WO2012053572A1

WO2012053572A1 - Method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions

Info

Publication number: WO2012053572A1
Application number: PCT/JP2011/074094
Authority: WO
Inventors: 佳余子阿部; ひろし前田; 竹内　謙一; 太田　義輝
Original assignee: 住友化学株式会社
Priority date: 2010-10-18
Filing date: 2011-10-13
Publication date: 2012-04-26
Also published as: JP2012197416A; JP2012197415A; CN103261166A

Abstract

A method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions, wherein the content of primary amine with respect to the total weight of the composition is 1 mass% or less, the method comprising a process of bringing a mixture containing 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof and, with respect to 100 parts by mass of the total of same, 2-6 parts by mass of a primary amine, into contact with 3-10 moles of a carboxylic acid anhydride with respect to 1 mole of the primary amine.

Description

Method for producing composition containing 2,2,4-trimethyl-1,2-dihydroquinoline polymer

The present invention relates to a process for producing a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition.

JP-A-53-145854 discloses a condensation reaction product of aniline and acetone as an anti-aging agent for vulcanized rubber used in the manufacture of automobile tires.
JP-A-6-228375 discloses a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition having a primary amine content of 1% by mass or less based on the total amount of the composition. Furthermore, as a production method thereof, 2,2,4-trimethyl-1,2-dihydroquinoline and 2,2,4-trimethyl-1,2-dihydroquinoline are distilled from a mixture containing 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof. A method comprising a step of removing and a step of polymerizing 2,2,4-trimethyl-1,2-dihydroquinoline removed in the previous step is also disclosed.

The present invention
[1] 2,2,4-Trimethyl-1,2-dihydroquinoline and a polymer thereof, a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total, and 1 mol of the primary amine 2,2,4-trimethyl-1,2-dihydro having a primary amine content of 1% by mass or less based on the total amount of the composition, comprising a step of contacting 3 to 10 mol of carboxylic acid anhydride with respect to Method for producing quinoline polymer-containing composition;
[2] Acetone and aniline are reacted to produce 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total. Obtaining a mixture comprising:
Contacting the resulting mixture with 3 to 10 moles of carboxylic anhydride per mole of primary amine;
The production method according to [1], comprising:
[3] A 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition obtained by the production method according to [1] or [2], wherein a molded product is obtained by the following preparation method. 2,2,4-trimethyl-1,2-dihydroquinoline polymerization characterized in that the transmittance of light at 600 nm after the molded product is kept at 100 ° C. for 1 hour is 0.5% or less. Product-containing composition;
<Method for preparing molded product>
A blend is obtained by blending 2 parts by weight of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition and 2 parts by weight of insoluble sulfur with 100 parts by weight of butadiene rubber. Preparing a 2 mm thick molding;
[4] 2 to 10 parts by mass of insoluble sulfur with respect to 100 parts by mass of raw rubber selected from the group consisting of natural rubber and diene rubber, and obtained by the production method according to [1] or [2] A rubber composition obtained by blending 0.5 to 5 parts by mass of a 2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition;
[5] Use of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition obtained by the production method according to [1] or [2] as an anti-aging agent for tires;
[6] Use of a composition obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic acid anhydride to improve the heat resistance of the vulcanized rubber;
[7] A method for improving the heat resistance of a vulcanized rubber, comprising the following steps (1), (2) and (3):
(1) 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total, and 1 mol of the primary amine Obtained by the step (2) of kneading the mixture obtained in the step (2) and the step (1) with the rubber component and the sulfur component. Vulcanizing the kneaded product to obtain a vulcanized rubber;
[8] The improvement method according to [7], wherein step (1) is performed in the absence of a rubber component;
[9] The improvement method according to [7] or [8], wherein step (1) is performed in the absence of a sulfur component;
[10] The amount of the carboxylic acid anhydride used in the step (1) is 0.6 to 5 mol with respect to 1 kg of the condensation reaction product of aniline and acetone. Improvement method as described;
[11] A heat resistance improver for vulcanized rubber obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic acid anhydride;
[12] A condensation reaction product of aniline and acetone is a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline, and primary The heat resistance improving agent for vulcanized rubber according to [11], which is a mixture containing an amine;
[13] The condensation reaction product of aniline and acetone is a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline, and 2 , 2,4-Trimethyl-1,2-dihydroquinoline and 2,2,4-trimethyl-1,2-dihydroquinoline in a total of 100 parts by mass, a mixture containing 2 to 6 parts by mass of a primary amine [11] or [12], wherein the heat resistance improver for vulcanized rubber is
[14] A product obtained by mixing a condensation reaction product of aniline and acetone with 3 to 10 moles of carboxylic acid anhydride per mole of primary amine contained in the condensation reaction product of aniline and acetone. 12] or [13], a heat resistance improver for vulcanized rubber;
[15] The product according to any one of [11] to [14], wherein the condensation reaction product of aniline and acetone is a product produced by condensation reaction of aniline and acetone in the absence of a sulfur component. A heat resistance improver for vulcanized rubber.

First, a method for producing a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition having a primary amine content of 1% by mass or less based on the total amount of the composition will be described. Such a production method includes 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and a mixture containing 2 to 6 parts by mass of a primary amine with respect to a total of 100 parts by mass (hereinafter referred to as “not yet”). A purified mixture ”) and a step of contacting 3 to 10 mol of carboxylic acid anhydride with respect to 1 mol of the primary amine.
<Unpurified mixture>
2,2,4-Trimethyl-1,2-dihydroquinoline and a polymer thereof have a structure mainly represented by the following formula (I).

