TWI583702B - Modified conjugated diene rubber, method and composition thereof - Google Patents

Description

Modified conjugated diene rubber and method and composition thereof

The present invention relates to a conjugated diene rubber, and more particularly to a conjugated diene rubber modified with two modifiers.

Solution styrene butadiene rubber (SSBR) is composed of butadiene and styrene units. First, the batch process was proposed by Phillips of the United States and the continuous process was proposed by Firestone, and the first industrialized production was realized. Since the solution-polymerized styrene-butadiene rubber has superior mechanical properties and rolling resistance than emulsion styrene butadiene rubber (ESBR), it is more widely used in the automotive industry and other rubber products.

With the recent reduction in fuel consumption requirements of automobiles, the demand for characteristics of rubber materials for tires has also increased. The conjugated diene rubber has low rolling resistance, excellent abrasion resistance, and more excellent steering stability due to resistance to wet skid, resulting in an increase in demand. On the other hand, the industry has proposed to add a silica compound or white smoke and carbon black as a reinforcing agent to the rubber composition of the tire. Tire treads containing white smoke or a mixture of white smoke and carbon black have low rolling resistance and resistance to slippage resulting in superior handling stability.

In order to make the conjugated diene rubber better compatible with the reinforcing agent, many techniques for modifying the conjugated diene rubber have been produced in the industry. No. 4,185,042 discloses a coupling agent for SBS block copolymers which reacts a lithium-containing polymer with a ruthenium-containing coupling agent to obtain a polymer having a coupling ratio of >90% and no Si-OR group present in the polymerization. In. U.S. Patent No. US 5,219,938 discloses a two-stage reforming step, by using two modifiers, a diene polymer chain end with a coupling agent R _n SiCl first lithium-containing polymer or a _4-n R _n SnCl _{4- The n} reaction is followed by modification with a coupling agent (R ⁵ R ⁶ R ⁷ -Si-(CH ₂ ) _n -NR ⁸ R ⁹ ). U.S. Patent 7,288,594 discloses the upgrading of lithium-containing styrene butadiene rubber in two stages with two different decane compounds. In addition, U.S. Patent No. 7,807,747 discloses the upgrading of lithium-containing styrene butadiene rubber in two stages with the same decane compound.

However, the modified conjugated diene rubber synthesized by the above prior art is often difficult and difficult to process, so the industry still needs a novel conjugated diene rubber upgrading technology to solve the problems caused by the prior art.

An aspect of the invention provides a method for producing a modified conjugated diene rubber, comprising: step (a): reacting an alkali metal ion-containing conjugated diene rubber with a first modifying agent, the first The modifier is as follows (I)

Wherein R ¹ , R ² , R ³ are each independently selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl and C ₆ -C ₁₂ aromatic, and R ^{4 is} selected from a group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy and C ₆ -C ₁₂ aromatic; and step (b): in this step (a) Then adding a second modifier, such as the following structural formula (II) (II) HO-R ⁵ -Y

Wherein R ^{5 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkenylene, C ₃ -C ₁₂ alicyclic group and C ₆ -C ₁₂ aryl group Y is selected from the group consisting of a C ₁ -C ₁₂ oxygen-containing group and a C ₁ -C ₁₂ nitrogen-containing group, and Y is bonded directly to a carbon atom of R ⁵ by an oxygen atom or a nitrogen atom thereof.

Another aspect of the present invention provides a modified conjugated diene rubber which is produced by the aforementioned manufacturing method, and a conjugated diene rubber composition comprising the modified conjugated diene rubber and a white Smoke (silica).

Yet another aspect of the present invention is to provide a modified conjugated diene rubber having the structural formula (III) or structural formula (IV) as follows:

D is a polymer chain composed of a conjugated diene unit or a conjugated diene unit and a vinyl aromatic unit, wherein R ^{4 is} selected from C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ a group consisting of an alkoxy group and a C ₆ -C ₁₂ aromatic group, and R ^{5 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkenylene, C ₃ -C ₁₂ a group consisting of an alicyclic group and a C ₆ -C ₁₂ aromatic group, Y is selected from the group consisting of a C ₁ -C ₁₂ oxygen-containing group and a C ₁ -C ₁₂ nitrogen-containing group, and Y is an oxygen atom thereof. Or a nitrogen atom thereof directly bonded to a carbon atom of R ⁵ ; and a conjugated diene rubber composition comprising the modified conjugated diene rubber and a silica.

