CN101511884A - Conjugated diene polymer and manufacturing method thereof, conjugated diene polymer compositions and manufacturing method thereof - Google Patents
Conjugated diene polymer and manufacturing method thereof, conjugated diene polymer compositions and manufacturing method thereof Download PDFInfo
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- CN101511884A CN101511884A CNA2006800558435A CN200680055843A CN101511884A CN 101511884 A CN101511884 A CN 101511884A CN A2006800558435 A CNA2006800558435 A CN A2006800558435A CN 200680055843 A CN200680055843 A CN 200680055843A CN 101511884 A CN101511884 A CN 101511884A
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
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Abstract
It is intended to provide a conjugated diene polymer, a process for producing the conjugated diene polymer, a conjugated diene polymer composition and a process for producing the conjugated diene polymer composition. The conjugated diene polymer is a conjugated diene polymer having a conjugated diene-based monomer unit and a group represented by the formula (I), wherein assuming the whole area of the molecular weight distribution curve obtained by gel permeation chromatography as 100%, the peak area of the molecular weight peak at the lowest molecular weight is 50% or more. [In the formula, R<1> and R<2> each independently represent a hydrocarbon group, a hydrocarbon oxy group or a hydroxyl group, m represents an integer of 0 to 10, and A<1> represents a polar functional group free of an active hydrogen atom.]
Description
Technical field
The present invention relates to the manufacture method of manufacture method, conjugated diolefine polymer composition and the conjugated diolefine polymer composition of conjugated diolefine polymer, conjugated diolefine polymer.
Background technology
In recent years,, save fuel oil for the automobile strong request and take,, also require to save fuel oil and take excellent performance even for the polymer composition that is used for automobile tyre because the concern of environmental problem is constantly promoted.As the polymer composition that doughnut is used, use contains the polymer composition of polyhutadiene or packing materials such as butadiene-styrene copolymer equiconjugate diolefinic polymer, carbon black or silicon-dioxide etc.For example known have: a kind of polymer composition that has used the polymkeric substance that conjugated diolefine polymer is carried out modification with the tin halides compound and obtain, wherein, described conjugated diolefine polymer is to make divinyl and vinylbenzene carry out copolymerization with lithium alkylide as polymerization starter (for example to form, Japanese kokai publication sho 60-255838 communique, USP4,742,124).
In addition, take well behaved polymer composition as saving fuel oil, proposition has: the polymer composition that has used the polymkeric substance that conjugated diolefine polymer is carried out modification with the acrylamide with dialkyl amido and obtain, wherein, described conjugated diolefine polymer is as polymerization starter divinyl and vinylbenzene to be carried out copolymerization with lithium alkylide to form (for example, Japanese kokai publication hei 1-217047 communique, USP5,189,109); Used the polymer composition of the polymkeric substance that conjugated diolefine polymer is carried out modification with the organoalkoxysilane with dialkyl amido and obtain, wherein, described conjugated diolefine polymer is to come the polymerization divinyl or divinyl and vinylbenzene are carried out copolymerization (for example to form as polymerization starter with lithium alkylide, Japanese kokai publication sho 63-186748 communique, USP4,957,976, TOHKEMY 2005-290355 communique, US2005/0203251A1) etc.
Summary of the invention
But the polymer composition of above-mentioned existing use conjugated diolefine polymer is particularly using under the situation of silicon-dioxide as weighting agent, can not satisfy fully at saving fuel oil expense aspect of performance.
In view of this situation, the problem that the present invention will solve provide cooperate weighting agent, particularly cooperate the manufacture method that can access the conjugated diene copolymer of saving fuel oil expense polymers of excellent properties composition, conjugated diolefine polymer under the situation of silicon-dioxide, cooperate conjugated diolefine polymer and silicon-dioxide and the polymer composition that obtains and the manufacture method of polymer composition.
The inventor carries out deep research in order to solve above-mentioned problem, thereby has finished the present invention.
Promptly, the invention provides a kind of conjugated diolefine polymer, it has monomeric unit and the group of being represented by formula (I) based on conjugated diolefine, wherein, to be made as 100% o'clock by the total area of the molecular weight distribution curve that obtains with gel permeation chromatography, the peak area at the molecular weight chromatography peak of lowest molecular weight side is more than 50%
[in the formula, R
1And R
2Represent alkyl,-oxyl or hydroxyl respectively independently, m represents 0～10 integer, A
1Expression does not have the polar functional group of active hydrogen].
The invention provides the manufacture method of conjugated diolefine polymer with operation 1 and 2.
Operation 1: in the presence of base metal catalysts, in hydrocarbon solvent, make the monomer polymerization that contains conjugated diolefine, had alkali-metal conjugated diolefine polymer endways from this catalyzer;
Operation 2: one time (a Time To) adds the silicon compound by formula (IV) expression in the hydrocarbon solution of this conjugated diolefine polymer, with this silicon compound this conjugated diolefine polymer carried out modification.
[in the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen].
In addition, the invention provides the conjugated diolefine polymer composition that contains above-mentioned conjugated diolefine polymer and silicon-dioxide.
In addition, the invention provides the manufacture method of conjugated diolefine polymer composition with operation 1,2 and 3.
Operation 1: in the presence of base metal catalysts, in hydrocarbon solvent, make the monomer polymerization that contains conjugated diolefine, had alkali-metal conjugated diolefine polymer endways from this catalyzer;
Operation 2: in the hydrocarbon solution of this conjugated diolefine polymer, once add silicon compound, this conjugated diolefine polymer is carried out modification with this silicon compound by formula (IV) expression; And
Operation 3: cooperate the conjugated diolefine polymer and the silicon-dioxide that obtain by operation 2.
[in the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen].
Description of drawings
Fig. 1 represents the example of the molecular weight distribution curve of polymkeric substance.
Fig. 2 represents the molecular weight chromatography peak of lowest molecular weight side and the marginal example of adjacent chromatographic peak.
Fig. 3 represents the example of area at the molecular weight chromatography peak of lowest molecular weight side.
Embodiment
Conjugated diolefine polymer of the present invention, be to have based on the monomeric unit of conjugated diolefine and the conjugated diolefine polymer of the group of representing by formula (I), wherein, to be made as 100% o'clock by the total area of the molecular weight distribution curve that obtains with gel permeation chromatography, the peak area at the molecular weight chromatography peak of lowest molecular weight side is more than 50%
[in the formula, R
1And R
2Represent alkyl,-oxyl or hydroxyl respectively independently, m represents 0～10 integer, A
1Expression does not have the polar functional group of active hydrogen].
