CN104487459B - Modified cis-1, 4-polybutadiene and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide: a modified cis-1, 4-polybutadiene which has excellent processability and low loss tangent; and a method for producing this modified cis-1, 4-polybutadiene. A method for producing a modified cis-1, 4-polybutadiene of the present invention does not require separation of cis-1, 4-polybutadiene after the production thereof, and is therefore an excellent production method which is simple and does not require complicated operations. The present invention is a modified cis-1, 4-polybutadiene which is obtained by reacting cis-1, 4-polybutadiene with a specific mono- to tri-substituted aromatic compound in the presence of a Lewis acid and an organic halogen compound.

Description

Modified cis-1,4-polybutadiene and its production method

technical field

The present invention relates to a modified cis-1,4-polybutadiene which can be used as a rubber material and is excellent in processability and low loss, and a method for producing the same.

Background technique

So far, a large number of proposals have been made on the polymerization catalysts of 1,3-butadiene, especially high cis-1,4-polybutadiene, that is, polybutadiene with high cis-1,4-bond content. , Mechanical aspects have excellent characteristics, so a variety of polymerization catalysts have been developed.

For example, Patent Document 1 discloses a method for producing high-cis-1,4-polybutadiene, which uses a catalyst composed of a cobalt compound, an acidic metal halide, an alkylaluminum compound, and water to make 1,3 - Polymerization of butadiene.

In addition, Patent Document 2 discloses the use of a catalyst composed of diethylaluminum chloride, water, and cobaltoctoate to convert 1,3-butadiene into linear or branched fatty acids. A method of polymerizing in a solvent composed of hydrocarbons.

Among the high cis-1,4-polybutadiene, the branching degree of the polymer chain is small, that is, the linear type high cis-1,4-polybutadiene has excellent heat resistance, washback elasticity, etc. characteristics. However, compared with the branch type high cis-1,4-polybutadiene with a high degree of branching, the processability of the blend obtained by blending carbon black and the like in the rubber is lowered, so the industry has been looking for solutions. Here's how to improve it.

As a method for improving the processability of polybutadiene, Patent Document 3 discloses a method of treating a polybutadiene polymerization solution with an organoaluminum compound and an alkyl halide compound. In addition, Patent Document 4 describes a method of dissolving a rubber having an unsaturated bond in a solvent, and reacting with an organic acid halide in the presence of a Lewis acid to modify the rubber. However, these methods all require a step of modifying the polymer after the polymerization step, and therefore development of a method that simplifies complicated operations is expected.

On the other hand, as a measure to improve the heat generation properties of rubber compositions, the use of silica instead of carbon black as a reinforcing material has increased in recent years. However, due to the existence of polar silanol groups on the surface of silica, the affinity between silica and hydrocarbon structures such as polybutadiene is low, so in rubber blended with silica, the Silicon particles are prone to coagulation and poor dispersibility. As a result, when the silica aggregates split, that is, the Payne effect occurs, a strong silica-silica interaction can be observed inside the silica aggregates, and the silica-rubber A large hysteresis loss (hysteresis loss) occurs between them, which becomes a cause of exothermic deterioration.

As a countermeasure to enhance the affinity or interaction between the polar silica surface and the non-polar rubber matrix, efforts have been made to study the use of dual-functional silane coupling agents or chemical modification of rubber. As a chemical modification technique for rubber, the following method has been reported for most chemically modified high-cis-1,4-polybutadiene: After living polymerization of 1,3-butadiene using a rare earth catalyst , and then use various effective alkoxysilane coupling agents to functionalize the molecular ends.

Patent Document 5 describes that after polymerizing polybutadiene rubber with a cobalt compound, it is further reacted with acid halides, halogen-containing sulfur compounds, mercapto-containing alkoxysilane compounds, etc. to improve cold flow properties. Methods.

Thereafter, in order to improve the balance between processability and low loss, polybutadiene rubber is polymerized with a cobalt compound and then modified with a predetermined amount of an organic halogen compound (Patent Documents 6 and 7). However, from the viewpoint of reducing environmental load and saving energy recently, expectations for further improvement in workability and low loss properties have been increasing.

[Patent Document 1] Japanese Patent Publication No. 38-1243

[Patent Document 2] Japanese Patent Publication No. 61-54808

[Patent Document 3] Japanese Patent Application Laid-Open No. 51-63891

[Patent Document 4] Japanese Patent Application Laid-Open No. 61-225202

[Patent Document 5] Japanese Patent Laid-Open No. 2001-114817

[Patent Document 6] Japanese Patent Laid-Open No. 2004-211048

[Patent Document 7] Japanese Unexamined Patent Publication No. 2011-79954

Contents of the invention

An object of the present invention is to provide a modified cis-1,4-polybutadiene excellent in processability and low loss, and a method for producing the same.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, found that a modified cis-1,4-polybutadiene obtained by reacting cis-1,4-polybutadiene with a specific aromatic compound in the presence of a Lewis acid and an organic halogen compound - 1,4-Polybutadiene is excellent in processability and low loss property, and thus completed the present invention.

That is, the first aspect of the present invention provides a modified cis-1,4-polybutadiene, which is characterized in that: in the presence of a Lewis acid and an organic halogen compound, the cis-1,4-polybutadiene Diene is obtained by reacting a 1-3 substituted aromatic compound represented by the following general formula (1).

In formula (1), Y represents hydrogen, hydroxyl, alkenyl or alkoxy having 1 to 10 carbons, and Z ¹ and Z ² represent hydrogen, hydroxyl, alkyl or alkoxy having 1 to 10 carbons, respectively.

In the modified cis-1,4-polybutadiene according to the first aspect of the present invention, the 1-3 substituted aromatic compound is preferably selected from phenol derivatives, catechol derivatives, and resorcinol derivatives , a hydroquinone derivative, and at least one of a 2-3 substituted aromatic alkenyl compound, more preferably a catechol derivative or a resorcinol derivative.

In addition, the Lewis acid is preferably an organoaluminum compound, and the organohalogen compound is preferably a tertiary halogenated alkyl group having 4 to 12 carbon atoms.

