CN102361886A

CN102361886A - Method for producing branched conjugated diene polymer

Info

Publication number: CN102361886A
Application number: CN2010800131949A
Authority: CN
Inventors: 北川裕一; 吉田淳一
Original assignee: Asahi Kasei Chemicals Corp
Current assignee: Asahi Kasei Corp
Priority date: 2009-05-13
Filing date: 2010-05-12
Publication date: 2012-02-22
Anticipated expiration: 2030-05-12
Also published as: TWI464181B; CN102361886B; KR101281324B1; BRPI1015312A2; SG174596A1; TW201100450A; WO2010131668A1; KR20110128894A

Abstract

Disclosed is a method for producing a branched conjugated diene polymer, comprising: a polymerization step of continuously polymerizing or copolymerizing a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound in a hydrocarbon solvent using an alkali metal initiator in a polymerization vessel, thereby obtaining a living polymer or copolymer; a coupling step of performing a coupling reaction by reacting the living polymer or copolymer with a polyfunctional compound in a coupling reactor connected to the polymerization vessel via a pipe provided at an outlet of the polymerization vessel, from which the living polymer or copolymer is discharged, and also connected to a pipe which is provided for discharging a reaction product from the coupling reactor and has an opening degree adjusting unit; and a solvent removal step, wherein the living polymer or copolymer is reacted with the multifunctional compound within 5 minutes after the polymerization step, and a pressure at the outlet of the polymerization vessel is controlled to 0.5 to 2 MPaG by the opening degree adjusting unit.

Description

The method of manufacture of branched conjugated diene polymer

Technical field

The present invention relates to the method for manufacture of branched conjugated diene polymer.

Background technology

A kind of method had been proposed in the past: through using the basic metal series initiators; In hydrocarbon solvent, make the conjugated diene compound polymerization, or make conjugated diene compound and vinyl aromatic compounds copolymerization; And then carry out linked reaction with the reaction of polyfunctional low molecular compound; Thereby obtain branched polymkeric substance or branched multipolymer (for example, referring to patent documentation 1).

In addition,, there is document to disclose and carries out the polymeric method continuously, wherein, add polyfunctional low molecular compound, carry out linked reaction (for example, referring to patent documentation 2) at first reaction zone through at least two reaction zones as the method that obtains the branched multipolymer.

In addition, there is document to disclose and uses two polymeric kettles to carry out the polymeric method continuously, wherein, in second polymeric kettle, add polyfunctional low molecular compound and carry out linked reaction (for example, referring to patent documentation 3).

In addition, there is document to disclose following technology: after using two polymeric kettles to carry out successive polymerization, to use static mixer to add polyfunctional low molecular compound, carry out linked reaction (for example, referring to patent documentation 4).

The prior art document

Patent documentation

Patent documentation 1: the special public clear 49-36957 communique of Japan

Patent documentation 2: the special public clear 54-6274 communique of Japan

Patent documentation 3: japanese kokai publication sho 61-255917 communique

Patent documentation 4: No. the 2006/104215th, International Publication

Summary of the invention

The problem that invention will solve

But; Thereby in the method for after the successive polymerization of conjugated diene polymer, carrying out linked reaction manufacturing branched conjugated diene polymer continuously; Process variations slightly can make a big impact to the quality of final product, and therefore in industry, stably making the branched conjugated diene polymer becomes important problem.

Therefore; The object of the present invention is to provide a kind of method; This method can in industry, stablize and the branched conjugated diene polymer is provided effectively, be the branched random copolymer rubber of branched conjugated diolefin polymer rubber or conjugated diene compound and vinyl aromatic compounds, and can make high-quality above-mentioned polymer rubber or copolymer rubber.

Be used to solve the scheme of problem

The inventor is in order to solve above-mentioned problem; For the method for manufacture of branched conjugated diene polymer (in this method; Use the basic metal series initiators in hydrocarbon solvent, to make conjugated diene compound polymerization or make conjugated diene compound and vinyl aromatic compounds copolymerization continuously continuously; Make resulting reactive polymer or active copolymer and multi-functional compounds reaction, thereby carry out linked reaction) study, the result finds; Through the time till carrying out linked reaction behind the controlled polymerization; And the pressure of outlet that is used to take out product to carrying out above-mentioned polymeric polymeric kettle is controlled, and can realize above-mentioned purpose, thereby accomplish the present invention.

That is, the present invention is described below.

[1]

A kind of method of manufacture of branched conjugated diene polymer, this method comprises following operation:

Polymerization process in polymeric kettle, uses the basic metal series initiators to make conjugated diene compound polymerization or make conjugated diene compound and vinyl aromatic compounds copolymerization continuously continuously in hydrocarbon solvent, obtains reactive polymer or active copolymer;

The coupling operation; In coupler reactor; Make said reactive polymer or active copolymer and multi-functional compounds reaction; Carry out linked reaction, said coupler reactor connects through the pipe arrangement that the exit at the said polymeric kettle that said reactive polymer or active copolymer are discharged is provided with, and the pipe arrangement that is used to discharge that is connected with this coupler reactor is provided with the aperture regulon; With

The desolventizing operation,

Behind the said polymerization process, reacted with the interior said reactive polymer or active copolymer and multi-functional compounds of making at 5 minutes,

Through said aperture regulon with the pressure-controlling in the exit of said polymeric kettle at 0.5～2MPaG.

[2]

Like the method for manufacture of above-mentioned [1] described branched conjugated diene polymer, wherein, said coupler reactor is the tank reactor of 0.5～50% capacity that possesses rotation mixer and have the capacity of said polymeric kettle.

[3]

Like the method for manufacture of above-mentioned [1] or [2] described branched conjugated diene polymer, wherein, said polymeric kettle is the tank reactor that possesses stirrer,

In the said polymerization process, in the presence of polar compound, make conjugated diolefine and vinyl aromatic random copolymerization.

[4]

Like the method for manufacture of each described branched conjugated diene polymer of above-mentioned [1]～[3], this method also comprises following operation:

Between said polymerization process to said coupling operation, said reactive polymer or active copolymer are sampled, measure the operation of mooney viscosity;

After the said coupling operation, when the residence time from the outlet of said polymeric kettle is lower than 15 minutes, said branched conjugated diene polymer is sampled, measure the operation of mooney viscosity.

[5]

Like the method for manufacture of each described branched conjugated diene polymer of above-mentioned [1]～[4], wherein,, use a tank reactor that possesses stirrer as said polymeric kettle.

[6]

Like the method for manufacture of each described branched conjugated diene polymer of above-mentioned [1]～[5], wherein,, use intramolecularly to have the amino polyepoxides of uncle as said multi-functional compounds.

[7]

Method of manufacture like each described branched conjugated diene polymer of above-mentioned [1]～[6]; Wherein, Said multi-functional compounds is amino and constitute with oligopolymer composition more than the dimer of the low molecular compound that contains glycidyl-amino of the glycidyl of this amino bonded and this low molecular compound that contains glycidyl-amino more than 3 by having 2 above uncles in the molecule

With respect to said multi-functional compounds's total amount, said low molecular compound is 75～95 quality %, and said oligopolymer is 25～5 quality %.

[8]

Like the method for manufacture of each described branched conjugated diene polymer of above-mentioned [1]～[7], wherein, said reactive polymer or said active copolymer and said multi-functional compounds's reaction ratio is 10～80 quality %.

[9]

Method of manufacture like each described branched conjugated diene polymer of above-mentioned [1]～[8]; Wherein, The MWD that said branched conjugated diene polymer is measured through GPC (GPC) is unimodal; In the conversion molecular weight based on PS, weight-average molecular weight is 500,000～2,000,000.

[10]

Like the method for manufacture of each described branched conjugated diene polymer of above-mentioned [1]～[9], wherein, said branched conjugated diene polymer is the multipolymer of conjugated diene compound and vinyl aromatic compounds,

The vinyl aromatic compounds of strand that the ozone decomposition method is produced joint is more than 40% with respect to said vinyl aromatic compounds total amount, the vinyl aromatic compounds that 8 chain links are above be below 5% with respect to said vinyl aromatic compounds total amount.

The effect of invention

High-quality branched conjugated diene polymer can be stablized, made effectively to manufacturing method according to the invention.

That is, the change that can make the viscosity and the degree of branching energy-conservation and continuously less, the branched conjugated diene polymer of short, high conversion of the residence time and the high degree of branching, and less generation gel.

Embodiment

Below, specific embodiments of the invention (below, be called " this embodiment ") be elaborated.

Need to prove, the invention is not restricted to following record, can in the scope of its main points, carry out various distortion and implement.

[method of manufacture of branched conjugated diene polymer]

The method of manufacture of the branched conjugated diene polymer of this embodiment comprises following operation:

The desolventizing operation.

Need to prove, the method is characterized in that, behind the said polymerization process, reacted with the interior said reactive polymer or active copolymer and multi-functional compounds of making at 5 minutes,

(implementing the manufacturing installation of the method for manufacture of branched conjugated diene polymer)

At first, the manufacturing installation of the method for manufacture of the branched conjugated diene polymer of implementing this embodiment (below, also abbreviate manufacturing installation sometimes as) is described.

Manufacturing installation possesses polymeric kettle and coupler reactor.

< polymeric kettle >

As polymeric kettle, preferably have the tank reactor of stirrer, from the aspect of easy startup and end, more preferably vertical polymeric kettle.

The structure that the vertical hub that is meant tank reactor is provided with vertically.

