TWI504623B - Terminal-modified copolymer of conjugated diene and vinyl aromatic hydrocarbon and the synthesis method thereof - Google Patents

Description

Terminal modified conjugated diene-vinyl aromatic copolymer and synthesis method thereof

This invention relates to an olefin polymer, and more particularly to a terminally modified conjugated diene-vinyl aromatic copolymer.

The terminally modified conjugated diene-vinyl aromatic copolymer can be used to manufacture tires. Therefore, in order to save energy and drive safety considerations, the properties of rolling resistance and wet skid resistance are very important. It is a common practice to add carbon black to the terminally modified conjugated diene-vinyl aromatic copolymer to increase the strength of the tire.

It is conventionally known that the modifier used to modify the conjugated diene-vinyl aromatic copolymer is formamide, which improves the dynamic effect of the tire, and the carbon black is not easily dispersed in the total modification of the methotrexate. The conjugated diene-vinyl aromatic copolymer requires an additional modifier to be tested for the conjugated diene-vinyl aromatic copolymer of the tire.

The invention provides a terminally modified conjugated diene-vinyl aromatic copolymer and a synthetic method thereof, wherein the synthesized terminal modified conjugated diene-vinyl aromatic copolymer has good compatibility with carbon black. Sex, can produce tires with good wet skid resistance and low rolling resistance.

The invention provides a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer, which comprises the following steps: First, a conjugated diene monomer and a vinyl group are used in a weight ratio of 2:1 to 5:1. The aromatic hydrocarbon monomer is reacted in the presence of a microstructure control agent and an organic alkali metal compound to form a conjugated diene-vinyl aromatic copolymer having a living end. Next, the conjugated diene-vinyl aromatic copolymer having the active end is reacted with the first modifier to form an intermediate product. The intermediate product is then reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer. It is to be noted that the first modifier may be a tin-containing compound, and the second modifier may be a compound containing a -CM-N<linkage group, wherein M is a sulfur atom or an oxygen atom. The molar ratio of the first modifier to the second modifier is 1:4 to 4:1.

In an embodiment of the invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the total amount of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer is 100 The total amount of the first modifier and the second modifier is 0.001 parts by weight to 1 part by weight, the total number of moles of the first modifier and the second modifier, and the The molar ratio of the organic alkali metal compound is 0.95 to 1.05.

In an embodiment of the invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the microstructure adjusting agent is selected from the group consisting of tetrahydrofuran, Diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene and 2,2-dual (2 At least one of the group consisting of -tetrahydrofuranyl)propane. The first modifier includes a tin halide compound or a halogenated organotin compound.

In an embodiment of the invention, the method for synthesizing the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyl Dibutyltin dichloride, tributyltin chloride (TBSnCl), diphenyltin dichloride or triphenyltin chloride.

In one embodiment of the present invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the second modifier comprises a guanamine compound, a quinone imine compound, and a ruthenium An amine compound, a urea compound or an isocyanuric acid derivative.

The present invention also provides a terminally modified conjugated diene-vinyl aromatic copolymer which is polymerized from (A) a conjugated diene monomer and (B) a vinyl aromatic hydrocarbon monomer to form a conjugated diene-ethylene After the base aromatic hydrocarbon copolymer is modified by (C) the first modifier, and (D) the second modifier is produced. In the terminally modified conjugated diene-vinyl aromatic copolymer, a repeating unit composed of (A) a conjugated diene monomer and a repeating unit composed of the (B) vinyl aromatic hydrocarbon monomer The weight ratio is 2:1~5:1. (C) The first modifier is a tin-containing compound. (D) The second modifier is a compound containing -CM-N <linkage, wherein M is a sulfur atom or an oxygen atom. (C) The molar ratio of the first modifier to the (D) second modifier is 1:4 to 4:1.

In an embodiment of the invention, the terminal modified conjugated diene-ethylene The aromatic hydrocarbon copolymer, wherein the first modifier comprises a tin halide compound or a halogenated organotin compound.

In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the tin halide compound comprises tin tetrachloride or tin tetrabromide.

In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyltin dichloride, chlorine Tributyltin, diphenyltin dichloride or triphenyltin chloride.

In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the second modifier comprises a guanamine compound, a quinone imine compound, an intrinsic amine compound , a urea compound or a derivative of isocyanuric acid.

The present invention also provides a rubber composition comprising carbon black and the above-mentioned terminal-modified conjugated diene-vinyl aromatic copolymer.

