CN1894288A - Polymer well compatible with inorganic fillers - Google Patents

Abstract

A modified hydrocarbon polymer obtained by reacting (A) a hydrocarbon polymer having an alkali metal-carbon linkage or an alkaline earth metal-carbon linkage with (B) at least one low-molecular compound having a molecular weight of 2,000 or below which is selected from among low molecular compounds having alkali metal-nitrogen linkages or alkaline earth metal-nitrogen linkages and low-molecular compounds having alkali metal-carbon linkages or alkaline earth metal-carbon linkages and containing amino groups and (C) a multifunctional modifier and having at least one modifying group and a weight-average molecular weight of 10,000 or above, in which the N/c ratio exceeds 1/2 wherein N is the number of moles of nitrogen atoms of the modifying group and c is the number of moles of functional groups of the multifunctional modifier (C); a process for the production of the modified hydrocarbon polymer; and compositions containing the modified hydrocarbon polymer. The invention provides polymers which are improved in the compatibility with inorganic fillers and therefore permit dispersion of inorganic fillers therein in the state of uniform and fine particles.

Description

Polymer with excellent affinity with inorganic fillers

technical field

The present invention relates to a hydrocarbon polymer having a functional group having an excellent affinity with an inorganic filler, a method for producing the same, and a composition thereof with an inorganic filler.

Background technique

Conventionally, excellent resin compositions or elastomer compositions can be obtained by combining organic polymer materials and inorganic fillers.

For example, Patent Document 1 discloses a composition in which affinity with an inorganic filler is improved by adding maleic anhydride to a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound.

In addition, Patent Document 2 discloses a polymer-modified silica composition obtained by reacting a polyfunctional compound having an epoxy group in a molecule with an active terminal of a rubbery polymer.

Patent Document 1: Japanese Patent Publication No. 62-54140

Patent Document 2: WO01-23467 Publication

Contents of the invention

However, in the combination of organic polymer materials and inorganic fillers, the dispersion state varies greatly depending on the kneading method and conditions, and obtaining always constant high performance has become a major industrial problem.

In order to solve the above-mentioned problems, the present inventors found that by reacting a polyfunctional low molecular compound with a high molecular weight hydrocarbon polymer having a metal-carbon bond, a low molecular weight compound having a metal-nitrogen bond or having an amino group and a metal -The method of reacting low-molecular compounds with carbon bonds can introduce modified groups with specific structures into polymers, and can suppress the coupling of multiple molecules caused by the reaction of multiple high-molecular-weight hydrocarbon polymers with multifunctional low-molecular compounds Through the joint reaction, the high molecular weight hydrocarbon polymer can be uniformly modified with functional groups. Therefore, it is found that in the combination of organic polymer materials and inorganic fillers, constant high performance can be obtained, thereby completing the present invention.

That is, the present invention is as follows.

(1) A modified hydrocarbon polymer obtained by reacting (A), (B) and (C),

(A) a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond;

(B) At least one molecular weight selected from low-molecular compounds having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, a low-molecular compound having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group is 2000 or Low molecular weight compounds below it; and

(C) Multifunctional modifier The modified hydrocarbon polymer has at least one modified group, and the weight average molecular weight is 10,000 or more. The ratio (N/c) of the number of moles of functional groups (c) of the modifier (C) is greater than 1/2.

(2) The modified hydrocarbon polymer as described in (1) above, wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond.

(3) The modified hydrocarbon polymer as described in (1) or (2) above, the polyfunctional modifier (C) has a glycidyl amino group as a functional group, and the number of epoxy groups in the molecule is 2 or more multifunctional modifiers.

(4) The modified hydrocarbon polymer as described in (1) above, the low-molecular compound (B) is selected from low-molecular compounds having lithium-nitrogen bonds or magnesium-nitrogen bonds, low-molecular compounds having lithium-carbon bonds or magnesium-nitrogen bonds, At least one of carbon-bonded and amino-containing hydrocarbon compounds.

(5) The modified hydrocarbon polymer as described in (1) above,

The hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond at the terminal,

The low-molecular compound (B) is at least one selected from low-molecular compounds having a lithium-nitrogen bond or a magnesium-nitrogen bond, hydrocarbon compounds having a lithium-carbon bond or a magnesium-carbon bond and containing an amino group,

The multifunctional modifier (C) is a multifunctional modifier having 2 or more diglycidyl amino groups as functional groups in the molecule,

A modifying group having N/c greater than 1/2 is present on at least one terminal of the polymer.

(6) A method for producing a modified hydrocarbon polymer, comprising the steps of: reacting (A), (B), and (C) in an inert solvent,

(A) Hydrocarbon polymers having alkali metal-carbon bonds or alkaline earth metal-carbon bonds and a weight-average molecular weight of 10,000 or more;

(B) At least one selected from low molecular compounds having an alkali metal-nitrogen bond, an alkaline earth metal-nitrogen bond, an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group has a bond with a metal Bonded, low-molecular-weight compounds with a molecular weight of 2,000 or less;

(C) A polyfunctional modifier having a molecular weight of 2000 or less.

(7) The method for producing a modified hydrocarbon polymer as described in (6) above, wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond.

(8) The method for producing a modified hydrocarbon polymer as described in (6) or (7) above, wherein the polyfunctional modifier (C) has a glycidyl amino group as a functional group, and the number of epoxy groups in the molecule is Two or more multifunctional modifiers.

(9) The method for producing a modified hydrocarbon polymer as described in (6) above, wherein the low-molecular compound (B) is selected from low-molecular compounds having a lithium-nitrogen bond or a magnesium-nitrogen bond, low-molecular compounds having a lithium-carbon bond, or at least one of hydrocarbon compounds containing a magnesium-carbon bond and an amino group.

(10) The method for producing a modified hydrocarbon polymer as described in the above (6),

The hydrocarbon polymer (A) is a conjugated diene polymer obtained by living anion polymerization having a lithium-carbon bond at the terminal,

The low-molecular compound (B) is at least one selected from low-molecular compounds having a lithium-nitrogen bond or a magnesium-nitrogen bond, hydrocarbon compounds having a lithium-carbon bond or a magnesium-carbon bond and containing an amino group,

The polyfunctional modifier (C) is a polyfunctional modifier having two or more diglycidylamino groups as functional groups in the molecule.

(11) A composition comprising 100 parts by weight of the modified hydrocarbon polymer described in (1) above, and 1 to 200 parts by weight of a compound selected from carbon dioxide dispersed in the modified hydrocarbon polymer. Silicon-based inorganic fillers, fillers for metal oxides and metal hydroxides.

(12) The composition as described in (11) above, wherein the filler is synthetic silicic acid having a primary particle diameter of 50 nm or less.

(13) A method for producing a composition comprising the step of mixing 100 parts by weight of the modified hydrocarbon polymer described in the above (1) and kneading synthetic silicic acid with a primary particle size to disperse the synthetic silicic acid in the modified hydrocarbon polymer.

(14) A composition for vulcanized rubber, comprising 1 to 100 parts by weight of a silica-based inorganic filler, 1 to 50 parts by weight of parts of carbon black.

The combination of the hydrocarbon polymer with functional groups obtained in the present invention and the inorganic filler can provide a polymer-inorganic material composition with constant high performance under mild and wide mixing conditions. Specifically, if the viscosity during kneading is not too high and the kneading operation is performed without trouble at an appropriate torque, the inorganic filler can be dispersed in a high-molecular-weight compound with a uniform and fine particle size in the obtained compounded composition. In hydrocarbon polymer matrices, the result is high performance.

Furthermore, specifically, when the high-molecular-weight hydrocarbon polymer is a rubber-like polymer, when inorganic fillers such as silica and carbon black are uniformly dispersed to form vulcanized rubber, in the use of tire treads, it is different from existing Compared with other products, it can further improve the balance between low rolling resistance and wet skid resistance, improve wear resistance, and then realize the improvement of strength and the improvement of modulus reduction rate at high temperature, etc., forming a suitable tire for tires. Compositions for rubber, anti-vibration rubber, shoes, etc.

In addition, when the high-molecular-weight hydrocarbon polymer is a thermoplastic elastomer, evenly dispersing inorganic fillers such as silica, metal oxides, and metal hydroxides can achieve better strength and flame retardancy than the existing ones. , elongation improvement, transparency improvement, etc., if it is used in asphalt composition, it can obtain the effect of improving the grip of aggregates, etc.

Furthermore, when the high-molecular-weight hydrocarbon polymer is a thermoplastic elastomer or thermoplastic resin, it can be uniformly and finely dispersed in a compound composition formed with other polar resins while improving compatibility.

Description of drawings

FIG. 1 is a graph showing Tan δ balance at low temperature and high temperature of modified copolymer compositions of Examples and Comparative Examples.

FIG. 2 is a graph showing Tan δ balance at low and high temperatures of modified copolymer compositions of Examples and Comparative Examples.

Both show the improvement effect of the modified copolymer composition of the present invention.

Detailed ways

The present invention will be specifically described below.

Examples of the hydrocarbon polymer (A) having an alkali metal-carbon bond or an alkaline earth metal-carbon bond in the present invention include those that initiate polymerization with an alkali metal initiator and/or an alkaline earth metal initiator, anion polymerization A hydrocarbon polymer having alkali metal-carbon bonds or alkaline earth metal-carbon bonds at a single terminal or multiple terminals obtained by reaction growth. In addition, an alkali metal-carbon bond or an alkaline earth metal-carbon bond can also be introduced into a hydrocarbon polymer polymerized by another method according to a known method.

As the alkali metal initiator or alkaline earth metal initiator, any alkali metal initiator or alkaline earth metal initiator capable of initiating polymerization can be used, and organic alkali metal compounds and organic alkaline earth metal compounds are preferably used. As the organoalkali metal compound, an organolithium compound is particularly preferable. Organolithium compounds include low-molecular-weight compounds, organolithium compounds with solubilized oligomers, compounds with a single lithium in one molecule, and compounds with multiple lithiums in one molecule. The combination of organic groups and lithium In terms of forms, there are compounds containing a carbon-lithium bond, compounds containing a nitrogen-lithium bond, compounds containing a tin-lithium bond, and the like. Specifically, as monoorganolithium compounds, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbene lithium, etc. can be cited; Organolithium compounds include 1,4-dilithium butane, the reactant of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiumbenzene, n-butyllithium and 1,3- Reactants of butadiene and divinylbenzene, reactants of n-butyllithium and polyacetylene compounds, etc.; further, 3-(N,N-dimethylamino)-1-propyllithium, 3- (N,N-diethylamino)-1-propyllithium, 3-morpholino-1-propyllithium, 3-imidazole-1-propyllithium, n-butyllithium and p-(2-N, Reactants of N-dimethylaminoethyl) styrene, and amino group-containing hydrocarbyl lithium such as low-molecular oligomers formed by polymerizing butadiene, isoprene, styrene, etc. using these compounds, and , as the compound containing a nitrogen-lithium bond, lithium dimethylamide, lithium dihexylamide, lithium diisopropylamide, lithium hexamethyleneimide, etc. may be mentioned. Furthermore, organic alkali metal compounds disclosed in US Patent No. 5,708,092, UK Patent No. 2,241,239, US Patent No. 5,527,753, etc. can also be used.

Particularly preferred are n-butyllithium and sec-butyllithium. These organolithium compounds may be used not only by 1 type but also as a mixture of 2 or more types.

Examples of other organic alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specifically, sodium naphthyl and potassium naphthyl can be used, and alkoxides, sulfonates, carbonates, amides, etc. of lithium, sodium, and potassium can be used, and they can also be used in combination with other organometallic compounds.

Typical examples of alkaline earth metal initiators are organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Specifically, dibutyl magnesium, ethyl butyl magnesium, propyl butyl magnesium, etc. are mentioned. In addition, compounds such as alkoxides, sulfonates, carbonates, and amides of alkaline earth metals can be used, and these organic alkaline earth metal compounds can also be used in combination with organic metal compounds other than organic alkali metal initiators.

In the production method of the present invention, when the polymer (A) is a polymer obtained by initiating polymerization with an alkali metal initiator and/or an alkaline earth metal initiator and growing through anionic polymerization, the polymerization can be performed in batches. Formula or continuous polymerization method to carry out.

In the production method of the present invention, the polymer (A) is preferably a polymer having a living terminal obtained by a growth reaction initiated by living anionic polymerization. As the polymer-forming monomer, all compounds that can be polymerized by living anionic polymerization can be used. For example, there are styrene, α-methylstyrene, 1,1-diphenylethylene, 1,3-butadiene, isoprene, piperylene, etc., which can be used alone or in the form of copolymerization use.

