JP2012144710A - Method for producing composition containing polycondensate of aniline with acetone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simpler method as a method for producing a composition containing a polycondensate of aniline with acetone, wherein the content of a primary amine is 1 pt.mass or less based on the total 100 pts.mass of a condensate of aniline with acetone and a polycondensate of aniline with acetone.SOLUTION: The method for producing the composition containing the polycondensate of aniline with acetone, where the content of the primary amine is 1 pt.mass or less based on the total 100 pts.mass of the condensate of aniline with acetone and the polycondensate of aniline with acetone, includes a step of bringing an isocyanate group-containing compound into contact with a mixture including the condensate of aniline with acetone and/or the polycondensate of aniline with acetone, and at least 2 pts.mass of the primary amine based on the total 100 pts.mass of the condensate and the polycondensate.

Description

  The present invention relates to a polycondensate-containing composition of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of a condensate of aniline and acetone and a polycondensate of aniline and acetone. It relates to a manufacturing method.

  As a method for producing a polycondensate-containing composition of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of a condensate of aniline and acetone and a polycondensate of aniline and acetone, Extracting 2,2,4-trimethyl-1,2-dihydroquinoline, which is a condensate of aniline and acetone, from a mixture of a condensate of aniline and acetone and a polycondensate of aniline and acetone by distillation; There is known a method including a step of polymerizing 2,2,4-trimethyl-1,2-dihydroquinoline obtained by the above step (Patent Document 1).

JP-A-6-228375

  As a method for producing a polycondensate-containing composition of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of a condensate of aniline and acetone and a polycondensate of aniline and acetone, A simpler method is desired.

The present invention includes the following inventions.
[1] A condensate of aniline and acetone and / or a polycondensate of aniline and acetone, a mixture containing 2 parts by mass or more of a primary amine with respect to a total of 100 parts by mass, an isocyanate group-containing compound, Containing a polycondensate of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of the condensate of aniline and acetone and the polycondensate of aniline and acetone. A method for producing the composition.

[2] Condensate of aniline and acetone and / or polycondensate of aniline and acetone, a mixture containing 2 to 6 parts by mass of a primary amine with respect to a total of 100 parts by mass, and 1 mol of the primary amine The process for producing a polycondensate-containing composition of aniline and acetone according to [1], comprising a step of contacting an isocyanate group-containing compound in an amount of 1 to 10 moles of the isocyanate group with respect to the above.

[3] Condensation product of aniline and acetone and / or polycondensation product of aniline and acetone by reacting acetone and aniline, and 2 parts by mass or more of primary amine with respect to 100 parts by mass in total. Obtaining a mixture;
A condensate of aniline and acetone and / or a polycondensate of aniline and acetone obtained in the above step, and a mixture containing 2 parts by mass or more of a primary amine with respect to 100 parts by mass in total, and an isocyanate Contacting the group-containing compound;
The production method according to [1] or [2].

[4] A polycondensate-containing composition of aniline and acetone obtained by the production method according to any one of [1] to [3].

[5] A polycondensate-containing composition of aniline and acetone obtained by the production method according to any one of [1] to [3], and when the molding is obtained by the following preparation method, the molding A polycondensate-containing composition of aniline and acetone, wherein the transmittance of light at 600 nm after holding the product at 100 ° C. for 1 hour is 0.5% or less.
<Method for preparing molded product>
A blend is obtained by blending 2 parts by weight of a polycondensate-containing composition of aniline and acetone 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. .

[6] With respect to 100 parts by mass of raw rubber selected from the group consisting of natural rubber and diene rubber, 2 to 10 parts by mass of insoluble sulfur and the production method according to any one of [1] to [3] A rubber composition obtained by blending 0.5 to 5 parts by mass of the resulting polycondensate-containing composition of aniline and acetone.

[7] Use of a polycondensate-containing composition of aniline and acetone obtained by the production method according to any one of [1] to [3] as an antioxidant for tires.

  According to the present invention, the weight of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of the condensate of aniline and acetone and the polycondensate of aniline and acetone is more simply. A condensate-containing composition can be produced.

  Hereinafter, the present invention will be described in detail.

（式中、ｎは０以上の整数を表す。ｎは０〜５が好ましい。） <Condensate of aniline and acetone and / or polycondensate of aniline and acetone, and a mixture containing 2 parts by mass or more of a primary amine with respect to 100 parts by mass in total (hereinafter referred to as “unrefined mixture”) )>
The condensate of aniline and acetone and / or the polycondensate of aniline and acetone has a structure mainly represented by the following formula. Examples of the condensate of aniline and acetone include a compound in which n is 0 in the following formula, and this compound is hereinafter referred to as “a monomer of 2,2,4-trimethyl-1,2-dihydroquinoline”. is there. Examples of the polycondensation product of aniline and acetone include compounds in which n is 1 or more in the following formula. A compound in which n is 1 is hereinafter referred to as “2,2,4-trimethyl-1,2-dihydroquinoline dimer”. May be described.

