CN1330678C - Method for preparing modified dienopolymer rubber - Google Patents

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

Method for preparing modified diene polymer rubber

technical field

The invention relates to a method for preparing a diene polymer rubber with good impact elasticity and both ends are modified. The polymer rubber obtained according to this method is most suitable for automobile tires, which can save fuel costs very well.

Background technique

Styrene-butadiene copolymers obtained by emulsion polymerization are recognized as rubbers for automobile tires. However, such copolymers have a problem that automobile tires containing such copolymers cannot meet the demand for saving fuel costs because such copolymers do not have good impact elasticity.

In order to obtain rubber with good impact elasticity, JP-B 5-46365 discloses a method, which includes the following steps: using an organolithium compound as an initiator, and a Lewis acid such as an ether as a microstructure control agent, converting butadiene Copolymerization with styrene in hydrocarbon solvents.

In addition, Japanese Patent No. 2540901 also introduces a method, which includes the following steps: reacting the alkali metal bonded at the end of the diene polymer rubber with a special acrylamide to obtain an improved impact elasticity Modified diene polymer rubber.

In addition, JP-A 2002-128824 also discloses a method comprising the steps of reacting an alkali metal bound at the end of a diene polymer rubber with a special amine to obtain an impact elasticity improved Modified diene polymer rubber that is easier to process.

However, in recent years, due to environmental considerations, the standard for saving the fuel cost of automobile tires has become higher and higher, so that it is difficult for any of the aforementioned synthetic rubbers to meet such requirements.

Contents of the invention

The object of the present invention is to provide a method for preparing modified polymer rubber with good impact elasticity.

The present invention is a kind of method for preparing the diene polymer rubber that both ends have been modified, and it comprises the following steps:

(1) In the presence of the compound shown in the following formula (1), the conjugated diene monomer or its mixture with the aromatic vinyl monomer is polymerized to obtain an active polymer with an alkali metal at the end, and then

(2) make this end have the active polymer of alkali metal and the amine compound shown in following formula (2)-(6), ketone compound, acrylamide compound, heterocyclic compound or silyl compound react respectively,

R-(CH ₂ ) _n -XM (1)

Wherein, in formula (1), R is a functional group containing a substituent with a nitrogen atom, and X is a saturated or unsaturated hydrocarbon group containing 0-10 conjugated diene monomer units or aromatic vinyl monomer units , n is an integer of 1-10, and M is an alkali metal; in formula (2), R ₁ , R ₂ and R ₃ are each independently an alkyl group containing 1-8 carbon atoms, and R ₄ is an alkyl group containing An alkoxy or alkyl group of 1-8 carbon atoms, and a is an integer of 1-8; in formula (3), R is _an alkyl group containing 1-8 carbon atoms, containing 1-8 carbon atoms Atomic alkoxy, phenyl or benzyl, and R ₆ is a cyclic amino group containing a substituent with a nitrogen atom; in formula (4), R ₇ is hydrogen or methyl, R ₈ and R ₉ are each other independently be an alkyl group, and p is an integer of 1-10; in formula (5), R ₁₀ is an alkyl group, alkoxyalkyl group, phenyl or benzyl group containing 1-4 carbon atoms, and Y is a nitrogen, oxygen or sulfur atom, which has an alkyl substituent containing 1-4 carbon atoms, an alkoxyalkyl substituent, a phenyl or a benzyl substituent; and, in formula (6), R ₁₁ For alkyl, cycloalkyl, phenyl or benzyl containing 1-4 carbon atoms, R ₁₂ and R ₁₃ are each independently alkyl, alkoxy, alkoxy containing 1-4 carbon atoms Alkyl, cycloalkyl, phenyl or benzyl, q is an integer of 0-1, r is an integer of 1-5, and Z is halogen, epoxy or vinyl.

The present invention also relates to a rubber composition comprising:

(1) 10-100 parts by weight of the diene polymer rubber that has been modified at both ends according to the above-mentioned method,

(2) 0-90 parts by weight of other rubbers,

(3) 0-100 parts by weight of carbon black,

(4) 5-100 parts by weight of silica,

(5) silane coupling agent of 0-20% by weight,

Wherein the total amount of components (1) and (2) is 100 parts by weight, and the amount of component (5) is calculated based on the amount of component (4).

