CN1330678C - Method for preparing modified dienopolymer rubber - Google Patents
Method for preparing modified dienopolymer rubber Download PDFInfo
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- CN1330678C CN1330678C CNB2004100085453A CN200410008545A CN1330678C CN 1330678 C CN1330678 C CN 1330678C CN B2004100085453 A CNB2004100085453 A CN B2004100085453A CN 200410008545 A CN200410008545 A CN 200410008545A CN 1330678 C CN1330678 C CN 1330678C
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Abstract
There is provided a process for producing a both end-modified diene polymer rubber comprising the steps of: (1) polymerizing a conjugated diene monomer or a combination thereof with an aromatic vinyl monomer in the presence of a compound represented by the following formula (1) to produce an alkali metal end-carrying active polymer, and (2) reacting the alkali metal end-carrying active polymer with an amine compound, a ketone compound, an acrylamide compound, a heterocyclic compound or a silyl compound represented by specific formulas, respectively: R-(CH2)n-X-M (1) wherein R is a functional group containing a substituent group-carrying nitrogen atom, X is a saturated or unsaturated hydrocarbon group comprising from 0 to 10 conjugated diene monomer units or aromatic vinyl monomer units, n is an integer of from 1 to 10, and M is an alkali metal.
Description
Technical field
The method of the two terminal dienopolymer rubbers that all have been modified that the present invention relates to that a kind of preparation has a good shock elasticity.The polymer rubber that obtains according to this method is best suited for doughnut, and it is the fuel economy cost well.
Background technology
The styrene-butadiene copolymer that obtains by emulsion polymerization is acknowledged as the rubber as doughnut.Yet there is such problem in this multipolymer, and that is exactly the requirement that the doughnut that contains this multipolymer can not satisfy the fuel economy cost, because this multipolymer does not have good shock elasticity.
In order to obtain having the rubber of good shock elasticity, JP-B 5-46365 discloses a kind of method, it may further comprise the steps: utilize organolithium compound as initiator, and lewis' acid for example ether as the microstructure control agent copolyreaction is taken place in divinyl and vinylbenzene in varsol.
In addition, Japanese Patent has also been introduced a kind of method No. 2540901, it may further comprise the steps: will be bonded to the reaction of the basic metal of dienopolymer rubber end and a kind of special acrylamide, and obtain the modified dienopolymer rubber that a kind of shock elasticity has been enhanced.
In addition, JP-A 2002-128824 also discloses a kind of method, it may further comprise the steps: basic metal and a kind of special amine that will be bonded to the dienopolymer rubber end react, and obtain be enhanced and the modified dienopolymer rubber easier processing of a kind of shock elasticity.
Yet, for consideration, require the standard of saving doughnut fuel cost more and more higher recent years to environmental factors, so, aforesaid any synthetic rubber all is difficult to satisfy such requirement.
Summary of the invention
The object of the present invention is to provide a kind of preparation to have the method for the modified polymer rubber of good shock elasticity.
The present invention is a kind of method for preparing two terminal dienopolymer rubbers that all have been modified, and it may further comprise the steps:
(1) in the presence of compound shown in the following formula (1), make the polymerization of mixtures of conjugate diene monomer or itself and aromatic vinyl monomer, obtain end and have alkali-metal reactive polymer, then
(2) make this end have alkali-metal reactive polymer and react with the amine compound shown in following formula (2)-(6), ketone compound, acrylamide compound, heterogeneous ring compound or silyl compound respectively,
R-(CH
2)
n-X-M (1)
Wherein, in formula (1), R contains the substituent functional group that has nitrogen-atoms, and X is for containing the unitary saturated or unsaturated alkyl of 0-10 conjugated diene monomeric unit or aromatic vinyl monomer, and n is the integer of 1-10, and M is a basic metal; In formula (2), R
1, R
2And R
3Separately independently of one another for containing the alkyl of 1-8 carbon atom, R
4Be alkoxyl group or the alkyl that contains 1-8 carbon atom, and a is the integer of 1-8; In formula (3), R
5Be the alkyl that contains 1-8 carbon atom, the alkoxyl group that contains 1-8 carbon atom, phenyl or benzyl, and R
6Amino for containing the substituent ring that has nitrogen-atoms; In formula (4), R
7Be hydrogen or methyl, R
8And R
9Be alkyl separately independently of one another, and p is the integer of 1-10; In formula (5), R
10Be alkyl, alkoxyalkyl, phenyl or the benzyl that contains 1-4 carbon atom, and Y is nitrogen, oxygen or sulphur atom, it has alkyl substituent, alkoxyalkyl substituting group, phenyl or the benzyl substituting group that contains 1-4 carbon atom; And, in formula (6), R
11Be alkyl, cycloalkyl, phenyl or the benzyl that contains 1-4 carbon atom, R
12And R
13Independently of one another for containing alkyl, alkoxyl group, alkoxyalkyl, cycloalkyl, phenyl or the benzyl of 1-4 carbon atom, q is the integer of 0-1 separately, and r is the integer of 1-5, and Z is halogen, epoxy group(ing) or vinyl.
The present invention also relates to a kind of rubber combination, it contains:
(1) two terminal dienopolymer rubbers that all have been modified of making according to aforesaid method of 10-100 weight part,
(2) other rubber of 0-90 weight part,
(3) carbon black of 0-100 weight part,
(4) tripoli of 5-100 weight part,
(5) silane coupling agent of 0-20 weight %,
Wherein the total amount of component (1) and (2) is 100 weight parts, and the amount of component (5) is based on that the amount of component (4) calculates.
Be included in term for example the term " monomeric unit " in " conjugated diene monomeric unit " be meant a unitary polymerization single polymerization monomer, unitary polymerized conjugated diene monomer for example.
