JPH02252703A - Halogenated polybutadiene elastomer, its production and composition containing the same elastomer - Google Patents

Abstract

PURPOSE:To obtain the an elastomer having halogen groups curable of heat- resistant crosslinking by reacting a polybutadiene elastomer with a specified active halogen compound in the presence of a specified organic halogenating agent. CONSTITUTION:The aimed elastomer is obtained by reacting a polybutadiene elastomer with at least one active halogen compound selected from among compounds of formulas II-VII (wherein X is a halogen atom; and R1-7 are each H, a 5C or lower alkyl or an alkoxy) in the presence of at least one organic halogenating agent selected from among an alkyl hyphalite, an N-haloamide compound of formula I (wherein Y is a halogen atom; D is a carboxylic acid residue or the like; and E is H or the like) and a trihaloisocyanuric acid. The elastomer is a halogenated polybutadiene elastomer wherein at least one repeating unit selected from among formulas VIII-X (wherein Y is a halogen atom; and A is formula XI or the like) is present in a random position along the polymer chain and the remaining molecular structure has a polybutadiene elastomer structure.

Description

Detailed Description of the Invention (Industrial Application Field) This invention relates to a halogenated polybutadiene elastomer, particularly a halogenated polybutadiene elastomer containing a halogen group that enables heat-resistant crosslinking, a method for producing the same, and the elastomer. This product relates to rubber compositions containing the following: especially for high-speed performance pneumatic tire treads, engine mounts, etc. that are used continuously under high-temperature conditions.
Shows suitable performance in rubber compositions used for oil hoses, etc.

(Conventional technology) In recent years, vehicle tires have become increasingly popular due to improved performance of automobiles, development of expressway networks, and higher speeds and higher performance of tires.
The operating temperature limit of tire treads is becoming higher and higher, and heat resistance is becoming more and more important as a performance requirement for tire treads.

In order to ensure the thermal stability of the rubber material, ie to minimize high temperature deterioration, it is particularly important that the crosslinking has high thermal stability.

In the future, methods to increase the number of monosulfide bonds in crosslinking have been proposed as techniques for improving heat resistance, but this is still at an insufficient level. Further, crosslinking using peroxide also has excellent heat resistance, but has poor scorch resistance and a slow crosslinking rate, so it is not practical.

On the other hand, it is known that chlorobutyl rubber or bromobutyl rubber undergoes a free sol fluorine reaction with aromatic amines, such as N,N'-diphenyl-p-phenylenediamine, to provide a crosslinked structure with high heat resistance. (Day-
・C. Edwards (D, C, Bdwards), Rubber Chemistry, and Technology (R, C, T
), Vol. 60, p. 62, 1987). This type of vulcanization will be referred to as TP pre-vulcanization.

On the other hand, it has long been known that when a halogen such as chlorine gas is applied to a polybutadiene elastomer such as styrene-butadiene rubber, halogen addition to unsaturated bonds occurs. However, the product has little practical value for forming heat-resistant crosslinks, and has hardly been studied in detail.

(Problem to be Solved by the Invention) The above TP pre-vulcanization method is
In order to apply this method to polybutadiene-based elastomers such as styrene-butadiene copolymers, a method for introducing effective active halogen groups into these rubbers is required, but this has not yet been successful. In this case, a halogen group bonded in the form of an allyl halogen structure or a benzyl halogen structure is promising as the active halogen group. In an attempt to introduce such an active halogen structure into a polybutadiene elastomer, a halogen such as chlorine gas was first reacted directly with the elastomer. However, in this case, since an addition reaction as shown in the following formula usually occurs, introduction of an allyl halogen structure has not been successful.

~CHz CH=CHCHg ~+CIl! An object of the present invention is to provide a halogenated polybutadiene elastomer having an allyl halogen structure or a benzyl halogen structure as an active halogen group.

Another object of the present invention is to provide an effective method for producing the halogenated polybutadiene elastomer.