The term "monomer unit" encompassed in terms such as "conjugated diene monomer unit" refers to one unit of polymerized monomer, such as one unit of polymerized conjugated diene monomer.

Detailed ways

Examples of conjugated diene monomers in the present invention are 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1, 3-butadiene and 1,3-hexadiene. Among them, 1,3-butadiene or isoprene is preferable from the viewpoint of the practicality and physical properties of the resulting modified polymer rubber.

Examples of the aromatic vinyl monomer in the present invention are styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene. Among them, styrene is preferable from the viewpoint of the practicality and physical properties of the resulting modified polymer rubber.

In the above formula (1), R is preferably N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-dibutylamino, morpholino group or imidazolyl group.

In formula (1), considering that the molecular weight of the compound shown in formula (1) should not be too large (so that the amount of the compound used is not large), X contains 0-10, preferably contains 1-5 A saturated or unsaturated hydrocarbon group of a conjugated diene monomer unit or an aromatic vinyl monomer unit. If the number is less than 1, that is, 0, the compounds will strongly associate with each other in the solvent, so that its solubility in hydrocarbon solvents is poor, which may lead to conjugation The polymerization ratio of the diene monomer or its mixture with the aromatic vinyl monomer decreases. X in formula (1) is particularly preferably a saturated or unsaturated hydrocarbon group containing 2 isoprene monomer units, because such a compound represented by formula (1) has excellent solubility in hydrocarbon solvents.

In formula (1), n is an integer of 1-10, preferably n is 3-10, because (i) the compound represented by such formula (1) is easy to prepare, and (ii) conjugated diene monomer or its The polymerization reaction with the mixture of aromatic vinyl monomers is easy to control.

Examples of M in formula (1) are lithium, sodium, potassium and cesium. Among them, lithium is preferable because such a compound represented by formula (1) has good solubility in hydrocarbon solvents.

Examples of compounds shown in formula (1) are 3-(N, N-dimethylamino)-1-propyllithium, 3-(N, N-diethylamino)-1-propyllithium, 3- (N,N-dipropylamino)-1-propyllithium, 3-(N,N-dibutylamino)-1-propyllithium, 3-morpholino-1-propyllithium, 3 -imidazolyl-1-propyl lithium, and compounds (oligomers) containing 1-10 butadiene units, isoprene units or styrene units, which are obtained by adding butane It is obtained by the polymerization reaction of alkene, isoprene or styrene with the above-mentioned compounds respectively. Among them, 3-(N,N-dimethylamino)-1-propyllithium is preferred, or by combining two isoprene units with 3-(N,N-dimethylamino)-1-propyl Active saturated or unsaturated hydrocarbons obtained by the polymerization of lithium, because (i) active polymers with precise molecular weight distribution can be obtained at a faster reaction rate, and (ii) the obtained polymers can significantly save fuel cost. Among them, from an industrial point of view, active saturated or unsaturated hydrocarbons obtained by polymerizing two isoprene units with 3-(N,N-dimethylamino)-1-propyl lithium are further preferred. , such hydrocarbons have excellent solubility in hydrocarbon solvents.

When using conjugated diene monomer and aromatic vinyl monomer in the above step (1) of the present invention, the weight ratio of the former to the latter, that is, conjugated diene monomer/aromatic vinyl monomer , preferably 50/50-90/10, more preferably 55/45-85/15. If the ratio is less than 50/50, the resulting living polymer is not soluble in hydrocarbon solvents, resulting in the impossibility of homogeneous polymerization in this step. If the ratio is greater than 90/10, the strength of the resulting living polymer may be reduced.

The polymerization method in step (1) is not particularly limited, and conventional methods can be used. In this step, conventional solvents and additives such as hydrocarbon solvents commonly used in the art can be used; a random function generator; the use of additives is to adjust the vinyl bond content contained in the resulting living polymer (the vinyl bond is produced by co- derived from conjugated diene monomers).

The above-mentioned hydrocarbon solvents refer to those solvents that do not deactivate the compound represented by formula (1). Suitable examples are aliphatic hydrocarbons, aromatic hydrocarbons and cycloaliphatic hydrocarbons. Particularly preferred examples are those hydrocarbons containing 2 to 12 carbon atoms. Specific examples of such are propane, n-butane, isobutane, n-pentane, isopentane, n-octane, cyclohexylamine, propylene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-octene, 2-octene, benzene, toluene, xylene and ethylbenzene, and mixtures of at least two of the foregoing solvents.