After in the polymerization process stated, particularly in the polymerization process with conjugated diolefine and vinyl aromatic random copolymerization, owing to be the high copolymerization of randomness and preferably use tank reactor.Need to prove,, use the method for decomposing based on ozone as the evaluation method of randomness.

The formation of polymeric kettle can enumerate use one have the formation of the tank reactor of stirrer, with 2 placed in-line formations of above polymeric kettle preferably use the formation of a polymeric kettle because activity rate is high.

< coupler reactor >

The pipe arrangement that the exit of the polymeric kettle that coupler reactor is discharged through the polymkeric substance that in above-mentioned polymeric kettle, obtains is provided with connects.

Need to prove, be connected with this coupler reactor, be used for being provided with the aperture regulon from the pipe arrangement that coupler reactor is discharged.

Through adjusting this aperture regulatory function, the pressure in exit that can the controlled polymerization still.

Of the back, in the coupler reactor, in the solution of reactive polymer that obtains through the polyreaction in the above-mentioned polymeric kettle or active copolymer, mix the multi-functional compounds, carry out linked reaction.

Coupler reactor is preferably the tank reactor of 0.5～50% capacity of the capacity that possesses rotation mixer and have said polymeric kettle, further is preferably the tank reactor of 1～20% capacity of capacity with said polymeric kettle.

Can access following advantage during for tank reactor: be difficult to occur produce inaccessible problem because of the gel that generates in the polymeric kettle.

Linked reaction is stably carried out in the change that in addition, can be directed against polymkeric substance and multi-functional compounds's flow.In addition, during for the volume of above-mentioned scope, can carry out more stable linked reaction.

If the volume of coupler reactor is excessive, then the residence time elongated, the amplitude of fluctuation of the viscosity of the branched chain polymer after the coupling, the degree of branching etc. increases, and is difficult to control.Need to prove that volume is the volume of liquid phase, have under the situation of gas phase, have under the situation of stirrer and other devices, in this part is not included in.

In addition, in the coupler reactor, inside diameter D (m) is more than 0.5 with the preferred d/D of relation of the oar footpath d (m) of stirrer, and more preferably d/D is more than 0.6.

When the oar of internal diameter and stirrer directly satisfied above-mentioned relation, even then smaller capacity, the viscosity of the coupling polymer that is generated and the change of the degree of branching were also few, can stably carry out linked reaction.

In addition, the rotation speed n (s of the rotation mixer of coupler reactor ^-1) be preferably more than 0.1 with the long-pending nd of oar footpath d (m), consider economy, more preferably 0.2～5 scope.

At this moment, the viscosity of the polymkeric substance that is generated and the change of the degree of branching still less but also can reduce the volume of coupler reactor.

(polymerization process)

Polymerization process is following operation: in above-mentioned polymeric kettle; In hydrocarbon solvent, use the basic metal series initiators to make conjugated diene compound polymerization or make conjugated diene compound and vinyl aromatic compounds copolymerization continuously continuously, obtain reactive polymer or active copolymer.

At first, the material that uses in the polymerization process is described, then concrete polymerization process is described.

< conjugated diene compound >

As conjugated diene compound, can enumerate but be not limited to for example 1,3-butadiene, isoprene, 2,3-dimethyl--1,3-butadiene, 1,3-pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 1,3-heptadiene, 1,3-hexadiene etc.Be preferably 1,3-butadiene, isoprene especially.

They can use separately, also can two or more combinations use.

< vinyl aromatic compounds >

As aromatic ethenyl compound, can enumerate but be not limited to for example vinylbenzene, p-methylstyrene, alpha-methyl styrene, vinyl ethylbenzene, vinyl-dimethyl benzene, vinyl naphthalene, diphenylethlene etc.Be preferably vinylbenzene especially.

They can use separately, also can two or more combinations use.

< hydrocarbon solvent >

As hydrocarbon solvent, use stable hydrocarbon, aromatic hydrocarbons etc., can enumerate for example aliphatic hydrocarbons such as butane, pentane, hexane, pentane, heptane; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane, methylcyclohexane; Aromatic hydrocarbonss such as benzene,toluene,xylene and the hydrocarbon that forms by their mixture.

For above-mentioned conjugated diene compound, aromatic ethenyl compound and hydrocarbon solvent; With it respectively individually or before mixed solution separately states polyreaction after supplying to; Through removing moisture, propadiene class, acetylene class and carbonyl class as impurity; The polymkeric substance of reactive terminal can be accessed, and then high degree of modification can be realized with high density.

As the amount of these impurity, with respect to the monomeric total mass that is supplied to polyreaction, moisture preferably is lower than 20ppm, and propadiene class and acetylene class preferably are lower than 200ppm.

But, be used for preventing that a spot of chain-transfer agent (for example propadiene class, specifically 1, propadiene) of polymerization generation gel preferably can be to exist in the scope that is lower than 200ppm.

As the basic metal series initiators, can use any alkali metal cpd that polymerization causes function that has.

Be preferably organolithium compound especially.

Organolithium compound comprises: the bonding mode that has the bonding mode that has organolithium compound, organic group and the lithium of the lithium more than 2 in the organolithium compound, 1 molecule of a lithium in the organolithium compound of low-molecular-weight organolithium compound, soluble oligopolymer, 1 molecule and be organolithium compound, organic group and the lithium of carbon-lithium key is that the bonding mode of organolithium compound, organic group and the lithium of nitrogen-lithium key is organolithium compound of tin-lithium key etc.

As above-mentioned basic metal series initiators organolithium, below enumerate single organolithium compound, multifunctional organolithium compound, comprise nitrogen-object lesson of the compound of lithium key.

As single organolithium compound, can enumerate but be not limited to for example n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyllithium, benzyl lithium, phenyl lithium, stilbene lithium etc.

As multifunctional organolithium compound; Can enumerate but for example be not limited to 1; The reaction product, 1 of 4-two lithium butane, s-butyl lithium and di isopropenylbenzene; 3, the reaction product of reaction product, n-Butyl Lithium and the polyacetylene compound of 5-three lithium benzene, n-Butyl Lithium and 1,3-butadiene and Vinylstyrene etc.

In addition, as the compound that comprises nitrogen-lithium key, can enumerate but be not limited to for example dimethylamino lithium, dihexyl Lithamide, lithium diisopropylamine, hexamethyleneimino lithium etc.

In addition, can also use USP the 5th, 708, No. 092 specification sheets, the 2nd, 241, No. 239 specification sheetss of English Patent, the 5th, 527, No. 753 disclosed organic alkali metal compounds such as specification sheets of USP.

As organolithium compound, more preferably n-Butyl Lithium, s-butyl lithium.

These organolithium compounds can use separately, also can share two or more.

As the organic alkali metal compound except that organolithium compound, can enumerate organosiloxane compound, organic potassium compound, organic rubidium compound, organic caesium cpd etc.

As the organic alkali metal compound except that organolithium compound,, can also use but be not limited to the alkoxide of lithium, sodium, potassium except for example sodium naphthalene, potassium naphthalene; The sulphonate of lithium, sodium, potassium; The carbonate of lithium, sodium, potassium; The acid amides of lithium, sodium, potassium etc.

The basic metal series initiators can share with other organometallic compounds.

Other organometallic compounds have for example organo-magnesium compound, organo-aluminium compound etc., specifically, can enumerate dibutylmagnesium, triethyl aluminum etc.

< polar compound >

Through using polar compound, can improve the polymerization velocity of initiation, the microstructure of conjugated diene unit in the controlling polymers, the reactwity of monomer ratio in the control copolymerization with above-mentioned basic metal series initiators.

As polar compound, can use but be not limited to for example ether compound, tertiary amine compound, metallic alkoxide compound, phosphine compound, organic sulfonic acid metallic compound etc.

Polar compound after have effective randomization effect in the copolymerization of the conjugated diene compound stated and aromatic ethenyl compound, can be as the adjustment agent of the distribution of aromatic ethenyl compound, the adjustment agent of styrene block amount.

For example, can enumerate THF, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxy benzene, 2, ethers such as 2-two (2-tetrahydrofuran base) propane; Tertiary amine compounds such as Tetramethyl Ethylene Diamine, dipiperidino ethane, Trimethylamine 99, triethylamine, pyridine, rubane; Alkali metal alcohol salt compounds such as tertiary amyl alcohol potassium, potassium tert.-butoxide, sodium tert-butoxide, sodium tert-amyl alcohol; Phosphine compounds such as triphenylphosphine; Alkyl or aryl such as Potassium dodecylbenzenesulfonate, X 2073 sulfoacid compound etc.

These polar compounds can use separately, also can two or more combinations use.

The consumption of polar compound can suitably be selected according to the degree of purpose and effect, usually, is 0.01～100 mole with respect to 1 mole of above-mentioned basic metal series initiators.

Such polar compound is except the adjustment of copolyreaction property ratio, and the microstructure regulator that can be used as polymkeric substance diene part comes an amount of use according to desired vinyl binding capacity.

As polar compound, have in the preferred molecule more than 2 ether and wherein at least 1 ether form the hydrocarbon compound that contains ether of ring.

Through using these polar compounds, can access the high effect of reactive polymer rate of few, the multipolymer of inactivation in monomer conversion height and the way.