In addition, it is preferable to immediately use the obtained polymer having an active metal for the next reaction. In particular, when a polymer having active lithium is left at a high temperature, lithium hydride may be generated and the active metal may be reduced. In this case, the modification rate of the polymer may decrease. Preferably, the monomer should be supplied to the next reaction immediately when the monomer is consumed substantially, and should be supplied to the next reaction within 5 minutes at least at a temperature of 80° C. or higher.

As a hydrocarbon polymer polymerized by another method, that is, a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond introduced by a known method, it can be obtained by mixing a soluble organic alkali metal compound or a soluble alkaline earth metal compound, and a hydrocarbon. It can be obtained by reacting the middle part or terminal part of the polymer-like main chain. According to this method, an alkali metal-carbon bond can be introduced into high-cis polybutadiene, EPDM, or the like. Specifically, it is carried out by the following method, that is, in a solution formed by dissolving the following hydrocarbon polymer in an inert solvent, an organic alkali metal compound and/or an organic alkaline earth metal compound are used in combination, and more preferably used in combination as an activation Polar substances selected from ethers and tertiary amines, preferably reacted at a temperature of 30 to 200°C, wherein the hydrocarbon polymer is in the main chain, side chain, terminal position, etc. of the molecule somewhere has a double bond. Furthermore, it is more preferable to use N,N,N',N'-tetramethylethylenediamine to react with sec-butyllithium at 50 to 100°C, and use the lithiated polymer immediately.

In the present invention, the hydrocarbon polymer may be any polymer that does not deactivate alkali metal-carbon bonds or alkaline earth metal-carbon bonds. As the hydrocarbon polymer, a hydrocarbon polymer or a saturated hydrocarbon polymer having a double bond in the molecule is preferably used.

As the hydrocarbon polymer having a double bond in the molecule, a polymer of a conjugated double bond compound; a copolymer containing two or more conjugated double bonds; and a conjugated double bond compound and the A copolymer formed of monomers copolymerized with conjugated double bond compounds. Specifically, polybutadiene, polyisoprene, butadiene-isoprene copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene ethylene-isoprene-styrene copolymer. The butadiene unit and the isoprene unit may be combined in any of 1,4, 1,2 or 3,4 combinations. In addition, as the coupling mode of the copolymer, either random coupling or block coupling may be used. The structure of the polymer may be either a linear polymer or a branched polymer. As the branched polymer, there are star, comb and the like. Any narrow to broad molecular weight distribution is acceptable. Specifically, a polymer having a molecular weight distribution represented by Mw/Mn generally within a range of 1.0 to 10 can be used.

Examples of random copolymers include butadiene-isoprene random copolymers, butadiene-styrene random copolymers, isoprene-styrene random copolymers, butadiene- Isoprene-styrene random copolymer. As random copolymers, there are completely random copolymers having a random composition close to statistical significance, tapered random copolymers having a tapered composition distribution, and the like. In addition, even if it is a homopolymer composed of a single monomer, it can have various structures, and it can be a polymer with a uniform composition formed by monomer bonding, such as 1, 4 bonding and 1, 2 bonding, or a polymer with a composition. Distributed polymers, or polymers in blocks.

As the block bonding, there are a homopolymer block bonding, a random polymer block bonding, a tapered random polymer block bonding, and the like. In addition, there are 2-block copolymers containing 2 types of these blocks, 3-block copolymers containing 3 types of these blocks, 4-block copolymers containing 4 types of these blocks, and the like. As an example of a block polymer, if S represents a block composed of vinyl aromatic compounds such as styrene, and B represents a block composed of conjugated diene compounds such as butadiene and isoprene. And/or blocks composed of copolymers of vinyl aromatic compounds and conjugated diene compounds, there are 2-block copolymers of S-B, 3-block copolymers of S-B-S, and 4-block copolymers of S-B-S-B , Block copolymers represented by (S-B)m-X, etc.

More generally, for example, a structure represented by the following general formula can be mentioned. (S-B)n, S-(B-S)n, B-(S-B)n, [(S-B)n]m-X, [(B-S)n-B]m-X, [(S-B)n-S]m-X (in the above formula, each embedding The boundary of the segment does not need to be clearly distinguished. In the case where block B is a copolymer formed of a vinyl aromatic compound and a conjugated diene compound, the vinyl aromatic hydrocarbon in block B may be uniformly distributed, or may be In addition, in block B, a plurality of uniformly distributed vinyl aromatic hydrocarbons and/or tapered distributions can coexist. In addition, in block B, the content of vinyl aromatic hydrocarbons is different A plurality of fragments can also coexist. In addition, n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents the number of coupling agents Residues or residues of multifunctional initiators. In the copolymer, when there are multiple blocks S and B respectively, their molecular weights, compositions, etc. can be the same or different. In addition , the structures of the polymer chains bound to X may be the same or different). In the present invention, it may also be any mixture of substances having the structure represented by the above general formula.

Examples of other hydrocarbon polymers include polystyrene, polyethylene, polypropylene, EPM, EPDM, and polybutene. In addition, these polymers may be copolymers of the main monomer and other monomers copolymerizable with the main monomer. For example, in the case of polystyrene, specific examples of other monomers that can be copolymerized with styrene include p-methylstyrene, α-methylstyrene, diphenylethylene, divinylbenzene, diisopropylene Benzene, esters of alcohols with 1 to 10 carbon atoms and methacrylic acid or acrylic acid, and acrylonitrile.

Although polymers of various structures as described above can be used, it is preferable to use the most suitable polymer structure in the field required for obtaining the optimum performance by the functional group.

The high molecular weight hydrocarbon polymer (A) having an alkali metal-carbon bond or an alkaline earth metal-carbon bond in the present invention is a polymer having a weight average molecular weight of 10,000 or more. When the molecular weight is high, it is easy to express various performances. On the other hand, if the molecular weight is too high, kneading may become difficult and performance may be difficult to express. In general, polymers that are difficult to knead independently due to their high molecular weight can be used by adding a plasticizer such as oil to lower the viscosity. From the viewpoint of kneadability, the weight average molecular weight is preferably 2 million or less. A preferable molecular weight is 30,000 to 1.5 million, more preferably 50,000 to 1.2 million. In addition, the molecular weight is represented by the weight average molecular weight correct|amended by the standard polystyrene measured using GPC.

In the present invention, the modifying group of the hydrocarbon polymer is a compound having functional groups such as oxygen, sulfur, phosphorus, nitrogen, and halogen derived from the low-molecular compound (B) and the polyfunctional modifier (C). residues.

In the present invention, as the low-molecular compound (B), a low-molecular compound having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, a low-molecular compound having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group can be used. At least one low-molecular compound having a molecular weight of 2,000 or less among low-molecular compounds.

As a low-molecular compound having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, the following compounds are preferred, that is, a metal selected from an alkali metal, an alkaline earth metal, an organic alkali metal compound, and an organic alkaline earth metal compound, and a low molecular weight compound. Compounds obtained by the reaction of secondary amines. Specifically, lithium dimethylamide, lithium dihexylamide, lithium diisopropylamide, lithium hexamethyleneimide, and the like can be mentioned. Furthermore, bis(diisopropylamino)magnesium, and mixtures of these compounds are preferably used. In addition, a compound having an alkali metal-nitrogen bond can also be obtained as a reaction product of a low molecular weight amide compound and an alkali metal compound. Specifically, there are reactants of N,N'-dimethylimidazolidinone and n-butyllithium, and the like.

As a low molecular weight compound having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group, there are, for example, 3-(N,N-dimethylamino)-1-propyllithium, 3-(N,N- Diethylamino)-1-propyllithium, 3-morpholino-1-propyllithium, 3-imidazole-1-propyllithium, bis-3-(N,N-dimethylamino)-1 -Propylmagnesium, bis-3-morpholino-1-propylmagnesium, bis-3-imidazole-1-propylmagnesium, etc. In addition, there are also those with alkali metal-nitrogen bonds or alkaline earth metal-nitrogen bonds Low-molecular-weight compounds or low-molecular-weight compounds having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group, such as a low-molecular oligomer formed by polymerizing butadiene, isoprene, styrene, etc. Hydrocarbyllithium, in addition, there are reactants of n-butyllithium and p-(2-N,N-dimethylaminoethyl)styrene, etc.

As these low-molecular-weight compounds (B), a metal-substituted compound having an amino group or an imino group bonded to a hydrocarbon group having a total carbon number of 4 to 140 or having a compound inert to an alkali metal-nitrogen bond is preferable. A radical, a hydrocarbon group with a total carbon number of 4 to 140. More preferably, the number of carbon atoms is 20 or less.

In the present invention, the molecular weight of the low molecular weight compound (B) is 2000 or less. Preferably it is 1000 or less. If the molecular weight is too large, the effect of the present invention cannot be obtained. More preferably, the molecular weight is 300 or less.

In the present invention, as the low molecular weight compound (C), a polyfunctional modifier having a molecular weight of 2000 or less can be used. As a multifunctional modifier, it is preferred to use a compound having a compound selected from the group consisting of epoxy group, carbonyl group, carboxylate group, carboxylic acid amido group, acid anhydride group, phosphate ester group, phosphite group, epithio group, thiocarbonyl group, thioxo Carboxylate group, dithiocarboxylate group, thiocarboxamide group, imino group, ethyleneamino group, halogen group, alkoxysilyl group, isocyanate group, thioisocyanate group, conjugated diene group , A compound having one or more functional groups in the aryl vinyl group.

In addition, for the calculation of the number of moles of functional groups, epoxy group, carbonyl group, epithiol group, thiocarbonyl group, imino group, ethyleneamino group, halogen group, conjugated diene group, aryl vinyl group, each The alkoxy group of the alkoxysilyl group is used as a functional group, and the carboxylate group, carboxylic acid amido group, acid anhydride group, thiocarboxylate group, dithiocarboxylate group, thiocarboxylic acid amido group, isocyanate A group and a thioisocyanate group are counted as two functions, and a phosphate group and a phosphite group are counted as three functions. The polyfunctional modifier (C) used in the present invention is one in which the sum of the functional numbers of the above-mentioned functional groups in one molecule is 2 or more. A polyfunctional modifier whose sum of functional numbers is 3 or more is preferable.

Specifically, for example, polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, polyglycidyl ethers of aromatic compounds such as diglycidylated bisphenol A, 1 , 4-diglycidylbenzene, 1,3,5-triglycidylbenzene, polyepoxides such as polyepoxidized liquid polybutadiene, 4,4'-diglycidyl-diphenyl Tertiary amines containing epoxy groups such as methylamine, 4,4'-diglycidyl-dibenzylmethylamine, diglycidyl aniline, diglycidyl o-toluidine, tetraglycidyl m-xylene Amine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane, etc. Diglycidyl amino compound, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxy Compounds having epoxy groups and other functional groups such as silane, epoxy-modified polysiloxane, epoxidized soybean oil, epoxidized linseed oil, etc.

In addition, for example, alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, alkyltriphenoxysilane, N-(1,3-dimethyl Butylene)-3-(triethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylene)-3-(tributoxysilyl)-1-propanamine, N-(1-methylpropylene)-3-(triethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, A compound having an imino group and an alkoxysilane group such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

In addition, for example, isocyanate compounds such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, diphenylethane diisocyanate, and 1,3,5-benzenetriisocyanate are mentioned.

Furthermore, for example, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monomethyltrichlorosilane, monoethyltrichlorosilane, monobutyltrichlorosilane, monohexyltrichlorosilane, mono Halosilane compounds such as methyltribromosilane and bis(trichlorosilyl)ethane, trimethoxychlorosilane, trimethoxybromosilane, dimethoxydichlorosilane, dimethoxydibromosilane , methoxytrichlorosilane, methoxytribromosilane and other alkoxyhalosilane compounds.

Furthermore, for example, tin tetrachloride, tin tetrabromide, monomethyl trichlorotin, monoethyl trichlorotin, monobutyl trichloride, monophenyl trichlorotin, bis(trichloromethane) Stannyl halides such as stannyl) ethane, polyhalogenated phosphine compounds such as phosphine trichloride and phosphine tribromide, etc.; further examples include trinonylphenyl phosphite, trimethyl phosphite, phosphite Phosphite compounds such as triethyl phosphate; Phosphate compounds such as trimethyl phosphate and triethyl phosphate. In addition, for example, dimethyl adipate, diethyl adipate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, diisophthalate, Carboxylate compounds such as methyl esters; compounds containing acid anhydride groups such as pyromellitic dianhydride and styrene-maleic anhydride copolymers; bisdimethylamide adipate, polymethacrylic acid dimethylamide, etc. Compounds containing amido groups; compounds containing carbonyl groups such as 4,4'-diacetylbenzophenone and 3-acetylpropoxytrimethoxysilane; divinylbenzene, diisopropenylbenzene, divinylbenzene Compounds containing aryl vinyl groups such as benzene oligomers; compounds containing halogenated hydrocarbon groups such as trichloropropane, tribromopropane, tetrachlorobutane, and 3-chloropropoxytrimethoxysilane. These compounds may be used alone or in combination.