Based on the above, the present invention proposes a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer. The terminally modified conjugated diene-vinyl aromatic copolymer synthesized according to this method has good compatibility with carbon black. Therefore, such terminally modified conjugated diene-vinyl aromatic copolymer is suitable for the manufacture of tires, and the tires produced thereof can exhibit excellent rolling resistance and excellent wet skid resistance.

The above described features and advantages of the invention will be apparent from the following description.

Hereinafter, a method of synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer will be described in detail according to an embodiment of the present invention.

In the present specification, if a group is not specifically indicated, whether or not a group is substituted, the group may represent a substituted or unsubstituted group. For example, "alkyl" can mean a substituted or unsubstituted alkyl group. Further, when a group crown is described by "Cx", it means that the main chain of the group has X carbon atoms.

In the present specification, the compound structure is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the functional group is clearly drawn in the structural formula, the manufacturer will prevail.

In the specification, "phr (part per hundred rubber)" is sometimes used as a unit of the amount of additives, which is a common term in the field of rubber synthesis, and means "parts by weight per 100 parts by weight of rubber. The term "rubber" as used herein means a conjugated diene-vinyl aromatic copolymer. Further, in the specification, the portion relating to the polymerization reaction is considered to be equal to the sum of the weight of the conjugated diene-vinyl aromatic copolymer and the weight of the conjugated diene monomer plus the vinyl aromatic hydrocarbon monomer. That is, when the amount of the additive is represented by phr in the polymerization reaction, the reference may be 100 parts by weight of the conjugated diene-vinyl aromatic copolymer, or 100 parts by weight of the conjugated diene monomer and ethylene. Aromatic aromatic hydrocarbon monomer.

<End-modified conjugated diene-vinyl aromatic copolymer>

According to an embodiment of the present invention, a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprises the steps of: (a) reacting a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer to Forming a conjugated diene-vinyl aromatic copolymer; (b) reacting the conjugated diene-vinyl aromatic copolymer with the first modifier to form an intermediate product; and (c) intermediate product The second modifier is reacted to form a terminally modified conjugated diene-vinyl aromatic copolymer.

The above various steps are described in detail below:

Step (a)

Step (a) can be carried out by any conventional method of polymerizing a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer. For example, the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer can be polymerized in the presence of a polymerization initiator to form an unmodified conjugated diene-vinyl aromatic copolymer having a living end. In the step (a), the weight ratio of the conjugated diene monomer to the vinyl aromatic hydrocarbon monomer is from about 2:1 to 5:1, so that the copolymer comprises the above-mentioned conjugated diene monomer. The weight ratio of the conjugated diene repeating unit and the vinyl aromatic hydrocarbon monomer unit composed of the above vinyl aromatic hydrocarbon monomer is also about 2:1 to 5:1. In one embodiment, the proportion of the conjugated diene monomer in the conjugated diene-vinyl aromatic copolymer may be between 74% and 84% by weight, and the vinyl aromatic hydrocarbon structural unit is Conjugated diene-vinyl aromatic copolymer The proportion may be between 16% and 26% by weight.

The polymerization initiator may be an organic alkali metal compound such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium or a combination thereof.

The conjugated diene monomer may be 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutyl Diene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene or a combination thereof.

The vinyl aromatic hydrocarbon monomer can be styrene, alpha-methyl styrene, divinyl benzene, or a combination thereof.

In one embodiment, the conjugated diene monomer is 1,3-butadiene and the vinyl aromatic hydrocarbon monomer is styrene.

The conjugated diene-vinyl aromatic copolymer obtained by the polymerization of the step (a) includes a conjugated diene structural unit and a vinyl aromatic hydrocarbon structural unit. Here, the "structural unit" (or monomer unit) means a repeating structure in which the above-mentioned conjugated diene monomer or vinyl aromatic hydrocarbon monomer is polymerized.

The conjugated diene structural unit may include a 1,3-butadiene structural unit, an isoprene structural unit, a 1,3-pentadiene structural unit, a 2-ethyl-1,3-butadiene structural unit, 2,3-dimethylbutadiene structural unit, 2-methylpentadiene structural unit, 4-methylpentadiene structural unit, 2,4-hexadiene structural unit or a combination thereof.

The vinyl aromatic hydrocarbon structural unit may include a styrene structural unit, an αmethylstyrene structural unit, a divinylbenzene structural unit, or a combination thereof.

In one embodiment, the conjugated diene structural unit is a 1,3-butadiene structure And the vinyl aromatic hydrocarbon structural unit is a styrene structural unit.