(In the formula, n represents an integer of 0 or more. N is preferably 0 to 5.)

  The condensate of aniline and acetone and / or the polycondensate of aniline and acetone is preferably obtained by reacting 2 to 20 mol of acetone with respect to 1 mol of aniline, in the presence of an acidic catalyst. More preferably, it is produced by a dehydration polycondensation reaction in which acetone is reacted with aniline in a heated state. After mixing the aniline and the acidic catalyst, it is preferable from the standpoint of maintaining the reaction temperature under normal pressure that the excess acetone is continuously fed and the unreacted component is recovered together with the produced water by distillation.

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; Lewis acids such as boron fluoride; and the like. 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 hydrogen halide is used, it is preferably used as an aqueous solution. 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 polycondensate having n of 2 or more in the above formula decreases, thereby preventing aging. 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 condensate of aniline and acetone and the amount of polycondensate of aniline and acetone 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 25 hours, preferably 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 content of aniline in the reaction mixture by ordinary analysis means such as high performance liquid chromatography or gas chromatography.

In the resulting reaction mixture, usually, a condensate of aniline and acetone, a polycondensate of aniline and acetone, and a total of 100 parts by mass of the primary amine is 2 parts by mass or more, preferably 2 to 6 parts. Part by mass, and 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 acidic catalyst and the like by post-treatment such as neutralization, washing, and concentration, You may use as an unpurified mixture in the manufacturing method of this invention.
After completion of the reaction, the catalyst is removed from the reaction mixture by a method such as neutralization, and then the reaction mixture is distilled under reduced pressure to remove the organic solvent and unreacted aniline. It is preferable to separate.

（式中、ｍは０以上の整数を表す。）

The “primary amine” in the present invention is mainly generated due to aniline and can take various structures, but typical examples include two of the following structures.

(In the formula, m represents an integer of 0 or more.)

Thus, primary amine is a general term for a plurality of types of compounds, and in this specification, the content of primary amine is an amount expressed by considering all primary amines as aniline (molecular weight: 93.13). That is, 1 mol of amino group (—NH ₂ ) 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, and using aniline. It is obtained from a calibration curve.

<A polycondensate-containing composition of aniline and acetone whose primary amine content is 1 part by mass or less with respect to a total of 100 parts by mass of the condensate of aniline and acetone and the polycondensate of aniline and acetone (hereinafter referred to as “purification” Sometimes referred to as “post-composition”) and production method thereof>
The composition after purification is obtained by bringing the unpurified mixture into contact with an isocyanate group-containing compound in an amount of 1 to 10 moles of isocyanate groups with respect to 1 mole of primary amine contained in the mixture.

  Examples of the isocyanate group-containing compound include aromatic diisocyanates such as phenyl isocyanate, 2,4-tolylene diisocyanate, and m-xylylene diisocyanate; hexamethylene diisocyanate, 3-isocyanatomethyl-3 , 5,5-trimethylcyclohexyl isocyanate and the like, and the like. Of these, aromatic diisocyanates are preferred, and 2,4-tolylene diisocyanate is more preferred.

  The amount of the isocyanate group-containing compound used is such that the isocyanate group is preferably 1 to 10 moles, more preferably 1 to 3 moles per mole of the primary amine contained in the unpurified mixture. It is.

  The contact between the crude mixture and the isocyanate group-containing compound may be carried out in the presence of a solvent inert to the reaction of the crude mixture and the isocyanate group-containing compound, or without substantially using such a solvent. You may implement. Examples of such solvents include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as heptane, octane and dimethylhexane; When using a solvent, the usage-amount is 0.5-10 mass parts normally with respect to 1 mass part of unpurified mixtures, Preferably it is 0.5-2 mass parts.

100-150 degreeC is preferable for the temperature at the time of making an unpurified mixture and an isocyanate group containing compound contact. The reaction end point can be determined, for example, by analyzing the content of aniline in the reaction mixture using high-speed chromatography or the like.
The contact between the crude mixture and the isocyanate group-containing compound is preferably carried out in the absence of a sulfur component.
The contact between the crude mixture and the isocyanate group-containing compound is preferably carried out in the absence of a rubber component.

  The obtained mixture can be subjected to post-treatments such as neutralization, washing and concentration as necessary, and the composition after purification can be taken out.

<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 usage-amount of the composition after refinement | purification is 0.5-5 mass parts normally with respect to 100 mass parts of raw rubber, Preferably it is 0.5-2 mass parts.