Embodiment
The example of the conjugate diene monomer among the present invention is 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene.Wherein, consider preferred 1,3-butadiene or isoprene from the practicality of resultant modified polymer rubber and the angle of physical property.
The example of the aromatic vinyl monomer among the present invention is vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl naphthalene, Vinylstyrene, trivinylbenzene and divinyl naphthalene.Wherein, consider optimization styrene from the practicality of resultant modified polymer rubber and the angle of physical property.
In above-mentioned formula (1), R is preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropyl amino, N, N-dibutylamino, morpholino base or imidazolyl.
In formula (1), consider the factor of the molecular weight not too big (amount of this compound use is also just little like this) of compound shown in the formula (1), X preferably contains the unitary saturated or unsaturated alkyl of 1-5 conjugated diene monomeric unit or aromatic vinyl monomer for containing 0-10.If number is less than 1, just 0, association will take place in this compound each other each other consumingly in solvent, so, its solvability in varsol is just very poor, and the possibility of result causes the polymerization ratio of the mixture of conjugate diene monomer or itself and aromatic vinyl monomer to reduce.X in the formula (1) is preferably the saturated or unsaturated alkyl that contains 2 isoprene monomer units especially, because compound has fabulous solvability shown in such formula (1) in varsol.
In formula (1), n is the integer of 1-10, and preferred n is 3-10, because (i) compound shown in such formula (1) is easy to preparation, and (ii) conjugate diene monomer or its polyreaction with the mixture of aromatic vinyl monomer are easy to control.
The example of M is lithium, sodium, potassium and caesium in the formula (1).Wherein, preferred lithium is because compound has good solubility shown in such formula (1) in varsol.
The example of compound is 3-(N shown in the formula (1), the N-dimethylamino)-the 1-propyl lithium, 3-(N, the N-diethylamino)-the 1-propyl lithium, 3-(N, N-dipropyl amino)-the 1-propyl lithium, 3-(N, the N-dibutylamino)-the 1-propyl lithium, 3-morpholino base-1-propyl lithium, 3-imidazolyl-1-propyl lithium, and contain 1-10 butadiene unit, the compound of isoprene unit or styrene units (oligopolymer), these compounds (oligopolymer) are by with divinyl, isoprene or vinylbenzene and above-mentioned each compound polymerization reaction take place respectively obtain.Wherein, preferred 3-(N, the N-dimethylamino)-the 1-propyl lithium, perhaps pass through two isoprene units and 3-(N, the N-dimethylamino)-1-propyl lithium polymerization reaction take place and the active saturated or unsaturated hydrocarbons that obtains, this is because (i) can obtain the accurate reactive polymer of molecular weight distribution with speed of reaction faster, and (ii) resulting polymkeric substance fuel economy cost significantly.Wherein, consider from the angle of industry, further preferred active saturated or unsaturated hydrocarbons by two isoprene units and 3-(N, N-dimethylamino)-1-propyl lithium polymerization reaction take place are obtained, such hydrocarbon has fabulous solvability in varsol.
When in above-mentioned steps of the present invention (1), using conjugate diene monomer and aromatic vinyl monomer simultaneously, the weight ratio of the former with the latter, just conjugate diene monomer/aromatic vinyl monomer is preferably 50/50-90/10, further preferred 55/45-85/15.If described ratio is less than 50/50, resulting reactive polymer just is not dissolved in varsol, and the result makes and in this step polymerization in homogeneous phase can not take place.If described ratio is greater than 90/10, the intensity of resulting reactive polymer just may reduce.
Polymerization process in the step (1) is had no particular limits, can use conventional methods.In this step, can use for example varsol of normally used conventional solvent in this area and additive; Randomizer; Using additive is in order to regulate ethylenic linkage content contained in the resultant reactive polymer (this ethylenic linkage is to be derived by conjugate diene monomer).
Above-mentioned varsol is meant the solvent that those can not make compound generation passivation shown in the formula (1).The example that is fit to is aliphatic hydrocarbon, aromatic hydrocarbons and clicyclic hydrocarbon.More preferred example is those hydrocarbon that contain 2-12 carbon atom.Such object lesson is propane, n-butane, Trimethylmethane, n-pentane, iso-pentane, n-octane, hexahydroaniline, propylene, 1-butylene, iso-butylene, anti--2-butylene, suitable-2-butylene, 1-amylene, 2-amylene, 1-octene, 2-octene, benzene,toluene,xylene and ethylbenzene, and the mixture of at least two kinds of above-mentioned solvents.
As the above-mentioned additive that is used for regulating ethylenic linkage content, for example lewis' base.Consider preferred ether or tertiary amine from the angle of industrial applicibility.
The example of above-mentioned ether has cyclic ethers for example tetrahydrofuran (THF), tetrahydropyrans and 1,4-dioxane; Aliphatic monoethers is diethyl ether and dibutyl ether for example; The aliphatics diether is vinyl ethylene glycol dimethyl ether, vinyl ethylene glycol bisthioglycolate ethyl ether, vinyl ethylene glycol bisthioglycolate butyl ether, DIETHYLENE GLYCOL Anaesthetie Ether and DIETHYLENE GLYCOL dibutyl ether for example; And aromatic oxide for example phenyl ether and methyl-phenoxide.
The example of above-mentioned tertiary amine is triethylamine, tripropylamine, tributylamine, N, N, N ', N ' ,-tetramethyl-ethylene base diamines, N, N-Diethyl Aniline, pyridine and quinoline.
Amine compound shown in the above-mentioned formula (2) is each R wherein preferably
1And R
2Be methyl; R
3Be methyl, ethyl, propyl group or butyl; R
4Be methoxyl group, oxyethyl group, propoxy-or butoxy; And a is those compounds of 1.
