acid in which the content of the structural units derived from (meth) acrylic acid is 7 to 15 mol% and the degree of neutralization with a metal ion such as Na, Zn, or Mg is 20% or more; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polylactic acid (PLA), polyhydroxyalkanoic acids (PHA), polylactone, polycaprolactone, polyethylene succinate polybutylene, polyethylene adipate, and polybutylene adipate succinate; polyamide (PA) resins such as nylon 4.6 (PA46), nylon 6 (PA6), nylon 6.6 (PA66), nylon 6.10 (PA610), nylon 6.12 (PA612), nylon 12 (PA12), nylon 6.T (PA6T) ), nylon 9.T (PA9T), reinforced polyamides, and modified polyamides made from hexamethylenediamine and terephthalic acid; acrylic polymers such as ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate (EEA) copolymer, ethylene-isopropyl acrylate copolymer, ethylene-ethylene 2-acrylate copolymer, ethylene-methacrylate copolymer methyl, ethylene-ethyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-hydroxyethyl methacrylate (HEMA) copolymer, ethylene-methacrylate 2-copolymer, hydrochloride-propylate 2 copolymers aminoalkyl ethylene-methacrylate copolymer, ethylene-glycidyl methacrylate (EGMA) copolymer, polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), and methacrylic-styrene copolymer (MS resin); polycarbonates (PC) such as poly-2,2-bis (hydroxyphenyl) propane carbonate; polyphenylene ethers (PPE) such as poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2- methyl-6-phenyl-1,4-phenylene), poly (2,6-dichloro-1,4-phenylene ether), and modified polyphenylene ether (modified PPE); polyvinyl acetate (PVAc), liquid crystalline polyester (LCP), polyacetal (POM), ABS resin, AES resin, ASA resin, EVA resin, ethylene-vinyl propionate copolymer, diaryl phthalate resin (DAP) ), phenol resin (PF), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyarylate (PAR), norbornene resin, polyethylene oxide, polyphenylene sulfide (PPS), polysulfone (PSU), and polyethersulfone (PES); polyester thermoplastic elastomers, polyurethane thermoplastic elastomers, polyamide thermoplastic elastomers, nitrile copolymer rubber, d-unsaturated acrylic ester-unsaturated diene, urethane rubber, chlorinated butyl rubber, brominated butyl rubber, acrylic rubber, ethylene rubber acrylic, epichlorohydrin rubber, epichlorohydrin-ethylene oxide rubber, and chloroprene rubber; and chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated polypropylene, oxazoline-modified polystyrene, and oxazoline-modified styrene-acrylonitrile copolymer.
[00177] These can be used alone or two or more of them can be used in combination.
[00178] Of the polymers exemplified as component (II-1) and component (II-2), due to the structure of the molecular chain of component (I), a polyethylene resin having a structural unit derived from ethylene, a resin of polypropylene having a structural unit derived from propylene, a resin based on polystyrene having a structural unit derived from an aromatic vinyl compound, a polyester resin such as polylactic acid or polyethylene terephthalate, a polyamide resin, an acrylic polymer, a copolymer ethylene-vinyl alcohol are particularly preferable since they are excellent in improving physical properties and applications of use can be extended.
[00179] Polymers exemplified as component (II-1) and component (II-2) can be synthetic resins using a monomer derived from biomass.
[00180] In the case where the second polymeric composition of the invention contains component (I) and component (II-1) or contains component (I) and component (II-2), the content ratio can be as follows in both cases. That is, when component (II-1) and component (II-2) are alluded to eqoq “eqorqpgpVg * KK +”, c eqorqpgpVg (I) icqnipqngntg * KK + * tcz «q go ocuuc + is preferably from 1 to 99/99 to 1, more preferably from 5 to 95/95 to 5, and more preferably from 10 to 90/90 to 10.
[00181] In the case where the second polymeric composition of the invention contains component (I), component (II-1), and component (II-2), the content ratio can be as follows. That is, component (II-1) / component (II-2) (mass ratio) is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, and most preferably 10 to 90/90 to 10, and the content of component (I) is preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight, and more preferably from 10 to 40 parts by weight when the total content of component (II-1) and component (II-2) is considered to be 100 parts by mass. <Component (III)>
[00182] The second polymeric composition of the invention may contain wo gpejgfqt * fcswk go fkcpVg Vcodfio cnwfkfq eqoq “eqorqpgpVg * KKK +” + o Qu examples of component (III) include magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, hydroxide , barium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, tin oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, barium sulfate, calcium sulfate, sodium sulfate, sodium sulfite calcium, calcium silicate, calcium carbonate, magnesium carbonate, composed of phosphate salt, carbon, glass beads, glass powder, asbestos, mica, talc, silica, zeolite, kaolin, silica sand, silica rock, dust quartz, Shirasu, inorganic fibers such as carbon fibers and metallic fibers, and inorganic hair crystals such as potassium titanate capillary crystals. These can be used alone or two or more of them can be used in combination.
[00183] Component (III) can be used without further treatment but, for the purpose of increasing the affinity with various polymers and the strength of interfacial bonding or the like, one can also be used one subjected to a superficial treatment with a fatty acid (examples: stearic acid, oleic acid, or palmitic acid) or a metallic salt thereof, paraffin, wax, polyethylene wax or a modified product thereof, an organic borane, an organic titanate, a silane coupling agent, a aluminum coupling agent, or the like.
[00184] Of these, examples of a use as a flame retardant include magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, and tin oxide. Of these, magnesium hydroxide, aluminum hydroxide, and calcium hydroxide are preferable since they are useful and also readily available in the industry. Magnesium hydroxide is particularly preferable due to its high flame retardant effect.
[00185] In the case of using a flame retardant, in order to enhance the flame retardant effect, a phosphorus based flame retardant such as a red phosphorus based flame retardant, a polyphosphate based flame retardant ammonium, or a phosphate ester, a silicone compound, quartz glass, or the like and, as a flame retardant aid, sodium metasilicate, a frit, a short silicon nitride fiber for drip prevention, or the like can also be used in combination.
[00186] The content of component (III) is when the total of polymeric components such as component (I) and component (II) is considered to be 100 parts by mass, preferably 1 to 90 parts by mass, and more preferably from 2 to 80 parts by mass. When the content of component (III) lies within the above range, properties such as flame retardancy and resistance can be communicated without inhibiting the effects of component (I), component (II-1), and component (II-2 ). <Other Components>
[00187] The second polymeric composition of the invention can be mixed with, in addition to the above components, as other additives, a stabilizer such as an anti-aging agent, a weather-resistant agent, a metal deactivator, a light stabilizer, an absorber UV, and a thermal stabilizer, an antibacterial / antifungal agent, a dispersing agent, a softener, a plasticizer, a crosslinking agent, a crosslinking coagent, a vulcanizing agent, a vulcanizing aid, a foaming agent, a foaming aid, a dye, a metallic ferrite powder or the like, an organic fiber such as an aramid fiber, and / or a composite fiber. Also, graphite, pumice, ebonite powder, cotton flake, cork powder, a fluororesin, polymeric pearls, polyolefin wax, cellulose powder, rubber powder, and a low molecular weight polymer can be mixed. When crosslinking is carried out, the method is not particularly limited and crosslinking with sulfur, crosslinking with peroxide, crosslinking with electron beam, crosslinking with ultraviolet, crosslinking with radiation, crosslinking with metal ion, crosslinking with silane, crosslinking with silane resin, and the like. Incidentally, the foaming agent will be collectively described at the time of explaining the foam molding. <Preparation of the Second Polymeric Composition>
[00188] For the preparation of the second polymeric composition of the invention, it is possible to use a conventionally known mixer such as an extruder, a pressure mixer, an open mixer (example: roller), or a closed type mixer (example: Banbury mixer ) or a mixer in which they are combined. In mixing, the ingredients can be collectively mixed or it is possible to adopt a multistage divisional mixing method in which the arbitrary components are mixed and subsequently the remaining components are added and mixed.
