JP4739025B2 - Polymer excellent in affinity with inorganic filler - Google Patents

Description

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

Conventionally, an excellent resin composition or elastomer composition by a combination of an organic polymer material and an inorganic filler has been obtained.
For example, Patent Document 1 discloses a composition in which maleic anhydride is added to a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound to improve the affinity with an inorganic filler.

Patent Document 2 discloses a silica composition of a modified polymer obtained by reacting an active terminal of a rubber-like polymer with a polyfunctional compound having an epoxy group in the molecule.
Japanese Examined Patent Publication No. 62-54140 WO01-23467

  However, in the combination of an organic polymer material and an inorganic filler, a great difference occurs in the dispersion state depending on the kneading method and conditions, and it has been a big industrial problem to always obtain a constant high performance.

  In order to solve the above problems, the inventors of the present invention have a low molecular weight compound having a metal-nitrogen bond at the same time when a polyfunctional low molecular compound is reacted with a high molecular weight hydrocarbon polymer having a metal-carbon bond. Or a method of reacting a low molecular compound having an amino group and a metal-carbon bond, introducing a modified group having a specific structure into the polymer, and a plurality of high molecular weight hydrocarbon polymers are polyfunctional low molecular compounds It has been found that the functional group modification is uniformly performed on the high molecular weight hydrocarbon polymer by suppressing the coupling reaction due to the multi-molecules caused by the reaction with the organic polymer. Therefore, the combination of the organic polymer material and the inorganic filler is always constant. As a result, the inventors have found that high performance can be obtained.

That is, the present invention is as follows.
(1) (A) a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond;
(B) at least selected from low molecular compounds having an alkali metal-nitrogen bond or alkaline earth metal-nitrogen bond, and low molecular compounds having an alkali metal-carbon bond or alkaline earth metal-carbon bond and having an amino group 1 type of low molecular weight compound having a molecular weight of 20 0 0 or less; and (C) a polyfunctional denaturant (A) moles of metal-carbon bond (a), metal (N) of nitrogen (B) and metal- As the total number of moles of carbon bonds (b) and the number of moles of functional groups (c) of the polyfunctional modifier of (C), (a + b) / c is 0. 0 5 to 1. At a rate of 5,
A modified hydrocarbon-based polymer having at least one modified group and having a weight average molecular weight of 10,000 or more, obtained by reacting, wherein the number of moles of nitrogen atoms (N) of the modified group is A modified hydrocarbon polymer in which the ratio (N / c) of the functional group mole number (c) of the functional modifier (C) exceeds 1/2.

(2) The modified hydrocarbon polymer according to (1), wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond.
(3) The above-mentioned (1) or (2), wherein the polyfunctional modifier (C) is a polyfunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in the molecule. ) Modified hydrocarbon polymer described in the above.

  (4) The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, and an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond. A modified hydrocarbon-based polymer as described in (1) above.

(5) The hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond at the end,
The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond,
The multifunctional modifier (C) is a multifunctional modifier having two or more diglycidylamino groups as functional groups in the molecule,
The modified hydrocarbon polymer according to (1) above, wherein N / c has a modifying group exceeding 1/2 at at least one terminal of the polymer.

(6) (A) A hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and having a weight average molecular weight of 10,000 or more;
(B) at least selected from a low molecular compound 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 having an amino group A low molecular weight compound having a molecular weight of 2,000 or less and having a bond with one kind of metal;
(C) A method for producing a modified hydrocarbon polymer comprising a step of reacting a polyfunctional modifier having a molecular weight of 2,000 or less in an inert solvent.

(7) The method for producing a modified hydrocarbon polymer according to the above (6), wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond.
(8) The above-mentioned (6) or (7), wherein the polyfunctional modifier (C) is a polyfunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in the molecule. ) For producing a modified hydrocarbon polymer.

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

(10) The hydrocarbon polymer (A) is a conjugated diene polymer obtained by living anion polymerization having a lithium-carbon bond at the end,
The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond,
The method for producing a modified hydrocarbon polymer according to the above (6), wherein the polyfunctional modifier (C) is a polyfunctional modifier having two or more diglycidylamino groups as functional groups in the molecule.

(11) From the group consisting of 100 parts by weight of the modified hydrocarbon polymer according to (1) above, and a silica-based inorganic filler, a metal oxide, and a metal hydroxide dispersed in the modified hydrocarbon polymer. A composition comprising 1 to 200 parts of a selected filler.

(12) The composition according to (11), wherein the filler is a synthetic silicic acid having a primary particle size of 50 nm or less.
(13) 100 parts by weight of the modified hydrocarbon polymer according to the above (1) and synthetic silicic acid having a primary particle size of 50 nm or less are kneaded at a temperature of 120 ° C. to 250 ° C., and the modified hydrocarbon heavy A method for producing a composition comprising a step of dispersing the synthetic silicic acid in a coalescence.

(14) A composition for vulcanized rubber in which 1 to 100 parts by weight of a silica-based inorganic filler and 1 to 50 parts by weight of carbon black are blended with 100 parts by weight of the modified hydrocarbon polymer according to (5).

  The hydrocarbon-based polymer having a functional group obtained by the present invention can provide a polymer-inorganic material composition having a constant and high performance under mild kneading conditions in combination with an inorganic filler. . Specifically, the viscosity during kneading is not too high, and the kneading operation is carried out with an appropriate torque without any trouble. In the resulting blended composition, the inorganic filler is uniform and fine in the high molecular weight hydrocarbon polymer matrix. As a result, high performance is exhibited.

  More 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 a vulcanized rubber, it is conventionally used in tire tread applications. Improvements in the balance between low rolling resistance and wet skid resistance, improved wear resistance, improved strength, improved modulus reduction at high temperatures, tire rubber, anti-vibration rubber, The composition is suitable for footwear and the like.

  In addition, when the high molecular weight hydrocarbon polymer is a thermoplastic elastomer, inorganic fillers such as silica, metal oxide, and metal hydroxide are uniformly dispersed, improving the strength more than before, improving flame retardancy, Effects such as improved elongation and transparency can be obtained. When used in an asphalt composition, effects such as improved aggregate graspability can be obtained.

Further, when the high molecular weight hydrocarbon polymer is a thermoplastic elastomer or a thermoplastic resin, uniform and fine dispersion can be obtained with improved compatibility in a blended composition with other polar resins.

FIG. 1 is a graph showing Tan δ balance at low and high temperatures of the modified copolymer compositions of Examples and Comparative Examples. FIG. 2 is a graph showing Tan δ balance at low and high temperatures of the modified copolymer compositions of Examples and Comparative Examples.

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

The present invention will be specifically described below.
The hydrocarbon polymer (A) having an alkali metal-carbon bond or alkaline earth metal-carbon bond of the present invention is polymerized with an alkali metal initiator and / or an alkaline earth metal initiator, and anionic polymerization is performed. Examples thereof include hydrocarbon polymers having an alkali metal-carbon bond or an alkaline earth metal-carbon bond at one terminal or a plurality of terminals obtained by growing by reaction. Further, it may be a hydrocarbon polymer polymerized by other methods, in which an alkali metal-carbon bond or an alkaline earth metal-carbon bond is introduced by 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. An earth metal compound is preferably used. As the organic alkali metal compound, an organic lithium compound is particularly suitable. Organic lithium compounds having a low molecular weight, solubilized oligomeric organic lithium compounds, those having a single lithium in one molecule, those having a plurality of lithiums in one molecule, and bonding of an organic group and lithium In the form, those comprising a carbon-lithium bond, those comprising a nitrogen-lithium bond, those comprising a tin-lithium bond, and the like are included. Specifically, n-butyllithium, sec-butyllithium, t-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenelithium, etc. as monoorganolithium compounds are 1,4 as polyfunctional organolithium compounds. -Dilithiobutane, a reaction product of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, a reaction product of n-butyllithium, 1,3-butadiene and divinylbenzene, n-butyllithium and a polyacetylene compound In addition, the reaction product of 3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3-morpholino-1-propyllithium, Imidazol-1-propyllithium, n-butyltri Aluminium and p- (2-N, N-dimethylaminoethyl) styrene reaction products, and amino group-containing lithium hydrocarbons such as low molecular weight oligomers obtained by polymerizing butadiene, isoprene, styrene, etc., and nitrogen- Examples of the compound comprising a lithium bond include dimethylaminolithium, dihexylaminolithium, diisopropylaminolithium, and hexamethyleneiminolithium. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

Particularly preferred are n-butyllithium and sec-butyllithium. These organolithium compounds are used not only as one kind but also as a mixture of two or more kinds.
Other organic alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, lithium, sodium, potassium alkoxides, sulfonates, carbonates, amides, and the like may be used, or they may be used in combination with other organometallic compounds.

  Representative examples of the alkaline earth metal initiator include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Specific examples include dibutyl magnesium, ethyl butyl magnesium, and propyl butyl magnesium. In addition, alkaline earth metal compounds such as alkoxides, sulfonates, carbonates, and amides are used. These organic alkaline earth metal compounds are sometimes used in combination with organic alkali metal initiators and other organic metal compounds.