The example of described amine compound is 1,1-dimethoxy Trimethylamine, 1,1-two-just-propoxy-Trimethylamine, 1,1-two-different-propoxy-Trimethylamine, 1,1-two-just-butoxy Trimethylamine, 1,1-two-three butoxy Trimethylamines, 1,1-diethoxy triethylamine, 1,1-two-just-and propoxy-triethylamine, 1,1-two-different-propoxy-triethylamine, 1,1-two-just-butoxy triethylamine, 1,1-two-three butoxy triethylamines.Wherein, preferably have low-molecular-weightly 1,1-dimethoxy Trimethylamine is because just can reduce fuel cost significantly by adding a spot of this amine compound.
The amount that amine compound uses is generally 0.1-10mol, is preferably the every mol reactive polymer of 0.5-2mol.If described amount is less than 0.1mol, fuel cost just reduces fewly.If described amount is greater than 10mol, unreacted amine compound will remain in the solvent, consider that from the angle of economy this is not preferred, because when circulating solvent additional step that these amine compound are separated of needs just when utilizing again from solvent.
Consider reactivity, R in the formula (3)
5Be preferably methyl, ethyl, propyl group, butyl, methoxyl group, oxyethyl group, propoxy-, butoxy, phenyl or benzyl.
R in the formula (3)
6Example be to derive respectively and the ring amino that contains nitrogen-atoms that comes by morpholine, tetrahydroglyoxaline, imidazoles, pyrazoles, piperazine, thiazine, azoles, thiazole, pyridine, pyrimidine and pyrazine.Wherein, consider the factor that reduces fuel cost, preferably derive and next ring amino by morpholine or imidazoles.
The example of compound shown in the formula (3) is 4-morpholino benzoylformaldoxime, 4-morpholino base benzophenone, 4 '-(imidazoles-1-yl)-methyl phenyl ketone, 4 '-(imidazoles-1-yl)-benzophenone, 4-pyrazolyl methyl phenyl ketone and 4-pyrazolyl benzophenone.Consider the factor that can significantly reduce fuel cost, preferred 4-morpholino benzoylformaldoxime, 4-morpholino base benzophenone or 4 '-(imidazoles-1-yl)-methyl phenyl ketone.
Amount and reason thereof that ketone compound uses are identical with aforesaid amine compound.Consider the factor that reduces fuel cost, R in the formula (4)
7-R
9Be preferably group with 2-4 carbon atom.
In the formula (4), p is preferably the integer of 2-5.If p is greater than 5, the molecular weight of the acrylamide compound shown in the formula (4) is bigger, and the result causes using a large amount of acrylamide compounds.
The example of the compound shown in the formula (4) is N, N-dimethylaminomethyl acrylamide, N, N-ethylmethylamino Methacrylamide, N, N-diethylamino methyl acrylamide, N, N-ethyl propyl amino methyl acrylamide, N, N-dipropyl amino methyl acrylamide, N, N-butyl propyl group amino methyl acrylamide, N, N-dibutylamino Methacrylamide, N, N-dimethyl aminoethyl acrylamide, N, N-ethylmethylamino ethyl acrylamide, N, N-diethylamino ethyl acrylamide, N, N-dimethyl aminoethyl acrylamide, N, N-ethyl propyl amino-ethyl acrylamide, N, N-dipropyl amino-ethyl acrylamide, N, N-butyl propyl group amino-ethyl acrylamide, N, N-dibutylamino ethyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-ethylmethylamino propyl group acrylamide, N, N-diethylamino propyl group acrylamide, N, N-ethyl propyl aminopropyl acrylamide, N, N-dipropyl aminopropyl acrylamide, N, N-butyl propyl group aminopropyl acrylamide, N, N-dibutylamino propyl group acrylamide, N, N-dimethylamino butyl acrylamide, N, N-ethylmethylamino butyl acrylamide, N, N-diethylamino butyl acrylamide, N, the amino butyl acrylamide of N-ethyl propyl, N, the amino butyl acrylamide of N-dipropyl, N, amino butyl acrylamide of N-butyl propyl group and N, N-dibutylamino butyl acrylamide, and by term in the above-claimed cpd " acrylamide " is replaced with the compound that " Methacrylamide " obtains.Wherein, preferred N, N-dimethylaminopropyl acrylamide is because it can reduce fuel cost significantly.
Amount and reason thereof that acrylamide compound uses are identical with aforesaid amine compound.
R in the formula (5)
10Be preferably the alkyl that contains 1-4 carbon atom, this is because use a spot of such compound just can reduce fuel cost.
Consider the factor that reduces fuel cost, Y is preferably the nitrogen-atoms of the alkyl replacement that is contained 1-4 carbon atom in the formula (5).
The example of compound is 1 shown in the formula (5), 3-dimethyl-2-imidazolidone, 1,3-diethyl-2-imidazolidone, 1,3-dipropyl-2-imidazolidone, 1,3-dibutyl-2-imidazolidone, 3-methyl-2- oxazolidone, 3-ethyl-2- oxazolidone, 3-propyl group-2- oxazolidone, 3-butyl-2- oxazolidone, 3-methyl-2-thiazolidone, 3-ethyl-2-thiazolidone, 3-propyl group-2-thiazolidone and 3-butyl-2-thiazolidone.Wherein, be preferably 1,3-dimethyl-2-imidazolidone, this is because it can reduce fuel cost significantly.
Amount and reason thereof that heterogeneous ring compound uses are identical with aforesaid amine compound.
Consider the factor that reduces fuel cost, the R in the formula (6)
11Be preferably the alkyl that contains 1-4 carbon atom, each R wherein
12And R
13Be preferably the alkoxyl group that contains 1-4 carbon atom.R in the formula (6) is preferably integer 2 or 3, and this is because (i) use the compound shown in a spot of this formula (6) just can reduce fuel cost, and the compound shown in the (ii) this formula (6) is very stable.