[00189] Also, for the preparation of the second polymeric composition of the invention, a twin screw extruder is particularly preferable and it is possible to use a corrotative type or a counterrotatory type properly. L / D (the ratio of the effective length (L) of the thread and the diameter (D) of the extruder thread) is preferably 30 to 80 and, like the mixing segments, general purpose mixing discs, rotors, VCMT threads (trademark: Kobe Steel, Ltd.), Twist Kneading (trademark: Japan Steel Works, Ltd.), BMS (trademark: Japan Steel Works, Ltd.), and the like can be used. The mixing conditions are not particularly limited and, for example, the temperature of the mixture is 150 to 290 ° C, the shear rate is 100 / s to 10,000 / s, the specific energy obtained by dividing the energy consumption of the mixer motor per unit time for a mixed amount per unit time is 0.1 to 6 kW © H / kg. In addition, extruders can be used with the connection of a double thread and a double thread, the connection of a double thread and a single thread, or the connection of a continuous mixer and a double thread. As manufacturers of the above extruders, Japan Steel Works, Ltd., Kobe Steel, Ltd., Werner, Ikegai Corporation, Toshiba Machine co., Ltd., and the like can be mentioned.
[00190] The polymeric composition thus obtained can be molded by a known method such as injection molding, two-color injection molding, extrusion molding, rotational molding, press molding, hollow molding, interleaved molding, compression molding, forming vacuum, powder mud molding, laminated molding, calender molding, or blow molding. If necessary, processing such as foaming, drawing, adhesion, printing, painting, or galvanizing can be carried out.
[00191] Since the second polymeric composition of the invention has the above configuration, it is possible to give an excellent molded body in the balance properties between thermal resistance, stiffness, impact resistance, resistance to surface impact, elongation at break, reflection speculate, and delamination using the composition.
[00192] Examples of the molded body compound of the second polymeric composition include food packaging containers, various trays, plates, tubes, films, fibers, laminates, coatings, electrical and electronic components of printed circuit boards, OA devices such as computers, appliance boxes, automobile interior and exterior materials, external plate parts, precision parts, and various industrial parts such as building materials. Furthermore, in these fields of use, as described below, the second polymeric composition of the invention can preferably be used even after defoaming.
[00193] The second polymeric composition of the invention can be molded by foaming using a foaming agent. The method for defoaming is not particularly limited and can be any method of a batch method or a continuous method. Specifically, the composition can be foamed by a molding method such as extrusion molding, injection molding, or press molding.
[00194] As the foaming agent, for example, a chemical foaming agent or a physical foaming agent can be used. The defoaming agent can be selected depending on the production method. The defoaming agent can be used alone or two or more of them can be used in combination. <Chemical Foaming Agent>
[00195] As the chemical foaming agent, for example, a thermal decomposition type foaming agent and a hollow particle foaming body can be mentioned.
[00196] The thermal decomposition foaming agent includes fg gurwoc agents> «q eqo dcug go pkVtquq Vcku eqoq P.pó- fkpkvtquqrgpvcogvkngpqvgvtcokpc g P.PÓ-dimethil-P.PÓ-dinitrosotereftam; azo-based foaming agents such as azodicarbonamide, barium azodicarboxylate, and barium azodicarboxylate; sulfoidrazide-based foaming agents such as p, p-oxybisbenzenesulfonyl hydrazide, 6.6O-oxybis (benzenesulfonyl hydrazide), and p-toluenesulfonyl semicarbazide; triazine based foaming agents such as trihydrazinotriazine; foaming agents based on tetrazole such as 5-phenylthetrazole, azobistetrazoldiguanidine, and azobistetrazolaminoguanidine; inorganic foaming agents such as sodium hydrogen carbonate. The thermal decomposition type defoaming agent can be used alone or two or more of them can be used in combination.
[00197] The amount of thermal decomposition foaming agent to be added is not particularly limited, but is, for example, from 0.1 to 100 parts by weight based on 100 parts by weight of the polymeric composition excluding the thermal decomposition defoaming.
[00198] The hollow particle defoaming agent is a thermally expandable microsphere encapsulating a blowing agent and having a thermoplastic resin as a shell component. As the blowing agent that constitutes the hollow particle defoaming agent, for example, the same defoaming agents as the thermal decomposition type defoaming agents can be mentioned above. The proportion of the blowing agent that occupies the hollow particle defoaming agent is preferably 5 to 30% by weight. Examples of the thermoplastic resin that constitutes the hollow particle defoaming agent include thermoplastic resins such as homopolymers or copolymers derived from (meth) acrylonitrile, (meth) acrylates, vinyl halides, vinylidene halides, styrene based monomers, acetate vinyl, butadiene, chloroprene, vinylpyridine, and the like. Thermoplastic resins can be crosslinked or crosslinkable with a crosslinking agent such as divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di (meth) acrylate 1 , 3-butylene glycol, (meth) allyl acrylate, triacrylformal, or trialyl isocyanurate. The hollow particle defoaming agent can be used alone or two or more of them can be used in combination. The mass average particle size of the hollow particle defoaming agent (in an unexpanded microsphere state) is preferably 1 to 100 µm.
[00199] The amount of the hollow particle defoaming agent to be added is not particularly limited and is, for example, from 0.1 to 100 parts by weight based on 100 parts by weight of the polymeric composition excluding the defoaming agent. hollow particle type. <Physical Foaming Agent>
[00200] Examples of the physical defoaming agent include aliphatic hydrocarbons such as propane, butane, and pentane; alicyclic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane; halogenated hydrocarbons such as chlorodifluoromethane, difluoromethane, trifluoromethane, trichlorofluoromethane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, trichlorofluoromethane, chloromethane, chloroethane, dichlorotrifluoroethane, dichlorofluoroethane, chlorodifluoroethane, dicloropenta-fluoroethane, pentafluoroethane, trifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, tetraclorodifluoroetano, chloropentafluoroethane and perfluorocyclobutane; inorganic gases such as carbon dioxide, nitrogen, and air; and water. In addition, it is also possible to shape the foamed body using a supercritical fluid. Examples of supercritical fluid include supercritical fluids of nitrogen or carbon dioxide. Physical foaming agents can be used alone or two or more of them can be used in combination.
