JPH0657767B2 - Modified rubber composition - Google Patents

Modified rubber composition

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Publication number
JPH0657767B2
JPH0657767B2 JP1926387A JP1926387A JPH0657767B2 JP H0657767 B2 JPH0657767 B2 JP H0657767B2 JP 1926387 A JP1926387 A JP 1926387A JP 1926387 A JP1926387 A JP 1926387A JP H0657767 B2 JPH0657767 B2 JP H0657767B2
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Japan
Prior art keywords
rubber
alkali metal
polymer
rubber composition
modified
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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JP1926387A
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Japanese (ja)
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JPS63186748A (en
Inventor
昭夫 今井
知明 関
宏美 高尾
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住友化学工業株式会社
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Priority to JP1926387A priority Critical patent/JPH0657767B2/en
Priority claimed from CA000553234A external-priority patent/CA1310787C/en
Publication of JPS63186748A publication Critical patent/JPS63186748A/en
Publication of JPH0657767B2 publication Critical patent/JPH0657767B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

TECHNICAL FIELD The present invention relates to a modified rubber composition which gives a vulcanized rubber having improved impact resilience and improved JIS hardness at low temperature, and more specifically to an active alkali metal terminal. And a conjugated diene polymer rubber having an alkali metal added thereto and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene polymer obtained by reacting the aminosilane compound The present invention relates to a modified rubber composition containing rubber as a rubber component.

<Prior Art> Conventionally, conjugated diene-based polymer rubbers such as polybutadiene and butadiene-styrene copolymer rubber have been used as rubbers for automobile tire treads, but in recent years, demand for low fuel consumption of automobiles and snow and ice Due to the requirement of driving safety, a rubber material having a small rolling resistance and a large road surface grip on snow and ice has been desired as a rubber for an automobile tire tread.

The rolling resistance correlates with the impact resilience of the polymer, and the higher the impact resilience, the smaller the rolling resistance.

On the other hand, the road grip on snow and ice is
It is known that there is a correlation with the IS hardness, and the lower the JIS hardness at low temperature, the greater the road surface grip on snow and ice. However, in the existing rubber material, these characteristics were not practically satisfactory.

<Problems to be Solved by the Invention> An object of the present invention is to provide a modified rubber composition containing a diene polymer rubber as a rubber component, which enhances impact resilience and reduces JIS hardness at low temperatures. .

<Means for Solving Problems> The present inventors have found that a rubber composition containing a conjugated diene-based polymer rubber as a rubber component has high impact resilience and J at low temperature.
As a result of repeated intensive studies to lower the IS hardness, an alkali metal-containing diene polymer is reacted with a specific compound,
It was found that a rubber composition containing a modified diene polymer rubber obtained by introducing a specific atomic group into a polymer as a rubber component can achieve the above-mentioned object and completed the present invention. .

That is, the present invention relates to a diene-based polymer rubber having an active alkali metal terminal or a conjugated diene-based rubber to which an alkali metal is added in a rubber composition comprising a rubber component and a compounding agent and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene polymer obtained by reacting the aminosilane compound The present invention relates to a modified rubber composition characterized by containing at least 10% by weight of rubber in a rubber component.

The alkali metal-containing diene polymer used in the present invention is obtained by polymerizing a diene monomer or the monomer and another monomer copolymerizable therewith with an alkali metal-based catalyst. Which has a conjugated diene unit in the polymer chain, regardless of the polymerization method (eg solution polymerization, emulsion polymerization, etc.) It means that an alkali metal is added by the reaction.

Examples of the diene polymer rubber include 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,
Polymer or copolymer rubber of conjugated diene monomer such as 3-dimethyl-1,3-butadiene and 1,3-hexadiene, or styrene, α-methylstyrene, vinyltoluene copolymerizable with the conjugated diene monomer and the monomer , Vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and other aromatic vinyl compounds, acrylonitrile and other unsaturated nitriles, (meth)
Examples thereof include, but are not limited to, a copolymer rubber with an ester of acrylic acid or vinyl pyridine.

Specifically, polybutadiene rubber, polyisoprene rubber,
Examples thereof include butadiene-isoprene copolymer rubber and butadiene-styrene copolymer rubber.