2,2,4-Trimethyl-1,2-dihydroquinoline and a polymer thereof are preferably produced by reacting acetone and aniline, and reacting aniline and acetone in the presence of an acidic catalyst in a heated state. More preferably, it is produced by a dehydration polycondensation reaction. In such a reaction, it is preferable to use 2 to 20 mol of acetone with respect to 1 mol of aniline. After mixing the aniline and the acidic catalyst, excess acetone is then continuously fed to the resulting mixture, and unreacted acetone is recovered by distillation together with the water formed to maintain the reaction temperature under normal pressure. This is preferable.
The reaction between acetone and aniline is usually carried out in the presence of an acidic catalyst. Examples of the acidic catalyst include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen fluoride, organic acids such as organic sulfonic acid, and Lewis acids such as boron fluoride. Hydrogen halide is preferable, and hydrogen chloride is more preferable. The acidic catalyst may be used as an aqueous solution, may be used as a liquid other than the aqueous solution, may be used as a solid, or may be introduced as a gas into the reaction system. When using a hydrogen halide, it is preferable to use an aqueous solution thereof. When hydrochloric acid is used, the concentration is preferably 15 to 35% by mass. The amount of the acidic catalyst used is preferably 0.05 to 0.5 mol with respect to 1 mol of aniline. If the amount of the acidic catalyst used is 0.05 mol or more, the reaction time is short, and if it is 0.5 mol or less, the amount of the polymer having n of 2 or more in the above formula (I) decreases. Aging prevention performance is improved.
The reaction between acetone and aniline may be carried out in the presence of an organic solvent inert to the reaction between acetone and aniline, but is preferably carried out without substantially using an organic solvent. The reaction temperature is preferably in the range of 100 to 150 ° C. When the reaction temperature is 100 ° C. or higher, the amount of unreacted aniline decreases, and the amount of 2,2,4-trimethyl-1,2-dihydroquinoline and its polymer increases. When the reaction temperature is 150 ° C. or lower, the amount of acetone used is small, which is economically preferable.
Such a reaction is usually completed in a reaction time of 2 to 16 hours. When a relatively large amount of acidic catalyst is used, the reaction time is relatively short.
The reaction end point may be appropriately determined by analyzing the aniline content in the reaction mixture by a general analysis means such as high performance liquid chromatography or gas chromatography.
After completion of the reaction, it is preferable to remove the catalyst in the reaction mixture by a method such as neutralization, and then remove the organic solvent and unreacted aniline by distillation under reduced pressure to remove the unpurified mixture.
The resulting reaction mixture usually contains 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total. However, this may be used as it is as an unpurified mixture in the production method of the present invention, or a mixture obtained by removing the acidic catalyst by post-treatment such as neutralization, washing, concentration, etc. is used as an unpurified mixture. You may use for the manufacturing method of invention.
In the present specification, “primary amine” means a primary amine produced mainly due to aniline, and such primary amine can have various structures, but representative examples thereof include the following formulas (II) and (III ). Two compounds having a structure represented by