Polyepoxides are preferred polyfunctional modifiers (C). Particularly preferred is a polyfunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in its molecule. Moreover, a compound having 2 or 3 diglycidyl amino groups in 1 molecule is more preferable. For example, tetraglycidyl-m-xylylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3 - Bisaminomethylcyclohexane and the like.

In the present invention, the molecular weight of the polyfunctional modifier (C) is 2000 or less. Preferably it is 1000 or less. If the molecular weight is too large, the effect of the present invention cannot be obtained.

In the present invention, as an inert solvent, it is preferred not to hinder the reaction of the high molecular weight hydrocarbon polymer (A), the low molecular weight compound (B) and the polyfunctional modifier (C), and to be able to fully dissolve the polymer (A) ) solvents, preferably hydrocarbon solvents. When the polymer (A) is obtained by initiating polymerization with an alkali metal initiator and/or an alkaline earth metal initiator and growing by anionic polymerization reaction, it is preferable to use a solvent for polymerization. Preferably, it is n-butane, n-pentane, n-hexane, n-heptane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, etc., or a mixture thereof. In addition, unsaturated hydrocarbons having low reactivity with organometallic compounds such as 1-butene, cis-2-butene, and 2-hexene may be mixed. The amount of the inert solvent used is usually an amount such that the concentration of the high molecular weight hydrocarbon polymer (A) becomes 1% by weight to 50% by weight.

When carrying out the polymerization reaction of the high-molecular-weight hydrocarbon polymer (A), in the case of using an alkali metal initiator or an alkaline earth metal initiator, in order to activate the polymerization reaction, change the combination of monomer units, or change Polar compounds can also be added according to the reactivity ratio of monomers during copolymerization. In addition, when carrying out the reaction of the high-molecular-weight hydrocarbon polymer (A), the low-molecular-weight compound (B) and the multifunctional modifier (C), a polar compound may also be added in the same manner. As polar compounds, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxy Ethers such as phenylbenzene, 2,2-bis(2-oxolyl)propane, etc.; tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinine tertiary amine compounds such as rings; alkali metal alkoxide compounds such as potassium tert-amylate and potassium tert-butoxide; phosphine compounds such as triphenylphosphine, and the like. These polar compounds may be used alone or in combination of two or more. The amount of polar compound used is selected according to the purpose and degree of effect. Usually, it is 0.01-100 mol with respect to 1 mol of initiators.

The weight average molecular weight of the modified hydrocarbon polymer of the present invention is 10000 or more. Preferably it is 2 million or less, and more preferably 30,000 to 1,500,000.

In the present invention, if (N) is used as the molar number of nitrogen atoms of the modified group, and (c) is used as the molar number of the functional group of the multifunctional modifier, the modified group of a specific structure introduced into the polymer It is a modifying group whose (N)/(c) is greater than 1/2. In this case, it is possible to obtain a polymer having excellent affinity with the inorganic filler which is characteristic of the present invention.

In the present invention, the structure of the hydrocarbon polymer with modifying group can be represented by the general formula: P-(C)-NR ¹ R ² or P-(C)-R-NR ¹ R ² (here , P: hydrocarbon polymer, (C): residue of multifunctional modifier, R, R ¹ , R ² : hydrocarbon group).

When using polyepoxides as the multifunctional modifier (C) of the modifying group, the structure of the obtained hydrocarbon polymer with the modifying group can be represented by the general formula: P-CR ⁵ R ⁶ -C( OH)R ⁴ R ³ -C(OH)R ⁷ -R-NR ¹ R ² to represent (here, P: hydrocarbon polymer, R, R ¹ , R ² , R ³ : hydrocarbon group or a group selected from O, S, the hydrocarbon group of the substituent in N, R ⁴ , R ⁵ , R ⁶ , R ⁷ : a compound group selected from hydrogen, a hydrocarbon group or a hydrocarbon group having a substituent selected from O, S, N).

It is particularly preferable to use a lithium organic amide as the low-molecular compound (B), and use a polyfunctional compound having two or more diglycidylamino groups as functional groups in the molecule as the polyfunctional modifying agent (C). Modifier, because in this way the excellent effect of the present invention can be obtained especially. In this case, a functional group of >N-CH ₂ -CH(OH)-N< is generated in the modifying group. In addition, glycidyl amino groups also exist, and a plurality of polymers (A) are bonded through the modifying groups containing these functional groups as the intermediary to form a bonded polymer in which a part has a branched structure.

In the present invention, in the reaction of the high molecular weight hydrocarbon polymer (A), the low molecular weight compound (B) and the multifunctional modifier (C), the reaction is preferably carried out under the following conditions, that is, when the When the metal-carbon bond is denoted as a mole, the total of the metal-nitrogen bond and the metal-carbon bond of (B) is denoted as b mole, and the functional group of the multifunctional modifier of (C) is denoted as c mole, in ( The reaction is carried out under the conditions that a+b)/c is 0.05-1.5, and a:b is 1:0.05-20. Within this range, the excellent effects of the present invention can be further exhibited. (a+b)/c is more preferably in the range of 0.2 to 1, and most preferably in the range of 0.3 to 0.9, and the effect can be further exhibited in these ranges. In addition, a:b is more preferably 1:0.5 to 8, most preferably 1:1 to 4, and within these ranges, further effects can be exhibited. When (a+b)/c is greater than 1.5, unreacted (A) and (B) increase. In addition, the calculation of the functional group c mole of the polyfunctional modifier (C) is a value obtained by multiplying the molar amount of the polyfunctional modifier (C) used by the number of functions per molecule as the functional group c mole. in use.

In the present invention, a:c is preferably 1:1.2-10, more preferably a:c is 1:1.8-6. Within this range, the excellent effects of the present invention can be further exhibited.

The high molecular weight hydrocarbon polymer (A) used in the present invention is preferably a polymer in which more than 60% by weight of all molecules of the polymer have an alkali metal-carbon bond or an alkaline earth metal-carbon bond. In this case, it is possible to obtain an excellent modified polymer in which more than 60% by weight of all the molecules of the obtained polymer contain the functional group component of the present invention. More preferably, 70% by weight or more of the molecules of the high-molecular-weight hydrocarbon polymer (A) have metal bonds to obtain a polymer containing functional group components in 70% by weight or more of the molecules. As a quantification method of the polymer having a functional group component, it can be measured by chromatography capable of separating a functional group-containing modified component and a non-modified component. As this chromatographic method, a GPC column using a polar substance such as silica capable of adsorbing functional group components as a filler, and a method in which non-adsorbed components are compared with an internal standard for quantification are suitably used.

In the present invention, the solution formed by the high molecular weight hydrocarbon polymer (A) in an inert solvent, the low molecular weight compound (B) and the multifunctional modifier (C) can be added at the same time to make them react, or they can be added sequentially make them react. Preferably: to the solution formed in the high molecular weight hydrocarbon polymer (A) in the inert solvent, add the low molecular weight compound (B) or its solution in the inert solvent, stir uniformly to obtain the mixture, in the mixture , Stir the polyfunctional modifier (C) or its solution in an inert solvent instantaneously according to the prescribed ratio to make it react. The reaction is performed batchwise or continuously.

When the polymer (A) is a hydrocarbon polymer having a double bond in the molecule, all or part of the double bond can be converted into a saturated hydrocarbon by hydrogenating the obtained hydrocarbon polymer with a functional group in an inert solvent. . Specifically, when the polymer (A) is a polymer formed of one or more monomer components selected from conjugated diene compounds and aromatic vinyl compounds, all or part of the double bonds can be converted into saturated hydrocarbons. In this case, the heat resistance and weather resistance can be improved, and the deterioration of the product during processing at high temperature can be prevented, so that the obtained product can exhibit excellent performance in applications requiring weather resistance such as automobile applications.

More specifically, in the present invention, the hydrogenation rate based on the unsaturated double bond of the conjugated diene can be arbitrarily selected according to the purpose, and is not particularly limited. In the case of obtaining a heat-shrinkable film with good heat resistance, thermal stability and weather resistance, it is recommended to have more than 70%, preferably 75% or more, further preferably 85% or more, particularly preferably 90% % or more of the unsaturated double bond based on the conjugated diene compound in the polymer is hydrogenated. In addition, when obtaining a polymer having good thermal stability, the hydrogenation rate in the polymer is preferably 3 to 70%, more preferably 5 to 65%, and particularly preferably 10 to 60%. In addition, the hydrogenation rate based on the aromatic double bond of the vinyl aromatic hydrocarbon in the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon is not particularly limited, but the hydrogenation rate is preferably 50% or less, Preferably it is 30% or less, More preferably, it is 20% or less. The hydrogenation rate can be obtained by a nuclear magnetic resonance apparatus (NMR).

As a hydrogenation method, a known method can be utilized. A particularly preferred method is hydrogenation by blowing gaseous hydrogen into the polymer solution in the presence of a catalyst. As the catalyst, a catalyst obtained by carrying a noble metal on a porous inorganic substance as a heterogeneous catalyst; a catalyst obtained by dissolving a salt of nickel, cobalt, etc., and reacting it with an organic aluminum, etc.; Titanocene and other metallocene catalysts. Among them, titanocene catalysts that can select mild hydrogenation conditions are particularly preferable. In addition, hydrogenation of aromatic groups can be performed by using a supported noble metal catalyst.

As specific examples of hydrogenation catalysts, it is possible to use: (1) Supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) So-called Ziegler-type hydrogenation catalysts using organic acid salts such as Ni, Co, Fe, Cr or transition metal salts such as acetylacetonate and reducing agents such as organoaluminum, (3) Ti, Ru Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as , Rh, and Zr. For example, as a hydrogenation catalyst, it can be used in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 1-53851. Hydrogenation catalysts described in Japanese Publication No. 2-9041 and Japanese Unexamined Patent Application Publication No. 8-109219. As a preferable hydrogenation catalyst, a titanocene compound and/or a mixture with a reducing organometallic compound can be mentioned.

In the present invention, if necessary, a reaction terminator may be added to the inert solvent solution of the polymer having a modifying group. As the reaction terminator, generally, alcohols such as methanol, ethanol, and propanol, organic acids such as stearic acid, lauric acid, and caprylic acid, water, and the like can be used.

In the present invention, the metals contained in the polymer may be deashed as needed. Generally, as a deashing method, a method of bringing water, an organic acid, an inorganic acid, or an oxidizing agent such as hydrogen peroxide into contact with a polymer solution to extract metals, and then separating the water layer Methods.

In the present invention, an antioxidant may be added to the inert solvent solution of the polymer having a modifying group. As the antioxidant, there are phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and the like.

A method for obtaining a polymer from a polymer solution can be performed using a known method. For example, the method of separating the solvent by steam stripping, filtering and separating the polymer, and then dehydrating and drying it to obtain the polymer; concentrating with a flash tank, and then performing volatilization with a ventilated extruder, etc. The method of removing it; the method of directly volatilizing it with a drum dryer, etc.

The polymer having a specific modifying group of the present invention has excellent affinity with an inorganic filler, and can exert its effect when dispersing the inorganic filler. In addition, it is also effective in bonding with inorganic compounds.

As inorganic fillers, there are natural silica, synthetic silica produced by wet or dry method, kaolin, mica, talc, clay, montmorillonite, zeolite, natural silicate, glass powder, glass fiber, silicon Silicates such as calcium oxide and aluminum silicate, metal oxides such as aluminum oxide, titanium oxide, magnesium oxide, and zinc oxide, metal hydroxides such as calcium hydroxide, aluminum hydroxide, and magnesium hydroxide, light carbonic acid Various surface treatments such as calcium and ground calcium carbonate, metal carbonates such as magnesium carbonate, metal sulfates such as barium sulfate, magnesium sulfate, and calcium sulfate, metal powders such as aluminum and bronze, carbon black, etc.