As conjugated diolefine, can enumerate: 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene etc., they can be a kind, also can be for more than 2 kinds.Acquisition easiness viewpoint from make is preferably 1,3-butadiene, isoprene.
R
1And R
2Represent alkyl,-oxyl or hydroxyl respectively independently.
As alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl etc.In addition, as alkyl, also can be the group that constitutes by the polymer chains such as polymer chain that have based on the monomeric unit of conjugated diolefine.As these alkyl, be preferably methyl, ethyl.
As-oxyl, can enumerate: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy etc.As these-oxyls, be preferably methoxyl group, oxyethyl group.
As R
1And R
2, save the viewpoint that fuel oil takes performance from improving, be preferably-oxyl, more preferably methoxyl group, oxyethyl group.
M represents 0～10 integer, saves the viewpoint that fuel oil takes performance from improving, and is preferably more than 3, and the viewpoint of the economy when making from improving is preferably below 4.
A
1Expression does not have the polar functional group of active hydrogen, can enumerate by the group of formula (II) expression, by the group of formula (III) expression etc.
[in the formula, R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively, R
3And R
4Also can be] in conjunction with forming ring structure.
[in the formula, the carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent, R
5Expression hydrogen or carbonatoms are 1～6 alkyl].
R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively.
As alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-hexyl, cyclohexyl, phenyl, methoxymethyl, methoxy ethyl, methoxy-propyl, methoxyl group butyl, methoxyl group amyl group, ethoxyl methyl, ethoxyethyl group, ethoxycarbonyl propyl.Oxyethyl group butyl, oxyethyl group amyl group, trimethyl silyl, t-butyldimethylsilyl etc.
R
3And R
4Also can in conjunction with, as R
3And R
4The group of be combined into can be enumerated: alkylidene groups such as trimethylene, tetramethylene, pentamethylene, hexa-methylene; Oxyalkylenes such as oxygen diethylidene, oxygen dipropylene; By-CH
2CH
2-NH-CH
2The group of-expression, by-CH
2CH
2Nitrogen-containing groups such as the group that-N=CH-represents etc.
As R
3And R
4, be preferably methyl, ethyl, n-propyl, trimethyl silyl.In addition, as R
3And R
4The group of be combined into is preferably by-CH
2CH
2-NH-CH
2The group of-expression, by-CH
2CH
2The group that-N=CH-represents etc.
The carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent.
As alkyl, can enumerate: ethylidene, propylidene, butylidene, 1-oxygen ethylidene, 1-oxygen trimethylene, 1-oxygen tetramethylene etc.
As X, be preferably 1-oxygen trimethylene.
R
5Expression hydrogen or carbonatoms are 1～6 alkyl.
As alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-hexyl, cyclohexyl, phenyl etc.
As R
5Be preferably hydrogen or methyl.
As group, can enumerate: non-annularity amino, cyclic amino by formula (II) expression.
As non-annularity amino, can enumerate: dimethylamino, diethylamino, ethylmethylamino, two (methoxymethyl) amino, two (methoxy ethyls) amino, two (ethoxyl methyls) amino, two (ethoxyethyl groups) amino, two (t-butyldimethylsilyl) amino, two (trimethyl silyl) amino etc.
As cyclic amino, can enumerate: 1-pyridine alkyl, piperidyl, 1-hexamethyleneimino (ヘ キ サ メ チ レ Application イ ミ ノ), 1-heptamethylene imino-(ヘ プ メ チ レ Application イ ミ ノ), 1-eight methylene radical imino-s (オ Network メ チ レ Application イ ミ ノ), 1-decamethylene imino-(デ カ メ チ レ Application イ ミ ノ), 1-ten dimethylene imino-s (De デ カ メ チ レ Application イ ミ ノ), 1-ten tetramethylene imino-s (テ ト ラ デ カ メ チ レ Application イ ミ ノ), 1-18 methylene radical imino-s 1-polymethylene imino-s (Port リ メ チ レ Application イ ミ ノ) such as (オ Network デ カ メ チ レ Application イ ミ ノ).In addition,, can enumerate: 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidyl, 1-piperazinyl, morpholinyl etc. as cyclic amino.
As group, can enumerate: 3-glycidoxy ethyl, 3-glycidoxy propyl group etc. by formula (III) expression.
As A
1,, be preferably group, more preferably non-annularity amino by formula (II) expression from economy and easy acquired consideration.
Conjugated diolefine polymer of the present invention except monomeric unit (conjugated diene unit) and the group by formula (I) expression based on conjugated diolefine, can also have based on other monomeric monomeric units.
As other monomer, can enumerate: aromatic vinyl, ethene nitrile, esters of unsaturated carboxylic acids etc.
As aromatic vinyl, can enumerate: vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl naphthalene, Vinylstyrene, trivinylbenzene, divinyl naphthalene.
As the ethene nitrile, can enumerate: vinyl cyanide etc.
In addition, as esters of unsaturated carboxylic acids, can enumerate: methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi etc.
Among them,, be preferably vinylbenzene from easy acquired viewpoint.
Conjugated diolefine polymer of the present invention, from improving the viewpoint of intensity, preferably has monomeric unit (aromatic vinyl unit) based on aromatic vinyl, as the unitary content of aromatic vinyl, when conjugated diene unit and the unitary total amount of aromatic vinyl are made as 100 weight %, be preferably 10 weight % above (content of conjugated diene unit is that 90 weight % are following), more preferably 15 weight % above (content of conjugated diene unit is that 85 weight % are following).In addition, save the viewpoint that fuel oil takes performance from improving, the unitary content of aromatic vinyl is preferably 50 weight % following (content of conjugated diene unit is more than the 50 weight %), more preferably 45 weight % following (content of conjugated diene unit is that 55 weight % are following).
Conjugated diolefine polymer of the present invention, save the viewpoint that fuel oil takes performance from improving, preferably the total area at the molecular weight distribution curve that will obtain by gel permeation chromatography was made as 100% o'clock, and the peak area at the molecular weight chromatography peak of the conjugated diolefine polymer of lowest molecular weight side is the conjugated diolefine polymer more than 50%.This peak area is more preferably more than 55%, more preferably more than 60%.In addition, from improving the viewpoint of mixing processibility, this peak area is preferably below 95%, more preferably below 90%.In addition, in the molecular weight distribution curve that obtains by gel permeation chromatography, the curve of the high molecular side at the molecular weight chromatography peak of lowest molecular weight side (below be designated as " chromatographic peak L ") is under the situation that does not drop to baseline (Fig. 1), promptly under chromatographic peak L and adjacent chromatographic peak eclipsed situation, minimal point from the curve between the summit of the summit of chromatographic peak L and adjacent chromatographic peak, setting will be the area (Fig. 3) of low-molecular-weight zone as chromatographic peak L apart from the boundary line with respect to the vertical boundary line of baseline (Fig. 2).