As the above-mentioned additive for adjusting the vinyl bond content, for example, Lewis base. From the viewpoint of industrial applicability, ethers or tertiary amines are preferable.

Examples of the aforementioned ethers are cyclic ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; aliphatic diethers such as vinyl glycol dimethyl base ether, vinyl glycol diethyl ether, vinyl glycol dibutyl ether, divinyl glycol diethyl ether and divinyl glycol dibutyl ether; and aromatic ethers such as di Phenyl ether and anisole.

Examples of the aforementioned tertiary amines are triethylamine, tripropylamine, tributylamine, N,N,N',N',-tetramethylethylenediamine, N,N-diethylaniline, pyridine and quinoline.

The amine compound represented by the above-mentioned formula (2) is preferably wherein each of R _{and R} is methyl; R is _methyl , ethyl, propyl or butyl; _R is methoxy, ethoxy , propoxy or butoxy; and those compounds in which a is 1.

Examples of said amine compounds are 1,1-dimethoxytrimethylamine, 1,1-di-n-propoxytrimethylamine, 1,1-di-iso-propoxytrimethylamine Amine, 1,1-di-n-butoxytrimethylamine, 1,1-di-tributoxytrimethylamine, 1,1-diethoxytriethylamine, 1,1- Di-n-propoxytriethylamine, 1,1-di-iso-propoxytriethylamine, 1,1-di-n-butoxytriethylamine, 1,1-di- Tributoxytriethylamine. Among them, 1,1-dimethoxytrimethylamine having a low molecular weight is preferable because fuel cost can be remarkably reduced by adding a small amount of this amine compound.

The amine compound is used usually in an amount of 0.1-10 mol, preferably 0.5-2 mol, per mol of active polymer. If the amount is less than 0.1 mol, the fuel cost is reduced little. If the amount is greater than 10 mol, unreacted amine compounds will remain in the solvent, which is not preferable from an economic point of view because a process for separating these amine compounds from the solvent is required when the solvent is recycled for reuse. Additional steps.

In consideration of reactivity, R in formula (3) is preferably _methyl , ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl or benzyl.

The example of R in formula (3) is the _cyclic amino group containing nitrogen atom derived from morpholine, imidazoline, imidazole, pyrazole, oxazine, thiazine, oxazole, thiazole, pyridine, pyrimidine and pyrazine respectively . Among them, cyclic amino groups derived from morpholine or imidazole are preferable in view of reducing fuel costs.

Examples of compounds represented by formula (3) are 4-morpholino acetophenone, 4-morpholino benzophenone, 4'-(imidazol-1-yl)-acetophenone, 4'-(imidazole -1-yl)-benzophenone, 4-pyrazolylacetophenone and 4-pyrazolylbenzophenone. Considering the fact that the fuel cost can be significantly reduced, 4-morpholinoacetophenone, 4-morpholinobenzophenone or 4'-(imidazol-1-yl)-acetophenone is preferred.

The amount of the ketone compound used and the reason thereof are the same as those of the aforementioned amine compound. In consideration of reducing fuel costs, R ₇ -R ₉ in formula (4) are preferably groups having 2-4 carbon atoms.

In formula (4), p is preferably an integer of 2-5. If p is greater than 5, the molecular weight of the acrylamide compound represented by formula (4) is large, resulting in the use of a large amount of acrylamide compound.

Examples of compounds represented by formula (4) are N, N-dimethylaminomethacrylamide, N, N-ethylmethylaminomethacrylamide, N, N-diethylaminomethacrylamide , N,N-Ethylpropylaminomethacrylamide, N,N-Dipropylaminomethacrylamide, N,N-Butylpropylaminomethacrylamide, N,N-Dibutylaminomethacrylamide Methacrylamide, N,N-dimethylaminoethylacrylamide, N,N-ethylmethylaminoethylacrylamide, N,N-diethylaminoethylacrylamide, N,N-di Methylaminoethylacrylamide, N, N-ethylpropylaminoethylacrylamide, N, N-dipropylaminoethylacrylamide, N, N-butylpropylaminoethylacrylamide, N , N-dibutylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-ethylmethylaminopropylacrylamide, N,N-diethylaminopropylacrylamide Amide, N,N-Ethylpropylaminopropylacrylamide, N,N-Dipropylaminopropylacrylamide, N,N-Butylpropylaminopropylacrylamide, N,N-Dibutyl Aminopropylacrylamide, N,N-Dimethylaminobutylacrylamide, N,N-ethylmethylaminobutylacrylamide, N,N-diethylaminobutylacrylamide, N,N- Ethylpropylaminobutylacrylamide, N,N-dipropylaminobutylacrylamide, N,N-butylpropylaminobutylacrylamide and N,N-dibutylaminobutylacrylamide, and compounds obtained by replacing the term "acrylamide" in the above compounds with "methacrylamide". Among them, N,N-dimethylaminopropylacrylamide is preferable because it can remarkably reduce fuel costs.