  In the production method of the present invention, when the polymer (A) is a polymer obtained by polymerizing with an alkali metal initiator and / or an alkaline earth metal initiator and growing by an anionic polymerization reaction, the polymerization is batchwise. Alternatively, the polymerization is carried out by a continuous polymerization method.

  In the production method of the present invention, the polymer (A) is preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Any monomer that can be polymerized by living anionic polymerization can be used as the monomer for forming the polymer. For example, there are styrene, α-methylstyrene, 1,1-diphenylethylene, 1,3-butadiene, isoprene, piperylene and the like, which are used alone or in copolymerization.

  The obtained polymer having an active metal is preferably used immediately in the next reaction. In particular, when a polymer having active lithium is allowed to stand at a high temperature, lithium hydride may be generated to reduce the active metal. In that case, the modification rate of the polymer may decrease. Preferably, it should be immediately subjected to the next reaction when the monomer is substantially consumed, and should be subjected to the next reaction within 5 minutes at 80 ° C. or higher.

  A hydrocarbon polymer polymerized by other methods, in which an alkali metal-carbon bond or alkaline earth metal-carbon bond is introduced by a known method, may be used in the middle of the main chain of the hydrocarbon polymer. It can be obtained by a method of reacting a soluble organic alkali metal compound or a soluble alkaline earth metal compound at a site or terminal site. According to this method, it is possible to introduce an alkali metal-carbon bond into high-cis polybutadiene, EPDM, or the like. Specifically, an organic alkali metal compound and / or an organic alkali is added to a solution of a hydrocarbon polymer having a double bond somewhere in the main chain, side chain, terminal portion, etc. in the molecule. An earth metal compound, more preferably a polar substance selected from ethers and tertiary amines as an activator is used in combination, and the reaction is preferably carried out at a temperature of 30 to 200 ° C. Further, it is more preferable to immediately use a polymer obtained by reacting sec-butyllithium with N, N, N ′, N′-tetramethylethylenediamine at 50 to 100 ° C. and lithiating.

In the present invention, the hydrocarbon polymer may be any polymer as long as it does not deactivate the alkali metal-carbon bond or alkaline earth metal-carbon bond. As the hydrocarbon polymer, a hydrocarbon polymer or a saturated hydrocarbon polymer having a double bond in the molecule is preferably used.
The hydrocarbon polymer having a double bond in the molecule includes a polymer of a conjugated double bond compound, a copolymer comprising two or more conjugated double bonds, a conjugated double bond compound and the conjugated double bond. A copolymer of the compound and a monomer copolymerizable is used. Specific examples include polybutadiene, polyisoprene, butadiene-isoprene copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, and butadiene-isoprene-styrene copolymer. The bonding mode of the butadiene unit and isoprene unit may be 1,4 bond, 1,2 or 3,4 bond. Further, the bonding mode of the copolymer may be either random bonding or block bonding. The structure of the polymer may be either a linear polymer or a branched polymer. Examples of the branched polymer include a radial type (radial type) and a comb type. The molecular weight distribution ranges from narrow to wide and may be any. Specifically, the molecular weight distribution represented by Mw / Mn is usually in the range of 1.0 to 10.

  Examples of the random copolymer include a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer. Examples of the random copolymer include a completely random copolymer having a statistically random composition, and a tapered random copolymer having a tapered distribution in composition. Even if it is a homopolymer of a single monomer composition, it is a polymer with a uniform composition due to its monomer bonding mode, that is, 1,4 bond and 1,2 bond, etc. Or various structures are possible.

  Examples of block bonds include those in which homopolymer blocks are bonded, blocks in which random polymers are bonded, and blocks in which tapered random polymers are bonded. Further, there are 2 type block copolymers composed of 2 blocks, 3 type block copolymers composed of 3 blocks, 4 type block copolymers composed of 4 blocks, and the like. As an example of a block polymer, a block composed of a vinyl aromatic compound such as styrene is S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of a vinyl aromatic compound and a conjugated diene compound. When represented by B, an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, and a block represented by (SB) m-X There are copolymers.

More generally, for example, a structure represented by the following general formula can be given. (SB) n, S- (BS) n, B- (SB) n, [(SB) n] m-X, [(BS) n-B] m-X , [(SB) n-S] m-X
(In the above formula, the boundaries between the blocks do not necessarily have to be clearly distinguished. When the block B is a copolymer of a vinyl aromatic compound and a conjugated diene compound, the vinyl aromatic hydrocarbon in the block B is uniform. The block B may have a portion where the vinyl aromatic hydrocarbon is uniformly distributed and / or a portion where the vinyl aromatic hydrocarbon is distributed in a tapered shape. A plurality of segments having different vinyl aromatic hydrocarbon contents may coexist in the block B. Also, n is an integer of 1 or more, preferably 1-5. M is an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator, block S and block B in the copolymer. Each When present, their structures such as molecular weight and composition may be the same or different, and the structures of the polymer chains bonded to X may be the same or different.) In the present invention, Any mixture having a structure represented by the general formula may be used.

  Examples of other hydrocarbon polymers include polystyrene, polyethylene, polypropylene, EPM, EPDM, and polybutene. Further, these polymers may be copolymers with other monomers copolymerizable with the main monomer. For example, in the case of polystyrene, other monomers copolymerizable with styrene, specifically, p-methylstyrene, α-methylstyrene, diphenylethylene, divinylbenzene, diisopropenylbenzene, and those having 1 to 10 carbon atoms. Examples include alcohol and methacrylic acid or an ester of acrylic acid, and acrylonitrile.

As described above, polymers having various structures can be used, but it is preferable to have an optimal polymer structure in the field necessary for deriving optimal performance by a functional group.
The high molecular weight hydrocarbon polymer (A) having an alkali metal-carbon bond or alkaline earth metal-carbon bond of the present invention is a polymer having a weight average molecular weight of 10,000 or more. When the molecular weight is high, various performances are easily developed. On the other hand, if the molecular weight is too high, it becomes difficult to knead and the performance may be difficult to be exhibited. Generally, those having a high molecular weight that are difficult to knead alone can be added with a plasticizing substance such as oil to lower the viscosity. The weight average molecular weight is preferably 2 million or less because of kneadability. The preferred molecular weight is 30,000 to 1,500,000, more preferably 50,000 to 1,200,000. The molecular weight is expressed as a weight average molecular weight in terms of standard polystyrene measured by GPC.

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

  In the present invention, the low molecular compound (B) is a low molecular compound having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, an alkali metal-carbon bond or an alkaline earth metal-carbon bond, and an amino group At least one low molecular compound having a molecular weight of 2000 or less selected from low molecular compounds to be used is used.

  The low molecular compound having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond is selected from a low molecular weight secondary amine, an alkali metal, an alkaline earth metal, an organic alkali metal compound, and an organic alkaline earth metal compound. Those obtained by reacting metals are preferred. Specific examples include dimethylaminolithium, dihexylaminolithium, diisopropylaminolithium, hexamethyleneiminolithium and the like. Furthermore, bisdiisopropylaminomagnesium and a mixture thereof are preferably used. 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, it is a reaction product of N, N′-dimethylimidazolidinone and n-butyllithium.

  Examples of the low molecular weight compound having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and containing an amino group include 3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3-morpholino-1-propyllithium, 3-imidazol-1-propyllithium, bis-3- (N, N-dimethylamino) -1-propylmagnesium, bis- 3-morpholino-1-propylmagnesium, bis-3-imidazole-1-propylmagnesium, and the like, and low molecular compounds having an alkali metal-nitrogen bond or an alkaline earth metal-nitrogen bond, or an alkali metal-carbon bond or Alkaline earth metal-Low molecular weight compounds with carbon bonds and amino groups. , Amino group-containing hydrocarbon lithium, such as low-molecular oligomers obtained by polymerizing styrene, but also, and n- butyl lithium p- (-2 N, N- dimethylaminoethyl), etc. The reaction product of styrene.