A further object of the present invention is to provide a rubber composition that uses the halogenated polybutadiene elastomer or a blended rubber of this elastomer and another conjugated diene polymer as a rubber component and provides an improved heat-resistant crosslinked structure. be.

(Means for Solving the Problems) As a result of repeated efforts to solve the above problems, the present inventors have developed an organic compound having an allyl halogen structure or a benzyl halogen structure for the carbon-carbon unsaturated bond of polybutadiene rubber. By adding an acid to produce a halogenated polybutadiene elastomer having the halogen structure, and by crosslinking this elastomer with a polyvalent amine, it was confirmed that crosslinking of rubber with excellent heat resistance could be achieved, and this invention was completed. I ended up doing it.

That is, first, the present invention is a halogenated polybutadiene elastomer having the formula I C=0 at random positions along the molecular chain, and the remaining molecular structure having a polybutadiene elastomer structure.

It represents an acid monoester residue, and E represents a hydrogen atom, a halogen atom, or a carboxylic acid residue. ) and a polybutadiene elastomer in the presence of at least one organic halogenating agent selected from the group consisting of N-haloamide compounds and trihaloisocyanuric acids represented by May be different, R1
-R1 represents a hydrogen atom, an alkyl group or an alkoxy group having 5 or less carbon atoms, and at least one repeating unit selected from the group consisting of repeating units represented by
or more polymer and at least one active halogen group-containing compound selected from the group consisting of compounds represented by (R1 to R7 each represent a hydrogen atom or an alkyl group or an alkoxy group having 5 or less carbon atoms, which may be different from each other). This is a method for producing the halogenated polybutadiene elastomer, which comprises reacting the halogenated polybutadiene elastomer.

Furthermore, thirdly, the present invention provides 30 to 100 parts by weight of the halogenated polybutadiene elastomer having a halogen element content of 0.1% by weight or more and less than 0.3% by weight, and 70 to 0 parts by weight of other conjugated diene polymers. This is a rubber composition prepared by blending 0.3 to 10 parts by weight of a polyvalent amine to 100 parts by weight of a raw material rubber consisting of parts by weight.

The above-mentioned invention can solve the above-mentioned problems.

(Function) The production of the halogenated polybutadiene elastomer is carried out by combining the polybutadiene elastomer and the general formula IV.
a+ IVbt IVc, Vt Via or■
The reaction is carried out by adding the above-mentioned organic halogenating agent (usually used in the form of a solution) to a solution prepared by dissolving the active halogen group-containing compound represented by b in an appropriate organic solvent and causing the reaction to occur.

Industrially, the production of the present invention can be continued as an elastomer solution using rubber cement after the polymerization reaction is completed, unreacted monomers are recovered, and if necessary, the catalyst is deactivated. It can be done to advantage.

The reaction temperature and reaction time are not particularly limited, but are usually 0.
The temperature is 3 minutes to 3 hours at 100°C to 100°C.

After carrying out the above reaction on the polybutadiene elastomer, operations such as neutralization are performed as necessary, and the elastomer is solidified by pouring the reaction mixture into a large amount of alcohol or hot water while stirring, and then solidifying the elastomer. After washing and removing residual impurities in the elastomer as necessary, the elastomer is dried to obtain a halogenated polybutadiene elastomer in high yield.

In the obtained halogenated polybutadiene elastomer, infrared spectroscopic analysis revealed that 1740 cm-
The ester bond of ' is clearly recognized. Therefore, depending on the structure of the butadiene units in this elastomer,
That is, when the butadiene unit has a 1,2-bond structure, the structure of the formula I or (2) has been introduced, and when the butadiene unit has a 1,4-bond structure, the structure of the formula III has been introduced.

For example, in the presence of tertiary butyl hypochloride, which is a typical alkyl hypohalide used in the production method of the present invention, in a toluene solvent, polybutadiene mainly having a 1.4 type structure and the above (
When reacting with IVa), (V) or (Vla), the reaction mechanism can be shown as follows.

