JP2001048929A - Modified polybutene polymer and rubber composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified polybutene polymer which can improve the tan δ balances and friction resistances of rubber compositions and is useful for tire tread materials and so on, by reacting a specific polymer containing isobutylene as a monomer with a proper reactant. SOLUTION: This modified polybutene polymer has isobutylene repeating units and has at least one kind of structures selected from (A) half-ester structures, (B) amic acid structures, (C) onium salt structures and (D) imide structured in the main molecular chain, the molecular terminals and/or the molecular side chains. The structures A each preferably contain a structure of formula I [R1 is a 1 to 25C hydrocarbon (containing O, N, Si)] or the like as a main component, and the structures B each preferably contains a structure of formula II [R2 and R3 are each a 1 to 25C hydrocarbon (containing O, N, Si) or H] or the like as a main component. The structures C each preferably contains a structure of formula III [R4 and R5 are each a 1 to 25C hydrocarbon (containing O, N, Si) or H] as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polybutene polymer and a rubber composition containing the same, and more particularly to a rubber composition having improved tan .delta. tanδ is increased and tanδ at 60 ° C. is reduced), the reinforcing effect of a reinforcing agent such as carbon black is improved to improve abrasion resistance, and a modified polybutene polymer and a rubber composition containing the same, particularly for a pneumatic tire. The present invention relates to a rubber composition useful as a tire tread.

[0002]

2. Description of the Related Art A polymer containing isobutylene as a monomer, especially butyl rubber, is expected to exhibit high gripping performance due to high tan δ in a wide temperature range, and particularly to improve wet braking performance due to high tan δ at 0 ° C. . However, a polymer containing isobutylene as a monomer has few double bonds in the molecule, and thus has a problem that the reinforcing property by carbon black is not sufficient and the abrasion resistance is poor.

[0003]

Accordingly, the present invention eliminates the above-mentioned problems of the conventional polymer containing isobutylene as a monomer, such as butyl rubber, and reduces the abrasion resistance without substantially reducing the abrasion resistance. Modified polybutene useful for compounding in a rubber composition having a high tan δ at 60 ° C. (that is, excellent in wet braking properties) and a low tan δ at 60 ° C. (that is, excellent in fuel economy) and having an excellent balance of tan δ. An object of the present invention is to provide a polymer and a rubber composition containing the polymer.

[0004]

According to the present invention, the present invention comprises an isobutylene repeating unit and comprises (A) a half ester structure, (B) an amic acid structure, (C) an onium salt structure, and (D) an imide structure. A modified polybutene polymer having at least one structure selected from the group in a molecular main chain, at a molecular terminal and / or in a molecular side chain is provided.

According to the present invention, there is provided a rubber composition containing the modified polybutene polymer.

[0006]

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, as described above, it comprises an isobutylene repeating unit, (A) a half ester structure, (B) an amic acid structure, (C) an onium salt structure and (D) an imide. A modified polybutene polymer having at least one structure selected from the group consisting of structures in the main chain of the molecule, at the terminal of the molecule and / or in the side chain of the molecule, at 0 ° C. without substantially lowering the abrasion resistance. It is possible to increase tan δ and decrease tan δ at 60 ° C.

According to the present invention, the half-ester structure (A) is formed in the molecule of the polymer having the repeating unit of isobutylene (ie, in the molecular main chain, at the molecular terminal and / or the side chain), preferably at the molecular terminal. The above object can be achieved by introducing an amide acid structure (B), an onium salt structure (C) and / or an imide structure (D).

The half-ester structure (A) (that is, a structure in which an ester group and a carboxyl group are present simultaneously in the molecule) has, for example, the formula (I):

[0009]

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Wherein R ¹ is an oxygen atom, a nitrogen atom and / or
Or a hydrocarbon group having 1 to 25 carbon atoms which may contain a silicon atom, and preferably a long-chain alkyl group such as a stearyl group). By blending the coalesced with the rubber composition, the affinity with the reinforcing agent is improved, and at the same time, the reinforcing property is improved by the pseudo-crosslinking effect by hydrogen bonding, and the viscoelastic properties and the abrasion resistance are improved. I found something.

The amide acid structure (B) (that is, a structure in which an amide group and a carboxyl group are present simultaneously in the molecule) has, for example, the formula (II):

[0012]

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(Wherein R ² and R ³ independently represent an oxygen atom,
1 carbon atom which may contain a nitrogen atom and / or a silicon atom
A modified polybutene polymer containing a hydrocarbon group or a hydrogen atom, preferably a long-chain alkyl group such as a stearyl group) in the molecule. In addition to improving the affinity with the reinforcing agent by blending it inside, at the same time, the pseudo-cross-linking effect due to hydrogen bonding improves the reinforcing properties, and has the effect of improving viscoelastic properties and abrasion resistance. I found it.