The conjugated diene monomer can be subjected to 1,4 polymerization and/or 1,2 polymerization to form 1,4 structural units (or vinyl 1,4 structures, hereinafter referred to as 1,4 structures) and/or 1,2 structures. Unit (or vinyl 1, 2 structure, hereinafter referred to as 1, 2 structure). In detail, "1,4 polymerization" means that the conjugated diene monomer is bonded to other monomers via its 1-position and 4-position carbon, and the 1,4 structure which is polymerized in this way can be further divided into Similarly, "1,2 polymerization" refers to a 1,2 structure in which a conjugated diene monomer is bonded to another monomer via its 1-position and 2-position carbons by polymerization of 1,2. It is a structure in which a vinyl group is located in a side chain. The 1,4 structure and the 1,2 structure may coexist in the polymer chain. For example, when polymerizing with a 1,3-butadiene monomer, a 1,2-polybutadiene structural unit or a 1,4-polybutadiene structural unit can be produced.

The ratio of the 1,2 structure to all of the conjugated diene structural units (i.e., the sum of the 1,4 structural units and the 1,2 structural units) may be between 10% and 90%. In one embodiment, the ratio of the 1,2 structure to the conjugated diene structural unit is between 50% and 90%, preferably between 55% and 70%.

The polymerization of the step (a) can be carried out in the presence of a solvent. The solvent may include a non-polar solvent such as, but not limited to, an aliphatic hydrocarbon such as pentane, hexane or heptane; an alicyclic hydrocarbon such as cyclopentane, cyclohexane, methylcyclopentane or methylcyclohexane; An aromatic hydrocarbon such as benzene, toluene or xylene or a mixture of the foregoing solvents.

In one embodiment of the present invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer further comprises adding a conjugated diene monomer to a vinyl aromatic hydrocarbon monomer. Dividing agents to increase the availability of a single molecular chain The active point of the quality makes the modification effect better. The diverging agent may be polyepoxides such as epoxidized linseed oil; polyesters such as diethyl adipate; polyhalides ), such as silicon tetrahalide; polyisocyanates, such as benzene-1,2,4-triisocyanate; polyimine (polyimines) ), such as tris(1-aziridinyl)phosphine oxide; polyaldehydes such as 1,4,7-naphthalene tricarboxylic aldehyde (1,4,7) -naphthalene tricarboxaldehyde); polyketones such as 2,4,6-heptanetrione; polyanhydrides such as pyromellitic Dianhydride); a polyvinylbenzene compound such as divinylbenzene (DVB) or a combination of the above compounds. The present invention preferably uses divinylbenzene.

Further, the polymerization of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer can be carried out in the presence of a microstructure control agent. The use of a microstructure adjusting agent enables random copolymerization of a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer. The microstructure modifier can be a polar compound and, in one embodiment, can act as a vinylating agent or a 1,2-vinyl configuration agent.

Microstructural modifiers include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, two Ethers such as methoxybenzene and 2,2-bis(2-tetrahydrofuryl)propane; a tertiary amine compound such as ethylenediamine, dipiperidineethane, trimethylamine, triethylamine, pyridine, quinuclidine, potassium third potassium pentoxide, potassium butoxide, sodium butoxide, An alkali metal alkoxide compound such as sodium pentaerythritol; a phosphine compound such as triphenyl phosphine; an alkylsulfonic acid compound or an arylsulfonic acid compound. The above polar compounds may be used singly or in combination of two or more kinds of polar compounds.

The amount of microstructure control agent can be selected according to actual needs and the effect of adjusting the structure. Typically, the microstructure modifier is from 0.01 moles to 100 moles relative to 1 mole of polymerization initiator. In one embodiment, the microstructure modifier is used in an amount from 0.05 phr to 0.5 phr. A polar compound (vinylating agent) can be used as a microstructure adjusting agent in an appropriate amount according to the desired amount of the 1,2 structure.

Further, after the polymerization of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, a substance sufficient to react with the unmodified conjugated diene-vinyl aromatic copolymer having the active end may be added first. The conjugated diene-vinyl aromatic copolymer is deactivated and then added with a modifier, or a modifier can be added directly as a polymerization terminator. It is preferred to add a modifier when the unmodified conjugated diene-vinyl aromatic copolymer has an active end.

In one embodiment, the unmodified conjugated diene-vinyl aromatic copolymer obtained in the step (a) may have a weight average molecular weight of 800,000 to 1500,000, and preferably 900,000 to 1,300,000, more preferably It is 970,000~1270,000.

Step (b)

In the step (b), the conjugated diene-vinyl aromatic copolymer obtained in the step (a) is reacted with the first modifier to form an intermediate product.