As have in the molecule more than 2 ether and wherein at least 1 ether form the hydrocarbon compound that contains ether of ring; For example can enumerate 2; The alkyl oxides of 2-two (2-tetrahydrofuran base) propane, THP trtrahydropyranyl methyl alcohol etc. are preferably 2,2-two (2-tetrahydrofuran base) propane.

< polymerization process >

Through above-mentioned polymeric kettle, use above-mentioned basic metal series initiators, in above-mentioned hydrocarbon solvent, make conjugated diene compound polymerization or make conjugated diene compound and vinyl aromatic compounds copolymerization continuously continuously, obtain reactive polymer or active copolymer.

Monomer concentration in the polymeric solution is preferably 5～30 quality %, more preferably 10～20 quality %.

In this polymerization process; Supply with necessary starting material such as monomer, hydrocarbon solvent, basic metal series initiators continuously from the predetermined nozzle more than 1 that is arranged at polymeric kettle, discharge continuously from the predetermined nozzles polymeric kettle outlet, different with said nozzle that are equivalent to the polymers soln behind the aggregated content thing is discharged then.

When carrying out polymerization process, the temperature out that preferably makes polymeric kettle is 70 ℃～110 ℃, more preferably 90～110 ℃, further is preferably 95 ℃～107 ℃.

Through making polymerization temperature is below 110 ℃, and activity rate improves, and can access high coupling yield.

On the other hand, be more than 70 ℃ through making polymerization temperature, can access high conversion.

The monomeric transformation efficiency in polymeric kettle exit is high more good more, is preferably more than 95%, more preferably more than 98%, further be preferably more than 99%.

Need to prove that transformation efficiency receives the temperature out of polymeric kettle, temperature distribution, whipped state, the amount of initiator, the kind of polar compound and the influence of amount and mean residence time in the polymeric kettle, preferred transformation efficiency improves activity rate in the time of high.If transformation efficiency enough height as above-mentioned, then the mean residence time in the polymeric kettle is short more, and the activity rate of resulting polymkeric substance is high more, after the coupling yield stated in the coupling operation high more.

Mean residence time in the polymeric kettle was preferably in 40 minutes.Further be preferably in 35 minutes, on the other hand, if the mean residence time in the polymeric kettle is too short, then transformation efficiency reduces, thereby is preferably more than 15 minutes.

(coupling operation)

The coupling operation is following operation: make the above-mentioned reactive polymer or active copolymer and the multi-functional compounds's reaction that obtain in the above-mentioned polymerization process, carry out linked reaction.

At first, the material that uses in the coupling operation is described, then concrete coupling operation is described.

< multi-functional compounds >

As the multi-functional compounds, use to have more than two with reactive polymer or active copolymer reaction in the molecule and form the compound of the functional group of bonding.

The multi-functional compounds has the identical or different functional group more than the 3 officials ability and passes through linked reaction to form at least 3 ramose compounds in 1 molecule, be preferably formed 4 branch～8 ramose multi-functional compounds.

In addition, also can be to introduce the compound of different types of functional group at the end of polymkeric substance or multipolymer behind the bonding reaction.

About multi-functional compounds's consumption,, be preferably 0.05～5 equivalent in multi-functional compounds's functional group, more preferably 0.1～2 equivalent with respect to 1 mole of above-mentioned basic metal series initiators.

As with the reaction of reactive polymer or active copolymer and form the functional group of bonding, can enumerate halogen radical for example, carbonyl, carboxylic acid ester groups, carboxamido-group, acid halide group, thiocarbonyl, thiocarboxylic acid ester group, thioamides base, sulfo-acid halide group, NCO, isothiocyanic acid ester group, epoxy group(ing), sulfo-epoxy group(ing), alkoxysilyl, as the vinyl of the two keys of functionality, imino-etc.

In addition, preferably use the material that in multi-functional compounds's molecule, has following functional group, this functional group perhaps has bonding reaction property not with the reactive terminal bonding but have consistency with filler.

Such functional group comprise uncle amino, with the primary amino of silicon compound protection or secondary amino group etc.

Preference as the multi-functional compounds; Can enumerate silicon tetrahalogen, two (three halogenation silyls) paraffinic hydrocarbons, four tin halide, four alkoxyl silicones, tri-alkoxy alkyl silicon, six alkoxyl group disilane, two (trialkoxysilyl) paraffinic hydrocarbons, two (trialkoxysilyl alkyl) alkylamine, two (trialkoxysilyl alkyl) trialkylsilkl amine, three (trialkoxysilyl alkyl) amine, 1; Two (trialkoxysilyl alkyl) piperazines, 1 of 4-; Two (trialkoxysilyl alkyl) imidazolidines, 1 of 3-; Two (trialkoxysilyl alkyl) hexahydro-pyrimidines, 1 of 3-; 1-dialkoxy-2 (trialkoxysilyl alkyl)-1-sila-2-aza-cyclopentane, 1; 1-dialkoxy-2 (trialkoxysilyl alkyl)-1-sila-2-piperidine, 1,1-dialkoxy-2 (trialkoxysilyl alkyl)-1-sila-2-azepan, dicarboxylic diester, tricarboxylic acid three esters, carbonic diester, have 3 above glycidyl ethers compound, have 3 above glycidyl-aminos compound, have the amino compound of 2 above diglycidyl etc.

Specifically; Can enumerate silicon tetrachloride, Silicon bromide, silicon tetraiodide, tin tetrachloride, 1; Two (Trichloromonosilane base) ethane of 2-, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, six oxyethyl group disilane, 1; Two (trimethoxysilyl) ethane, 1 of 2-; Two (trimethoxysilyl) ethane of 1-, two (3-triethoxysilylpropyltetrasulfide) methylamine, two (2-trimethoxysilylethylgroup group) propylamine, two (3-trimethoxy-silylpropyl) trimethyl silyl amine, three (trimethoxysilyl methyl) amine, three (3-triethoxysilylpropyltetrasulfide) amine, 1; Two [3-(trimethoxysilyl) propyl group] piperazines, 1 of 4-, two [3-(triethoxysilyl) propyl group] piperazines, 1 of 4-, two [3-(trimethoxysilyl) propyl group] imidazolidines, 1 of 3-; Two [3-(triethoxysilyl) propyl group] imidazolidines, 1 of 3-; Two [3-(trimethoxysilyl) propyl group] hexahydro-pyrimidines, 1 of 3-, two [3-(triethoxysilyl) propyl group] hexahydro-pyrimidines, 1 of 3-, two [3-(the three butoxy silyls) propyl group]-1 of 3-; 2; 3,4-tetrahydropyrimidine, 1,1-dimethoxy-2 (3-trimethoxy-silylpropyl)-1-sila-2-aza-cyclopentane, 1; 1-diethoxy-2-(3-triethoxysilylpropyltetrasulfide)-1-sila-2-aza-cyclopentane, 1; 1-dimethoxy-2-(3-dimethoxy-methyl silyl propyl group)-1-sila-2-aza-cyclopentane, 1,1-dimethoxy-2 (4-trimethoxysilyl butyl)-1-sila-2-piperidine, 1,1-dimethoxy-2 (5-trimethoxysilyl amyl group)-1-sila-2-azepan, dimethyl adipate, trimethyl trimellitate, trimesic acid triethyl, methylcarbonate, glycerine triglycidyl group ether, tetramethylolmethane four glycidyl ethers, four glycidyl group-1; The two amino methyl hexanaphthenes of 3-, four glycidyl group m-xylene diamine, four glycidyl group-4; 4 '-diaminodiphenyl-methane, N, N-diglycidyl-4-(4-glycidyl-1-piperazinyl) aniline, N, N-diglycidyl-4-glycidoxy aniline.

As multi-functional compounds's preferred instance, can enumerate intramolecularly and have the amino polyepoxides of uncle.Epoxy group(ing) is 3 can obtain branched chain polymer when above.

At this moment, do not produce by product, resulting branched chain polymer is as the excellent performance of rubber.

Specifically; Can enumerate four glycidyl group-1; The two amino methyl hexanaphthenes of 3-, four glycidyl group m-xylene diamine, four glycidyl group-4; 4 '-diaminodiphenyl-methane, N, N-diglycidyl-4-(4-glycidyl-1-piperazinyl) aniline, N, N-diglycidyl-4-glycidoxy aniline.

Further preferred examples as the multi-functional compounds; Can enumerate following multi-functional compounds; It is amino and constitute with oligopolymer composition more than the dimer of the low molecular compound that contains glycidyl-amino of the glycidyl of this amino bonded and this low molecular compound that contains glycidyl-amino more than 3 by having 2 above uncles in the molecule; Total amount with respect to the multi-functional compounds; The said low molecular compound that contains 75～95 quality % contains the said oligopolymer of 25～5 quality %.

Specifically, can enumerate the mixture that two amino methyl hexanaphthenes of 3-and oligopolymer composition thereof constitute by four glycidyl group-1.

Through using above-mentioned multi-functional compounds, the branched conjugated diene compound has as the more excellent rerum natura of rubber.

< coupling operation >

In this coupling operation, to reactive polymer of discharging or active copolymer solution, mix the multi-functional compounds, make its reaction from the polymeric kettle outlet.

At this moment; Need in advance above-mentioned polymeric kettle and coupler reactor be connected in series with the pipe arrangement of the outlet that is arranged at polymeric kettle; And the mean residence time after the outlet of auto-polymerization still is discharged is in 5 minutes; In reactive polymer of discharging or active copolymer solution, mix the multi-functional compounds, make its reaction by the polymeric kettle outlet.Mean residence time was preferably in 3 minutes, in more preferably 2 minutes.