The amount of the acrylamide compound used and the reason thereof are the same as the aforementioned amine compound.

R ₁₀ in formula (5) is preferably an alkyl group having 1 to 4 carbon atoms, because fuel cost can be reduced by using a small amount of such a compound.

In view of reducing fuel costs, Y in formula (5) is preferably a nitrogen atom substituted by an alkyl group containing 1-4 carbon atoms.

Examples of compounds represented by formula (5) are 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone Ketone, 1,3-dibutyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, 3-propyl-2-oxazolidinone ketone, 3-butyl-2-oxazolidinone, 3-methyl-2-thiazolidinone, 3-ethyl-2-thiazolidinone, 3-propyl-2-thiazolidinone and 3-butane Base-2-thiazolidinone. Among them, 1,3-dimethyl-2-imidazolidinone is preferable because it can significantly reduce fuel costs.

The amount of the heterocyclic compound used and the reason thereof are the same as the aforementioned amine compound.

Considering the factor of reducing fuel cost, R in formula (6) is preferably an alkyl group containing 1-4 carbon atoms, and each R ₁₂ and R _{13 wherein} is preferably an alkoxy group containing 1-4 carbon atoms base. r in the formula (6) is preferably an integer of 2 or 3, because (i) the fuel cost can be reduced by using a small amount of the compound represented by the formula (6), and (ii) the compound represented by the formula (6) The compounds shown are very stable.

Considering the factor of reducing fuel cost, Z in the formula (6) is preferably an epoxy group.

Examples of compounds shown in formula (6) are 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 2 -Trimethoxysilylethyl chloride, 3-trimethoxysilylpropyl chloride, 4-trimethoxysilylbutyl chloride, 2-trimethoxysilylethyl bromide , 3-trimethoxysilylpropyl bromide, 4-trimethoxysilylbutyl bromide, and vinyltrimethoxysilane. Among them, 3-glycidoxypropyltrimethoxysilane is preferable because the use of such a compound in a small amount can significantly reduce fuel costs.

The amount of the silyl compound used and the reason thereof are the same as the aforementioned amine compound.

The reaction of step (2) occurs rapidly. A preferred method of bringing various reagents into contact with each other in this step is, for example, adding an amine compound to the mixture obtained in step (1). The reaction temperature here is usually room temperature to 80° C., and the reaction time is usually several seconds to several hours.

Considering the kneading processability of the obtained modified polymer rubber, the coupling agent shown in the following formula can be added in the active polymer before or after step (2):

_{R'b M'X'c}

Wherein R' is an alkyl group, an alkoxy group, an aryl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon; M' is a silicon or tin atom; X' is a halogen atom; b is an integer of 0-2; and c is An integer of 2-4.

The amount of the above-mentioned coupling agent added is usually 0.005-0.4 mol per 1 mol of active polymer, preferably 0.01-0.3 mol. If the added amount is less than 0.005 mol, the improvement of the kneading processability of the modified polymer rubber is negligible. If the added amount is more than 0.4 mol, the ratio of the active polymer reacting with the amine compound is relatively small, resulting in a small reduction in fuel cost, and the viscosity of the solution may also be high.

The modified polymer rubber contained in the reaction mixture obtained in step (2) can be coagulated by coagulation, which is usually used to prepare rubber by solution polymerization, such as (i) adding a coagulation accelerator agent, and (ii) the method of adding water vapor. There is no particular limitation on the solidification temperature.

The coagulated modified polymer rubber is dried using dryers such as belt dryers and squeeze dryers, which are generally used in the production of synthetic rubber. The drying temperature is not particularly limited.