The preferred embodiments of the present invention are exemplified below in order to fully understand the invention and the scope of the claims. In order to avoid obscuring the content of the present invention, the following description may omit conventional components, related materials, and related processing techniques. The following are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention; any equivalent changes or modifications made without departing from the spirit of the present invention should be included in the following. Within the scope of the patent application.

Polymerization: formation of conjugated diene rubber containing alkali metal ions

The method for producing an alkali metal ion-containing conjugated diene rubber of the present invention comprises a method of polymerizing a conjugated diene monomer or a conjugated diene monomer by an anionic polymerization method using an organic alkali metal compound as an initiator in a suitable solvent. And a vinyl aromatic monomer to form a conjugated diene rubber containing an alkali metal ion.

The polymer of the present invention may be a conjugated diene monomer polymer, or a conjugated diene monomer (such as butadiene or isoprene) and a vinyl aromatic monomer (such as benzene). a copolymer of styrene or methyl styrene. The polymerizable monomer of the conjugated diene rubber of the present invention is not limited to butadiene, isoprene, and styrene, and any of the above suitable derivatives can be used in the present invention. For example, the conjugated diene monosystem is independently selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3- Butadiene (2,3-dimethyl-1,3-butadiene), 3-butyl-1,3-octadiene, isoprene, 1 1-methylbutadiene, 2-phenyl-1,3-butadiene, and any combination thereof. The vinyl aromatic monomer can be independently selected from the group consisting of styrene, methylstyrene and all of its isomers, ethylstyrene and all of its isomers. , cyclohexylstyrene, vinyl biphenyl, 1-vinyl-5-hexyl naphthalene, vinyl naphthalene, vinyl anthracene (vinyl anthracene) and any combination of the above.

When the polymerization is carried out, an organolithium compound is preferably used as the initiator, and thus an alkali metal ion conjugated diene rubber having a carbon lithium ion at the end of the molecular chain can be obtained. Specific examples of the organolithium starter include n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, phenyllithium, tolyllithium, and the like, preferably It is n-butyl lithium.

A suitable solvent for the polymerization reaction, such as a passive organic solvent, which means a solvent which does not participate in the reaction in the polymerization reaction, such solvent contains butane, isobutane, and positive Aliphatic hydrocarbons of pentane, isopentane, 2,2,4-trimethylpentane, isohexane, n-hexane, isoheptane, n-heptane, isooctane, n-octane; or ring Hexane, methylcyclohexane, ethylcyclohexane, cyclopentane, cycloheptane, methylcyclopentane, or benzene, toluene, xylene, ethylbenzene, diethylbenzene, and propylbenzene The isomeric hydrocarbon compound is preferably a cyclohexane suitable for use in the present invention. The concentration of the polymerization solution of the conjugated diene rubber is generally from 5% to 35%, preferably from 10% to 30%. In general, if a passive organic solvent is used as a solvent alone, the polymerization rate of the vinyl aromatic or conjugated diene is slow and the polymerization reactivity of the two is quite different. In this case, a polar solvent can be added. get over. Specific examples of the polar solvent suitable for use in the present invention include ethers such as tetrahydrofuran, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol, dimethyl ether, methyl ethyl ether and the like. The compound and tetramethylethylenediamine are preferably tetrahydrofuran and diethyl ether.

The initial temperature of the polymerization can be from 10 ° C to 80 ° C, and the final temperature can be from 30 ° C to 150 ° C. The temperature control method can be adiabatic reaction, thermostatic control or partial cooling.

According to various embodiments of the present invention, the initial number average molecular weight (Mi) of the polymer after the completion of the polymerization but not yet reacted with the modifier is from 80 kg/mole to 2000 kg/mole, preferably from 100 kg/mole to 1500 kg/mole, More preferably between 150 kg/mole and 1000 kg/mole. The determination of the number molecular weight is carried out using a gel permeation chromatography (GPC), which is commonly used by those skilled in the art.

