WO2013111895A1

WO2013111895A1 - Method for producing condensation product of resorcin and acetone

Info

Publication number: WO2013111895A1
Application number: PCT/JP2013/051687
Authority: WO
Inventors: 一祐松井; 板橋　太門; 竹内　謙一; 豊望玉登
Original assignee: 住友化学株式会社
Priority date: 2012-01-25
Filing date: 2013-01-22
Publication date: 2013-08-01
Also published as: TW201335144A

Abstract

A method for producing a condensation product of resorcin and acetone, said condensation product satisfying the conditions (1a), (2a) and (3a) described below. The method for producing a condensation product of resorcin and acetone comprises: a step (1A) wherein resorcin and acetone are reacted in the presence of an acid; a step (2A) wherein the mixture obtained by the step (1A) is mixed with a base; a step (3A) wherein water is removed from the mixture obtained by the step (2A); and a step (4A) wherein the mixture obtained by the step (3A) is mixed with an acid. (1a) The area ratio of the peak of 2,4,4-trimethyl-2'-4'-7-trihydroxyflavan to the total area of all the peaks as determined by gel permeation chromatography (differential refractive index detection) is 25-55%. (2a) The area ratio of the first elution peak to the total area of all the peaks as determined by gel permeation chromatography (differential refractive index detection) is 10-30%. (3a) The weight average molecular weight of the first elution peak is 800 or more.

Description

Method for producing condensate of resorcin and acetone

The present invention relates to a method for producing a condensate of resorcin and acetone.

A condensate of resorcin and acetone is useful as a reinforcing agent for rubber compositions.
In US Pat. No. 5,665,799, resorcin and acetone are reacted in the presence of an acid and an organic solvent, and then the acid is neutralized with an aqueous sodium hydroxide solution. A method for obtaining a condensate of resorcin and acetone by drying under reduced pressure is described.

The present invention includes the following inventions.
[1] Step 1A in which resorcin and acetone are reacted in the presence of an acid;
A second A step of mixing the mixture obtained in the first A step and a base;
A 3A step of removing water from the mixture obtained by the 2A step;
4A process which mixes the mixture and acid which were obtained by 3A process,
A method for producing a condensate of resorcin and acetone satisfying the following (1a), (2a) and (3a):
(1a) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as measured by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2a) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 30% (3a) of the first elution peak The weight average molecular weight is 800 or more [2] Step 1A in which resorcin and acetone are reacted in the presence of an acid;
A second A step of mixing the mixture obtained in the first A step and a base;
A 3A step of removing water from the mixture obtained by the 2A step;
4A process which mixes the mixture and acid which were obtained by 3A process,
Step 5A for mixing the mixture obtained in Step 4A with a base;
A 6A step of washing the mixture obtained in the 5A step with water;
The manufacturing method of [1] description containing.
[3] The production method according to any one of [1] or [2], wherein the step 3A is a step of removing water by-produced by the reaction of the resorcin and acetone in the presence of an organic solvent.
[4] The process according to any one of [1] to [3], wherein the step 3A is a step of removing water by-produced by the reaction between the resorcin and acetone by azeotropic distillation in the presence of an organic solvent. The manufacturing method as described.
[5] A condensate of resorcin and acetone satisfying the following (1b), (2b) and (3b), which comprises the first step B in which resorcin and acetone are reacted in the presence of an acid and in the absence of a solvent Production method.
(1b) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2b) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3b) of the first elution peak The weight average molecular weight is 800 or more [6] Step 1B is a step in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent [5] Manufacturing method.
[7] Step 1B in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
A second B step of mixing the mixture obtained in the first B step and the organic solvent;
A third B step of heating the mixture obtained in the second B step to 50-70 ° C;
The production method according to [5] or [6].
[8] Step 1B in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
Step 4B for mixing the mixture obtained in Step 1B and the base;
A 5B step of washing the mixture obtained in the 4B step with water;
The production method according to any one of [5] to [7], comprising:
[9] Step 1B in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
A second B step of mixing the mixture obtained in the first B step and the organic solvent;
A third B step of heating the mixture obtained in the second B step to 50-70 ° C;
Step 4B for mixing the mixture obtained in Step 3B and the base;
A 5B step of washing the mixture obtained in the 4B step with water;
The production method according to any one of [5] to [8], comprising:
[10] including a first C step of reacting resorcin and acetone in the presence of hydrochloric acid,
A method for producing a condensate of resorcin and acetone satisfying the following (1c), (2c) and (3c).
(1c) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2c) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3c) of the first elution peak [11] The production method according to [10], wherein the step 1C is a step of reacting resorcin and acetone in the presence of hydrochloric acid and an organic solvent.
[12] Step 1C in which resorcin and acetone are reacted in the presence of hydrochloric acid;
A second C step of mixing the mixture obtained in the first C step with a base;
Step 3C for washing the mixture obtained in Step 2C with water;
The production method according to [10] or [11].
[13] p-toluenesulfone for resorcin, comprising a first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate The amount of at least one selected from the group consisting of acid and p-toluenesulfonic acid hydrate is 0.1 to 10 mol%,
A method for producing a condensate of resorcin and acetone satisfying the following (1d), (2d) and (3d).
(1d) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as measured by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2d) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3d) of the first elution peak The weight average molecular weight is 800 or more. [14] In the first step D, resorcin and acetone are selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate, and an organic solvent. [13] The production method according to [13], which is a step of reacting in the presence.
[15] A first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate;
A second D step of mixing the mixture obtained in the first D step with a base;
A 3D step of washing the mixture obtained in the 2D step with water;
The production method according to [13] or [14].
[16] A condensate obtained by the production method according to any one of [1] to [15].
[17] A rubber composition comprising a condensate obtained by the production method according to any one of [1] to [15], a rubber component, a filler, and a sulfur component.
[18] A tire belt comprising a steel cord coated with the rubber composition according to [17].
[19] A tire carcass comprising a carcass fiber cord coated with the rubber composition according to [17].
[20] A tire cap tread or a tire undertread comprising the rubber composition according to [17].
[21] A pneumatic tire produced by processing the rubber composition according to [17].