Thus, “primary amine” in the present specification is a general term for a plurality of kinds of compounds, and the content of primary amine is an amount expressed by considering all primary amines as aniline (molecular weight: 93.13). It is. That is, an amino group (—NH ₂ ) 1 mol is converted as 93.13 g of primary amine. Specifically, the primary amine content is determined by dissolving the mixture in chloroform, adding hydrochloric acid and p-dimethylaminobenzaldehyde to prepare a sample solution, measuring the absorbance of the obtained sample solution, It is obtained from the calibration curve used.
<A 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition having a primary amine content of 1% by mass or less based on the total amount of the composition (hereinafter also referred to as “the composition after purification”) And manufacturing method thereof>
A composition after purification is obtained by bringing the crude mixture into contact with 3 to 10 moles of carboxylic acid anhydride per mole of the primary amine contained in the mixture.
As the carboxylic acid anhydride, an intramolecular anhydride of an aromatic dicarboxylic acid such as phthalic anhydride or pyromellitic anhydride, an intramolecular anhydride of an aliphatic dicarboxylic acid such as succinic anhydride, glutaric anhydride or maleic anhydride, Examples include intermolecular anhydrides of aliphatic carboxylic acids such as acetic anhydride, and intermolecular anhydrides of aromatic carboxylic acids such as benzoic anhydride. Among these, an intramolecular anhydride of an aromatic dicarboxylic acid or an intramolecular anhydride of an aliphatic dicarboxylic acid is preferable, an intramolecular anhydride of an aromatic dicarboxylic acid is more preferable, and phthalic anhydride is particularly preferable.
The amount of the carboxylic anhydride used is 3 to 10 mol, preferably 3 to 5 mol, per 1 mol of the primary amine contained in the unpurified mixture.
The contact between the crude mixture and the carboxylic acid anhydride may be carried out in the presence of a solvent inert to the reaction between the crude mixture and the carboxylic acid anhydride, or substantially without using such a solvent. May be. Examples of such a solvent include aromatic hydrocarbon solvents such as xylene and toluene, and aliphatic hydrocarbon solvents such as heptane, octane, and dimethylhexane. When a solvent is used, the amount used is usually 0.5 to 10 parts by mass, preferably 0.5 to 2 parts by mass with respect to 1 part by mass of the unpurified mixture.
The contact between the crude mixture and the carboxylic acid anhydride is preferably carried out in the absence of a sulfur component.
The contact between the crude mixture and the carboxylic anhydride is preferably carried out in the absence of the rubber component.
The contact temperature between the crude mixture and the carboxylic acid anhydride is preferably 100 to 150 ° C. The reaction end point can be determined, for example, by analyzing the reaction mixture by high-speed chromatography or the like.
The composition after purification can be taken out by subjecting the obtained mixture to treatments such as neutralization, washing, and concentration as necessary.
<Rubber composition>
The rubber composition of the present invention comprises 2 to 10 parts by weight of insoluble sulfur and 0.5 to 5 parts by weight of the composition after purification with respect to 100 parts by weight of raw rubber selected from the group consisting of natural rubber and diene rubber. It is obtained by blending.
Examples of natural rubber include unmodified natural rubber, epoxidized natural rubber, deproteinized natural rubber, and other modified natural rubber.
Examples of the diene rubber include highly unsaturated rubbers such as styrene / butadiene copolymer rubber and polybutadiene rubber.
Insoluble sulfur is amorphous polymeric sulfur that is insoluble in carbon disulfide, and the amount used is usually 2 to 10 parts by mass, preferably 3 to 6 parts by mass with respect to 100 parts by mass of the raw rubber. It is.
The amount of the purified composition used is usually 0.5 to 5 parts by mass, preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the raw rubber.
The rubber composition of the present invention may further contain a filler, a vulcanization accelerator, zinc oxide, fatty acids, cobalt salt and the like.
Examples of the filler include carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide and the like that are usually used in the rubber field. Carbon black and silica are preferably used, and carbon black is more preferably used. The The amount of the filler used is not limited, but is preferably in the range of 5 to 100 parts by mass, particularly preferably in the range of 30 to 80 parts by mass, per 100 parts by mass of the raw rubber.
Examples of the carbon black include those described on page 494 of the “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. HAF (High Ablation Furnace), SAF (Super Ablation Furnace), ISAF (Intermediate SAF). Carbon blacks such as FEF (Fast Extension Furnace), MAF, GPF (General Purpose Furnace), SRF (Semi-Reinforming Furnace) are preferable.
Silica has a CTAB specific surface area of 50 to 180 m. ² / G silica and nitrogen adsorption specific surface area 50-300m ² / G of silica, Tosoh Silica Co., Ltd. “AQ”, “AQ-N”, Degussa “Ultrasil (registered trademark) VN3”, “Ultrasil (registered trademark) 360”, “ "Ultrasil (registered trademark) 7000", Rhodia's "Zeosil (registered trademark) 115GR", "Zeosil (registered trademark) 1115MP", "Zeosil (registered trademark) 1205MP", "Zeosil (registered trademark) Z85MP", Nippon Silica Commercial products such as “Nip Seal (registered trademark) AQ” manufactured by the company are preferable. Further, silica having a pH of 6 to 8, silica containing 0.2 to 1.5% by mass of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, and ethoxysilyl group It is also preferable to blend a silica having a surface treatment with an alcohol such as ethanol or polyethylene glycol, or a silica having two or more different nitrogen adsorption specific surface areas.
When silica is blended, it is preferable to blend 5 to 50 parts by mass of carbon black per 100 parts by mass of the raw rubber, and the blending ratio of silica / carbon black is particularly preferably 0.7 / 1 to 1 / 0.1. When silica is used as the filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75 manufactured by Degussa) It is preferable to add a compound having an element such as silicon or a functional group such as alkoxysilane which can be bonded to silica such as “)”, a so-called silane coupling agent.
As aluminum hydroxide, nitrogen adsorption specific surface area 5 ~ 250m ² / G aluminum hydroxide and aluminum hydroxide having a DOP oil supply amount of 50 to 100 mL / 100 g.
Examples of vulcanization accelerators include thiazole vulcanization accelerators and sulfenamides described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). And guanidine vulcanization accelerators.
Specifically, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2-benzothiazoli Examples include rusulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG). Also, morpholine disulfide, which is a known vulcanizing agent, can be used. When carbon black is used as the filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl It is preferable to use either 2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) in combination with diphenylguanidine (DPG). When silica and carbon black are used in combination as fillers, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N , N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is preferably used in combination with diphenylguanidine (DPG).
The amount of the vulcanization accelerator used is not limited, but is preferably 0.5 to 5 parts by mass, particularly preferably 0.5 to 2 parts by mass per 100 parts by mass of the raw rubber.
The amount of zinc oxide used is preferably 1 to 15 parts by mass and more preferably 3 to 8 parts by mass per 100 parts by mass of the raw rubber.
The fatty acids are preferably stearic acid, and the amount used is preferably 1 to 15 parts by mass, more preferably 1 to 7 parts by mass, per 100 parts by mass of the raw rubber.
A cobalt salt includes cobalt naphthenate. The amount used is preferably 0.02 to 2 parts by mass, more preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the raw rubber as the cobalt content.
Furthermore, various rubber chemicals commonly used in the rubber industry, such as anti-degradation agents, crosslinking agents, retarders, peptizers, softeners, petroleum resins, lubricants, plasticizers, tackifiers, resorcins and resorcin resins Such an adhesive may be used in combination as necessary.
Generally, rubber compounding is performed in two steps. That is, a first step of blending raw rubber, filler, refined composition and, if necessary, zinc oxide, etc. at a relatively high temperature, and insoluble sulfur and, if necessary, a vulcanization accelerator, etc. at a relatively low temperature. It is the 2nd process mix | blended with.
The compounding temperature in the first step is preferably 80 to 200 ° C, more preferably 110 to 160 ° C.
The compounding temperature in the second step is preferably 60 to 110 ° C.
The rubber composition of the present invention thus blended is particularly preferably used for an internal member of an automobile tire. Examples of the internal member of the automobile tire include a belt, a carcass, an inner liner, and an under tread.
In the rubber composition of the present invention, the composition after purification is used as an anti-aging agent for tires.
The rubber composition of the present invention becomes a target product by being vulcanized after being processed into a specific state.
Vulcanization conditions vary depending on the target product, but are usually selected from a range of about 120 to 200 ° C. and a range of about 1 minute to 2 hours.
The composition after purification has a primary amine content of 1% by mass or less with respect to the total amount of the composition, so that insoluble sulfur is not uniformly dissolved in the rubber composition in the second step and is vulcanized. Therefore, sulfur is not unevenly distributed on the surface of the rubber composition (hereinafter sometimes referred to as “bloom”), and as a result, there is an advantage that a sufficient vulcanization effect is easily obtained inside the rubber composition. is there.
<Evaluation of solubility of insoluble sulfur>
The solubility of insoluble sulfur is greatly influenced by the composition after purification, and can be evaluated as follows. That is, when a molded product is obtained by the following preparation method, if the molded product is kept at 100 ° C. for 1 hour and the light transmittance at 600 nm is 0.5% or less, insoluble sulfur is almost dissolved. Such a post-purification composition is preferred.
<Method for preparing molded product>
A blend is obtained by blending 2 parts by weight of the composition after purification and 2 parts by weight of insoluble sulfur with 100 parts by weight of butadiene rubber, and a molded product having a thickness of 2 mm is prepared from the blend.
Subsequently, use of a composition obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic anhydride to improve the heat resistance of the vulcanized rubber, and improvement of the heat resistance of the vulcanized rubber The method will be described.
The method for improving the heat resistance of the vulcanized rubber of the present invention includes the following steps (1), (2) and (3).
(1) 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total, and 1 mol of the primary amine Contacting 3 to 10 moles of carboxylic acid anhydride with respect to
(2) Kneading the mixture obtained in step (1), the rubber component and the sulfur component
(3) Step of vulcanizing the kneaded product obtained in step (2) to obtain vulcanized rubber
In the present specification, “to improve the heat resistance of vulcanized rubber” means to change the tensile properties (JIS K6251) of the test piece in the heat resistance test (JIS K6257) of the vulcanized rubber.
Hereinafter, each of the steps (1), (2) and (3) will be described. In addition, such an explanation will also explain an invention relating to the use of a composition obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic acid anhydride to improve the heat resistance of the vulcanized rubber. .
First, the above step (1), that is, 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total. And a step of bringing 3 to 10 moles of carboxylic acid anhydride into contact with 1 mole of the primary amine will be described.
2,2,4-Trimethyl-1,2-dihydroquinoline and a polymer thereof, and a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total are formed by condensation reaction of aniline and acetone. It is preferable that it is a thing.
