JP2012214436A - Method for producing composition containing oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simpler method for producing a composition mainly comprising an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline and having a primary amine content of ≤1 mass%.SOLUTION: The method for producing a composition containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline includes a step of mixing a polycondensate of aniline and acetone and having ≥2 mass% of a primary amine obtained by converting one amino group (-NH) into one aniline molecule with at least one glycidyl ether compound selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2) and a compound represented by formula (3).

Description

  The present invention is a composition mainly containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline, and has a primary amine content (in this specification, one amino group is converted as one molecule of aniline). It is related with the manufacturing method of the composition etc. which are 1 mass% or less.

The oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline is useful as an anti-aging agent for tires.
As a method for producing a composition mainly containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline and having a primary amine content of 1% by mass or less, there may be used a mixture of aniline and acetone. A step of separating the monomer of 2,2,4-trimethyl-1,2-dihydroquinoline from the condensate by separating it from the primary amine by distillation, and polymerizing the monomer obtained in the step to produce 2,2,4-trimethyl. A method including a step of obtaining a composition mainly containing an oligomer of -1,2-dihydroquinoline is known (Patent Document 1).

JP-A-6-228375

  A simpler method is desired as a method for producing a composition mainly containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline and having a primary amine content of 1% by mass or less. ing.

（式中、Ｒ^１は炭素数１〜６のアルカンジイル基又はアリーレン基を表す。ｋは０〜３の整数を表す。ｋが１〜３のとき、複数存在するＲ^１は、互いに同一であっても異なっていてもよい。）
で示される化合物、式（２）

（式中、Ｒ^２及びＲ^４は、それぞれ独立に水素原子又は炭化水素１〜５のアルキル基を表す。Ｒ^３は単結合又は炭化水素１〜５のアルカンジイル基を表す。ｍは０〜３の整数を表す。ｍが１〜３のとき、複数存在するＲ^２は、互いに同一であっても異なっていてもよく、複数存在するＲ^３は、互いに同一であっても異なっていてもよく、複数存在するＲ^４は、互いに同一であっても異なっていてもよい。）
で示される化合物、及び、式（３）

（式中、Ｒ^５は水素原子、メチル基又はヒドロキシ基を表す。ｎは０〜３の整数を表す。
複数存在するＲ^５は互いに同一であっても異なっていてもよい。）
で示される化合物からなる群から選ばれる少なくとも１種のグリシジルエーテル化合物とを混合する工程を含む、２，２，４−トリメチル−１，２−ジヒドロキノリンのオリゴマー含有組成物の製造方法。 The present invention includes the following inventions.
[1] A polycondensate of aniline and acetone, a polycondensate having a primary amine content calculated by converting one amino group (—NH ₂ ) to one molecule of aniline is 2% by mass or more, 1)

(In the formula, R ¹ represents an alkanediyl group having 1 to 6 carbon atoms or an arylene group. K represents an integer of 0 to 3. When k is 1 to 3, a plurality of R ¹ are mutually identical. It may or may not be.)
A compound of formula (2)

(In the formula, R ² and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 hydrocarbons. R ³ represents a single bond or an alkanediyl group having 1 to 5 hydrocarbons. Represents an integer of 3. When m is 1 to 3, a plurality of R ² may be the same or different from each other, and a plurality of R ³ may be the same or different from each other. Well, a plurality of R ⁴ may be the same or different from each other.)
And a compound represented by formula (3)

(.N representing wherein, ^{R 5} is a hydrogen atom, a methyl group or a hydroxy group represents an integer of 0 to 3.
A plurality of R ⁵ may be the same as or different from each other. )
A method for producing an oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline, comprising a step of mixing at least one glycidyl ether compound selected from the group consisting of the compounds represented by formula (1).

[2] A polycondensate of aniline and acetone, wherein a primary amine content obtained by converting one amino group (—NH ₂ ) to one molecule of aniline is 2 to 6% by mass, The compound represented by the formula (1), the compound represented by the formula (2), and the formula (3) in such an amount that the epoxy group is 4 to 15 moles relative to 1 mole of the amino group constituting the primary amine. The production method according to [1], comprising a step of mixing at least one glycidyl ether compound selected from the group consisting of compounds.