The diene polymer rubber in which an alkali metal is bonded to the end of the diene polymer rubber is, as described above, obtained by polymerizing the diene polymer rubber with an alkali metal-based catalyst, and at least the polymer chain. It is a living polymer before the termination of polymerization, in which an alkali metal is bonded to one end. It is possible to use a commonly used one such as an alkali metal-based catalyst, a polymerization solvent, a randomizer, a microstructure modifier for conjugated diene units, and the method for producing the polymer is not particularly limited.

Diene polymer rubbers obtained by adding an alkali metal to diene polymer rubbers include alkali metal base catalysts, alkaline earth metal base catalysts, solution polymerization using Ziegler catalysts, redox type catalysts, etc. Diene copolymer rubber obtained by polymerizing or copolymerizing the conjugated diene monomer or the conjugated diene monomer and a monomer copolymerizable therewith by a usual polymerization method such as emulsion polymerization (specifically, polybutadiene rubber, Polyisoprene rubber, butadiene-styrene copolymer rubber, butadiene-
Examples thereof include isoprene copolymer rubber, polypentadiene rubber, butadiene-piperylene copolymer rubber, and butadiene-propylene alternating copolymer rubber), but with an alkali metal added thereto.

Alkali metal addition to the diene polymer rubber may be carried out by a commonly used method. For example, a diene polymer rubber may be added to a hydrocarbon solvent in a conventional alkali metal base catalyst and an ether compound, an amine compound or a phosphine compound. The addition reaction is carried out in the presence of such a polar compound at a temperature of 30 to 100 ° C. for several tens of minutes to several ten hours. The amount of the alkali metal-based catalyst used may be usually in the range of 0.1 to 10 mmol per 100 g of the diene polymer rubber. If it is less than 0.1 mmol, the impact resilience cannot be improved, and if it exceeds 10 mmol, crosslinking of the polymer, Side reactions such as cutting occur and do not contribute to the improvement of impact resilience.

The polar compound is usually used for 1 mol of the alkali metal-based catalyst.
It is 0.1 to 10 mol, preferably 0.5 to 2 mol. An example of the alkali metal-based catalyst used in the polymerization and the addition reaction is as follows.

It is a complex with lithium, sodium, potassium, rubidium, cesium metal or their hydrocarbon compounds or polar compounds.

Preferred are lithium or sodium compounds having 2 to 20 carbon atoms.

For example, ethyl lithium, n-propyl lithium, iso
-Propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, 4-cyclopentyl lithium, 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, sodium salt of α-methylstyrene tetramer and the like.

The polymerization reaction and the alkali metal addition reaction are carried out in a hydrocarbon solvent or a solvent that does not destroy the alkali metal-based catalyst such as tetrohydrofuran, tetrahydropyran and dioxane.

The suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, and particularly has 2 to 2 carbon atoms.
Propane having twelve, n-butane, iso-butane,
n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene,
2-Pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like are preferable. Further, these solvents can be used as a mixture of two or more kinds.

Next, the compound to be reacted with the above-mentioned alkali metal-containing diene polymer rubber used in the present invention is represented by the general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer).

Specific examples of such aminosilane compounds are shown below.

3-dimethylaminomethyltrimethoxysilane, 3-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminobutyltrimethoxysilane, 3-dimethylaminomethyldimethoxymethylsilane, 3-dimethylaminoethyl Dimethoxymethylsilane, 3-dimethylaminopropyldimethoxymethylsilane, 3-dimethylaminobutyldimethoxymethylsilane, 3-dimethylaminomethyltriethoxysilane, 3-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3 -Dimethylaminobutyltriethoxysilane,
3-dimethylaminomethyldiethoxymethylsilane, 3
-Dimethylaminoethyldiethoxymethylsilane, 3-
Dimethylaminopropyldiethoxymethylsilane, 3-
Examples thereof include dimethylaminobutyldiethoxymethylsilane, and particularly preferred is 3-dimethylaminopropyldiethoxymethylsilane.

The amount of the aminosilane compound used is such that when an alkali metal is added to an alkali metal-based catalyst or a diene polymer rubber used in the production of a diene polymer rubber in which an alkali metal is bonded to the terminal, in a subsequent reaction. The amount is usually 0.05 to 10 mol, preferably 0.2 to 2 mol, per mol of the alkali metal-based catalyst used.

Since the reaction between the aminosilane compound and the active conjugated diene-based polymer rubber having an alkali metal terminal or the conjugated diene-based polymer rubber to which an alkali metal is added occurs rapidly,
The reaction temperature and reaction time can be selected over a wide range, but are generally room temperature to 100 ° C. and several seconds to several hours.