The condensation reaction product of aniline and acetone contains a condensation reaction product of aniline and acetone represented by the above formula (I) (usually a mixture of compounds having different n in the above formula (I)) as a main component. .
The condensation reaction product of aniline and acetone is preferably obtained by reacting 2 to 20 moles of acetone with respect to 1 mole of aniline. In the presence of an acidic catalyst, aniline and acetone are heated. More preferably, it is produced by a dehydration polycondensation reaction. After mixing the aniline and the acidic catalyst, excess acetone is then continuously fed to the resulting mixture, and unreacted acetone is recovered by distillation together with the water formed to maintain the reaction temperature under normal pressure. This is preferable.
The reaction between acetone and aniline is usually carried out in the presence of an acidic catalyst. Examples of the acidic catalyst include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen fluoride, organic acids such as organic sulfonic acid, and Lewis acids such as boron fluoride. Hydrogen halide is preferable, and hydrogen chloride is more preferable. The acidic catalyst may be used as an aqueous solution, may be used as a liquid other than the aqueous solution, may be used as a solid, or may be introduced as a gas into the reaction system. When using a hydrogen halide, it is preferable to use an aqueous solution thereof. When hydrochloric acid is used, the concentration is preferably 15 to 35% by mass. The amount of the acidic catalyst used is preferably 0.05 to 0.5 mol with respect to 1 mol of aniline. If the amount of the acidic catalyst used is 0.05 mol or more, the reaction time is short, and if it is 0.5 mol or less, the amount of the polymer having n of 2 or more in the above formula (I) decreases. Aging prevention performance is improved.
The reaction between acetone and aniline may be carried out in the presence of an organic solvent inert to the reaction between acetone and aniline, or may be carried out without substantially using an organic solvent. The reaction temperature is preferably in the range of 100 to 150 ° C. When the reaction temperature is 100 ° C. or higher, the amount of unreacted aniline decreases, and the amount of 2,2,4-trimethyl-1,2-dihydroquinoline and its polymer increases. When the reaction temperature is 150 ° C. or lower, the amount of acetone used is small, which is economically preferable.
Such a reaction is usually completed in a reaction time of 2 to 16 hours. When a relatively large amount of acidic catalyst is used, the reaction time is relatively short.
The reaction end point may be appropriately determined by analyzing the aniline content in the reaction mixture by a general analysis means such as high performance liquid chromatography or gas chromatography.
After completion of the reaction, the catalyst in the reaction mixture is removed by a method such as neutralization, and then the reaction product of the condensation reaction product of aniline and acetone is reacted by distillation under reduced pressure to remove the organic solvent and unreacted aniline. It is preferable to remove from the mixture.
The resulting reaction mixture may be directly mixed with a carboxylic acid anhydride as a condensation reaction product of aniline and acetone, or a mixture obtained by removing the acidic catalyst by post-treatment such as neutralization, washing, and concentration. May be mixed with a carboxylic acid anhydride as a condensation reaction product of aniline and acetone. These condensation reaction products contain 2,6 parts by weight of primary amines with respect to 2,2,4-trimethyl-1,2-dihydroquinoline and its polymer, and a total of 100 parts by weight thereof.
As the carboxylic acid anhydride, an intramolecular anhydride of an aromatic dicarboxylic acid such as phthalic anhydride or pyromellitic anhydride, an intramolecular anhydride of an aliphatic dicarboxylic acid such as succinic anhydride, glutaric anhydride or maleic anhydride, Examples include intermolecular anhydrides of aliphatic carboxylic acids such as acetic anhydride, and intermolecular anhydrides of aromatic carboxylic acids such as benzoic anhydride. Among these, an intramolecular anhydride of an aromatic dicarboxylic acid or an intramolecular anhydride of an aliphatic dicarboxylic acid is preferable, an intramolecular anhydride of an aromatic dicarboxylic acid is more preferable, and phthalic anhydride is more preferable.
The amount of the carboxylic acid anhydride used is preferably 3 to 10 mol, more preferably 3 to 5 mol, per 1 mol of the primary amine.
The amount of carboxylic anhydride used is preferably 0.6 to 5 moles, more preferably 0.6 to 2 moles, per 1 kg of the condensation reaction product of aniline and acetone. If the amount of the carboxylic acid anhydride used is in the above range, the composition obtained by mixing the condensation reaction product of aniline and acetone and the carboxylic acid anhydride, the rubber component and the sulfur component are kneaded, and then The heat resistance of the vulcanized rubber obtained by vulcanization tends to be improved, which is preferable.
Mixing of the condensation reaction product of aniline and acetone and the carboxylic acid anhydride may be carried out in the presence of a solvent inert to the reaction of the condensation reaction product and the carboxylic acid anhydride. You may implement without using it. Examples of such a solvent include aromatic hydrocarbon solvents such as xylene and toluene, and aliphatic hydrocarbon solvents such as heptane, octane, and dimethylhexane. When the solvent is used, the amount used is usually 0.5 to 10 parts by mass, preferably 0.5 to 2 parts by mass with respect to 1 part by mass of the condensation reaction product of aniline and acetone.
Mixing of the condensation reaction product of aniline and acetone and the carboxylic anhydride is preferably carried out in the absence of a sulfur component. The sulfur component will be described in detail in step (2).
Mixing of the condensation reaction product of aniline and acetone and the carboxylic anhydride is preferably carried out in the absence of the rubber component.
The mixing temperature of the condensation reaction product of aniline and acetone and the carboxylic acid anhydride is preferably 100 to 150 ° C.
The obtained composition may be used in the step (2) as it is, or may be used in the step (2) after being subjected to post-treatment such as neutralization, washing and concentration as necessary. The composition thus obtained may be hereinafter referred to as “the present composition”.
Next, the step (2), that is, the step of kneading the composition (the present composition) obtained in the step (1), the rubber component and the sulfur component will be described. Hereinafter, the kneaded product obtained in this step may be referred to as “the rubber composition”.
Examples of the rubber component include rubber selected from the group consisting of natural rubber and diene rubber.
Examples of natural rubber include unmodified natural rubber, epoxidized natural rubber, deproteinized natural rubber, and other modified natural rubber.
Examples of the diene rubber include highly unsaturated rubbers such as styrene / butadiene copolymer rubber and polybutadiene rubber.
Sulfur components include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Powdered sulfur is preferable, and insoluble sulfur is preferable when the rubber composition is used for a tire member having a large amount of sulfur such as a belt member. The amount used is not limited, but is preferably 2 to 10 parts by mass, more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the rubber component.
The amount of the composition used is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component.
The rubber composition may further contain a filler, a vulcanization accelerator, zinc oxide, fatty acids, cobalt salt and the like.
Examples of the filler include those similar to those described above, and carbon black and silica are preferably used, and carbon black is more preferably used. The amount of the filler used is not limited, but is preferably 5 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the rubber component.
Examples of the carbon black include those similar to those described above, HAF (High Absorption Furnace), SAF (Super Absorption Furnace), ISAF (Intermediate SAF), FEF (Fast Extraction Furnace), MAFce, PF ), Carbon black such as SRF (Semi-Reinforcing Furnace) is preferable.
Examples of the silica include those similar to those described above. “AQ” and “AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrazil (registered trademark) VN3” manufactured by Degussa, “Ultrazil ( (Registered trademark) 360 "," Ultrasil (registered trademark) 7000 "," Zeosil (registered trademark) 115GR "," Zeosil (registered trademark) 1115MP "," Zeosil (registered trademark) 1205MP "," Zeosil (registered) "manufactured by Rhodia (Trademark) Z85MP "and" Nip Seal (registered trademark) AQ "manufactured by Nippon Silica Co., Ltd. are preferable. Further, silica having a pH of 6 to 8, silica containing 0.2 to 1.5% by mass of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, and ethoxysilyl group It is also preferable to blend a silica having a surface treatment with an alcohol such as ethanol or polyethylene glycol, or a silica having two or more different nitrogen adsorption specific surface areas.
When silica is blended, it is preferable to blend 5 to 50 parts by mass of carbon black per 100 parts by mass of the rubber component, and the blending ratio of silica / carbon black is particularly preferably 0.7 / 1 to 1 / 0.1. When silica is used as the filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75 manufactured by Degussa) It is preferable to add a compound having an element such as silicon or a functional group such as alkoxysilane which can be bonded to silica such as “)”, a so-called silane coupling agent.
Examples of the aluminum hydroxide include the same ones as described above.
Examples of the vulcanization accelerator include the same ones as described above. When carbon black is used as the filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl 2-Benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is preferably used in combination with diphenylguanidine (DPG). When silica and carbon black are used in combination as fillers N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide ( DCBS), dibenzothiazyl disulfide It is preferred that either the de (MBTS) in combination with diphenyl guanidine (DPG).
The amount of the vulcanization accelerator used is not limited, but is preferably 0.5 to 5 parts by mass and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component.
The amount of zinc oxide used is preferably 1 to 15 parts by mass and more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the rubber component.
As the fatty acids, stearic acid is preferable, and the amount used is preferably 1 to 15 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the rubber component.
A cobalt salt includes cobalt naphthenate. The amount used is preferably 0.02 to 2 parts by mass, more preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the rubber component as a cobalt content.
Furthermore, various rubber chemicals commonly used in the rubber industry, such as anti-degradation agents, crosslinking agents, retarders, peptizers, softeners, petroleum resins, lubricants, plasticizers, tackifiers, resorcins and resorcin resins Such an adhesive may be used in combination as necessary.
As a procedure for kneading each component, a rubber component and a filler are kneaded (hereinafter sometimes referred to as “procedure 1”), and then the composition obtained in procedure 1 and a sulfur component are kneaded. (Hereinafter also referred to as “procedure 2”). The composition is preferably kneaded in the procedure 1.
The kneading temperature in Procedure 1 is preferably 80 to 200 ° C, more preferably 110 to 160 ° C.
The kneading temperature in step 2 is preferably 60 to 110 ° C.
The rubber composition thus obtained is particularly preferably used for an internal member of an automobile tire. Examples of the internal member of the automobile tire include a belt, a carcass, an inner liner, and an under tread.
Finally, the step (3), that is, the step of vulcanizing the kneaded product (present rubber composition) obtained in the step (2) to obtain a vulcanized rubber will be described.
The rubber composition is processed into a specific state and then vulcanized to obtain a target product.
Vulcanization conditions vary depending on the target product, but are usually selected from a range of about 120 to 200 ° C. and a range of about 1 minute to 2 hours.
A rubber composition is obtained by blending a condensation reaction product of aniline and acetone (not mixed with a carboxylic acid anhydride), and this rubber composition is added in comparison with a vulcanized rubber obtained by vulcanizing the rubber composition. The heat resistance of the vulcanized rubber obtained by vulcanization is improved.