(1) + CHz CH=C41CHz÷+(
CH:l) 3COCRC=0 (2) +CB! Cl=CHCHHz ++ (
CH3) tcOcf+CII□-CH=CII-CL÷
+(CH:+) 3COCR+BrCIIz CC0
OH Noisy CH.

〇=O BrCHz C=C1h In this manner, a polybutadiene elastomer having an active halogen group introduced into the molecule, that is, a halogenated polybutadiene elastomer, can be produced by the method of the present invention.

In this invention, the polybutadiene elastomer used in the above production includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-methacrylic acid copolymer, butadiene-methyl methacrylate copolymer, butadiene -isoprene copolymers, etc., with butadiene-styrene copolymers and polybutadiene being preferred.

The molecular weight of these elastomers is not limited in any way and can be selected as appropriate depending on the purpose and use of the elastomer, but it is preferable to use one with a molecular weight of about 100,000 or more.

In this invention, the above-mentioned polybutadiene elastomer is used after being dissolved in a suitable solvent.

The solvent used is one that has good solubility for the polybutadiene elastomer used, and that contains alkyl hypohalite, N-
A solvent that stably dissolves the haloamide or trihaloisocyanuric acid and the active halogen group-containing compound is selected and used as a single solvent or a mixed solvent. Specific examples of solvents include aliphatic solvents such as pentane, hexane, heptane, and octane, alicyclic solvents such as cyclohexane, aromatic solvents such as benzene and toluene, polar solvents such as acetone, methyl ethyl ketone, and ethyl acetate, and chloride. Halogenated hydrocarbon solvents such as methylene, chloroform, and carbon tetrachloride, and among them, benzene, toluene,
These are hexane, cyclohexane, acetone, and methyl ethyl ketone.

The active halogen group-containing compound used in this invention has the general formula IVa, IVb, IVc,
V.

It is represented by VIa or vtb, of which IVa and ■ are preferred, especially R+ = Rz = Rx = R4 = H
, Rs = H is preferred.

Specific examples of IVa, IVb or IVc include p, m or 0-bromomethylbenzoic acid, p, respectively.

m- or O-chloromethylbenzoic acid, etc.; specific examples of Examples of vtb include methylacrylic acid, α-chloromethylacrylic acid, α-bromomethylcrotonic acid, etc. Specific examples of vtb include β-bromomethylacrylic acid, β-chloromethylacrylic acid, β
-bromomethylcrotonic acid, etc. When producing an elastomer for the purpose of heat-resistant crosslinking, these active halogen group-containing compounds are usually added in an amount of o, ooi to 0.03 mol, preferably 0.002 to 0.020 mol, per 100 g of polybutadiene elastomer. used in such amounts as to If the amount added is less than 0.001 mol/100 g of elastomer, no significant improvement in the heat resistance of the vulcanizate will be observed, and if it exceeds 0.030 mol/100 g of elastomer, the vulcanizate will lose its original properties as a polybutadiene rubber. It loses its properties and exhibits disadvantages such as a significant decrease in tensile strength and elongation.

Among the organic halogenating agents (reaction aids) used in the method of this invention, examples of alkyl hypohalides include primary alkyl hypohalides, secondary alkyl hypohalides, and tertiary alkyl hypohalides, among which the most stable are Preferred examples include tertiary butyl hypochloride, tertiary butyl hypopromite, and tertiary amyl hypochloride, which are tertiary hypohalides. In addition, N-haloamide compounds having a carbonate monoester residue include N,N-dichloroethyl urethane, N,N-
Examples include dichloromethylurethane. Further, typical examples having a sulfonic acid residue include N,N-dichlorobenzenesulfonamide, N,N-dibromobenzenesulfonamide, and N,N dichlorotoluenesulfonamide. Further, those having a carboxylic acid residue include N,N-dichloroacetamide, N-chlorosuccinimide, N-bromosuccinimide, and the like.

Furthermore, trichloroisocyanuric acid is representative as the trihalogenoisocyanuric acid.

In carrying out the method of this invention, the above reaction aids are:
It is usually used in a molar ratio of 1:1 to the active halogen group-containing compound, but this ratio can be changed as necessary.