Further, the onium salt structure (C) has, for example, the formula (III):

[0015]

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(Wherein R ⁴ and R ⁵ are independently an oxygen atom,
A hydrocarbon group or a hydrogen atom having 1 to 25 carbon atoms which may contain a nitrogen atom and / or a silicon atom, and preferably a long-chain alkyl group such as a stearyl group). By compounding the modified polybutene polymer containing this in the molecule into the rubber composition,
It was also found that this also improved the affinity with the reinforcing agent, and at the same time, the reinforcing property was improved by the pseudo-crosslinking effect by hydrogen bonding, and the viscoelastic properties and the abrasion resistance were improved.

Further, the imide structure (D) has, for example, the formula (IV):

[0018]

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(Wherein R ⁶ is a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom and / or a silicon atom, and is preferably a long-chain alkyl group such as a stearyl group. The main component is the structure of (a), and by blending a modified polybutene polymer containing this in the molecule into the rubber composition, this also improves the affinity with the reinforcing agent, and at the same time, the hydrogen bonding Has been found to have an effect of improving the viscoelastic properties and abrasion resistance due to the pseudo-crosslinking effect of the compound.

The modified polybutene polymer having the structures (A) to (D) in the molecule is based on a polymer having at least one kind of isobutylene as a monomer,
Examples of such a polymer include polyisobutylene, polybutene, butyl rubber, brominated butyl rubber, isobutylene / maleic anhydride copolymer, isobutylene / p-methylstyrene / p-bromomethylstyrene copolymer, and the like. Although the molecular weight is not particularly limited, it is generally preferable that the weight average molecular weight is 1,000 to 1,000,000. In the present invention, such a basic polymer can be modified by reacting with an appropriate reactant as shown in the following Production Examples.

According to the present invention, (i) 100 parts by weight of at least one kind of diene raw rubber, (ii) 10 parts by weight or more, preferably 15 to 100 parts by weight of at least one kind of reinforcing agent, and (iii) There is provided a rubber composition comprising 0.1 to 80 parts by weight, preferably 1 to 30 parts by weight, more preferably 3 to 30 parts by weight of a modified polybutene polymer, and the rubber composition has abrasion resistance. Increasing tan δ at 0 ° C. without substantially reducing
The tan δ at 60 ° C. can be reduced. Here, when the amount of the reinforcing agent is too small, bleeding of the reinforcing agent and the modified polybutene is caused, and the mechanical properties of the rubber composition itself are inferior. Also, if the blending amount of the modified polybutene polymer is too small, the desired effect cannot be obtained, which is not preferable.On the contrary, if it is too large, mixing property, roll processability is deteriorated, or tack is left on the vulcanized rubber, which is not preferable. .

According to the present invention, (i) 100 parts by weight of at least one kind of diene-based raw rubber, (ii) 10 parts by weight or more of at least one kind of reinforcing agent, preferably 15 to 1 part by weight.
(Iii) at least one kind of the modified polybutene polymer, preferably 0.1 to 80 parts by weight, more preferably 1 to 30 parts by weight, more preferably 3 to 30 parts by weight, and (iv) (a)
A polybutene polymer modified with an acid anhydride group, and / or a nitroxide radical or hydrazyl radical stably present at room temperature and in the presence of oxygen, comprising a polybutene polymer modified with an acid anhydride group and / or (b) containing an isobutylene repeat unit; Modified polybutene polymer having at least one kind of free radical selected from the group consisting of allyloxy radical and trityl radical in the molecule 0.1 to 80
Parts by weight, preferably 1 to 30 parts by weight, more preferably 3 parts by weight.
There is provided a rubber composition comprising about 30 parts by weight. This rubber composition also improves the affinity with the reinforcing agent, and at the same time, the reinforcing property is improved and the viscoelastic properties are good.

Also in this composition, if the amount of the reinforcing agent is too small, bleeding of the modified polybutene is caused, and the mechanical properties of the rubber composition itself are not preferable. Also, if the amount of the modified polybutene polymer (iii) is too small, the desired effect cannot be obtained, so that it is not preferable. If the amount is too large, the mixing property and the roll processability are deteriorated.
It is not preferable because tack is left on the vulcanized rubber. Further, if the amount of the modified polybutene polymer (iv) is too small, the desired effect cannot be obtained, so that it is not preferable.
It is not preferable because the mixing property and the roll processability are deteriorated and tack is left on the vulcanized rubber.