In addition, the second aspect of the present invention provides a method for producing modified cis-1,4-polybutadiene, which is characterized in that 1,3-butane Diene is polymerized to produce cis-1,4-polybutadiene, and then, an organic halogen compound and a 1-3 substituted aromatic compound represented by the following general formula (1) are added to the polymerization system, and the Lewis acid and In the presence of the above-mentioned organic halogen compound, the above-mentioned cis-1,4-polybutadiene is reacted with a 1-3 substituted aromatic compound represented by the following general formula (1).

In formula (1), Y represents hydrogen, hydroxyl, alkenyl or alkoxy having 1 to 10 carbons, and Z ¹ and Z ² represent hydrogen, hydroxyl, alkyl or alkoxy having 1 to 10 carbons, respectively.

In the method for producing modified cis-1,4-polybutadiene according to the second aspect of the present invention, the transition metal compound is preferably at least one selected from cobalt compounds, nickel compounds, and titanium compounds.

In addition, the above-mentioned 1-3 substituted aromatic compound is preferably selected from phenol derivatives, catechol derivatives, resorcinol derivatives, hydroquinone derivatives, and 2-3 substituted aromatic alkenyl groups. at least one of the compounds.

The modified cis-1,4-polybutadiene in the first aspect of the present invention has a polar functional group interacting with silica particles in the molecule, so the modified cis-1,4-polybutadiene is used A diene rubber composition suppresses aggregation of silica and has excellent low loss properties, and is preferably used as a tire. In addition, in the method for producing modified cis-1,4-polybutadiene according to the second aspect of the present invention, it is not necessary to separate cis-1,4-polybutadiene after producing it, which is simple and trouble-free. Excellent manufacturing method for operation.

Description of drawings

Fig. 1 is a diagram for calculating the degree of modification of the modified cis-1,4-polybutadiene of the present invention.

detailed description

(1) Production of cis-1,4-polybutadiene

Cis-1,4-polybutadiene can be produced by polymerizing 1,3-butadiene in the presence of a polymerization catalyst containing a transition metal compound and an organoaluminum compound.

(polymerization catalyst)

Examples of the transition metal compound used in the polymerization catalyst include cobalt compounds, nickel compounds, titanium compounds, and the like, and cobalt compounds are preferably used. In addition, examples of the organoaluminum compound include halogen-containing alkylaluminum compounds and alkylaluminum compounds, and these compounds may be used alone or in combination. For example, as a catalyst system using a cobalt compound (hereinafter, sometimes referred to as a cobalt-based catalyst composition), it is preferable to use a catalyst system composed of a cobalt compound, a halogen-containing alkylaluminum compound, and water or a catalyst system composed of a cobalt compound, a halogen-containing A catalyst system composed of an alkylaluminum compound, water and an alkylaluminum compound.

The cobalt compound in the cobalt-based catalyst composition is preferably a salt or complex of cobalt, and the most preferred ones can include: cobalt chloride, cobalt bromide, cobalt nitrate, cobalt 2-ethylhexanoate (cobalt octanoate), naphthene cobalt acid, cobalt octenate, cobalt acetate, cobalt malonate and other cobalt salts; or diacetylacetonate or triacetylacetonate of cobalt, cobalt ethyl acetoacetate, triarylphosphine complexes of cobalt halides , organic base complexes such as trialkylphosphine complexes, pyridine complexes or picoline complexes, and cobalt complexes such as ethanol complexes.

In addition, the halogen-containing alkylaluminum compound in the cobalt-based catalyst composition is preferably R ¹ _3-n AlX _n (wherein, R ¹ represents a hydrocarbon group with 1 to 10 carbons, X represents a halogen, and n is 1 to 2 number) means. For example, dialkyl aluminum halides such as dialkyl aluminum chloride and dialkyl aluminum bromide; alkyl aluminum sesquihalides such as alkyl aluminum sesquichloride and alkyl aluminum sesquibromide; Alkyl aluminum dichloride, alkyl aluminum dibromide and the like, alkyl aluminum dihalide, etc. Specific compounds can be listed: diethyl aluminum monochloride, diethyl aluminum monobromide, dibutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, dicyclohexyl monochloride aluminum chloride, diphenyl aluminum monochloride, etc., among them, diethyl aluminum monochloride and diisobutyl aluminum monochloride are more preferable.

In addition, the alkylaluminum compound in the cobalt-based catalyst composition is preferably represented by R ² ₃ Al (wherein, R ² represents a hydrocarbon group having 1 to 10 carbon atoms). Examples include trialkylaluminum compounds, more specifically triethylaluminum, trimethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, base aluminum etc.

In addition, aluminoxane can also be used. Aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, which can be exemplified by the general formula (-Al(R')O-) _n (wherein, R' represents a hydrocarbon group with 1 to 10 carbons, including A chain aluminoxane or a cyclic aluminoxane represented by one partially substituted with a halogen atom and/or an alkoxy group. n is a degree of polymerization, and is 5 or more, preferably 10 or more. Preferable examples of R' include methyl, ethyl, propyl, and isobutyl, most preferably methyl and ethyl. Examples of organoaluminum compounds used as aluminoxane raw materials include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

(polymerization of 1,3-butadiene)

1,3-Butadiene is polymerized as follows, for example. First, 1,3-butadiene and a solvent were put into a pressure vessel whose interior was replaced with nitrogen, and then water, a molecular weight regulator, and an organoaluminum compound were added and stirred. After adjusting the pressure vessel to a predetermined temperature, a transition metal polymerization catalyst is put in to start polymerization. The polymerization is carried out under normal pressure or under increased pressure up to about 10 atmospheres (gauge pressure).

The order of addition of the catalyst components is preferably such that water is added to an inert solvent and uniformly mixed, then an organoaluminum compound is added, and then a cobalt compound is added to start polymerization. It is preferable to add the cobalt compound after aging for a predetermined time after adding the organoaluminum compound. The aging time is preferably 0.1-24 hours, and the aging temperature is preferably 0-80°C.

When using a cobalt-based catalyst composition composed of a cobalt compound, a halogen-containing alkylaluminum compound, and water as a polymerization catalyst, the cobalt compound is preferably present at 1×10 ^-7 per 1 mol of 1,3-butadiene ~1×10 ^-3 mole range. In addition, the halogen-containing alkylaluminum compound is preferably within the range of 1×10 ^-5 to 1×10 ^-1 mol relative to 1 mol of 1,3-butadiene. In addition, water is preferably within a range of 1×10 ^-5 to 1×10 ^-1 mol relative to 1 mol of 1,3-butadiene.