The halogenated polybutadiene elastomer of the present invention has a total amount of repeating units I, II, and III of 0.001 per 100 g of the halogenated polybutadiene elastomer.
Those containing in the range of 0.03 to 0.03 gram equivalent are effective as a rubber composition, and those containing in the range of 0.002 to 0.02 gram equivalent are preferable.

In other words, the halogen element content corresponding to the total amount of repeating units I, II, and III of the halogenated polybutadiene-based elastomer is 0.1 to 3.5 by simple conversion.
Although it is effective at 0.1% by weight or more and less than 0.3% by weight in order to suppress the halogen content as low as possible and exhibit the effect, it is preferably 0.2% by weight or more and less than 0.3% by weight.
Less than is preferred. If the halogen content is less than 0.1% by weight, sufficient crosslinking density cannot be obtained, while if it exceeds 3.5% by weight, problems arise in terms of scorching during processing. Further, if it is less than 0.3% by weight, it is more preferable to obtain a vulcanized rubber with low hardness.

The amount of the halogenated polybutadiene elastomer in 100 parts by weight of the raw rubber needs to be at least 30 parts by weight in order to obtain sufficient heat resistance of the crosslinked rubber. Other conjugated diene polymers to be blended are not particularly limited, but commonly used natural rubber, polyisoprene rubber, emulsion styrene butadiene rubber, solution polymerized styrene butadiene rubber, polybutadiene rubber, etc. be.

Examples of polyvalent amines include hexamethylenediamine, heptamethylenediamine, methylenebis(cyclohexylamine), 1.3-di-4-piperidylpropane, 4.4
aliphatic or alicyclic primary or secondary diamines such as '-dipiperidyl, alicyclic tertiary diamines such as triethylene diamine, aromatic primary diamines such as 4,4' methylene dianiline, Aromatic secondary diamines such as N,N'-diphenyl-p-phenylenediamine (DPPD), p-octyldiphenylamine, p,p-dioctyldiphenylamine, di-β-naphthylphenylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylene Examples include trivalent or higher valence amine compounds such as pentamine, and N,N'-diphenyl-p-phenylenediamine is preferred.

The amount of amine added is 0.3 to 10 parts by weight, preferably 0.5 to 5.0 parts by weight. If it is less than 0.3 parts by weight, sufficient crosslinking will not be obtained, while if it exceeds 10 parts by weight, problems will occur in terms of scorch.

Crosslinking reactions are classified into two types depending on the type of polyvalent amine used. When using a polyvalent amine such as an aliphatic or cycloaliphatic primary or secondary diamine, the following formula
A condensation reaction occurs to form a crosslink (referred to as amine vulcanization).

÷CH2CHCI CTo+ (CHz CHCHCHt + In addition, when an aromatic secondary amine such as N,N'-diphenyl-p-phenylenediamine (DPPD) is used, a Friedel-Krach type reaction as shown in the following formula (■) occurs. is carried out to obtain crosslinking (referred to as TP vulcanization).

The type of reinforcing agent added to the halogenated polybutadiene elastomer is not particularly limited, but GP
F 5FEF, HAF, l5AF, ll5A
-F.

Furnace black such as SAF, thermal black such as FT, MT, channel black or acetylene black such as RPC, etc. Average particle size of 10 mμ to 500 mμ
Carbon black, anhydrous silicic acid produced by dry method, hydrated silicic acid produced by wet method, etc., with an average particle size of 10 mμ to 1゜Om.
μ silica-based reinforcing agents are preferred.

Further, as the filler, calcium carbonate, clay talc, etc. are used as appropriate.

When blending reinforcing agents and fillers, the blending amount is usually 1 to 200 parts by weight, preferably 10 to 12 parts by weight, per 100 parts by weight of the halogenated polybutadiene elastomer, depending on the purpose.
0 parts by weight.