[00201] The amount of the physical foaming agent to be added is not particularly limited, but is, for example, from 0.1 to 100 parts by weight based on 100 parts by weight of the polymeric composition excluding the physical foaming agent.
[00202] Among the foaming agents, supercritical carbon dioxide is preferable since it becomes a supercritical state at relatively low temperature and pressure, it is suitable for foaming molding due to a rapid impregnation rate in the polymeric composition in a molten state and high density contamination capacity, and uniform air bubbles can be obtained. <Foaming Nucleation Agent>
[00203] The second polymeric composition of the invention may contain a defoaming nucleating agent (nucleating agent).
[00204] Examples of the foaming nucleating agent include powders of inorganic compounds such as calcium carbonate, talc, mica, silica and titania. By incorporating the foaming nucleating agent into the polymeric composition, the diameter of the foam cell can be easily controlled and a molded foamed body having appropriate flexibility and the like can be obtained.
[00205] The particle diameter of the defoaming nucleating agent is preferably 0.1 ~ 50 om, and more preferably 0.1 ~ 20 om. When the particle diameter of the foaming nucleating agent is the lower limit of the range or more, the effect as a foaming nucleating agent is easily obtained, the diameter of the foam cell becomes small, and the diameter of the foaming cell foam tends to be uniform. When the particle diameter of the defoaming nucleating agent is the upper limit of the range or less, the diameter of the foam cell and the number of the foam cells become appropriate and the damping properties of the foamed body tend to be excellent .
[00206] The content ratio of the defoaming nucleating agent is preferably from 0 to 20 parts by weight, more preferably from 0.01 to 15 parts by weight, and more preferably from 0.1 to 10 parts by weight based on 100 parts by mass of the polymeric composition. Incidentally, it is also preferable to add the foaming nucleating agent to a molding machine, for example, as a polypropylene resin masterbatch or the like. Examples
[00207] The following will describe the present invention more specifically on the basis of Examples, but the invention is not limited to these Examples. In describing the following Examples and the like, parts are shown on a mass basis unless otherwise specified. <Hydrogenation Catalyst Production>
[00208] According to Japanese Patent No. 3777810, bis (j5-cyclopentadienyl) titanium (furfuryloxy) chloride (hereinafter Vcodfio cnwfkfq eqoq “cle„ zkfq fg enqtqdku * 4.6-cyclopentadienil) titanium (IV) li ^) swg fi wo ecVcnkucfqt fg jkftqigpc> «q hqk qdvkfqo <Physical Property Values of Conjugated Diene Polymer (Hydrogenated)>
[00209] The physical property values of conjugated (hydrogenated) diene polymers were measured by the following methods. However, the physical property values of the following (1) to (3) are those for polymers before hydrogenation and the physical property values of the following (4) to (7) are those for polymers after hydrogenation. (1) Vinyl bond content and styrene unit content
[00210] The vinyl bond content was determined by the infrared absorption spectrum method (Morello method). However, the unit of the vinyl bond content is on a mole percent basis. The content of the styrene unit was determined by preparing a calibration curve using the infrared absorption spectrum method (Morello method). However, the unit of styrene unit content is on a mass% basis. (2) Weighted average molecular weight (Mw)
[00211] Weighted average molecular weight (Mw) is the weighted average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) (HLC-8120 manufactured by Tosoh Corporation). - Development solvent: tetrahydrofuran (THF) - Measurement temperature: 40 ° C - Column: TSKgel GMH ^ 1 (3) Coupling rate
[00212] The coupling rate is a value that indicates the content of the coupled or branched polymers in the total polymer. It was determined from the ratio of the coupled polymer after the addition of a coupling agent, by GPC analysis. (4) Hydrogenation rate
[00213] The hydrogenation rate was calculated from the spectrum of 1H-NMR at 400 MHz using carbon tetrachloride as a solvent. (5) Fusion flow (MFR)
[00214] The melt flow rate (MFR) was measured under temperature conditions: 230 ° C and load: 2.16 kg according to JIS K7210. (6) Mooney viscosity (MV1 + 4)
[00215] Mooney's viscosity (MV1 + 4) was measured using an L rotor under preheating conditions for 1 minute, a rotor operating time of 4 minutes, and a temperature of 125 ° C in the case of hydrogenated BR or a temperature of 100 ° C in the case of hydrogenated SBR according to JIS K6300. (7) Glass transition temperature (Tg)
[00216] The glass transition temperature (Tg) was determined according to ASTM D3418. [Production of Hydrogenated Conjugated Diene Polymer (Hydrogenated BR)] [Example 1A]
[00217] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 25.6 kg of cyclohexane, 38.4 kg of tetrahydrofuran, 3,200 g of 1,3 -butadiene, and 29.1 mmoles of N- (tert-butyldimethylsilyl) piperazine and 38.0 mmoles of n-butylithium as a polymerization initiator, and adiabatic polymerization from a polymerization initiation temperature of 40 ° C was performed .
[00218] After the completion of the polymerization, 32.3 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and a reaction was carried out for 15 minutes. Then, under the supply of hydrogen gas at a pressure of 0.4 MPa-Manometric in the system, the stirring was carried out for 10 minutes.
[00219] The reaction liquid was controlled at 80 ° C or more, 4.48 g of enqtgVq fg fkgVüanwoípko. 5.3 3 i fg enqtgVq fg dku * ^ 7-cyclopentadienyl) titanium (furfuryloxy), and 1.18 g of n-butyllithium were added, and a hydrogenation reaction was carried out in order to maintain a hydrogen pressure of 1.0 MPa . At the moment when the hydrogen absorption reached an accumulative amount in which an objective hydrogenation rate was reached, the reaction liquid was returned to normal temperature and normal pressure and was extracted from the reaction vessel to obtain a polymer solution.