The first modifier may be a tin-containing compound such as a tin halide compound or a halogenated organotin. The tin halide compound includes tin tetrachloride, tin tetrabromide or the like. The halogenated organotin compound includes diethyltin dichloride, dibutyltin dichloride, tributyltin chloride, diphenyltin dichloride, triphenyltin chloride or the like. In view of the safety of processing and storage, the first modifier is preferably a tin compound having a low degree of halogenation, such as tributyltin chloride or triphenyltin chloride.

The above first modifying agent may be used singly or in combination of two or more kinds of first modifying agents.

In one embodiment, the first modifier is used in an amount of from 0.01 phr to 0.3 phr, preferably from 0.08 phr to 0.3 phr, and more preferably from 0.08 phr to 0.12 phr.

Step (c)

In the step (c), the intermediate product obtained in the step (b) is reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer.

The second modifier may be a compound containing -CM-N < linking group, wherein M is a sulfur atom or an oxygen atom. The -CM-N<linking group-containing compound is, for example, a guanamine compound, a quinone imine compound, an indoleamine compound, a urea compound or a heterocyanuric acid derivative.

Indoleamines include formamide, dimethylformamide (N, N-dimethylformamide), acetamide, N,N-dimethylaminoacetamide, N,N-dimethyl-N', N'-di N,N-dimethyl-N', N'-dimethylaminoacetamide, N,N-dimethyl-N'-ethylacetamide (N,N-dimethyl-N'-ethylaminoacetamide ), acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, nicotine oxime Nicotinamide, isonicotitinamide, picolinic acid amide, N,N-dimethylisonicotinamide, succinic acid Amide), phthalic acid amide, N,N,N'N'-tetramethylphthalic acid amide, grass carp Oxamide, N, N, N'N'-tetramethyloxamide (N, N, N'N'-tetramethyloxamide), N,N-dimethyl-2-furancarboxylic acid decylamine (N, N-dimethyl-2-furan carboxylic acid amide), quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinoline-2-carboxylic acid hydrazine (N-ethyl-N-methyl-quinoline carboxylic acid amide) or the like.

The quinone imines include succinic imide, N-methylsuccinic imide, maleimide, phthalimide, N-methylphthalimide, 1,2-cyclohexanedicarboxyimide or the like.

Indoleamines include ε-caprolactam (N-caprolactam), N- Methyl-ε-caprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2- 2-piperidone, N-methyl-2-piperidone, 2-quinolone, N-methyl-2-quinolinone (N-methyl-2-quinolone) or an analogue thereof.

Urea compounds include urea (urea), N, N'-dimethylurea (N, N'-dimethylurea), N, N'-diethyl urea (N, N'-diethylurea), N, N, N ',N'-tetramethylurea (N,N,N',N'-tetramethylurea), N,N-dimethyl-N',N'-diphenylurea (N,N-dimethyl-N' , N'-diphenylurea) or an analogue thereof. The urethane derivative includes methyl carbamate, N, N-dimethyl methyl carbamate or the like. The isomeric cyanuric acid derivative includes isocyanuric acid or the like.

The above second modifying agent may be used singly or in combination of two or more kinds of second modifying agents.

In one embodiment, the second modifier is used in an amount of from 0.001 phr to 1 phr, preferably from 0.001 phr to 0.5 phr, and more preferably from 0.01 phr to 0.05 phr.

In one embodiment, the molar ratio of the first modifier to the second modifier may be 1:4 to 4:1, preferably 1:1 to 5:2, and more preferably 3: 1~7:3~.

In one embodiment, the ratio of the total number of moles of the modifier (the sum of the amount of the first modifier to the second modifier) to the molar amount of the polymerization initiator (eg, an organic alkali metal compound) It can be from 0.95 to 1.05, and preferably from 0.98 to 1.02.

After completion of step (c), a total of end-modifications can be added to the reaction system. A poor solvent of the conjugated diene-vinyl aromatic copolymer, such as an alcohol (such as methanol, ethanol or isopropanol), precipitates the terminally modified conjugated diene-vinyl aromatic copolymer, or is higher than The terminally modified conjugated diene-vinyl aromatic copolymer is separated from the mixture by hot water at the boiling point of the solvent or by removing the solvent with water vapor.

In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer is synthesized by reacting a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer to form a total of active ends. After the conjugated diene-vinyl aromatic copolymer, a first or second modifier is added.

In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer is polymerized from (A) a conjugated diene monomer and (B) a vinyl aromatic hydrocarbon monomer to form a conjugated diene-vinyl group. After the aromatic hydrocarbon copolymer is modified by (C) the first modifier and (D) the second modifier. When the polymerization reaction is carried out, the weight ratio of the (A) conjugated diene monomer to the (B) vinyl aromatic hydrocarbon monomer is from 2:1 to 5:1. (C) The first modifier may be a tin-containing compound. (D) The second modifier may be a compound containing -CM-N<, wherein M is a sulfur atom or an oxygen atom. The amount of the (C) first modifier and the (D) second modifier are respectively, based on 100 parts by weight of the total of the (A) conjugated diene monomer and the (B) vinyl aromatic hydrocarbon monomer. 0.001 parts by weight to 1 part by weight and 0.001 parts by weight to 1 part by weight.