[3] A reaction product of acetone and aniline, which is a polycondensate of aniline and acetone, and the primary amine content obtained by converting one amino group (—NH ₂ ) to one molecule of aniline is 2% by mass or more Obtaining a polycondensate which is
A polycondensation product of aniline and acetone, comprising a polycondensation product having a primary amine content of 2% by mass or more calculated by converting one amino group (—NH ₂ ) to one molecule of aniline, and the primary amine The group consisting of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3) in such an amount that the epoxy group is 4 to 15 mol per 1 mol of the amino group And a step of mixing at least one glycidyl ether compound selected from: [1] or [2].

[4] An oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline obtained by the production method according to any one of [1] to [3].

[5] 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, and 2,2,4-trimethyl-1,2- described in [4] A rubber composition obtained by blending 0.5 to 5 parts by mass of an oligomer-containing composition of dihydroquinoline.

[6] Use of the oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline according to [4] as an anti-aging agent for tires.

  According to the present invention, a composition mainly containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline and having a primary amine content of 1% by mass or less is more easily produced. can do.

  Hereinafter, the present invention will be described in detail.

<Polycondensate of aniline and acetone having a primary amine content of 2% by mass or more (hereinafter sometimes referred to as “unpurified polycondensate”)>
An unpurified polycondensate is obtained by reacting aniline and acetone. That is, the production method of the present invention may further include a step of obtaining an unpurified polycondensate by reacting acetone and aniline. Such a reaction is preferably carried out using 2 to 20 mol of acetone with respect to 1 mol of aniline, and more preferably produced by a dehydration polycondensation reaction in which acetone is reacted with aniline in the presence of an acidic catalyst. . 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.

Such a reaction 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 oxyfluoride; 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, an aqueous solution having a concentration of 15 to 35% by mass is preferably used. 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 polycondensate having n of 2 or more in the following formula is reduced, 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, 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 unpurified polycondensate 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.
After the reaction, if necessary, the solvent and the acidic catalyst are removed by post-treatment such as neutralization, washing, and concentration to obtain an unpurified polycondensate.

（式中、ｎは０以上の整数を表し、０〜５の整数が好ましい。） The crude polycondensate mainly contains an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline represented by the following formula. Usually, it is a mixture containing compounds having different values as n. In the following formula, 2,2,4-trimethyl-1,2-dihydroquinoline, which is a compound in which n is 0, may be hereinafter referred to as “TMDQ”. Further, a compound in which n is 1 in the following formula may be referred to as “TMDQ dimer” hereinafter.

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

（式中、ｍは０以上の整数を表し、０〜５の整数が好ましい。）

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, and an integer of 0 to 5 is preferable.)

Thus, primary amine is a generic name for a plurality of types of compounds, and in this specification, the content of primary amine is an amount expressed by regarding one primary amine as one molecule of aniline (molecular weight: 93.13). is there. That is, 1 mol of amino group (—NH ₂ ) is converted as 93.13 g of primary amine. Specifically, the content of the primary amine is determined by dissolving the unpurified polycondensate or the purified composition in chloroform, adding hydrochloric acid and p-dimethylaminobenzaldehyde to prepare a sample solution, and then obtaining the sample solution. Is obtained by a calibration curve using aniline.

  When the primary amine content in the unpurified polycondensate obtained above (excluding organic solvents and components other than those mentioned above in the reaction is excluded) is determined by this method, it is usually 2 parts by mass or more. , Preferably 2 to 6% by mass.

<Composition mainly containing oligomers of 2,2,4-trimethyl-1,2-dihydroquinoline, and a composition having a primary amine content of 1% by mass or less (hereinafter referred to as “post-purification composition”) And its manufacturing method>
By mixing the unpurified polycondensate and the glycidyl ether compound, a composition after purification can be obtained. Purification by mixing the unpurified polycondensate and an amount of glycidyl ether compound in which the epoxy group is 4 to 15 mol with respect to 1 mol of the amino group constituting the primary amine contained in the unpurified polycondensate. It is preferable to obtain a post-composition.

In the above formula (1), examples of the alkanediyl group having 1 to 6 carbon atoms represented by R ¹ include methanediyl group, ethane-1,2-diyl group, propane-1,3-diyl group, butane- Examples include 1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group and the like. Examples of the arylene group include a phenylene group.

  Examples of the compound (1) include hexane-1,6-diglycidyl ether, butane-1,4-diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol glycidyl ether, and the like. .

In the above formula (2), examples of the alkyl group having 1 to 5 carbon atoms represented by R ² and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and t-butyl. Group, pentyl group and the like. Examples of the alkanediyl group having 1 to 5 carbon atoms represented by R ³ include methanediyl group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, A pentane-1,5-diyl group and the like can be mentioned.