In addition; In this embodiment, as stated, on the pipe arrangement that is used to discharge that is connected with coupler reactor, be provided with the aperture regulon of the pressure in the exit that can control above-mentioned polymeric kettle in advance; Thus, with the pressure-controlling in the exit of polymeric kettle at 0.5～2MPaG.

The preferred pressure set(ting)value fully is higher than the vapour pressure in the polymeric kettle, thereby so long as the pressure of the degree that does not gasify gets final product, is preferably the scope of 0.6～1.5MPaG, more preferably the scope of 0.7～1.2MPaG.In addition, pressure with respect to the scope of set(ting)value change preferably in ± 0.2MPa, more preferably in ± 0.1MPa, more little good more.

As the aperture regulon, can use pressure controlled valve, orifice plate of automatic or manual etc.Preferred especially automatic pressure valve.Use under the situation of automatic pressure valve, when the aperture of valve significantly changes, preferably share manual pressure controlled valve with the automatic pressure valve.

From above-mentioned polymerization process,, in the whole operations of manufacturing, carry out the pressure-controlling in the exit of this polymeric kettle as the branched conjugated diene polymer of target through the coupling operation.

Like this; The position that is provided with through with the aperture regulon is defined as the pipe arrangement that being used for of being connected with coupler reactor discharge from coupler reactor; And the pressure in the exit of controlled polymerization still; Can make the change of viscosity and the degree of branching of the branched conjugated diene polymer that is generated few thus, can stably produce.

The position that is provided with of aperture regulon is the pipe arrangement that is used to discharge that connects in the downstream of coupler reactor, so long as to the way of subsequent processing, where all can.

The pipe arrangement that is used to discharge that is connected with coupler reactor also can be provided with mixed additive or fill the mixing machine of wet goods.

In the method for manufacture of the branched conjugated diene polymer of this embodiment; The pressure that causes for the operation that prevents the aperture regulon sharply reduces and sharply reduces owing to pressure the gasification of the solvent that causes; And concentration, flow velocity remained uniform state, use the poly-unit that the aperture regulon is arranged at the downstream of coupler reactor.

Pressure-controlling through with the exit of polymeric kettle is 0.5～2MPaG, can guarantee sufficient transformation efficiency, in addition, can utilize relatively more easy equipment to implement, thereby also preferred economically.

Need to prove; Making the pressure in the exit of polymeric kettle is necessary in this scope in fact; Be used for carrying out automatically the outlet that the position is not limited to polymeric kettle that is provided with of pressure controlled pressure detector; Can be the pipe arrangement in the polymeric kettle, in the way, any one of coupler reactor, need only the upper reaches at the aperture regulon.

In addition, also can on the outlet pipe arrangement of the outlet pipe arrangement of polymeric kettle and coupler reactor, the aperture regulon be set respectively.Under this situation; The control of the top hole pressure of polymeric kettle also preferably mainly utilizes the aperture regulon of the outlet pipe arrangement of coupler reactor to carry out; The pressure-controlling that the aperture regulon of outlet pipe arrangement that in addition, also can be through being arranged at polymeric kettle assists the aperture regulon that utilizes the outlet pipe arrangement that is arranged at coupler reactor to be carried out.

As stated; Through within the short period of time, carrying out under than higher temperature and accomplishing polymerization process and coupling operation; The change that can make the viscosity and the degree of branching energy-conservation and continuously less, short, high conversion of the residence time and branched conjugated diene polymer with any degree of branching, can reduce gel simultaneously and generate.

[viscosity tube science and engineering preface]

In the method for manufacture of the branched conjugated diene polymer of this embodiment, preferably also has following operation: between above-mentioned polymerization process to above-mentioned coupling operation, said reactive polymer or active copolymer are sampled, measure the operation of mooney viscosity; After the coupling operation, when the residence time from the outlet of said polymeric kettle is lower than 15 minutes, the branched conjugated diene polymer is sampled, measure the operation of mooney viscosity.

Thus, can realize the viscosity of branched conjugated diene polymer and stablizing of the degree of branching.The residence time till the outlet of said polymeric kettle to the sampling was more preferably less than 10 minutes.

As after state shown in [embodiment], mooney viscosity is measured as follows: use mooney's viscosimeter, according to JIS K6300-1, usually with the arbitrary temp preheating of 100 ℃ to 130 ℃ scope after 1 minute, change to make its rotation with PM 2, measure the viscosity after 4 minutes.

At length say; Preferably in the outlet of polymeric kettle or adding multi-functional compounds's last stage; Measure the mooney viscosity of reactive polymer the coupling last stage or active copolymer and it is managed from predetermined sample nozzle, in addition, in the outlet of coupler reactor or thereafter; The residence time from the polymeric kettle outlet is lower than 15 minutes position, manages by the mooney viscosity of the branched conjugated diene polymer that obtains after the predetermined sample nozzle mensuration coupling operation and to it.

Above-mentioned sample nozzle is preferably following formation: on predetermined pipe arrangement etc., Zhi Peiguan is set, the container with the required capacity of sampling is set, predetermined segregaion valve is set in front and back, and then the pipe arrangement that imports rare gas element to container is set as required.

Need to prove that the above-mentioned residence time is that the volume with the liquid phase through equipment is that basic calculation goes out.

Have under the situation of gas phase, have under the situation of stirrer and other devices, in this part is not included in.

Before the coupling operation and after the coupling operation; Measure the mooney viscosity of reactive polymer or active copolymer respectively and it is managed; And then make from the residence time of polymeric kettle outlet shorter; Thereby can discover the change of product in the operation as early as possible and tackle, finally realize the viscosity of branched conjugated diene polymer and stabilization this purpose of the degree of branching.

In this embodiment; Reactive polymer before the coupling operation or active copolymer are preferably 50～100 scope at 110 ℃ mooney viscosity (ML-I), and branched conjugated diene polymer after the coupling operation or multipolymer are preferably 100～150 scope at 110 ℃ mooney viscosity (ML-C).

In addition, above-mentioned (ML-C) is preferably 1.2～3 times the scope of above-mentioned (ML-I).

As the span of management of the mooney viscosity before the coupling operation, with respect to target value preferably in ± 10, more preferably in ± 5.

In addition, the span of management of the mooney viscosity after the coupling operation with respect to target value preferably in ± 15, more preferably in ± 8.

Need to prove, preferably manage so that the amplitude of the mooney viscosity before the coupling operation is in the numerical range narrower than the amplitude of the mooney viscosity after the coupling operation.

As management for the method for these numerical ranges, for example, in order to make mooney viscosity before the coupling in span of management, increase and decrease amount of initiator during management, in order to make mooney viscosity after the coupling in span of management, the increase and decrease multi-functional compounds measures during management.

Through such management, can make viscosity, molecular weight, the degree of branching as the branched conjugated diene polymer of the target appropriateness that becomes, at the processibility of rubber and the aspect of performance of vulcanized rubber, also can guarantee stable quality.

[qualitative control operation]

In the method for manufacture of the branched conjugated diene polymer of this embodiment; The following qualitative control operation of preferred enforcement: after above-mentioned coupling operation; The solution above-mentioned aperture regulon, branched conjugated diene polymer (multipolymer) that will pass through on the pipe arrangement that is used for discharging of coupler reactor, to be provided with temporarily is stored in storage tank, and quality is managed.

Above-mentioned storage tank preferably remains the pressure about 0.05～0.3MPaG.

Need to prove, be stored in before the storage tank or in storage tank, or discharge the back before the desolventizing operation from storage tank, can further add terminator, neutralizing agent, inhibitor, perhaps add the processing wet goods as required.In the qualitative control operation, as inspection item, measure mooney viscosity, the degree of branching, additive capacity, measure ratio of components etc. under the situation of multipolymer.

[desolventizing operation]

After the above-mentioned qualitative control operation, utilize predetermined pump etc. with branched conjugated diene polymer (multipolymer) solution or oil-filled after branched conjugated diene polymer (multipolymer) solution deliver to predetermined finishing machine, carry out desolventizing.

Thus, obtain branched conjugated diene polymer as target.

As carrying out desolventizing, can utilize existing known method to obtain the method for branched conjugated diene polymer.

For example, can utilize following method: after branch exsolution agent such as stripping, filter, and then it is implemented dehydration and the method for drying treatment with acquisition branched conjugated diene polymer; Concentrate with flash tank, and then with the method for devolatilizations such as vented extruder; Method with direct devolatilizations such as rotary drum dryer; Or the like.

[branched conjugated diene polymer]

Through experiencing above-mentioned each operation, obtain branched conjugated diene polymer as target.

Below, the characteristic of the branched conjugated diene polymer that obtains through the method for manufacture of implementing this embodiment is described.

(with multi-functional compounds's reaction ratio)

Branched conjugated diene polymer that method of manufacture through this embodiment obtains and above-mentioned multi-functional compounds's reaction ratio are preferably 10～80 quality %.

With multi-functional compounds's reaction ratio when the above-mentioned scope, then can form the degree of branching of appropriateness, processibility is good, can access excellent rerum natura when processing vulcanized rubber.

(MWD)

The branched conjugated diene polymer that method of manufacture through this embodiment obtains is a peak, promptly unimodal based on the MWD of GPC (GPC); In the conversion molecular weight based on PS, weight-average molecular weight is preferably 500,000～2,000,000.