  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 particularly preferable. Preferably used. Although the usage-amount of this filler is not specifically limited, The range of 5-100 mass parts per 100 mass parts of raw rubber is preferable. Especially preferably, it is 30-80 mass parts.

  Examples of the carbon black include those described on page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate). Carbon blacks such as SAF), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), and SRF (Semi-Reinforcing Furnace) are preferred.

Examples of the silica include silica having a CTAB specific surface area of 50 to 180 m ² / g and silica having a nitrogen adsorption specific surface area of 50 to 300 m ² / g. “AQ” and “AQ-N” manufactured by Tosoh Silica Co., Ltd. Degussa's "Ultra Gil (registered trademark) VN3", "Ultra Gil (registered trademark) 360", "Ultra Gil (registered trademark) 7000", Rhodia "Zeosil (registered trademark) 115GR", "Zeosil (registered) (Trademark) 1115MP "," Zeosil (registered trademark) 1205MP "," Zeosil (registered 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 or 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, or 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 usually used as a filler, bis (3-triethoxysilylpropyl) tetrasulfide ("Si-69" manufactured by Degussa) or bis (3-triethoxysilylpropyl) disulfide ("Si-" manufactured by Degussa) 75 ") or the like, or a compound having a functional group such as silicon or an element such as silicon that can be bonded to silica, a so-called silane coupling agent is preferably added.

Examples of the aluminum hydroxide include aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m ² / g and aluminum hydroxide having a DOP oil supply amount of 50 to 100 ml / 100 g.

  Examples of vulcanization accelerators include thiazole-based vulcanization accelerators and sulfur compounds described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.

  Specifically, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2 -Benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), 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-dicyclo When hexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is used in combination with diphenylguanidine (DPG), 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-benzothiazoli Rusulfenamide (DCBS), dibenzothiazyl disulfide It is preferred that either the de (MBTS) in combination with diphenyl guanidine (DPG).

  Although the usage-amount of this vulcanization accelerator is not specifically limited, The range of 0.5-5 mass parts per 100 mass parts of raw rubber is preferable. Especially preferably, it is 0.5-2 mass parts.

  The amount of zinc oxide used is preferably in the range of 1 to 15 parts by mass and more preferably in the range of 3 to 8 parts by mass per 100 parts by mass of the raw rubber.

  As the fatty acids, stearic acid is preferable, and the amount used thereof is preferably in the range of 1 to 15 parts by mass, more preferably in the range of 1 to 7 parts by mass, per 100 parts by mass of the raw rubber.

  An example of the cobalt salt is cobalt naphthenate. The amount used is preferably in the range of 0.02 to 2 parts by mass and more preferably in the range of 0.1 to 0.5 parts by mass as the cobalt content per 100 parts by mass of the raw rubber.

  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, the first step of blending raw rubber, filler, post-refining composition and zinc oxide if necessary at a relatively high temperature, blending insoluble sulfur and, if necessary, a vulcanization accelerator at a relatively low temperature It is the 2nd process to do.

  The blending 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 the range of about 120 to 200 ° C. and about 1 minute to 2 hours.

  The composition after purification has a primary amine content of 1% by mass or less based on the total amount of the composition, so that insoluble sulfur does not dissolve in the second step and is uniformly dispersed in the rubber composition. Since it dissolves for the first time, it is difficult for sulfur to be 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. .

<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.

  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 monomer amount of 2,2,4-trimethyl-1,2-dihydroquinoline and the dimer amount of 2,2,4-trimethyl-1,2-dihydroquinoline were measured using Eclipse XDB-C18A as a column. Analysis was performed by high-performance liquid chromatography using a gradient method, using water as liquid A and methanol as liquid B.

  The primary amine content in each example and production example was 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 the sample solution by spectroscopic analysis. It measured with the photometer (measurement wavelength 440nm), and calculated | required from the calibration curve using aniline.

Production Example 1
In a 300 mL round bottom flask equipped with a thermometer, a stirrer and a distillation apparatus, 46.5 g (0.50 mol) of aniline and 4.4 g of 35% by mass hydrochloric acid (0.04 mol, 0.08 mol per 1 mol of aniline) ) And the temperature was raised to 110 ° C. 290.4 g of acetone (5.0 mol, 10 mol with respect to 1 mol of aniline) was added dropwise thereto at 110 ° C. to 140 ° C. over 16 hours, and the mixture was kept at 135 ° C. to 140 ° C. for 4 hours. Thereafter, the reaction mixture was cooled to 90 ° C., diluted with toluene, neutralized with an aqueous sodium hydroxide solution, and allowed to stand for 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 resulting crude mixture contained 0.1% by weight of monomer of 2,2,4-trimethyl-1,2-dihydroquinoline and 14% by weight of dimer of 2,2,4-trimethyl-1,2-dihydroquinoline. Each contained. The primary amine content was 4.0% by mass. Components other than the primary amine in the crude mixture were substantially only a condensate of aniline and acetone and a polycondensate of aniline and acetone.