1. First embodiment of the present invention
<Step 1A of reacting resorcin and acetone in the presence of an acid>
Commercially available resorcinol and acetone can be used. The amount of acetone used is preferably 1 to 6 moles, more preferably 1.5 to 4 moles per mole of resorcin. If the usage-amount of acetone is 1 mol or more, the content rate of resorcin in the condensate obtained can be reduced.
The acid acts as a catalyst in the reaction between resorcin and acetone. Examples of the acid include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, oxalic acid, phosphoric acid, polyphosphoric acid, borofluoric acid, hydrochloric acid, sulfuric acid, and the like. P-toluenesulfonic acid , At least one acid selected from the group consisting of p-toluenesulfonic acid hydrate, hydrochloric acid and sulfuric acid is preferred. The acid can be used as it is or as an aqueous solution having an appropriate concentration. The amount of the acid used is preferably from 0.1 to 10 mol, more preferably from 0.5 to 5 mol, per 100 mol of resorcin.
The reaction between resorcin and acetone is preferably performed in the presence of an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Examples of aliphatic hydrocarbons are hexane, heptane, octane, decane, etc., examples of aromatic hydrocarbons are toluene, xylene, ethylbenzene, etc., examples of halogen-substituted aromatic hydrocarbons are chlorobenzene, dichlorobenzene, etc. Etc. The organic solvent is preferably an aromatic hydrocarbon, more preferably toluene or xylene. The amount of the organic solvent used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin.
The reaction temperature of the reaction between resorcin and acetone is preferably 30 ° C or higher and 65 ° C or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
The mixing of resorcin, acetone and acid can be carried out, for example, by mixing resorcin and acetone in the presence of an organic solvent as necessary, and mixing the resulting mixture and acid under reaction temperature conditions. . As the reaction proceeds, acetone may be added to the mixture continuously or intermittently. As the reaction proceeds, 2,4,4-trimethyl-2′4′7-trihydroxyflavan, which is one of the compounds contained in the condensate of resorcin and acetone, may precipitate. In order to prevent the deposit from sticking to the wall of the reaction vessel, 2,4,4-trimethyl-2′4′7-trihydroxyflavan may be used as a seed crystal.
As a compound contained in the condensate of resorcin and acetone, 2,4,4-trimethyl-2′4′7-trihydroxyflavan (compound represented by the formula (A)),

7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-2,2′-spirobichroman (compound represented by formula (B)),