Weight-average molecular weight is when above-mentioned numerical range, and then processibility is good, can access excellent rerum natura when processing vulcanized rubber.

About the MWD based on GPC, Mw (weight-average molecular weight)/Mn (number-average molecular weight) is preferably 1.7～3.0, and more preferably 1.8～2.8.

MWD is when above-mentioned scope, and then processibility is good, can access excellent rerum natura when processing vulcanized rubber.

(preferred configuration of branched conjugated diene polymer)

The branched conjugated diene polymer that method of manufacture through this embodiment obtains is with conjugated diene compound polymerization or material that conjugated diene compound and vinyl aromatic compounds copolymerization are formed.

For example, be preferably polyhutadiene, TR 301, butadiene isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene multipolymer, styrene butadiene-isoprene copolymer, more preferably styrene-butadiene copolymer.

When the branched conjugated diene polymer is the branched random copolymers of conjugated diene compound and vinyl aromatic compounds; The mass ratio of conjugated diene compound is preferably 50～80 quality % in this branched random copolymers, and the quality ratio of vinyl aromatic compounds is preferably 50～20 quality %.

In addition, the vinyl structure of the conjugated diolefine of this multipolymer part is preferably 30～65 moles of %.

When above-mentioned scope, of the back, then use branched conjugated diene polymer (multipolymer) to make vulcanized rubber, and when its tyre surface as doughnut used rubber, the balance of anti-slippery and oil consumption property was good.

When the branched conjugated diene polymer that the method for manufacture through this embodiment obtains was the branched random copolymers of conjugated diene compound and vinyl aromatic compounds, the chain link length of optimization aromatic vinyl was that the composition more than 30 exists less or not.

Specifically; The branched conjugated diene polymer that method of manufacture through this embodiment obtains is under the situation of BS, through method (I.M.KOLTHOFF, the et al. of Kolthoff; J.Polym.Sci.1; 429 (1946) methods put down in writing) decompose the branched conjugated diene polymer, and when utilizing the known method that the PS amount (block styrene amount) that is insoluble to methyl alcohol is analyzed to measure, with respect to the branched conjugated diene polymer of whole amounts; Above-mentioned block styrene amount is preferably below the 5 quality %, more preferably below the 3 quality %.

In more detail; The branched conjugated diene polymer that will be obtained by the method for manufacture of this embodiment through the method for decomposing based on ozone decomposes; And when distributing through the gpc analysis styrene chain; Then separating phenylethylene, be that the chain link of styrene units is that 1 vinylbenzene (vinylbenzene of strand joint) is preferably more than the 40 quality % with respect to whole combined styrene amounts, the long-chain block styrene, be that the chain link of styrene units is that vinylbenzene more than 8 is preferably below the 5 quality % with respect to whole combined styrene amounts.

Need to prove, be not limited to vinylbenzene, the vinyl aromatic compounds that constitutes the branched conjugated diene polymer is all preferably in above-mentioned numerical range.

Through being above-mentioned numerical range, used the vulcanized rubber of branched conjugated diene polymer can realize the distortion of mobility, for example rubber and the reduction of the living heat when recovering.

[oil extended polymer]

The branched conjugated diene polymer that obtains through the method for manufacture in this embodiment can add treated oil as required before above-mentioned desolventizing operation, form oil extended polymer.

As above-mentioned treated oil, preference such as aromatic hydrocarbon oil, naphthenic oil, alkane oil and be the aromatic hydrocarbon oil substitute below the 3 quality % based on the Ppolynuclear aromatic composition of IP346 method.

From the environmental safety aspect with prevent that oil impregnate and wet road from grabbing the aspect of ground characteristic, especially preferably using the Ppolynuclear aromatic composition is the aromatic hydrocarbon oil substitutes below the 3 quality %.

As the aromatic hydrocarbon oil substitute, except the TDAE shown in the Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), MES etc., can enumerate RAE etc.

The consumption of extending oil is arbitrarily, usually, is 10～60 mass parts with respect to 100 mass parts branched conjugated diene polymers.Generally be preferably 20～37.5 mass parts.

[branched conjugated diene polymer composition]

Through in the branched conjugated diene polymer that as above obtains, adding predetermined material and mixing, can access the vulcanizate compositions of branched conjugated diene polymer.

The branched conjugated diene polymer generally with normally used method processing in the rubber industry, uses with the form of rubber item.

Used the vulcanizate compositions of branched conjugated diene polymer to obtain as follows: in above-mentioned branched conjugated diene polymer, to mix other predetermined elastomeric materials as required; And mixed filler; Adding silane coupling agent, softener of rubber, vulcanizing agent, vulcanization aid, other additives are processed, and obtain to have used the vulcanizate compositions of branched conjugated diene polymer thus.

Specifically; Use can controlled temperature mixing roll; In the branched conjugated diene polymer, add other elastomeric materials, weighting agent (silicon-dioxide and/or carbon black), silane coupling agent, softener of rubber, inhibitor etc. as required and carry out mixingly, obtain rubber stock.At this moment, can carry out or carry out with one section with multistage.In order to improve the dispersion of weighting agent, preferably carry out mixing with multistage.After resulting rubber stock cooling, add vulcanizing agent, vulcanization aid etc. and carry out mixing.Through with its moulding and sulfuration, thereby obtained as the use of target the vulcanizate compositions of branched conjugated diene polymer.

As above-mentioned other elastomeric materials, can utilize tree elastomer and viton.As viton, can enumerate for example low-cis-polybutadiene, high-cis polybutadiene, VCR (vinyl-cis-Butadiene Rubber), SBR (styrene-butadiene rubber(SBR)), synthetic polyisoprene, butyl rubber, EPDM (terpolymer EP rubber) etc.

As above-mentioned weighting agent, can enumerate for example inorganic fibrous materials such as carbon black, settleability silicon-dioxide, fumed silica, clay, talcum, mica, zeyssatite, wollastonite, polynite, zeolite, spun glass etc.

Especially preferably use carbon black, settleability silicon-dioxide.

Above-mentioned silane coupling agent has the interaction that makes above-mentioned rubber constituent and the silica-based inorganic filler function closely that becomes, and is the compound that has respectively to the group of the affinity of rubber constituent and silica-based inorganic filler or associativity.

As silane coupling agent, use has the compound of sulphur bound fraction, alkoxysilyl, silanol group part in a part usually.

Silane coupling agent can be enumerated but be not limited to for example two [3-(triethoxysilyl)-propyl group]-tetrasulfides, two-[3-(triethoxysilyl)-propyl group]-disulphide, two-[2-(triethoxysilyl)-ethyl]-tetrasulfide etc.

As above-mentioned softener of rubber, suitable MO or liquid or low-molecular-weight synthetic tenderizer or the vegetal tenderizer of using.

As above-mentioned vulcanizing agent, can use radical initiator, sulphur, sulfocompound etc.

As above-mentioned vulcanization aid, can use zinc white, Triple Pressed Stearic Acid etc.

As other additives, can use vulcanization accelerator, inhibitor, wax, static eliminator, tinting material etc.

Embodiment

Below, enumerate concrete embodiment and comparative example and describe, but the present invention is not limited to this.

At first, be applicable to that the measuring method of the rerum natura of embodiment and comparative example, evaluation method are as follows.

[(1) combined styrene amount]

The sample of measuring usefulness is processed chloroform soln, and the UV-2450 that uses Shimadzu Seisakusho Ltd. to make measures cinnamic phenyl and is the absorbed dose under the ultraviolet ray (UV) of 254nm at wavelength, measures combined styrene amount (quality %).

[(2) styrene chain]

Obtain measuring the osmic acid degradation production of the sample of usefulness according to the method for Korthoff, use this product, in methyl alcohol, separate out the insoluble PS that is equivalent to the block PS.

This insoluble PS amount is carried out quantitatively, calculate the block styrene amount with form with respect to the quality % of polymkeric substance.

In addition; The following analysis of content of the vinylbenzene strand joint of 1 styrene units and 8 continuous vinylbenzene long-chains that form of above styrene units tried to achieve: according to people's such as Tanaka method (Polymer; 22; 1721 (1981)), after with ozone the styrene butadiene copolymer rubber being decomposed, utilize GPC (GPC) to analyze.

[microstructure (1,2-vinyl binding capacity) of (3) divinyl part]

The sample of measuring usefulness is processed dithiocarbonic anhydride solution, use the solution cuvette, the FT-IR230 that makes through Japanese beam split Co., Ltd. is at 600～1000cm ^-1Scope measure ir spectra, according to the calculation formula of Hampton (Ha Application プト Application) method, obtain the microstructure (1,2-vinyl binding capacity) of divinyl part by the absorbancy of predetermined wave number.

[(4) mooney viscosity]

According to JIS K6300-1, use L type rotor, the viscosity after 4 minutes is measured in preheating 1 minute.

Need to prove, measure temperature will after put down in writing with numeric data in the explanation of [embodiment 1], [comparative example 1], [comparative example 2] stated.

[(5) molecular-weight average and MWD]

Use GPC (GPC) to measure color atlas; Wherein connect and used 3 with the post of polystyrene gel as weighting agent; According to relation through resulting RV of the calibration curve that has used polystyrene standard and molecular weight; Calculate the frequency of each molecular weight ranges according to ordinary method, calculate number-average molecular weight, weight-average molecular weight and MWD with respect to total peak area.

Elutriant uses THF (THF).