Preferably, the obtained modified polymer rubber has a Mooney viscosity (ML ₁₊₄ ) of 10-200, more preferably 20-150. If the viscosity is less than 10, its mechanical properties such as the tensile strength of its vulcanized rubber will decrease. If the viscosity is greater than 200, when the modified polymer rubber is used as one of the rubber components to be mixed with other components such as other rubbers, the miscibility will be poor so that it is difficult to obtain a rubber composition, resulting in The tensile strength of its vulcanized rubber composition deteriorates.

The vinyl bond content derived from the conjugated diene monomer is also contained in the obtained modified polymer rubber, preferably 10-70%, particularly preferably 15-60%. If the vinyl bond content is less than 10%, the glass transition temperature of the modified polymer rubber is low, resulting in poor grip properties of tires containing the modified polymer rubber. If the vinyl bond content is greater than 70%, the glass transition temperature of the modified polymer rubber increases, resulting in poor impact elasticity of the modified polymer rubber.

The resulting modified polymer rubber can be used in admixture with other components such as other rubbers and various additives.

Examples of other rubbers are styrene-butadiene copolymer rubber obtained by the emulsion polymerization method; polybutadiene rubber obtained by the emulsion polymerization method using a catalyst such as an anionic polymerization catalyst and a Ziegler catalyst, butadiene-iso Pentadiene copolymer rubber and styrene-butadiene copolymer rubber; natural rubber; and mixtures of at least two of the foregoing rubbers.

The proportion of this modified polymer rubber contained in the rubber composition containing the modified polymer rubber and other rubbers is preferably not less than 10% by weight, more preferably not less than 20% by weight, wherein the total amount of the two is 100% by weight. If the ratio is less than 10% by weight, the impact elasticity of the obtained rubber composition is hardly improved, and its handleability is not good.

The kind and amount of the above-mentioned additives may depend on the application purpose of the obtained rubber composition. Examples of additives commonly used in the field of rubber industry are vulcanizing agents such as sulfur; stearic acid; zinc white; thiazole vulcanization accelerators; vulcanization accelerators such as thiuram vulcanization accelerators and sulfenamide vulcanization accelerators; oxides; reinforcing agents such as carbon blacks, such as HAF carbon black and ISAF carbon black; silica; fillers such as calcium carbonate and talc; extender oils; processing linkers; and antioxidants.

The rubber composition according to the present invention preferably contains 30-90 parts by weight of silica, and 0-40 parts by weight of carbon black in consideration of achieving a balance between wet skid resistance and rolling resistance. The silane coupling agent contained in the rubber composition increases the bonding strength between silica and the rubber component, thus improving abrasion resistance. If the content of the silane coupling agent is greater than 20% by weight, a higher coupling ratio can be obtained, however, the properties of the composition obtained at this content will not be improved. Considering the dispersion effect and coupling effect of silica, the amount of the silane coupling agent is preferably 2-15% by weight.

For the above-mentioned silane coupling agents, any kind of silane coupling agents which are generally used in admixture with silica fillers can be used. Examples of these silane coupling agents are bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, 3-mercaptopropyltrimethyl Oxysilane, bis(2-triethoxysilyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) Disulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltriethoxysilane. Among them, considering the addition effect of the coupling agent, bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide or 3 - Mercaptopropyltrimethoxysilane.

There is no limitation on the method of preparing the above-mentioned rubber composition. Examples of this are processes comprising the step of mixing the components in mixers known in the art, such as tumble drums and Banbury mixers. The obtained rubber composition is usually vulcanized and used as a vulcanized rubber composition.

Since the modified polymer rubber obtained according to the method of the present invention is quite good in terms of impact elasticity and handleability, the rubber composition containing this modified polymer rubber is most suitable for automobile tires, which can be easily Good for reducing fuel costs. The rubber composition is also applicable to uses such as shoe soles, flooring materials, and shockproof rubber.

Example

The present invention is described with reference to the following examples, which are not meant to limit the scope of the present invention.

Example 1

A stainless steel polymerization reactor having an internal volume of 20 liters was cleaned and dried, then purged with dry nitrogen. Then, 11.2 mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200 CE, prepared by FMC lithium, cyclohexylamine solution Prepared) Active saturated or unsaturated hydrocarbons obtained by polymerization reaction, 1420g 1,3-butadiene, 580g styrene, 324g tetrahydrofuran and 10.2kg hexane were polymerized under stirring at 65°C for 3 hours.