4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) and isomers thereof,

2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof,

Compounds represented by formula (III) and isomers thereof,

Compounds represented by formula (IV) and isomers thereof,

[In the formula (IV), n represents an integer of 2 or more. ]
Etc.
<2A process which mixes the mixture and base which were obtained by 1A process>
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The pH of the mixture obtained by mixing with the base is preferably 5 to 9, and more preferably 6 to 8.
<Step 3A for removing water from the mixture obtained in Step 2A>
As a method for removing water, for example, a method of adding a substance capable of adsorbing water or a substance capable of decomposing water to the mixture obtained in Step 2A, and distilling the mixture obtained in Step 2A Distillation is preferred, and azeotropic distillation of an organic solvent and water in the presence of an organic solvent is more preferred. The water can be removed by removing the fraction containing water. When the fraction is separated into an organic layer and an aqueous layer, it is preferable that only the aqueous layer is separated and removed, and the organic layer is returned to the mixture. The removal of water is preferably carried out until the water content of the mixture obtained by removing water becomes 0.01 to 2% by weight, more preferably until the water content becomes 0.01 to 1% by weight. preferable.
As the organic solvent, the organic solvent used for the reaction between resorcin and acetone is usually used, but other organic solvents can also be used. Examples of organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methylene chloride, chloroform, and four Chlorinated hydrocarbons such as carbon chloride, trichrene, barkrene, ethylene dichloride, and benzene chloride; esters such as methyl acetate, ethyl acetate, and propyl acetate; nitriles such as acetonitrile; aromatic hydrocarbons are preferred, and toluene Xylene is more preferable.
<4A process which mixes the mixture and acid obtained by 3A process>
Step 4A is a step in which an acid is mixed with a mixture containing a condensate of resorcin and acetone, and the remaining resorcin is reacted with acetone.
The acid used in Step 4A is preferably the same acid used in Step 1A. The amount of the acid used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, per 100 mol of resorcin used in Step 1A.
For the purpose of improving the reaction rate of resorcin, acetone may be additionally mixed in the mixture obtained in the third A step or the mixture after the acid is mixed in the fourth A step. The amount of acetone added in Step 4A is preferably such that the total amount of acetone used in Step 1A is 1 to 6 moles per mole of resorcin used in Step 1A. Step 4A is carried out while confirming the content of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan and the content of resorcin by ordinary analytical means such as GC, HPLC, and GPC. It is preferable.
The organic solvent used in Step 4A is preferably the same organic solvent used in Step 1A. Examples of organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methylene chloride, chloroform, and four Chlorinated hydrocarbons such as carbon chloride, trichrene, barkrene, ethylene dichloride, and benzene chloride; esters such as methyl acetate, ethyl acetate, and propyl acetate; nitriles such as acetonitrile; aromatic hydrocarbons are preferred, and toluene Xylene is more preferable.
The reaction temperature of the reaction between resorcin and acetone is preferably 30 ° C or higher and 65 ° C or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
<5A process which mixes the mixture and base which were obtained by the 4th process>
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The pH of the mixture obtained by mixing with the base is preferably 5 to 9, and more preferably 6 to 8.
The mixture obtained in the 5A step may be directly subjected to a post-treatment step which will be described later, or may be further subjected to a post-treatment step after being subjected to a 6A step which will be described later.
<Step 6A of washing the mixture obtained in Step 5A>
Step 6A is a step of removing unreacted resorcin by mixing the mixture obtained in Step 5A with water and washing with water. When the mixture obtained in Step 5A is a slurry in which a condensate of resorcin and acetone is deposited, the precipitate may be dissolved by mixing an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve precipitates among those that can be used in Step 1A, but acetone is preferred from the viewpoint of liquid separation. The amount of the organic solvent used is preferably 2 parts by weight or less with respect to 1 part by weight of resorcin used in Step 1A. The amount of water used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin used in Step 1A.
For the purpose of increasing resorcin removal efficiency, it may be further mixed with a base and washed with water under alkaline conditions. The pH of the mixture obtained by mixing with the base is preferably 7 to 11, and more preferably 8 to 10.
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The temperature at which washing and liquid separation are performed is preferably 45 ° C or higher and 80 ° C or lower. The residual resorcin content can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like. It is preferable to determine the number of washings while confirming the content of resorcin.
<Post-processing process>
A condensate of resorcin and acetone can be obtained by subjecting the mixture obtained in Step 5A or Step 6A to a post-treatment step such as filtration or concentration.
<Condensate obtained>