Add modifier

The upgrading reaction of the present invention uses two modifiers to form a modified conjugated diene rubber, which comprises the step (a) of reacting an alkali metal ion-containing conjugated diene rubber with a first modifying agent. The first modifier is of the following structural formula (I):

It is known from the structural formula (I) that the first modifier is a decane, wherein R ¹ , R ² , and R ³ are each independently selected from a C ₁ -C ₁₂ alkyl group, a C ₂ -C ₁₂ alkenyl group, and a C group. _a group consisting of _6- C ₁₂ aromatic groups, and R ^{4 is} selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy and C ₆ -C ₁₂ aromatic The group that makes up. In various embodiments of the first modifier of the present invention, each of R ¹ , R ² , R ³ , and R ⁴ is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. Isobutyl, tert-butyl, hexyl, 2-ethylhexyl; R ¹ , R ² , R ³ , R ^{4 are} each an alkenyl group, examples of which are vinyl, propenyl, n-butenyl, isobutenyl, pentene Examples of the aryl group; R ¹ , R ² , R ³ , and R ⁴ each being an aryl group are a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, and a propylphenyl group. Examples of the alkoxy group for R ⁴ are a methaneoxy group, an ethaneoxy group, a propoxy group, a n-butoxy group, and an isobutoxy group. A particularly preferred example of the first modifier is R ¹ , R ² , R ³ , and R ⁴ are all methyl trimethoxy(methyl)silane.

The alkali metal ion-containing conjugated diene rubber of the step (a) may be a polymer formed as described in the above polymerization step, or a suitable polymer formed by other means. When the upgrading reaction of the step (a) is carried out, the first modifier is separated from the alkali metal-containing The diene chain end of the conjugated diene rubber is bonded. The molar ratio of the first modifier to the conjugated diene rubber containing an alkali metal ion is ≧0.5, preferably ≧0.6, more preferably ≧0.7, but less than 10.

The upgrading reaction method of the present invention further comprises the step (b): after the step (a), a second modifying agent is added, and the second modifying agent is the following structural formula (II) (II) HO-R ⁵ -Y

Wherein R ^{5 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkenylene, C ₃ -C ₁₂ alicyclic and C ₆ -C ₁₂ aryl Y is selected from the group consisting of a C ₁ -C ₁₂ oxygen-containing group and a C ₁ -C ₁₂ nitrogen-containing group, and Y is bonded directly to a carbon atom of R ⁵ by an oxygen atom or a nitrogen atom thereof. It is known from the structural formula (II) that the second modifying agent is an alcohol having a hetero atom of O or N. Examples of the alkylene group wherein R ⁵ is an alkylene group are ethylene (-CH ₂ CH ₂ -), propyl (-CH ₂ CH ₂ CH ₂ -), and butyl (-CH ₂ CH ₂ CH). ₂ CH ₂ -); R ⁵ is an alkenylene (vinylene, -CHCH-), a propenyl group (-CH=CHCH ₂ -), a butenyl group (-CH=CHCH _{2 )} CH ₂ -), hexenyl (-CH2CH=CHCH2CH2CH2-); examples of R ⁵ being an aryl group are phenyl, tolyl, ethylphenyl, xylyl, propylphenyl; R ⁵ is an alicyclic group Examples are cyclopropane, cyclobutyl, cyclopentyl, cyclohexane, cycloheptyl. Examples of the oxygen-containing group wherein Y is C ₁ -C ₁₂ are a methaneoxy group, an ethaneoxy group, a propoxy group, a n-butoxy group, and an isobutoxy group. Examples of nitrogen-containing groups wherein Y is C ₁ -C ₁₂ are diethylamino, dimethylamino, methylethylamino. A particularly preferred example of the second modifier is 3-methoxyphenol or dimethylaminoethanol. The molar ratio of the second modifier to the conjugated diene rubber containing an alkali metal ion is ≧0.5, preferably ≧0.6, more preferably ≧0.7, but less than 10.

Water contact reaction

The conjugated diene rubber of the present invention may be brought into contact with water after the first modifier and the second modifier are added as described above, and the ratio of the amount of the conjugated diene rubber to the amount of water may be determined depending on the desired condition. If the stability of the Mooney viscosity is further improved, it may be contacted with a large amount of water, and the method may include a steam stripping method or other suitable methods. Taking steam stripping as an example, the solvent-containing conjugated diene rubber solution can be contacted with water at a temperature of 90 ° C, wherein the ratio of the amount of water to the solvent contained in the conjugated diene rubber solution is 0.1 or more. Preferably, it is 0.5 or more, preferably 1 or more, and the pH can be between 6 and 10. The temperature at which the two are in contact may be from 20 to 150 ° C, more preferably from 30 to 140 ° C, most preferably from 40 to 130 ° C, and the contact time between the two is from 5 minutes to 10 hours, more preferably from 10 minutes to 8 hours. The best is 30 minutes to 6 hours. The conjugated diene rubber solution may be removed by steam, electrothermal, hot air or other heat source simultaneously with or after contact with water, and then subjected to well-known drying methods such as mechanical dehydration, oven drying or apolon dryer. The treatment, or, for example, the rubber is dried at 110 ° C by hot roll. The coupling ratio of the conjugated diene rubber of the present invention measured after the above water contact treatment is 10% to 95%, preferably 20 to 80%, more preferably 25 to 75%, and the best is 30~70%.