Mooney viscosity (the ML of conjugated diolefine polymer of the present invention
1+4), from improving the viewpoint of physical strength, be preferably more than 10, more preferably more than 20.In addition, from improving the viewpoint of processibility, be preferably below 200, more preferably below 150.Mooney viscosity (ML
1+4) be to measure down at 100 ℃ according to JIS K6300 (1994).
The vinyl bonds amount of conjugated diolefine polymer of the present invention when the content with conjugated diene unit is made as 100 moles of %, is taken the viewpoint of performance from improve saving fuel oil, is preferably 70 moles below the %, more preferably 60 moles below the %.In addition,, be preferably 10 moles more than the %, more preferably 15 moles more than the % from improving the viewpoint of grabbing (Network リ Star プ) performance of tire.The vinyl bonds amount is to be 910cm by infrared spectrographic method by the absorption peak of vinyl
-1Near absorption intensity is tried to achieve.
As the manufacture method of conjugated diolefine polymer of the present invention, can enumerate the method that for example has following operation 1 and operation 2.
Operation 1: in the presence of base metal catalysts, in hydrocarbon solvent, make the monomer polymerization that contains conjugated diolefine, had alkali-metal conjugated diolefine polymer endways from this catalyzer; And
Operation 2: in the hydrocarbon solution of this conjugated diolefine polymer, once add silicon compound, this conjugated diolefine polymer is carried out modification with this silicon compound by formula (IV) expression.
[in the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen].
As the base metal catalysts that uses in the operation 1, can enumerate: the complex compound of basic metal, organic alkali metal compound, basic metal and polar compound, have alkali-metal oligopolymer etc.
As basic metal, can enumerate: lithium, sodium, potassium, rubidium, caesium etc.
As organic alkali metal compound, can enumerate: lithium ethide, the n-propyl lithium, the sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, uncle's octyl group lithium, positive decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyllithium, the cyclohexyl lithium, 4-cyclopentyl lithium, the dimethylaminopropyl lithium, the diethylamino propyl lithium, tertiary butyl dimethyl Si base propyl lithium, N-morpholinyl propyl lithium, the hexa-methylene imide li, the tetramethyleneimine lithium, the piperidines lithium, eight methylene radical imide lis, ten dimethylene imide lis, 1,4-two lithiums-butene-2, naphthalene sodium, biphenyl sodium, naphthalene potassium etc.
As the complex compound of basic metal and polar compound, can enumerate: potassium-tetrahydrofuran complex, potassium-diethoxyethane complex compound etc.
In addition, as having alkali-metal oligopolymer, can enumerate: the sodium salt of alpha-methyl styrene tetramer.
Among them, be preferably organolithium compound or organosiloxane compound, more preferably carbonatoms is 2～20 organolithium compound or organosiloxane compound.
The hydrocarbon solvent that uses in operation 1 is the solvent that makes the base metal catalysts inactivation, can enumerate: aliphatic hydrocarbon, aromatic hydrocarbons, clicyclic hydrocarbon etc.
As aliphatic hydrocarbon, can enumerate: propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, propylene, 1-butylene, iso-butylene, trans-2-butene, cis-2-butene, 1-amylene, 2-amylene, 1-hexene, 2-hexene etc.
As aromatic hydrocarbons, can enumerate: benzene,toluene,xylene, ethylbenzene.
In addition, as clicyclic hydrocarbon, can enumerate: pentamethylene, hexanaphthene etc.
They can be used singly or in combination of two or more thereof.Among them, preferred carbonatoms is 2～12 hydrocarbon.
In operation 1, make the monomer polymerization that contains conjugated diolefine, be manufactured on end and have alkali-metal conjugated diolefine polymer from above-mentioned base metal catalysts.
As conjugated diolefine, can enumerate: 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene.They can be used singly or in combination of two or more thereof.Among them,, be preferably 1,3-butadiene, isoprene from the viewpoint of easy acquisition.
In operation 1, can carry out the independent polymerization of conjugated diolefine, also can make up conjugated diolefine and other monomers carry out polymerization.
As other monomer, can enumerate: aromatic vinyl, ethene nitrile, esters of unsaturated carboxylic acids etc.
As aromatic vinyl, can illustration: vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl naphthalene, Vinylstyrene, trivinylbenzene, divinyl naphthalene.
As the ethene nitrile, can enumerate: vinyl cyanide etc.
As esters of unsaturated carboxylic acids, can enumerate: methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi etc.
Among them, the viewpoint from easy acquisition is preferably vinylbenzene.
The polymerization of operation 1, can the conditioning agent of the vinyl bonds amount of conjugated diene unit, in the conjugated diolefine polymer chain conjugated diene unit with based on the conditioning agent of the distribution of the monomeric monomeric unit beyond the conjugated diolefine (below be referred to as " conditioning agent ") etc. in the presence of carry out.
As conditioning agent, can enumerate: ether compound, tertiary amine, phosphine compound etc.
As ether compound, can enumerate: tetrahydrofuran (THF), tetrahydropyrans, 1, cyclic ethers such as 4-diox; Aliphatic monoethers such as Anaesthetie Ether, dibutyl ether; Aliphatics diether such as ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol diethyl ether, Diethylene Glycol dibutyl ether; Aromatic ether such as diphenyl ether, methyl-phenoxide etc.
As tertiary amine, can enumerate: triethylamine, tripropyl amine, Tributylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N-Diethyl Aniline, pyridine, quinoline etc.
In addition, as phosphine compound, can enumerate: trimethyl-phosphine, triethyl phosphine, triphenylphosphine etc.
They can use separately, also can make up more than 2 kinds and use.
The polymerization temperature of operation 1 is generally 30～100 ℃, is preferably 35～65 ℃, and polymerization time is generally 10 minutes～and 5 hours.
In operation 2, in the hydrocarbon solution that has alkali-metal conjugated diolefine polymer endways that obtains by operation 1, add silicon compound by formula (IV) expression, with silicon compound conjugated diolefine polymer is carried out modification.
[in the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen].
R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl.R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, preferred R
6, R
7And R
8It all is the-oxyl of carbonatoms 1～4.
As R
6, R
7And R
8Carbonatoms be 1～4 alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl.As these alkyl, be preferably methyl or ethyl.