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

  In the present invention, the molecular weight of the low molecular compound (B) is 2,000 or less. Preferably it is 1,000 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, a multifunctional modifier having a molecular weight of 2,000 or less is used as the low molecular compound (C). The polyfunctional modifier is preferably an epoxy group, a carbonyl group, a carboxylic acid ester group, a carboxylic acid amide group, an acid anhydride group, a phosphoric acid ester group, a phosphite ester, an epithio group, a thiocarbonyl group, or a thiocarboxylic acid. One or more selected from acid ester groups, dithiocarboxylic acid ester groups, thiocarboxylic acid amide groups, imino groups, ethyleneimine groups, halogen groups, alkoxysilane groups, isocyanate groups, thioisocyanate groups, conjugated diene groups, and arylvinyl groups A compound having a functional group of

  In the calculation of the number of moles of functional groups, one per epoxy group, carbonyl group, epithio group, thiocarbonyl group, imino group, ethyleneimine group, halogen group, conjugated diene group, arylvinyl group, alkoxysilane group. The alkoxy group is monofunctional, the carboxylic acid ester group, the carboxylic acid amide group, the acid anhydride group, the thiocarboxylic acid ester group, the dithiocarboxylic acid ester group, the thiocarboxylic acid amide group, the isocyanate group, and the thioisocyanate group are difunctional. Acid ester groups and phosphite groups should be calculated as trifunctional. As the polyfunctional modifier (C) used in the present invention, the sum of the functional numbers of the above functional groups in one molecule is 2 or more. A polyfunctional modifier having a sum of functional numbers of 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, polyepoxy compounds such as polyepoxidized liquid polybutadiene, epoxy group-containing tertiary amines such as 4,4′-diglycidyl-diphenylmethylamine, 4,4′-diglycidyl-dibenzylmethylamine , Diglycidylaniline, diglycidyl orthotoluidine, tetraglycidyl metaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane Sun, diglycidylamino compounds such as tetraglycidyl-1,3-bisaminomethylcyclohexane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, Examples thereof include compounds having an epoxy group and other functional groups such as epoxy-modified silicone, epoxidized soybean oil, and epoxidized linseed oil.

  Further, for example, alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and alkyltriphenoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine N- (1,3-dimethylbutylidene) -3- (tributoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N Examples thereof include compounds having an imino group and an alkoxysilane group such as ethylidene-3- (triethoxysilyl) -1-propanamine and N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole.

  Further, for example, isocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, diphenylethane diisocyanate, 1,3,5-benzene triisocyanate can be mentioned.

  Further, for example, halogenated silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monomethyltrichlorosilicon, monoethyltrichlorosilicon, monobutyltrichlorosilicon, monohexyltrichlorosilicon, monomethyltribromosilicon, bistrichlorosilylethane, etc. Examples thereof include alkoxyhalogenated silane compounds such as silane compounds, monochlorotrimethoxysilane, monobromotrimethoxysilane, dichlorodimethoxysilane, dibromodimethoxysilane, trichloromethoxysilane, and tribromomethoxysilane.

Furthermore, for example, tin halide compounds such as tin tetrachloride, tin tetrabromide, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monophenyltrichlorotin, bistrichlorostannylethane, trichlorophosphine, tribromo Examples include polyhalogenated phosphorus compounds such as phosphine, phosphite compounds such as trisnonylphenyl phosphite, trimethyl phosphite, and triethyl phosphite, and phosphate ester compounds such as trimethyl phosphite and triethyl phosphite. . Also, for example, carboxylic acid ester compounds such as dimethyl adipate, diethyl adipate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, acids such as pyromellitic anhydride and styrene-maleic anhydride copolymer Anhydride group-containing compounds, amide group-containing compounds such as adipic acid bisdimethylamide, polymethacrylic acid dimethylamide, carbonyl group-containing compounds such as 4,4′-diacetylbenzophenone and 3-acetylpropoxytrimethoxysilane, divinylbenzene, di Aryl vinyl group-containing compounds such as isopropenylbenzene and divinylbenzene oligomer, and halogenated hydrocarbon groups such as trichloropropane, tribromopropane, tetrachlorobutane and 3-chloropropoxytrimethoxysilane Containing compounds. These may be used alone or in combination.

  A preferred polyfunctional modifier (C) is a polyepoxy compound. Particularly preferred is a polyfunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in the molecule. More preferably, it is a compound having 2 or 3 diglycidylamino groups in one molecule. For example, tetraglycidyl metaxylenediamine, 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 2,000 or less. Preferably it is 1,000 or less. If the molecular weight is too large, the effect of the present invention cannot be obtained.
In the present invention, as the inert solvent, the polymer (A) does not inhibit the reaction of the high molecular weight hydrocarbon polymer (A), the low molecular compound (B), and the polyfunctional modifier (C). Is preferable, and a hydrocarbon solvent is preferable. When the polymer (A) is obtained by polymerizing with an alkali metal initiator and / or an alkaline earth metal initiator and growing by an anionic polymerization reaction, a solvent for the polymerization is preferably used. Suitably, one or a mixture of n-butane, n-pentane, n-hexane, n-heptane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene and the like is preferable. Further, unsaturated hydrocarbons having low reactivity with organometallic compounds such as 1-butene, cis-2-butene, and 2-hexene may be mixed therein. The amount of the inert solvent used is usually such an amount that the high molecular weight hydrocarbon polymer (A) has a concentration of 1% by weight to 50% by weight.

  In the polymerization reaction of the high molecular weight hydrocarbon polymer (A), when an alkali metal initiator or an alkaline earth metal initiator is used, the polymerization reaction is activated and the coupling mode of the monomer units is changed or co-polymerized. In the polymerization, a polar compound may be added in order to change the reactivity ratio of the monomers. Further, in the reaction of the high molecular weight hydrocarbon polymer (A), the low molecular compound (B) and the polyfunctional modifier (C), a polar compound may be added in the same manner. Polar compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl) propane, tetra Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine, alkali metal alkoxide compounds such as potassium tert-amylate, potassium tertbutylate, triphenylphosphine, etc. A phosphine compound such as is used. These polar compounds can be used alone or in combination of two or more. The amount of the polar compound used is selected according to the purpose and the degree of effect. Usually, it is 0.01-100 mol normally with respect to 1 mol of initiators.

The weight average molecular weight of the modified hydrocarbon polymer of the present invention is 10,000 or more. Preferably it is 2 million or less, More preferably, it is 30,000-1 million.
In the present invention, as a modifying group having a specific structure to be introduced into the polymer, (N) is the number of moles of nitrogen atom of the modifying group, (c) is the number of moles of functional group of the polyfunctional modifier, and (N) / (C) is a modifying group exceeding 1/2. In that case, a polymer excellent in affinity with the inorganic filler, which is a feature of the present invention, can be obtained.

In the present invention, the structure of the hydrocarbon-based polymer having a modifying group is 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 polyfunctional modifier, R, R ¹ , R ² : hydrocarbon group).

When a polyepoxy compound is used as the polyfunctional modifier (C) for the modifying group, the structure of the resulting hydrocarbon-based polymer having the modifying group is represented by the general formula: P—CR ⁵ R ⁶ —C (OH) R ^4. represented by (in this case ^{-R 3 -C (OH) R 7} -R-NR 1 R 2, P: hydrocarbon ^{polymers, R, R 1, R 2} , R 3: a hydrocarbon radical or O, A hydrocarbon group having a substituent selected from S and N, R ⁴ , R ⁵ , R ⁶ and R ⁷ : selected from hydrogen, a hydrocarbon group or a hydrocarbon group having a substituent selected from O, S and N Compound group).

Particularly preferably, as the low molecular compound (B), organic amino lithium is used, and as the polyfunctional modifier (C), a polyfunctional modifier having two or more diglycidylamino groups as functional groups in the molecule is used. In particular, the excellent effects of the present invention can be obtained. In that case, a functional group of> N—CH ₂ —CH (OH) —N <is generated in the modifying group. In addition, a glycidylamino group also exists, and a plurality of polymers (A) are bonded through a modifying group containing these functional groups, and some of them are bonded with 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 polyfunctional modifier (C), the metal-carbon bond a mole of (A), (B) The total b mole of metal-nitrogen bond and metal-carbon bond, and the functional group c mole of the polyfunctional modifier of (C), (a + b) / c is preferably 0.05 to 1.5, and a: b is It is preferable to make it react on the conditions which are 1: 0.05-20. Within this range, the excellent effect of the present invention is 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. In these ranges, the effect is further exhibited. Further, a: b is more preferably 1: 0.5 to 8, and most preferably 1: 1 to 4, and further effects are exhibited in these ranges. When (a + b) / c exceeds 1.5, unreacted (A) and (B) increase. In addition, the calculation of the functional group c mol of the polyfunctional modifier (C) is obtained by multiplying the use molar amount of the polyfunctional modifier (C) by the number of functions per molecule as the functional group c mol. It shall be used.

  In the present invention, a: c is preferably 1: 1.2 to 10, and more preferably a: c is 1: 1.8 to 6. Within that range, the excellent effect of the present invention is further exhibited.

  As the high molecular weight hydrocarbon polymer (A) used in the present invention, a molecule exceeding 60% by weight of the whole polymer molecule has an alkali metal-carbon bond or an alkaline earth metal-carbon bond. Is preferred. In that case, an excellent modified polymer containing the functional group component of the present invention in a molecule exceeding 60% by weight of the obtained polymer molecule can be obtained. More preferably, a polymer having a metal bond in 70% by weight or more of the high molecular weight hydrocarbon polymer (A) is contained in 70% by weight or more of the molecule from which a functional group component can be obtained. As a method for quantifying a 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 a chromatography method, a GPC column using a polar substance such as silica that adsorbs a functional group component as a filler is used, and a method of quantifying the internal standard of the non-adsorbed component by comparison is suitable.