  Examples of the compound (2) include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.

  Examples of the compound (3) include cresol novolac diglycidyl ether and phenol novolac diglycidyl ether.

  The amount of the glycidyl ether compound used is such that the epoxy group is 4 to 15 mol, preferably 6 to 10 mol, based on 1 mol of the amino group constituting the primary amine contained in the unpurified polycondensate. It is. The glycidyl ether compound used in the present invention only needs to contain any one of the compounds (1) to (3). When a plurality of compounds among them are included, the total of the epoxy groups possessed by each compound is as described above. Any amount is sufficient. If the amount of the glycidyl ether compound used is 4 mol or more with respect to 1 mol of the amino group constituting the primary amine contained in the unpurified polycondensate, the tire rubber composition containing the mixture after purification and insoluble sulfur This sulfur has a merit that it is difficult to be unevenly distributed on the surface of the rubber composition, and as a result, a sufficient vulcanization effect is easily obtained inside the rubber composition. Further, if the amount of glycidyl ether used is 15 mol or less (preferably 10 mol or less) with respect to 1 mol of the amino group constituting the primary amine contained in the unpurified polycondensate, it is likely to be economically advantageous. There are advantages.

  Mixing of the unpurified polycondensate and the glycidyl ether compound may be carried out in the presence of a solvent inert to the reaction between the unpurified polycondensate and the glycidyl ether compound, or such a solvent should be used substantially. You may implement without. Examples of such solvents include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as heptane, octane and dimethylhexane; alcohol solvents such as methanol and ethanol; and the like. When using a solvent, the usage-amount is 0.5-10 mass parts normally with respect to 1 mass part of unpurified polycondensates, Preferably it is 0.5-2 mass parts.

  As for the temperature at the time of mixing an unpurified polycondensate and a glycidyl ether compound, 50-110 degreeC is preferable. The reaction end point can be determined, for example, by analyzing the reaction mixture using high-speed chromatography or the like for the content of aniline in the reaction mixture.

  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 preferably used. 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 use an organosilicon compound containing silane, silica surface-treated with an alcohol such as ethanol or polyethylene glycol, and 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, coughing agents, 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, a filler and, if necessary, zinc oxide at a relatively high temperature, a second step of blending insoluble sulfur and, if necessary, a vulcanization accelerator at a relatively low temperature. It is.

  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.

  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.

  Since the composition after purification has a primary amine content of 1% by mass or less based on the total amount of the composition, insoluble sulfur is not dissolved in the second step and is uniformly dispersed in the rubber composition. Since it dissolves, 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 amount of TMDQ and the amount of TMDQ dimer were analyzed by high performance liquid chromatography using a gradient method using Eclipse XDB-C18A as a column, water as A liquid, and methanol as B liquid.

  The primary amine content in each example and production example is determined by dissolving the unpurified polycondensate or the purified composition in chloroform, adding hydrochloric acid and p-dimethylaminobenzaldehyde to prepare a sample solution, and the absorbance of the sample solution. Was measured 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 heated to 110 ° C. Acetone 290.4g was dripped there over 110 hours at 110 to 140 degreeC, Then, it heat-retained at 135 to 140 degreeC 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 distilled off by further distillation at an internal temperature of 200 ° C. and a reduced pressure of 2 mmHg to obtain 80.3 g of an unpurified polycondensate. The obtained unpurified polycondensate was substantially composed of a polycondensate 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 3.5% by mass.

Example 1
In a 200 mL four-necked round bottom flask equipped with a thermometer, a stirrer, a Dean Stark bottle and a condenser, 20.0 g of the unpurified polycondensate obtained in Production Example 1 and 6.02 g of resorcinol diglycidyl ether (constituting a primary amine) The amount of the epoxy group with respect to 1 mol of amino groups: 7.2 mol) and 40.0 g of methanol were charged and dissolved at 25 ° C. Thereafter, the reaction mixture was kept at 65 ° C. for 6 hours. The solvent was distilled off to obtain a composition after purification. The primary amine content of the obtained purified composition was 0.5% by mass.

Example 2
In Example 1, in place of resorcinol glycidyl ether, 9.46 g of bisphenol A diglycidyl ether (amount of epoxy group with respect to 1 mol of amino group constituting primary amine: 7.4 mol) was used. Thus, a purified composition was obtained. The primary amine content of the obtained purified composition was 0.5% by mass.