Consider the factor that reduces fuel cost, Z is preferably epoxy group(ing) in the formula (6).
The example of compound shown in the formula (6) is the 2-epoxy third oxygen ethyl trimethoxy silane, the 3-glycidoxy-propyltrimethoxy silane, the 4-epoxy third oxygen-butyl Trimethoxy silane, 2-trimethoxysilylethylgroup group muriate, 3-trimethoxy-silylpropyl muriate, 4-trimethoxysilyl butyl muriate, 2-trimethoxysilylethylgroup group bromide, 3-trimethoxy-silylpropyl bromide, 4-trimethoxysilyl butyl bromide and vinyltrimethoxy silane.Wherein, preferred 3-glycidoxy-propyltrimethoxy silane, this is because use a spot of such compound can reduce fuel cost significantly.
Amount and reason thereof that silyl compound uses are identical with aforesaid amine compound.
The reaction of step (2) takes place very soon.In this step, preferably allow method that all ingredients is in contact with one another such as in the resulting mixture of step (1), adding amine compound.The temperature of reaction here is generally room temperature to 80 ℃, and the reaction times is generally several seconds to several hours.
Consider the kneading handlability of resultant modified polymer rubber, can before or after step (2), in reactive polymer, add the coupling agent shown in the following formula:
R’
bM’X’
c
Wherein R ' is alkyl, alkoxyl group, aryl, alkenyl, cycloalkenyl group or aromatic hydrocarbon; M ' is silicon or tin atom; X ' is a halogen atom; B is the integer of 0-2; And c is the integer of 2-4.
The amount that above-mentioned coupling agent adds is generally every 1mol reactive polymer 0.005-0.4mol, is preferably 0.01-0.3mol.If it is add-on is less than 0.005mol, just very insignificant to the improvement of the kneading handlability of modified polymer rubber.If add-on is greater than 0.4mol, the ratio of the reactive polymer that reacts with amine compound is just smaller, and the result makes that the reduction of fuel cost is also little, and the viscosity of solution also may be very high in addition.
The modified polymer rubber that is included in the resulting reaction mixture of step (2) can solidify by the method for solidifying, this method of solidifying normally is used for preparing rubber by solution polymerization process, for example (i) adds the method for setting accelerator, and the method that (ii) adds water vapor.The temperature of solidifying is had no particular limits.
Modified polymer rubber after utilizing drying machine for example conveyor dryer and extruding type drying machine will solidifying carries out drying, and these drying machines normally are used for elastomeric production.The exsiccant temperature is had no particular limits.
Mooney viscosity (the ML of preferred resulting modified polymer rubber
1+4) be 10-200, more preferably 20-150.If viscosity is less than 10, its mechanical characteristics for example tensile strength of its vulcanized rubber will reduce.If viscosity is greater than 200, when for example other rubber mixes as one of rubber components and other component with this modified polymer rubber, blendability will be very poor, so that be difficult to obtain rubber combination, the result makes the tensile strength of its vulcanizate compositions become bad.
Derive and the content of the ethylenic linkage that comes by conjugate diene monomer, be also contained in simultaneously in the resulting modified polymer rubber, be preferably 10-70%, be preferably 15-60% especially.If the content of ethylenic linkage is less than 10%, the glass transition temp of this modified polymer rubber will be lower, and the result makes that the clamping of the tire contain this modified polymer rubber is bad.If the content of ethylenic linkage is greater than 70%, the glass transition temp of this modified polymer rubber will raise, and the result makes the shock elasticity variation of this modified polymer rubber.
Resulting modified polymer rubber can with other component for example other rubber and various additive mix use.
The example of other rubber is the styrene-butadiene copolymer rubber that obtains by emulsion polymerisation process; Utilize for example polybutadiene rubber, butadiene isoprene copolymer rubber and the styrene-butadiene copolymer rubber that obtain by emulsion polymerisation process of anionic polymerization catalyst and Z-type catalyst of catalyzer; Natural rubber; And the mixture of at least two kinds of above-mentioned rubber.
The ratio that contains this modified polymer rubber that is contained in the rubber combination of this modified polymer rubber and other rubber is preferably and is not less than 10 weight %, more preferably is not less than 20 weight %, and wherein the total amount of the two is 100 weight %.If this ratio will be difficult to improve less than the shock elasticity of the resultant rubber combination of 10 weight %, and its handlability is also bad.
The kind of above-mentioned additive and consumption can depend on the application purpose of resultant rubber combination.The example of the normally used additive in rubber industry field is a for example sulphur of vulcanizing agent; Stearic acid; Zinc white; The thiazoles vulcanization accelerator; Vulcanization accelerator is thiurams vulcanization accelerator and sulfinylamines vulcanization accelerator for example; Organo-peroxide; Toughener is carbon black for example, such as HAF carbon black and ISAF carbon black; Silica; Weighting agent is lime carbonate and talcum for example; Extending oil; Processing associating agent; And antioxidant.
Consider to reaching balance between the power, preferably contain the tripoli of 30-90 weight part and the carbon black of 0-40 weight part according to rubber combination of the present invention at wet skid resistance and anti-rolling.Be included in silane coupling agent in the rubber combination and increased bonding strength between silica and the rubber components, so just improved abrasion resistance.If the content of silane coupling agent, just can obtain a higher coupling ratio greater than 20 weight %, yet, can't improve according to the characteristic of this content resultant composition.Consider the dispersion effect and the coupling effect of silica, dosage of silane coupling agent is preferably 2-15 weight %.