  In the present invention, a solution of a high molecular weight hydrocarbon polymer (A) in an inert solvent, a low molecular compound (B) and a polyfunctional modifier (C) may be added and reacted at the same time. You may let them. Preferably, the low molecular weight compound (B) or its inert solvent solution is added to a solution of the high molecular weight hydrocarbon polymer (A) in an inert solvent, and the mixture is stirred uniformly to obtain a polyfunctional modification. It is preferable that the solution of the agent (C) or an inert solvent thereof is reacted with stirring at a predetermined ratio instantaneously. The reaction is carried out batchwise or continuously.

  When the polymer (A) is a hydrocarbon polymer having a double bond in the molecule, the obtained hydrocarbon polymer having a functional group is further hydrogenated in an inert solvent. , All or part of the double bonds can be converted to saturated hydrocarbons. Specifically, when the polymer (A) is a polymer comprising at least one monomer component selected from a conjugated diene compound and an aromatic vinyl compound, all or part of the double bond is saturated carbonized. Can be converted to hydrogen. In that case, heat resistance and weather resistance can be improved, and deterioration of the product when processed at high temperature can be prevented, and the resulting product exhibits excellent performance in applications that require weather resistance such as automotive applications.

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

  As a hydrogenation method, a known method can be used. Particularly preferred is a method in which hydrogenation is performed by blowing gaseous hydrogen into a polymer solution in the presence of a catalyst. Examples of the catalyst include a heterogeneous catalyst, a catalyst in which a noble metal is supported on a porous inorganic substance, a catalyst in which a salt such as nickel or cobalt is solubilized and reacted with organoaluminum, or a catalyst using a metallocene such as titanocene. Used. Of these, a titanocene catalyst capable of selecting mild hydrogenation conditions is particularly preferable. Also, hydrogenation of aromatic groups is possible by using a noble metal supported catalyst.

  Specific examples of the hydrogenation catalyst include (1) a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) Ni, A so-called Ziegler type hydrogenation catalyst using a transition metal salt such as an organic acid salt such as Co, Fe or Cr or an acetylacetone salt and a reducing agent such as organic aluminum, (3) an organic metal such as Ti, Ru, Rh or Zr A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as a compound is used. For example, as a hydrogenation catalyst, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2- The hydrogenation catalyst described in Japanese Patent Application Laid-Open No. 9041 and Japanese Patent Application Laid-Open No. 8-109219 can be used. A preferred hydrogenation catalyst is a mixture with a titanocene compound and / or a reducing organometallic compound.

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

  In the present invention, if necessary, metals contained in the polymer can be deashed. Usually, the deashing method is performed by bringing water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide or the like into contact with the polymer solution to extract metals, and then separating the aqueous layer.

  In the present invention, an antioxidant can be added to an inert solvent solution of a polymer having a modifying group. Antioxidants include phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers and the like.

  The method for obtaining the polymer from the polymer solution can be carried out by a known method. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain a polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. A method, a method of directly devolatilizing with a drum dryer or the like can be adopted.

  The polymer having a specific modifying group of the present invention is excellent in affinity with an inorganic filler, and exhibits its effect when the inorganic filler is dispersed. It is also effective in bonding with inorganic compounds.

  Inorganic fillers include natural silica, synthetic silica produced by wet or dry methods, kaolin, mica, talc, clay, montmorillonite, zeolite, natural silicate, glass powder, glass fiber, calcium silicate, aluminum silicate Silicates such as alumina, titanium oxide, magnesium oxide, zinc oxide, etc., metal hydroxides such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, light calcium carbonate, heavy calcium carbonate, various Surface treatment 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 and the like.

As a method of producing a composition of a polymer having a specific modifying group and an inorganic filler according to the present invention, a master batch in which an inorganic filler is previously mixed with the polymer having a specific modifying group of the present invention is used. Is possible. As a method for producing the master batch, a method of mixing in a solution or a method of kneading with a mixer is possible.
In the present invention, when a polymer selected from the group consisting of a silica-based inorganic filler, a metal oxide and a metal hydroxide is dispersed in the polymer having the modifying group of the present invention, a more excellent effect is obtained. .

  Preferably, 1 to 200 parts of a filler selected from the group consisting of a silica-based inorganic filler, a metal oxide and a metal hydroxide is added to 100 parts by weight of the hydrocarbon-based polymer having a modifying group obtained by the method of the present invention. It is a dispersed composition.

  Particularly preferred is a case where synthetic silica having a primary particle diameter of 50 nm or less is used as the silica-based inorganic filler. In that case, the filler is quickly and uniformly dispersed in a reproducible manner by kneading in a short time, and the physical properties obtained are extremely favorable.

  As a more preferable method, when the synthetic silicic acid having a primary particle diameter of 50 nm or less is dispersed in 100 parts by weight of the hydrocarbon-based polymer having a modifying group obtained by the method of the present invention, the temperature is 120 ° C. or more and 250 ° C. or less. This is a method of kneading at a temperature.

In the present invention, the case of a conjugated diene rubber as one of preferred embodiments will be described in more detail.
A conjugated diene or a combination of conjugated diene and styrene is used as a monomer, and a living conjugated diene homopolymer or a conjugated diene and styrene living random copolymer is obtained in an inert solvent using an organic monolithium compound as an initiator. This is referred to as polymer (A). The polymer (A) has a glass transition temperature in the range of −100 ° C. to −20 ° C., and the ratio of 1,4-bond to 1,2 or 3,4 bond in the conjugated diene part is from 10% to 90%. 90% to 10%. The chain distribution of styrene in the copolymer is a completely random structure. That is, the isolated styrene (one unit of styrene) is 50% by weight or more of the total bonded styrene, and the chain styrene (a series of 8 or more styrene) is 5% by weight or less of the total bonded styrene, preferably Is 2.5% by weight or less. The lithium amide compound is preferably added as (B) to the living polymer (A) solution, and the mixture is stirred and mixed uniformly. Furthermore, a predetermined amount of trifunctional or higher, preferably 4-6 functional polyepoxy compound is added as (C), and the mixture is stirred and reacted. The obtained polymer becomes 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 application and purpose. Usually, the raw rubber for vulcanized rubber is controlled to Mooney viscosity (100 ° C. 1 + 4 minutes) 20 to 100. When the Mooney viscosity is high, the oil is usually extended with an extender oil within this range. As the extending oil, aroma oil, naphthenic oil, paraffin oil, and extending oils such as TDAE and MES shown in Kautschuk Gummi Kunstoffe 52 (12) 799 (1999) are preferably used. An oil having a cyclic aroma component of 3% by weight or less. The amount of the extender oil used is arbitrary, but is usually 10 to 50 parts by weight with respect to 100 parts by weight of the polymer. Generally 20 to 37.5 parts by weight are used.

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

  Carbon black can also be used as a reinforcing agent. Carbon black is not particularly limited, and for example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among these, furnace black is particularly preferable.

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

  As an effect of the present invention, the dispersibility of the inorganic filler is good and the performance of the vulcanized rubber is excellent stably. Specifically, when the inorganic filler, particularly silica, is uniformly dispersed to obtain a vulcanized rubber, a rubber having little storage elastic modulus strain dependency can be obtained. For tire tread applications, the balance between rolling resistance and wet skid resistance is improved and wear resistance is improved, and strength is improved and modulus reduction rate at high temperatures is improved. The composition is suitable for rubber, anti-vibration rubber, footwear and the like.

  In the present invention, the polymer of the present invention is used alone or in admixture with other rubber as required. When used in combination with other rubber, if the proportion of the polymer of the present invention is too small, the effect of the modification of the present invention is not sufficiently exhibited, which is not preferable. Other rubbers include, for example, natural rubber, polyisoprene rubber, emulsion polymerization styrene-butadiene copolymer rubber, solution polymerization random SBR (bonded styrene 5 to 50% by weight, butadiene bond unit portion 1,2-vinyl bond amount 10) ˜80%), high trans SBR (1,4-trans bond content of butadiene bond unit portion 70 to 95%), low cis polybutadiene rubber, high cis polybutadiene rubber, high trans polybutadiene rubber (1,4 of butadiene bond unit portion) -Trans bond amount 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 Polymer rubber, an acrylonitrile - butadiene copolymer rubber, high vinyl SBR- low vinyl SBR block copolymer rubber, and polystyrene - polybutadiene - block copolymer and the like, such as polystyrene block copolymer. These can be appropriately selected according to required characteristics.

  When the polymer of the present invention and other rubber are used as the rubber component, the ratio of each component is usually 10 to 95:90 to 5, preferably 20 to 90:80 to 10, more preferably 30 in weight ratio. It is the range of -80: 70-20. As the other rubber, any rubber other than the present invention can be used, but preferably a high-cis polybutadiene rubber, solution polymerization SBR, solution polymerization SIBR, emulsion polymerization SBR, natural rubber, polyisoprene rubber, VCR, IIR, halogenated IIR, etc.