Example 3
A rubber composition was obtained by blending 2 parts by mass of the purified composition obtained in Examples and 2 parts by mass of insoluble sulfur with respect to 100 parts by mass of butadiene rubber.

Test example 1
The rubber composition obtained in Example 3 was sandwiched between polyethylene terephthalate films and molded to a thickness of 2 mm. 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 0.03%.

Example 4
In Example 3, a rubber composition was obtained in the same manner as in Example 3, except that the purified composition obtained in Example 2 was used instead of the purified composition obtained in Example 1.

Test example 2
In Test Example 1, in place of the rubber composition obtained in Example 3, the formed composition after heat retention was obtained in the same manner as in Test Example 1 except that the rubber composition obtained in Example 4 was used. The transmittance of 600 nm light was 0.06%.

Reference Example In Example 3, a rubber composition was obtained in the same manner as in Example 3, except that the unpurified polycondensate obtained in Production Example 1 was used in place of the purified composition obtained in Example 1. .

Reference Test Example In Test Example 1, a molded product after heat insulation was obtained in the same manner as in Test Example 1 except that the rubber composition obtained in Reference Example was used instead of the rubber composition obtained in Example 3. The transmittance of 600 nm light was 20.07%.

Example 5: Production of rubber composition <First step>
Using a Banbury mixer (600 ml Labo 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, a composition mainly containing an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline and having a primary amine content of 1% by mass or less is easily produced. be able to. The oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline is useful as an anti-aging agent for tires. When the primary amine content is 1% by mass or less, sulfur in the rubber composition is less likely to be unevenly distributed on the surface of the rubber composition, and as a result, there is an advantage that a sufficient vulcanization effect is easily obtained inside the rubber composition. .

Claims (6)

A polycondensate of aniline and acetone, a polycondensate having a primary amine content of 2% by mass or more obtained by converting one amino group (—NH ₂ ) to one molecule of aniline, and a formula (1)

(In the formula, R ¹ represents an alkanediyl group having 1 to 6 carbon atoms or an arylene group. K represents an integer of 0 to 3. When k is 1 to 3, a plurality of R ¹ are mutually identical. It may or may not be.)
A compound of formula (2)

(In the formula, R ² and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 hydrocarbons. R ³ represents a single bond or an alkanediyl group having 1 to 5 hydrocarbons. Represents an integer of 3. When m is 1 to 3, a plurality of R ² may be the same or different from each other, and a plurality of R ³ may be the same or different from each other. Well, a plurality of R ⁴ may be the same or different from each other.)
And a compound represented by formula (3)

(.N representing wherein, ^{R 5} is a hydrogen atom, a methyl group or a hydroxy group represents an integer of 0 to 3.
A plurality of R ⁵ may be the same as or different from each other. )
A method for producing an oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline, comprising a step of mixing at least one glycidyl ether compound selected from the group consisting of the compounds represented by formula (1). A polycondensate of aniline and acetone, a polycondensate having a primary amine content of 2 to 6% by mass obtained by converting one amino group (—NH ₂ ) to one molecule of aniline, and the primary amine It consists of a compound represented by the formula (1), a compound represented by the formula (2), and a compound represented by the formula (3) in such an amount that the epoxy group is 4 to 15 mol per 1 mol of the amino group constituting The manufacturing method of Claim 1 including the process of mixing the at least 1 sort (s) of glycidyl ether compound chosen from a group. A polycondensate of aniline and acetone obtained by reacting acetone and aniline, and a primary amine content obtained by converting one amino group (—NH ₂ ) to one molecule of aniline is 2% by mass or more. Obtaining a condensate;
A polycondensation product of aniline and acetone, comprising a polycondensation product having a primary amine content of 2% by mass or more calculated by converting one amino group (—NH ₂ ) to one molecule of aniline, and the primary amine The group consisting of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3) in such an amount that the epoxy group is 4 to 15 mol per 1 mol of the amino group The process of mixing with the at least 1 sort (s) of glycidyl ether compound chosen from these. An oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline obtained by the production method according to claim 1. 5 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, and 2,2,4-trimethyl-1,2-dihydroquinoline of claim 4, A rubber composition obtained by blending 0.5 to 5 parts by mass of an oligomer-containing composition. Use of the oligomer-containing composition of 2,2,4-trimethyl-1,2-dihydroquinoline according to claim 4 as an antioxidant for tires.