[00220] The polymer solution obtained was subjected to removal of solvent by stripping with steam, and then dried by a hot roller which was controlled at temperature at 110 ° C, thereby obtaining a hydrogenated conjugated diene polymer A. [Example 2A]
[00221] A hydrogenated conjugated diene polymer B was obtained in the same manner as in Example 1A except that the N- (tert- dwVüfkogVüuüü + rkrgtazkpc fok Vtqecfc rctc powder- (N, N-bis (trimethylsilyl) amino-ethyl) piperazine in the Example 1A. [Example 3A]
[00222] A hydrogenated conjugated diene polymer C was obtained in the same manner as in Example 1A except that the operation in which 32.3 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and a reaction was carried out for 15 minutes was switched to the operation in which 1.60 mmol of silicon tetrachloride was added and a reaction was carried out for 5 minutes and then 29.1 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and a reaction was carried out for 15 minutes , in Example 1A. [Example 4A]
[00223] A hydrogenated conjugated diene polymer D was obtained in the same manner as in Example 1A except that, after the polymer solution after the hydrogenation reaction was obtained, 32.1 mmoles of silicon tetrachloride as an onion forming agent were added and a reaction was carried out for 5 minutes, in Example 1A. [Comparative Example 1A]
[00224] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 25.6 kg of cyclohexane, 38.4 kg of tetrahydrofuran, 3200 g of 1,3-butadiene were added , and 38.0 mmoles of n-butyllithium as a polymerization initiator, and adiabatic polymerization from a polymerization initiation temperature of 40 ° C was performed. After the completion of the polymerization, under the supply of hydrogen gas at a pressure of 0.4 MPa-Manometric in the system, agitation was carried out for 10 minutes. The reaction liquid was controlled at 80 ° C or more, 2.32 g of diethyl aluminum chloride and 5.19 g of clqtgVq fg dku * ^ 7-cyclopentadienyl) titanium (furfuryloxy) were added, and a hydrogenation reaction was carried out in order to maintain a hydrogen pressure of 1.0 MPa. At the moment when the hydrogen absorption reached an accumulative amount in which an objective rate of hydrogenation was achieved, the reaction liquid was returned to normal temperature and normal pressure and was extracted from the reaction vessel to obtain a polymer solution. The polymer solution obtained was subjected to removal of solvent by stripping with steam, and then dried by a hot roller that was controlled in temperature at 110 ° C, thereby obtaining a hydrogenated conjugated diene polymer E. [Comparative Example 2A]
[00225] A conjugated diene polymer F was obtained in the same manner as in Example 1A except that the hydrogenation reaction was not carried out. [Comparative Example 3A]
[00226] A hydrogenated conjugated diene polymer G was obtained in the same manner as in Example 1A except that N- (tert-butyldimethylsilyl) piperazine was switched to piperidine in Example 1A. [Example 4A]
[00227] A hydrogenated conjugated diene polymer H was obtained in the same manner as in Example 1A except that the operation in which 29.1 mmoles of N- (tert-butyldimethylsilyl) piperazine and 38.0 mmoles of n-butylithium as an initiator of polymerization were added was switched to the operation in which 38.0 mmoles of n-butyllithium were added, in Example 1A. [Mixing Method and Characteristic Evaluation of the Polymeric Composition]
[00228] Using a plastomill (internal capacity: 250 ml) adapted with a temperature control device, as a mixture of the first stage, the conjugated (hydrogenated) diene polymer obtained in each of the Examples and Comparative Examples, zinc white, stearic acid, silica, a coupling agent, carbon SRF, and a softener were mixed under the conditions of a fill rate of 72% by volume, a rotational number of 60 rpm, and 100 ° C, according to the formulation of mixture from Table 2. Then, as a second stage mixture, after cooling the mixture obtained above to room temperature, a crosslinking agent was mixed according to the mixture formulation in Table 2. The mixed product was molded and then vulcanized in a vulcanization press at 160 ° C for a predetermined time to manufacture a reticulated body, and the following characteristic evaluation was carried out.
[00229] [Characteristic Assessment of Physical Properties in Ordinary State] Tensile strength at break (TB), tensile strength at break (EB): They were measured at a measuring temperature of 23 ° C according to JIS K6251. A higher numerical value indicates that the cross-linked body has more excellent mechanical properties. Hardness (Hard A) was measured according to JIS K6253.
[00230] [Characteristic Evaluation of Physical Properties at High Temperature] A Tensile strength at break (TB), tensile strength at break (EB): They were measured at a measuring temperature of 120 ° C according to JIS K6251. A higher numerical value indicates that the cross-linked body has more excellent mechanical properties.
[00231] [Characteristic Evaluation of Dynamic Module] dynamic / static ratio: Using a test piece formed in block, a dynamic module 1 at 70 Hz was measured under the conditions of a 1% dynamic stress and a temperature of 25 ° C according to JIS K6394. Also, similarly, a dynamic module 2 at 0.1 Hz was measured under the conditions of a 10% dynamic stress and a temperature of 25 ° C. Incidentally, when measuring, a device that measures viscoelasticity (trade name “CTGU” + hcdtkecfq rgnc TjgqogVtke Kpeo hqk wucfqo The dynamic / static ratio was determined as a value calculated from the following expression. Incidentally, the dynamic / static ratio indicates that the reticulated body is more superior in vibration damping properties when the ratio is closer to 1.
[00232] Expression: Dynamic / static ratio = (Dynamic module 1 at 70 Hz) / (Dynamic module 2 at 0.1 Hz) [Table 1] Table 1: Polymerization Formulation BR

[Table 2] Table 2: Formulation Table BR
(1) Zinc white <pqog eqogtekcn "¥ knc Qzkfg LKU% 4" (manufactured by Hakusui Tech Co., Ltd.) * 4 + èekfq guVgárieq <pqog eqogtekcn "NUPCE U52" (manufactured by Kao Corporation) * 5 + Uínkec <pqog eqogtekcn "Pkruü GT" * hcdtkecfq rgnc Vquqj Silica Corporation) (4) AcorncogpVq agent <pqog eqogtekcn "VUN: 592" (manufactured by GE Toshiba Siliconas Co., Ltd.) * 7+ URH ectdqpq <pqn U ”* hcdtkecfq rgnc Tokai Carbon Co., Ltd.) * 8+ CocekcpVg <pqog eqogtekcn“ Fkcpc Rtqeguuq RY; 2 ”(manufactured by Idemitsu Kosan Co., Ltd.) * 9+ CigpVg fg tgVkewnc>« q 3 <pqog eqogtekcn “RGREUMKN F- 62” * hcdtkecfq rgnc PQH Eqtrqtcvkqp + *: + CigpVg fg tgVkewnc> «q 4 <pqog eqogtekcn“ KQU ”* hcdtkecfq by Tsurumi Chemical Industry Co., Ltd.)
[00233] In Comparative Example 4A, since n-butylithium which is a conventional polymerization initiator is used, it is assumed that the dynamic / static ratio evaluation is poor. In Comparative Example 3A, since a modified polymerization initiator compound of n-butyllithium and piperidine is used, the dynamic / static ratio evaluation is supposed to be poor. In Comparative Example 2A, since no hydrogenation reaction is performed, the evaluation of Tb and Eb is assumed to be low. Conversely, in Example 1A, since a modified n-butyllithium polymerization initiator compound and a specific amine compound is used, the dynamic / static ratio evaluation is supposed to be excellent. [Production of Hydrogenated Conjugated Diene Polymer (hydrogenated SBR)] [Example 1B]
[00234] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 25.6 kg of cyclohexane, 179 g of tetrahydrofuran, 864 g of styrene, 2336 g of 1, were added 3-butadiene, and 23.8 mmoles of N- (tert-butyldimethylsilyl) piperazine and 33 mmoles of n-butylithium as a polymerization initiator, and adiabatic polymerization from a polymerization initiation temperature of 45 ° C was performed . At the moment when the polymerization conversion reached 99%, 64 g of 1,3-butadiene were added over a period of 2 minutes and the polymerization was continued for another 3 minutes.
[00235] After the completion of the polymerization, 26.5 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and a reaction was carried out for 15 minutes. Then, under the supply of hydrogen gas at a pressure of 0.4 MPa-Manometric in the system, the stirring was carried out for 10 minutes.