As the rubber compounding agent, for example, silane coupling agents, reinforcing agents, vulcanizing agents, vulcanization accelerators, vulcanization aids, oils, and the like can be further used.
As the silane coupling agent, a compound having an alkoxysilane in the molecule and further having a polysulfide bond is preferably used. For example, bis- (3-triethoxysilyl-propyl) tetrasulfide (TESPT), bis- (3-triethoxysilyl-propyl) disulfide and the like are used.

  The vulcanizing agent is not particularly limited. For example, 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. And organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide. Among these, sulfur is preferable, and powder sulfur is particularly preferable.

The blending ratio of the vulcanizing agent is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component. .

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

The vulcanization aid is not particularly limited, and for example, stearic acid or zinc oxide can be used.
As the oil, for example, aroma oil, naphthene oil, paraffin oil, silicone oil or the like is selected according to the application. The amount of extender oil used is usually in the range of 1 to 150 parts by weight, preferably 2 to 100 parts by weight, and 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 dispersing effect of the reinforcing agent,
Tensile strength, wear resistance, heat resistance, etc. are balanced to high values.

  In addition to the above components, the composition using the rubber of the present invention includes fillers such as calcium carbonate and talc, amine-based and phenol-based anti-aging agents, ozone degradation inhibitors, and silane coupling agents according to conventional methods. In addition, an activator such as diethylene glycol, a processing aid, a tackifier, and other compounding agents such as wax can be contained in necessary amounts.

The composition using the rubber of the present invention is produced by mixing each of the above components using a known rubber kneading machine such as a roll or a Banbury mixer.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

Preparation of Copolymer (Sample A to Sample J) Using an autoclave with an internal volume of 10 liters and a temperature control with a stirrer and jacket, 625 g of butadiene, 225 g of styrene, 5500 g of cyclohexane from which impurities were removed Then, 1.10 g of 2,2-bis (2-oxolanyl) propane as a polar substance was put into the reactor, and the temperature inside 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 start of the reaction, the temperature in the reactor began to rise due to the exotherm caused by the polymerization. Over 8 to 13 minutes after addition of the polymerization initiator, 50 g of butadiene was supplied at a rate of 10 g / min. The final reactor temperature reached 77 ° C. After completion of the polymerization reaction, 9.14 mmol of diisopropyl lithium amide was added. After mixing for 1 minute, 9.14 mmolg of tetraglycidyl-1,3-bisaminomethylcyclohexane, which is a tetrafunctional polyepoxy compound, was added to the reactor, and the modification reaction was carried out by stirring at 75 ° C. for 5 minutes. After adding 1.8 g of an antioxidant (BHT) to the polymer solution, the solvent was removed to obtain a styrene-butadiene copolymer (sample A) having a modifying component.

  As a result of analyzing Sample A, the amount of bound styrene was 25% by weight, the amount of bound butadiene was 75%, and the Mooney viscosity of the polymer was 70. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer is 61%, and the polystyrene-equivalent molecular weight by GPC measurement is the weight 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. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 84%.

  Furthermore, the polymerization was carried out in the same manner as that for obtaining Sample A, the amount of n-butyllithium, the amount of polar substance, the alkali metal-nitrogen bond compound added at the end of the polymerization, the type of polyfunctional modifier, and Various styrene-butadiene copolymers having different amounts used for the reaction were obtained. Among the various copolymers, (Sample J) is an alkali metal-nitrogen bond compound, an equimolar reaction product of hexamethyleneimine and n-butyllithium, and (Sample I) is DMI (dimethylimidazolidinone) and n. -After equimolar reaction with butyllithium was reacted, it was quickly added into the polymerization vessel, and then a polyfunctional modifier was added to prepare a sample. The preparation results are shown in Table 1.

Among the samples in Table 1, the copolymers of the present invention are the samples (A), (C), (D), (E), (F), (G), (I), and (J). B) and (H) are copolymers outside the present invention in which a compound having an alkali (or alkaline earth metal) -nitrogen bond was not used.

Preparation of Copolymer (Sample K to Sample T) Internal volume of 10 liters, with an inlet at the bottom, an outlet at the top, an autoclave with a stirrer and a temperature adjusting jacket, connected in series as two reactors, or A static mixer was installed between the two reactors. The butadiene from which impurities were previously removed was mixed at 13.0 g / min, styrene at 7 g / min, and n-hexane at 97.6 g / min, and this mixed solution was passed through a dehydration column filled with activated alumina, and further impurities In order to remove water, the n-butyllithium was mixed with a static mixer at a rate of 0.003 g / min (0.0469 mmol) immediately before entering the first reactor, and then at the bottom of the first reactor. Further, 2,2bis (2-oxolanyl) propane as a polar substance was supplied at a rate of 0.015 g / min, and n-butyllithium as a polymerization initiator was 0.009 g / min (0.141 mmol). Was supplied to the bottom of the first reactor at a rate of 5 ° C., and the temperature in the reactor was maintained at 85 ° C. The polymer solution was continuously withdrawn from the top of the first group and supplied to the second reactor. Sampling from the outlet of the first reactor in a stable state of the first reactor, adding enough ethanol to deactivate the active sites, adding stabilizers and removing the solvent, Mooney viscosity Was measured. The resulting copolymer before modification had a Mooney viscosity of 85. However, the polymerization rate at the first outlet reached about 100%. Keep the temperature of the second reactor at 80 ° C., and add tetraglycidyl-1,3-bisaminomethylcyclohexane, which is a tetrafunctional polyepoxy compound, from the bottom of the second reactor at a rate of 0.071 mmol / min. The denaturation reaction was carried out. Antioxidant (BHT) was continuously added to this modified polymer solution at 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 copolymer after modification was 165. Furthermore, 37.5 parts by weight of aromatic oil (X-140 manufactured by Japan Energy Co., Ltd.) per 100 parts by weight of the polymer was added to the copolymer solution to obtain an oil-extended copolymer (sample L). The Mooney viscosity of the obtained oil-extended copolymer was 73. As a result of analyzing the sample (L), the amount of bound styrene of this copolymer was 35%, and the amount of bound butadiene was 65%. The 1,2-bond content of the butadiene moiety determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 38%. The weight average molecular weight (Mw) 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%.

  Oil-extracting high molecular weight, that is, having a high Mooney viscosity in advance, facilitates the production of the obtained copolymer, or improves the processability such as mixing with a filler in subsequent processing, It is effective in improving performance by improving the dispersion of fillers, and has been widely applied in the rubber industry.

  After obtaining the sample (L), diisopropyllithium amide was added at a rate of 0.0469 mmol / min to the copolymer solution continuously flowing in the static mixer installed between the first and second units. Mix in a tech mixer. The modification reaction with tetraglycidyl-1,3-bisaminomethylcyclohexane in the second group was continued. With the reaction stabilized, an antioxidant (BHT) was continuously added to the modified polymer solution to terminate the modification reaction, and then the solvent was removed to obtain a modified copolymer. The Mooney viscosity of the copolymer after this modification was 144. Furthermore, 37.5 parts by weight of aromatic oil (X-140 manufactured by Japan Energy Co., Ltd.) per 100 parts by weight of the polymer was added to the copolymer solution to obtain an oil-extended copolymer (Sample K). The Mooney viscosity of the obtained oil-extended copolymer was 63. The amount of bound styrene and the amount of 1,2-bond in the butadiene portion were the same as in sample (L). The weight average molecular weight (Mw) 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 diisopropyllithium amide binds the low molecular weight amino group to the modifying agent and suppresses the coupling reaction, resulting in a decrease in Mooney viscosity.

  Further, the polymerization and modification reaction were carried out in the same manner as the sample (K) was obtained, and the amount of styrene, the amount of butadiene, the amount of n-butyllithium, the amount of polar substance, and the alkali metal added at the end of the polymerization Various styrene-butadiene copolymers with different amounts used for the reaction and the types of nitrogen-binding compound and polyfunctional modifier were obtained. Among the various copolymers, (Sample Q) is an alkali metal-nitrogen bond compound, an equimolar reaction product of hexamethyleneimine and n-butyllithium, and (Sample T) is DMI (dimethylimidazolidinone) and n. -After reacting the equimolar reaction product with butyllithium, it was quickly added to a static mixer, and then a polyfunctional modifier was added to prepare a sample. The preparation results are shown in Table 2.

Among the samples in Table 2, the copolymers of the present invention are the samples (K), (M), (N), (O), (P), (Q), (R), and (T). L) and (S) are outside the scope of the present invention.

Preparation of copolymer (U to Z) 1) 4.5 kg of cyclohexane and 0.25 kg and 1.3 kg of styrene treated with activated alumina after the inside of an autoclave equipped with a temperature adjusting jacket and a stirrer with an internal volume of 10 L was sufficiently replaced with nitrogen. -0.75 kg of butadiene was charged. While stirring, the temperature was raised to 52 ° C., and 11.875 mmol of n-butyllithium (20% cyclohexane solution, hereinafter the same) was added to initiate polymerization. The polymerization temperature reached 91 ° C., and after 2 minutes, a cyclohexane solution containing 11.875 mmol of tetraglycidyl-1.3-bisaminomethylcyclohexane was added to carry out a denaturation reaction for 10 minutes. The polymerization conversion rate when the modifier was added was about 100%. To the modified rubber polymerization solution thus obtained, 10 ml of methanol as an active lithium decomposing agent was added and mixed, then 2 g of BHT was added and mixed as a stabilizer, and the solvent was removed to obtain a solid modified rubber (sample U). It was.