The above examples illustrate that the conjugated diene rubber which has been reacted with the first modifier is first mixed with the second modifier, and then contacted with water as a preferred embodiment. However, the present invention also includes the use of an appropriate method to simultaneously add the second modifier to the water, or to effect the addition of the second modifier after the conjugated diene rubber reacted with the first modifier is first contacted with water. example. For example, after the first modifier is reacted The conjugated diene rubber is subjected to steam stripping, and the second modifier is added during the steam stripping process; or the conjugated diene rubber reacted by the first modifier is steam stripped to steam vapor After the completion of the addition, the second modifier is added.

Modification reaction mechanism

The reaction mechanism for the above modifications is reasonably presumed as follows:

Step (a): reacting an alkali metal ion-containing conjugated diene rubber with a first modifier

Wherein (A) represents a conjugated diene rubber containing an alkali metal ion lithium (Li), and D in (A) represents a polymer chain composed of a conjugated diene unit or a conjugated diene unit and a vinyl aromatic unit, After reacting with the first modifier oxirane (I), the metal ion lithium in the conjugated diene rubber (A) is replaced by the first modifier oxirane (I) to form a ruthenium oxyalkyl group. Conjugated diene rubber (B).

Step (b): After the step (a), the second modifier (II) is added, except that the second modifier is only mixed into the polymer solution without a modification reaction. Step (c): adding water to produce a hydrolysis reaction

The process in which the conjugated diene rubber (B) having a decyloxy group is contacted with water (for example, steam stripping) undergoes a hydrolysis reaction to form a hydrolyzate (D).

Step (d): the hydrolysis product (D) is reacted with the second modifier (II)

The hydrolyzate (D) will be reacted with the second modifier (II) to form a decane conjugated diene rubber having an N or O atom (denoted by Y), such as structural formula (III) or structural formula (IV). ) the polymer shown. It can be seen from the above that the sulfonate functional group is introduced into the conjugated diene rubber by the first modifier, and then the functional group containing the N or O atom is introduced into the oxirane by the second modifier. Conjugated diene rubber.

Modified conjugated diene rubber

After the above modification reaction, a modified conjugated diene rubber having the following structural formula (III) or structural formula (IV) can be formed:

Wherein R ^{4 is} selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy and C ₆ -C ₁₂ aryl, and R ^{5 is} selected from C ₁ - a group consisting of C ₁₂ alkylene, C ₂ -C ₁₂ alkenylene, C ₃ -C ₁₂ alicyclic group and C ₆ -C ₁₂ aromatic group, Y is selected from C ₁ -C _A group consisting of an oxygen-containing group and a C ₁ -C ₁₂ nitrogen-containing group, Y is bonded directly to the carbon atom of R ⁵ by its oxygen atom or its nitrogen atom. In a preferred embodiment R ⁴ is methyl. In a preferred embodiment wherein Y is a C ₁ -C ₁₂ oxygen-containing group, Y may be an alkyl group, an aryl group, or an alkenyl group linking the oxygen atom; and Y is a C ₁ -C ₁₂ nitrogen-containing group. In a preferred embodiment, Y may be a monoalkyl, aryl, or alkenyl group attached to the nitrogen atom. For examples of alkyl, aryl, alkenyl or alicyclic groups, reference may be made to the description in the above-described upgrading reaction. In a particularly preferred embodiment, -OR ⁵ -Y in structural formula (III) and structural formula (IV) is -O-(C ₆ H ₄ )-OCH ₃ or -O-CH ₂ CH ₂ N(CH ₃ ) ₂ .