[00236] The reaction liquid was controlled at 80 ° C or more, 3.67 g of enqtgVq fg fkgVücnwoípkq. 4.49 i fg enqtgVq fg dku * ^ 7-cyclopentadienyl) titanium (furfuryloxy), and 0.83 g of n-butyllithium were added, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa . After the reaction, the reaction liquid was returned to normal temperature and normal pressure, and was extracted from the reaction vessel to obtain a polymer solution.
[00237] The polymer solution obtained was subjected to solvent removal by stripping with steam, and then dried by a hot roller which was controlled at 110 ° C, thereby obtaining a hydrogenated conjugated diene copolymer A. [Example 2B]
[00238] A hydrogenated conjugated diene copolymer b was obtained in the same manner as in Example 1B except that N- (tert- dwVüfkogVüuüü + rkrgrazkpc fok Vtqecfc rctc powder- (N, N-bis (trimethylsilyl) amino-ethyl) piperazine in the Example 1B. [Example 3B]
[00239] A hydrogenated conjugated diene copolymer was obtained in the same manner as in Example 1B except that the operation in which 26.5 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and a reaction was carried out for 15 minutes was switched to the operation in which 1.33 mmol of silicon tetrachloride was added and a reaction was carried out for 5 minutes and then 22.2 mmoles of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and a reaction was carried out by 15 minutes, in Example 1B. [Example 4B]
[00240] A d copolymer of hydrogenated conjugated diene was obtained in the same manner as in Example 1B except that, after the polymer solution after the hydrogenation reaction was obtained, 26.8 mmoles of silicon tetrachloride as an onium forming agent was added and a reaction was carried out for 5 minutes, in Example 1B. [Comparative Example 1B]
[00241] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 25.6 kg of cyclohexane, 179 g of tetrahydrofuran, 864 g of styrene, 2336 g of 1, were added 3-butadiene, and 33 mmoles of n-butyllithium as a polymerization initiator, and adiabatic polymerization from a polymerization initiation temperature of 45 ° C was performed. At the moment when the polymerization conversion reached 99%, 64 g of 1,3-butadiene were added over a period of 2 minutes and the polymerization was continued for another 3 minutes. After the completion of the polymerization, under the supply of hydrogen gas at a pressure of 0.4 MPa-Manometric in the system, agitation was carried out for 10 minutes. The reaction liquid was controlled at 80 ° C or more, 3.67 g of diethyl aluminum chloride, 3.79 g of dku * ^ 7-cyclopentadienyl) titanium (furfuryloxy), and 0.83 g of n-butyllithium were added, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. After the reaction, the reaction liquid was returned to normal temperature and normal pressure and was extracted from the reaction vessel to obtain a polymer solution. The polymer solution obtained was subjected to removal of solvent by stripping with steam, and then dried by a hot roller which was controlled in temperature at 110 ° C, thereby obtaining a copolymer and hydrogenated conjugated diene. [Comparative Example 2B]
[00242] A conjugated diene copolymer f was obtained in the same manner as in Example 1B except that the hydrogenation reaction was not carried out. [Comparative Example 3B]
[00243] A g copolymer of hydrogenated conjugated diene was obtained in the same manner as in Example 1B except that N- (tert-butyldimethylsilyl) piperazine was switched to piperidine in Example 1B. [Comparative Example 4B]
[00244] A hydrogenated conjugated diene h copolymer was obtained in the same manner as in Example 1B except that the operation in which 23.8 mmoles of N- (tert-butyldimethylsilyl) piperazine and 33 mmoles of n-butylithium as a polymerization initiator were added was changed to the operation in which 33 mmoles of n-butyllithium were added, in Example 1B. [Mixing Method and Characteristic Evaluation of Polymeric Composition]
[00245] Using a plastomill (internal capacity: 250 ml) adapted with a temperature control device, as a mixture of the first stage, the conjugated diene copolymer (hydrogenated) obtained in any of the Examples and Comparative Examples, zinc white , stearic acid, silica, a coupling agent, and an anti-aging agent were mixed under the conditions of a filling rate of 72% by volume, a rotational number of 60 rpm, and 100 ° C, according to the mixture formulation. from Table 4. Then, as a second stage mixture, after cooling the mixture obtained above to room temperature, a cross-linking agent and a cross-linking aid were mixed according to the mixture formulation in Table 4. The mixed product was molded and then vulcanized in a vulcanization press at 160 ° C for a predetermined time to prepare a reticulated body and the following characteristic evaluation was carried out. (i) 0 ° Ctanf: It was measured under the conditions of a 0.14% dynamic tractive effort, an angular velocity of 100 radians per second, and 0 ° C using the above reticulated body as a measurement sample and using a dynamic spectrometer (manufactured by Rheometrics of US). The value is indicated as an index where Comparative Example 1B is taken as 100 and a higher numerical value means greater and better wet skid resistance. (ii) 70 ° Ctanf: It was measured under the conditions of a 0.7% dynamic tractive effort, an angular velocity of 100 radians per second, and 70 ° C using the above reticulated body as a measurement sample and using a dynamic spectrometer (manufactured by Rheometrics of US). The value is indicated as an index where Comparative Example 1B is taken as 100 and a higher numerical value means better and lesser low hysteresis loss properties. (iii) Abrasion resistance: It was measured at 25 ° C with a 10 N load according to JIS K6264 using the cross-linked body above as a measurement sample and using a DIN abrasion tester (manufactured by Toyo Seiki Co., Ltd .). The value is indicated as an index where Comparative Example 1B is taken as 100 and a higher numerical value means better resistance to abrasion. (iv) Tensile strength at break (TB), tensile strength at break (EB): The measurement was performed at room temperature (23 ° C) according to JIS K6251 using the cross-linked body above as a measurement sample. A higher numerical value indicates more excellent mechanical properties. [Table 3] Table 3: SBR Polymerization Formulation

[Table 4] Table 4: SBR blend formulation
(1) Zinc white: trade name “Zinc Oxide JIS # 2” (manufactured by Hakusui Tech Co., Ltd.) (2) Stearic acid: trade name “LUNAC S30” (manufactured by Kao Corporation) * 3+ Dtcpeq fg zkneq <nqog eqogtekcn “¥ kne Qzkfg LKU% 4” (manufactured by Hakusui Tech Co., Ltd.) * 4+ èekfq guVgárieq <nqog eqogtekan “NUPCE U52” (manufactured by Kao Corporation) * 5+ Uínkea “nqog ¥ eqog GQUUKN 3387OR ”* fadtkeafq by Rhodia) * 6+ CignVg fg aeqrnamgnVq <nqog eqogtekan“ Uk97 ”* hadricated by Evonik Degussa Japan) * 7+ CignVg anVkgnxgnjgekognVq <nqog eqogqkkkk“ Qkm ”¥ Nvf0 + * 8+ CignVg fg tgVkewna> «q <nqog eqogtekan“ KQU ”* hadtkeafq by Tsurumi Chemical Industry Co., Ltd.) (7) Crosslinking accelerator-3 <nqog eqogtekan“ CEEGN VN ”* hadtkeafq rgna Mayokwejk Eq0. NVf0 ++ (8) Cross-linking accelerator-2: trade name “PQEEGNGT FO” * hadtkeafq rgna Qwejk Ujknmq Ejgoiean KnfwuVtkd Ctr. Ltd.) (9) Cross-linking accelerator-3: trade name “PQEEGNGT F” * hadtkjk U Cd. Ltd.) (10) Crosslink accelerator-4: trade name “PQCCGNGT C ¥” * fadtkecfq rgnc Qwejk Ujkpmq Ejgokecn KnfwuVtkcn Ed. Ltd.) [Production of Hydrogenated Conjugated Diene Block Copolymer] [Example 1C] SEBS
[00246] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 24 kg of cyclohexane, 473 g of styrene, 568 g of tetrahydrofuran, and 11.1 g of N - (tert-butyldimethylsilyl) piperazine and 5.5 g of n-butylithium as a polymerization initiator, and the polymerization of the first stage was carried out at a temperature of initiation of polymerization of 50 ° C and then, after the temperature was controlled at 15 ° C, 4471 g of 1,3-butadiene was added and the polymerization of the second stage was carried out under an adiabatic condition. Thereafter, the temperature was controlled at 80 ° C, 316 g of styrene was added, and the third stage of polymerization was carried out under an adiabatic condition. After completion of the polymerization, the whole was left to stand for 10 minutes, under supply of hydrogen gas at a pressure of 0.4 MPa-Manometric.