In addition as R
1, R
2And R
3Carbonatoms be 1～4-oxyl, can enumerate: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy.As these-oxyls, be preferably methoxyl group or oxyethyl group.
N represents 0～10 integer.Save the viewpoint that fuel oil takes performance from improving, be preferably more than 3, the viewpoint of the economy when making from improving is preferably below 4.
A
2Expression does not have the polar functional group of active hydrogen, can enumerate by the group of formula (II) expression, by the group of formula (III) expression etc.
[in the formula, R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively, R
3And R
4Also can be] in conjunction with forming ring structure.
[in the formula, the carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent, R
5Expression hydrogen or carbonatoms are 1～6 alkyl].
A
2In, by the group of formula (II) expression, by group, the R of formula (III) expression
3, R
4And R
5And the illustration of X, respectively with A
1In the group by formula (II) expression, by group, the R of formula (III) expression
3, R
4And R
5And the illustration of X is identical, by the group of formula (II) expression, by group, the R of formula (III) expression
3, R
4And R
5And the preferred group of X, respectively with A
1In the group by formula (II) expression, by group, the R of formula (III) expression
3, R
4And R
5And the preferred group of X is identical.In addition, A
2Preferred group and A
1Preferred group identical.
For for the silicon compound of formula (IV) expression, as A
2For compound, can enumerate: [3-(dimethylamino) propyl group] Trimethoxy silane by the non-annularity amino of formula (II) expression, [3-(diethylamino) propyl group] Trimethoxy silane, [3-(dimethylamino) propyl group] triethoxyl silane, [3-(diethylamino) propyl group] triethoxyl silane, [(3-methyl-3-ethylamino) propyl group] Trimethoxy silane, [(3-methyl-3-ethylamino) propyl group] triethoxyl silane, [3-(dimethylamino) propyl group] methyl dimethoxysilane, [3-(diethylamino) propyl group] methyl dimethoxysilane, [3-(dimethylamino) propyl group] ethyl dimethoxy silane, [3-(diethylamino) propyl group] ethyl dimethoxy silane, [3-(dimethylamino) propyl group] dimethyl methyl TMOS, [3-(dimethylamino) propyl group] diethyl methoxy silane, [3-(diethylamino) propyl group] dimethyl methyl TMOS, [3-(diethylamino) propyl group] diethyl methoxy silane, [(3-methyl-3-ethylamino) propyl group] methyl dimethoxysilane, [(3-methyl-3-ethylamino) propyl group] ethyl dimethoxy silane, [3-(dimethylamino) propyl group] methyldiethoxysilane, [3-(diethylamino) propyl group] methyldiethoxysilane, [3-(dimethylamino) propyl group] ethyl diethoxy silane, [3-(diethylamino) propyl group] ethyl diethoxy silane, [3-(dimethylamino) propyl group] dimethylethoxysilane, [3-(dimethylamino) propyl group] diethyl Ethoxysilane, [3-(diethylamino) propyl group] dimethylethoxysilane, [3-(diethylamino) propyl group] diethyl Ethoxysilane, [(3-methyl-3-ethylamino) propyl group] methyldiethoxysilane, [(3-methyl-3-ethylamino) propyl group] ethyl diethoxy silane, [3-(dimethoxy-methyl amino) propyl group] Trimethoxy silane, [3-(dimethoxy-ethyl amino) propyl group] Trimethoxy silane, [3-(dimethoxy-methyl amino) propyl group] triethoxyl silane, [3-(dimethoxy-ethyl amino) propyl group] triethoxyl silane, [3-(diethoxy ethylamino) propyl group] Trimethoxy silane, [3-(diethoxymethyl amino) propyl group] Trimethoxy silane, [3-(diethoxy ethylamino) propyl group] triethoxyl silane, [3-(diethoxymethyl amino) propyl group] triethoxyl silane, 3-[two (trimethyl silyl) amino] and propyl group } Trimethoxy silane, 3-[two (trimethyl silyl) amino] and propyl group } triethoxyl silane, 3-[two (t-butyldimethylsilyl) amino] and propyl group } Trimethoxy silane, 3-[two (t-butyldimethylsilyl) amino] and propyl group } triethoxyl silane, 3-[two (trimethyl silyl) amino] and propyl group } methyl dimethoxysilane, 3-[two (trimethyl silyl) amino] and propyl group } methyldiethoxysilane, 3-[two (t-butyldimethylsilyl) amino] and propyl group } methyl dimethoxysilane, 3-[two (t-butyldimethylsilyl) amino] and propyl group } methyldiethoxysilane, 3-[two (trimethyl silyl) amino] and propyl group } the dimethyl methyl TMOS, 3-[two (trimethyl silyl) amino] and propyl group } dimethylethoxysilane, 3-[two (t-butyldimethylsilyl) amino] and propyl group } the dimethyl methyl TMOS, 3-[two (t-butyldimethylsilyl) amino] propyl group }, [3-(ethylmethylamino) propyl group] Trimethoxy silane, [3-(ethylmethylamino) propyl group] triethoxyl silane, [3-(ethylmethylamino) propyl group] methyl dimethoxysilane, [3-(ethylmethylamino) propyl group] ethyl dimethoxy silane, [3-(diethylmethyl amino) propyl group] methyldiethoxysilane, [3-(ethylmethylamino) propyl group] ethyl diethoxy silane etc.
As A
2For silicon compound by the non-annularity amino of formula (II) expression, save the viewpoint that fuel oil takes from improving, be preferably [3-(diethylin) propyl group] Trimethoxy silane, [3-(dimethylamino) propyl group] triethoxyl silane.Wherein, from acquired and prolonged preservation stability that when saving the fuel oil expense, makes compound and the viewpoint of depositing, be preferably [3-(diethylamino) propyl group] methyl dimethoxysilane.