In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer has a weight average molecular weight of from 800,000 to 1,500,000 and a number average molecular weight of from 450,000 to 900,000. The polydispersity is 1.5~2.0.

<Rubber Composition>

The present invention further provides a method of producing a rubber composition. In one embodiment, a method of making a rubber composition includes kneading rubber and carbon black to obtain a rubber composition, wherein the rubber comprises any of the terminally modified conjugated diene-vinyl aromatic copolymers as described in detail above. In one embodiment, the rubber comprises a terminally modified conjugated diene-vinyl aromatic copolymer and another unmodified conjugated diene-vinyl aromatic copolymer. It is noted that the other unmodified conjugated diene-vinyl aromatic copolymer may be the same or different from the conjugated diene-vinyl aromatic copolymer used to form the terminal modification. Unmodified conjugated diene-vinyl aromatic copolymer.

The terminally modified conjugated diene-vinyl aromatic copolymer and another unmodified conjugated diene-vinyl aromatic copolymer may respectively comprise a conjugated diene structural unit and a vinyl aromatic hydrocarbon structure. A unit in which a conjugated diene structural unit contains a vinyl structure (1, 2 structure).

In one embodiment, the vinyl structure in the terminally modified conjugated diene-vinyl aromatic copolymer has a percentage in its conjugated diene structural unit that is substantially the same as another unmodified. The percentage of the vinyl structure in the conjugated diene-vinyl aromatic copolymer in the conjugated diene structural unit.

The rubber composition to which the terminal-modified conjugated diene-vinyl aromatic copolymer of the present invention is applied may be optionally added with various chemicals or additives which are often added in the rubber industry as needed. Those which can be added to the rubber composition include a filler, an antioxidant, a coupling agent, a vulcanization reaction activator, a vulcanization accelerator, a vulcanizing agent, an antioxidant, a process oil, and the like.

The filling material can be carbon black, and the amount of carbon black can be 10% of the rubber used. It is preferably from 20 to 90 parts by weight to 100 parts by weight.

The antioxidant includes a phenolic compound having at least one hindered phenol functional group (for example, Ix-1076 manufactured by CIBA); a dialkylphenyl triphosphite antioxidant; naphthylamines, Aminated antioxidants of diphenylamines or p-phenylenediamines; phenolic antioxidants of trialkyl phenols, hydroquinones or polyphenols, or combinations of the foregoing . The antioxidant may be used in an amount of from 0.2 to 1 part by weight based on the rubber used.

The coupling agent includes bis-(3-triethoxysilylpropyl)tetrasulfide, bis-3-(triethoxymethanealkylpropyl) disulfide Bis-(3-triethoxysilylpropyl)disulfide, bis-(2-triethoxysilylethyl)tetrasulfide, 3-mercaptopropyltriethoxylate 3-mercaptopropyltriethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide or an analogue thereof. The coupling agent may be used in an amount of from 1 to 15 parts by weight, based on the rubber used, preferably from 5 to 10 parts by weight.

The vulcanization aid includes a vulcanization reaction activator and a vulcanization accelerator.

The vulcanization reaction activator is, for example, zinc oxide or stearic acid.

The vulcanization accelerator may be mercapto-benzthiazoles, sulfenamides, guanidines, dithiocarbamates, thioureas or thiocarbonates. (thiocarbonates). The vulcanization accelerator is preferably a sulfenamide accelerator, wherein the sulfoximine vulcanization accelerator is, for example, cyclohexylbenzothiazole-sulfenamide or dicyclohexylbenzothiazole. Dicyclohexylbenzothiazole-sulfenamide, butylbenzo-thiazolesulfenamide or a combination of the above compounds. The vulcanization accelerator is more preferably N-cyclohexyl-2-benzothiazole sulphide (CBS), diphenylguanidine (DPG) or a combination of the above compounds.

A vulcanizing agent such as sulfur or an organic sulfur supplier. The total amount of the vulcanization aid (vulcanization reaction activator, vulcanization accelerator) and vulcanizing agent may be 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on the rubber used.

The antioxidant is, for example, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD). The antioxidant may be used in an amount of from 1 to 10 parts by weight based on the rubber used.