[00247] The reaction liquid was controlled at 80 ° C, 2.5 g of silicon tetrachloride, 1.2 g fg enqtgVq fg fkgVücnwoínkq, g 4 .; i fg enqtgVq dku * ^ 7- cyclopentadienyl) titanium (furfuryloxy) was added as a hydrogenation catalyst, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00248] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 125,000, and a melt flow rate (230 ° C, 2.16 kg) of 30 g / 10 minutes. The vinyl bond content measured at the end point of the third stage block polymerization was calculated to be 79 mol%. The styrene unit content was 15% by weight. ] Gzgornqu "Eqorctcvkxqu" 3E "g" 3EÓ_ "UGDU
[00249] The hydrogenated block copolymers were obtained in the same manner as in Example 1C except that the operation in which 11.1 g of N- (tert-butyldimethylsilyl) piperazine and 5.5 g of n-butylithium as a polymerization initiator were added was switched to the operation in which 4.7 g of piperidine and 5.5 g of n-butyllithium were added in Comparative Example 1C or the operation in which only 5.5 g of n-butyllithium was added in the Exempnq "Eqorctcvkxq "3EÓ." Because "Gzgornq" 3E0 [Example 2C] SEBS
[00250] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 24 kg of cyclohexane, 472 g of styrene, 201 g of tetrahydrofuran, and 13.1 g of N - (tert-butyldimethylsilyl) piperazine and 6.6 g of n-butyllithium as a polymerization initiator, and the polymerization of the first stage was carried out at a start temperature of polymerization of 50 ° C and then, after the temperature was controlled at 15 ° C, 4771 g of 1,3-butadiene were added and the polymerization of the second stage was carried out under an adiabatic condition. After completion of the polymerization, 3.2 g of methyldichlorosilane were added and a reaction was carried out for 30 minutes. Then, the whole was left to stand for 10 minutes, under the supply of hydrogen gas at a pressure of 0.4 MPa-Manometric.
[00251] The reaction liquid was controlled at 80 ° C, 0.95 g silicon tetrachloride, 1.1 g diethyl aluminum chloride, and 3.1 g dku chloride * ^ 7-cyclopentadienyl) titanium (furfuryloxy ) were added as a hydrogenation catalyst, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00252] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 170,000, a coupling rate of 60%, and a melting flow rate (230 ° C, 2.16 kg) of 7 g / 10 minutes. The vinyl bond content measured at the end point of the second stage block polymerization was calculated to be 64 mol%. The styrene unit content was 9% by weight. [Comparative Example 2C] SEBS
[00253] A hydrogenated block copolymer was obtained in the same manner as in Example 2C except that the operation in which 13.1 g of N- (tert-butyldimethylsilyl) piperazine and 6.6 g of n-butylithium as a polymerization initiator were added was changed to the operation in which only 6.6 g of n-butyllithium was added, in Example 2C. [Example 3C] SEBS (silazane modification)
[00254] In a reaction vessel having an internal volume of 50 liters, which was subjected to nitrogen substitution, 22 kg of cyclohexane, 562 g of styrene, 7.4 g of 2,2-di (tetrahydrofuryl) were added ) propane, and 11.3 g of N- (tert-butyldimethylsilyl) piperazine and 5.6 g of n-butylithium as a polymerization initiator, and the polymerization of the first stage was carried out at a polymerization start temperature of 50 ° C and then, after the temperature was controlled at 15 ° C, 5184 g of 1,3-butadiene were added and the polymerization of the second stage was carried out under an adiabatic condition. Thereafter, the temperature was controlled at 80 ° C, 375 g of styrene was added, and the polymerization of the third stage was carried out under an adiabatic condition. Then, 125 g of 1,3-butadiene was added.
[00255] After the completion of the polymerization, 22.7 g of [N, N-bis (trimethylsilyl) aminopropyl] methyldiethoxysilane were added and a reaction was carried out for 30 minutes, and the whole was left to stand for 10 minutes, under supply of hydrogen gas at a pressure of 0.4 MPa- Manometric.
[00256] The reaction liquid was controlled at 80 ° C, 9.4 g of fkgVklclwoípkq chloride. 9.8 i fg enqtgVq fg bku (jp-cyclopentadienyl) titanium (furfuryloxy), and 2.0 g of n-butylithium were added as a hydrogenation catalyst, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00257] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 135,000, and a melt flow rate (230 ° C, 2.16 kg) of 15 g / 10 minutes. The vinyl bond content measured at the end point of the fourth stage block polymerization was calculated to be 80 mol%. The styrene unit content was 15% by weight. [Comparative Example 3C] SEBS (silazane modification)
[00258] A hydrogenated block copolymer was obtained in the same manner as in Example 3C except that the operation in which 11.3 g of N- (tert-butyldimethylsilyl) piperazine and 5.6 g of n-butylithium as a polymerization initiator were added was changed to the operation in which only 5.6 g of n-butyllithium were added, in Example 3C. [Example 4C] CEBC
[00259] In a reaction vessel having an internal volume of 50 liters, which was subjected to nitrogen replacement, 26 kg of cyclohexane, 973 g of 1,3-butadiene, 1.3 g of tetrahydrofuran, and 5.7 g of N- (tert-butyldimethylsilyl) piperazine and 2.8 g of n-butylithium as a polymerization initiator, and the polymerization of the first stage was carried out at a polymerization start temperature of 70 ° C. Then, after the temperature was controlled at 20 ° C and 31 g of tetrahydrofuran were added, 2270 g of 1,3-butadiene were added and the polymerization of the second stage was carried out under an adiabatic condition.