Example 1
Into a 100 mL four-necked round bottom flask equipped with a thermometer, stirrer, Dean-Stark tube and condenser, 7.74 g of the crude mixture obtained in Production Example 1 and 0.55 g (0.95) of 2,4-tolylene diisocyanate were obtained. The amount of isocyanate groups per mole of primary amine and 1.9 moles of primary amine) and 50 ml of xylene were charged and kept at 140 ° C. for 3 hours. The solvent was distilled off to obtain a composition after purification. The primary amine content in the obtained purified composition was 1.0%.
Components other than the primary amine in the composition after purification were substantially only a condensate of aniline and acetone and a polycondensate of aniline and acetone.

Test example 1
A blend was 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 was 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 0.06%.

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%.

Example 2: Production of rubber composition <First step>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), the initial temperature is 110 ° C., 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) Parts, 3 parts by mass of stearic acid, 5 parts by mass of zinc oxide and 2 parts by mass of the purified composition obtained in Example 1 are mixed and kneaded to obtain a first step product.
<Second step>
The first step product obtained by the first step and the vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazolylsulfenamide) 0 at a temperature of 60 to 80 ° C. in an open roll machine 7 parts by mass, 6 parts by mass of insoluble sulfur (as sulfur component) and 2 parts by mass of cobalt naphthenate are blended and kneaded to obtain a rubber composition.
<Third step>
The rubber composition obtained in the second step is vulcanized at 150 ° C. to obtain a vulcanized rubber. The obtained vulcanized rubber is suitable as a belt.

  According to the present invention, the weight of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of the condensate of aniline and acetone and the polycondensate of aniline and acetone is more simply. A condensate-containing composition can be produced. A polycondensate-containing composition of aniline and acetone is useful as an anti-aging agent for tires. Since the primary amine content is 1 part by mass or less with respect to 100 parts by mass of the total of the condensate of aniline and acetone and the polycondensate of aniline and acetone, sulfur in the rubber composition for tires is the surface of the rubber composition. As a result, there is an advantage that a sufficient vulcanization effect is easily obtained inside the rubber composition.

Claims (7)

An isocyanate group-containing compound is brought into contact with a condensate of aniline and acetone and / or a polycondensate of aniline and acetone, and a mixture containing 2 parts by mass or more of a primary amine with respect to 100 parts by mass in total. A composition containing a polycondensate of aniline and acetone having a primary amine content of 1 part by mass or less with respect to a total of 100 parts by mass of a condensate of aniline and acetone and a polycondensate of aniline and acetone. Production method. A condensate of aniline and acetone and / or a polycondensate of aniline and acetone, 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 The manufacturing method of the polycondensate containing composition of the aniline and acetone of Claim 1 including the process of making the isocyanate group containing compound of the quantity which an isocyanate group becomes 1-10 mol. Acetone and aniline are reacted to obtain a condensate of aniline and acetone and / or a polycondensate of aniline and acetone, and a mixture containing 2 parts by mass or more of a primary amine with respect to 100 parts by mass in total. Process,
A condensate of aniline and acetone and / or a polycondensate of aniline and acetone obtained in the above step, and a mixture containing 2 parts by mass or more of a primary amine with respect to 100 parts by mass in total, and an isocyanate Contacting the group-containing compound;
The manufacturing method of Claim 1 or 2 containing. A polycondensate-containing composition of aniline and acetone obtained by the production method according to claim 1. It is a polycondensate-containing composition of aniline and acetone obtained by the production method according to any one of claims 1 to 3, and when the molded product is obtained by the following preparation method, the molded product is 100 ° C. And a polycondensate-containing composition of aniline and acetone, wherein the transmittance of light at 600 nm after being kept warm for 1 hour is 0.5% or less.
<Method for preparing molded product>
A blend is obtained by blending 2 parts by weight of a polycondensate-containing composition of aniline and acetone 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. . The aniline obtained by the production method according to any one of claims 1 to 3, and 2 to 10 parts by mass of insoluble sulfur with respect to 100 parts by mass of a raw rubber selected from the group consisting of natural rubber and diene rubber A rubber composition obtained by blending 0.5 to 5 parts by mass of a polycondensate-containing composition with acetone. Use of the polycondensate-containing composition of aniline and acetone obtained by the production method according to any one of claims 1 to 3 as an anti-aging agent for tires.