The addition amount of the halogen-containing alkylaluminum compound used in the above-mentioned cobalt-based catalyst composition is 0.9-3.0 times, preferably 1.0-2.0 times, relative to the added water. If it exceeds this range, desired physical properties will not be obtained, and if it is less than this range, processability will tend to deteriorate. The ratio of the added amount of the halogen-containing alkylaluminum compound to the added water is especially important in controlling the linearity of the polybutadiene.

Examples of polymerization solvents include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; 1-butene , cis-2-butene, trans-2-butene and other C4 fractions and other olefin-based hydrocarbons, mineral spirits, solvent naphtha, kerosene and other hydrocarbon-based solvents; or dichloromethane and other halogenated hydrocarbon-based solvents, etc. In addition, 1,3-butadiene itself can also be used as a polymerization solvent.

Among these, benzene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene, etc. can be preferably used.

A known molecular weight regulator can be used during polymerization, for example, non-conjugated dienes such as cyclooctadiene and allene, or α-olefins such as ethylene, propylene, and 1-butene. Cyclooctadiene is most preferable, and it is preferably 0.5 to 40 mmol, more preferably 1 to 10 mmol, and most preferably 1 to 7 mmol relative to 1 mol of 1,3-butadiene. When the amount outside this range is used, polymer processability tends to deteriorate.

The polymerization temperature is preferably in the range of -30 to 100°C, most preferably in the range of 30 to 80°C. The polymerization time is preferably in the range of 5 minutes to 12 hours, more preferably 10 minutes to 6 hours, and most preferably 15 minutes to 1 hour.

(Properties of cis-1,4-polybutadiene)

The cis-1,4-polybutadiene used in the present invention has a Mooney viscosity of 10-120, preferably 15-100, more preferably 20-70. When the Mooney viscosity exceeds the above range, processing becomes difficult, and when it is less than the above range, abrasion resistance and low loss properties tend to decrease.

In addition, the ratio (Tcp/ML ₁₊₄ ) of the solution viscosity (Tcp) to the Mooney viscosity (ML ₁₊₄ ) of the 5% by weight toluene solution is preferably 1.0 to 6.0. Also, Mw/Mn is preferably 1.2 to 5.0, most preferably 1.5 to 4.5.

(2) Modification of cis-1,4-polybutadiene

The modified cis-1,4-polybutadiene according to one embodiment of the present invention can be produced by combining cis-1,4-polybutadiene with a compound as The modifier is reacted with a 1-3 substituted aromatic compound represented by the following general formula (1).

In formula (1), Y represents hydrogen, hydroxyl, alkenyl or alkoxy having 1 to 10 carbons, and Z ¹ and Z ² represent hydrogen, hydroxyl, alkyl or alkoxy having 1 to 10 carbons, respectively.

(Modifier)

Examples of the modifying agent represented by the above general formula (1) specifically include: anisole, phenetole, n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, isobutoxybenzene, di Grade butoxybenzene, n-pentoxybenzene, isopentoxybenzene, neopentyloxybenzene, n-hexyloxybenzene, (2-ethylbutoxy)benzene, n-octyloxybenzene, n-decyloxybenzene Benzene, o-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,2-diethoxybenzene, 1,3-diethoxybenzene, 1, 4-diethoxybenzene, 1,2-di-n-propoxybenzene, 1,3-di-n-propoxybenzene, 1,4-di-n-propoxybenzene, 1,2-di-n-butoxy Benzene, 1,3-di-n-butoxybenzene, 2-ethoxymethoxybenzene, 3-ethoxymethoxybenzene, 4-ethoxymethoxybenzene, 2-propoxymethoxybenzene phenyl, 3-propoxymethoxybenzene, 4-propoxymethoxybenzene, 1,4-di-n-butoxybenzene, 1,2-methylenedioxybenzene, 1,2,3 -Trimethoxybenzene, 1,2,4-trimethoxybenzene, 1,3,5-trimethoxybenzene, phenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol , 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,6-dimethoxyphenol, 3,4-dimethoxyphenol, 3,5-dimethoxy Phenol, catechol, 3-methoxycatechol, resorcinol, 2-methoxyresorcinol, 5-ethoxyresorcinol, hydroquinone, hydroquinone Phenol monomethyl ether, anethole, safrole, isosafrole, eugenol, methyl eugenol, isoeugenol, methyl isoeugenol, gallol, gallinol trimethyl ether, phloroglucinol, phloroglucinol trimethyl ether Wait. Among them, it is preferable to use at least one modification selected from phenol derivatives, catechol derivatives, resorcinol derivatives, hydroquinone derivatives, and 2-3 substituted aromatic alkenyl compounds. Agents, more preferably phenol derivatives, catechol derivatives, resorcinol derivatives, most preferably anisole, phenetole, anethole, o-dimethoxybenzene, 1,3-dimethoxy Benzene, 1,3-diethoxybenzene, 1,2-methylenedioxybenzene, safrole, isosafrole, methylisoeugenol. In addition, there is no problem in using two or more of these modifiers in combination.

(Lewis acid)

As the Lewis acid used in the modification reaction, known ones can be used. Representative examples thereof include halides of metals or semimetals, such as Be, B, Al, Si, P, S, Ti, V, Fe, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, Cd, Sn, Sb, Te, Hf, Ta, W, Hg, Bi, U and other elements, or halides or organic halides of oxygen-element combinations such as PO, SeO, SO, SO ₂ , VO, or these halides Compounds, etc. More specifically, BF ₃ , BF ₃ ·O(C ₂ H ₅ ) ₂ , (CH ₃ ) ₂ BF, BCl ₃ , AlCl ₃ , AlBr ₃ , (C ₂ H ₅ )AlCl ₂ , POCl ₃ , TiCl ₄ , VCl ₄ , MoCl ₆ , SnCl ₄ , (CH ₃ )SnCl ₃ , SbCl ₅ , TeCl ₄ , TeBr ₄ , FeCl ₃ , WCl ₆ , Sc(OTf) ₃ , Hf(OTf) ₃ , Sb(OTf ) ₃ , Bi(OTf) ₃ and Ga(OTf) ₃ etc. Among them, aluminum halides or aluminum organic halides are preferable.