[00260] After the completion of the polymerization, 1.7 g of methyldichlorosilane was added and a reaction was carried out for 30 minutes, and the whole was left to stand for 10 minutes, under supply of hydrogen gas at a pressure of 0.4 MPa- Manometric.
[00261] The reaction liquid was controlled at 80 ° C, 0.24 g of diethylalwoípkq chloride. 4.3 i fg enqtgVq fg bku (jp-cyclopentadienyl) titanium (furfuryloxy), and 0.26 g of n-butylithium were added as a hydrogenation catalyst, and a reaction was carried out for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00262] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 275,000, an coupling rate of 80%, and a melting flow rate (230 ° C, 2.16 kg) of 4.5 g / 10 minutes. The vinyl bond content (block A vinyl bond content) of the 1,3-butadiene unit measured at the end point of the first stage block polymerization was 15 mol%. In addition, the vinyl bond content (block B vinyl content) of the 1,3-butadiene unit in the second stage block was calculated to be 36 mol% of the vinyl bond content of the 1-unit , 3-butadiene measured at the end point of the block polymerization in the second stage and the vinyl bond content of the first stage. [Comparative Example 4C] CEBC
[00263] A hydrogenated block copolymer was obtained in the same manner as in Example 4C except that the operation in which 5.7 g of N- (tert-butyldimethylsilyl) piperazine and 2.8 g of n-butylithium as a polymerization initiator were added was switched to the operation in which only 2.8 g of n-butyllithium was added, in Example 4C. [Example 5C] SEBS
[00264] In a reaction vessel having an internal volume of 50 liters, which was replaced with nitrogen, 24 kg of cyclohexane, 1846 g of 1,3-butadiene, 1.2 g of tetrahydrofuran, and 11.6 g of N- (tert-butyldimethylsilyl) piperazine and 5.8 g of n-butyllithium as a polymerization initiator, and the polymerization of the first stage was carried out at a polymerization start temperature of 70 ° C. Then, after the temperature was controlled to 20 ° C and 52 g of tetrahydrofuran were added, 2374 g of 1,3-butadiene and 791 g of styrene were added and the polymerization of the second stage was carried out under an adiabatic condition. Thereafter, the temperature was controlled to 80 ° C, 264 g of styrene was added, and the polymerization of the third stage was carried out under an adiabatic condition. After completion of the polymerization, the whole was left to stand for 10 minutes, under supply of hydrogen gas at a pressure of 0.4 MPa-Manometric.
[00265] The reaction liquid was controlled at 80 ° C, 3.2 g of methyldichlorosilane and 2.7 g of dku * ^ 7-cyclopentadienyl) titanium (furfuryloxy) chloride were added as a hydrogenation catalyst, and a reaction was performed for 2 hours in order to maintain a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00266] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 140,000, and a melt flow (230 ° C, 2.16 kg) of 5.5 g / 10 minutes. The vinyl bond content (block A vinyl bond content) of the 1,3-butadiene unit measured at the end point of the first stage block polymerization was 15 mol%. In addition, the vinyl bond content (block B vinyl content) of the 1,3-butadiene unit in the second stage block was calculated to be 41 mol% of the vinyl bond content of the 1-unit , 3-butadiene measured at the end point of the block polymerization in the second stage and the vinyl bond content of the first stage. The styrene unit content was 20 wt% (the styrene unit content of block B was 25 wt%). [Comparative Example 5C] ESCB
[00267] A hydrogenated block copolymer was obtained in the same manner as in Example 5C except that the operation in which 11.6 g of N- (tert-butyldimethylsilyl) piperazine and 5.8 g of n-butylithium as a polymerization initiator were added was changed to the operation in which only 5.8 g of n-butyllithium were added, in Example 5C. [Example 6C] ESCB (modification of silazane)
[00268] In a reaction vessel having an internal volume of 50 liters, which was subjected to substitution with nitrogen, 25 kg of cyclohexane, 829 g of 1,3-butadiene, 1.3 g of tetrahydrofuran, and 7.4 g of N- (tert-butyldimethylsilyl) piperazine and 3.7 g of n-butylithium as a polymerization initiator, and the polymerization of the first stage was carried out at a polymerization start temperature of 70 ° C and then, after the temperature was controlled at 20 ° C and 52 g of tetrahydrofuran were added, 3027 g of 1,3-butadiene were added and the polymerization of the second stage was carried out under an adiabatic condition. Thereafter, the temperature was controlled at 80 ° C, 207 g of styrene was added, and the polymerization of the third stage was carried out under an adiabatic condition. Then, 83 g of 1,3-butadiene was added.
[00269] After completion of the polymerization, 14 g of [N, N-bis (trimethylsilyl) aminopropyl] methyldiethoxysilane were added and a reaction was carried out for 30 minutes, and the whole was left to stand for 10 minutes, under supply of hydrogen gas at a pressure of 0.4 MPa- Manometric.
[00270] The reaction liquid was controlled at 80 ° C, 1.5 g of tetrachloride fg uüíekq. 4.: i fg enqtgVq fg fkgVüdwoípkq. 5.4 i fg enqtgVq fg dku * ^ 7 - cyclopentadienyl) titanium (furfuryloxy), and 1.2 g of n-butylithium were added as a hydrogenation catalyst, and a reaction was carried out for 2 hours while maintaining a hydrogen pressure of 1.0 MPa. The reaction liquid was poured into a large amount of methanol, and the precipitated solid was recovered and then dried in a vacuum dryer to obtain a hydrogenated block copolymer.