For above-mentioned silane coupling agent, can use those to mix the silane coupling agent of any kind of that uses usually with silica filled dose.The example of these silane coupling agents is two (3-triethoxysilylpropyltetrasulfide) tetrasulfides, two (3-triethoxysilylpropyltetrasulfide) disulphide, 3-sulfydryl propyl trimethoxy silicane, two (2-triethoxysilyl) tetrasulfide, two (3-trimethoxy-silylpropyl) tetrasulfide, two (3-trimethoxy-silylpropyl) disulphide, two (2-trimethoxysilylethylgroup group) tetrasulfide, 3-sulfydryl propyl-triethoxysilicane.Wherein, consider the additive effect of coupling agent, preferred two (3-triethoxysilylpropyltetrasulfide) tetrasulfides, two (3-triethoxysilylpropyltetrasulfide) disulphide or 3-sulfydryl propyl trimethoxy silicane.
To the method for preparing above-mentioned rubber combination without limits.Such example is the method that comprises the steps: at mixing tank known in the art, for example in rotating cylinder and the Banbury mixer each component is mixed.Resulting rubber combination cures usually, and then is used as vulcanizate compositions.
Because is being pretty good according to the resulting modified polymer rubber of the inventive method aspect shock elasticity and the handlability, therefore the rubber combination that contains this modified polymer rubber is suitable for doughnut most, and this tire can reduce fuel cost well.Described rubber combination also can be applicable to for example purposes aspect of sole, flooring material and Shockproof rubber.
Embodiment
Present invention is described with reference to the following examples, and these embodiment and not meaning that limit the scope of the invention.
Embodiment 1
With an internal capacity is that 20 liters stainless steel polymerization reactor is cleaned and dry, purifies with drying nitrogen then.Then, to wherein adding 11.2mmol with two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200 CE, obtain by FMC lithium, hexahydroaniline formulations prepared from solutions) the polymerization reaction take place active saturated or unsaturated hydrocarbons, the 1420g 1 that obtain, 3-divinyl, 580g vinylbenzene, 324g tetrahydrofuran (THF) and 10.2kg hexane, polyase 13 hour under 65 ℃ agitation condition.
In resulting polymerization reaction mixture, add 0.4mol tin tetrachloride (coupling agent), under 65 ℃ agitation condition, continue reaction 30 minutes.Add 1 of 9.6mmol again in resulting reaction mixture, 1-dimethoxy Trimethylamine (amine compound) continues reaction 30 minutes again under 65 ℃ agitation condition.
In resulting reaction mixture, add 10ml methyl alcohol, continue to stir 5 minutes down at 65 ℃.Take out resulting reaction mixture and with 10g 2, the 6-Di-Tert-Butyl-P-Cresol, commodity are called SUMILIZERBHT, Sumitomo Chemical Co., Ltd. make, and mix.Then most hexane is removed in evaporation then, under reduced pressure 55 ℃ of dried residue are 12 hours, has so just obtained the polymer rubber that two ends all have been modified.
Embodiment 2
Except (1) will be by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, obtaining by FMC lithium, hexahydroaniline formulations prepared from solutions) amount that adds of the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place changes into 10.3mmol, and (2) 1, the amount that 1-dimethoxy Trimethylamine (amine compound) adds is changed into outside the 8.68mmol, repeats embodiment 1 and obtains two terminal polymer rubbers that all have been modified.
Embodiment 3
Except (1) will be by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, obtaining by FMC lithium, hexahydroaniline formulations prepared from solutions) amount that adds of the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place changes into 14.9mmol, (2) 1, the amount that 1-dimethoxy Trimethylamine (amine compound) adds is changed into outside the 14.9mmol, repeats embodiment 1 and obtains two terminal polymer rubbers that all have been modified.
Embodiment 4
Except (1) will be by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, by the FMC lithium, the hexahydroaniline formulations prepared from solutions obtains) amount that adds of the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place changes into 10.1mmol, (2) amount of tetrahydrofuran (THF) adding is changed into 300g, (3) amount of tin tetrachloride (coupling agent) adding is changed into 0.32mmol, and (4) 1, the amount that 1-dimethoxy Trimethylamine (amine compound) adds is changed into outside the 8.8mmol, repeats embodiment 1 and obtains two terminal polymer rubbers that all have been modified.
The comparative example 1
Except (1) with 11.2mmol by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, obtaining by FMC lithium, hexahydroaniline formulations prepared from solutions) the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place replaces with the n-Butyl Lithium (hexane solution) of 11.0mmol, (2) do not add tin tetrachloride (coupling agent), and (3) 1, the amount that 1-dimethoxy Trimethylamine (amine compound) adds is changed into outside the 11.0mmol, repeats embodiment 1 and obtains two terminal polymer rubbers that all have been modified.
The comparative example 2
Except (1) changes into 9.4mmol with the amount that n-Butyl Lithium (hexane solution) adds, (2) amount of tetrahydrofuran (THF) adding is changed into 123g, and (3) do not add tin tetrachloride (coupling agent) and 1, outside the 1-dimethoxy Trimethylamine (amine compound), repeat comparative example 1 and obtain polymer rubber.
The foregoing description 1-4 and comparative example 1 and 2 resulting polymer rubbers are carried out following test.What record the results are summarized in the table 2.
1. mooney viscosity
Record under 100 ℃ according to JIS K-6300.
2. the content of vinyl bonds
Record according to infrared spectrum analysis.
3. the content of styrene units
Record according to the specific refractory power method.
4. the shock elasticity of vulcanized rubber
Record by the method that comprises following step:
(1) in the experiment plastometer, polymer rubber and the listed component of table 1 are mediated, are obtained mediating product,
(2) should mediate formed product with 6 inches rotating cylinder and obtain sheet material,
(3) resulting sheet material was vulcanized 45 minutes down at 160 ℃, obtain vulcanizing sheet material, then
(4) utilize the Luepke resilience meter to measure this sulfuration sheet material 60 ℃ shock elasticity.