0.4 mol of tin tetrachloride (coupling agent) was added to the obtained polymerization reaction mixture, and the reaction was continued for 30 minutes under stirring at 65°C. Further, 9.6 mmol of 1,1-dimethoxytrimethylamine (amine compound) was added to the obtained reaction mixture, and the reaction was continued for another 30 minutes under stirring at 65°C.

To the resulting reaction mixture was added 10 ml of methanol, and stirring was continued at 65°C for 5 minutes. The resulting reaction mixture was taken out and mixed with 10 g of 2,6-di-tert-butyl-p-cresol, trade name SUMILIZERBHT, manufactured by Sumitomo Chemical Co., Ltd. Then, most of the hexane was removed by evaporation, and the residue was dried at 55°C for 12 hours under reduced pressure, thus obtaining a polymer rubber in which both ends were modified.

Example 2

Except (1) will be produced by two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution) The amount of active saturated or unsaturated hydrocarbons obtained by the polymerization reaction is changed to 10.3mmol, and (2) 1,1-dimethoxytrimethylamine (amine compound) is changed to 8.68mmol, and the implementation is repeated In Example 1, a polymer rubber having both ends modified was obtained.

Example 3

Except (1) will be produced by two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution) The amount of active saturated or unsaturated hydrocarbons that the polymerization reaction obtains is changed to 14.9mmol, and (2) 1,1-dimethoxytrimethylamine (amine compound) is changed to 14.9mmol, and the embodiment is repeated 1 Obtain a polymer rubber in which both ends have been modified.

Example 4

Except (1) will be produced by two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution) The active saturated or unsaturated hydrocarbon that polymerization reaction obtains adds the amount that changes to 10.1mmol, (2) the amount that tetrahydrofuran adds changes to 300g, (3) the amount that tin tetrachloride (coupling agent) adds changes to 0.32mmol, and (4) Example 1 was repeated except that the amount of 1,1-dimethoxytrimethylamine (amine compound) added was changed to 8.8 mmol to obtain a polymer rubber with both ends modified.

Comparative Example 1

In addition to (1) 11.2mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution Prepared) the active saturated or unsaturated hydrocarbon obtained by the polymerization reaction is replaced by 11.0mmol of n-butyllithium (hexane solution), (2) without adding tin tetrachloride (coupling agent), and (3) 1, Except that the amount of 1-dimethoxytrimethylamine (amine compound) added was changed to 11.0 mmol, Example 1 was repeated to obtain a polymer rubber with both ends modified.

Comparative Example 2

Except for (1) changing the amount of n-butyllithium (hexane solution) added to 9.4 mmol, (2) changing the amount of tetrahydrofuran added to 123 g, and (3) not adding tin tetrachloride (coupling agent) and 1 , 1-dimethoxytrimethylamine (amine compound), repeat Comparative Example 1 to obtain a polymer rubber.

The following tests were carried out on the polymer rubbers obtained in the above-mentioned Examples 1-4 and Comparative Examples 1 and 2. The measured results are summarized in Table 2.

1. Mooney viscosity

Measured at 100°C according to JIS K-6300.

2. Vinyl bond content

Measured according to infrared spectroscopic analysis method.

3. Content of styrene units

Measured according to the refractive index method.

4. Impact elasticity of vulcanized rubber

Determined by a method comprising the following steps:

(1) knead the polymer rubber and the components listed in Table 1 in the experimental plastometer to obtain the kneaded product,

(2) Forming the kneaded product with a 6-inch drum to obtain a sheet,

(3) vulcanize the obtained sheet at 160° C. for 45 minutes to obtain a vulcanized sheet, and then

(4) The impact elasticity of the vulcanized sheet at 60° C. was measured using a Luepke elasticity meter.

Table 1

components Proportion (parts by weight) polymer rubber 100 Silica ^*1 78.4 Silane coupling agent ^*2 6.4 carbon 6.4 Extender oil ^*3 47.5 Antioxidant ^*4 1.5 Zinc white 2 Vulcanization accelerator ^*5 1 Vulcanization accelerator ^*6 1 Paraffin ^*7 1.5 sulfur 1.4

^* 1: The trademark is ULTRASIL VN3-G, manufactured by Degussa.

^* 2: Si69, manufactured by Degussa.