In the present invention, the “first elution peak” means a peak having the shortest retention time among all peaks in a chromatogram obtained by gel permeation chromatography (differential refractive index detection) measurement. “Peak” means a peak having the second shortest retention time among all peaks in a chromatogram obtained by gel permeation chromatography (differential refractive index detection), and “third elution peak” It means the peak with the third shortest retention time among all the peaks in the chromatogram obtained by gel permeation chromatography (differential refractive index detection) measurement.
In gel permeation chromatography (differential refractive index detection) measurement, the compound represented by formula (IV) and its isomer are the first elution peak, and the compound represented by formula (III) and its isomer are the second elution. As a peak, the compound represented by formula (I) and its isomer, and the compound represented by formula (II) and its isomer are detected as a third eluting peak.
The obtained condensate satisfies (1a), (2a) and (3a).
(1a) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as determined by gel permeation chromatography (differential refractive index detection) is 25 to 55 %
(2a) The area ratio of the first elution peak to the total area of all peaks is 10 to 30% as measured by gel permeation chromatography (differential refractive index detection).
(3a) The weight average molecular weight of the first elution peak is 800 or more.
The weight average molecular weight of the first elution peak as measured by gel permeation chromatography (differential refractive index detection) is preferably 800 to 1400, more preferably 800 to 1200.
The content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan contained in the obtained condensate is preferably 25 to 55% by weight, more preferably 30 to 50% by weight.
4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) contained in the resulting condensate and And its isomers, 2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof The total content of the body is preferably 10 to 30% by weight.
The total content of the compound represented by the formula (III) and the isomer thereof contained in the obtained condensate is preferably 10 to 20% by weight.
The total content of the compound represented by formula (IV) and the isomer thereof contained in the obtained condensate is preferably 10 to 30% by weight, and more preferably 10 to 20% by weight.
The softening point of the obtained condensate is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.
The content of resorcin contained in the obtained condensate is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less.
The obtained condensate is useful as a rubber reinforcing agent, and particularly useful as a tire rubber reinforcing agent.
2. Second embodiment of the present invention
<Step 1B in which resorcin and acetone are reacted in the presence of an acid and in the absence of a solvent>
Commercially available resorcinol and acetone can be used. The amount of acetone used is preferably 1 to 6 moles, more preferably 1.5 to 4 moles per mole of resorcin. If the usage-amount of acetone is 1 mol or more, the content rate of resorcin in the condensate obtained can be reduced.
The acid acts as a catalyst in the reaction between resorcin and acetone. Examples of the acid include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, oxalic acid, phosphoric acid, polyphosphoric acid, borofluoric acid, hydrochloric acid, sulfuric acid, and the like. P-toluenesulfonic acid , At least one acid selected from the group consisting of p-toluenesulfonic acid hydrate, hydrochloric acid and sulfuric acid is preferred. These acids can be used as they are or as an aqueous solution having an appropriate concentration. The amount of the acid used is preferably from 0.1 to 10 mol, more preferably from 0.5 to 5 mol, per 100 mol of resorcin.
The reaction temperature of the reaction between resorcin and acetone is preferably −5 ° C. or higher and 45 ° C. or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
The mixing of resorcin, acetone and acid can be carried out, for example, by mixing resorcin and acetone and mixing the resulting mixture and acid under reaction temperature conditions.
The compounds contained in the condensate of resorcin and acetone include 2,4,4-trimethyl-2′4′7-trihydroxyflavan (compound represented by the above formula (A)), 7,7′-dihydroxy. -4,4,4 ', 4'-tetramethyl-2,2'-spirobichroman (compound represented by the above formula (B)), 4,6-bis (7-hydroxy-2,4,4) -Trimethylchroman-2-yl) -1,3-benzenediol (compound represented by the above formula (I)) and its isomer, 2,4-bis (7-hydroxy-2,4,4-trimethyl) Chroman-2-yl) -1,3-benzenediol (compound represented by the above formula (II)) and isomers thereof, compound represented by the above formula (III) and isomers thereof, and the above formula And compounds represented by (IV) and isomers thereof It is.
The mixture obtained in the 1B step may be directly applied to the 4B step which will be described later, or may be applied to the 4B step after being applied to the 2B and 3B steps which will be described later if necessary. Good.
<Second B step of mixing the mixture obtained in the first B step and the organic solvent>
The 2B step is a 3B step, which will be described later. In order to maintain the content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan, the mixture obtained in the 1B step and the organic solvent Is a step of crystallizing 2,4,4-trimethyl-2′4′7-trihydroxyflavan by mixing.
Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Examples of aliphatic hydrocarbons are hexane, heptane, octane, decane, etc., examples of aromatic hydrocarbons are toluene, xylene, ethylbenzene, etc., examples of halogen-substituted aromatic hydrocarbons are chlorobenzene, dichlorobenzene, etc. Etc. The organic solvent is preferably an aromatic hydrocarbon, more preferably toluene or xylene. The amount of the organic solvent used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin.