A nitroxide radical, a hydrazyl radical, an allyloxy radical, a trityl radical which is stably present in the molecule of the polymer having isobutylene repeating units used in the present invention, preferably at the molecular terminal, at room temperature and in the presence of oxygen The modified polybutene polymer having the formula (1) can be obtained, for example, by reacting a polymer having an isobutylene repeating unit with the compound having a free radical, as shown in the following Production Examples. In the reaction, it is preferable that the polymer having a repeating unit of isobutylene is modified with an arbitrary reactive group which reacts with the above-mentioned free radical compound at a desired position, for example, at the terminal to bind the free radical. Examples of such a reactive group include an alkoxysilyl group, an acid anhydride group, an ester group and the like, which can be appropriately assumed by those skilled in the art. The reaction conditions are not particularly limited.

Examples of the polybutene polymer modified with an acid anhydride group include those represented by formulas (V) to (VIII):

[0026]

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[0027] Those having a maleic anhydride-modified polybutene as a main component can be used.

Here, polybutene refers to isobutylene, 1,2-butene, 2,3-butylene obtained by naphtha decomposition or the like.
A polymer obtained by polymerizing a C ₄ hydrocarbon fraction containing butene or the like in the presence of a catalyst such as boron trifluoride or aluminum chloride, and a product obtained by hydrogenating a double bond in polybutene can also be used. .

The introduction of the maleic anhydride units of the formulas (V) to (VIII) is a conventional method. For example, the terminal olefin reacts with the maleic anhydride under heating and stirring conditions by the Ene reaction to form polyisobutylene. Can be introduced. By mixing the acid anhydride-modified polybutene thus obtained, the maleic anhydride unit reacts with, for example, a hydroxyl group or a carbonyl group on the carbon black and binds to the carbon black. On the other hand, the isobutylene unit improves tan δ balance (and abrasion resistance). If the amount of the acid anhydride-modified polybutene is too small, the desired effect cannot be obtained, which is not preferable. On the other hand, if the amount is too large, there is a problem that the mixing property and the roll processability are deteriorated and tack is left on the vulcanized rubber.

The raw rubber compounded as a main component in the rubber composition according to the present invention may be any diene rubber conventionally compounded generally in various rubber compositions, for example, natural rubber (NR), polyisoprene rubber (IR), diene rubbers such as various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), acrylonitrile-butadiene copolymer rubbers (NBR), and butyl rubber (IIR) alone or as an arbitrary blend. Can be used.

The rubber composition according to the present invention further contains a general reinforcing agent. Examples of the reinforcing agent include carbon black and silica.
10 parts by weight or more, preferably 15 to 100 parts by weight, of the reinforcing agent is added to the parts by weight. If the amount is too small, the reinforcing properties required for the rubber composition cannot be obtained, which is not preferable. These polyisobutylene-based polymers can be used after being reacted (bulk or solution) with a reinforcing agent such as carbon black or silica in advance, and then compounded with rubber.

When silica is compounded in the rubber composition according to the present invention, for example, 5 to 30% by weight of a silane coupling agent with respect to the silica compounding amount may be compounded as in the conventional case. In this case, furthermore, in this case, the silanol condensation catalyst may be used in an amount of 0.05 to less than the compounding amount of the silane coupling agent.
50% by weight can be blended. As the silane coupling agent used in the silica-containing rubber composition according to the present invention, any silane coupling agent conventionally used as a silica filler can be used.

In the rubber composition according to the present invention, in addition to the above-mentioned essential components, vulcanizing or cross-linking agents, vulcanizing or cross-linking accelerators, various oils, anti-aging agents, plasticizers, etc. Various additives generally compounded for rubber can be compounded, and such compounds can be kneaded and vulcanized into a composition by a general method, and used for vulcanization or crosslinking. it can. The compounding amounts of these additives can also be conventional general compounding amounts as long as they do not contradict the object of the present invention.

The rubber composition according to the present invention can be used for belts, hoses, rubber cushions, rollers, sheet linings, rubberized cloths, sealing materials, gloves, fenders and the like, in addition to tires.

[0035]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.

The following commercially available products were used for the components shown in the tables used in the following Examples and Comparative Examples except for the modified polybutene polymer. The method for measuring physical properties is also shown below.