[00271] The hydrogenated block copolymer obtained had a hydrogenation rate of 98%, a weighted average molecular weight of 155,000, and a melt flow rate (230 ° C, 2.16 kg) of 3 g / 10 minutes. The vinyl bond content (block A vinyl bond content) of the 1,3-butadiene unit measured at the end point of the first stage block polymerization was 15 mol%. In addition, the vinyl bond content (block B vinyl content) of the 1,3-butadiene unit in the second stage block was calculated to be 42 mol% of the vinyl bond content of the 1-unit , 3-butadiene measured at the end point of the block polymerization in the second stage and the vinyl bond content of the first stage. The styrene unit content was 5 wt%. [Comparative Example 6C] ESCB (modification of silazane)
[00272] A hydrogenated block copolymer was obtained in the same manner as in Example 6C except that the operation in which 7.4 g of N- (tert-butyldimethylsilyl) piperazine and 3.7 g of n-butylithium as a polymerization initiator were added was changed to the operation in which only 3.7 g of n-butyllithium was added, in Example 6C. [Production of Polymeric Composition] [Example 1D]
[00273] In a Henschel mixer, 68 parts of polypropylene * pqog eqogtekcn “DE28E” hadtkeafq rgnc Lcran Polypropylene Corporation), 49 hydrogenated block obtained in Example 1C, and 0.1 part of anti-aging agent (trade name “Ktiapqz 3232”. hadtkeafq rgla DCUH + photon okutwtafqu pa tgorgtatwta ambient for 30 seconds. Then, the resulting mixture was fed to a double screw extruder (screw same direction without interlocking, L / D = 33.5, manufactured by Ikegai Corporation, noog fq rtqfwtq “REO-67” + go a discharge rate of 20 kg / hour and the extrusion was carried out at a temperature of 200 ° C at a screw rotation number of 200 rpm (shear rate: 470 s-1) to obtain granules The obtained granules were dried at 80 ° C for 5 hours using a dehumidifying dryer to obtain a thermoplastic resin composition The composition of resi in the resulting thermoplastic it was molded at a processing temperature of 200 ° C in an injection molding machine (manufactured by Japan Steel Works, Ltd.) to obtain a test piece for the evaluation of physical property. ] Gzgornqu "4F" g "5F" g "Gzgornqu" Eqorctcvkxqu "3F" c "5F" g "3FÓ_
[00274] Thermoplastic resin compositions and test pieces for the assessment of physical property were obtained in the same manner as in Example 1D except that the type of the hydrogenated block copolymer was changed as described in Table 5, in Example 1D. [Example 4D]
[00275] In a Henschel mixer, 63 parts of rqnkgVkngpq terephthalate * pqog eqogtekcn “TV745E” hcdtkecfq rgnc Pkrrqp WpkrgV EOO. NVfo +. 49 rcrtgu fg rqnkgVkngpq * pqog eqogtekcn "PqxcVge UH553" hcdtkecfq by Japan Polypropylene Corporation), 10 parts of hydrogenated block copolymer obtained in Example 4C, and 0.1 part of anti-aging agent * pqog eqogtekcn "32 Kpq. hcdtkecfq rgnc DCUF + fbtco okuVwtcfqu pc at room temperature for 30 seconds. Then, the resulting mixture was fed to a double screw extruder (same direction thread without interlocking, L / D = 33.5, manufactured by Ikegai Corporation, name of rtqfwVq “REO-67” + go woc Vczc fg fguectic fg 42 miljqtc gc gzVtwu «q fqk performed at a temperature of 280 ° C at a thread rotation number of 200 rpm (shear rate: 470 s-1) to obtain granules. The granules obtained were dried at 80 ° C for 5 hours using a dehumidifying dryer to obtain a thermoplastic resin composition The resulting thermoplastic resin composition was molded at a processing temperature of 280 ° C in an injection molding machine (manufactured by Japan Steel Works, Ltd.) to obtain a test piece to assess physical property. [Examples 5D and 6D and Comparative Examples 4D to 6D]
[00276] The thermoplastic resin compositions and test pieces for the evaluation of physical property were obtained in the same way as in Example 4D except that the type of the hydrogenated block copolymer was changed as described in Table 6, in Example 4D.
[00277] Using the thermoplastic resin compositions and test pieces obtained in the above, the following evaluation was carried out. [Assessment Methods for Test Pieces] (1) Rigidity
[00278] A flexural module of the test piece was measured under the temperature condition of 23 ° C by a three point flexion test method according to ISO 178. The magnitude of the flexural module was used as an indicator of stiffness of the test piece. (2) Impact Resistance (Charpy impact resistance)
[00279] According to ISO 179, the Charpy impact resistance of the test piece was measured under the temperature condition of 23 ° C in a Charpy impact tester. The magnitude of Charpy's impact resistance was taken as an indicator that represents the test piece's impact resistance. Incidentally, NB indicates that the test piece was not destroyed in this test. (3) Impact resistance (resistance to surface impact)
[00280] As another indicator representing the impact resistance of the test piece, the impact resistance of the test piece surface was measured. As for resistance to surface impact, a test piece formed on a 55 mm • 80 mm • 2.4 mm flat plate obtained by injection molding the resin composition obtained in each of the Examples and the like was placed in a hole of 25 mmh, the test piece was hit at a speed of 2.4 mm / s using a 15.7 mmh hit bar having a hemisphere tip, and the breaking energy was calculated from the measurement displacement and load until the test piece is broken. The magnitude of the burst energy was taken as an indicator of resistance to surface impact. (4) Tensile strength at break and elongation strength at break
[00281] According to ISO 527, a tensile test of the test piece was carried out under the temperature condition of 23 ° C to measure the tensile strength at break and the tensile strength at break. (5) Specular reflection
[00282] The surface of the test piece that was molded into a flat plate shape by injection molding the resin composition obtained in each of the Examples and the like was visually observed according to the following criteria to assess the specular reflection of the test piece.
[00283] O: the distortion of an image that reflected in the test piece is small. F: the distortion of an image that reflected on the test piece is between 0 and •. •: the distortion of an image that is reflected in the test piece is great. (6) Delamination
[00284] The test piece that was molded into a flat plate shape by injection molding the resin composition obtained in each of the Examples and the like was marked in a grid pattern with a cutter and an adhesive tape was placed over the cut. Immediately, the tape was removed by pulling the tape slowly so that the angle between the tape and the test piece was 90fl, it was visually observed if at least a part of the surface layer of the test piece was peeled or no, and the delamination of the test piece was evaluated according to the following criteria. : the surface is not peeled. •: the surface is peeled.
[00285] The results are shown in Table 5 and Table 6. As is evident from the results, the Examples in which a specific modified polymerization initiator was used were excellent in assessing stiffness, impact resistance, and tensile strength. elongation at break when compared to Comparative Examples where the primer was not used. Table 5 [Table 5]

[Table 6]

权利要求:
Claims (5)
[0001]
1. Method for producing a hydrogenated conjugated diene polymer, the method characterized by the fact that it comprises a step of polymerizing at least one conjugated diene compound in the presence of a polymerization initiator compound of at least one amine compound selected from a compound represented by the formula (x1), a compound represented by the formula (x2) and a compound represented by the formula (y) and at least one metallic compound selected from alkali metal compounds and alkaline earth metal compounds to obtain a conjugated diene polymer and a step of hydrogenating the conjugated diene polymer. [Chemical Substance 1]
[0002]
Method for producing a hydrogenated conjugated diene polymer according to claim 1, characterized in that the amine compound having a structure represented by the formula (y) is at least one compound selected from a compound represented by the formula (y1 ) and a compound represented by the formula (y2): [Chemical Substance 3]
[0003]
3. Hydrogenated conjugated diene polymer, characterized by the fact that it has at least one group selected from a group represented by formula (X1), a group represented by formula (X2), a group represented by formula (Y1) and one group represented by the formula (Y2) at the end of the polymer: [Chemical Substance 4]
[0004]
4. Polymeric composition, characterized by the fact that it comprises the hydrogenated conjugated diene polymer, as defined in claim 3, and at least one selected from carbon black and silica.
[0005]
5. Polymeric composition, characterized by the fact that it comprises the hydrogenated conjugated diene polymer, as defined in claim 3, and at least one polymer selected from a non-polar polymer and a polar polymer.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/02/2014, 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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JP2013-026616|2013-02-14|

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JP2013026616|2013-02-14|

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PCT/JP2014/053419|WO2014126184A1|2013-02-14|2014-02-14|Method for producing hydrogenated conjugated diene polymer|

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