Table 1
| Component | Ratio (weight part) |
| Polymer rubber | 100 |
| Silica *1 | 78.4 |
| Silane coupling agent *2 | 6.4 |
| Carbon | 6.4 |
| Extending oil *3 | 47.5 |
| Antioxidant *4 | 1.5 |
| Zinc white | 2 |
| Vulcanization accelerator *5 | 1 |
| Vulcanization accelerator *6 | 1 |
| Paraffin *7 | 1.5 |
| Sulphur | 1.4 |
*1: trade mark is ULTRASIL VN3-G, and Degussa makes.
*2:Si69, Degussa makes.
*3: perfume oil, trade mark are X-140, Kyodo Oil Co., and Ltd makes.
*4: antioxidant, trade mark are ANTIGEN 3C, Sumitomo Chemical Co., and Ltd. makes.
*5: vulcanization accelerator, trade mark are SOXINOL CZ, Sumitomo Chemical Co., and Ltd. makes.
*6: vulcanization accelerator, trade mark are SOXINOL D, Sumitomo Chemical Co., and Ltd. makes.
*7: trade mark is SUNNOCN, Ouchishinko Chemical Industrial Co., and Ltd. makes.
Table 2
| Embodiment | The comparative example | |||||
| 1 | 2 | 3 | 4 | 1 | 2 | |
| Styrene units content (wt%) | 23 | 22 | 22 | 19 | 23 | 29 |
| Vinyl contains (wt%) | 58 | 58 | 58 | 57 | 59 | 42 |
| Mooney viscosity (ML 1+4100℃) | 74 | 79 | 47 | 93 | 77 | 66 |
| Formula (1) compound *1 | I | I | I | I | - | - |
| Properties-correcting agent *2 | II | II | II | II | II | - |
| 60 ℃ of shock elasticitys, % | 60 | 60 | 60 | 62 | 56 | 51 |
*1I: by two isoprene monomer units and the 3-active saturated or unsaturated hydrocarbons that (N, N-dimethylamino)-1-propyl lithium polymerization reaction take place obtains.
*2II:1,1-dimethoxy Trimethylamine
Embodiment 5
Except with 1,1-dimethoxy Trimethylamine (amine compound) replaces with outside 4 '-(imidazoles-1-yl)-methyl phenyl ketone (ketone compound), repeats embodiment 1 and obtains modified polymer rubber.
The comparative example 3
Except (1) with 11.2mmol by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, by the FMC lithium, the hexahydroaniline formulations prepared from solutions obtains) the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place replaces with the n-Butyl Lithium (hexane solution) of 9.55mmol, (2) amount of tetrahydrofuran (THF) adding is changed into 122g, (3) amount of tin tetrachloride (coupling agent) adding is changed into 0.57mmol, and (4) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with outside 4 ' of 7.2mmol-(imidazoles-1-yl)-methyl phenyl ketone (ketone compound), repeats embodiment 1 and obtains modified polymer rubber.
The comparative example 4
Except (1) changes into 9.80mmol with the amount that n-Butyl Lithium (hexane solution) adds, (2) amount of tetrahydrofuran (THF) adding is changed into 324g, (3) amount of tin tetrachloride (coupling agent) adding is changed into 0.39mmol, and the amount that (4) 4 '-(imidazoles-1-yl)-methyl phenyl ketone (ketone compound) adds changes into outside the 8.33mmol, repeats comparative example 3 and obtains modified polymer rubber.
To the foregoing description 5 and 6 and comparative example 2,3 and 4 resulting polymer rubbers carry out the test of front.What record the results are summarized in the table 3.
Table 3
| Embodiment 5 | The comparative example | |||
| 3 | 4 | 2 | ||
| Styrene units content (wt%) | 23 | 29 | 22 | 29 |
| Contents of ethylene (wt%) | 59 | 42 | 58 | 42 |
| Mooney viscosity (ML 1+4100℃) | 75 | 67 | 70 | 66 |
| Formula (1) compound *1 | I | - | - | - |
| Properties-correcting agent *2 | II | II | II | - |
| 60 ℃ of shock elasticitys, % | 61 | 55 | 57 | 51 |
*1I: by two isoprene monomer units and the 3-active saturated or unsaturated hydrocarbons that (N, N-dimethylamino)-1-propyl lithium polymerization reaction take place obtains.
*2II:4 '-(imidazoles-1-yl)-methyl phenyl ketone.
Embodiment 6
Except with 1,1-dimethoxy Trimethylamine (amine compound) replaces with N, outside the N-dimethylaminopropyl acrylamide (acrylamide compound), repeats embodiment 1 and obtains modified polymer rubber.
The comparative example 5
Except (1) with 11.2mmol by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, by the FMC lithium, the hexahydroaniline formulations prepared from solutions obtains) the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place replaces with the n-Butyl Lithium (hexane solution) of 12.5mmol, (2) amount of tin tetrachloride (coupling agent) adding is changed into 1.63mmol, and (3) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with the N of 5.63mmol, outside the N-dimethylaminopropyl acrylamide (acrylamide compound), repeat embodiment 1 and obtain modified polymer rubber.
The foregoing description 6 and comparative example 2 and 5 resulting polymer rubbers are carried out the test of front.What record the results are summarized in the table 4.
Table 4
| Embodiment 6 | The comparative example | ||
| 5 | 2 | ||
| Styrene units content (wt%) | 23 | 22 | 29 |
| Contents of ethylene (wt%) | 58 | 58 | 42 |
| Mooney viscosity (ML 1+4100℃) | 75 | 72 | 66 |
| Formula (1) compound *1 | I | - | - |
| Properties-correcting agent *2 | II | II | - |
| 60 ℃ of shock elasticitys, % | 60 | 56 | 51 |
*1I: by two isoprene monomer units and the 3-active saturated or unsaturated hydrocarbons that (N, N-dimethylamino)-1-propyl lithium polymerization reaction take place obtains.