As a method for producing the composition of the polymer having a specific modifying group of the present invention and an inorganic filler, a masterbatch in which an inorganic filler is previously mixed with the polymer having a specific modifying group of the present invention can be used . As a method for producing a masterbatch, a method of mixing in a solution or a method of kneading with a mixer can be used.

In the present invention, when a filler selected from silica-based inorganic fillers, metal oxides and metal hydroxides is dispersed in the polymer having a modifying group of the present invention, more excellent Effect.

The following composition is preferred, which is dispersed in 100 parts by weight of the hydrocarbon polymer having a modified group obtained by the method of the present invention, and disperses 1 to 200 parts by weight of a silica-based inorganic filler, a metal Formed as fillers in oxides and metal hydroxides.

It is particularly preferable to use a synthetic silicic acid having a primary particle diameter of 50 nm or less as the silica-based inorganic filler. In this case, the filler can be quickly, uniformly and finely dispersed with good reproducibility by kneading for a short time, and the obtained physical properties are very good.

As a further preferred method, when dispersing synthetic silicic acid with a primary particle diameter of 50 nm or less in 100 parts by weight of the hydrocarbon polymer having a modified group obtained by the method of the present invention, the A method of kneading at a temperature of ~250°C.

Next, the conjugated diene-based rubber which is a preferred embodiment of the present invention will be described in more detail.

Use conjugated diene, or the combination of conjugated diene and styrene as monomer, organic monolithium compound as initiator, in an inert solvent to obtain active conjugated diene homopolymer or conjugated diene and Living random copolymer of styrene. Let this be a polymer (A). The polymer (A) has a glass transition temperature in the range of -100°C to -20°C, and a ratio of 1,4-bonding to 1,2 or 3,4-bonding of the conjugated diene moiety is 10% to 90% %: 90% to 10%. The chain distribution of styrene in the copolymer is a completely random structure. That is, single styrene (1 unit of styrene) is 50% by weight or more of all bound styrene, and chain styrene (8 or more styrenes are connected) is 50% by weight or more of all bound styrene. % by weight or less, preferably 2.5% by weight or less. In the solution of the active polymer (A), preferably, a lithium amide compound is added as (B), stirred, and uniformly mixed. Furthermore, a predetermined amount of trifunctional or more, preferably 4 to 6 functional polyepoxides is added as (C), stirred momentarily, and reacted. The obtained polymer is a polymer having a hydroxyl group, an amino group, and an epoxy group at an arbitrary ratio at the terminal.

The molecular weight of the polymer is controlled according to the use and purpose. Usually, Mooney viscosity (100° C., 1+4 minutes) is controlled at 20 to 100 as raw material rubber for vulcanized rubber. When the Mooney viscosity is high, an extender oil is usually used for oil extension so that the Mooney viscosity is within this range. As the extender oil, extender oils such as aromatic oil, naphthenic oil, paraffin oil, and TDAE and MES shown in Kautschuk GummiKunststoffe 52 (12) 799 (1999) can be preferably used. These extender oils are polycyclic oils specified in IP346. An oil having an aromatic component of 3% by weight or less. The usage-amount of extender oil is arbitrary, but it is normally 10-50 weight part with respect to 100 weight part of polymers. Generally, 20 to 37.5 parts by weight are used.

When used in vulcanized rubber applications such as tires and anti-vibration rubber for automobile parts and shoes, silica-based inorganic fillers are preferably used as reinforcing agents, and synthetic silicic acid having a primary particle size of 50 nm or less is particularly preferred. As synthetic silicic acid, wet-process silica and dry-process silica are preferably used.

As a reinforcing agent, carbon black can also be used. The carbon black is not particularly limited, and for example, furnace black, acetylene black, pyrolytic black, channel black, graphite, and the like can be used. Among them, furnace carbon black is particularly preferable.

In the present invention, a vulcanized rubber composition comprising 1 to 100 parts by weight of silica-based particles and 0 to 50 parts by weight of carbon black is preferably blended with 100 parts by weight of the polymer of the present invention. More preferably, it is a vulcanized rubber composition in which 1 to 100 parts by weight of silica-based particles and 1 to 50 parts by weight of carbon black are blended with 100 parts by weight of the polymer of the present invention.

The effect of the present invention is that the dispersibility of the inorganic filler is good and stable, and the performance of the vulcanized rubber is excellent. Specifically, when the inorganic filler, especially silica, is uniformly dispersed to form a vulcanized rubber, a rubber with little strain dependence of the storage modulus can be obtained. When used in tire tread applications, compared with existing products, the balance between low rolling resistance and wet skid resistance can be further improved, and wear resistance can be improved. Modulus reduction rate improvement, etc., to form a composition suitable for rubber for tires, anti-vibration rubber, shoes, etc.

In the present invention, the polymer of the present invention may be used alone, or mixed with other rubbers as necessary. When used in combination with other rubbers, if the ratio of the polymer of the present invention is too small, the modifying effect of the present invention cannot be sufficiently exerted, so it is not preferable. Examples of other rubbers include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized random SBR (bound styrene is 5 to 50% by weight, butadiene-bonded unit Part of the 1,2-vinyl binding amount is 10-80%), high-trans SBR (the 1,4-trans-binding amount of the butadiene binding unit is 70-95%), and the low-cis polybutadiene Vinyl rubber, high cis polybutadiene rubber, high trans polybutadiene rubber (1,4-trans bonded amount of butadiene bonded unit is 70-95%), styrene-isoprene Copolymer rubber, butadiene-isoprene copolymer rubber, solution polymerization random styrene-butadiene-isoprene copolymer rubber, emulsion polymerization random styrene-butadiene-isoprene copolymer rubber, Emulsion-polymerized styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low vinyl SBR block copolymer rubber, and polystyrene-polybutadiene-polystyrene Such a block copolymer etc., such as a block copolymer etc. These rubbers can be appropriately selected according to required properties.

In the case of using the polymer of the present invention and other rubbers as rubber components, the ratio of each component is usually 10-95:90-5, preferably 20-90:80-10, more preferably In the range of 30-80:70-20. As other rubbers, all rubbers other than the present invention can be used, but high-cis polybutadiene rubber, solution-polymerized SBR, solution-polymerized SIBR, emulsion-polymerized SBR, natural rubber, polyisoprene rubber, VCR, IIR are preferable , Halogenated IIR, etc.

As the rubber compounding agent, further, for example, a silane coupling agent, a reinforcing agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization auxiliary agent, oil and the like can be used.

As the silane coupling agent, a compound having an alkoxysilane and further a polysulfide bond in the molecule is preferably used. For example, bis-(3-triethoxysilylpropyl)tetrasulfide (TESPT), bis-(3-triethoxysilylpropyl)disulfide, and the like can be used.

The vulcanizing agent is not particularly limited, and examples thereof include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur, and sulfur halides such as sulfur monochloride and sulfur dichloride. Organic peroxides such as dicumyl peroxide and di-tert-butyl peroxide, and the like. Among them, sulfur is preferred, and powdered sulfur is particularly preferred.

The mixing ratio of the vulcanizing agent is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.

Examples of the vulcanization accelerator include sulfenamide-based, thiourea-based, thiazole-based, dithiocarbamic acid-based, and xanthic acid-based vulcanization accelerators. The mixing ratio of the vulcanization accelerator is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.

The vulcanization aid is not particularly limited, and stearic acid, zinc oxide, or the like can be used, for example.

As the oil, extender oils such as aromatic hydrocarbons, naphthenes, paraffins, and polysiloxanes can be selected according to the application. The amount of extender oil used is usually 1 to 150 parts by weight, preferably 2 to 100 parts by weight, more preferably 3 to 60 parts by weight, per 100 parts by weight of the rubber component. When the amount of oil used is within this range, the balance between the dispersion effect of the reinforcing agent, tensile strength, abrasion resistance, heat resistance, and the like becomes high.

The composition using the rubber of the present invention, in addition to the above-mentioned components, can contain fillers such as calcium carbonate, talc, etc., anti-aging agents of amines and phenols, anti-ozone aging agents, silane coupling agents, etc. Linking agent, activators such as diethylene glycol, processing aids, tackifiers, waxes and other compounding agents.

The composition using the rubber of the present invention can be produced by mixing the above-mentioned components using a known rubber kneading machine, such as a drum, a Banbury mixer, and the like.

Example

Below, illustrate the present invention in more detail by embodiment, but the present invention is not limited to these

Example.

Preparation of copolymer (sample A to sample J)

Use an autoclave with an internal volume of 10 liters, a stirrer and a jacket that can control the temperature as a reactor, and fill the reactor with 625g of butadiene, 225g of styrene, 5500g of cyclohexane, 1.10 g 2,2-bis(2-oxolyl)propane as a polar substance, and the temperature in the reactor was kept at 30°C. A cyclohexane solution containing 9.14 mmol of n-butyllithium as a polymerization initiator was supplied to the reactor. After the reaction started, the temperature inside the reactor started to rise due to heat generated by the polymerization. During 8 minutes to 13 minutes after the addition of the polymerization initiator, 50 g of butadiene was supplied at a rate of 10 g/min. The temperature in the final reactor reached 77°C. After the end of the polymerization reaction, 9.14 mmol of lithium diisopropylamide was added. After mixing for 1 minute, 9.14 mmolg of tetraglycidyl-1,3-bisaminomethylcyclohexane, which is a tetrafunctional polyepoxide, was added to the reactor and stirred at 75°C for 5 minutes to carry out a modification reaction . After adding 1.8 g of an antioxidant (BHT) to this polymer solution, the solvent was removed to obtain a styrene-butadiene copolymer (sample A) having a modified component.

As a result of analyzing sample A, the amount of bound styrene was 25% by weight, the amount of bound butadiene was 75% by weight, and the Mooney viscosity of the polymer was 70. According to the results of measurement using an infrared spectrophotometer, the 1,2-incorporation amount of the microstructure of the butadiene part was calculated according to the Hampton method to be 61%, and the polystyrene-corrected molecular weight obtained by GPC measurement, its weight The average molecular weight (Mw) was 594,000, the number average molecular weight (Mn) was 402,000, the molecular weight distribution was trimodal, and (Mw/Mn) was 1.48. In addition, the modification ratio determined by GPC using a silica-based adsorption column was 84%.

Furthermore, the polymerization was carried out in the same manner as the sample A was obtained, and the amount of n-butyllithium, the amount of polar substances, the alkali metal-nitrogen bond compound added at the end of the polymerization, the type of multifunctional modifier and The amount used in the reaction varies to obtain various styrene-butadiene copolymers. Among the various copolymers, (Sample J) reacts equimolar reactants of hexamethyleneimine and n-butyllithium as alkali metal-nitrogen bond compounds, and then quickly adds them to the polymerization vessel , in addition (sample I) is after DMI (dimethyl imidazolidinone) and the equimolar reactant of n-butyllithium are reacted, add to the polymerization vessel rapidly, after that, add multifunctional modifier, come Modulated samples. The modulation results are shown in Table 1.

In the sample of table 1, the multipolymer of the present application invention is sample (A), (C), (D), (E), (F), (G), (I), (J), test Samples (B) and (H) are copolymers other than the present invention in which no compound having an alkali (or alkaline earth metal)-nitrogen bond is used.