SBR: Nipol 1502 (manufactured by Nippon Zeon) Carbon black: HAF Show Black N339
(Showa Cabot) Silica: Nip Seal AQ (manufactured by Nippon Silica Industry) Silane coupling agent: Si69 (manufactured by DEGUSSA) Zinhua: Ginrei Zinhua R (manufactured by Toho Zinc) Stearic acid: Beads stearic acid Kiri (manufactured by Nippon Oil & Fat) Anti-aging Agent: N-phenyl-N '-(1,3-dimethylbutyl) -P-phenylenediamine Sulfur: oil-treated sulfur (produced by Karuizawa Refinery) Vulcanization accelerator CZ: Noxeller CZ-G (produced by Ouchi Shinko Chemical) Auxiliary agent DPG: Noxeller D (Ouchi Shinko Chemical) Aroma oil: Desolex 3 (Showa Shell Sekiyu)

Tan δ (0 ° C.): 20 Hz, 10 ± 2% expansion / contraction, 0 ° C. tan δ tan δ at 60 mm sample width (60 ° C.): 20 Hz, 10 ± 2% expansion / contraction, 60 ° C. tan δ resistance at (sample width 5 mm) Abrasion (index): two-run Lambourn test (slip ratio 2)
5%, load 5 kg, time 4 minutes, room temperature RT, using K-80 grindstone). In addition, the result was shown as an index with the value of the comparative example being 100. The larger the value, the better the wear resistance.

Examples 1-4 and Comparative Examples 1-2 Synthesis of Modified Polybutene First, maleated polybutene (manufactured by Nippon Petrochemical Co., Ltd.)
(Number average molecular weight 2,900, maleation ratio 70%)
53 g and propanol 1.11 g (0.0185 mol)
Or 5.00 g of stearyl alcohol (0.0185 mol
l) was heated and stirred at 80 ° C. for 12 hours to cause a reaction, and propyl half ester type polybutene (POH-PIB) or stearyl half ester type polybutene (SOH-PI
B) was synthesized (see the following reaction formula). IR of reaction product
Was analyzed, the absorption of the carbonyl of 1715 cm ^-1 is shifted to 1738 cm ^-1, the reaction was confirmed that in progress.

[0040]

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(Wherein R is C ₃ H ₇ (POH-PIB)
Or C ₁₈ H ₃₇ (SOH-PIB), and PBT represents polybutene. )

Preparation of Samples Among the components (parts by weight) shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded for 3 to 5 minutes in a 1.8 liter hermetic mixer and reached 165 ± 5 ° C. The vulcanization accelerator and sulfur were kneaded with an 8-inch open roll to the masterbatch released at this time, to obtain a rubber composition.

Next, this composition was placed in a size of 15 × 15 × 0.2 cm.
A test specimen (rubber sheet) was prepared by press vulcanization at 160 ° C. for 20 minutes in a mold of No. 1, and the vulcanization physical properties 50% modulus, tan δ (0 ° C. and 60 ° C.) and abrasion resistance were evaluated. . The results are shown in Table I.

[0044]

[Table 1]

Examples 5 to 8 and Comparative Examples 3 and 4 Synthesis of Modified Polybutene Maleated polybutene (Nippon Petrochemical Co., Ltd., number average molecular weight 2,900, maleation ratio 70%) 76.53
g, 1.153 g (0.0195 mol) of propylamine or 5.256 g (0.0195 mol) of stearylamine was heated and stirred at 80 ° C. for 12 hours to obtain a propylamine-type modified polybutene (PNH-PIB) (see the following reaction formula). ) Or stearylamine-type modified polybutene (SNH-PI)
B) was synthesized. Was subjected to IR analysis of the reaction product, the absorption of the carbonyl of 1715 cm ^-1, 1712 cm ^-1
To confirm that the reaction was in progress.

[0046]

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Wherein R is C ₃ H ₇ (PNH-PIB)
Or C ₁₈ H ₃₇ (SNH-PIB), and PBT represents polybutene. )

Preparation of Samples Among the components (parts by weight) shown in Table II, the components other than the vulcanization accelerator and sulfur were kneaded for 3 to 5 minutes in a 1.8 liter hermetic mixer and reached 165 ± 5 ° C. The vulcanization accelerator and sulfur were kneaded with an 8-inch open roll to the master batch released at the time of the release to obtain a rubber composition.