The temperature at which the organic solvent is mixed may be the same as the reaction temperature in Step 1B, but in order to promote crystallization of 2,4,4-trimethyl-2′4′7-trihydroxyflavane, The reaction temperature may be lower than the reaction temperature. The temperature for mixing the organic solvent is preferably -5 to 20 ° C.
<3B process of heating the mixture obtained in the 2B process to 50 to 70 ° C.>
Step 3B is a step of reacting by heating to 50 to 70 ° C. in the presence of an organic solvent to further react unreacted resorcin with acetone.
The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
<The 4th B process which mixes the mixture and base which were obtained at the 1st B process or the 3rd B process>
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The pH of the mixture obtained by mixing with the base is preferably 5 to 9, and more preferably 6 to 8.
<5B process of washing the mixture obtained in 4B process with water>
Step 5B is a step of removing unreacted resorcin by mixing the mixture obtained in Step 4B and water and washing with water. When the mixture obtained in Step 4B is a slurry in which a condensate of resorcin and acetone is deposited, the precipitate may be dissolved by mixing an organic solvent. Although it will not specifically limit if it is an organic solvent which can melt | dissolve a precipitate among what can be used by 1B process as an organic solvent, Acetone is preferable from the point of a liquid separation property. The amount of the organic solvent used is preferably 2 parts by weight or less with respect to 1 part by weight of resorcin used in Step 1B. The amount of water used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin used in Step 1B.
For the purpose of increasing resorcin removal efficiency, a mixture obtained by mixing water in the step 5B and a base may be mixed and washed under alkaline conditions. The pH of the mixture obtained by mixing with the base is preferably 7 to 11, and more preferably 8 to 10.
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The temperature at which washing and liquid separation are performed is preferably 45 ° C or higher and 80 ° C or lower. The residual resorcin content can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like. It is preferable to determine the number of washings while confirming the content of resorcin.
<Post-processing process>
A condensate of resorcin and acetone can be obtained by subjecting the mixture obtained in step 5B to a post-treatment step such as filtration or concentration.
<Condensate obtained>
In the present invention, “first elution peak”, “second elution peak”, and “third elution peak” have the same meaning as described above.
In gel permeation chromatography (differential refractive index detection) measurement, the compound represented by formula (IV) and its isomer are the first elution peak, and the compound represented by formula (III) and its isomer are the second elution. As a peak, the compound represented by formula (I) and its isomer, and the compound represented by formula (II) and its isomer are detected as a third eluting peak.
The obtained condensate satisfies (1b), (2b) and (3b).
(1b) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. %
(2b) The area ratio of the first elution peak to the total area of all peaks is 10 to 25% by gel permeation chromatography (differential refractive index detection) measurement.
(3b) The weight average molecular weight of the first elution peak is 800 or more.
The weight average molecular weight of the first elution peak measured by gel permeation chromatography (differential refractive index detection) is preferably 800 to 1200.
The content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan contained in the obtained condensate is preferably 25 to 55% by weight, more preferably 30 to 50% by weight.
4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) contained in the resulting condensate and And its isomers, 2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof The total content of the body is preferably 20 to 30% by weight.
The total content of the compound represented by the formula (III) and the isomer thereof contained in the obtained condensate is preferably 10 to 20% by weight.
The total content of the compound represented by formula (IV) and the isomer thereof contained in the obtained condensate is preferably 10 to 25% by weight, and more preferably 10 to 20% by weight.
The softening point of the obtained condensate is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.
The content of resorcin contained in the obtained condensate is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less.
The obtained condensate is useful as a rubber reinforcing agent, and particularly useful as a tire rubber reinforcing agent.
3. Third embodiment of the present invention
<Step 1C of reacting resorcin and acetone in the presence of hydrochloric acid>
Commercially available resorcinol and acetone can be used. The amount of acetone used is preferably 1 to 6 moles, more preferably 1.5 to 4 moles per mole of resorcin. If the usage-amount of acetone is 1 mol or more, the content rate of resorcin in the condensate obtained can be reduced.
As hydrochloric acid, for example, commercially available 35% hydrochloric acid can be used as it is or diluted to an appropriate concentration with water. The amount of hydrochloric acid used is preferably from 0.1 to 10 mol, more preferably from 0.5 to 8 mol, per 100 mol of resorcin.
The reaction between resorcin and acetone is preferably performed in the presence of an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Examples of aliphatic hydrocarbons are hexane, heptane, octane, decane, etc., examples of aromatic hydrocarbons are toluene, xylene, ethylbenzene, etc., examples of halogen-substituted aromatic hydrocarbons are chlorobenzene, dichlorobenzene, etc. Etc. The organic solvent is preferably an aromatic hydrocarbon, more preferably toluene or xylene. The amount of the organic solvent used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin.