Conjugated diene rubber composition

The modified conjugated diene rubber of the present invention can be formed into a conjugated diene rubber composition by mixing with other rubber components. Specific examples of other rubber components include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. Specific examples further include natural rubber, ethylene-propylene copolymer rubber, and ethylene-octene copolymer rubber. The above composition may be a mixed application of two or more types. The composition of the conjugated diene rubber composition containing the modified conjugated diene rubber may be such that when the total amount of all the rubber components is 100 parts by weight, the content of the modified conjugated diene rubber is preferably at least 10 parts by weight. Parts, and more preferably at least 20 parts by weight.

Further, the conjugated diene rubber composition of the present invention may contain an additive. Specific examples of the additive include a vulcanizing agent such as sulfur; a vulcanization accelerator such as a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator or a sulfenamide-based vulcanization accelerator; a vulcanization activator such as stearic acid or zinc oxide; an organic peroxide; a reinforcing agent such as white smoke or carbon black; a filler such as calcium carbonate or talc; a decane coupling agent; a filling oil; a processing aid; an antioxidant; Lubricants, etc.

In the example in which white smoke is used as a reinforcing agent to be mixed into the conjugated diene rubber composition of the present invention, when the total amount of all the rubber components is 100 parts by weight, the content of white smoke is usually from 10 parts by weight to 200 parts by weight. . From the viewpoint of fuel economy, the amount to be mixed is preferably at least 20 parts by weight, and more preferably at least 30 parts by weight. From the viewpoint of the reinforcing effect, it is preferably not more than 180 parts by weight, and more preferably not more than 150 parts by weight. White smoke can be amorphous synthetic white smoke, for example obtained by acidification of a soluble silicate such as sodium citrate or co-precipitation of citrate with aluminate. In general, such precipitated white smoke is well known to those of ordinary skill in the art. Synthetic white smoke (staining white smoke) The BET specific surface area, as measured by nitrogen, can be, for example, between about 50 and about 300 square meters per gram, and alternatively between about 100 and about 250 square meters per gram. The white smoke may also have a dibutylphthalate (DBP) absorption value, for example, ranging from about 100 cc/g to about 500 cc/g, preferably ranging from about 120 cc/g to about 350 cc/ Between g. Various other commercially available synthetic white smokes are contemplated for use in the present invention, including but not limited to, commercially available white smoke, such as those supplied by PPG Industries, such as the trademark Hi-Sil trademark Models 210, 243, etc.; by Rhodia Corporation Commercially available white smoke provided, such as the commercial models Zeosil 1165 MP and Zeosil 165GR; commercially available white smoke provided by EVONIK, such as the product models VN2, VN3, 7000GR, 9000GR; and the commercial market provided by Huber White smoke is sold, for example, the model number Zeopol 8745.

In the example in which the conjugated diene rubber composition of the present invention is blended with non-white smoke as a reinforcing agent, from the viewpoint of the reinforcing effect, when the total amount of all the rubber components is 100 parts by weight, the non-white smoke The content of the reinforcing agent is preferably not more than 120 parts by weight, and more preferably not more than 100 parts by weight. From the viewpoint of fuel economy, it is preferably at least 1 part by weight, and more preferably at least 3 parts by weight. A preferred specific example of the non-white smoke reinforcing agent is carbon black.

The method for producing a conjugated diene rubber composition by mixing the modified conjugated diene rubber of the present invention with another rubber component, an additive or the like can be, for example, a conventional mixer such as a roller or a 10,000-mass closed batch mixing. A Banbury mixer, or an internal mixer, is used to knead the components. Regarding the conditions of the kneading, in addition to the vulcanizing agent or the vulcanization accelerator, when the additive, the filler, the white smoke, and/or the other reinforcing agent are mixed, the kneading temperature is usually from 50 ° C to 200 ° C, preferably from 80 ° C to 150. °C, and when kneading The interval is usually from 30 seconds to 30 minutes, preferably from 1 minute to 30 minutes. When the vulcanizing agent or the vulcanization accelerator is mixed, the kneading temperature is usually not more than 100 ° C, preferably from room temperature to 90 ° C. The composition mixed by the vulcanizing agent or the vulcanization accelerator can be carried out by a vulcanization treatment such as press vulcanization. The temperature of the vulcanization treatment is usually from 120 ° C to 200 ° C, preferably from 140 ° C to 180 ° C.

The modified conjugated diene rubber of the present invention and the conjugated diene rubber composition thereof can be used for tires, soles, flooring materials, vibration-resisting materials, etc., and are particularly suitable for use in tires to improve the tire tread. Rolling resistance and improved handling stability and reliability due to resistance to slip.