For for the silicon compound of formula (IV) expression, as A
2Be compound by the cyclic amino of formula (II) expression, can enumerate: 3-morpholine propyl trimethoxy silicane, 3-morpholine propyl-triethoxysilicane, 3-morpholine propyl group methyl dimethoxysilane, 3-morpholine propyl group ethyl dimethoxy silane, 3-morpholine propyl group methyldiethoxysilane, 3-morpholine propyl group ethyl diethoxy silane, 3-piperidyl propyl trimethoxy silicane, 3-piperidyl propyl-triethoxysilicane, 3-piperidyl propyl group methyl dimethoxysilane, 3-piperidyl propyl group ethyl dimethoxy silane, 3-piperidyl propyl group methyldiethoxysilane, 3-piperidyl propyl group ethyl diethoxy silane, N-(3-trimethoxy-silylpropyl)-4, the 5-glyoxalidine, N-(3-triethoxysilylpropyltetrasulfide)-4, the 5-glyoxalidine, N-(3-trimethoxy-silylpropyl)-4, the 5-imidazoles, N-(3-triethoxysilylpropyltetrasulfide)-4, the 5-imidazoles, 3-hexamethyleneimino propyl trimethoxy silicane, 3-hexamethyleneimino propyl-triethoxysilicane, 3-hexamethyleneimino propyl group methyl dimethoxysilane, 3-hexamethyleneimino propyl group ethyl dimethoxy silane, 3-hexamethyleneimino propyl group methyldiethoxysilane, 3-hexamethyleneimino propyl group ethyl diethoxy silane etc.
As A
2Be silicon compound by the cyclic amino of formula (II) expression, save the viewpoint that fuel oil takes from improving, be preferably N-(3-trimethoxy-silylpropyl)-4,5-glyoxalidine, N-(3-triethoxysilylpropyltetrasulfide)-4,5-glyoxalidine, N-(3-trimethoxy-silylpropyl)-4,5-imidazoles, N-(3-triethoxysilylpropyltetrasulfide)-4, the 5-imidazoles.
For the silicon compound of formula (IV) expression, as A
2Be silicon compound by the group of formula (III) expression, can illustration: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group ethyl dimethoxy silane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group ethyl diethoxy silane etc.
As A
2Be silicon compound, save fuel oil and take the viewpoint of performance and the acquisition easiness of raising compound, the viewpoint of prolonged preservation stability, be preferably (3-glycidoxy propyl group) Trimethoxy silane from improving by the group of formula (III) expression.
In operation 2, add silicon compound, carry out next time at the state that stirs hydrocarbon solution by formula (IV) expression.The interpolation speed of silicon compound is saved the viewpoint (viewpoint of the area of the chromatographic peak L of raising conjugated diolefine polymer) that fuel oil takes performance from improving, and is preferably 6 mmole/second/m in the per unit volume of hydrocarbon solvent and the time per unit
3More than, be preferably 10 mmole/second/m
3More than.In addition, from improving the viewpoint of operability, interpolation speed is preferably 10000 mmole/second/m
3Below.
The addition of silicon compound, in per 1 mole of the basic metal of the base metal catalysts that in operation 1, uses, save the viewpoint (viewpoint of the area of the chromatographic peak L of raising conjugated diolefine polymer) that fuel oil takes performance from improving, be preferably more than 0.5 mole, more preferably more than 0.8 mole.In addition, the viewpoint of the economy when making from improving is preferably below 10 moles, more preferably below 2 moles.
Silicon compound can dissolve in tetrahydrofuran (THF), hexane etc. makes the solvent of base metal catalysts inactivation, and adds in the hydrocarbon solution with the form of the solution that obtains thus.
As the concentration of adding the conjugated diolefine polymer in the silicon compound hydrocarbon solution before, save the viewpoint (viewpoint of the area of the chromatographic peak L of raising conjugated diolefine polymer) that fuel oil takes performance from improving, be preferably below the 30 weight %, more preferably below the 20 weight %.In addition, from the viewpoint of boosting productivity, be preferably more than the 5 weight %, more preferably more than the 10 weight %.
The stirring velocity of the hydrocarbon solution during as the interpolation silicon compound, save the viewpoint (viewpoint of the area of the chromatographic peak L of raising conjugated diolefine polymer) that fuel oil takes performance from improving, be preferably more than the 30rpm, more preferably more than the 50rpm, more preferably more than the 70rpm.In addition, from improving the viewpoint of economy, be preferably below the 400rpm, more preferably below the 300rpm, more preferably below the 200rpm.In addition, the temperature of the hydrocarbon solution during as the interpolation silicon compound is generally 35～65 ℃.
Preferably after adding silicon compound, hydrocarbon solution is stirred.As stirring velocity, be generally more than the 100rpm, be generally more than 35 ℃ as temperature, as the time be generally 1 second～30 minutes.
In addition, before or after the silicon compound that adds by formula (IV) expression, on the end that obtains by operation 1, have in the hydrocarbon solution of alkali-metal conjugated diolefine polymer, also can add the coupler that is expressed from the next.
R
9 aML
4-a
(in the formula, R
9Expression alkyl, alkenyl, cycloalkenyl group or aromatic hydrocarbyl, M represents Siliciumatom or tin atom, L represents halogen atom, a represents 0～2 integer).
As the coupler of representing by above-mentioned formula, can enumerate: silicon tetrachloride, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane, tin tetrachloride, methyl tin trichloride, dimethyltin chloride, trimethyltin chloride etc.
The addition of coupler, in per 1 mole of the basic metal of base metal catalysts, the viewpoint from the mixing processibility that improves conjugated diolefine polymer is preferably more than 0.03 mole, more preferably more than 0.05 mole.In addition, save the viewpoint that fuel oil takes performance, be preferably below 0.4 mole, more preferably below 0.3 mole from improving.
Conjugated diolefine polymer, can by known recovery method, for example (1) in the hydrocarbon solution of conjugated diolefine polymer, add the method for peptizer, (2) add steam in the hydrocarbon solution of conjugated diolefine polymer method, reclaim the hydrocarbon solution of the conjugated diolefine polymer after the processing of operation 2.The conjugated diolefine polymer that reclaims can carry out drying with known drying machines such as conveyor dryer or extrusion type drying machines.
Conjugated diolefine polymer of the present invention also can cooperate other polymerization composition or additive etc. to make the conjugated diolefine polymer composition and use.
As other component of polymer, can enumerate: existing styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene isoprene copolymer rubber, isoprene-isobutylene rubber etc.In addition, also can enumerate: natural rubber, ethylene-propylene copolymer, ethylene-octene copolymer etc.These component of polymer also can make up 2 kinds with on use.
As additive, can use known additive, can illustration: vulcanizing agents such as sulphur; Vulcanization accelerators such as thiazoles vulcanization accelerator, thiurams vulcanization accelerator, sulfinylamines vulcanization accelerator; Vulcanization activator such as stearic acid, zinc oxide; Organo-peroxide; Weighting agents such as silicon-dioxide, carbon black, lime carbonate, talcum; Silane coupling agent; Extension oil; Processing aid; Antiaging agent; Lubricant.
In using conjugated diolefine polymer of the present invention, be combined with under the situation of conjugated diolefine polymer composition of weighting agent, preferably use silicon-dioxide as weighting agent.