The reaction temperature of the reaction between resorcin and acetone is preferably 30 ° C or higher and 70 ° C or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
The mixing of resorcin, acetone and hydrochloric acid can be carried out, for example, by mixing resorcin and acetone in the presence of an organic solvent as necessary, and mixing the resulting mixture and hydrochloric acid under reaction temperature conditions. . The method for adding hydrochloric acid is not particularly limited, and it may be charged all at once, or may be added dropwise to reduce heat generation during mixing. As the reaction proceeds, acetone may be added to the mixture continuously or intermittently.
The compounds contained in the condensate of resorcin and acetone include 2,4,4-trimethyl-2′4′7-trihydroxyflavan (compound represented by the above formula (A)), 7,7′-dihydroxy. -4,4,4 ', 4'-tetramethyl-2,2'-spirobichroman (compound represented by the above formula (B)), 4,6-bis (7-hydroxy-2,4,4) -Trimethylchroman-2-yl) -1,3-benzenediol (compound represented by the above formula (I)) and its isomer, 2,4-bis (7-hydroxy-2,4,4-trimethyl) Chroman-2-yl) -1,3-benzenediol (compound represented by the above formula (II)) and isomers thereof, compound represented by the above formula (III) and isomers thereof, and the above formula And compounds represented by (IV) and isomers thereof It is.
<Second C step of mixing the mixture obtained in the first C step and the base>
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The pH of the mixture obtained by mixing with the base is preferably 5 to 9, and more preferably 6 to 8.
<3C process of washing the mixture obtained in 2C process with water>
The mixture obtained in the second C step may be directly subjected to a post-treatment step to be described later, or may be further subjected to a post-treatment step after being subjected to a third C step to be described later if necessary.
Step 3C is a step of removing unreacted resorcin by mixing the mixture obtained in Step 2C with water and washing with water. When the mixture obtained in Step 2C is a slurry in which a condensate of resorcin and acetone is deposited, the precipitate may be dissolved by mixing an organic solvent. Although it will not specifically limit if it is an organic solvent which can melt | dissolve a precipitate among what can be used at 1C process as an organic solvent, Acetone is preferable from the point of a liquid separation property. The amount of the organic solvent used is preferably 2 parts by weight or less with respect to 1 part by weight of resorcin used in Step 1C. The amount of water used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin used in Step 1C.
For the purpose of increasing resorcin removal efficiency, the mixture obtained by mixing water in the step 3C and a base may be mixed and washed under alkaline conditions. The pH of the mixture obtained by mixing with the base is preferably 7 to 11, and more preferably 8 to 10.
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The temperature at which washing and liquid separation are performed is preferably 45 ° C. or higher and 80 ° C. or lower. The residual resorcin content can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like. It is preferable to determine the number of washings while confirming the content of resorcin.
<Post-processing process>
A condensate of resorcin and acetone can be obtained by subjecting the mixture obtained in Step 2C or Step 3C to a post-treatment step such as filtration or concentration.
<Condensate obtained>
In the present invention, “first elution peak”, “second elution peak”, and “third elution peak” have the same meaning as described above.
In gel permeation chromatography (differential refractive index detection) measurement, the compound represented by formula (IV) and its isomer are the first elution peak, and the compound represented by formula (III) and its isomer are the second elution. As a peak, the compound represented by formula (I) and its isomer, and the compound represented by formula (II) and its isomer are detected as a third eluting peak.
The obtained condensate satisfies (1c), (2c) and (3c).
(1c) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. %
(2c) The ratio of the area of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25%.
(3c) The weight average molecular weight of the first elution peak is 800 or more.
The weight average molecular weight of the first elution peak measured by gel permeation chromatography (differential refractive index detection) is preferably 800 to 1200.
The content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan contained in the obtained condensate is preferably 25 to 55% by weight, more preferably 30 to 50% by weight.
4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) contained in the resulting condensate and And its isomers, 2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof The total content of the body is preferably 25 to 35% by weight.
The total content of the compound represented by the formula (III) and the isomer thereof contained in the obtained condensate is preferably 10 to 20% by weight.
The total content of the compound represented by formula (IV) and the isomer thereof contained in the obtained condensate is preferably 10 to 25% by weight, and more preferably 10 to 20% by weight.
The softening point of the obtained condensate is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.
The content of resorcin contained in the obtained condensate is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less.
The obtained condensate is useful as a rubber reinforcing agent, and particularly useful as a tire rubber reinforcing agent.
4). Fourth embodiment of the present invention
<First Step D in which resorcin and acetone are reacted in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate>