<Example> Example 1

First, 8 kg of cyclohexane was added to the reaction tank as a solvent, and the temperature of the reaction system was maintained at 45 °C. Next, take 6.4 g of 2,2-bis(2-tetrahydrofuran) 2,2-di(2-tetrahydrofuryl) propane (DTHFP) was added to the reaction vessel as a microstructure modifier. Then, 0.8 g of n-butyllithium (n-BL) was added to the reaction tank as a starter for the polymerization. Here, the molar ratio of the microstructure control agent to the polymerization initiator is substantially about 2:1. Next, 447 g of styrene was used as the vinyl aromatic hydrocarbon monomer, and 1683 g of butadiene was used as the conjugated diene monomer, and was added to the reaction vessel for polymerization. Thereafter, 74.6 g of butadiene monomer was added to carry out the reaction. At this time, after sampling and removing the solvent of the sample, the content of the 1,2 structure in the copolymer was measured by IR or NMR, and it was found that the ratio of the 1,2 structure in all the butadiene structural units was 63%. The styrene structural unit of the copolymer accounts for about 21% by weight of the entire butadiene structural unit and the styrene structural unit, and the butadiene structural unit accounts for about 79% by weight of the entire butadiene structural unit and the styrene structural unit.

After the reaction in the reaction tank was reacted for about 15 minutes, 0.12 phr (2.6 g) of tin tetrachloride (TBSnCl) was added as the first modifier. Next, after 15 minutes of reaction, 0.004 phr (0.09 g) of formamide was further added as a second modifier. The amount of the first modifier is 8.00×10 ^-3 mole (=2.6/325.51); the amount of the second modifier is 2×10 ^-3 mole (=0.09/45); and the molar ratio of the two It is 8:2.

Next, the crude product may be precipitated using an alcohol such as methanol, ethanol or isopropanol, or the solvent may be removed with water vapor to obtain a crude product. After drying the above crude product, the oil-free terminal modified conjugated diene-vinyl aromatic copolymer of Example 1 was obtained.

Example 2-3 and Comparative Example 4-6

The terminally modified conjugated diene-vinyl aromatic copolymer of Examples 2-3 and Comparative Examples 4-6 was prepared in the same manner as in Example 1. However, the difference is the amount of the first modifier and the second modifier (as shown in Table 1).

Comparative Example 7

The terminally modified conjugated diene-vinyl aromatic copolymer of Comparative Example 7 was prepared in the same manner as in Example 1. However, the difference is that the amount of tributyltin chloride (TBSnCl) and formamide used is 5:5, which is the same as in Example 3, but the order of the modification reaction is reversed (first made with formamide). It is the first modifier, and then tin tetrachloride (TBSnCl) is used as the second modifier.

<Experimental example> Experimental example 1

First, 790 g (100 phr) of the oil-free terminal-modified conjugated diene-vinyl aromatic copolymer of the above Example 1 was kneaded with the following to prepare a rubber composition. Carbon black (HAF 330; 50 phr, 395 g), oil (Treated Distillate Aromatic Extract, TDAE, 5.0 phr, 39.5 g), ZnO (3 phr, 23.7 g), and stearic acid (1.5 phr, 11.9 g) were placed in the rubber. After the temperature rises to 150 ° C, the material is aged at room temperature for 24 hours. In this way, the glue can be obtained. The above procedure is done with a banbury mixer. The discharged rubber was vulcanized by adding 1.25 phr of N-cyclohexyl-2-benzothiazole sulfenamide, 1.75 phr of sulfur in a roll mixer to obtain a rubber composition. Information on the materials used in the preparation of the rubber composition is as follows.

Carbon black: HAF 300, manufactured by China Rubber.

Oil: Manufactured by Treated Distillate Aromatic Extract, TDAE, Vivtec 500, H&R.

Zinc oxide: ZnO, manufactured from HA.

N-cyclohexyl-2-benzothiazole sulfoximine: N-cyclohexyl-2-benzothiazolesulphenamide, CBS, manufactured by FLEXSYS.

Sulfur: Triangle.

Stearic acid: TPSA 1865, manufactured by CV. Pacific Indochem.

Experimental Example 2 - Experimental Example 3

Experimental Example 2 - The rubber composition of Experimental Example 3 was prepared in the same manner as in Experimental Example 1. However, the difference was that the rubber compositions of Experimental Example 2 and Experimental Example 3 were replaced with the terminal modified conjugated diene-vinyl aromatic hydrocarbon copolymer of Example 2 and Example 3, respectively, in place of the end of Example 1. A modified conjugated diene-vinyl aromatic copolymer is prepared.