^* 3: Aroma oil, trademark X-140, manufactured by Kyodo Oil Co., Ltd.

^* 4: Antioxidant, trademark ANTIGEN 3C, manufactured by Sumitomo Chemical Co., Ltd.

^* 5: Vulcanization accelerator, trademarked SOXINOL CZ, manufactured by Sumitomo Chemical Co., Ltd.

^* 6: Vulcanization accelerator, trademark SOXINOL D, manufactured by Sumitomo Chemical Co., Ltd.

^* 7: The trademark is SUNNOCN, manufactured by Ouchishinko Chemical Industrial Co., Ltd.

Table 2

Example Comparative example 1 2 3 4 1 2 Styrene unit content (wt%) twenty three twenty two twenty two 19 twenty three 29 Vinyl content (wt%) 58 58 58 57 59 42 Mooney Viscosity (ML ₁₊₄ 100℃) 74 79 47 93 77 66 Compound of formula (1) ^*1 I I I I - - modifier ^*2 II II II II II - Impact elasticity 60℃, % 60 60 60 62 56 51

^* 1I: Active saturated or unsaturated hydrocarbon obtained by polymerization of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium.

^* 2II: 1,1-dimethoxytrimethylamine

Example 5

Except replacing 1,1-dimethoxytrimethylamine (amine compound) with 4'-(imidazol-1-yl)-acetophenone (ketone compound), repeat Example 1 to obtain modified polymer rubber.

Comparative Example 3

In addition to (1) 11.2mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution Prepared) active saturated or unsaturated hydrocarbon obtained by polymerization reaction is replaced by 9.55mmol n-butyllithium (hexane solution), (2) the amount of tetrahydrofuran added is changed to 122g, (3) tin tetrachloride (coupling agent) was changed to 0.57mmol, and (4) 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) was replaced by 7.2mmol of 4'-(imidazol-1-yl)-benzene Except for acetone (ketone compound), Example 1 was repeated to obtain a modified polymer rubber.

Comparative Example 4

In addition to (1) changing the amount of n-butyl lithium (hexane solution) added to 9.80mmol, (2) changing the amount of tetrahydrofuran added to 324g, and (3) changing the amount of tin tetrachloride (coupling agent) added to 0.39mmol, and (4) the amount of 4'-(imidazol-1-yl)-acetophenone (ketone compound) added was changed to 8.33mmol, and the modified polymer rubber was obtained by repeating Comparative Example 3.

The preceding tests were carried out on the polymer rubbers obtained in Examples 5 and 6 and Comparative Examples 2, 3 and 4 above. The measured results are summarized in Table 3.

table 3

Example 5 Comparative example 3 4 2 Styrene unit content (wt%) twenty three 29 twenty two 29 Vinyl content (wt%) 59 42 58 42 Mooney Viscosity (ML ₁₊₄ 100℃) 75 67 70 66 Compound of formula (1) ^*1 I - - - modifier ^*2 II II II - Impact elasticity 60℃, % 61 55 57 51

^* 1I: Active saturated or unsaturated hydrocarbon obtained by the polymerization reaction of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium.

^* 2II: 4'-(imidazol-1-yl)-acetophenone.

Example 6

Except replacing 1,1-dimethoxytrimethylamine (amine compound) with N,N-dimethylaminopropyl acrylamide (acrylamide compound), repeat Example 1 to obtain modified polymer rubber .

Comparative Example 5

In addition to (1) 11.2mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution Prepared) the active saturated or unsaturated hydrocarbon obtained by the polymerization reaction is replaced by 12.5mmol of n-butyllithium (hexane solution), (2) the amount of tin tetrachloride (coupling agent) added is changed to 1.63mmol, and (3) In addition to replacing 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) with 5.63mmol of N,N-dimethylaminopropylacrylamide (acrylamide compound), repeat the example 1 to obtain a modified polymer rubber.

The preceding tests were carried out on the polymer rubbers obtained in the above-mentioned Example 6 and Comparative Examples 2 and 5. The measured results are summarized in Table 4.

Table 4

Example 6 Comparative example 5 2 Styrene unit content (wt%) twenty three twenty two 29 Vinyl content (wt%) 58 58 42 Mooney Viscosity (ML ₁₊₄ 100℃) 75 72 66 Compound of formula (1) ^*1 I - - modifier ^*2 II II - Impact elasticity 60℃, % 60 56 51

^* 1I: Active saturated or unsaturated hydrocarbon obtained by polymerization of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium.