In addition, in this embodiment, an organoaluminum compound can be used as the Lewis acid in the modification reaction. Therefore, the organoaluminum compound used in the above-mentioned polymerization of 1,3-butadiene can continue to be used as the Lewis acid. By continuing to use the organoaluminum compound used in the polymerization of 1,3-butadiene as the Lewis acid, it is not necessary to add a new Lewis acid during the modification reaction, which is preferable. In this embodiment, for example, it is preferable to use the same halogen-containing alkylaluminum compound as used in the above-mentioned cobalt-based catalyst composition. Furthermore, an organoaluminum compound may be additionally added as a Lewis acid during the modification reaction.

(Organohalogen compounds)

The organohalogen compound used in the modification reaction is not particularly limited as long as it can react with a Lewis acid to form a carbocation. For example, a halogenated alkyl group represented by the following general formula (2) can be used.

In formula (2), R ³ and R ⁴ are hydrogen, chlorine, bromine or alkyl, aryl, chlorine-substituted alkyl, alkoxy, etc. with 1 to 12 carbons, and R ⁵ is chlorine, bromine or 1 carbon ~6 alkyl, aryl, chlorine-substituted alkyl, alkoxy, etc., X is halogen such as chlorine or bromine. When ^R3 and ^R4 are hydrogen, ^R5 is preferably aryl. The above-mentioned alkyl group may be saturated or unsaturated, and may be linear, branched or cyclic.

Specific compounds include chlorides, bromides, or iodides of methyl, ethyl, isopropyl, isobutyl, tert-butyl, phenyl, benzyl, benzoyl, benzylidene, and the like. In addition, methyl chloroformate, bromoformate, chlorodiphenylmethane, chlorotriphenylmethane, etc. are mentioned. In this embodiment, in terms of the stability of the generated carbocation, etc., it is preferably a tertiary halogenated alkyl group, most preferably a tertiary halogenated alkyl group with 4 to 12 carbons, specifically, a tertiary halogenated alkyl group is preferred. Butyl chloride and tertiary butyl bromide.

In addition, as the organic halogen compound used in the modification reaction, acyl halide compound represented by the following general formula (3) can be used.

In formula ( ³ ), R6 is hydrogen, chlorine, bromine, or alkyl, aryl, chlorine-substituted alkyl, alkoxy, etc. with 1 to 12 carbons, and X is halogen such as chlorine, bromine, or the like.

(Modification reaction)

The modification reaction may be performed immediately after the polymerization of 1,3-butadiene is terminated, or may be performed after removing the solvent or unreacted monomers remaining in the reaction product. Moreover, after drying a polymer by steam stripping method, a vacuum drying method, etc., it can also carry out after redissolving in solvents, such as cyclohexane. When the polymerization system contains a Lewis acid component such as a halogen-containing aluminum compound, it is preferable to carry out the modification reaction immediately after the polymerization of 1,3-butadiene.

When the modification reaction is performed immediately after the polymerization of 1,3-butadiene, the modifier may be added after the polymerization, and then the organic halogen compound may be added at a predetermined temperature and stirred for a predetermined time. At this time, a Lewis acid may also be added if necessary. The temperature at which the modifier and polybutadiene are reacted is preferably 20 to 100°C, more preferably 40 to 100°C, and still more preferably 50 to 90°C. If it is higher than this temperature range, gelation will be promoted, which is not preferable. On the other hand, if it is lower than this temperature range, it will be difficult to effectively generate the modification reaction. The reaction time is preferably 1 to 600 minutes. More preferably, stirring and mixing are performed for 10 to 90 minutes.

The amount of the modifier is preferably 1×10 ^-3 to 100 moles relative to 1 mole of 1,3-butadiene units in cis-1,4-polybutadiene, most preferably 1×10 ^{- 2} to 10 moles. Furthermore, the amount of the organohalogen compound is 0.05 to 50 times, preferably 1 to 20 times, the amount of the organoaluminum compound during the polymerization reaction. If it is less than this amount, the modification reaction may not proceed sufficiently and a desired polymer may not be obtained. Moreover, when too much, gelation by the reaction of polybutadiene molecules will be accelerated|stimulated, and a desired polymer may not be obtained. After the modification reaction, if necessary, the pressure inside the reaction tank is released, and after-treatments such as washing and drying steps are performed.

(degree of modification)

The degree of modification of the modified cis-1,4-polybutadiene of this embodiment was calculated by a method measured using gel permeation chromatography (GPC). This will be described in detail with reference to FIG. 1 .

In FIG. 1 , the vertical axis represents the ratio of the peak area value UV obtained by measuring the UV (ultraviolet, ultraviolet) absorbance of the polymer obtained by GPC to the peak area value RI obtained by the differential refractive index (RI), that is, UV/RI values.

The horizontal axis represents the value of (1/Mn)×10 ⁴ , and Mn is the number average molecular weight. In Fig. 1, Li-BR (unmodified) is the UV/RI value of the polymer itself obtained by polymerizing 1,3-butadiene by anionic polymerization using a Li-based catalyst, and the five types of number average molecular weight Mn The drawing of different polymers can be approximated as a straight line. In addition, Li-BR (modification) refers to the UV/A value of the polymer obtained by modifying the polymerization terminal with 3,5-dimethoxybenzyl bromide after polymerization by anionic polymerization using a Li-based catalyst. The value of RI can be approximated as a straight line by plotting five kinds of polymers having different number average molecular weights Mn.

In the case of anionic polymerization, one molecule of the polymer reacts quantitatively with one molecule of the modifier, so the UV/RI value of Li-BR (modified) at a certain number average molecular weight (Mn1) is compared with that of Li-BR (unmodified) The difference in the UV/RI value of modified) was set to A. It is expressed as the amount of change in the UV/RI value when one molecular chain of the number average molecular weight (Mn1) reacts with one molecule of the modifying agent, so the degree of modification can be calculated based on this value.