Next, this composition was placed in a 15 × 15 × 0.2 cm
A test specimen (rubber sheet) was prepared by press vulcanization at 160 ° C. for 20 minutes in a mold of No. 1, and the vulcanization physical properties 50% modulus, tan δ (0 ° C. and 60 ° C.) and abrasion resistance were evaluated. . The results are shown in Table II.

[0050]

[Table 2]

Examples 9 to 16 and Comparative Examples 5 to 6 Synthesis of modified polybutene (i) 502 g (0.3267 mol) of maleated terminal polybutene (Nippon Petrochemical Co., Ltd., number average molecular weight 1, 2)
60, maleinization rate 82%) and 44.8 g (0.326)
7 mol) and aminobenzoic acid were heated and stirred at 150 ° C. for 2 hours and at 120 ° C. for 5 hours. 3 pp by NMR
The disappearance of the absorption of the maleic ring near m was confirmed, and it was confirmed that the reaction had progressed. The product 290.4
12.53 g of propylamine in g (0.212 mol)
(0.212 mol) or 57.14 g of stearylamine
(0.212 mol), and the mixture was heated and stirred at 120 ° C. for 5 hours, and propylonium salt-type modified polybutene (PAO-PI
B) (see the following reaction formula) or a stearylonium salt type modified olibutene (SAO-PIB) was synthesized. NMR confirmed the disappearance of the absorption of the carboxylic acid at around 8 ppm and the absorption of the amine at around 5 ppm, confirming that the reaction was proceeding.

[0052]

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(Wherein R is C ₃ H ₇ (PAO-PIB)
Or C ₁₈ H ₃₇ (SAO-PIB), and PBT represents polybutene. )

(Ii) Maleated polybutene (Nippon Petrochemical Co., Ltd., number average molecular weight 2,900, maleation ratio 7)
0%) 76.53 g, propylamine 1.153 g
(0.0195 mol), or stearylamine 5.256
g (0.0195 mol) was heated and stirred at 80 ° C. for 12 hours to synthesize. An IR analysis of the reaction product revealed that 1
Absorption of the carbonyl of 715 cm ^-1 is shifted to 1712 cm ^-1, the reaction was confirmed that in progress. Further, the product was heated and stirred under reduced pressure at 120 ° C. for 5 hours, dehydrated and defoamed to obtain a propylimide-type modified polybutene (PAI-
PIB) (see the following reaction formula) or stearylimide-type modified polybutene (SAI-PIB) was synthesized. IR analysis confirmed that the carbonyl absorption had shifted to 1702 cm ^-1 and that the reaction had proceeded.

[0055]

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Wherein R is C ₃ H ₇ (PAI-PIB)
Or C ₁₈ H ₃₇ (SAI-PIB), and PBT represents polybutene. )

Preparation of Samples Among the components (parts by weight) shown in Table III, the components excluding the vulcanization accelerator and sulfur were mixed in a 1.8 liter hermetic mixer to 3 to 5 parts.
The mixture was kneaded for 1 minute and the masterbatch released when the temperature reached 165 ± 5 ° C. was kneaded with an 8-inch open roll with a vulcanization accelerator to obtain a rubber composition.

Next, this composition was placed in a 15 × 15 × 0.2 cm
A test specimen (rubber sheet) was prepared by press vulcanization at 160 ° C. for 20 minutes in a mold of No. 1, and the vulcanization physical properties 50% modulus, tan δ (0 ° C. and 60 ° C.) and abrasion resistance were evaluated. . The results are shown in Table III.

[0059]

[Table 3]

[0060]

[Table 4]

Examples 17 to 29 and Comparative Examples 7 to 8 Synthesis of Modified Polybutene Polymer (i) Maleated Polybutene ( Maleated PIB) Nisseki Chemical Lab Synthetic Product (ii) TEMPO-PIB Maleated Polybutene (Number Average Molecular Weight) 2,900, maleation rate 70%) 100 g and 4-hydroxy-TEM
4.81 g (0.0243 mol) of PO at 120 ° C.
After heating and stirring for 2 hours, MPIB-TEM
PO was synthesized. The reaction was confirmed by IR,
Carbonyl absorption of the acid anhydride of 5 cm ^-1 was confirmed to be shifted to 1738 cm ^-1 in the esterification by ring opening. (Iii) SOH-PIB Modified polybutene synthesized in Examples 1-4 (iv) SAO-PIB Modified polybutene synthesized in Examples 9-16 (v) SNH-PIB Modified polybutene synthesized in Examples 5-8 (vi ) SAI-PIB Maleated polybutene synthesized in Examples 9-16

(Vii) AS-PIB (aminosilane-PI
B) 100 g of maleated polybutene (number average molecular weight 2,900, maleation rate 70%, (Nippon Petrochemical)) and 9.13 g (0.0509 mol) of 3-aminopropyltrimethoxysilane (A1110 from Nippon Unicar) To 80
The solution was synthesized by heating and stirring at 12 ° C. for 12 hours. Reaction product I
Was subjected to R analysis, absorption of carbonyl of 1715 cm ^-1 is shifted to 1738 cm ^-1, it was confirmed that the following reaction proceeds.