Commercially available resorcinol and acetone can be used. The amount of acetone used is preferably 1 to 6 moles, more preferably 1.5 to 4 moles per mole of resorcin. If the usage-amount of acetone is 1 mol or more, the content rate of resorcin in the condensate obtained can be reduced.
As p-toluenesulfonic acid and p-toluenesulfonic acid hydrate, for example, commercially available products can be used as they are or after being dissolved in an organic solvent or the like and diluted to an appropriate concentration. The amount of the acid used is preferably from 0.1 to 10 mol, more preferably from 0.5 to 8 mol, per 100 mol of resorcin.
The reaction between resorcin and acetone is preferably performed in the presence of an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Examples of aliphatic hydrocarbons are hexane, heptane, octane, decane, etc., examples of aromatic hydrocarbons are toluene, xylene, ethylbenzene, etc., examples of halogen-substituted aromatic hydrocarbons are chlorobenzene, dichlorobenzene, etc. Etc. The organic solvent is preferably an aromatic hydrocarbon, more preferably toluene or xylene. The amount of the organic solvent used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin.
The reaction temperature of the reaction between resorcin and acetone is preferably 30 ° C or higher and 70 ° C or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC). It is preferable to determine the reaction end point while confirming the progress of the reaction.
The mixing of resorcin, acetone and acid can be carried out, for example, by mixing resorcin and acetone in the presence of an organic solvent as necessary, and mixing the resulting mixture and acid under reaction temperature conditions. . The method for charging the acid is not particularly limited, and the acid solid may be charged all at once, or the acid may be dissolved in an organic solvent or the like and added dropwise in order to reduce the heat generated during mixing. As the reaction proceeds, acetone may be added to the mixture continuously or intermittently.
The compounds contained in the condensate of resorcin and acetone include 2,4,4-trimethyl-2′4′7-trihydroxyflavan (compound represented by the above formula (A)), 7,7′-dihydroxy. -4,4,4 ', 4'-tetramethyl-2,2'-spirobichroman (compound represented by the above formula (B)), 4,6-bis (7-hydroxy-2,4,4) -Trimethylchroman-2-yl) -1,3-benzenediol (compound represented by the above formula (I)) and its isomer, 2,4-bis (7-hydroxy-2,4,4-trimethyl) Chroman-2-yl) -1,3-benzenediol (compound represented by the above formula (II)) and isomers thereof, compound represented by the above formula (III) and isomers thereof, and the above formula And compounds represented by (IV) and isomers thereof It is.
<Second D step of mixing the mixture obtained in the first D step and the base>
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The pH of the mixture obtained by mixing with the base is preferably 5 to 9, and more preferably 6 to 8.
<3D process of washing the mixture obtained in the 2D process with water>
The mixture obtained in the second D step may be directly subjected to a post-treatment step to be described later, or may be further subjected to a post-treatment step after being subjected to a third D step to be described later if necessary.
The 3D step is a step of removing unreacted resorcin by mixing the mixture obtained in the 2D step with water and washing with water. When the mixture obtained in the second step D is a slurry in which a condensate of resorcin and acetone is deposited, the precipitate may be dissolved by mixing an organic solvent. Although it will not specifically limit if it is an organic solvent which can melt | dissolve a precipitate in what can be used at 1D process as an organic solvent, Acetone is preferable from the point of a liquid separation property. The amount of the organic solvent used is preferably 2 parts by weight or less with respect to 1 part by weight of resorcin used in Step 1D. The amount of water used is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin used in Step 1D.
For the purpose of increasing resorcin removal efficiency, a mixture obtained by mixing water in the third step D and a base may be mixed and washed under alkaline conditions. The pH of the mixture obtained by mixing with the base is preferably 7 to 11, and more preferably 8 to 10.
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, etc., and alkali metal hydroxides are preferred. Sodium hydroxide is more preferable. The base is preferably used as an aqueous solution having an appropriate concentration.
The temperature at which washing and liquid separation are performed is preferably 45 ° C or higher and 80 ° C or lower. The residual resorcin content can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like. It is preferable to determine the number of washings while confirming the content of resorcin.
<Post-processing process>
A condensate of resorcin and acetone can be obtained by subjecting the mixture obtained in the second or third step to a post-treatment step such as filtration or concentration.
<Condensate obtained>
In the present invention, “first elution peak”, “second elution peak”, and “third elution peak” have the same meaning as described above.
In gel permeation chromatography (differential refractive index detection) measurement, the compound represented by formula (IV) and its isomer are the first elution peak, and the compound represented by formula (III) and its isomer are the second elution. As a peak, the compound represented by formula (I) and its isomer, and the compound represented by formula (II) and its isomer are detected as a third eluting peak.
The obtained condensate satisfies (1d), (2d) and (3d).
(1d) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as measured by gel permeation chromatography (differential refractive index detection) is 25 to 55. %