Make the conjugated diolefine polymer method for compositions as in conjugated diolefine polymer of the present invention, cooperating other component of polymer or additive to wait, can use known method, for example carry out mixing method by roller or the so known mixing machine of Banbury mixer.
When being combined with the conjugated diolefine polymer composition of silicon-dioxide in making conjugated diolefine polymer of the present invention, the use level of silicon-dioxide is generally 10～150 weight parts.In addition, when the use level with conjugated diolefine polymer of the present invention is made as 100 weight parts, save the viewpoint that fuel oil takes performance from improving, use level is preferably more than 20 weight parts, more preferably more than 30 weight parts.In addition, from improving the viewpoint of reinforcement, be preferably below 120 weight parts, more preferably below 100 weight parts.
When in conjugated diolefine polymer of the present invention, cooperating other component of polymer, the use level of conjugated diolefine polymer of the present invention, save the viewpoint that fuel oil takes performance from improving, when the total use level with component of polymer is made as 100 weight parts, be preferably more than 10 weight parts, more preferably more than 20 weight parts.
When in conjugated diolefine polymer of the present invention, cooperating the weighting agent beyond the silicon-dioxide, the use level of the weighting agent beyond the silicon-dioxide, when the total use level with weighting agent is made as 100 weight parts, save the viewpoint that fuel oil takes performance from improving, be preferably below 50 weight parts, more preferably below 30 weight parts.In addition, from improving the viewpoint of reinforcement, be preferably more than 1 weight part, more preferably more than 3 weight parts.
As the manufacture method of the composition that is combined with conjugated diolefine polymer of the present invention and silicon-dioxide, for example can enumerate: the manufacture method that except above-mentioned operation 1 and operation 2, also has following operation 3.
Operation 3: cooperate the conjugated diolefine polymer and the silicon-dioxide that obtain by operation 2.
In operation 3, also can cooperate other component of polymer or other additive etc.As the fitting method in the operation 3, can use known method, for example each composition be carried out mixing method by roller or the so known mixing machine of Banbury mixer.
As the mixing condition of operation 3, during additive beyond cooperating vulcanizing agent and vulcanization accelerator, melting temperature is generally 50～200 ℃, is preferably 80～190 ℃, and mixing time is generally 30 seconds～and 30 minutes, be preferably 1 minute～30 minutes.When cooperating vulcanizing agent, vulcanization accelerator, melting temperature is generally below 100 ℃, is preferably room temperature～80 ℃.In addition, be combined with the composition of vulcanizing agent, vulcanization accelerator, when carrying out sulfidizing such as press vulcanization, use usually.As curing temperature, be generally 120～200 ℃, be preferably 140～180 ℃.
In operation 3, the use level of the weighting agent beyond the use level of the conjugated diolefine polymer that is obtained by operation 2, the use level of silicon-dioxide, the use level that cooperates other component of polymer, the silicon-dioxide is preferably above-mentioned use level.
The saving fuel oil of conjugated diolefine polymer of the present invention and conjugated diolefine polymer composition takes excellent performance.In addition, processibility, grabbing property, wearability, intensity etc. are also good.
Conjugated diolefine polymer of the present invention and conjugated diolefine polymer composition are used for tire, sole, flooring material, vibration isolating material etc., are specially adapted to tire.
Embodiment
It is following that the present invention will be described according to embodiment.
Physical property measurement carries out as follows.
1. mooney viscosity (ML
1+4)
Measure under 100 ℃ according to JIS K6300 (1994).
2. contents of ethylene (unit: mole %)
According to infrared spectrophotometry, be 910cm by the absorption peak of vinyl
-1Near absorption intensity is tried to achieve.
3. the content of styrene units (unit: mole %)
Try to achieve by specific refractory power according to JIS K6383 (1995).
4. molecular weight distribution curve
Use gel permeation chromatography (GPC) method, measure according to following condition (1)～(8).
(1) device: the HLC-8020 that eastern Cao makes
(2) separation chromatography post: the GMH-XL (2 series connection) that eastern Cao makes
(3) measure temperature: 40 ℃
(4) carrier: tetrahydrofuran (THF)
(5) flow: 0.6mL/ minute
(6) injection rate: 5 μ L
(7) detector: differential refraction
(8) molecular weight standard: polystyrene standard
5. save fuel oil and take performance
Use determination of viscoelasticity device (the smart mechanism of Japan), under the condition of distortion 1% and frequency 10Hz, measure the loss tangent (tan δ (70 ℃)) of 70 ℃ of temperature.This value is more little, and saving fuel oil, to take performance excellent more.
Embodiment 1
With internal volume is 20 liters the washing of stainless steel polymerization reactor, drying, after replacing with drying nitrogen, drops into hexane (proportion 0.68g/cm
3) 10.2kg, 1,3-divinyl 608g, vinylbenzene 192g, tetrahydrofuran (THF) 6.1mL, ethylene glycol bisthioglycolate ethyl ether 5.0mL, then, n-Butyl Lithium 13.8 mmoles being made hexane solution, drop into, is 65 ℃ with the temperature regulation in the polymerization reactor, with 1,3-divinyl and vinylbenzene supply in the polymerization reactor, carry out polymerization in 3 hours, obtain polymers soln.The feed rate of the 1,3-butadiene in polymerization in 3 hours is 912g, and cinnamic feed rate is 288g.
Stirring velocity with 130rpm stirs resulting polymers soln, in polymers soln with adding [3-(diethylamino) propyl group] Trimethoxy silane 11.3 mmoles 1 second, stirred polymers soln 60 minutes, then in polymers soln, add methyl alcohol 10mL, polymers soln is carried out stirring in 5 minutes again.
In polymers soln, add the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (Sumitomo Chemical system, trade(brand)name: ス ミ ラ イ ザ-GM) 8g, tetramethylolmethane four (3-lauryl propionic ester) (Sumitomo Chemical system, trade(brand)name: the 4g of ス ミ ラ イ ザ-TP-D), then, polymers soln was evaporated 24 hours at normal temperatures, 55 ℃ of following drying under reduced pressure 12 hours, obtain polymkeric substance again.The physical property measurement of polymkeric substance be the results are shown in table 1.