The process of the polymerization reaction and the upgrading reaction of the present invention will be described in detail by way of examples below.

Example 1 (Y is a nitrogen-containing group)

An autoclave reactor was provided with an initial capacity of about 5 liters filled with nitrogen. 2750 g of cyclohexane, 82.5 g of tetrahydrofuran, 100 g of styrene and 390 g of 1,3-butadiene were charged in an autoclave reactor. When the temperature of the reactor contents reached 30 ° C, 310 mg (4.80 mmole) of n-butyl lithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions with a maximum temperature of 83 °C. When the polymerization was almost completed, 10 g of 1,3-butadiene was added and polymerization was carried out for about 5 minutes. Then, 1.308 mg (9.60 mmole) of trimethoxy(methyl)silane (hereinafter referred to as M1) was added for the first stage of the modification reaction for about 10 minutes. Then, 1.28 g (14.4 mmole) of dimethylaminoethanol (hereinafter referred to as M2) was further added and mixed for about 10 minutes. Next, add 2,6-di-tert-butyl-pair Phenol (2,6-di-tert-butyl-p-cresol) terminates the reaction in a polymer solution. Next, the polymer solution is desolvated to contact the modified conjugated diene rubber with a large amount of water, and then the solvent and moisture are removed using a viable heat source. The steam stripping step is carried out at 90 ° C, the ratio of the amount of water to the solvent is 1 or more, and the pH is between 6 and 10 for 3 hours. The obtained rubber was then subjected to hot roll drying at 110 °C. The modified conjugated diene rubber subjected to each of the above steps was defined as the rubber of Example 1. The molar ratio of the first modifier and the second modifier of Example 1 to the conjugated diene rubber containing an alkali metal ion, the initial molecular weight (Mi), and various properties of the obtained product are detailed in the attached In Table 1.

Example 2 (Y is a nitrogen-containing group)

The procedure of Example 2 can be referred to the procedure of Example 1, which uses the same solvent and reactants, and the reaction conditions differ only in the content of each reactant. The reaction conditions of the examples, such as the molar ratio of the modifier to the conjugated diene rubber containing an alkali metal ion, the initial molecular weight (Mi), and various properties of the obtained product are detailed in Table 2 below.

Example 3-4 (Y is an oxygen-containing group)

The procedure of Examples 3-4 can be referred to the procedure of Example 1. The reaction conditions differ only in that the second modifier of Examples 3-4 uses 3-methoxyphenol (hereinafter referred to as M3). The reaction conditions of the respective examples, such as the molar ratio of the first modifier and the second modifier to the conjugated diene rubber containing an alkali metal ion, the initial molecular weight (Mi), and various properties of the obtained product are detailed. It is listed in the attached Table 2. Examples 3-4 all used the same solvent and reactants, and the reaction conditions differ only in the content of each reactant.

Comparative example 1

The polymerization step was the same as in Example 1. In the case of the reforming reaction, 0.327 mg (2.40 mmole) of trimethoxy(methyl)silane (hereinafter referred to as M1) was carried out for about 10 minutes. Next, without adding a second modifier, 2,6-di-tert-butyl-p-cresol was directly added to the polymer solution to terminate the reaction. After the polymer solution rubber was desolvated, the modified conjugated diene rubber was obtained by hot roll drying at 110 ° C, which was defined as the rubber of Comparative Example 1. The molar ratio of the modifier of Comparative Example 1 to the conjugated diene rubber containing an alkali metal ion, the initial molecular weight (Mi), and various properties of the obtained product are detailed in Table 1 attached below.

Comparative examples 2 and 3

The procedure of Comparative Examples 2 to 3 can be referred to the procedure of Comparative Example 1, with the main difference being the different types of reactants. The modifier used in Comparative Example 1 was trimethoxy(methyl)silane (M1); the modifier used in Comparative Example 2 was tetraethoxysilane (TEOS); Comparative Example 3 The modifier used was tetramethoxysilane (TMOS). The molar ratio of the modifier of the comparative example to the conjugated diene rubber containing an alkali metal ion, the reaction conditions such as the initial molecular weight (Mi), and the characteristics of the product obtained after the reaction are detailed in Table 1 attached below.

The method of preparing the conjugated diene rubber composition of the rubber obtained in each of the above examples of the present invention and further forming a vulcanized sheet film to test the loss tangent will be described below.