Preparation of Samples Among the components (parts by weight) shown in Table IV, the components other than the vulcanization accelerator and sulfur were kneaded for 3 to 5 minutes in a 1.8 liter hermetic mixer, and the mixture reached 165 ± 5 ° C. The vulcanization accelerator and sulfur were kneaded with an 8-inch open roll to the master batch released at the time of the release to obtain a rubber composition.

Next, this composition was placed in a 15 × 15 × 0.2 cm
A test specimen (rubber sheet) was prepared by press vulcanization at 160 ° C. for 20 minutes in a mold of No. 1, and the vulcanization physical properties 50% modulus, tan δ (0 ° C. and 60 ° C.) and abrasion resistance were evaluated. . The results are shown in Table IV.

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

As described above, according to the present invention, by mixing an acid anhydride-modified polybutene polymer with a diene rubber, the tan δ balance (that is, the grip performance of a tire when used as a tire tread material) is improved. In addition, it is useful as a rubber composition for pneumatic tires, because it has improved wear resistance.

Continued on the front page F-term (reference) 4J002 AC011 AC031 AC061 AC071 AC112 BB181 BB202 BB203 BB213 BB282 DA036 DJ016 FB096 FD016 GN01 4J100 AA04P AA05P AA06P AB04Q AB09R AK32Q AS03Q CA31 DA01 HA35 HA45 HC29 HC29 HC29 HC29

Claims (8)

[Claims] 1. A method comprising: (A) a half ester structure; (B) an amic acid structure;
A modified polybutene polymer having at least one structure selected from the group consisting of (C) an onium salt structure and (D) an imide structure in a molecular main chain, a molecular terminal and / or a molecular side chain. 2. The method according to claim 1, wherein the half ester structure (A) has the formula (I): 2. The modified compound according to claim 1, wherein the modified compound has a structure of the following formula: wherein R ¹ is a hydrocarbon group having 1 to 25 carbon atoms which may contain an oxygen atom, a nitrogen atom and / or a silicon atom. Polybutene polymer. 3. The method according to claim 1, wherein the amide acid structure (B) has the formula (II): (Wherein R ² and R ³ are independently a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom and / or a silicon atom). The modified polybutene polymer according to claim 1. 4. The onium salt structure (C) having the formula (III): (Wherein R ⁴ and R ⁵ are independently a hydrocarbon group having 1 to 25 carbon atoms or a hydrogen atom which may contain an oxygen atom, a nitrogen atom and / or a silicon atom). The modified polybutene polymer according to claim 1. 5. The imide structure (D) having the formula (IV): 2. The method according to claim 1, wherein R ⁶ is a hydrocarbon group having 1 to 25 carbon atoms which may contain an oxygen atom, a nitrogen atom and / or a silicon atom, or a hydrogen atom. The modified polybutene polymer according to the above. 6. The modified polybutene polymer according to claim 1, wherein (i) 100 parts by weight of at least one kind of diene-based raw rubber, (ii) 10 parts by weight or more of at least one kind of reinforcing agent, and (iii) A rubber composition comprising 0.1 to 80 parts by weight of at least one of the above. 7. The modified polybutene polymer according to claim 1, wherein (i) 100 parts by weight of at least one kind of diene-based raw rubber, (ii) 20 parts by weight or more of at least one kind of reinforcing agent, and (iii) At least one of 0.1 to 80 parts by weight and (iv) (a) an isobutylene repeating unit,
It comprises a polybutene polymer modified with an acid anhydride group and / or (b) a nitroxide radical, a hydrazyl radical, an allyloxy radical and a trityl radical stably present at room temperature and in the presence of oxygen, containing a repeating unit of isobutylene. A rubber composition comprising 0.1 to 80 parts by weight of a modified polybutene polymer having at least one free radical selected from the group in a molecule. 8. The polybutene polymer modified with an acid anhydride group has the formula (V) to (VIII): The rubber composition according to claim 7, which is mainly composed of maleic anhydride-modified polybutene.