Furthermore, the above heat-resistant crosslinking and other vulcanization systems may be used in combination, if necessary. Typical vulcanizing agents used in combination are sulfur and sulfur donors such as thiuram and thiazole, but peroxides, urethane vulcanizing agents, resin vulcanizing agents, etc. can also be used as desired. . In addition, sulfenamide-based vulcanization accelerators,
Thiuram type, thiazole type, guanidine type, mercaptotriazine type, aldehyde-amine type, etc. As vulcanization aids, carboxylic acids such as stearic acid and oleic acid,
Metal compounds such as zinc stearate, zinc oxide, magnesium oxide, calcium hydroxide, and lead carbonate are used, process oils such as paraffin, naphthenic, and aromatic are used as softeners, and rosin and petroleum are used as tackifiers. Examples of anti-aging agents include hydrocarbon resins, coumaron resins, phenol/terpene resins, and amine-based and phenol-based anti-aging agents. The above-mentioned vulcanization accelerator and vulcanization aid are mainly used in vulcanization in which sulfur or a sulfur donor is used in combination.

The method of mixing each component is not particularly limited, and usually various rubber kneading machines are used. In particular, carbon black and various process oils are mixed with rubber in the raw rubber manufacturing process or halogenation process. It can also be used as a carbon masterbatch or an oil masterbatch.

(Examples) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Implementation ■Top high styrene SBR (styrene content 46%, product name JS
R0202) 25g to 500ml of toluene? Dissolve and add 0.43 g of α-bromophenyl acetic acid (0,
002 mol; 0.008 mol/100 g elastomer) was added.

Stir this mixture at 75°C and add 0.22 g (0°002 mol) of tertiary butyl hypochloride to 10 mjl of toluene. A solution dissolved in was added dropwise over 5 minutes, and the reaction was further allowed to proceed for 1 hour. Then add 20g of the reaction mixture
The elastomer was coagulated by pouring it into 2Il of methanol containing an anti-aging agent (2,6-di-t-butyl-4-methylphenol: BHT), and the finely chopped coagulum was thoroughly washed with fresh methanol containing BIT. Thereafter, sample a was obtained by drying in a vacuum dryer overnight. Halogen content 0.70% by weight. In addition, as a result of infrared spectroscopic analysis of sample a, it was found that 1740 cm-
Absorption based on the ester bond of ' was clearly observed. This indicates that a "benzyl halogen structure" was introduced into sample a according to the following formula. Note that sample a does not contain gel, and the molecular weight before and after the reaction is almost unchanged.

r j-c, l(, ocz 0°C 0 C=O α Bromophenyl acetic acid was replaced with p-bromomethylbenzoic acid, but the process was carried out in exactly the same manner as in the example to obtain an elastomer sample. Halogen content: 0 .6% by weight.Sample a
shows similar absorption in infrared spectroscopy. The sample contains no sumo gel, and the molecular weight before and after the reaction is almost unchanged.

3-4 611 Sample a of Example 1, sample S of Example 2, and high styrene SBR (JSR0202) were kneaded on small rolls according to the compounding procedures shown in Table 1 to obtain an unvulcanized compound. was prepared.

In Table 1, unvulcanized formulation S-A is the sample a prepared by only vulcanization with methylenebis(cyclohexylamine) (MBCA), and unvulcanized formulation S-B is the sample a. N,N'-diphenyl-p
- Only vulcanization with phenylenediamine (DPPD) occurred, and unvulcanized formulation S-C was JSR0202 (high styrene SBR) as a control.
It is for sulfur vulcanization. Figure 1 shows the vulcanization curves at 230°C using these oscillating disk rheometers (Monosand type). Table 1 also shows the tensile properties of the vulcanizates.

l 5 6 2 High cis polybutadiene (trade name JSRBROI, manufactured by Japan Synthetic Rubber Co., Ltd.) in place of high styrene 5BRO in Example 1
Elastomer sample d was obtained in exactly the same manner as in Example 1, except that . Contains 10.75% by weight of halogen. As a result of infrared spectroscopy, 1740c was not found in the starting material (BROI).
Absorption based on the m-' ester bond was clearly observed.