EXAMPLES Hereinafter, although an Example, a test example, a manufacture example, etc. are given and this invention is demonstrated concretely, this invention is not limited to these.
In the following production examples, the amount of 2,2,4-trimethyl-1,2-dihydroquinoline (hereinafter sometimes referred to as “TMDQ”) and the amount of TMDQ dimer are Eclipse XDB-C18A as a column and water as A liquid. Methanol was used as liquid B, respectively, and analyzed by high performance liquid chromatography using a gradient method.
The primary amine content is determined by dissolving the unpurified mixture or the purified composition in chloroform, adding hydrochloric acid and p-dimethylaminobenzaldehyde to prepare a sample solution, and measuring the absorbance of this sample solution with a spectrophotometer (measurement wavelength: 440 nm). And obtained from a calibration curve using aniline.
Production Example 1
A 300 mL round bottom flask equipped with a thermometer, a stirrer and a distillation apparatus was charged with 46.5 g of aniline and 4.4 g of 35 mass% hydrochloric acid, and the resulting mixture was heated to 110 ° C. Thereto, 290.4 g of acetone was added dropwise at 110 ° C. to 140 ° C. over 16 hours. The obtained mixture was kept at 135 ° C. to 140 ° C. for 4 hours. The obtained reaction mixture was cooled to 90 ° C., diluted with toluene, neutralized with an aqueous sodium hydroxide solution, and allowed to stand for liquid separation to remove the aqueous layer. After the toluene in the oil layer was distilled off, the low boiling point component was further distilled off by distillation at an internal temperature of 200 ° C. and a reduced pressure of 2 mmHg to obtain 80.3 g of an unpurified mixture. The obtained crude mixture was substantially composed of a condensation reaction product of aniline and acetone, and contained 0.1% by mass of TMDQ and 14% by mass of TMDQ dimer, respectively. The primary amine content was 3.2% by mass.
Example 1
A 100 mL four-necked round bottom flask equipped with a thermometer, a stirrer, a Dean-Stark tube and a condenser was charged with 20.0 g of the crude mixture obtained in Production Example 1, 4.83 g of phthalic anhydride and 100 mL of xylene. After the obtained mixture was kept at 140 ° C. for 5 hours, the solvent was distilled off to obtain a composition after purification. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.1% by mass.
Example 2
In Example 1, instead of 4.83 g of phthalic anhydride, 3.26 g of succinic anhydride was used and the temperature was kept at 140 ° C. for 3 hours. Obtained. The resulting purified composition consists essentially of phthalic anhydride and a reaction product of primary amine and phthalic anhydride, except for the component derived from the condensate of aniline and acetone. It was 0.1 mass%.
Example 3
In Example 1, in place of 20.0 g of the crude mixture obtained in Production Example 1, 10.0 g of the crude mixture obtained according to Production Example 1 (primary amine content: 2.9% by mass) was used. Purified in the same manner as in Example 1 except that 1.75 g of phthalic anhydride was used instead of 4.83 g of acid, 20 mL of xylene was used instead of 100 mL of xylene, and the temperature was kept at 140 ° C. for 4 hours. A post-composition was obtained. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.3% by mass.
Example 4
In Example 3, 20 mL of toluene was used in place of 20 mL of xylene, and the same procedure was performed as in Example 3 except that the temperature was kept at 110 ° C. to obtain a purified composition. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.2% by mass.
Example 5
In Example 1, instead of 20.0 g of the unpurified mixture obtained in Production Example 1, 20.0 g of the unpurified mixture (primary amine content: 3.5% by mass) obtained according to Production Example 1 was used. Purified in the same manner as in Example 1 except that 4.24 g of phthalic anhydride was used instead of 4.83 g of acid, 40 g of xylene was used instead of 100 mL of xylene, and the incubation time was changed to 140 ° C. for 3 hours. A post-composition was obtained. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.1% by mass.
Example 6
In Example 5, 40 g of toluene was used in place of 40 g of xylene, and the same procedure was performed as in Example 5 except that the temperature was kept at 110 ° C. to obtain a purified composition. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.1% by mass.
Example 7
In a 100 mL four-necked round bottom flask equipped with a thermometer, stirrer, Dean-Stark tube and condenser, 20.0 g of an unpurified mixture (primary amine content: 2.9% by mass) obtained according to Production Example 1 and anhydrous phthalate 3.46 g of acid was charged. The obtained mixture was kept at 140 ° C. for 2 hours to obtain a composition after purification. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.1% by mass.
Example 8
In Example 7, it carried out similarly to Example 7 except having carried out heat retention conditions at 120 degreeC for 4 hours, and obtained the composition after refinement | purification. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.2% by mass.
Example 9
In Example 7, the crude mixture (primary amine content: 3) obtained according to Production Example 1 instead of 20.0 g of the crude mixture obtained according to Production Example 1 (primary amine content: 2.9% by mass). 0.5 mass%) 20.0 g was used, and the same procedure as in Example 7 was carried out except that 4.24 g of phthalic anhydride was used instead of 3.46 g of phthalic anhydride to obtain a purified composition. The resulting purified composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the components derived from the condensation reaction product of aniline and acetone. The amine content was 0.0% by mass.
Reference Example In a 100 mL four-necked round bottom flask equipped with a thermometer, stirrer, Dean-Stark tube and condenser, 25.0 g of an unpurified mixture (primary amine content: 2.9% by mass) obtained according to Production Example 1 and 1.25 g of phthalic anhydride was charged. After the obtained mixture was kept at 140 ° C. for 3 hours, the solvent was distilled off to obtain a composition. The resulting composition consists essentially of phthalic anhydride and the reaction product of primary amine and phthalic anhydride, except for the component derived from the condensation reaction product of aniline and acetone, and has a primary amine content. Was 1.8% by mass.