*2II:N, N-dimethylaminopropyl acrylamide.
Embodiment 7
Except (1) changes into 0.22mmol with the amount that tin tetrachloride (coupling agent) adds, and (2) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with 1 of 10.3mmol, outside 3-dimethyl-2-imidazolidone (heterogeneous ring compound), repeat embodiment 1 and obtain modified polymer rubber.
Embodiment 8
Except (1) will be by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, obtaining by FMC lithium, hexahydroaniline formulations prepared from solutions) amount that adds of the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place changes into 9.72mmol, (2) do not add tin tetrachloride (coupling agent), and (3) 1, the amount that 3-dimethyl-2-imidazolidone (heterogeneous ring compound) adds is changed into outside the 9.72mmol, repeats embodiment 7 and obtains modified polymer rubber.
The comparative example 6
Except (1) with 11.2mmol by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, by the FMC lithium, the hexahydroaniline formulations prepared from solutions obtains) the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place replaces with the n-Butyl Lithium (hexane solution) of 9.90mmol, (2) amount of tin tetrachloride (coupling agent) adding is changed into 0.50mmol, and (3) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with 1 of 7.52mmol, outside 3-dimethyl-2-imidazolidone (heterogeneous ring compound), repeat embodiment 1 and obtain modified polymer rubber.
To the foregoing description 7 and 8 and comparative example 2 and 6 resulting polymer rubbers carry out the test of front.What record the results are summarized in the table 5.
Table 5
| Embodiment 6 | The comparative example | |||
| 7 | 8 | 6 | 2 | |
| Styrene units content (wt%) | 22 | 22 | 22 | 29 |
| Contents of ethylene (wt%) | 58 | 60 | 58 | 42 |
| Mooney viscosity (ML 1+4100℃) | 71 | 99 | 69 | 66 |
| Formula (1) compound *1 | I | I | - | - |
| Properties-correcting agent *2 | II | II | II | - |
| 60 ℃ of shock elasticitys, % | 65 | 65 | 56 | 51 |
*1I: by two isoprene monomer units and the 3-active saturated or unsaturated hydrocarbons that (N, N-dimethylamino)-1-propyl lithium polymerization reaction take place obtains.
*2II:1,3-dimethyl-2-imidazolidone.
Embodiment 9
Except (1) changes into 0.22mmol with the amount that tin tetrachloride (coupling agent) adds, and (2) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with outside the 3-glycidoxy-propyltrimethoxy silane (silyl compound) of 10.3mmol, repeats embodiment 1 and obtains modified polymer rubber.
Embodiment 10
Except (1) will be by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, obtaining by FMC lithium, hexahydroaniline formulations prepared from solutions) amount that adds of the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place changes into 12.4mmol, (2) tin tetrachloride of 0.22mmol (coupling agent) is changed into the silicon tetrachloride of 0.25mmol, and the amount that (3) 3-glycidoxy-propyltrimethoxy silane (silyl compound) adds changes into outside the 11.4mmol, repeats embodiment 9 and obtains modified polymer rubber.
The comparative example 7
Except (1) with 11.2mmol by two isoprene monomer units and 3-(N, the N-dimethylamino)-1-propyl lithium (AI-200CE, by the FMC lithium, the hexahydroaniline formulations prepared from solutions obtains) the active saturated or unsaturated hydrocarbons that obtains of polymerization reaction take place replaces with the n-Butyl Lithium (hexane solution) of 10.50mmol, (2) amount of tin tetrachloride (coupling agent) adding is changed into 0.42mmol, and (3) 9.6mmol 1,1-dimethoxy Trimethylamine (amine compound) replaces with outside the 3-glycidoxy-propyltrimethoxy silane (silyl compound) of 8.82mmol, repeats embodiment 1 and obtains modified polymer rubber.
To the foregoing description 9 and 10 and comparative example 2 and 7 resulting polymer rubbers carry out the test of front.What record the results are summarized in the table 6.
Table 6
| Embodiment 6 | The comparative example | |||
| 9 | 10 | 7 | 2 | |
| Styrene units content (wt%) | 23 | 23 | 23 | 29 |
| Contents of ethylene (wt%) | 59 | 58 | 60 | 42 |
| Mooney viscosity (ML 1+4100℃) | 77 | 61 | 71 | 66 |
| Formula (1) compound *1 | I | I | - | - |
| Properties-correcting agent *2 | II | II | II | - |
| 60 ℃ of shock elasticitys, % | 68 | 65 | 60 | 51 |
*1I: by two isoprene monomer units and the 3-active saturated or unsaturated hydrocarbons that (N, N-dimethylamino)-1-propyl lithium polymerization reaction take place obtains.
*The 2II:3-glycidoxy-propyltrimethoxy silane.
Claims (14)
1. method for preparing two terminal dienopolymer rubbers that all have been modified, the method includes the steps of:
(1) in the presence of compound shown in the following formula (1), make the polymerization of mixtures of conjugate diene monomer or itself and aromatic vinyl monomer, obtain end and have alkali-metal reactive polymer, then
(2) make this end have alkali-metal reactive polymer and react with the amine compound shown in following formula (2)-(4), ketone compound or acrylamide compound respectively,
R-(CH
2)
n-X-M (1)
Wherein, in formula (1), R contains the substituent functional group that has nitrogen-atoms, and X is for containing the unitary saturated or unsaturated alkyl of 0-10 conjugated diene monomeric unit or aromatic vinyl monomer, and n is the integer of 1-10, and M is a basic metal; In formula (2), R
1, R
2And R
3Separately independently of one another for containing the alkyl of 1-8 carbon atom, R
4Be alkoxyl group or the alkyl that contains 1-8 carbon atom, and a is the integer of 1-8; In formula (3), R
5Be the alkyl that contains 1-8 carbon atom, the alkoxyl group that contains 1-8 carbon atom, phenyl or benzyl, and R
6Amino for containing the substituent ring that has nitrogen-atoms; In formula (4), R
7Be hydrogen or methyl, R
8And R
9Be alkyl separately independently of one another, and p is the integer of 1-10.
2. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein the compound that has an alkali-metal reactive polymer reaction with this end contains the amine compound shown in the formula (2).
3. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein the compound that has an alkali-metal reactive polymer reaction with this end contains the ketone compound shown in the formula (3).
4. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein the compound that has an alkali-metal reactive polymer reaction with this end contains the acrylamide compound shown in the formula (4).
5. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, R in its Chinese style (1) is N, N-dimethylamino, N, N-diethylamino, N, N-dipropyl amino, N, N-dibutylamino, morpholino base or imidazolyl.
6. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein this end has alkali-metal reactive polymer and contains 0-5 conjugated diene monomeric unit or aromatic vinyl monomer unit.
7. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, the n in its Chinese style (1) is the integer of 3-10.
8. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, the X in its Chinese style (1) is the saturated or unsaturated alkyl that contains 2 isoprene monomer units.
9. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, the M in its Chinese style (1) is a lithium.
10. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein, in formula (2), R
1And R
2Be methyl separately; R
3Be methyl, ethyl, propyl group or butyl; R
4Be methoxyl group, oxyethyl group, propoxy-or butoxy; And a is 1.
11. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein, in formula (3), R
5Be methyl, ethyl, propyl group, butyl, methoxyl group, oxyethyl group, propoxy-, butoxy, phenyl or benzyl.
12. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein, in formula (3), R
6Be morpholino base or imidazolyl.
13. according to the method for the two terminal dienopolymer rubbers that all have been modified of the described preparation of claim 1, wherein, in formula (4), R
7Be hydrogen or methyl, R
8And R
9All independently of one another for containing the alkyl of 2-4 carbon atom, p is the integer of 2-5 separately.
14. a rubber combination, it contains:
(1) two terminal dienopolymer rubbers that all have been modified of making according to the described method of claim 1 of 10-100 weight part,
(2) other rubber of 0-90 weight part,
(3) carbon black of 0-100 weight part,
(4) tripoli of 5-100 weight part,
(5) silane coupling agent of 0-20 weight %,
Wherein the total amount of group (1) and (2) is 100 weight parts, and the amount of component (5) is based on the amount calculating of component (4).
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| JP50755/03 | 2003-02-27 | ||
| JP50756/03 | 2003-02-27 | ||
| JP50756/2003 | 2003-02-27 | ||
| JP2003085102 | 2003-03-26 | ||
| JP85102/03 | 2003-03-26 | ||
| JP85102/2003 | 2003-03-26 | ||
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| JP109967/03 | 2003-04-15 |
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| CN109563195A (en) * | 2016-07-22 | 2019-04-02 | 公共型股份公司希布尔控股 | For producing the method for branched modification rubber and the rubber composition and application thereof of the branched modification rubber comprising preparing by the method |
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| CN101248092B (en) * | 2005-08-22 | 2012-12-05 | 株式会社普利司通 | Functionalized polymers and improved tires therefrom |
| SG155870A1 (en) * | 2008-03-31 | 2009-10-29 | Sumitomo Chemical Co | Conjugated diene polymer, process for producing same, and conjugated diene polymer composition and vulcanizate |
| WO2011105362A1 (en) * | 2010-02-26 | 2011-09-01 | 日本ゼオン株式会社 | Conjugated diene rubber, rubber composition, crosslinked rubber, tire, and process for production of conjugated diene rubber |
| BR112014002423A2 (en) * | 2011-08-03 | 2017-02-21 | Sumitomo Rubber Ind | rubber and pneumatic composition |
| JP5918259B2 (en) | 2011-11-24 | 2016-05-18 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5918261B2 (en) | 2011-11-24 | 2016-05-18 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| US9120890B2 (en) | 2011-11-24 | 2015-09-01 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
| WO2013077020A1 (en) | 2011-11-24 | 2013-05-30 | 住友ゴム工業株式会社 | Rubber composition, and pneumatic tire |
| US9284438B2 (en) | 2011-12-26 | 2016-03-15 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
| US9359491B2 (en) | 2011-12-26 | 2016-06-07 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
| FR3012460B1 (en) * | 2013-10-25 | 2015-12-11 | Michelin & Cie | RUBBER COMPOSITION COMPRISING DIENIC ELASTOMER HAVING IMIDAZOLE FUNCTIONS RANDOMLY DISTRIBUTED ALONG THE CHAIN |
| US9688837B2 (en) | 2013-11-25 | 2017-06-27 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| US9109103B2 (en) * | 2013-11-25 | 2015-08-18 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| CN105732921B (en) * | 2014-12-11 | 2018-06-01 | 中国石油天然气股份有限公司 | Double-end functionalized ternary copolymer rubber and preparation method thereof |
| TWI663177B (en) * | 2015-09-21 | 2019-06-21 | 日商Ｅｔｉｃ有限公司 | Method for producing solution-polymerized diene-based rubber for filling silica and rubber composition therefrom |
| JP6564882B2 (en) * | 2015-11-02 | 2019-08-21 | エルジー・ケム・リミテッド | Organolithium compound, method for producing modified conjugated diene polymer using the same, and modified conjugated diene polymer |
| CN105566692B (en) * | 2016-01-25 | 2018-06-29 | 中国热带农业科学院农产品加工研究所 | A kind of native rubber composite material and preparation method thereof |
| FR3097224B1 (en) * | 2019-06-11 | 2021-05-21 | Michelin & Cie | GRAFT POLYMER WITH FUNCTIONAL PENDANT GROUPS IMIDAZOLE. |
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