Employed post has guard column: eastern Cao TSK guard column HHR-H, post: eastern Cao TSK gel G6000HHR, TSK gel G5000HHR, TSK gel G4000HHR, oven temperature: 40 ℃, THF flow 1.0mL/ minute, GPC: eastern Cao makes HLC-8020, detector: RI.

Mensuration with sample use with the 20mg sample dissolution in the THF of 20mL and material, inject 200 μ L and measure.

[(6) linked reaction rate]

It is the characteristic of the GPC post of weighting agent that utilization is adsorbed in silica-based gel through the composition of modification; Use contains the sample solution of mark PS molecular weight 5000 (PS does not adsorb) in sample and the lower molecular weight; Measure polystyrene gel (eastern Cao's system: (the eastern Cao's system: of GPC TSK) of above-mentioned (5) HLC-8020) with silicon-dioxide bitt (guard column: DIOL 4.6 * 12.5mm 5micron; Post: Zorbax PSM-1000S, PSM-300S, PSM-60S; Oven temperature: 40 ℃, THF flow 0.5ml/ minute) GPC (eastern Cao's system: CCP8020 series enhancement type GPC system; AS-8020, SD-8022, CCPS, CO-8020, RI-8021) these two color atlass, be benchmark with interior mark PS peak, according to their difference, be determined at the adsorptive capacity on the silica column, obtain the linked reaction rate.

Use sample as measuring, all 20mg determination object and 5mg polystyrene standard together to be dissolved among the THF of 20mL and to use, to inject 200 μ L during mensuration.

Concrete step is following: if use the total peak area of the color atlas of PS bitt is 100, and the peak area of establishing sample is that the peak area of P1, polystyrene standard is P2; If used the total peak area of the color atlas of silicon-dioxide bitt is 100, and the peak area of establishing sample is that the peak area of P3, polystyrene standard is P4, obtains respectively, and the linked reaction rate is calculated through following formula.

Linked reaction rate (%)=[1-(P2 * P3)/(P1 * P4)] * 100

[multi-functional compounds's who uses in (7) linked reaction low molecular compound and oligopolymer composition quantitatively]

Use eastern Cao TSK gel G3000HXL, eastern Cao TSK gel G2000HXL, eastern Cao TSK gel G1000HXL as the GPC post, use THF, use eastern Cao to make the HLC-8220GPC device as elutriant.

Detector is RI, and oven temperature is 40 ℃, and the elutriant flow is 1.0mL/ minute, measures the THF solution that uses 1.0mg/mL with sample, injects 200 μ L mensuration and carries out GPC mensuration with sample.

Need to prove, carry out the correction of molecular weight according to polystyrene standard.

Thus, obtain " have in the molecule 2 above uncles amino with more than 3 with the low molecular compound that contains glycidyl-amino of the glycidyl of this amino bonded " and " this contains the oligopolymer composition more than the dimer of low molecular compound of glycidyl-amino " content in the multi-functional compounds.

[(8) transformation efficiency]

In the bottle that is sealed with as the 100mL of the toluene of interior target n-proplbenzene 0.50mL and about 20mL, inject the polymers soln that about 20mL is obtained by the polymeric kettle outlet, the making sample.

With this sample of gas chromatograph for determination; Said gas chromatograph has been installed the packed column that load has apiezon grease; Obtain the levels of residual monomers in the polymers soln by the calibration curve of divinylic monomer that obtains in advance and styrene monomer, obtain the transformation efficiency of divinylic monomer and styrene monomer.

[(9) MSR (Mooney stress relaxation)]

The VR1132 that the island makes manufacturing in the use is as the mooney viscosity tester, and through the method for regulation among ISO289-1 and the ISO289-4 (2003), making temperature is 120 ℃, measures mooney viscosity and Mooney relaxation rate.

At first, 120 ℃ of preheatings 1 minute,, measure the moment of torsion after 4 minutes, as mooney viscosity (ML thereafter with the 2rpm rotor ₁₊₄)., stop the rotation of rotor immediately, stop 1.6～5 seconds the per 0.1 second moment of torsion (T) in back, obtain moment of torsion and the collinear slope of time (t (second)) when making bilogarithmic graph with mooney unit record thereafter, with its absolute value as Mooney relaxation rate (MSR).

Under the situation that mooney viscosity equates, side chain is many more, and then Mooney relaxation rate (MSR) is more little, therefore can be as the index of the degree of branching.

[embodiment 1]

Use 1 vertical polymeric kettle, its internal volume is 10 liters, and inner height and diameter ratio (L/D) are 4, and the bottom has inlet, and the top has outlet, possesses stirrer and the chuck that is used for attemperation.

Before being about to add polymeric kettle; 1 of impurity such as moisture will have been removed in advance with static mixer; The 3-divinyl mixes with 0.006g/ minute speed with 182.9g/ minute, n-Butyl Lithium with 12.9g/ minute, hexane with 27.3g/ minute, vinylbenzene, is supplied to the bottom of polymeric kettle thereafter continuously with above-mentioned speed, and then; Will be as 2 of polar material; 2-two (2-tetrahydrofuran base) propane with 0.0402g/ minute speed, will be supplied to the polymeric kettle bottom with 0.0133g/ minute speed as the n-Butyl Lithium of polymerization starter, making the interior temperature of polymeric kettle outlet is 105 ℃, carries out polyreaction continuously.The interior mean residence time of polymeric kettle this moment is 30 minutes.

Need to prove, contain the 1 of 70ppm in the employed 1,3-butadiene.

As above carried out flowing out reactive polymer solution continuously through the pipe arrangement that is connected with the polymeric kettle top after the polyreaction.

Need to prove that pipe arrangement is provided with the nozzle that is used to sample in the way.

Pipe arrangement is guided the bottom of the coupler reactor that carries out subsequent processing into, and the pipe arrangement in front of this coupler reactor is supplied with the multi-functional compounds.

The residence time that is exported to the above-mentioned reactive polymer solution of coupler reactor front from polymeric kettle is 1 minute.

As the multi-functional compounds; Use is by four glycidyl group-1; The mixture that two amino methyl hexanaphthenes of 3-and the above oligopolymer composition of dimer thereof constitute; The above-mentioned four glycidyl group-1 that wherein contains 90 quality % with respect to multi-functional compounds's total amount, the above-mentioned oligopolymer of the two amino methyl hexanaphthenes of 3-, 10 quality %.

With hexanaphthene said mixture is processed 1000 times of diluents, supply with above-mentioned multi-functional compounds, promptly supply with 1000 times of diluents, in above-mentioned coupler reactor, implement linked reaction with 9.5g/ minute speed with 0.0095g/ minute speed.

The internal volume of coupler reactor is 1.5 liters, is the volumetrical 15% of polymeric kettle.

Mean residence time in the coupler reactor is 4.3 minutes.

Coupler reactor uses drum, possesses the reactor drum of stirring rake.The inside diameter D of coupler reactor is 0.104m, and the diameter d of stirring rake is 0.083m, and the diameter of stirring rake is 0.8 with respect to the ratio d/D of internal diameter.

The rotation speed n of stirrer is 10s ^-1, the long-pending nd in rotating speed and oar footpath is 0.83.

Coupler reactor utilizes the steam companion to guarantee that temperature, interior temperature are 95 ℃.

Be used for being provided with the automatic pressure valve as the aperture regulon from the pipe arrangement that coupler reactor is discharged.

Detect the pressure of the top exit of above-mentioned polymeric kettle, and control above-mentioned aperture regulon, so that this pressure is 0.9MPaG.

With above-mentioned being used for from the pipe arrangement importing capacity that coupler reactor is discharged is 100 liters the storage tank that has stirrer.

Be provided with the nozzle that is used to sample in the downstream of above-mentioned automatic pressure valve.

From the residence time that is exported to this nozzle that is used to sample of above-mentioned polymeric kettle be 6.5 minutes, the residence time till being about to get into before the storage tank is 7 minutes.

Before getting into storage tank, add inhibitor, extending oil continuously.

With respect to the polymkeric substance that obtains after the above-mentioned linked reaction of 100 mass parts, promptly from polymers soln, removed the polymkeric substance behind the solvent; Add the BHT (butylated hydroxytoluene) of 0.5 mass parts, and add the S-RAE oil (Japan Energy Corporation make NC-140) of 37.5 mass parts as extending oil as inhibitor.

Need to prove, the pipe arrangement that is exported to storage tank from polymeric kettle has been implemented sufficient insulation.

The pressure of storage tank is 0.2MPa.

The polymers soln of storage tank is delivered to finishing machine, carry out desolventizing, reclaim polymkeric substance.

As finishing machine, use rotary drum dryer.

Under the polyreaction stable status in above-mentioned polymeric kettle; With polymers soln bit by bit from the mixing solutions that is used for being discharged to about 1mL methyl alcohol and about 30mL hexanaphthene from the sample nozzle that the pipe arrangement that polymeric kettle is discharged is provided with; Simultaneously must note not coming in contact with air; After interpolation is the inhibitor (BHT) of 0.2g with respect to the above-mentioned polymkeric substance of 100g, except that desolvating, obtain the sample that mooney viscosity is measured usefulness with rotary drum dryer.

And then, with 6 inches rollers that are set at 110 ℃ sample is passed through 10 times.

Increase and decrease the amount of the polymerization starter n-Butyl Lithium that uses in the above-mentioned polyreaction, making sample is 70 ± 3 scope in 110 ℃ mooney viscosity (ML-I) and mobility scale thereof.