Like Li-BR, for the modified cis-1,4-polybutadiene of the present embodiment with a certain number average molecular weight (Mn1), and the unmodified polybutadiene obtained in the same method as that used in the modification The modified cis-1,4-polybutadiene of this embodiment can be represented by the following formula if the UV/RI values are calculated separately and the difference is defined as B. degree of modification.

Modification degree = B/A (mathematical formula 1)

The degree of modification of the cis-1,4-polybutadiene of the present embodiment obtained by the method described above is not particularly limited, but is preferably more than 0.1, and more preferably more than 0.5. In addition, the degree of modification is preferably not more than 20, more preferably not more than 15. If the degree of modification is 0.1 or less, the modification effect may not be sufficient, and if the degree of modification is 20 or more, the inherent properties of cis-1,4-polybutadiene may be impaired.

(3) Manufacture of rubber composition

The modified cis-1,4-polybutadiene of this embodiment can be blended alone, or blended with other synthetic rubber or natural rubber, extended with process oil if necessary, and then added with carbon black Or fillers (fillers) such as silica, silane coupling agents, vulcanizing agents, vulcanization accelerators, and other common admixtures are vulcanized to obtain rubber compositions.

(other synthetic rubber)

The other synthetic rubber contained in the rubber composition is preferably a vulcanizable rubber, specifically, ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), polyisoprene, high-cis polybutadiene rubber, low-cis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated Butyl rubber, acrylonitrile-butadiene rubber, etc. Among them, SBR is preferable. Furthermore, among SBRs, solution-polymerized styrene-butadiene copolymer rubber (S-SBR) is most preferable. These rubbers may be used alone or in combination of two or more.

Regarding the microstructure of solution-polymerized styrene-butadiene copolymer rubber (S-SBR), the styrene content is 15 to 35% by weight, preferably 17 to 30% by weight, and the vinyl bond content of the butadiene portion is 30 to 30% by weight. 75%, preferably 32-72%. The above effects can be exhibited by using 30 to less than 90 parts by weight of the S-SBR with respect to 100 parts by weight of the rubber component, preferably 50 to 80 parts by weight. If the blending amount of S-SBR is too small, the wet performance will be lowered, which is unfavorable. Conversely, if too large, the abrasion resistance and low loss property will be deteriorated, which is not preferable. This S-SBR is known, and for example, commercially available products such as NiPol from Zeon in Japan and Asaprene from Asahi Kasei can be used.

(silane coupling agent)

The silane coupling agent used in the rubber composition is an organosilicon compound represented by the general formula R ⁷ _n SiR ⁸ _4-n , and R ⁷ is an organic silicon compound selected from vinyl, acyl, allyl, allyloxy, amine An organic group with ¹ to 20 carbon atoms in a reactive group such as an epoxy group, a mercapto group, a chlorine group, an alkyl group, a phenyl group, a hydrogen group, a styryl group, a methacryloyl group, an acryloyl group, a ureido group, etc. It is a hydrolyzable group selected from a chloro group, an alkoxy group, an acetoxy group, an isopropenyloxy group, an amino group, etc., and n represents the integer of 1-3.

The ^R7 component of the silane coupling agent preferably contains a vinyl group and/or a chlorine group.

As specific silane coupling agents, commercially available ones include, for example, the following silane coupling agents, but are by no means limited to these. Specific silane coupling agents are: bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilane) propyl) disulfide, bis(2-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2-trimethoxysilyl) Propyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethoxysilane, 3-triethyl Oxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2- Triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl Benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, vinyltrichlorosilane, methyl Vinyldichlorosilane, divinyldichlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, dimethyl Divinylsilane, Ethoxydimethylvinylsilane, Diacetoxymethylvinylsilane, Allyloxydimethylvinylsilane, Diethoxymethylvinylsilane, Bis(di Methylamino)methylvinylsilane, phenylvinyldichlorosilane, triacetoxyvinylsilane, 3-chloropropylmethyldivinylsilane, diethoxydivinylsilane, methyl Isobutyl Ketoxime Vinylsilane, Dimethylisobutoxyvinylsilane, Triethoxyvinylsilane, Methylphenylvinylchlorosilane, Methylphenylvinylsilane, Dimethylisoamylsilane Oxyvinylsilane, 4-bromophenyldimethylvinylsilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, dimethylpiperene Pyridylmethylvinylsilane, Dimethyl-2-[(2-Ethoxyethoxy)ethoxy]vinylsilane, Divinylmethylphenoxysilane, Dimethyl-P-methylsilane Oxyphenylvinylsilane, Tris(1-methylvinyloxy)vinylsilane, Triisopropoxyvinylsilane, Diethoxy-2-piperidinylethoxyvinylsilane, Diphenyl Vinylchlorosilane, 3-dimethylvinylphenyl-N,N-diethylcarbamate, triphenoxyvinylsilane, 1,3-divinyl-1,1,3, 3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1-(4-methylpiperidinylmethyl)-1, 1,3,3-Tetramethyl-3-vinyldisiloxane, 1,4-bis(dimethylvinylsilyl)benzene, 1,4-bis(dimethylvinylsilyloxy) Benzene, 1,3-bis(dimethylvinylsilyloxy)benzene, 1,1,3,3-tetraphenyl-3-divinyldisiloxane, 1,3,5-trimethyl -1,3,5-trivinylcyclotri Siloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, tetrakis(dimethylvinylsiloxymethyl)methane, 3- Chloropropyltrimethoxysilane, etc.

The amount of the silane coupling agent added is preferably 0.2 to 20%, most preferably 5 to 15%, relative to the amount of the filler. If it is less than the said range, since it will cause coking, it is unpreferable. Moreover, when it exceeds the said range, since it will cause deterioration of tensile characteristics and ductility, it is unpreferable.

(4) Production of rubber-modified impact-resistant polystyrene resin composition

In addition, the modified cis-1,4-polybutadiene of this embodiment can also be used as a modifier for plastics, such as impact-resistant polystyrene, that is, rubber-modified impact-resistant polystyrene can also be produced. Vinyl resin composition.