Table 1 sample A B C D. E. f G h I J within the scope of the invention outside the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention outside the scope of the invention within the scope of the invention within the scope of the invention Butadiene (g) 625 625 625 625 625 625 670 670 670 670 Additional butadiene (g) 50 50 50 50 50 50 50 50 50 50 Styrene (g) 225 225 225 225 225 225 180 180 180 180 n-Butyllithium (mmol): (a') 9.14 9.78 9.14 7.77 7.38 9.14 9.56 10.33 9.56 9.56 n-Butyl lithium (mmol) (a') × modification rate: a 7.68 8.019 7.68 6.37 5.98 7.68 8.13 8.574 8.13 8.03 Polar substances (*1) BOP BOP BOP BOP BOP TMEDA BOP BOP BOP TMEDA Amount of polar substances added (g) 1.1 1.177 1.1 0.92 0.86 1.15 0.85 0.75 0.85 0.9 Compounds containing metal-nitrogen bonds (*2) DPLA none DPLA DPLA DPLA DPLA DPLA none DMI+BuLi HMI+BuLi Addition amount of compound containing metal-nitrogen bond in mmol: b 9.14 - 4.07 15.54 14.76 22.0 9.56 - 9.56 9.56 Modifier(*3) TGAMH TGAMH TGAMH TGAMH TGAMH TES TGAMH TGAMH TGAMH TGAMH Addition amount of modifier mmol 9.14 9.78 9.14 7.77 3.69 9.14 9.56 10.33 9.56 9.56 Modifier functional group mmol: c 36.6 39.12 36.6 31.08 14.76 36.6 38.2 41.32 38.2 38.2 (a+b)/c 0.46 0.20 0.32 0.70 1.41 0.81 0.46 0.21 0.46 0.46 a:b 1:1.19 1:0 1:0.53 1:2.44 1:2.47 1:286 1:1.18 1:0 1:1.18 1:1.19 N/c 0.75 0.50 0.61 1.00 1.50 0.60 0.75 0.50 0.75 0.75 Modification rate (%) 84 82 84 82 81 84 85 83 85 84 Mooney viscosity 70 73 74 65 66 67 73 71 74 75 Bound styrene amount (%) 25 25 25 25 25 25 20 20 20 20 1,2-vinyl binding amount (%) 61 61 62 61 62 62 56 56 55 55 Weight average molecular weight (Mw) million 59.4 60.3 62.5 56.5 58.2 57.9 56.3 55.2 58.9 59.3 Number average molecular weight (Mn) million 40.2 44.3 44.0 37.4 41.6 40.5 39.0 41.2 42.1 42.6 Mw/Mn 1.48 1.36 1.42 1.51 1.4 1.43 1.44 1.34 1.40 1.40

*1 BOP: 2,2-bis(2-oxolyl)propane

TMEDA: Tetramethylethylenediamine

*2 DPLA: lithium diisopropylamide

DMI: Dimethylimidazolidinone

HMI: Hexamethyleneimine

BuLi: n-butyllithium

*3 TGAMH: Tetraglycidyl-1,3-bis(aminomethyl)cyclohexane

TES: Tetraethoxysilane

Preparation of copolymer (sample K to sample T)

Two autoclaves with an inner volume of 10 liters, an inlet at the bottom and an outlet at the top are connected in series as reactors, or a static mixer is placed between the two reactors, and Autoclave with stirrer and jacket for temperature regulation. Butadiene, styrene, and n-hexane from which impurities have been removed in advance are mixed at speeds of 13.0g/min, 7g/min, and 97.6g/min respectively, and the mixed solution is passed through a dehydration column filled with activated alumina, in order to further Impurities are removed, and immediately before entering the first reactor, mixed with n-butyllithium in a static mixer at a rate of 0.003 g/min (0.0469 mmol), and then continuously supplied to the bottom of the first reactor, Furthermore, to the bottom of the first reactor, 2,2-bis(2-oxolane) propane as a polar substance was supplied at a rate of 0.015 g/min, and 0.009 g/min (0.141 mmol) N-butyllithium was supplied as a polymerization initiator at a high speed, and the temperature in the reactor was maintained at 85°C. The polymer solution was continuously discharged from the top of the first reactor and supplied to the second reactor. Take a sample from the outlet of the first reactor in a stable state, add enough ethanol to inactivate the active site, add a stabilizer, remove the solvent, and measure the Mooney viscosity. The Mooney viscosity of the obtained polymer before modification was 85. And, the polymerization rate at the outlet of the first reactor reached about 100%. Keeping the temperature of the second reactor at 80°C, tetraglycidyl-1,3-bisaminomethyl, which is a 4-functional polyepoxide, was added from the bottom of the second reactor at a rate of 0.071 mmol/min. Cyclohexane, to carry out the modification reaction. An antioxidant (BHT) was continuously added to the modified polymer solution at a rate of 0.05 g/min (n-hexane solution) to terminate the modification reaction, and then the solvent was removed to obtain a modified copolymer. The Mooney viscosity of the modified copolymer was 165. Furthermore, 37.5 parts by weight of aromatic hydrocarbon oil (X-140 manufactured by Japan Energy Co., Ltd.) was added to this copolymer solution per 100 parts by weight of the polymer to obtain an oil-extended copolymer (sample L). The Mooney viscosity of the obtained oil-extended copolymer was 73. In addition, as a result of analyzing the sample (L), the amount of bound styrene in the copolymer was 35%, and the amount of bound butadiene was 65%. As a result of measurement using an infrared spectrophotometer, the 1,2-bonding amount of the butadiene moiety calculated according to the Hampton method was 38%. The weight average molecular weight (Mw) obtained by GPC measurement using THF as a solvent was 900,000, and the molecular weight distribution (Mw/Mn) was 2.00. The modification rate of the modified copolymer was 82%.

The method of pre-extending high molecular weight polymers with high Mooney viscosity has been widely used in the rubber industry, because this can make the manufacture of the obtained copolymers easier, or, in subsequent processing, for It is effective in improving the processability such as the mixing property of the agent, and improving the performance due to the improvement in the dispersibility of the filler.

After obtaining the sample (L), add lithium diisopropylamide at a rate of 0.0469mmol/min to the copolymer solution continuously flowing into the static mixer set between the first and second reactors , mixed in a static mixer. In the second reactor, the modification reaction is continued with tetraglycidyl-1,3-bisaminomethylcyclohexane. In a state where the reaction is stable, an antioxidant (BHT) is continuously added to the modified polymer solution to terminate the modification reaction, and then the solvent is removed to obtain a modified copolymer. The Mooney viscosity of the modified copolymer was 144. Furthermore, 37.5 parts by weight of aromatic hydrocarbon oil (X-140 manufactured by Japan Enagi Co., Ltd.) was added to this polymer solution per 100 parts by weight of the polymer to obtain an oil-extended copolymer (sample K). The Mooney viscosity of the obtained oil-extended copolymer was 63. The bound styrene amount and the 1,2-bound amount of the butadiene moiety were the same as those of the sample (L). The weight average molecular weight (Mw) obtained by GPC measurement using THF as a solvent was 800,000, and the molecular weight distribution (Mw/Mn) was 1.90. The modification rate of the modified copolymer was 81%. It can be seen that the addition of lithium diisopropylamide binds the low-molecular-weight amino group to the modifier to suppress the coupling reaction, and as a result, the Mooney viscosity decreases.

Furthermore, carry out polymerization and modification reaction with the method same as obtaining sample (K), make the amount of styrene, the amount of butadiene, the amount of n-butyllithium, the amount of polar substance and at the end of polymerization Various styrene-butadiene copolymers are obtained by varying the types of the alkali metal-nitrogen bond compound and the polyfunctional modifier and the amount used in the reaction. Among the various copolymers, (sample Q) was quickly added to the static mixer after reacting equimolar reactants of hexamethyleneimine and n-butyllithium as alkali metal-nitrogen bond compounds. In addition, (sample T) is to react DMI (dimethylimidazolidinone) and n-butyllithium equimolar reactants, add them to the static mixer quickly, and then add the multifunctional modifier , to modulate the sample. The results of modulation are shown in Table 2.

In the sample of Table 2, the copolymer of the present invention is sample (K), (M), (N), (O), (P), (Q), (R), (T), sample (L) and (S) are copolymers other than the invention of the present application.

Table 2 sample K L m N o P Q R S T within the scope of the invention outside the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention within the scope of the invention outside the scope of the invention within the scope of the invention Butadiene (g/min) 13 13 13 13 13 13 13 15 15 15 Styrene (g/min) 7.0 7.0 7.0 7.0 7.0 7.0 7.0 5.0 5.0 5.0 n-BuLi (mmol/min): (a') 0.141 0.141 0.127 0.127 0.117 0.117 0.117 0.120 0.134 0.134 n-Butyl lithium (a') × modification rate: a 0.116 0.116 0.103 0.103 0.092 0.094 0.095 0.092 0.103 0.105 Polar substances BOP BOP BOP BOP TMEDA TMEDA BOP BOP BOP BOP Amount of polar substances added (g/min) 0.015 0.015 0.013 0.013 0.014 0.014 0.013 0.027 0.029 0.029 Compounds Containing Metal-Nitrogen Bonds DPLA none DPLA DPLA DPLA DPLA HMI+BuLi DPLA none DMI+BuLi Addition amount of compound containing metal-nitrogen bond in mmol/min: b 0.141 - 0.127 0.052 0.234 0.304 0.117 0.120 - 0.134 modifier TGAMH TGAMH TGAMH TGAMH TGAMH TES TGAMH TGAMH TGAMH TGAMH Addition amount of modifier mmol/min 0.071 0.071 0.127 0.064 0.058 0.117 0.117 0.120 0.067 0.067 Modifier functional group mmol/min: c 0.284 0.284 0.508 0.256 0.232 0.468 0.468 0.480 0.268 0.268 (a+b)/c 0.90 0.41 0.45 0.69 1.41 0.85 0.45 0.44 0.38 0.89 a:b 1:1.22 1:0 1:1.23 1:0.50 1:2.54 1:3.23 1:1.23 1:1.30 1:0 1:1.28 N/c 1.00 0.50 0.75 0.70 1.50 0.65 0.75 0.82 0.50 1.00 Modification rate 82 82 81 81 79 80 81 77 77 78 Mooney viscosity before oil extension 144 165 145 162 159 158 163 149 164 166 37.5 parts by weight Filled Mooney Viscosity 63 73 63 72 70 70 72 65 71 73 Bound styrene amount (%) 35 35 35 35 35 35 35 25 25 25 1,2-vinyl binding amount (%) 38 38 37 39 38 37 38 63 63 64 Weight average molecular weight (Mw) million 80.0 90.0 81.0 88.8 87.5 86.9 87.3 82.5 93.3 94.5 Number average molecular weight (Mn) million 42.0 45.0 43.1 45.5 43.3 45.7 45.0 43.4 46.0 46.1 Mw/Mn 1.90 2.00 1.88 1.95 2.02 1.9 1.94 1.9 2.03 2.05

Preparation of Copolymer (U～Z)

1) Use nitrogen to fully replace the autoclave with an internal volume of 10 liters, a jacket for temperature regulation and a stirrer, and fill with 4.5kg of cyclohexane and 0.25kg of styrene and 0.75 kg of activated alumina. kg 1,3-butadiene. While stirring, the temperature was raised to 52° C., and 11.875 mmol of n-butyllithium (20% cyclohexane solution, the same below) was added to start polymerization. The polymerization temperature reached 91° C., and 2 minutes later, a cyclohexane solution containing 11.875 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to carry out a modification reaction for 10 minutes. The polymerization conversion when the modifier is added is about 100%. In the modified rubber polymerization solution thus obtained, add 10 ml of methanol as an active lithium decomposer, mix, add 2 g of BHT as a stabilizer, mix, and remove the solvent to obtain a solid modified rubber (sample U ).

During the polymerization process, the monomer conversion rate measurement samples were collected from the autoclave at several time points, and the conversion rate, the amount of bound styrene, and the amount of styrene blocks were analyzed. The results confirmed that the conversion rate was about 80%. At this point in time, the resulting copolymer was a random copolymer with 9.5% by weight of bound styrene and 0.0% by weight of styrene blocks.

Next, as a result of analyzing the finally obtained modified rubber, the amount of bonded styrene was 25.0% by weight, the amount of styrene blocks was 15.5% by weight, and the amount of vinyl bonds was 13.2%. From this, it was confirmed that about 20% of the polymer ends of the finally obtained modified rubber were tapered block copolymers in which the bonded amount of styrene gradually increased to form terminal styrene blocks.

By GPC measurement, the molecular weight of the copolymer before modification was 191,000, the molecular weight of one molecule of modified styrene block in the styrene block analysis sample was 22,100, and the modification rate of the copolymer was 74%.

The total coupling rate of the 2-molecule coupling modification, 3-molecule coupling modification, and 4-molecule coupling modification was 61%, and the 1-molecule modification rate of the copolymer was 13%.

In addition, the Mooney viscosity (ML1+4, 100° C.) of this modified rubber was 72.

In addition, by GPC measurement of the styrene block, it was found that in addition to one molecule of the modified styrene block, a total of 56% of the styrene block with a molecular weight of twice the molecular weight and a styrene block with a molecular weight of three times the molecular weight existed, and it was confirmed that the styrene block The ends were indeed bonded with tetraglycidyl-1,3-bisaminomethylcyclohexane as a modifier.

Polymerization was carried out in the same manner as the obtained (sample U), and after confirming that the polymerization conversion rate reached about 100%, 11.875 mmol of lithium diisopropylamide was added to the polymerizer. After mixing for 1 minute, 11.875 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to the reactor, and a modification reaction was performed for 10 minutes. Thereafter, (sample V) was obtained by performing exactly the same operation as when obtaining (sample U). The modification ratio was 74%, and the Mooney viscosity was 52. From the GPC measurement, compared with (sample U), the coupling of 4 molecules or 3 molecules was found to be very little.