The reaction may be carried out by contacting the alkali metal-containing diene polymer rubber with the aminosilane compound. For example, the diene polymer rubber is polymerized using an alkali metal base catalyst and the aminosilane is added to the polymer rubber solution. A method of adding a predetermined amount of a compound, a method of reacting by adding the aminosilane compound after the completion of the alkali metal addition reaction in a diene polymer rubber solution can be exemplified as a preferable state, but is not limited to this method. Not something.

The resulting modified diene polymer rubber has an aminosilane compound introduced at the molecular end or in the molecular chain.

After completion of the reaction, the modified diene polymer rubber is used as it is in the coagulation method used in the production of rubber by ordinary solution polymerization such as addition of a coagulant from the reaction solution or steam coagulation, and the coagulation temperature is Is not restricted from

The crumb separated from the reaction system can also be dried by using a band dryer, an extrusion type dryer or the like used in the usual production of synthetic rubber, and the drying temperature is not limited at all.

The modified diene-based polymer rubber thus obtained has improved impact resilience and JIS hardness at low temperatures as compared with unmodified rubber, and thus is preferably used especially for automobile tires. Also, it can be used as a raw material rubber for various industrial purposes such as shoe soles, floor materials, anti-vibration rubbers, etc.

In the present invention, the modified modified diene polymer rubber is required to be contained as a rubber component in the rubber composition at least 10% by weight, preferably 20% by weight or more.

If the content of the rubber component is less than 10% by weight, improvement in impact resilience cannot be expected.

When the modified diene polymer rubber and other rubber are used in combination, the other rubber is emulsion-polymerized styrene-butadiene copolymer rubber, polybutadiene produced by solution polymerization (anionic polymerization catalyst, Ziegler type catalyst, etc.). Rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber and the like and natural rubber are included, and one or more of these rubbers are selected and used according to the purpose. .

Mooney viscosity of the modified modified diene polymer rubber (M
L 1 + 4 100 ° C.) is usually in the range of 10 to 200, preferably 20 to 150. If it is less than 10, mechanical properties such as tensile strength are inferior, and if it exceeds 200, miscibility is poor when it is used in combination with other rubber and processing operability becomes difficult, and a vulcanized product of the obtained rubber composition is obtained. It is not preferable because the mechanical properties of are deteriorated.

All or part of the rubber component used in the present invention can be used as an oil-extended rubber.

The rubber composition of the present invention is produced by mixing the rubber component and various compounding agents with a mixing machine such as a roll and Banbury. The various compounding agents to be used may be selected from those commonly used in the rubber industry, and those suitable for the purpose of use of the rubber composition may be selected, and are not particularly limited.

Usually, the vulcanization type is sulfur, stearic acid, zinc white, various vulcanization accelerators (thiazole type, thiuram type, sulfenamide type, etc.) or organic peroxides, and the reinforcing agent is various types such as HAF and ISAF. Grades of carbon black, silica and the like, fillers such as calcium carbonate and talc, and other compounding agents such as process oils, processing aids and antiaging agents. The type and amount of these compounding agents are selected according to the purpose of use of the rubber composition, and are not particularly limited in the present invention.

The modified rubber composition of the present invention has impact resilience and JIS at low temperature.
Since it has improved hardness, it is preferably used especially for automobile tires, but it can also be used as various industrial raw material rubbers for shoe soles, floor materials, anti-vibration rubbers, etc.

<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A polymerization reactor made of stainless steel having an internal volume of 10 was washed, dried and replaced with dry nitrogen, and then 1000 g of 1,3-butadiene,
4300 g of n-hexane, 40 mmol of ethylene glycol diethyl ether and 4.7 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring.

After the completion of the polymerization, 4.1 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes while stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.

Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd.
Riser BHT) and add most of the n-hexane to steam.
After emission, it was dried under reduced pressure at 60 ° C. for 24 hours.

The Mooney viscosity and 1,2-bond unit content (by infrared spectroscopy) of the resulting polymer rubber were measured.

The resulting polymer rubber had a Mooney viscosity of 85 and a vinyl content of 70%.

Comparative Example 1 A polymer was obtained by the same method as in Example 1 except that 3-dimethylaminopropyldiethoxymethylsilane was not added.

The polymer rubber produced has a Mooney viscosity of 85 and a vinyl content of 7
It was 0%.