100 parts by weight of each example rubber, 78.4 parts by weight of white smoke (trade name Ultrasil 7000GR, manufactured by EVONIK), and 6.9 parts by weight a decane coupling agent (trade name: Si69, manufactured by EVONIK Co., Ltd.), 50.0 parts by weight of a extender oil (butyl DAE, manufactured by IRPC Co., Ltd.), 1.5 parts by weight of an antioxidant (trade name Antigene 3C), and 2 parts by weight of stearic acid. 2 parts by weight of zinc oxide, 1.5 parts by weight of wax, 1.4 parts by weight of sulfur, and 2 parts by weight of a vulcanization accelerator (trade name CZ and D each 1 part by weight) were kneaded to form a composition. The composition was molded into a sheet film by a two-roller machine, and the sheet film was heated to 160 ° C for 45 minutes to be vulcanized, thereby obtaining a vulcanized sheet film.

The loss tangent (tan δ (60 ° C)) of the vulcanized sheet film at 60 ° C can be measured by using a viscoelastometer, and the measurement conditions are 1% strain and a frequency of 10 Hz. For example, with Comparative Example 2 as a standard and Comparative Example 2 as 100%, the higher the value of the embodiment, the better the energy saving effect. The loss tangent (tan δ (0 ° C)) of the vulcanized sheet at 0 ° C can be measured by using a viscoelastic instrument, and the measurement conditions are a strain of 0.5% and a frequency of 10 Hz. For example, with Comparative Example 2 as a standard and Comparative Example 2 as 100%, the higher the value of the embodiment, the better the safety effect of gripping the vehicle. The loss tangent obtained by the vulcanized sheet film of each example is shown in Table 1 and Table 2.

The above Acronyce wear rate wear resistance, tan δ (0 ° C) table wet grip, tan δ (60 ° C) table rolling resistance, the higher the three values, the better.

In Tables 1 and 2, Mooney Viscosity (MV, Mooney Viscosity) was measured by preheating for 1 minute and at 100 ° C for 4 minutes. The Mooney viscosity measurement time points are: after the modification reaction is completed and the solvent is removed (marked as direct solvent removal); after steam stripping and mechanical drying (labeled as stripping and drying); and after 90 ° C, relative humidity 80 % and 40 hours after storage test (marked as after storage test). The MV (after stripping and drying) and MV (after storage test) values are approximately equal, representing an improvement in the stability of the Mooney viscosity. Coupling ratio (C/R%) is measured by gel permeation chromatography (GPC) and refractive index meter. It refers to the ratio of the polymer with a molecular weight higher than the molecular weight before uncoupling to the total polymer. Tetrahydrofuran was used as the mobile phase during the measurement. The coupling rate measurement points are: the state of the polymer solution after completion of the modification reaction (labeled as a polymer solution); steam stripping and mechanical drying (labeled as stripping and drying). Other characteristics were tested by techniques well known to those skilled in the art, such as styrene content and vinyl content as measured by Fourier Transform Infrared Spectroscopy (FTIR). Akron abrasion wear resistance was measured using an Akron abrasion tester at a load of 6 pounds and 3300 revolutions. The higher the index, the less the wear is.

Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and the present invention can be modified and retouched without departing from the spirit and scope of the present invention. The scope of protection shall be as defined in the scope of the patent application attached hereinafter.

Claims (21)