2) In the same preparation method as (sample U), except changing the amount of styrene, butadiene, n-butyllithium, and tetraglycidyl-1,3-bisaminomethylcyclohexane, (Sample W) was obtained in the same manner as (Sample U) except that 16 g of tetrahydrofuran was added before the start of polymerization. Measurement of monomer conversion rate during polymerization, analysis of bonded styrene, and analysis of styrene blocks confirmed that 30.9% of bonded styrene and 0% of styrene blocks were formed as about 70% of the first half of the polymer. of copolymers. It was confirmed by the styrene block analysis after the completion of the polymerization reaction that about 30% of the second half of the polymer was a tapered terminal styrene block copolymer. The Mooney viscosity (ML1+4, 100° C.) of the modified rubber was 73.

(Sample X) is a modified copolymer obtained by polymerizing in the same manner as (Sample W), and adding 8.333 mmol of lithium diisopropylamide to the polymerizer after completion of the polymerization. , and then 6.284 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to carry out a modification reaction for 10 minutes. The Mooney viscosity (ML1+4, 100°C) of the modified rubber was 62. It can be seen that by adding lithium diisopropylamide, the amino group of the low-molecular-weight residue of lithium amide is bonded to the modifier, and as a result, the Mooney viscosity is lowered.

3) Use nitrogen to fully replace the autoclave with an internal volume of 10 liters, a jacket for temperature regulation and a stirrer, and fill with 4.5kg of cyclohexane and 0.90kg of activated alumina treated as the first stage Monomer 1,3-butadiene. While stirring, the temperature was raised to 56° C., and a cyclohexane solution containing 14.844 mmol of n-butyllithium was added to start polymerization. When the polymerization temperature reached 82°C, the polymerization of butadiene was terminated. Next, 0.10 kg of styrene was added as a second-stage monomer to carry out polymerization. After the polymerization temperature reached the maximum of 89° C., 5 minutes later, 7.422 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added, and a modification reaction was performed for 8 minutes. The polymerization conversion when the modifier is added is about 100%. To the modified rubber polymerization solution thus obtained, 10 ml of methanol as an active lithium decomposer was added and mixed, and then 2 g of BHT as a stabilizer was added and mixed, and the solvent was removed to obtain (sample Y).

The analysis values of this modified rubber were 10.0% by weight of bonded styrene, 9.9% by weight of styrene blocks, and 13.3% of bonded vinyl. By GPC measurement, the molecular weight of the copolymer before modification was 122,000, the molecular weight of the styrene block was 9500, and the modification rate of the copolymer was 86%.

The total coupling rate of 2-molecule coupling modification, 3-molecule coupling modification, and 4-molecule coupling modification was 79%, and the 1-molecule modification rate of the copolymer was 7%. In addition, the Mooney viscosity (ML1+4, 100° C.) of this modified rubber was 60.

(Sample Z) is a modified copolymer obtained by polymerizing in the same manner as (Sample Y), and adding 7.422 mmol of lithium diisopropylamide to the polymerizer after completion of the polymerization. , and then 7.422 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to carry out a modification reaction for 10 minutes. The Mooney viscosity (ML1+4, 100° C.) of the modified rubber was 54. It can be seen that by adding lithium diisopropylamide, the amino group of the low-molecular-weight residue of lithium amide is bonded to the modifier, and as a result, the Mooney viscosity is lowered.

Among the samples in Table 3, the copolymers of the invention of the present application are samples (V), (X), and (Z), and the samples (U), (W), and (Y) are copolymers other than the invention of the present application .

table 3 sample u V W x Y Z outside the scope of the invention within the scope of the invention outside the scope of the invention within the scope of the invention outside the scope of the invention within the scope of the invention Butadiene in stage 1 (g) 750 750 570 570 900 900 Styrene in Stage 1 (g) 250 250 430 430 - - Styrene in Stage 2 (g) - - - - 100 100 n-Butyllithium (mmol): (a') 11.875 11.875 12.500 12.500 14.844 14.844 n-Butyl lithium (a') × modification rate: a 8.79 8.79 9.75 9.75 12.766 12.766 Polar substances none none THF THF none none Amount of polar substances added (g) - - 16 16 - - Compounds Containing Metal-Nitrogen Bonds none DPLA none DPLA none DPLA Addition amount of compound containing metal-nitrogen bond mmmol: b - 11.875 - 8.333 - 7.422 modifier TGAMH TGAMH TGAMH TGAMH TGAMH TGAMH Addition amount of modifier mmol 11.875 11.875 6.284 6.284 7.422 7.422 Modifier functional group mmol: c 47.5 47.5 25.136 25.136 29.688 29.688 (a+b)/c 0.19 0.44 0.39 0.72 0.43 0.68 a:b 1:0 1:1.35 1:0 1:0.85 1:0 1:0.58 N/c 0.50 0.75 0.50 0.83 0.50 0.75 Modification rate (%) 74 74 78 78 86 86 Mooney viscosity 72 52 73 62 60 54 Bound styrene amount (%) 25 25 43 43 10 10 Block styrene (%) 15.5 15.9 13.5 13.6 9.9 9.9 1,2-vinyl binding amount (%) 13.2 13.2 25.0 24.9 13.3 13.3

In addition, the analysis of the sample was performed by the following method.

(1) Amount of bound styrene

The sample was made into a chloroform solution, and the amount of bound styrene (wt %) was measured by the absorption of phenyl groups of styrene at UV254 nm.

(2) Styrene block amount

It is obtained by the decomposition method of osmium oxide.

(3) Microstructure of the butadiene part

Prepare the sample as a carbon disulfide solution, use the solution measuring cell to measure the infrared spectrum in the range of 600-1000 cm ^-1 , and obtain the microstructure of the butadiene part according to the specified absorbance and the calculation formula of the Hampton method.

(4) Mooney viscosity

According to JIS K 6300, preheat at 100°C for 1 minute, and measure the viscosity after 4 minutes.

(5) Molecular weight and molecular weight distribution

GPC was used to determine the chromatogram, and the GPC adopted 3 connected chromatographic columns with polystyrene gel as filler, and standard polystyrene was used to calculate the molecular weight and molecular weight distribution through a calibration curve. As a solvent, tetrahydrofuran was used.

(6) Modification rate

Using the GPC chromatographic column with silica-based gel as a filler to adsorb the modified components, for the sample solution containing the sample and low-molecular-weight internal standard polystyrene, determine the polystyrene-based gel in the above 5 The difference between the chromatograms of GPC (manufactured by Showa Denko: Shodex) and silica-based column GPC (Zorbax produced by Dupont Corporation) was used to measure the amount of adsorption of modified components on the silica column , to obtain the modification rate.

Preparation of Copolymers A1, A2, A3

2 autoclaves with an inner volume of 10 liters, an inlet at the bottom, an outlet at the top, and a stirrer are connected in series as reactors, or a static mixer is placed between the two reactors and a jacketed autoclave for temperature regulation. Butadiene, styrene, and n-hexane from which impurities have been removed in advance are mixed at speeds of 16.4g/min, 3.6g/min, and 97.6g/min respectively, and the mixed solution is passed through a dehydration column filled with activated alumina. Then remove impurities, just before entering the first reactor, n-butyllithium is mixed in a static mixer at a speed of 0.003g/min (0.0469mmol), and then continuously supplied to the bottom of the first reactor, Furthermore, to the bottom of the first reactor, 2,2-bis(2-oxolane) propane as a polar substance was supplied at a rate of 0.017 g/min, and 0.035 g/min (0.547 mmol) N-butyllithium was supplied as a polymerization initiator at a high speed, and the temperature in the reactor was maintained at 85°C. The polymer solution was continuously discharged from the top of the first reactor and supplied to the second reactor. In addition, the polymerization rate at the outlet of the first reactor reached about 100%. The temperature of the second reactor was kept at 80°C, and tetraglycidyl-1,3-bisaminomethyl as a 4-functional polyepoxide was added from the bottom of the second reactor at a rate of 0.273 mmol/min. Cyclohexane, to carry out the modification reaction. To this modified polymer solution, an antioxidant (BHT) was continuously added at a rate of 0.05 g/min (n-hexane solution) to terminate the modification reaction, and then the solvent was removed to obtain a modified copolymer. As a result of its analysis, the copolymer had a bound styrene content of 18% and a bound butadiene content of 82%. As a result of measurement using an infrared spectrophotometer, the 1,2-bonding amount of the butadiene moiety calculated according to the Hampton method was 31%. The weight average molecular weight (Mw) obtained by GPC measurement using THF as a solvent was 321,000, and the molecular weight distribution (Mw/Mn) was 1.95. The modification rate of the modified copolymer was 86%. Do not add antioxidant in this modified copolymer, the modified copolymer solution of 7.5 liters is charged in the hydrogenation reactor (10 liters), according to the modified copolymer of every 100 parts by weight, in terms of Ti, for The hydrogenation catalyst described later was added in the form of 100ppm, and hydrogenation reaction was carried out under the conditions of hydrogen pressure of 0.7MPa and temperature of 70°C. After that, methanol in an amount equivalent to 10 times the molar amount of n-butyllithium used in polymerization was added, and then , a solution obtained by dissolving 2 g of an antioxidant (BHT) in n-hexane was added, followed by desolventization to obtain a hydrogenated modified copolymer (A1). The hydrogenation rate of the butadiene moiety was 85%.

In addition to supplying n-butyllithium as a polymerization initiator at a rate of 0.469 mmol/min and supplying 2,2-bis(2-oxolyl)propane as a polar substance at a rate of 0.015 g/min, other Use the same method as (sample A1) to obtain the copolymer, then, in the polymer solution that continuously flows into the static mixer installed in the middle of the 1st reactor and the 2nd reactor, at 0.469mmol/min Add lithium diisopropylamide at a constant speed and mix in a static mixer. In the second reactor, tetraglycidyl-1,3-bisaminomethylcyclohexane was added at a rate of 0.469 mmol/min to perform a modification reaction using it. When the reaction is in a stable state, an antioxidant (BHT) is continuously added to the modified polymer solution to terminate the modification reaction, and then the solvent is removed to obtain a modified copolymer. The bound styrene amount and the 1,2-bound amount of the butadiene moiety of this modified copolymer were the same as those of the sample (A1). The weight average molecular weight (Mw) was 285,000, and the molecular weight distribution (Mw/Mn) was 1.89. The modification rate of the modified copolymer was 85%. This modified copolymer was hydrogenated and desolvated by the same method as that used to obtain the sample (A1), to obtain a hydrogenated modified copolymer (A2) with a hydrogenation rate of 83%.

(Sample A3) is a hydrogenated non-modified copolymer obtained by changing the amounts of n-butyllithium and polar substances used in the polymerization to perform polymerization, without performing a modification reaction, and using Obtain (sample A1 and sample A2) the same method to carry out hydrogenation, desolvation treatment, its weight average molecular weight (Mw) is 339,000, molecular weight distribution (Mw/Mn) is 1.80, hydrogenation rate is 82%. The modulation results are shown in Table 4.

The hydrogenated modified copolymer of the invention of the present application is sample (A2), and samples (A1) and (A3) are copolymers other than the invention of the present application.

Table 4 sample A1 A2 A3 outside the scope of the invention within the scope of the invention outside the scope of the invention Butadiene (g/min) 16.4 16.4 16.4 Styrene (g/min) 3.6 3.6 3.6 n-BuLi (mmol/min): (a') 0.547 0.469 0.270 n-Butyl lithium (a') × modification rate: a 0.470 0.399 - Polar substances BOP BOP BOP Amount of polar substances added (g/min) 0.017 0.015 0.08 Compounds Containing Metal-Nitrogen Bonds - DPLA - Addition amount of compound containing metal-nitrogen bond mmol/min: b - 0.469 - modifier TGAMH TGAMH - Addition amount of modifier mmol/min 0.273 0.469 - Modifier functional group mmol/min: c 1.092 1.876 - (a+b)/c 0.43 0.46 - a:b 1:0 1:1.18 1:0 N/c 0.50 0.75 - Analytical results before hydrogenation 1) Modification rate (%) 86 85 - 2) Amount of bound styrene (%) 18 18 18 3) 1,2-vinyl binding amount (%) 31 31 30 4) Weight average molecular weight (Mw) million 32.1 28.5 33.9 5)Mw/Mn 1.95 1.89 1.80 Hydrogenation rate of butadiene moiety (%) 85 83 82

In addition, the preparation of the hydrogenation catalyst and the measurement of the hydrogenation rate of the butadiene moiety were implemented by the following methods.