Test example 1
A blend is obtained by blending 2 parts by weight of the purified composition obtained in Example 1 and 2 parts by weight of insoluble sulfur with respect to 100 parts by weight of butadiene rubber, and the blend is sandwiched between polyethylene terephthalate films and 2 mm. Molded to a thickness of The obtained molded product was kept at 100 ° C. for 1 hour. The transmittance of 600 nm light of the molded product after the heat retention was 0.00%.
Test examples 2-9
In Test Example 1, in place of the purified composition obtained in Example 1, the molded product after heat insulation was obtained in the same manner as in Test Example 1 except that the purified compositions obtained in Examples 2 to 9 were used. Obtained. Table 2 below shows the transmittance of 600 nm light of the molded product after the heat retention together with Test Example 1.

Reference test example 1
In Test Example 1, in place of the purified composition obtained in Example 1, the molded product after heat retention was obtained in the same manner as in Test Example 1 except that the unpurified mixture obtained in Production Example 1 was used. The transmittance of 600 nm light was 20.07%.
Reference test example 2
In Test Example 1, in place of the composition after purification obtained in Example 1, a molded article after heat retention was obtained in the same manner as in Test Example 1 except that the composition obtained in Reference Example was used. The transmittance of 600 nm light was 6.39%.
Example 10: Production of rubber composition <First step>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by mass of natural rubber (RSS # 1), 45 parts by mass of carbon black (N330), 10 parts by mass of hydrous silica (Nipsil AQ), 3 parts by mass of stearic acid Then, 5 parts by mass of zinc oxide and 2 parts by mass of the purified composition obtained in Example 1 were blended and kneaded to obtain a kneaded product.
<Second step>
The kneaded product obtained in the first step and 0.7 parts by mass of a vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazolylsulfenamide) at a temperature of 60 to 80 ° C. in an open roll machine. Then, 6 parts by mass of insoluble sulfur (as sulfur component) and 2 parts by mass of cobalt naphthenate were blended and kneaded to obtain a rubber composition of the present invention.
<Third step>
The rubber composition obtained in the second step was vulcanized at 150 ° C. to obtain a vulcanized rubber.
Examples 11 and 12
The rubber of the present invention was carried out in the same manner as in Example 10 except that the purified composition obtained in Examples 7 and 8 was used in place of the purified composition obtained in Example 1 in Example 10. A composition and vulcanized rubber were obtained.
Test examples 10-12
The following tests were conducted on the rubber compositions and vulcanized rubbers obtained in Examples 10 to 12, respectively. The results are shown in Table 3 below.
1) Rebound resilience: According to JIS K 6255, the rebound resilience of the vulcanized rubber was measured at 25 ° C.
2) Hardness: According to JIS K 6253, the durometer type A was used to measure the hardness of the vulcanized rubber at 25 ° C.