With resulting polymkeric substance 100 weight parts, silicon-dioxide (デ グ Star サ corporate system, trade(brand)name: 78.4 weight parts ウ Le ト ラ シ Le VN3-G), silane coupling agent (デ グ Star サ corporate system, trade(brand)name: Si69) 6.4 weight parts, carbon 6.4 weight parts, extension oil (common oil company system, trade(brand)name: X-140) 47.6 weight parts, antiaging agent (sumitomo chemical company system, ア Application チ ゲ Application 3C) 1.5 weight parts, stearic acid 2 weight parts, zinc white 2 weight parts, vulcanization accelerator (sumitomo chemical company system, trade(brand)name: 1 weight part ソ Network シ ノ-Le CZ), vulcanization accelerator (sumitomo chemical company system, trade(brand)name: 1 weight part ソ Network シ ノ-Le D), wax (the emerging chemical industrial company of imperial palace system, trade(brand)name: 1.5 weight parts サ Application ノ Star Network N), sulphur 1.4 weight parts carry out mixing with laboratory mixed with resin machine (ラ ボ プ ラ ス ト ミ Le), the resulting thing that mixes is configured as sheet material with 6 inches rollers.Sheet material was heated 45 minutes down at 160 ℃, make its sulfuration, the saving fuel oil expense performance of the sheet material after the sulfuration is estimated.Evaluation result is shown in table 1.
Comparative example 1
N-Butyl Lithium 20.7 mmoles are made hexane solution, drop into, the beginning polymerization, and [3-(diethylamino) propyl group] Trimethoxy silane 18.2 mmoles are made the solution of hexane 50mL, add in the polymers soln with 10 minutes, in addition, carry out similarly to Example 1.The physical property measurement result of resulting polymkeric substance and the saving fuel oil expense performance evaluation of the sheet material after the sulfuration be the results are shown in table 1.
Table 1
Embodiment 2
With internal volume is 20 liters stainless steel polymerization reactor washing, and drying after replacing with drying nitrogen, drops into hexane (proportion 0.68g/cm
3) 10.2kg, 1,3-butadiene 608g, vinylbenzene 192g, tetrahydrofuran (THF) 6.1mL, ethylene glycol bisthioglycolate ethyl ether 5.0mL.Then, n-Butyl Lithium 16.7 mmoles being made hexane solution, drop into, is 65 ℃ with the temperature regulation in the polymerization reactor, and 1,3-butadiene and vinylbenzene are supplied in the polymerization reactor, carries out polymerization in 3 hours, obtains polymers soln.The feed rate of the 1,3-butadiene in polymerization in 3 hours is 912g, and cinnamic feed rate is 288g.
Stirring velocity with 130rpm stirs resulting polymers soln, in polymers soln with adding 3-glycidoxypropyltrime,hoxysilane 14.3 mmoles 1 second, stirred polymers soln 60 minutes, then in polymers soln, add methyl alcohol 10mL, polymers soln is carried out stirring in 5 minutes again.
In polymers soln, add the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (Sumitomo Chemical system, trade(brand)name: ス ミ ラ イ ザ-GM) 8g, tetramethylolmethane four (3-lauryl propionic ester) (Sumitomo Chemical system, trade(brand)name: the 4g of ス ミ ラ イ ザ-TP-D), then, polymers soln was evaporated 24 hours at normal temperatures, 55 ℃ of following drying under reduced pressure 12 hours, obtain polymkeric substance again.The physical property measurement of polymkeric substance be the results are shown in table 2.
With resulting polymkeric substance 100 weight parts, silicon-dioxide (デ グ Star サ corporate system, trade(brand)name: 78.4 weight parts ウ Le ト ラ シ Le VN3-G), silane coupling agent (デ グ Star サ corporate system, trade(brand)name: Si69) 6.4 weight parts, carbon 6.4 weight parts, extension oil (common oil company system, trade(brand)name: X-140) 47.6 weight parts, antiaging agent (sumitomo chemical company system, ア Application チ ゲ Application 3C) 1.5 weight parts, stearic acid 2 weight parts, zinc white 2 weight parts, vulcanization accelerator (sumitomo chemical company system, trade(brand)name: 1 weight part ソ Network シ ノ-Le CZ), vulcanization accelerator (sumitomo chemical company system, trade(brand)name: 1 weight part ソ Network シ ノ-Le D), wax (the emerging chemical industrial company of imperial palace system, trade(brand)name: 1.5 weight parts サ Application ノ Star Network N), sulphur 1.4 weight parts carry out mixing with laboratory mixed with resin machine, the resulting thing that mixes is configured as sheet material with 6 inches rollers.Sheet material was heated 45 minutes down at 160 ℃, make its sulfuration, the saving fuel oil expense performance of the sheet material after the sulfuration is estimated.Evaluation result is shown in table 2.
Comparative example 2
The 3-glycidoxypropyltrime,hoxysilane is made tetrahydrofuran (THF) 50mL solution, add in the polymers soln with 10 minutes, in addition, carry out similarly to Example 2.The physical property measurement result of resulting polymkeric substance and the saving fuel oil expense performance evaluation of the sheet material after the sulfuration be the results are shown in table 2.
Table 2
The possibility of utilizing on the industry
According to the present invention, be provided at cooperate filler, particularly cooperate in the situation of silica passable Be saved conjugated diene copolymer, the conjugated diene of the polymer composition of fuel oil expense excellent performance The manufacture method of base polymer, the polymer group that cooperates conjugated diolefine polymer and silica to form The manufacture method of compound and polymer composition.
Claims (15)
1. conjugated diolefine polymer, it is characterized in that, it has based on the monomeric unit of conjugated diolefine with by the group of formula (I) expression, wherein, the total area of the molecular weight distribution curve that will obtain with gel permeation chromatography was made as 100% o'clock, the peak area at the molecular weight chromatography peak of lowest molecular weight side is more than 50%
In the formula, R
1And R
2Represent alkyl,-oxyl or hydroxyl respectively independently, m represents 0～10 integer, A
1Expression does not have the polar functional group of active hydrogen.
2. conjugated diolefine polymer according to claim 1, wherein, the A in the formula (I)
1Expression by formula (II) or (III) expression group,
In the formula, R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively, R
3And R
4Also can be in conjunction with forming ring structure,
In the formula, the carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent, R
5Expression hydrogen or carbonatoms are 1～6 alkyl.
3. conjugated diolefine polymer according to claim 1 and 2, wherein, the R in the formula (I)
1And R
2Be-oxyl.
4. the manufacture method of a conjugated diolefine polymer wherein, has operation 1 and 2,
Operation 1: in the presence of base metal catalysts, in hydrocarbon solvent, make the monomer polymerization that contains conjugated diolefine, had alkali-metal conjugated diolefine polymer endways from this catalyzer;
Operation 2: in the hydrocarbon solution of this conjugated diolefine polymer, once add silicon compound, thereby this conjugated diolefine polymer is carried out modification with this silicon compound by following formula (IV) expression,
In the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen.