^* 2II: N,N-Dimethylaminopropylacrylamide.

Example 7

In addition to (1) changing the amount of tin tetrachloride (coupling agent) added to 0.22mmol, and (2) replacing 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) with 10.3mmol of Except for 1,3-dimethyl-2-imidazolidinone (heterocyclic compound), Example 1 was repeated to obtain a modified polymer rubber.

Example 8

Except (1) will be produced by two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution) The amount of active saturated or unsaturated hydrocarbons obtained by the polymerization reaction is changed to 9.72mmol, (2) tin tetrachloride (coupling agent) is not added, and (3) 1,3-dimethyl-2-imidazolidinone (Heterocyclic compound) except that the added amount was changed to 9.72 mmol, Example 7 was repeated to obtain a modified polymer rubber.

Comparative Example 6

In addition to (1) 11.2mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution Prepared) the active saturated or unsaturated hydrocarbon obtained by the polymerization reaction is replaced by 9.90mmol of n-butyllithium (hexane solution), (2) the amount of tin tetrachloride (coupling agent) added is changed to 0.50mmol, and (3) In addition to replacing 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) with 7.52mmol of 1,3-dimethyl-2-imidazolidinone (heterocyclic compound), repeat the implementation Example 1 obtained modified polymer rubber.

The preceding tests were carried out on the polymer rubbers obtained in Examples 7 and 8 and Comparative Examples 2 and 6 above. The measured results are summarized in Table 5.

table 5

Example 6 Comparative example 7 8 6 2 Styrene unit content (wt%) twenty two twenty two twenty two 29 Vinyl content (wt%) 58 60 58 42 Mooney Viscosity (ML ₁₊₄ 100℃) 71 99 69 66 Compound of formula (1) ^*1 I I - - modifier ^*2 II II II - Impact elasticity 60℃, % 65 65 56 51

^* 1I: Active saturated or unsaturated hydrocarbon obtained by polymerization of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium.

^* 2II: 1,3-Dimethyl-2-imidazolidinone.

Example 9

In addition to (1) changing the amount of tin tetrachloride (coupling agent) added to 0.22mmol, and (2) replacing 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) with 10.3mmol of Except for 3-glycidoxypropyltrimethoxysilane (silyl compound), Example 1 was repeated to obtain a modified polymer rubber.

Example 10

Except (1) will be produced by two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution) The amount of active saturated or unsaturated hydrocarbons added by the polymerization reaction is changed to 12.4mmol, and the tin tetrachloride (coupling agent) of (2) 0.22mmol is changed to the silicon tetrachloride of 0.25mmol, and (3) 3-ring Except that the amount of oxypropoxypropyltrimethoxysilane (silyl compound) added was changed to 11.4 mmol, Example 9 was repeated to obtain a modified polymer rubber.

Comparative Example 7

In addition to (1) 11.2mmol of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium (AI-200CE, prepared from FMC lithium, cyclohexylamine solution Prepared) the active saturated or unsaturated hydrocarbon obtained by the polymerization reaction is replaced by 10.50mmol of n-butyllithium (hexane solution), (2) the amount of tin tetrachloride (coupling agent) added is changed to 0.42mmol, and (3) In addition to replacing 9.6mmol of 1,1-dimethoxytrimethylamine (amine compound) with 8.82mmol of 3-glycidoxypropyltrimethoxysilane (silyl compound), repeat the implementation Example 1 obtained modified polymer rubber.

The preceding tests were carried out on the polymer rubbers obtained in Examples 9 and 10 and Comparative Examples 2 and 7 above. The measured results are summarized in Table 6.

Table 6

Example 6 Comparative example 9 10 7 2 Styrene unit content (wt%) twenty three twenty three twenty three 29 Vinyl content (wt%) 59 58 60 42 Mooney Viscosity (ML ₁₊₄ 100℃) 77 61 71 66 Compound of formula (1) ^*1 I I - - modifier ^*2 II II II - Impact elasticity 60℃, % 68 65 60 51

^* 1I: Active saturated or unsaturated hydrocarbon obtained by polymerization of two isoprene monomer units and 3-(N,N-dimethylamino)-1-propyllithium.

^* 2II: 3-Glycidoxypropyltrimethoxysilane.

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).