Production Example 2
A 300 mL round bottom flask equipped with a thermometer, a stirrer and a distillation apparatus was charged with 46.5 g of aniline and 4.4 g of 35 mass% hydrochloric acid, and the resulting mixture was heated to 110 ° C. Thereto, 290.4 g of acetone was added dropwise at 110 ° C. to 140 ° C. over 16 hours. The obtained mixture was kept at 135 ° C. to 140 ° C. for 4 hours. The obtained reaction mixture was cooled to 90 ° C., diluted with toluene, neutralized with an aqueous sodium hydroxide solution, and allowed to stand for liquid separation to remove the aqueous layer. After the toluene in the oil layer was distilled off, the low boiling point component was distilled off by distillation at an internal temperature of 200 ° C. and a reduced pressure of 2 mmHg to obtain 80.3 g of a condensation reaction product of aniline and acetone.
Production Example 3: Step (1)
In a 100 mL four-necked round bottom flask equipped with a thermometer, a stirrer, a Dean-Stark apparatus and a condenser, 25.0 g of a condensation reaction product of aniline and acetone obtained according to Production Example 2 and 3.46 g of phthalic anhydride were added. Prepared. The obtained mixture was kept at 140 ° C. for 2 hours to obtain the present composition.
Production Example 4: Step (1)
In Production Example 3, the present composition was obtained in the same manner as in Production Example 3 except that the temperature was kept at 120 ° C. for 4 hours.
Production Example 5: Step (1)
In a 100 mL four-necked round bottom flask equipped with a thermometer, stirrer, Dean Stark apparatus and condenser, 20.0 g of the condensation reaction product of aniline and acetone obtained in Production Example 2, 11.2 g of phthalic anhydride and xylene 40 0.0 mL was charged. The obtained mixture was kept at 140 ° C. for 3 hours to obtain the present composition.
Production Example 6: Step (1)
The same composition as in Production Example 5 was obtained except that 22.3 g of phthalic anhydride was used instead of 11.2 g of phthalic anhydride in Production Example 5.