As a method for producing the above-mentioned rubber-modified impact-resistant polystyrene-based resin composition, a styrene-based monomer is polymerized in the presence of the modified cis-1,4-polybutadiene of the present embodiment. The methods of block polymerization or block suspension polymerization are economically advantageous methods. Styrenic monomers, such as styrene, alkyl-substituted styrenes such as α-methylstyrene and p-methylstyrene, and halogen-substituted styrenes such as chlorostyrene, have been used as rubber-modified impact-resistant polystyrenes. A mixture of at least one or at least two types of styrene-based monomers known for the production of resin compositions. Among them, styrene is preferred.

During production, in addition to the above-mentioned modified cis-1,4-polybutadiene, if necessary, within 50% by weight relative to the above-mentioned modified cis-1,4-polybutadiene, a combination of Styrene-butadiene copolymer, ethylene-propylene polymer, ethylene-vinyl acetate polymer, acrylic rubber, etc. Furthermore, resins produced by these methods can also be blended. Furthermore, polystyrene-type resin which does not contain the resin manufactured by these methods can also be mixed and manufactured. Take an example to illustrate the above block polymerization method: Dissolve modified cis-1,4-polybutadiene (1-25% by weight) in styrene monomer (99-75% by weight), and add The solvent, the molecular weight regulator, the polymerization initiator, etc. are transformed into particles dispersed with modified cis-1,4-polybutadiene until the conversion rate of styrene monomer is 10-40%. Before the rubber particles are produced, the rubber phase is the continuous phase. Polymerization is further continued, and after phase inversion (granulation step) in which the form of rubber particles becomes a dispersed phase, polymerization is carried out until a conversion rate of 50 to 99% is achieved, thereby producing rubber-modified impact-resistant polystyrene A resin composition.

Modified cis-1,4-polybutadiene dispersed particles (rubber particles) are particles dispersed in resin, and are composed of modified cis-1,4-polybutadiene and polystyrene resin, The polystyrene-based resin is graft-bonded to modified cis-1,4-polybutadiene, or is not graft-bonded but adsorbed to modified cis-1,4-polybutadiene. In the present embodiment, a resin composition in which the dispersed particles of modified cis-1,4-polybutadiene have a particle diameter in the range of 0.5 to 7.0 μm, preferably in the range of 1.0 to 3.0 μm, can be preferably produced.

Regarding the graft rate, it is preferable to manufacture a resin composition having a graft rate in the range of 150-350. A batch method or a continuous method may be used, and it is not particularly limited.

The above-mentioned raw material solution mainly composed of styrene-based monomer and modified cis-1,4-polybutadiene is polymerized in a fully mixed reactor, as long as the fully mixed reactor can make the raw material solution in the reactor It is sufficient to maintain a uniformly mixed state, and preferred examples include stirring blades of types such as helical ribbons, double helical ribbons, and anchors. It is preferable to install a draft tube (draft tube) on the helical ribbon type stirring blade, and to further enhance the up-and-down circulation in the reactor.

Stabilizers such as antioxidants and ultraviolet absorbers, release agents, lubricants, colorants, and various fillers can be added to the rubber-modified impact-resistant polystyrene resin composition as appropriate during or after production. Agents and various plasticizers, higher fatty acids, organopolysiloxanes, polysiloxane oils, flame retardants, antistatic agents or foaming agents and other known additives.

The rubber composition obtained by using the modified cis-1,4-polybutadiene of this embodiment can be used for industrial products such as tires, anti-vibration rubber, belts, hoses, and shock-absorbing rubber, or men's shoes Various rubber applications such as women's shoes, sports shoes and other footwear. In this case, it is preferable to blend at least 10% by weight of the modified cis-1,4-polybutadiene of the present embodiment into the rubber component. In addition, rubber-modified impact-resistant polystyrene-based resin compositions can be used in various known molded products, and are suitable for electrical-industrial applications and packaging materials due to their excellent flame retardancy, impact resistance, and tensile strength. , housing-related materials, OA equipment (office automation equipment, office automation equipment) materials, tools, daily necessities, etc. For example, it can be used in a wide range of applications such as casings for TVs, personal computers, and air conditioners, outer packaging materials for office equipment such as photocopiers and printers, and food containers for frozen foods, yogurt drinks, and ice cream.

Example

(assessment method)

Hereafter, although an Example is given and this invention is concretely demonstrated, this invention is not limited to these Examples at all. In addition, Mooney viscosity, toluene solution viscosity, number average molecular weight, processability, washback elasticity of a sulfide, tan δ of a sulfide, and permanent strain in an Example were measured by the following method.

Mooney Viscosity (ML ₁₊₄ , 100°C): According to JIS-K6300, using a Mooney Viscometer (SMV-300) manufactured by Shimadzu Corporation, preheated at 100°C for 1 minute, then carried out for 4 minutes Measured and expressed as the Mooney viscosity (ML ₁₊₄ , 100° C.) of the rubber.

Viscosity of toluene solution (Tcp): After dissolving 2.28 g of polymer in 50 ml of toluene, a standard solution for viscometer calibration (JIS Z8809) was used as a standard solution, and a Cannon-Fenske viscometer No. 400 was measured at 25°C.

Number average molecular weight: Measured by GPC (manufactured by Shimadzu Corporation) at a temperature of 40°C using polystyrene as a standard substance and tetrahydrofuran as a solvent, using a calibration curve obtained from the obtained molecular weight distribution curve Calculations were performed to obtain the number average molecular weight.

Degree of modification: as described above, the difference between the UV/RI value of Li-BR (modified) and the UV/RI value of Li-BR (unmodified) at the same number average molecular weight as the target example was set as A is A, and the UV/RI value of the target example is B, and the modification degree is calculated|required by the following formula.

Modification degree = B/A (mathematical formula 2)

Processability: Processability was evaluated by the Mooney viscosity of the unsulfurized compound. Prototype 2 or 3 is expressed as an index with 100, and the larger the index, the better the conversion.

The washback elasticity of the sulfide: according to BS903, the washback elasticity was measured at room temperature using a Dunlop tripsometer, and the sample 2 or 3 was set as 100 to represent it as an index. The larger the index, the better the low loss property.

Strain dependence of storage elastic modulus (G′) (Payne effect): dynamic strain analysis was performed under conditions of 120° C. and a frequency of 1 Hz using a rubber processability analyzer RPA-2000 manufactured by Alpha Technology. The Payne effect is expressed as an index when the ratio (G' _45% /G' _0.5% ) of G' at a strain of 45% to G' at a strain of 0.5% of sample 2 or 3 is 100. The larger the index, the better the dispersibility of the enhancer.