Example 2 A polymerization reactor made of stainless steel with an internal volume of 10 was washed, dried, and purged with dry nitrogen.
g, 250 g of styrene, 4300 g of n-hexane, 23 g of tetrahydrofuran and 5.2 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring. After the completion of the polymerization, 4.4 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes with stirring, then 10 milliliter of methanol was added, and the mixture was further stirred for 5 minutes.

Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.

Mooney viscosity, vinyl content (by infrared spectroscopy) and styrene content (by refractive index method) of the resulting polymer rubber
Was measured.

The resulting polymer rubber had a Mooney viscosity of 85, a styrene content of 25% and a vinyl content of 40%.

Comparative Example 2 A polymer was obtained by the same method as in Example 2 except that 3-dimethylaminopropyldiethoxymethylsilane was not added.

The resulting polymer rubber had a Mooney viscosity of 85, a styrene content of 25% and a vinyl content of 40%.

The produced polymer rubbers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were kneaded on a roll according to the compounding recipe of Table 1 to obtain compounded rubber, which was 160 ° C. × 30. Press vulcanization was performed under the condition of minutes.

The impact resilience of the vulcanized rubber was measured at 60 ° C. using a Lupkeresilien tester. JIS hardness is JIS K63
01 at -20 ° C.

The results are shown in Table 2. From these results, the modified rubber composition of the present invention has the same Mooney viscosity as the rubber composition containing the polymer obtained by the same method as the polymer of the present invention and the polymer of the present invention except that the aminosilane compound is not added. The impact resilience is significantly higher than that of the rubber composition containing a polymer containing no aminosilane compound, and the J
It can be seen that the IS hardness is extremely low.

Example 3 and Comparative Example 3 A stainless steel polymerization reactor having an internal volume of 10 was washed and dried to give a styrene-butadiene copolymer (Moonie viscosity 5
1, styrene content 25%, vinyl content 40%) 500g,
4300 g of n-hexane was charged and dissolved with stirring. Then n
-Butyl lithium (n-hexane solution) (6.4 mmol) and tetramethylethylenediamine (6.4 mmol) were added, and the mixture was reacted at 70 ° C for 1 hour.

Next, 6.4 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes while stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.

Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours. The obtained polymer mu
The knee viscosity was 51.

The resulting polymer rubber was compounded in the same manner as in Example 1 and the vulcanized rubber physical properties were measured.

For comparison, the styrene-butadiene copolymer (modified Mooney viscosity 51, styrene content 25%, vinyl content 40%) before modification was compounded by the same method and the physical properties of the vulcanized rubber were measured. .

The results are shown in Table 2.

<Effects of the Invention> As described above, according to the present invention, it is possible to provide a modified rubber composition containing, as a rubber component, a diene polymer rubber that enhances impact resilience and reduces JIS hardness at low temperatures.

Claims (1)

[Claims]
1. A rubber composition comprising a rubber component and a compounding agent, wherein a diene polymer rubber having an active alkali metal terminal or a conjugated diene rubber having an alkali metal added thereto and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene-based compound obtained by reacting the aminosilane compound A modified rubber composition, characterized in that the rubber component contains at least 10% by weight of a united rubber.
JP1926387A 1987-01-28 1987-01-28 Modified rubber composition Expired - Lifetime JPH0657767B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1926387A JPH0657767B2 (en) 1987-01-28 1987-01-28 Modified rubber composition

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP1926387A JPH0657767B2 (en) 1987-01-28 1987-01-28 Modified rubber composition
CA000553234A CA1310787C (en) 1986-12-01 1987-12-01 Process for preparing modified diene polymer rubbers
DE19873789203 DE3789203D1 (en) 1986-12-01 1987-12-01 Process for the preparation of modified rubber-diene polymers.
DE19873789203 DE3789203T2 (en) 1986-12-01 1987-12-01 Process for the preparation of modified rubber-diene polymers.
EP19870117741 EP0270071B1 (en) 1986-12-01 1987-12-01 Process for preparing modified diene polymer rubbers
US07/415,380 US4957976A (en) 1986-12-01 1989-09-29 Process for preparing diene polymer rubbers
US07/501,700 US5015692A (en) 1986-12-01 1990-03-30 Process for preparing modified diene polymer rubbers

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JPS63186748A JPS63186748A (en) 1988-08-02
JPH0657767B2 true JPH0657767B2 (en) 1994-08-03

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