Example 13
<Step (2) Procedure 1>
Using a Banbury mixer (600 mL Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by mass of natural rubber (RSS # 1), 45 parts by mass of carbon black (N330), 10 parts by mass of hydrous silica (Nipsil AQ), 3 parts by mass of stearic acid Then, 5 parts by mass of zinc oxide and 2 parts by mass of the present composition obtained in Production Example 3 were blended and kneaded to obtain a composition.
<Step (2) Procedure 2>
The composition obtained by the step (2) procedure 1 in an open roll machine at 60 to 80 ° C., 0.7 parts by mass of a vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazolylsulfenamide), 6 parts by mass of insoluble sulfur (as sulfur component) and 2 parts by mass of cobalt naphthenate were blended and kneaded to obtain the rubber composition.
<Step (3)>
Step (2) The rubber composition obtained in the procedure 2 was vulcanized at 150 ° C. to obtain a vulcanized rubber.
Examples 14 and 15
In Example 13, this rubber composition and vulcanized rubber were used in the same manner as in Example 13 except that the compositions obtained in Production Examples 4 and 5 were used in place of the compositions obtained in Production Example 3. Got.
Comparative Example 1
In Example 13, the rubber composition and vulcanization were carried out in the same manner as in Example 13 except that the condensation reaction product of aniline and acetone obtained in Production Example 2 was used instead of the present composition obtained in Production Example 3. Got rubber.
Comparative Example 2
In Example 13, a rubber composition and a vulcanized rubber were obtained in the same manner as in Example 13 except that the present composition obtained in Production Example 6 was used instead of the present composition obtained in Production Example 3.
Test Examples 13-15, Comparative Test Examples 1 and 2
The following heat resistance tests were performed on the rubber compositions and vulcanized rubbers obtained in Examples 13 to 15 and Comparative Examples 1 and 2, respectively.
Heat resistance test: A heat resistance test at 100 ° C. for 48 hours was performed by a JIS K6257 B-1 method using a dumbbell No. 3 test piece according to JIS K6251. The elongation at break (EB) was measured according to JIS K6251 using the test piece after the heat resistance test. The relative EB when the value using the rubber composition and vulcanized rubber obtained in Comparative Example 1 is taken as 100 is shown.

It can be said that the greater the relative EB, the better the heat resistance. Therefore, if this composition is used, the heat resistance which the vulcanized rubber used for manufacture of a tire has can be improved more easily.

According to the present invention, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition having a primary amine content of 1% by mass or less based on the total amount of the composition is more easily produced. Can do. The 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition is useful as an anti-aging agent for tires. When the primary amine content is 1% by mass or less with respect to the total amount of such a composition, sulfur in the tire rubber composition is less likely to be unevenly distributed on the surface of the rubber composition, and as a result, sufficient addition inside the rubber composition. There is an advantage that a sulfur effect is easily obtained.
Moreover, according to this invention, the method of improving the heat resistance which the vulcanized rubber used for manufacture of a tire has more simply can be provided.

Claims

2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass of these in total, and with respect to 1 mol of the primary amine A 2,2,4-trimethyl-1,2-dihydroquinoline polymer having a primary amine content of 1% by mass or less based on the total amount of the composition, comprising a step of contacting with 3 to 10 moles of carboxylic acid anhydride A method for producing a composition.
Acetone and aniline are reacted to produce 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, and a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total. Obtaining a step;
Contacting the resulting mixture with 3 to 10 moles of carboxylic anhydride per mole of primary amine;
The manufacturing method of Claim 1 containing this.
A 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition obtained by the production method according to claim 1 or 2, wherein when a molded product is obtained by the following preparation method, 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition characterized in that the transmittance of light at 600 nm after holding the molded article at 100 ° C. for 1 hour is 0.5% or less object.
<Method for preparing molded product>
A blend is obtained by blending 2 parts by weight of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition and 2 parts by weight of insoluble sulfur with 100 parts by weight of butadiene rubber. A molded product having a thickness of 2 mm is prepared.
The insoluble sulfur is 2 to 10 parts by mass with respect to 100 parts by mass of a raw rubber selected from the group consisting of natural rubber and diene rubber, and 2, 2, 4 obtained by the production method according to claim 1 or 2. -A rubber composition obtained by blending 0.5 to 5 parts by mass of a composition containing trimethyl-1,2-dihydroquinoline polymer.
Use of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing composition obtained by the production method according to claim 1 or 2 as an anti-aging agent for tires.
Use of a composition obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic acid anhydride to improve the heat resistance of the vulcanized rubber.
A method for improving the heat resistance of a vulcanized rubber, comprising the following steps (1), (2) and (3).
(1) 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof, a mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total, and 1 mol of the primary amine Obtained by the step (2) of kneading the mixture obtained in the step (2) and the step (1) with the rubber component and the sulfur component. Of vulcanizing the kneaded material to obtain vulcanized rubber
The improvement method according to claim 7, wherein step (1) is performed in the absence of a rubber component.
The improvement method according to claim 7 or claim 8, wherein step (1) is performed in the absence of a sulfur component.
10. The improvement method according to any one of claims 7 to 9, wherein the amount of the carboxylic acid anhydride used in step (1) is 0.6 to 5 mol with respect to 1 kg of the condensation reaction product of aniline and acetone.
A heat resistance improver for vulcanized rubber obtained by mixing a condensation reaction product of aniline and acetone and a carboxylic acid anhydride.
The condensation reaction product of aniline and acetone contains 2,2,4-trimethyl-1,2-dihydroquinoline, a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, and a primary amine The heat resistance improver for vulcanized rubber according to claim 11, which is a mixture.
The condensation reaction product of aniline and acetone is a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline, and 2,2,4- A mixture containing 2 to 6 parts by mass of a primary amine with respect to 100 parts by mass in total of a polymer of 4-trimethyl-1,2-dihydroquinoline and 2,2,4-trimethyl-1,2-dihydroquinoline. Item 13. The heat resistance improver for vulcanized rubber according to Item 11 or 12.
13. A product obtained by mixing a condensation reaction product of aniline and acetone with 3 to 10 moles of carboxylic acid anhydride per mole of primary amine contained in the condensation reaction product of aniline and acetone. The heat resistance improving agent for vulcanized rubber according to claim 13.
15. The product for a vulcanized rubber according to claim 11, wherein the condensation reaction product of aniline and acetone is a product produced by a condensation reaction of aniline and acetone in the absence of a sulfur component. Heat resistance improver.