Tanδ of sulfide: Measured using EPLEXOR 100N manufactured by GABO under the conditions of temperature 50°C, frequency 10Hz, and dynamic strain 0.3%. The index is expressed by setting the sample 2 or 3 as 100, and the larger the index, the conversion For the better.

Calorific value and permanent strain: Measured according to the measuring method specified in JIS K6265, and express as an index by setting trial product 2 or 3 as 100, and the larger the index, the better the conversion.

(Example 1)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 600 mL of a cyclohexane-C4 fraction mixed solution containing 32.4% by weight of 1,3-butadiene (containing 26.4% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 39.2% by weight), followed by adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride for stirring, and adding 5.1 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.005 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 430 mmol of modifier 1,3-dimethoxybenzene (DMOB) was added, and the temperature of the autoclave was raised. When the internal temperature reached 70°C, 3.8 mmol of tertiary butyl chloride was added to react for 60 minutes. An anti-aging agent was added thereto, and vacuum drying was performed at 80°C for 3 hours. The degree of modification of the obtained modified cis-1,4-polybutadiene was 0.35. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 2)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 7.3 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.1 mmol of modifier 1,3-dimethoxybenzene (DMOB) was added, and the temperature of the autoclave was raised to 70° C. at the inner temperature. Then, 15.8 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 3)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.0 mmol of modifier 1,3-dimethoxybenzene (DMOB) was added, and the temperature was raised to 80°C. Then, 3.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 4)

The reaction was carried out in the same manner as in Example 3 except that the modifying agent was replaced with 1,3-diethoxybenzene (DEOB). Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 5)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 7.3 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.2 mmol of o-dimethoxybenzene as a modifier was added, and the temperature was raised to 70°C. Then, 31.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 6)

The reaction was carried out in the same manner as in Example 3 except that the modifying agent was replaced with 1,2-methylenedioxybenzene (MDB). Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 7)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene was charged (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.3 mmol of modifier anisole was added, and the temperature was raised to 70°C. Then, 3.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Embodiment 8)

The reaction was carried out in the same manner as in Example 7 except that the modifying agent was replaced with phenetole. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 9)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.3 mmol of modifier anethole was added, and the temperature was raised to 70°C. Then, 7.9 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 10)

Except having replaced the modifying agent with safrole, it reacted similarly to Example 3. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 11)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 500 mL of a mixed solution of cyclohexane-C4 fraction containing 30.3% by weight of 1,3-butadiene (containing 37.3% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.2% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.0 mmol of modifier isosafrole was added, and the temperature was raised to 70°C. Then, 3.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 12)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 600 mL of a mixed solution of cyclohexane-C4 fraction containing 30.6% by weight of 1,3-butadiene (containing 36.8% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.1% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 18 mmol of modifier 1,2-methylenedioxybenzene (MDB) was added, and the temperature was raised to 80°C. Then, 3.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(Example 13)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 600 mL of a mixed solution of cyclohexane-C4 fraction containing 30.6% by weight of 1,3-butadiene (containing 36.8% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.1% by weight), followed by adding 1.1 mmol of water and 1.6 mmol of diethylaluminum monochloride for stirring, and adding 4.5 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.003 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After the polymerization reaction, 9.0 mmol of modifier isosafrole was added, and the temperature was raised to 80°C. Then, 3.3 mmol of tertiary butyl chloride was added and reacted for 15 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained modified cis-1,4-polybutadiene.

(comparative example 1)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 600 mL of a cyclohexane-C4 fraction mixed solution containing 32.4% by weight of 1,3-butadiene (containing 26.4% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction (39.2% by weight), followed by adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride for stirring, and adding 5.3 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.005 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained cis-1,4-polybutadiene.

(comparative example 2)

Into a stainless steel autoclave with a capacity of 1.5 liters whose interior was fully replaced with nitrogen, 600 mL of a mixed solution of cyclohexane-C4 fraction containing 30.6% by weight of 1,3-butadiene (containing 36.8% by weight of cyclohexane in cis -2-butene as the main component of the C4 fraction 31.1% by weight), followed by adding 1.3 mmol of water and 1.9 mmol of diethylaluminum monochloride for stirring, and adding 5.3 mmol of cyclooctadiene. The autoclave was heated up, and when the internal temperature reached 60°C, 0.005 mmol of cobalt octoate was added, and polymerization was carried out at 60°C for 25 minutes. After adding the antiaging agent, the polymer was precipitated with ethanol, and vacuum-dried at 80° C. for 3 hours. Table 1 shows the physical properties of the obtained cis-1,4-polybutadiene.

Table 1

(Prototype 1)

Using the modified cis-1,4-polybutadiene obtained in Example 1, according to the blending formula shown in Table 2, SBR and silicon dioxide were mixed by a 250cc mixing test machine (laboplastomill). After curing, the vulcanizing agent and vulcanization aids are mixed using open rollers. Then, press vulcanization was performed at a temperature of 160° C., and the physical properties of the obtained vulcanized test pieces were evaluated. The results are shown in Table 3.

(Prototype 2)

Except having used the cis-1,4-polybutadiene obtained in the comparative example 1, it carried out the blending process similarly to the trial product 1, and performed the physical property evaluation. The results are shown in Table 3.

Table 2

Prototype 1 Prototype 2 BR obtained in Example 1 30 BR obtained in Comparative Example 1 30 SBR 70 70 silica 75 75 Silane coupling agent 6 6 Oil 21.5 21.5 Zinc oxide 3 3 stearic acid 1 1 anti aging agent 1 1 Vulcanization accelerator 1 1.7 1.7 Vulcanization accelerator 2 2 2 sulfur 1.4 1.4

The details of the compounds used in the blending are shown below.

SBR: styrene content is 23%, ML ₁₊₄ (100°C) is 70

Silica: manufactured by Tosoh Silica Co., Ltd., trade name Nipsil AQ

Silane coupling agent: manufactured by Evonik, trade name Si69

Oil: Sunthene Oil 4240, manufactured by SUNOCO

Zinc oxide: Sakai Chemical Industry Sazex No. 1

Stearic Acid: Kao Stearic Acid

Anti-aging agent: Sumitomo Chemical Antigen 6C

Sulfur: Manufactured by Hosoi Chemical Industry Co., Ltd.