  During the polymerization, several monomer conversion rate measurement samples were sampled from the autoclave and analyzed for conversion rate, bound styrene content, and styrene block content. When the conversion rate was about 80%, the copolymer produced was bound styrene 9 It was confirmed to be a random copolymer of 0.5 wt% and styrene block 0.0 wt%.

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

  In GPC measurement, the molecular weight of the copolymer before modification was 19.11,000, the molecular weight of one molecule-modified styrene block in the styrene block analysis sample was 22100, and the modification rate of the copolymer was 74%.

The coupling rate, which is the sum of the two-molecule coupling modification, the three-molecule coupling modification, and the four-molecule coupling modification, was 61%, and the single-molecule modification of the copolymer was 13%.
The modified rubber had a Mooney viscosity (ML1 + 4, 100 ° C.) of 72.

  In addition, in the GPC of styrene block, there is a total of 56% of 2 times molecular weight styrene block and 3 times molecular weight styrene block in addition to 1 molecule modified styrene block, and the end of styrene block is surely modified with tetraglycidyl-1.3-bisamino. It was confirmed that it was bonded to methylcyclohexane.

  Polymerization was carried out in the same manner as in (Sample U), and after confirming that the polymerization conversion reached about 100, 11.875 mmol of diisopropyllithium amide was added to the polymerization vessel. After mixing for 1 minute, 11.875 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added to the reactor, and a denaturation reaction was carried out for 10 minutes. Thereafter, the same operation as that for obtaining (Sample U) was performed to obtain (Sample V). The modification rate was 74% and the Mooney viscosity was 52. Compared with (Sample U), it was found from the GPC measurement that there were very few 4 or 3 molecule couplings.

  2) In the same preparation method as in (Sample U), except that the amount of styrene, the amount of butadiene, the amount of n-butyllithium, the amount of tetraglycidyl-1,3-bisaminomethylcyclohexane were changed, and 16 g of tetrahydrofuran was added before the start of polymerization. Obtained (Sample W) in the same manner as (Sample U). Measurement of monomer conversion during polymerization, analysis of bonded styrene and analysis of styrene block confirmed that about 70% of the first half of the polymer formed a copolymer of 30.9% bonded styrene and 0% styrene block. . Styrene block analysis after completion of the polymerization reaction confirmed that about 30% of the latter 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) was polymerized in the same manner as (Sample W). After completion of the polymerization, 8.333 mmol of diisopropyl lithium amide was added to the polymerization vessel, and 6.284 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added. It is a modified copolymer obtained by adding and allowing a modification reaction for 10 minutes. The Mooney viscosity (ML1 + 4, 100 ° C.) of the modified rubber was 62. It can be seen that the addition of diisopropyl lithium amide combined the amino group of the low molecular weight residue of the lithium amide with the modifier, resulting in a decrease in Mooney viscosity.

  3) The inside of an autoclave with a temperature adjustment jacket and a stirrer with an internal volume of 10 L was thoroughly charged with nitrogen and charged with 4.5 kg of cyclohexane treated with activated alumina and 0.90 kg of 1.3-butadiene as the first-stage monomer. The temperature was raised to 56 ° C. while stirring, and a cyclohexane solution containing 14.844 mmol of n-butyllithium was added to initiate polymerization. The polymerization temperature reached 82 ° C. to complete the polymerization of butadiene. Next, 0.10 kg of styrene as the second-stage monomer was added for polymerization. The polymerization temperature reached a maximum of 89 ° C., and after 5 minutes, 7.422 mmol of tetraglycidyl-1.3-bisaminomethylcyclohexane was added and a modification reaction was performed for 8 minutes. The polymerization conversion rate when the modifier was added was about 100%. To the modified rubber polymerization solution thus obtained, 10 ml of methanol as an active lithium decomposing agent was added and mixed, then 2 g of BHT as a stabilizer was added and mixed, and the solvent was removed to obtain (Sample Y).

  The analytical values of this modified rubber were 10.0% by weight of bound styrene, 9.9% by weight of styrene block, and 13.3% of vinyl bond. In 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 coupling rate, which is the sum of the bimolecular coupling modification, the trimolecular coupling modification, and the tetramolecular coupling modification, was 79%, and the monomolecular modification of the copolymer was 7%. The modified rubber had a Mooney viscosity (ML1 + 4, 100 ° C.) of 60.

  (Sample Z) was polymerized in the same manner as (Sample Y), and after completion of polymerization, 7.422 mmol of diisopropyl lithium amide was added to the polymerization vessel, and then 7.422 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane was added. It is a modified copolymer obtained by adding and allowing a modification reaction for 10 minutes. The Mooney viscosity (ML1 + 4, 100 ° C.) of the modified rubber was 54. It can be seen that the addition of diisopropyl lithium amide combined the amino group of the low molecular weight residue of the lithium amide with the modifier, resulting in a decrease in Mooney viscosity.

Of the samples in Table 3, the copolymers of the present invention are the samples (V), (X), (Z), and the samples (U), (W), (Y) are outside the present invention.

The sample was analyzed by the following method.
(1) Amount of bound styrene A sample was used as a chloroform solution, and the amount of bound styrene (wt%) was measured by absorption at UV254 nm by the phenyl group of styrene.
(2) Amount of styrene block (3) Microstructure of butadiene portion determined by osmium oxide decomposition method A sample is a carbon disulfide solution, and an infrared spectrum is measured in a range of 600 to 1000 cm −1 using a solution cell. From the absorbance, the microstructure of the butadiene portion was determined according to the formula of the Hampton method.
(4) Mooney viscosity JIS K 6300 measured the viscosity after 4 minutes at 100 ° C. and 1 minute of preheating.
(5) Molecular weight and molecular weight distribution The chromatogram was measured using GPC used by connecting three columns with a polystyrene gel as a filler, and the molecular weight and molecular weight distribution were calculated with a calibration curve using standard polystyrene. Tetrahydrofuran was used as the solvent.
(6) Modification rate Applying the property that the modified component is adsorbed to a GPC column with a silica gel as a filler, the above-mentioned polystyrene gel (Showa Denko) Both chromatograms of GPC (manufactured by Shodex) and silica-based column GPC (Zorbax manufactured by DuPont) were measured, and the amount of adsorption to the silica column was measured from the difference between them to determine the modification rate.

Preparation of Copolymers A1, A2, and A3 An internal volume of 10 liters, an inlet at the bottom, an outlet at the top, and an autoclave having a stirrer and a temperature adjusting jacket were connected in series as two reactors. A static mixer was installed in the middle of the reactor. The butadiene from which impurities were previously removed was mixed at 16.4 g / min, styrene at 3.6 g / min, and n-hexane at 97.6 g / min, and this mixed solution was passed through a dehydration column packed with activated alumina. In order to further remove impurities, the n-butyllithium was mixed with a static mixer at a rate of 0.003 g / min (0.0469 mmol) immediately before entering the first reactor, and then the first reactor was mixed. Continuously fed to the bottom, 2,2bis (2-oxolanyl) propane as a polar substance was added at a rate of 0.017 g / min, and n-butyllithium as a polymerization initiator was 0.035 g / min (0. 547 mmol) was fed to the bottom of the first reactor, and the reactor internal temperature was maintained at 85 ° C. The polymer solution was continuously withdrawn from the top of the first group and supplied to the second reactor. However, the polymerization rate at the first outlet reached about 100%. Keeping the temperature of the second reactor at 80 ° C., add tetraglycidyl-1,3-bisaminomethylcyclohexane, which is a tetrafunctional polyepoxy compound, from the bottom of the second reactor at a rate of 0.273 mmol / min. The denaturation reaction was carried out. Antioxidant (BHT) was continuously added to this modified polymer solution at 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 analysis, this copolymer had a bound styrene content of 18% and a bound butadiene of 82%. The 1,2-bond amount of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 31%. The weight average molecular weight (Mw) 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%. Without adding an antioxidant to this modified copolymer, 7.5 liters of the modified copolymer solution was received in a hydrogenation reactor (10 liters), and the hydrogenation catalyst described below per 100 parts by weight of the modified copolymer, 100 ppm of Ti was added, a hydrogenation reaction was carried out under conditions of a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C., and then 10 times moles of methanol of n-butyllithium used for the polymerization was added, and an antioxidant (BHT) was added. 2 g) was added in an n-hexane solution, and then the solvent was removed to obtain a hydrogenated modified copolymer (A1). The hydrogenation rate of the butadiene portion was 85%.
In the same manner as (Sample A1), except that n-butyllithium as a polymerization initiator was supplied at a rate of 0.469 mmol / min and 2,2bis (2-oxolanyl) propane as a polar substance was supplied at a rate of 0.015 g / min. After obtaining the polymer, diisopropyl lithium amide was added at a rate of 0.469 mmol / min to the copolymer solution continuously flowing in the static mixer installed between the first and second groups. Mixed in. The modification reaction with tetraglycidyl-1,3-bisaminomethylcyclohexane in the second group was carried out at a rate of 0.469 mmol / min. With the reaction stabilized, an antioxidant (BHT) was continuously added to the modified polymer solution to terminate the modification reaction, and then the solvent was removed to obtain a modified copolymer. The amount of bound styrene in this modified copolymer and the amount of 1,2-bond in the butadiene portion were the same as in 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 by the same method as that for obtaining the sample (A1), and the solvent was removed to obtain a hydrogenated modified copolymer (A2) having a hydrogenation rate of 83%.