(1) Preparation of hydrogenation catalyst

Charge 1 liter of dry and purified cyclohexane into a reaction vessel replaced with nitrogen, add 100 mmol of bis(η5-cyclopentadienyl) titanium dichloride, and add 200 mmol of bis(η5-cyclopentadienyl) titanium dichloride while fully stirring The n-hexane solution of trimethylaluminum was reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.

(2) Determination of hydrogenation rate

It measured using the nuclear magnetic resonance apparatus (Germany, the BRUKER company make, DPX-400).

Examples 1-9 and Comparative Examples 1-3

Using the samples (sample A to sample J) shown in Table 1 as the raw material rubber, rubber compositions were obtained with the compounding recipe shown in Table 5 using the following kneading method. Embodiment 1～8, comparative example 1～2 use single sample, and embodiment 9 and comparative example 3, are as rubber component, according to (sample A) and (sample B) be 75 parts by weight, polybutylene The vinyl rubber was compounded at 25 parts by weight and implemented.

[Kneading method]

Use a closed mixer (1.7 liters of internal capacity) with a temperature control device, the temperature control device utilizes external circulating water to carry out temperature control, as the mixing of the first stage, when the filling rate is 65%, the rotor rotates Under the condition of 66/77rpm, the raw rubber, filler material (silica and carbon black), organosilane coupling agent, aromatic hydrocarbon oil, zinc white, and stearic acid were kneaded. At this time, the rubber composition was obtained in a state where the temperature of the internal mixer was controlled so that the discharge temperature (compound) was 155 to 160°C.

Next, as the second stage of kneading, after cooling the complex obtained above to room temperature, an anti-aging agent was added, and kneading was performed again in order to improve the dispersion of silica. Also in this case, the discharge temperature (complex) was adjusted to 155 to 160° C. by controlling the temperature of the mixer.

After cooling, as the third stage of kneading, sulfur and a vulcanization accelerator were kneaded in an open roll at a temperature of 70°C.

This was molded, vulcanized in a vulcanization press at 160°C for a predetermined time, and its physical properties were measured. Table 6 shows the results of physical property measurement.

               Table 5 Compatible Prescription (Combined Prescription-1)

Rubber 100.0 parts

Silica (Ultrasilicon VN3 manufactured by Degussa Co., Ltd.) 45.0 parts

Carbon (シ一ストKH manufactured by Tokai Kaibon Co., Ltd.) 5.0 parts

Silane coupling agent (Si69 manufactured by Degussa) 4.5 parts

Aromatic oil (X149 manufactured by Japan Enaji I Co., Ltd.) 5.0 parts

Zinc China 3.0 copies

Stearic acid 2.0 parts

Antiaging agent (N-isopropyl-N'-phenyl-p-phenylenediamine) 1.0 parts

Sulfur 1.4 parts

Vulcanization accelerator (N-cyclohexyl-2-benzothiazole sulfenamide) 1.0 parts

Vulcanization accelerator (diphenylguanidine) 1.5 parts

Total 169.4 copies

Table 6 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Example 6 Example 7 Example 8 Comparative example 2 Example 9 Comparative example 3 Copolymer A C D. E. f B G I J h A B Complex Mooney Viscosity 98 102 91 90 91 103 103 110 105 101 81 83 Bound Rubber Amount (%) 46 44 42 40 42 35 47 43 44 38 39 31 300% modulus Mp 14.5 14.3 14 13.6 14.6 13 12.2 11.9 11.8 12 10.1 10 Tensile strength Mp 19.5 19.3 19 18.8 19.2 18.5 17.5 17.3 17.1 16.9 17.3 16.9 Resilience at 50°C (%) 62.5 62 61 59.5 59 56 74.5 72.5 73.0 69.0 66.0 60.5 0℃Tanδ(strain 1%) 1.12 1.08 1.03 1.00 0.98 1.02 0.405 0.388 0.390 0.378 0.313 0.307 50℃Tanδ(strain 3%) 0.105 0.109 0.115 0.127 0.115 0.145 0.065 0.075 0.073 0.095 0.090 0.120 50℃G'Mp (strain 3%) 3.60 3.81 3.92 4.05 4.1 4.5 2.73 3.12 3.05 3.7 3.95 4.7 50℃ΔG'Mp 0.7 0.81 0.84 1.04 1.21 1.35 0.48 0.69 0.58 1.02 0.95 1.55

Example 9 and Comparative Example 3 were carried out by mixing the copolymers A and B with the high-cis polybutadiene rubber at a ratio of 75/25.

The measurement methods of the respective physical properties were carried out by the following methods.

(1) bonded rubber

About 0.2 g of the compound after the second-stage kneading was cut into a square of about 1 mm, put into a Harris basket (made of 100-mesh metal mesh), and the weight was measured. Then, after immersing in toluene for 24 hours, dry, measure the weight, consider the non-dissolved components, calculate the amount of rubber bound to the filler, and find the ratio of the rubber bound to the filler to the amount of rubber in the original compound .

(2) Tensile test

Measured by the tensile test method of JIS-K6251.

(3) Determination of viscoelastic properties

Measurement was performed at a frequency of 10 Hz by a torsion method using an Ares viscoelasticity testing machine manufactured by Reometrix Corporation.

The Payne effect (ΔG') is represented by the difference between the minimum value and the maximum value in the range of strain from 0.1% to 10%. The smaller the Payne effect, the better the dispersibility of fillers such as silica, the higher the low-temperature Tanδ, the better the wet slip (grip) performance, and the lower the high-temperature Tanδ, the lower the hysteresis loss Less, low rolling resistance of the tire, that is, excellent performance of low fuel consumption.

(4) Determination of resilience

The rebound resilience at 50°C is measured according to the リュプケ type rebound resilience test method of JIS K6255.

As shown in Table 6, from the results of Examples 1 to 5 and Comparative Example 1, and Examples 6 to 8 and Comparative Example 2 with different bound styrene amounts and vinyl bound amounts, compared with Comparative Example , the composition of the present invention has low Tanδ at high temperature (50° C.), low hysteresis loss, can reduce rolling resistance of tires, and improve low fuel cost performance. In addition, the balance of low-temperature (0°C) Tanδ and high-temperature (50°C) Tanδ is also good, and the tire has an excellent balance between wet skid resistance and low fuel consumption performance.

In addition, the resilience at high temperature (50°C) is high, which is closely related to the decrease of Tanδ at high temperature (50°C). The effects of the invention of the present application can be exhibited regardless of whether the copolymer is used alone or, as shown in Example 9 and Comparative Example 3, by blending other rubbers.

Compared with the comparative example, it can be seen that the composition of the present invention has a low modulus, has very little strain dependence, and has improved silica dispersibility. Utilizing this effect, the rolling resistance of the above-mentioned tires can be reduced, and at the same time, it can be applied to applications that require dispersibility of fillers such as silica, or all applications that require low hysteresis loss, or require wear resistance that greatly affects dispersibility. sexual use. It can be used in a wide range of applications including tires, shoes, anti-vibration rubber, and other industrial products.

Examples 10-18 and Comparative Examples 4-6

Using the samples (sample K to sample T) shown in Table 2 as raw rubber, rubber compositions were obtained using the compounding recipes shown in Table 7. Embodiment 10～17, comparative example 4～5 use single sample, embodiment 18 and comparative example 6, are as rubber component, according to (sample M) and (sample L) be 75 parts by weight, polybutylene The vinyl rubber was compounded at 25 parts by weight and implemented.

The kneading method, molding, and vulcanization were carried out in exactly the same manner as in Examples 1-9. The physical property measurement results are shown in Table 8 and Table 9.

                Table 7 Compatible Prescription (Combined Prescription-2)

Rubber 100.0 parts

Silica (Ultrasilicon VN3 manufactured by Degussa Co., Ltd.) 63.0 parts

Carbon (シ一ストKH manufactured by Tokai Kaibon Co., Ltd.) 7.0 parts

Silane coupling agent (Si69 manufactured by Degussa) 6.3 parts

Aromatic oil (X149 manufactured by Japan Enaji Co., Ltd.) 37.5 parts

Zinhua 2.5 parts

Stearic acid 1.0 parts

Antiaging agent (N-isopropyl-N'-phenyl-p-phenylenediamine) 2.0 parts

Sulfur 1.1 parts

Vulcanization accelerator (N-cyclohexyl-2-benzothiazole sulfenamide) 1.7 parts

Vulcanization accelerator (diphenylguanidine) 2.0 parts

Total 224.1 copies

Table 8 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative example 4 Copolymer K m N o P Q L Complex Mooney Viscosity 76 79 84 83 85 86 84 Bound Rubber Amount (%) 47 50 48 46 48 50 43 300% modulus Mp 10.8 11.2 12 10.8 12.2 12.3 11.0 Tensile strength Mp 24.0 24.9 25.5 twenty four 25.5 25.3 23.5 Resilience at 50°C (%) 59.0 62.0 61.0 58.0 60.0 60.0 55.0 0℃Tanδ(strain 1%) 0.639 0.665 0.645 0.65 0.635 0.634 0.640 50℃Tanδ(strain 3%) 0.138 0.125 0.130 0.142 0.130 0.126 0.167 50℃G'Mp (strain 3%) 3.35 3.40 3.50 3.63 3.69 3.63 3.92 50℃ΔG′Mp 1.69 1.39 1.53 1.86 2.05 1.55 2.45

Table 9 Example 16 Example 17 Comparative Example 5 Example 18 Comparative example 6 Copolymer R T S m L Complex Mooney Viscosity 72 78 75 65 70 Bound Rubber Amount (%) 47 46 40 44 37 300% modulus Mp 10.7 10.5 10.0 10.0 9.5 Tensile strength Mp 22.5 22.3 twenty one 23.8 twenty three Resilience at 50°C (%) 55.5 54.5 50.0 63.5 57.5 0℃Tanδ(strain 1%) 1.08 1.02 1.03 0.353 0.345 50℃Tanδ(strain 3%) 0.134 0.143 0.180 0.130 0.170 50℃G'Mp (strain 3%) 3.45 3.50 3.78 3.59 4.02 50℃ΔG′Mp 1.43 1.64 2.79 1.95 3.22

Example 18 and Comparative Example 7 were implemented by mixing the copolymers M and L with the high-cis polybutadiene rubber in a ratio of 75/25.

The measurement methods of each physical property were carried out in exactly the same manner as in Examples 1-9.

In Examples 10 to 18 and Comparative Examples 4 to 6, samples in which a high molecular weight copolymer was oil-extended during continuous polymerization were used, and a relatively high filler was blended to achieve the effect of the invention of the present application.

As shown in Table 8 and Table 9, from the results of Examples 10-15 and Comparative Example 4, and Examples 16-17 and Comparative Example 5 with different bound styrene amounts and vinyl bound amounts, the present application The composition of the invention has lower Tan δ at high temperature (50° C.) than that of the comparative example, has small hysteresis loss, can reduce rolling resistance of tires, and improves performance of low fuel cost. In addition, the balance between low-temperature (0°C) Tanδ and high-temperature (50°C) Tanδ is also good, and the tire has an excellent balance between wet skid resistance and low fuel consumption performance.

In addition, the resilience at high temperature (50°C) is high, which is closely related to the decrease of Tanδ at high temperature (50°C). The effects of the invention of the present application can be exerted regardless of using the copolymer alone or by blending other rubbers as shown in Example 18 and Comparative Example 6.

Comparing the composition of the present invention with the comparative example, it can be seen that the strain dependence of the modulus is very small and the dispersibility of silica is improved. By improving the dispersibility of silica, the compounding amount of silica can be increased further, and it can be applied to various compounding and various purposes. Suitable for various industrial products such as tires and belts.

Examples 19-21 and Comparative Examples 7-9

Using the samples (sample U to sample Z) shown in Table 3 as raw rubbers, rubber compositions were obtained using the blends shown in Table 10.

The kneading method, molding, and vulcanization were carried out in exactly the same manner as in Examples 1-9. Table 11 shows the measurement results of physical properties.