This sample and the high cis polybutadiene were each
Unvulcanized formulations S-D and S-E were prepared by kneading on small rolls according to the formulations shown in the table. In Table 2,
Unvulcanized formulation S-D is a sample d in which only vulcanization by MBCA occurs, and unvulcanized formulation S-E is a control in which the BROI is sulfur-vulcanized. be.

Figure 2 shows S-D and S- obtained in the same manner as in Figure 1.
The vulcanization curve of sample E at 230°C is shown.

The tensile properties of the vulcanizates are also shown in Table 2.

Dissolve 100g of SBR#1502 in 21g of toluene, and add 1.72g of α-bromo-phenylacetic acid (0,00
8 mol/100 g elastomer) was added.

While stirring this mixture, 0.87 g (0,008 mol) of tertiary butyl hypochloride was added to 40 m of toluene at 75°C. ! , was added dropwise over a period of 5 minutes, and the reaction was further allowed to proceed for 1 hour. After that, anti-aging agent (2,
6-sheet t-butyl-4-methylphenol diBIT)
The elastomer was coagulated by pouring it into methanol 81 containing 20 g, and the coagulated material was thoroughly washed with fresh BIT-containing methanol, and then dried in a vacuum dryer overnight to obtain sample f. The halogen content (weight %) of this sample was 0.6%. As a result of infrared spectroscopic analysis of sample f, 1740c, which is not found in the starting material (SBR#1502)
Absorption based on the m-' ester bond was clearly observed. This shows that a "benzyl halogen structure" is introduced into sample f according to the following formula.

r t-CJqOCff C=0 Furthermore, by changing the amount of the halogenating reagent in the same manner, the halogen content (wt%) of sample g was 1.0%, and the halogen content (wt%) of sample h was 6.0%. I got it.

A rubber composition was prepared using this sample by kneading it with the formulation shown in Table 3 using a small Banbury mixer.

Table 2: L-Clothing Elastomer AF Aroma Stearate Polyvalent Amine *1 Zinc White DPG $2 DM *3 Sulfur Weight: L Part 2 See Table 4 0.3 1.2 See Table 4 Heat Resistance Blowout temperature as a measure of sex is shown in Table 4. The vulcanization conditions were 155°C x 30 minutes.

*2 Diphenylguanidine *3 Dibenzothiazyl disulfide Based on the formulation in Table 3, Mooney scorch time as a measure of processability of various rubber compositions with different types of elastomer, polyvalent amine content, and sulfur content, the above evaluation is as follows: The following method was used.

Mooney scorch time: Conducted based on Section 5 of JIS K6300.

Blowout test: This measurement is approximately 7 un x 7
A vulcanized rubber sample piece of mm x 3.5 mm was placed in an electric crucible furnace manufactured by Isuzu Seisakusho Co., Ltd., and the temperature was raised from 180°C to 250°C at 2°C intervals, while being left at each temperature for about 20 minutes. After that, it was taken out, cut in half, and visually checked to see if air bubbles were generated inside.

Sample 11 had a halogen content of 0.75% by weight; I got it.

Rubber compositions were prepared using this sample i and control sample BROI by kneading them in a small-sized Banbury mixer according to the formulations shown in Table 5.

1 a to 14 Sa No. LJL-Elastomer AF Aromastearic acid polyvalent amine *1 Zinc white DPG *2 DM *3 Sulfur enamel L-Plate Refer to Table 6 0.3 1.2 See Table 6 *1 414'-methylene dianiline *2 Diphenylguanidine *3 Dibenzothiazyl disulfide Table 6 shows the Mooney scorch time and blowout temperature of the rubber compositions containing sample i and control sample BROI. The vulcanization conditions were 155°C x 30 minutes.

6th person Bii・This 12th JL shadow Suj
1 case” - BROI
100 samples 1100 (Halogen content 0.75% by weight) 4I41-methylene dianiline -1,0 sulfur
1.5 1.0 Mooney Scorch Time (min') 19.8 19
．． 1 blowout temperature (,”C) 181
217 The above evaluation was performed in the same manner as in Examples 6-8.