  (Sample A3) is polymerized by changing the amount of n-butyllithium and polar substance used for the polymerization, does not carry out the modification reaction, and is hydrogenated in the same manner as obtained (Sample A1 and Sample A2), This is a hydrogenated non-modified copolymer obtained by desolvation, the weight average molecular weight (Mw) is 330,000, the molecular weight distribution (Mw / Mn) is 1.80, and the hydrogenation rate is 82. %Met. The preparation results are shown in Table 4.

The hydrogenated copolymer of the present invention is sample (A2), and samples (A1) and (A3) are outside the present invention.

The hydrogenation catalyst was prepared and the hydrogenation rate of the butadiene portion was measured by the following method.
(1) Preparation of hydrogenation catalyst 1 liter of dried and purified cyclohexane was charged into a nitrogen-substituted reaction vessel, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and 200 mmol of trimethylaluminum with sufficient stirring. N-Hexane solution was added and reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.
(2) Measurement of hydrogenation rate It measured using the nuclear magnetic resonance apparatus (Germany, the product made by BRUKER, DPX-400).

Examples 1-9 and Comparative Examples 1-3
Using the samples shown in Table 1 (Sample A to Sample J) as raw material rubber, rubber blends were obtained by the following kneading method using the blends shown in Table 5. Examples 1 to 8 and Comparative Examples 1 and 2 are samples alone, and Example 9 and Comparative Example 3 are blended with 75 parts by weight of (Sample A) and (Sample B) as rubber and 25 parts by weight of polybutadiene rubber. did.
[Kneading method]
Using a closed kneader (with an internal volume of 1.7 liters) attached with a temperature control device using circulating water from the outside, as the first stage kneading, under the conditions of a filling rate of 65% and a rotor speed of 66/77 rpm , Filler (silica and carbon black), organic silane coupling agent, aromatic oil, zinc white, and stearic acid were kneaded. At this time, the temperature of the closed mixer was controlled, and the rubber composition was obtained at a discharge temperature (compound) of 155 to 160 ° C.

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

After cooling, as a third stage kneading, sulfur and a vulcanization accelerator were kneaded with an open roll set at 70 ° C.
This was molded, vulcanized with a vulcanizing press at 160 ° C. for a predetermined time, and measured for physical properties. The physical property measurement results are shown in Table 6.

Table 5 Formulation (Formulation Formula-1)

Rubber 100.0 parts Silica (Degussa Ultrasil VN3) 45.0 parts Carbon (Tokai Carbon Seast KH) 5.0 parts Silane coupling agent (Degussa Si69) 4.5 parts Aromatic oil (Japan) Energy X149) 5.0 parts Zinc flower 3.0 parts Stearic acid 2.0 parts Anti-aging agent (N-Isofluoro-N'-phenyl-P-phenylenediamine) 1.0 part Sulfur 1.4 parts Vulcanization Accelerator (N-cyclohexyl-2-benzthiazylsulfenamide) 1.0 part Vulcanization accelerator (diphenylguanidine) 1.5 parts





Total 169.4 parts

The measuring method of each physical property was implemented with the following method.
(1) Bound rubber About 0.2 grams of the blend after the second stage kneading is cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight is measured. After soaking in toluene for 24 hours, dry, weigh, take into account undissolved components, calculate the amount of rubber bound to the filler, rubber bound to filler relative to the amount of rubber in the initial formulation The ratio was calculated.
(2) Tensile test It measured by the tension test method of JIS-K6251.
(3) Measurement of viscoelastic property Using an Ares viscoelasticity tester manufactured by Rheometrics, a measurement was performed at a frequency of 10 Hz by a torsion method.

The Payne effect (ΔG ′) is indicated by the difference between the minimum value and the maximum value at a strain of 0.1% to 10%. The smaller the Payne effect, the better the dispersibility of the filler such as silica, the higher the low temperature Tanδ, the better the wet skid (grip) performance, the lower the high temperature Tanδ, the lower the hysteresis loss, the lower the rolling resistance of the tire, That is, the fuel efficiency is excellent.
(4) Measurement of rebound resilience The rebound resilience at 50 ° C. was measured by the Lüpke-type rebound resilience test method according to 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 having different amounts of bound styrene and vinyl bonds, the composition of the present invention was at a high temperature (50 ° C.). Tan δ is lower than that of the comparative example, hysteresis loss is small, rolling resistance of the tire is reduced, and fuel efficiency can be improved. Further, the balance between the low temperature (0 ° C.) Tan δ and the high temperature (50 ° C.) Tan δ is good, and the balance between the tire wet skid resistance and the low fuel consumption is excellent.

  Further, the resilience at high temperature (50 ° C.) is high and correlates well with the decrease in Tan δ at high temperature (50 ° C.). The effect of the present invention is exhibited even when the copolymer is used alone or when other rubbers are blended as shown in Example 9 and Comparative Example 3.

Compared with the comparative example, it can be seen that the elastic modulus is low and the strain dependency is very small, and the dispersibility of silica is improved. This effect can reduce the rolling resistance of the tires described above, and can be used for applications that require dispersibility of fillers such as silica, or for all applications that require low hysteresis loss, or resistance to which dispersibility is greatly affected. It can be applied to applications that require wear. As a use, it can be widely applied not only to tires but also to shoes, anti-vibration rubber and other industrial products.

Examples 10-18 and Comparative Examples 4-6
Using the samples shown in Table 2 (Sample K to Sample T) as raw rubber, rubber compositions were obtained with the formulations shown in Table 7. Examples 10 to 17 and Comparative Examples 4 to 5 are samples alone, and Example 18 and Comparative Example 6 are blended with 75 parts by weight of (Sample M) and (Sample L) as rubber and 25 parts by weight of polybutadiene rubber. did.

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 Tables 8 and 9.

Table 7 Formulation (Formulation-2)

Rubber 100.0 parts Silica (Degussa Ultrasil VN3) 63.0 parts Carbon (Tokai Carbon Co., Ltd. Seest KH) 7.0 parts Silane coupling agent (Degussa Si69) 6.3 parts Aromatic oil (Japan) Energy X149) 37.5 parts Zinc flower 2.5 parts Stearic acid 1.0 parts Anti-aging agent (N-Isopropyl-N'-phenyl-P-phenylenediamine) 2.0 parts Sulfur 1.1 parts Vulcanization Accelerator (N-cyclohexyl-2-benzthiazylsulfenamid) 1.7 parts Vulcanization accelerator (diphenylguanidine) 2.0 parts





224.1 parts in total

The measuring method of each physical property was implemented by the completely same method as Examples 1-9.
Examples 10 to 18 and Comparative Examples 4 to 6 show the effects of the present invention with a relatively high filler blend using samples oil-extended into a high molecular weight copolymer in continuous polymerization.

  As shown in Tables 8 and 9, from the results of Examples 10 to 15 and Comparative Example 4 and Examples 16 to 17 and Comparative Example 5 having different amounts of bound styrene and vinyl bonds, the composition of the present invention was at a high temperature ( Tan δ at 50 ° C.) is lower than that of the comparative example, hysteresis loss is small, tire rolling resistance is reduced, and fuel efficiency can be improved. Further, the balance between the low temperature (0 ° C.) Tan δ and the high temperature (50 ° C.) Tan δ is good, and the balance between the tire wet skid resistance and the low fuel consumption is excellent.

  Further, the resilience at high temperature (50 ° C.) is high and correlates well with the decrease in Tan δ at high temperature (50 ° C.). The effect of the present invention is exhibited even when the copolymer is used alone or when other rubbers are blended as shown in Example 18 and Comparative Example 6.

It can be seen that the composition of the present invention has a very small strain dependency of the elastic modulus and improved silica dispersibility as compared with the comparative example. By improving the dispersibility of silica, the amount of silica can be further increased, and it can be applied to various formulations and various uses. It is suitable for various industrial products such as tires and belts.

Examples 19-21 and Comparative Examples 7-9
Using the samples shown in Table 3 (Sample U to Sample Z) as raw rubber, rubber compositions were obtained with the formulations shown in Table 10.

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 11.