Experimental Example 4 - Experimental Example 7

Experimental Example 4 - The rubber composition of Experimental Example 7 was prepared in the same manner as in Experimental Example 1. However, the difference was that the rubber composition of Experimental Example 4 - Experimental Example 7 was replaced with the terminal modified conjugated diene-vinyl aromatic copolymer of Comparative Example 4 - Comparative Example 7, respectively, in place of the end of Example 1. A modified conjugated diene-vinyl aromatic copolymer is prepared.

<Evaluation method>

Viscosity

Mooney viscosity: measured by Alpha Technology model MV-2000 with reference to ASTM D-1646, measuring temperature conditions of 100 ° C, measuring time of 1 + 4 minutes, respectively measuring copolymers (examples and comparative examples) ), rubber (experimental example) composition of the Mooney viscosity (mixey viscosity (mooney), rubber composition viscosity and the difference between the two ΔMooney). The lower the Mooney viscosity, the better the processability of the rubber composition. △Mooney indicates that the lower the viscosity increase after processing, the easier it is to process.

2. Wear resistance

The wear resistance was measured by the wear resistance tester GT-7012-D with reference to DIN 53 516, and the test piece size was 29 cm (diameter) × 12.5 mm (thickness). The smaller the value of the wear resistance, the better the resistance to wear.

3. Dynamic storage elastic modulus difference (△E')

The dynamic storage elastic modulus of the rubber composition was measured using a viscoelasticity measuring device manufactured by TA Instruments, Model DMA Q800. The measurement mode is the tensile mode, and the measurement frequency is 20 Hz. The temperature at which the dynamic storage elastic modulus (E) was measured was set at 60 ° C, and the degree of deformation was measured to be 0.5% to 10%. The dynamic storage elastic modulus measured at a deformation degree of 0.5% minus the dynamic storage elastic modulus measured at 10% of the deformation degree is the dynamic storage elastic modulus difference (ΔE'), and the unit is MPa. △E' is also called the Payne Effect, and the smaller the value of ΔE', the better the compatibility of the rubber composition with carbon black.

4. Loss tangent (Tan δ (0 ° C) and Tan δ (60 ° C))

The loss tangent (tan δ) of the rubber composition was measured using a viscoelasticity measuring device manufactured by TA Instruments, model DMA Q800. The temperature at which the loss tangent was measured was selected at 0 ° C and 60 ° C, and the rate of temperature rise for measuring the loss tangent was 3 ° C per minute. The test at 0 °C can be regarded as the performance of the simulated tire on the icy road surface, the higher the loss tangent, the better the wet skid resistance of the rubber composition; the test at 60 ° C It can be regarded as the performance of the simulated tire at high speed, and the lower the loss tangent, the lower the rolling resistance of the rubber composition.

The evaluation results of the rubber mixture and the rubber composition of Example 1 - Example 6 and Comparative Example 1 - Comparative Example 3 are shown in Table 2.

<Evaluation results>

Referring to Table 2, Experimental Example 4 is a rubber composition prepared using only the second modifier. In contrast, Experimental Example 1 - Experimental Example 3 used a rubber composition prepared by using a first modifier and a second modifier. From the experimental results, the viscosity, wear resistance and dynamic storage elastic modulus difference (ΔE') of Experimental Example 4 were higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ of Experimental Example 4 (60 ° C) ) is lower than Experimental Example 1 - Experimental Example 3. From this, it is understood that the rubber composition prepared using only the second modifier has poor processability, wet skid resistance, and compatibility with carbon black.

Experimental Example 6 is a rubber composition prepared using only the first modifier. From the experimental results, the viscosity and dynamic storage elastic modulus difference (ΔE') of Experimental Example 6 were higher than those of Experimental Example 1 - Experimental Example 3. From this, it is understood that the rubber composition prepared using only the first modifier has poor processability and compatibility with carbon black.

Experimental Example 5 is a rubber composition prepared using a first modifier and a second modifier (having a molar ratio of 0.5:9.5). In contrast, Example 1 - Experimental Example 3 is a rubber composition prepared using a first modifier and a second modifier (having a molar ratio of 5:5 to 8:2). From the experimental results, the wear resistance and dynamic storage elastic modulus difference (ΔE') of Experimental Example 5 were higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ (0 ° C) of Experimental Example 5 was low. In Experimental Example 1 - Experimental Example 3. It can be seen that the rubber composition prepared by using the conjugated diene-vinyl aromatic copolymer having a molar ratio of the first modifier to the second modifier of 0.5:9.5 has wet skid resistance and The compatibility of carbon black is not good.