Specifically, if mooney viscosity is near the upper limit, then increase the amount of 1% n-Butyl Lithium, if opposite mooney viscosity, then reduces the amount of 1% n-Butyl Lithium near lower limit, controls with this.

About leaving the polymerisation conversion at polymeric kettle place, divinyl reaches 99.5% in addition, and vinylbenzene reaches 98.5%.

Will be from the mixing solutions that is used for being discharged to bit by bit about 1mL methyl alcohol and about 30mL hexanaphthene from the polymers soln that the sample nozzle that the pipe arrangement that above-mentioned coupler reactor is discharged is provided with is sampled; Simultaneously must note not coming in contact with air; After interpolation is the inhibitor (BHT) of 0.2g with respect to the 100g polymkeric substance; Except that desolvating, obtain the sample that mooney viscosity is measured usefulness with rotary drum dryer.

Branched conjugated diene polymer after this linked reaction is 135 ± 3 110 ℃ mooney viscosity (ML-C) and mobility scale thereof.

The MWD of the branched conjugated diene polymer that is obtained by GPC is unimodal, and weight-average molecular weight (Mw-C) is 830,000, and weight-average molecular weight is 2.5 with the ratio (Mw-C/Mn-C) of number-average molecular weight.

In addition, the combined styrene amount is 32 quality %, and 1 in the divinyl combining unit, 2-binding capacity are 38 moles of %.

Vinylbenzene chain link aspect; The block styrene amount of utilizing the method for Korthoff to obtain is 0 quality %; Decomposing the vinylbenzene strand joint that produces through ozone is 47 quality % with respect to the vinylbenzene total amount, and the containing ratio of the vinylbenzene long-chain that the above styrene units of 8 chain links connects into is 1 quality %.

The linked reaction rate, be that the ratio of the adsorbed branched conjugated diene polymer of silica column is 45 quality %.

Method through ISO289-4:2003 is measured mooney viscosity and Mooney relaxation rate (MSR), and 120 ℃ mooney viscosity ML1+4 is 125, and MSR is 0.351.

In addition; In this branched conjugated diene polymer solution, add with respect to 100 mass parts branched conjugated diene polymers is the S-RAE oil (Japan Energy Corporation makes NC-140) of 37.5 mass parts; Remove then and desolvate, obtain oil-filled branched conjugated diene polymer (sample PA).

Need to prove, confirm, in resulting branched conjugated diene polymer and equipment, all do not observe the generation of gel.

[comparative example 1]

The automatic pressure valve is not arranged at " be used for discharge pipe arrangement ", is used for the pipe arrangement of discharging from above-mentioned polymeric kettle and be arranged at from coupler reactor.

Other conditions and embodiment 1 are same, implement with this.

The multipolymer that carries out the last stage of linked reaction is 70 ± 3 110 ℃ mooney viscosity (ML-I) and mobility scale thereof, and the branched conjugated diene polymer after the linked reaction is 128 ± 9 110 ℃ mooney viscosity (ML-C) and mobility scale thereof.

In addition, the weight-average molecular weight (Mw-C) of the branched conjugated diene polymer after the linked reaction is 790,000, and weight-average molecular weight is 2.7 with the ratio (Mw-C/Mn-C) of number-average molecular weight.

The linked reaction rate, be that the ratio of the adsorbed branched conjugated diene polymer of silica column is 40 quality %.

Likewise measuring mooney viscosity and Mooney relaxation rate (MSR), is 117 at 120 ℃ mooney viscosity ML1+4, and MSR is 0.422.

And then oil-filled, obtain oil-filled branched conjugated diene polymer (sample PB).

In resulting branched conjugated diene polymer and storage tank, confirm the generation of a little gel.

[comparative example 2]

Before being about to add polymeric kettle; After with static mixer divinyl being mixed with 0.003g/ minute speed with 91.45g/ minute and n-Butyl Lithium with 6.45g/ minute, hexane with 13.65g/ minute, vinylbenzene; Be supplied to the polymeric kettle bottom continuously with above-mentioned speed; And then, will be as 2 of polar material, 2-two (2-tetrahydrofuran base) propane with 0.0201g/ minute speed, will be supplied to the polymeric kettle bottom with 0.00665g/ minute speed as the n-Butyl Lithium of polymerization starter; Making the interior temperature of polymeric kettle outlet is 105 ℃, carries out polyreaction.

The interior mean residence time of polymeric kettle this moment is 60 minutes.

Flow out reactive polymer solution continuously by the polymeric kettle top, be provided with the nozzle that is used to sample on the pipe arrangement that is used for the discharging way at polymeric kettle top.

Above-mentioned pipe arrangement is guided the bottom of in subsequent processing, carrying out the coupler reactor of linked reaction into, supplies with the multi-functional compounds in the pipe arrangement in front of this coupler reactor.

From the length that is exported to the pipe arrangement in front of the coupler reactor of polymeric kettle 3 times for the device that uses the embodiment 1.

The residence time that is exported to the coupler reactor front from polymeric kettle is 6 minutes.

With hexanaphthene said mixture is processed 1000 times of diluents, supply with above-mentioned multi-functional compounds, promptly supply with 1000 times of diluting solns, implement linked reaction with 4.75g/ minute speed with 0.00475g/ minute speed.

Mean residence time in the coupler reactor is 8.3 minutes.

Detect the pressure of the top exit of above-mentioned polymeric kettle, and control aperture regulon, so that this pressure is 0.9MPaG.

The mean residence time that is exported to the sample nozzle after the linked reaction from polymeric kettle is 18 minutes.

Active copolymer before the linked reaction is 70 ± 7 110 ℃ mooney viscosity (ML-I) and mobility scale thereof, and the branched conjugated diene polymer after this coupling is 123 ± 9 110 ℃ mooney viscosity (ML-C) and mobility scale thereof.

In addition, the weight-average molecular weight (Mw-C) of the branched conjugated diene polymer after the linked reaction is 750,000, and weight-average molecular weight is 2.8 with the ratio (Mw-C/Mn-C) of number-average molecular weight.

The linked reaction rate, be that the ratio of the adsorbed branched conjugated diene polymer of silica column is 35 quality %.

Likewise measure mooney viscosity and Mooney relaxation rate (MSR), 120 ℃ mooney viscosity ML1+4 is 113, and MSR is 0.473.

And then oil-filled, obtain oil-filled branched conjugated diene polymer (sample PC).In resulting branched conjugated diene polymer and polymeric kettle, confirm the generation of a little gel.

Among the embodiment 1, the deviation of the mooney viscosity of resulting branched conjugated diene polymer is few, and in addition, the linked reaction rate is also high.

In the comparative example 1; The position of automatic pressure valve is not to be arranged to be used for the pipe arrangement of discharging from coupler reactor; Be used for the pipe arrangement of discharging from polymeric kettle but be arranged at, thereby the mooney viscosity of resulting branched conjugated diene polymer reduces, the deviation of mooney viscosity is also big; In addition, the linked reaction rate and the degree of branching also reduce.

In the comparative example 2; Be exported to residence time of adding till the multi-functional compounds outside scope of the present invention from polymeric kettle, thereby the mooney viscosity of resulting branched conjugated diene polymer reduces, the deviation of mooney viscosity is also big; In addition, the linked reaction rate and the degree of branching also reduce.

With (sample PA)～(the sample PC) that as above makes, be oil-filled branched conjugated diene polymer as crude rubber, make rubber combination according to the proportioning shown in the below table 1.

[table 1]

About the starting material shown in the above-mentioned table 1, as follows.

(1) silicon-dioxide Ultrasil VN3:Evonik Degussa Japan Co., Ltd. makes

(2) SEAST KH:Cabot Japan K.K. manufacturing, SHOBLACK N339

(3) Si75:Evonik Degussa Japan Co., Ltd. makes

(4) SUNNOC N (WAX): the emerging chemical industry of imperial palace Co., Ltd. makes

(5) inhibitor 810NA: the emerging chemical industry of imperial palace Co., Ltd. makes, NOCRAC 810-NA

(6) accelerator CZ: the emerging chemical industry of imperial palace Co., Ltd. makes, NOCCELER CZ-G

(7) accelerator D: the emerging chemical industry of imperial palace Co., Ltd. makes, NOCCELER D

[method of manufacture of rubber combination]

Use possesses the banburying machine (0.3 liter of inner capacities) of temperature-control device; Mixing as first section, compounding raw materials rubber, weighting agent (silicon-dioxide and carbon black), organosilane coupler, oil, zinc white, Triple Pressed Stearic Acid under the condition of filling ratio 65%, rotor speed 50/57rpm.

At this moment, the temperature of control banburying machine obtains the crude rubber mixture 155 ℃～165 ℃ outflow temperatures (mixture).

Next, mixing as second section with the above-mentioned crude rubber mixture cool to room temperature that obtains, adds inhibitor thereafter, carries out mixingly once more, to improve the dispersion of silicon-dioxide, obtains rubber stock.In this case, also outflow temperature (mixture) is adjusted to 155 ℃～160 ℃ through the temperature control of mixing roll.

After the cooling, mixing as the 3rd section is with the mixing sulphur of open roll, the vulcanization accelerator that are set in 70 ℃.

With its moulding, vulcanize 160 ℃ of conditions with preset time, press vulcanization, obtain vulcanizate compositions as target.

Measure the rerum natura of above-mentioned rubber stock and vulcanizate compositions through following method, measure the result and be listed in the table below 2.