A method for producing a modified conjugated diene rubber, comprising: step (a): reacting an alkali metal ion-containing conjugated diene rubber with a first modifying agent, the alkali metal ion-containing conjugated diene The rubber is formed by polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer by an anionic polymerization method using an organic alkali metal compound as an initiator, and the first modifier is as follows (I) ) Wherein R ¹ , R ² , R ³ are each independently selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl and C ₆ -C ₁₂ aromatic, and R ^{4 is} selected from a group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy and C ₆ -C ₁₂ aromatic; step (b): after step (a) Adding a second modifier, such as the following formula (II) (II) HO-R ⁵ -Y wherein R ^{5 is} selected from C ₁ -C ₁₂ alkylene, C ₂ a group of -C ₁₂ alkenylene, C ₃ -C ₁₂ alicyclic and C ₆ -C ₁₂ aryl, Y selected from C ₁ -C ₁₂ oxygen-containing groups and C ₁ -C ₁₂ a group consisting of nitrogen-containing groups, Y having its oxygen atom or its nitrogen atom bonded directly to a carbon atom of R ⁵ , wherein Y has a monoalkyl group, an alkenyl group, or an aromatic group bonded to the oxygen atom or the nitrogen atom Y has only one oxygen atom or one nitrogen atom; and step (c): adding water molecules simultaneously or before or after the step (b), wherein a hydrolyzate obtained in the step (c) is The second modifier reacts to form the modified conjugated diene rubber. The method for producing a modified conjugated diene rubber according to claim 1, wherein the R ¹ , R ² and R ³ are each independently selected from the group consisting of a methyl group, an ethyl group, and a propyl group. The method for producing a modified conjugated diene rubber according to claim 1, wherein the R ^{4 is} selected from the group consisting of a methyl group, an ethyl group, and a propyl group. The method for producing a modified conjugated diene rubber according to the above item 1, wherein the second modifier is 3-methoxyphenol or dimethylaminoethanol. The method for producing a modified conjugated diene rubber according to claim 1, wherein the molar ratio of the first modifier to the alkali metal ion-containing conjugated diene rubber is ≧0.5. The method for producing a modified conjugated diene rubber according to claim 1, wherein the molar ratio of the second modifier to the alkali metal ion-containing conjugated diene rubber is ≧0.5. The method for producing a modified conjugated diene rubber according to claim 1, wherein the method of adding water molecules in the step (c) comprises steam stripping. The method for producing a modified conjugated diene rubber according to claim 1, wherein the initial number of the alkali metal ion-containing conjugated diene rubber before the step (a) is carried out The average molecular weight is from 80 kg/mole to 2000 kg/mole. The method for producing a modified conjugated diene rubber according to claim 1, wherein the coupling ratio of the modified conjugated diene rubber after the step (c) is between 10% and 95%. A modified conjugated diene rubber produced by the production method according to any one of claims 1 to 9. A conjugated diene rubber composition comprising: the modified conjugated diene rubber according to claim 10; and a white silica. The conjugated diene rubber composition according to claim 11, wherein the content of the modified conjugated diene rubber is 10 when the total amount of all the rubber components of the conjugated diene rubber composition is 100 parts by weight. More than the weight. The conjugated diene rubber composition according to claim 11, wherein when the total amount of all the rubber components of the conjugated diene rubber composition is 100 parts by weight, the content of the white smoke is 10 to 200 parts by weight. A modified conjugated diene rubber having the structural formula (III) or structural formula (IV) is as follows: D is a polymer chain composed of a conjugated diene unit or a conjugated diene unit and a vinyl aromatic unit, and the conjugated diene monomer or the conjugated diene is polymerized by an anionic polymerization method using an organic alkali metal compound as an initiator. And a vinyl aromatic monomer formed, wherein R ^{4 is} selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy and C ₆ -C ₁₂ aromatic Group, R ^{5 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkenylene, C ₃ -C ₁₂ alicyclic group and C ₆ -C ₁₂ aryl group Group, Y is selected from the group consisting of C ₁ -C ₁₂ oxygen-containing groups and C ₁ -C ₁₂ nitrogen-containing groups, and Y is bonded directly to the carbon atom of R ⁵ by its oxygen atom or its nitrogen atom, wherein Y has a monoalkyl, alkenyl, or aryl group attached to the oxygen atom or the nitrogen atom, and Y has only one nitrogen atom or one oxygen atom. The modified conjugated diene rubber of claim 14, wherein the R ^{4 is} selected from the group consisting of methyl, ethyl, and propyl. The modified conjugated diene rubber according to claim 14, wherein the structural formula (III) and the -OR ⁵ -Y in the structural formula (IV) are -O-(C ₆ H ₄ )-OCH ₃ or -O-CH ₂ CH ₂ N(CH ₃ ) ₂ . The modified conjugated diene rubber according to claim 14, wherein the modified conjugated diene rubber has a coupling ratio of between 10% and 95%. The conjugated diene rubber composition according to claim 14, wherein the modified conjugated diene rubber is subjected to water contact treatment. A conjugated diene rubber composition comprising: the modified conjugated diene rubber according to any one of claims 14-18; and a white silica. The conjugated diene rubber composition according to claim 19, wherein the content of the modified conjugated diene rubber is 10 when the total amount of all the rubber components of the conjugated diene rubber composition is 100 parts by weight. More than the weight. The conjugated diene rubber composition according to claim 19, wherein when the total amount of all the rubber components of the conjugated diene rubber composition is 100 parts by weight, the content of the white smoke is from 10 to 200 parts by weight.