(Effects) As is clear from the above Examples, the production method of the present invention makes it possible to efficiently produce a novel halogenated polybutadiene elastomer having an allyl halogen structure or a benzyl halogen structure. The rubber composition of the present invention containing a halogenated elastomer and a polyvalent amine reacts under normal vulcanization conditions to form an effective heat-resistant crosslinking bond without impairing processability, and is suitable for conventional sulfur vulcanization systems. In comparison, a rubber composition with significantly improved heat resistance is obtained without substantially reducing tensile properties.

Therefore, the rubber composition of the present invention is useful for rubber compositions that require heat resistance, such as tire components such as automobile tires, particularly racing tires, motorsport tires, and high-speed passenger car tires, especially rubber compositions for treads. Furthermore, it is advantageously used in compositions for carcass rubber, belt rubber, sidewall rubber, inner liner rubber, bead filler rubber, and the like. Of course, it can also be used for carcass, treads, sidewalls, bead fillers, inner liners, various anti-vibration rubbers, industrial belts, etc. of regular passenger car tires and large tires for trucks and buses.

[Brief explanation of drawings]

FIG. 1 shows two types of halogenated polybutadiene elastomers (S-A and 5-B) obtained according to the method of the present invention.
) and High Steel 1/7SBR at 230°C. Figure 2 is a vulcanization curve comparing vulcanization at 230°C with polybutadiene.

Claims (1)

[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (Formula Y in I, II and III represents a halogen atom, and A has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates a group, where X is a halogen atom and may be the same or different from Y, R_7
represents a hydrogen atom or an alkyl group or alkoxy group having 5 or less carbon atoms. ) has at least one repeating unit selected from the group consisting of repeating units represented by () at random positions along the polymer molecular chain, and the remaining molecular structure has a polybutadiene-based elastomer structure. Characteristic halogenated polybutadiene elastomer. 2. The halogenated polybutadiene elastomer according to claim 1, wherein Y is a chlorine atom. 3. The halogenated polybutadiene elastomer according to claim 1 or 2, which is a halogenated styrene-butadiene copolymer. 4. The halogenated polybutadiene elastomer according to claim 1 or 2, which is a halogenated polybutadiene polymer. 5. The total amount of repeating units I, II, and III is 0.001 to 100 g of halogenated polybutadiene elastomer.
The halogenated polybutadiene elastomer according to any one of claims 1 to 4, containing the elastomer in an amount of 0.03 gram equivalent. 6. The total amount of repeating units I, II, and III is 0.002 to 100 g of halogenated polybutadiene elastomer.
The halogenated polybutadiene elastomer according to claim 5, containing the elastomer in an amount of 0.02 gram equivalent. 7. Alkylhybohalite, general formula ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (Y in the formula represents a halogen atom, D
represents a carboxylic acid residue, a sulfonic acid residue, or a carbonic acid monoester residue, and E represents a hydrogen atom, a halogen atom, or a carboxylic acid residue. ) Polybutadiene elastomer in the presence of at least one organic halogenating agent selected from the group consisting of N-haloamide compounds and trihaloisocyanuric acids represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (IVa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IVb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IVc) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼ (VIa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VIb) (X in formulas IVa, IVb, IVc, V, VIa and VIb is a halogen atom and may be the same or different from Y. , R_1 to R_7 are hydrogen atoms or have 5 carbon atoms
The following alkyl groups or alkoxy groups are shown. ) The production of a halogenated polybutadiene-based elastomer according to any one of claims 1 to 6, wherein the elastomer is reacted with at least one active halogen group-containing compound selected from the group consisting of compounds represented by Method. 8. Halogen element content is 0.1% by weight or more and 0.3% by weight
The halogenated polybutadiene elastomer 30 according to any one of claims 1 to 4, which is less than
~100 parts by weight and 70 parts by weight of other conjugated diene polymers
A rubber composition comprising 0.3 to 10 parts by weight of a polyvalent amine to 100 parts by weight of a raw rubber consisting of 0 parts by weight.