             Table 10 Compatible Prescription (Combined Prescription-3)

Rubber 100.0 parts

Silica (Ultrasilicon VN3 manufactured by Degussa Co., Ltd.) 40.0 parts

Silane coupling agent (Si69 manufactured by Degussa) 2.0 parts

Naphthenic oil (Shellflex 371J) 5.0 parts

Zinc China 5.0 copies

Stearic acid 2.0 parts

Anti-aging agent (styrene phenol) 1.0 parts

Sulfur 1.7 parts

Vulcanization accelerator (dibenzothiazole disulfide) 1.5 parts

Vulcanization accelerator (diphenylguanidine) 1.5 parts

Total 159.7 copies

Table 11 Example 19 Comparative Example 7 Example 20 Comparative Example 8 Example 21 Comparative Example 9 Copolymer V u x W Z Y 300% modulus Mp 10.4 10.3 11.3 11 6.2 5.8 Tensile strength Mp 16.9 15.9 16.8 15.6 14.7 13.8 Resilience at 23°C (%) 68.0 63.0 32.0 24.0 70.0 65.0 Resilience at 70°C (%) 72.0 69.0 65.0 62.0 75.0 73.0 C-Set(%) 16.0 23.0 19.0 27.0 14.0 22.0 Exothermic (starting from 50°C) 30 37 28 34 - - Acron wear cc 0.145 0.180 0.095 0.120 - - 50℃G'(0.1% strain)Mp 4.02 4.85 4.35 5.36 3.58 3.86 50℃G'(10% strain)Mp 3.62 4.02 3.86 4.12 3.32 3.31 50℃ΔG' 0.40 0.83 0.49 1.24 0.26 0.55 0℃Tanδ(0.1% strain) 0.111 0.129 0.170 0.216 0.083 0.101 0℃Tanδ(3% strain) 0.116 0.137 0.179 0.239 0.086 0.106 0℃Tanδ(10% strain) 0.117 0.140 0.181 0.246 0.090 0.115 50℃Tanδ(0.1% strain) 0.080 0.097 0.154 0.189 0.074 0.083 50℃Tanδ(3% strain) 0.083 0.104 0.159 0.196 0.075 0.085 50℃Tanδ(10% strain) 0.084 0.109 0.161 0.202 0.078 0.091 Strain dependence of Tanδ at 50℃ 5.0 12.4 4.5 6.9 5.4 9.6 70℃Tanδ(0.1% strain) 0.100 0.113 0.158 0.192 0.074 0.084 70°C Tanδ (3% strain) 0.105 0.121 0.189 0.221 0.076 0.092 70℃Tanδ(10% strain) 0.111 0.125 0.193 0.224 0.079 0.093 Temperature dependence of 3% Tanδ 10.0 24.1 11.2 18 12.8 19.8

In addition, the measurement of the viscoelastic property value and the compression set was carried out by the following method.

(1) Strain dependence and temperature dependence of Tanδ

Tan δ at 0°C, 50°C, and 70°C was measured at 0°C, 50°C, and 70°C by a torsion method at a frequency of 10 Hz using an Ares viscoelasticity testing machine manufactured by Reometrix Co., Ltd., and calculated by the following formula.

The strain dependence is a numerical value calculated using (10% Tanδ at 50° C.-0.1% Tanδ)×100(%)/0.1% Tanδ.

The temperature dependence is a numerical value calculated using (3% Tanδ at 0°C-3% Tanδ at 50°C)×100(%)/3% Tanδ at 50°C.

(2) Compression set (c-set)

According to JIS-K6262 compression set test method, it is measured under the condition of 70°C-22 hours.

(3) Fever

Use Goodrich flexometer (Flexometer), under the conditions of rotation speed 1800rpm, stroke 0.225 inches, load 55 lbs, measurement start temperature 50°C, use the difference between the temperature after 20 minutes and the start temperature To represent.

(4) Akron (akron) wear

Abrasion Resistance Using an Akron abrasion tester, the amount of abrasion at a load of 6 pounds and a number of revolutions of 1,000 was measured.

As shown in Table-11, even when the copolymer of the present invention is a styrene-butadiene copolymer having a styrene block, it has excellent properties. If Example 19 is compared with Comparative Example 7, Example 20 and Comparative Example 8, and Example 21 and Comparative Example 9, it can be seen that the modulus (G') and Tanδ of the composition using the copolymer of the present application invention are compared. The strain dependence is small, and the temperature dependence is small. In addition, it has good heat generation properties and wear resistance, and further has excellent characteristics such as small compression set due to improved dispersibility of silica. Utilizing such characteristics, the modified rubber composition of the present invention is suitable for shockproof rubber applications and transparent compounded shoes containing silica. The modified rubber composition of the present invention having such excellent properties can also be suitably used for other industrial products and the like.

Example 22 and Comparative Examples 10, 11

Using the samples (sample A1 to sample A3) shown in Table 4 as raw rubber, rubber compositions were obtained using the compounding recipes shown in Table 12. The kneading method, molding, and vulcanization were carried out in exactly the same manner as in Examples 1-9. Table 13 shows the results of physical property measurement.

             Table 12 Compatible Prescription (Combined Prescription-4)

Rubber 100.0 parts

Silica (Ultrasil VN3 manufactured by Degussa Co., Ltd.) 50.0 parts

Silane coupling agent (Si69 manufactured by Degussa) 4.0 parts

Paraffin oil (Idemitsu Kosan Co., Ltd. PW-380) 20.0 parts

Zinc China 5.0 copies

Stearic acid 1.0 parts

Sulfur 1.5 parts

Vulcanization accelerator (tetramethylthiuram disulfide) 1.5 parts

Vulcanization accelerator (2-mercaptobenzothiazole) 0.5 parts

Total 183.5 copies

Table 13 Example 22 Comparative Example 10 Comparative Example 11 Copolymer A2 A1 A3 Complex Mooney Viscosity 72 78 90 Bound Rubber Amount (%) 52 42 18 Tensile strength Mp 21.4 20.3 17.3 Resilience at 50°C (%) 71.0 64.0 56.0 C-Set(%) 11 19 30 50℃ΔG′Mp 0.15 0.43 2.3 Adhesive (Kg/cm) aluminum plate 7 7 3 Bonding (Kg/cm) stainless steel 12 11 11

In addition, in this physical property evaluation, the physical property was measured by the method shown below.

(1) Compression set (c-set)

According to JIS-K6262 compression set test method, it is measured under the condition of 100°C-70 hours.

(2) Cohesion of vulcanized rubber

According to JIS K-6256, the 180-degree peel test is carried out to measure the peel strength of the rubber bonded to the metal. As primers, Metroloc G and Metroloc PH-50 (manufactured by Toyo Kagaku Laboratories, Japan, Ltd.) were used.

Other physical properties were measured by the same method as in Examples 1-9.

As shown in Table 13, in terms of viscoelastic properties, the hydrogenated modified copolymer of the present invention has further improved modulus deformation dependence, has excellent compression set, good resilience, and is compatible with metal Adhesiveness was also good. These characteristics can be effectively used in a wide range of industrial goods fields such as anti-vibration rubber, belts, hoses, and shoes.

Although the present invention was described in detail with reference to the examples, it is obvious to those skilled in the art that various changes and corrections can be made without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2003-415855 ) filed on December 15, 2003, the contents of which are incorporated herein by reference.

industrial availability

The hydrocarbon polymer having functional groups obtained by the present invention is a polymer in which an inorganic filler is dispersed in a high molecular weight hydrocarbon polymer matrix with a uniform and fine particle size, and as a result, high performance is realized.

When the high-molecular-weight hydrocarbon polymer is a rubber-like polymer, inorganic fillers such as silica and carbon black are uniformly dispersed, and in the case of vulcanized rubber, when used for tire tread applications, it is different from existing products In comparison, the balance between low rolling resistance and wet skid resistance can be further improved, wear resistance can be improved, and further, strength can be improved, modulus reduction rate at high temperature can be improved, etc., thus becoming a rubber suitable for tires , anti-shock rubber, shoes and other compositions. In addition, when the high-molecular-weight hydrocarbon polymer is a thermoplastic elastomer, inorganic fillers such as silica, metal oxides, and metal hydroxides are uniformly dispersed, and compared with existing products, it is possible to further improve strength and improve Effects such as flame retardancy, improvement of elongation, and improvement of transparency can be obtained by using it in an asphalt composition to improve the graspability of aggregates. Furthermore, when the high-molecular-weight hydrocarbon polymer is a thermoplastic elastomer or a thermoplastic resin, in a blended composition with other polar resins, the compatibility can be improved, and at the same time, uniform and fine dispersion can be obtained.

Claims (14)

1. A modified hydrocarbon polymer obtained by reacting (A), (B), and (C), (A) a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond; (B) At least one selected from low-molecular compounds having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, and a low-molecular compound having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group, with a molecular weight of 2000 or below low molecular weight compounds; and (C) Multifunctional modifier The modified hydrocarbon polymer has at least one modifying group and a weight average molecular weight of 10,000 or more, The ratio (N/c) of the number of moles of nitrogen atoms (N) of the modifying group to the number of moles of functional groups (c) of the multifunctional modifier (C) is greater than 1/2. 2. The modified hydrocarbon polymer according to claim 1, wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond. 3. The modified hydrocarbon polymer as claimed in claim 1 or 2, the polyfunctional modifier (C) has a glycidyl amino group as a functional group, and the number of epoxy groups in its molecule is 2 or more The above multifunctional modifiers. 4. The modified hydrocarbon polymer as claimed in claim 1, the low-molecular compound (B) is selected from low-molecular compounds with lithium-nitrogen bonds or magnesium-nitrogen bonds, lithium-carbon bonds or magnesium-carbon bonds and at least one of hydrocarbon compounds containing an amino group. 5. The modified hydrocarbon polymer as claimed in claim 1, The hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond at the terminal, The low-molecular compound (B) is at least one selected from low-molecular compounds having a lithium-nitrogen bond or a magnesium-nitrogen bond, hydrocarbon compounds having a lithium-carbon bond or a magnesium-carbon bond and containing an amino group, The multifunctional modifier (C) is a multifunctional modifier having 2 or more diglycidyl amino groups as functional groups in the molecule, A modifying group having N/c greater than 1/2 is present on at least one terminal of the polymer. 6. A method for producing a modified hydrocarbon polymer, comprising the steps of: reacting (A), (B), and (C) in an inert solvent, (A) Hydrocarbon polymers with alkali metal-carbon bonds or alkaline earth metal-carbon bonds and a weight-average molecular weight of 10,000 or more; (B) At least one selected from low-molecular compounds having alkali metal-nitrogen bonds or alkaline earth metal-nitrogen bonds, low-molecular compounds having alkali metal-carbon bonds or alkaline earth metal-carbon bonds and containing amino groups, Low-molecular-weight compounds with a molecular weight of 2,000 or less; (C) A polyfunctional modifier having a molecular weight of 2000 or less. 7. The method for producing a modified hydrocarbon polymer according to claim 6, wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond. 8. the manufacture method of modified hydrocarbon polymer as claimed in claim 6 or 7, polyfunctional modifying agent (C) has glycidyl amino as functional group, the number of the epoxy group in its molecule is 2 One or more multifunctional modifiers. 9. The manufacture method of modified hydrocarbon polymer as claimed in claim 6, low molecular compound (B) is selected from the low molecular compound with lithium-nitrogen bond or magnesium-nitrogen bond, with lithium-carbon bond or magnesium - At least one type of hydrocarbon compound containing a carbon bond and an amino group. 10. the manufacture method of modified hydrocarbon polymer as claimed in claim 6, The hydrocarbon polymer (A) is a conjugated diene polymer obtained by living anion polymerization having a lithium-carbon bond at the terminal, The low-molecular compound (B) is at least one selected from low-molecular compounds having a lithium-nitrogen bond or a magnesium-nitrogen bond, hydrocarbon compounds having a lithium-carbon bond or a magnesium-carbon bond and containing an amino group, The polyfunctional modifier (C) is a polyfunctional modifier having two or more diglycidylamino groups as functional groups in the molecule. 11. A composition comprising 100 parts by weight of the modified hydrocarbon polymer according to claim 1, and 1 to 200 parts by weight of a compound selected from the group consisting of silicon dioxide dispersed in the modified hydrocarbon polymer. Inorganic fillers, fillers for metal oxides and metal hydroxides. 12. The composition according to claim 11, wherein the filler is synthetic silicic acid having a primary particle diameter of 50 nm or less. 13. A method for producing a composition, comprising the following steps: at a temperature of 120° C. to 250° C., 100 parts by weight of the modified hydrocarbon polymer according to claim 1 and a primary polymer having a thickness of 50 nm or less. The synthetic silicic acid having a particle size is kneaded to disperse the synthetic silicic acid in the modified hydrocarbon polymer. 14. A composition for vulcanized rubber, comprising 1 to 100 parts by weight of a silica-based inorganic filler, 1 to 50 parts by weight of the modified hydrocarbon polymer of claim 5 in 100 parts by weight of carbon black.