Vulcanization accelerator 1: Nocceler CZ manufactured by Ouchi Shinshin Chemical Co., Ltd.

Vulcanization accelerator 2: Nocceler D manufactured by Ouchi Shinshin Chemical Co., Ltd.

Table 3 shows the evaluation results of the obtained blends. Each evaluation item of the trial product 2 was set to 100, and compared with the trial product 1. For each item, the larger the numerical value, the better the characteristics.

table 3

Prototype 1 Prototype 2 Processability 100 100 washback elasticity 103 100 Payne effect (unsulfide) 108 100 tanδ 112 100 permanent strain 125 100

(Prototype 3)

Using the cis-1,4-polybutadiene obtained in Comparative Example 2, according to the blending formula shown in Table 4, after mixing SBR and silica etc. through a 250cc mixing tester, the open-type The roller mixes vulcanizing agent and vulcanizing aid. Then, press vulcanization was performed at a temperature of 160° C., and the physical properties of the obtained vulcanized test pieces were evaluated. The results are shown in Table 5.

(Prototype 4)

Except for using the modified cis-1,4-polybutadiene obtained in Example 12, blending processing was performed in the same manner as in Prototype 3, and physical property evaluation was performed. The results are shown in Table 5.

(Prototype 5)

Except for using the modified cis-1,4-polybutadiene obtained in Example 13, blending processing was performed in the same manner as in Prototype 3, and physical property evaluation was performed. The results are shown in Table 5.

Table 4

Prototype 3 Prototype 4 Prototype 5 BR obtained in Comparative Example 2 30 BR obtained in Example 12 30 BR obtained in Example 13 30 SBR 70 70 70 silica 75 75 75 Silane coupling agent 6 6 6 Oil 21.5 21.5 21.5 Zinc oxide 3 3 3 stearic acid 1 1 1 anti aging agent 1 1 1 Vulcanization accelerator 1 1.7 1.7 1.7 Vulcanization accelerator 2 2 2 2 sulfur 1.4 1.4 1.4

The details of the compounds used in the blending are shown below.

SBR: styrene content is 23%, ML ₁₊₄ (100°C) is 70

Silica: manufactured by Evonik, trade name Ultrasil 7000GR

Silane coupling agent: manufactured by Evonik Degussa, trade name Si75

Oils: Alternatives to Aroma Oils

Zinc oxide: Sakai Chemical Industry Sazex No. 1

Stearic acid: Kao stearic acid

Anti-aging agent: Sumitomo Chemical Antigen 6C

Sulfur: Manufactured by Hosoi Chemical Industry Co., Ltd.

Vulcanization accelerator 1: Nocceler CZ manufactured by Ouchi Shinshin Chemical Co., Ltd.

Vulcanization accelerator 2: Nocceler D manufactured by Ouchi Shinshin Chemical Co., Ltd.

Table 5 shows the evaluation results of the obtained blends. Each evaluation item of the trial product 3 was set to 100, and it compared with the trial products 4 and 5. For each item, the larger the numerical value, the better the characteristics.

table 5

Prototype 3 Prototype 4 Prototype 5 Processability 100 105 100 washback elasticity 100 103 103 Calorific value 100 102 105 tanδ 100 102 107 Payne effect (unsulfide) 100 102 96

Claims (8)

1. a kind of modified cis- 1，4-polybutadiene, it is in the presence of lewis acid and organohalogen compound, to make cis- 1, 1～3 substituted aromatic compound that 4- polybutadiene is represented with following formulas (1) is reacted in 20～100 DEG C and is obtained：

In formula (1), Y represents the alkoxyl of hydrogen, hydroxyl, thiazolinyl or carbon number 1～10, Z¹、Z²Hydrogen, hydroxyl, alkyl or carbon are represented respectively The alkoxyl of number 1～10, wherein, Y, Z¹、Z²At least one of represent the alkoxyl of hydroxyl or carbon number 1～10.

2. modified cis- 1，4-polybutadiene according to claim 1, wherein, 1～3 substituted aromatic compound choosing From phenol derivativess, catechol derivatives, resorcinol derivatives, hydroquinone derivative and 2～3 substituted aromatic series At least one in alkenyl compound.

3. modified cis- 1，4-polybutadiene according to claim 1 and 2, wherein, lewis acid is organo-aluminium chemical combination Thing.

4. modified cis- 1，4-polybutadiene according to claim 1 and 2, wherein, organohalogen compound is carbon number 4 ～12 three-level halogenated alkyl.

5. modified cis- 1，4-polybutadiene according to claim 3, wherein, organohalogen compound is carbon number 4～12 Three-level halogenated alkyl.

6. a kind of manufacture method of modified cis- 1，4-polybutadiene, uses containing transistion metal compound and organo-aluminium chemical combination The polymerization catalyst of thing, makes 1,3-butadiene be polymerized and manufactures cis- 1，4-polybutadiene, then, adds in the polymerization system 1～3 substituted aromatic compound that organohalogen compound and following formulas (1) are represented, in lewis acid and organic halogen In the presence of plain compound, make 1～3 substituted aromatic compound that the cis- 1，4-polybutadiene is represented with following formulas (1) in 20～100 DEG C are reacted：

In formula (1), Y represents the alkoxyl of hydrogen, hydroxyl, thiazolinyl or carbon number 1～10, Z¹、Z²Hydrogen, hydroxyl, alkyl or carbon are represented respectively The alkoxyl of number 1～10, wherein, Y, Z¹、Z²At least one of represent the alkoxyl of hydroxyl or carbon number 1～10.

7. the manufacture method of modified cis- 1，4-polybutadiene according to claim 6, wherein, transistion metal compound At least one in cobalt compound, nickel compound and titanium compound.

8. the manufacture method of modified cis- 1，4-polybutadiene according to claim 7, wherein, 1～3 substituted fragrance Compounds of group takes selected from phenol derivativess, catechol derivatives, resorcinol derivatives, hydroquinone derivative and 2～3 At least one in the aromatic series alkenyl compound in generation.