Table 10 Formulation (Formulation-3)

Rubber 100.0 parts Silica (Degussa Ultrasil VN3) 40.0 parts
Silane coupling agent (Sigus, manufactured by Degussa) 2.0 parts Naphthenic oil (Shellflex 371J) 5.0 parts Zinc flower 5.0 parts Stearic acid 2.0 parts Anti-aging agent (styrenated phenol) 1.0 part Sulfur 1 .7 parts Vulcanization accelerator (dibenzene disulfide) 1.5 parts Vulcanization accelerator (diphenylguanidine) 1.5 parts





Total 159.7 parts

In addition, the measurement of a viscoelastic characteristic value and compression set was implemented with the following method.
(1) Strain dependence and temperature dependence of Tan δ Tan δ at 0 ° C, 50 ° C and 70 ° C was measured at a frequency of 10 Hz by a torsion method using an Ares viscoelasticity tester manufactured by Rheometrics, and calculated by the following formula: did.

Strain dependency is a numerical value calculated by (10% tan δ−0.1% tan δ at 50 ° C.) × 100 (%) / 0.1% tan δ.
Temperature dependence is a numerical value calculated by (3% tan δ at 0 ° C.−50 ° C. 3 tan δ) × 100 (%) / 50 ° C. 3% tan δ (2) compression set (c-set)
The measurement was performed under the conditions of 70 ° C.-22 hours in accordance with the compression set test method of JIS-K6262.
(3) Exothermic property A Goodrich flexometer was used, the number of revolutions was 1800 rpm, the stroke was 0.225 inches, the load was 55 pounds, the measurement start temperature was 50 ° C., and the difference between the temperature after 20 minutes and the start temperature was shown.
(4) Akron Wear Abrasion resistance was measured using an Akron wear tester and a wear amount of 6 pounds and 1000 revolutions was measured.

As shown in Table-11, the copolymer of the present invention has excellent performance even in a styrene-butadiene copolymer having a styrene block. When Example 19 and Comparative Example 7, Example 20 and Comparative Example 8, and Example 21 and Comparative Example 9 are compared, the composition using the copolymer of the present invention is strain dependent on elastic modulus (G ′) and Tan δ. Low temperature dependency. Further, it has excellent exothermic properties and wear resistance, and further has excellent characteristics due to improved dispersibility of silica such as a small compression set. The modified rubber composition of the present invention utilizes such characteristics and is suitable for footwear applications including anti-vibration rubber applications and transparent formulations containing silica. The modified rubber composition of the present invention having such excellent characteristics can be suitably used for other industrial products.

Example 22 and Comparative Examples 10 and 11
Using the samples shown in Table 4 (Sample A1 to Sample A3) as raw rubber, a rubber composition was obtained with the formulation 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 physical property measurement results.

Table 12 Formulation (Formulation-4)

Rubber 100.0 parts Silica (Degussa Ultrasil VN3) 50.0 parts
Silane coupling agent (Sigus, manufactured by Degussa) 4.0 parts Paraffin oil (PW-380, manufactured by Idemitsu Kosan Co., Ltd.) 20.0 parts Zinc flower 5.0 parts Stearic acid 1.0 parts
Sulfur 1.5 parts Vulcanization accelerator (tetramethylthiuram sulfite) 1.5 parts Vulcanization accelerator (2-mercaptobenzodiazole) 0.5 parts





183.5 copies in total

In this physical property evaluation, physical properties were measured by the following methods.
(1) Compression set (c-set)
The measurement was performed under conditions of 100 ° C.-70 hours in accordance with the compression set test method of JIS-K6262.
(2) Adhesiveness of vulcanized rubber A 180 degree peel test based on JIS K-6256 was performed, and the peel strength of the rubber adhered to the metal was measured. Metallok G and metalloc PH-50 (made by Toyo Chemical Research Co., Ltd.) were used as primers.

Other physical properties were measured by the same method as in Examples 1-9.
As shown in Table 13, the hydrogenated copolymer of the present invention has further improved strain dependency of elastic modulus in viscoelastic properties, excellent compression set and rebound resilience, and Adhesiveness is also good. These characteristics can be effectively used in a wide range of industrial products such as anti-vibration rubber, belts, hoses and shoes.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

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

The hydrocarbon polymer having a functional group obtained by the present invention is one in which an inorganic filler is dispersed with a uniform and fine particle size in a high molecular weight hydrocarbon polymer matrix. It is expressed.
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 a vulcanized rubber, the rolling resistance is lower than in conventional tire tread applications. Suitable for tire rubber, anti-vibration rubber, footwear, etc. with improved balance of wet skid resistance and improved wear resistance, as well as improved strength and reduced modulus at high temperatures. It becomes a composition. In addition, when the high molecular weight hydrocarbon polymer is a thermoplastic elastomer, inorganic fillers such as silica, metal oxide, and metal hydroxide are uniformly dispersed, improving the strength more than before, improving flame retardancy, Effects such as improved elongation and transparency can be obtained. When used in an asphalt composition, effects such as improved aggregate graspability can be obtained. Further, when the high molecular weight hydrocarbon polymer is a thermoplastic elastomer or a thermoplastic resin, uniform and fine dispersion can be obtained with improved compatibility in a blended composition with other polar resins.

Claims (14)

(A) a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond;
(B) at least selected from low molecular compounds having an alkali metal-nitrogen bond or alkaline earth metal-nitrogen bond, and low molecular compounds having an alkali metal-carbon bond or alkaline earth metal-carbon bond and having an amino group 1 type of low molecular weight compound having a molecular weight of 20 0 0 or less; and (C) a polyfunctional denaturant (A) moles of metal-carbon bond (a), metal (N) of nitrogen (B) and metal- As the total number of moles of carbon bonds (b) and the number of moles of functional groups (c) of the polyfunctional modifier of (C), (a + b) / c is 0. 0 5 to 1. At a rate of 5,
A modified hydrocarbon-based polymer having at least one modified group and having a weight average molecular weight of 10,000 or more, obtained by reacting, wherein the number of moles of nitrogen atoms (N) of the modified group is A modified hydrocarbon polymer in which the ratio (N / c) of the functional group mole number (c) of the functional modifier (C) exceeds 1/2.   The modified hydrocarbon polymer according to claim 1, wherein the hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond.   The modified carbonization according to claim 1 or 2, wherein the multifunctional modifier (C) is a multifunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in the molecule. Hydrogen polymer.   The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, and an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond. 2. The modified hydrocarbon polymer according to 1. The hydrocarbon polymer (A) is a conjugated diene polymer having a lithium-carbon bond at the end,
The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond,
The multifunctional modifier (C) is a multifunctional modifier having two or more diglycidylamino groups as functional groups in the molecule,
The modified hydrocarbon polymer according to claim 1, wherein N / c has a modifying group exceeding 1/2 at least at one terminal of the polymer. (A) a hydrocarbon polymer having an alkali metal-carbon bond or an alkaline earth metal-carbon bond and having a weight average molecular weight of 10,000 or more;
(B) at least selected from a low molecular compound 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 having an amino group A low molecular weight compound having a molecular weight of 2,000 or less and having a bond with one kind of metal;
(C) A method for producing a modified hydrocarbon polymer comprising a step of reacting a polyfunctional modifier having a molecular weight of 2,000 or less in an inert solvent.   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.   The modified carbonization according to claim 6 or 7, wherein the multifunctional modifier (C) is a multifunctional modifier having a glycidylamino group as a functional group and having two or more epoxy groups in the molecule. A method for producing a hydrogen-based polymer.   The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, and an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond. 6. A process for producing a modified hydrocarbon polymer according to 6. The hydrocarbon polymer (A) is a conjugated diene polymer obtained by living anionic polymerization having a lithium-carbon bond at the end,
The low molecular compound (B) is at least one selected from a low molecular compound having a lithium-nitrogen bond or a magnesium-nitrogen bond, an amino group-containing hydrocarbon compound having a lithium-carbon bond or a magnesium-carbon bond,
The method for producing a modified hydrocarbon polymer according to claim 6, wherein the multifunctional modifier (C) is a multifunctional modifier having two or more diglycidylamino groups as functional groups in the molecule. 100 parts by weight of the modified hydrocarbon polymer according to claim 1, and a filler selected from the group consisting of a silica-based inorganic filler, a metal oxide, and a metal hydroxide dispersed in the modified hydrocarbon polymer. A composition comprising 1 to 200 parts.   The composition according to claim 11, wherein the filler is a synthetic silicic acid having a primary particle size of 50 nm or less.   100 parts by weight of the modified hydrocarbon polymer according to claim 1 and synthetic silicic acid having a primary particle size of 50 nm or less are kneaded at a temperature of 120 ° C. or more and 250 ° C. or less, and the synthesis is performed on the modified hydrocarbon polymer. A method for producing a composition comprising a step of dispersing silicic acid.   A composition for vulcanized rubber, wherein 100 parts by weight of the modified hydrocarbon polymer according to claim 5 is blended with 1 to 100 parts by weight of a silica-based inorganic filler and 1 to 50 parts by weight of carbon black.

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