[measuring method of the rerum natura of rubber stock and vulcanizate compositions]

< (1) bound rubber (quality %) >

Rubber stock after the above-mentioned second section mixing operation termination of about 0.2g is sheared the square shape of written treaty 1mm, join Harris's cage (Ha リスかご, 100 order wire cloth systems), gravimetry.

In toluene soak 24 hour, implement drying treatment then, gravimetry thereafter.

By the amount calculating of non-solvent components and the amount of weighting agent bonded rubber, obtain and the ratio of weighting agent bonded rubber phase for the rubber mass in the initial rubber stock.

< (2) rubber stock mooney viscosity >

Mooney viscosity about the rubber stock after the above-mentioned second section mixing operation termination uses mooney's viscosimeter, according to JIS K6300-1, utilizes L type rotor, after 1 minute, makes its rotation with PM 2 commentaries on classics 130 ℃ of preheatings, measures the viscosity after 4 minutes.

If the value of mooney viscosity is little, judge that then the little energy, the processibility that consume when mixing are good.

< hardness of (3) vulcanizate compositions >

According to JIS K6253, the level pressure device " CL-150L type " of loading is used for the digital durometer " DD2-A type " that polymer gauge Co., Ltd. makes, measure sclerometer A type hardness tester.

< (4) are to the tension test of vulcanizate compositions >

Tension test method according to JIS K6251; Use No. 3 shapes of dumbbell shape, (the unit: MPa), 300% tensile stress (300%Mo) (unit: MPa), tensile strength (unit: MPa), cut off elongation (unit: %) when stretching of the tensile stress (100%Mo) when 100% of determination test sheet stretches.

Tensile strength, to cut off elongation high more, and it is good more then to judge.

< rebound resilience (%) of (5) vulcanizate compositions >

According to the LUPKE formula resiliency test method of JIS K6255, measure the rebound resilience of 0 ℃ and 50 ℃.

0 ℃ rebound resilience is used as anti-slippery, is the index of earth-catching property that the low more then judgement of rebound resilience is good more.

50 ℃ rebound resilience is used as the index of the rolling resistance property of tire, and the high more then judgement of rebound resilience is good more.

The heat generation of (6) vulcanizate compositions (℃)

Use Goodrich flexometer (Goodrich Flexometer), under the condition of rotating speed 1800rpm, 0.225 inch of stroke, 55 pounds of loads, measure.Measuring starting temperature is 50 ℃, representes heat generation with the temperature after 20 minutes and the difference of starting temperature.

Be worth more for a short time, judge that then heat generation is more excellent.

< mensuration of the viscoelastic property of (7) vulcanizate compositions >

Use the Ares test for viscoelastic machine of Rheometric Scientific corporate system, with helical pattern, at frequency 10Hz, respectively measure and change distortion under temperature (0 ℃ and the 50 ℃) condition, mensuration tan δ.

Need to prove; The tan δ (angle of loss tangent) that under the condition of low temperature (0 ℃), distortion 1%, measures is high more; Then judge anti-slippery, be that earth-catching property is good more; The tan δ (angle of loss tangent) that under the condition of high temperature (50 ℃), distortion 3%, measures is low more, and then magnetic hysteresis loss is few more, judges that the promptly low oil consumption property of rolling resistance property of tire is more excellent.

< wear resistant (index) of (8) vulcanizate compositions >

About wear resistant, the smart mechanism in use peace field is made manufacturing Akron rubber abrasion trier, according to JISK6264-2, measures the wear loss of 3000 commentaries on classics with TP A, load 44.1N.

In order to embodiment 1 100 o'clock exponential representation.

Index is high more, and then wear loss is few more, and it is good more to be judged as.

[table 2]

Embodiment/comparative example	Embodiment 1	Comparative example 1	Comparative example 2
				Polymer sample	PA	PB	PC
Bound rubber quality %	45	38	36
				The rubber stock mooney viscosity	74	65	60
Hardness A type	62	62	60
				Tension test
100％Mo MPa	2.1	2	1.9
				300％Mo MPa	10.1	9.2	8.9
Tensile strength MPa	20	19.4	17.6
				Cut off elongation %	500	480	470
0 ℃ of % of Rupke rebound resilience	10	10	10
				50 ℃ of % of Rupke rebound resilience	59	56.5	56
Goodrich is given birth to hot Δ T ℃	25	29	33
				Visco-elasticity ARES
Tan δ (0 ℃) 1% distortion	0.41	0.4	0.395
				Tan δ (50 ℃) 3% distortion	0.185	0.19	0.193
The Akron abrasion index	100	95	93

Embodiment 1, comparative example 1, comparative example 2 by above-mentioned table 2 can be known; Used the bound rubber amount height of the rubber stock of the branched conjugated diene polymer of making through the method for manufacture of this embodiment; The pyritous rebound resilience of vulcanizate compositions is high, and in addition, pyritous tan δ (angle of loss tangent) is low; Thereby magnetic hysteresis loss is few, and the promptly low oil consumption property of the rolling resistance property of tire is excellent.

In addition, the balance of low oil consumption property and anti-slippery (cryogenic tan δ) is also excellent, and then gives birth to heat and lack, and wear resistant is also good.

In the comparative example 1; The position of automatic pressure valve is not to be arranged to be used for the pipe arrangement of discharging from coupler reactor; Be used for the pipe arrangement of discharging from polymeric kettle but be arranged at, thereby the mooney viscosity of resulting multipolymer reduces, the deviation of mooney viscosity is also big; In addition, the linked reaction rate also reduces.

Therefore, the bound rubber amount is low, and the pyritous rebound resilience is low, and pyritous tan δ is high, thereby magnetic hysteresis loss is big, and the promptly low oil consumption property of the rolling resistance property of tire is poor.

In addition, the balance of low oil consumption property and anti-slippery (cryogenic tan δ) is also poor, and then Sheng Regao, and wear resistant is also poor.

In the comparative example 2; Be exported to residence time of adding till the multi-functional compounds outside scope of the present invention from polymeric kettle, thereby the mooney viscosity of resulting branched conjugated diene polymer reduces, the deviation of mooney viscosity is also big; In addition, the linked reaction rate also reduces.

Therefore, the bound rubber amount is low, and breaking tenacity is poor, and the pyritous rebound resilience is low, and pyritous tan δ is high, thereby magnetic hysteresis loss is big, and the promptly low oil consumption property of the rolling resistance property of tire is poor.In addition, the balance of low oil consumption property and anti-slippery (cryogenic tan δ) is also poor, and then Sheng Regao, and wear resistant is also poor.

The Japanese patent application that the application submitted to the Japan special permission Room based on May 13rd, 2009 (the special 2009-116541 of hope of Japan) is introduced this specification sheets with the form of reference with its content.

Industrial applicibility

The method of manufacture of branched conjugated diene polymer of the present invention is suitable for tyre rubber, vibration-proof rubber, footwear as formation and has industrial applicibility with the manufacturing technology of the branched conjugated diene polymer of the rubber combination of rubber etc.

Claims

1. the method for manufacture of a branched conjugated diene polymer, this method comprises following operation:

The desolventizing operation,

Through said aperture regulon with the pressure-controlling in the exit of said polymeric kettle at 0.5MPaG～2MPaG.

2. the method for manufacture of branched conjugated diene polymer as claimed in claim 1, wherein, said coupler reactor is the tank reactor of 0.5%～50% capacity that possesses rotation mixer and have the capacity of said polymeric kettle.

3. according to claim 1 or claim 2 the method for manufacture of branched conjugated diene polymer, wherein, said polymeric kettle is the tank reactor that possesses stirrer,

4. like the method for manufacture of each described branched conjugated diene polymer of claim 1～3, this method also comprises following operation:

5. like the method for manufacture of each described branched conjugated diene polymer of claim 1～4, wherein,, use a tank reactor that possesses stirrer as said polymeric kettle.

6. like the method for manufacture of each described branched conjugated diene polymer of claim 1～5, wherein,, use intramolecularly to have the amino polyepoxides of uncle as said multi-functional compounds.

7. like the method for manufacture of each described branched conjugated diene polymer of claim 1～6; Wherein, Said multi-functional compounds is amino and constitute with oligopolymer composition more than the dimer of the low molecular compound that contains glycidyl-amino of the glycidyl of this amino bonded and this low molecular compound that contains glycidyl-amino more than 3 by having 2 above uncles in the molecule

With respect to said multi-functional compounds's total amount, said low molecular compound is 75 quality %～95 quality %, and said oligopolymer is 25 quality %～5 quality %.

8. like the method for manufacture of each described branched conjugated diene polymer of claim 1～7, wherein, said reactive polymer or said active copolymer and said multi-functional compounds's reaction ratio is 10 quality %～80 quality %.

9. like the method for manufacture of each described branched conjugated diene polymer of claim 1～8; Wherein, The MWD that said branched conjugated diene polymer is measured through GPC (GPC) is unimodal; In the conversion molecular weight based on PS, weight-average molecular weight is 500,000～2,000,000.

10. like the method for manufacture of each described branched conjugated diene polymer of claim 1～9, wherein, said branched conjugated diene polymer is the multipolymer of conjugated diene compound and vinyl aromatic compounds,

The vinyl aromatic compounds of the strand joint that the ozone decomposition method is produced is more than 40% with respect to said vinyl aromatic compounds total amount, and the above vinyl aromatic compounds of 8 chain links is below 5% with respect to said vinyl aromatic compounds total amount.