5. method according to claim 1, wherein, in operation 2, with respect to per 1 mole of the basic metal of the base metal catalysts that uses in the operation 1, addition by the silicon compound of formula (IV) expression is 0.1～10 mole, and, be 6 mmole/second/m by the interpolation speed of the silicon compound of formula (IV) expression with respect to the per unit volume and the time per unit of hydrocarbon solution
3More than.
6. according to claim 4 or 5 described methods, wherein, the A in the formula (IV)
2Expression by following formula (II) or (III) expression group,
In the formula, R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively, R
3And R
4Also can be in conjunction with forming ring structure,
In the formula, the carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent, R
5Expression hydrogen or carbonatoms are 1～6 alkyl.
7. according to each described method in the claim 4～6, wherein, the R in the formula (IV)
6, R
7And R
8It all is the-oxyl of carbonatoms 1～4.
8. conjugated diolefine polymer, it obtains by each described manufacture method in the claim 4～7.
9. conjugated diolefine polymer composition, it contains each described conjugated diolefine polymer and silicon-dioxide in the claim 1～3.
10. conjugated diolefine polymer composition according to claim 9, wherein, in per 100 weight parts of the use level of conjugated diolefine polymer, the use level of silicon-dioxide is 10～150 weight parts.
11. the manufacture method of a conjugated diolefine polymer composition wherein, has operation 1,2 and 3,
Operation 1: in the presence of base metal catalysts, in hydrocarbon solvent, make the monomer polymerization that contains conjugated diolefine, had alkali-metal conjugated diolefine polymer endways from this catalyzer;
Operation 2: in the hydrocarbon solution of this conjugated diolefine polymer, once add silicon compound, thereby this conjugated diolefine polymer is carried out modification with this silicon compound by formula (IV) expression;
Operation 3: cooperate the conjugated diolefine polymer and the silicon-dioxide that obtain by operation 2,
In the formula, R
6, R
7And R
8Represent independently that respectively carbonatoms is that 1～4 alkyl or carbonatoms are 1～4-oxyl, R
6, R
7And R
8In at least one be that carbonatoms is 1～4-oxyl, n represents 0～10 integer, A
2Expression does not have the polar functional group of active hydrogen.
12. method according to claim 11, wherein, in operation 2, with respect to per 1 mole of the basic metal of the base metal catalysts that uses in the operation 1, addition by the silicon compound of formula (IV) expression is 0.1～10 mole, and, be 6 mmole/second/m by the interpolation speed of the silicon compound of formula (IV) expression with respect to the per unit volume and the time per unit of hydrocarbon solution
3More than.
13. according to claim 11 or 12 described methods, wherein, the A in the formula (IV)
2Expression by following formula (II) or (III) expression group,
In the formula, R
3And R
4The expression carbonatoms that can have nitrogen-atoms, Sauerstoffatom or a Siliciumatom is 1～6 alkyl independently respectively, R
3And R
4Also can be in conjunction with forming ring structure,
In the formula, the carbonatoms that X represents to have Sauerstoffatom is the alkyl of 1～6 divalent, R
5Expression hydrogen or carbonatoms are 1～6 alkyl.
14. according to each described method in the claim 11～13, wherein, the R in the formula (IV)
6, R
7And R
8It all is the-oxyl of carbonatoms 1～4.
15., wherein, in operation 3,, cooperate silica 1 0～150 weight part with respect to per 100 weight parts of the conjugated diolefine polymer that obtains by operation 2 according to each described method in the claim 11～14.
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| CN110461893A (en) * | 2017-03-31 | 2019-11-15 | 住友化学株式会社 | The manufacturing method of conjugated diene polymer and conjugated diene polymer |
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| JPS60255838A (en) | 1984-06-01 | 1985-12-17 | Japan Synthetic Rubber Co Ltd | Tire rubber composition |
| JPH0657767B2 (en) * | 1987-01-28 | 1994-08-03 | 住友化学工業株式会社 | Modified rubber composition |
| EP0270071B1 (en) | 1986-12-01 | 1994-03-02 | Sumitomo Chemical Company, Limited | Process for preparing modified diene polymer rubbers |
| JP2540901B2 (en) | 1988-02-25 | 1996-10-09 | 住友化学工業株式会社 | Modified rubber composition |
| US5189109A (en) | 1988-02-25 | 1993-02-23 | Sumitomo Chemical Company, Limited | Modified diene polymer rubbers |
| CA1338805C (en) * | 1988-05-02 | 1996-12-17 | Akio Imai | Modified diene polymer rubbers |
| FR2722503A1 (en) * | 1994-07-15 | 1996-01-19 | Michelin & Cie | FUNCTIONAL DIENE POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN ELASTOMERIC SILICA-FILLED COMPOSITIONS FOR USE IN TIRE ENVELOPES |
| JPH0987426A (en) * | 1995-09-20 | 1997-03-31 | Bridgestone Corp | Production of rubber composition |
| JP4598909B2 (en) * | 1999-12-02 | 2010-12-15 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| US7288594B2 (en) * | 2001-12-03 | 2007-10-30 | Bridgestone Corporation | Process for producing modified polymer modified polymer obtained by the process and rubber composition |
| JP2005290355A (en) * | 2004-03-11 | 2005-10-20 | Sumitomo Chemical Co Ltd | Modified diene polymer rubber and its production method |
| US20050203251A1 (en) | 2004-03-11 | 2005-09-15 | Sumitomo Chemical Company, Limited | Process for producing modified diene polymer rubber |
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| CN109476778A (en) * | 2016-09-23 | 2019-03-15 | 日本弹性体株式会社 | The manufacturing method of modified conjugated diene polymer, modified conjugated diene polymer composition, tire and modified conjugated diene polymer |
| CN109476778B (en) * | 2016-09-23 | 2021-05-11 | 日本弹性体株式会社 | Modified conjugated diene polymer, modified conjugated diene polymer composition, tire, and method for producing modified conjugated diene polymer |
| CN110461893A (en) * | 2017-03-31 | 2019-11-15 | 住友化学株式会社 | The manufacturing method of conjugated diene polymer and conjugated diene polymer |
| CN110461893B (en) * | 2017-03-31 | 2023-10-27 | 住友化学株式会社 | Conjugated diene polymer and method for producing conjugated diene polymer |
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| WO2008032417A1 (en) | 2008-03-20 |
| DE112006004023T5 (en) | 2009-07-23 |
| DE112006004023B4 (en) | 2020-08-27 |
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