Experimental Example 7 is a rubber composition prepared by using a terminally modified conjugated diene-vinyl aromatic copolymer having different upgrading reaction sequences, and Experimental Example 1 - Experimental Example 3 is the first use of the first modification. A rubber composition prepared by using a second modified agent to carry out a modified terminally modified conjugated diene-vinyl aromatic copolymer. From the experimental results, the dynamic storage elastic modulus difference (ΔE') of Experimental Example 7 is higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ (0 ° C) of Experimental Example 7 is lower than Experimental Example 1 Experimental Example 3. From this, it was found that the rubber composition prepared by modifying the terminally modified conjugated diene-vinyl aromatic copolymer having different order of modification reaction has poor wet skid resistance and compatibility with carbon black.

In summary, the present invention proposes a terminally modified conjugated diene-vinyl group. A method for synthesizing an aromatic hydrocarbon copolymer, wherein a tin-containing compound and a compound containing a -CM-N<linking group are used as a modifier. The terminally modified conjugated diene-vinyl aromatic copolymer synthesized according to this method not only has good compatibility with carbon black, but also has good processability. One possible reason is that a -CM-N <linking group is introduced at the end of the conjugated diene-vinyl aromatic copolymer during the synthesis to increase the kneading uniformity with the carbon black. Therefore, such terminally modified conjugated diene-vinyl aromatic copolymer is suitable for the manufacture of tires, and the tires produced thereof exhibit excellent rolling resistance at high speeds and excellent performance on icy road surfaces. Wet slip resistance.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (10)

A method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprises: arranging a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer in a microstructure at a weight ratio of 2:1 to 5:1 The conditioning agent is reacted with an organic alkali metal compound to form a conjugated diene-vinyl aromatic copolymer having a living end; and the conjugated diene-vinyl aromatic copolymer having the active end is first The modifier is reacted to form an intermediate product; the intermediate product is reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer, the first modifier Is a tin-containing compound, the second modifier is a compound containing -CM-N<linking group, wherein M is a sulfur atom or an oxygen atom, wherein the first modifier and the second modifier The molar ratio of the molar ratio is 1:4~4:1. A method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer as described in claim 1, wherein the total amount of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer is The total amount of the first modifier and the second modifier is 0.001 parts by weight to 1 part by weight, and the first modifier and the second modifier are 100 parts by weight The ratio of the total number of moles to the number of moles of the organic alkali metal compound is from 0.95 to 1.05. The method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer according to claim 1, wherein the microstructure adjusting agent is selected from the group consisting of tetrahydrofuran, diethyl ether, dioxane, and ethylene. a group consisting of glyceryl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene and 2,2-bis(2-tetrahydrofuryl)propane At least one of the group, the first modifier includes a tin halide compound or a halogenated organotin compound. End-modified conjugated diene-vinyl aryl as described in claim 3 A method for synthesizing a sweet hydrocarbon copolymer, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyltin dichloride, tributyltin chloride, diphenyltin dichloride or triphenyl chloride Tin. The method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer according to claim 1, wherein the second modifying agent comprises a guanamine compound, a quinone imine compound, and the like. A guanamine compound, a urea compound or an isocyanuric acid derivative. A terminally modified conjugated diene-vinyl aromatic copolymer obtained by polymerizing (A) a conjugated diene monomer and (B) a vinyl aromatic hydrocarbon monomer to form a conjugated diene-vinyl aromatic copolymer Thereafter, the (C) first modifier is modified and then modified with (D) a second modifier, wherein the terminally modified conjugated diene-vinyl aromatic copolymer is (A) The weight ratio of the repeating unit composed of the conjugated diene monomer to the repeating unit composed of the (B) vinyl aromatic hydrocarbon monomer is 2:1 to 5:1, and the (C) first The modifier is a tin-containing compound, and the (D) second modifier is a compound containing a -CM-N<linking group, wherein M is a sulfur atom or an oxygen atom, and the (C) first modification The molar ratio of the agent to the (D) second modifier is 1:4 to 4:1. The terminally modified conjugated diene-vinyl aromatic copolymer as described in claim 6, wherein the first modifier comprises a tin halide compound or a halogenated organotin compound. The terminally modified conjugated diene-vinyl aromatic copolymer according to claim 7, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyltin dichloride, Tributyltin chloride, diphenyltin dichloride or triphenyltin chloride. The terminally modified conjugated diene-vinyl aromatic copolymer according to claim 6, wherein the second modifying agent comprises a guanamine compound, a quinone imine compound, an indole amine a compound, a urea compound or an isocyanuric acid derivative. A rubber composition comprising carbon black and a terminally modified conjugated diene-vinyl aromatic copolymer as described in any one of claims 6 to 9.