(2d) The area ratio of the first elution peak to the total area of all peaks is 10 to 25% by gel permeation chromatography (differential refractive index detection) measurement.
(3d) The weight average molecular weight of the first elution peak is 800 or more.
The weight average molecular weight of the first elution peak measured by gel permeation chromatography (differential refractive index detection) is preferably 800 to 1200.
The content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan contained in the obtained condensate is preferably 25 to 55% by weight, more preferably 30 to 50% by weight.
4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) contained in the resulting condensate and And its isomers, 2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof The total content of the body is preferably 25 to 35% by weight.
The total content of the compound represented by the formula (III) and the isomer thereof contained in the obtained condensate is preferably 10 to 20% by weight.
The total content of the compound represented by formula (IV) and the isomer thereof contained in the obtained condensate is preferably 10 to 25% by weight, and more preferably 10 to 20% by weight.
The softening point of the obtained condensate is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.
The content of resorcin contained in the obtained condensate is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less.
The obtained condensate is useful as a rubber reinforcing agent, and particularly useful as a tire rubber reinforcing agent.
5. A rubber composition comprising a condensate of resorcin and acetone, a rubber component, a filler, and a sulfur component
The rubber composition of the present invention contains the above condensate of resorcin and acetone, a rubber component, a filler, and a sulfur component.
Examples of the rubber component include natural rubber, styrene butadiene copolymer rubber, butadiene rubber, isoprene rubber, and the like, and rubber components containing these as main components. The amount of the condensate of resorcin and acetone used is preferably 0.5 to 3 parts by weight and more preferably 1 to 2 parts by weight with respect to 100 parts by weight of the rubber component.
Examples of the filler include carbon black, silica, talc, and clay that are usually used in the rubber field, and carbon black is preferable. As carbon black, HAF (High Ablation Furnace), SAF (Super Ablation Furnace), ISAF (Intermediate SAF) and the like are preferable. It is also preferable to combine several kinds of fillers such as a combination of carbon black and silica. The amount of the filler used is preferably 10 to 100 parts by weight per 100 parts by weight of the rubber component. More preferably, it is 30 to 70 parts by weight.
Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Powdered sulfur and insoluble sulfur are preferred. The amount of the sulfur component used is preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight per 100 parts by weight of the rubber component.
The rubber composition may further contain a vulcanization accelerator, a methoxylated methylol melamine resin, an organic cobalt compound and / or zinc oxide.
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. The amount of the vulcanization accelerator used is preferably 0.5 to 1 part by weight, more preferably 0.6 to 0.8 part by weight per 100 parts by weight of the rubber component.
Examples of the methoxylated methylol melamine resin include hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylol melamine, tetrakis (methoxymethyl) dimethylol melamine and the like which are usually used in the rubber industry. Methoxymethyl) melamine alone or a mixture based on it is preferred. The methoxylated methylol melamine resin can be used alone or in combination, and the amount used is preferably 0.5 to 6.0 parts by weight, and 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component. Part is more preferred.
Examples of the organic cobalt compound include acid cobalt salts such as cobalt naphthenate and cobalt stearate, and a fatty acid cobalt / boron complex compound (for example, trade name “Manobond C (registered trademark)” manufactured by Manchem). The amount of the organic cobalt compound used is preferably 0.1 to 0.4 parts by weight, more preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight of the rubber component.
The rubber composition includes various rubber chemicals commonly used in the rubber industry, for example, anti-aging agents such as antioxidants and ozone degradation inhibitors, peptizers, processing aids, waxes, oils, stearic acid, 1 type, or 2 or more types, such as a tackifier, may be included. The amount of these chemicals used varies depending on the use of the rubber composition, but is an amount usually used in the rubber industry.
A rubber product is obtained by molding and vulcanizing the rubber composition. Molding and vulcanization can be carried out in accordance with ordinary methods in the rubber industry. Rubber products include various parts of tires such as cap treads, under treads, belts, carcass, beads, sidewalls, rubber chafers; anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes and exhaust hangers; hoses Rubber belt; and the like.
A tire belt can be produced by coating a steel cord with a rubber composition. Steel cords are usually used in an aligned state.
From the viewpoint of adhesion to rubber, the steel cord is preferably plated with brass, zinc, or an alloy containing nickel or cobalt, and is preferably subjected to brass plating. is there. In particular, a steel cord subjected to a brass plating process in which the Cu content of the brass plating is 75% by weight or less, preferably 55 to 70% by weight is suitable. The twist structure of the steel cord is not limited.
A plurality of belts may be laminated and used. The belt is mainly used as a carcass reinforcing material.
A carcass can also be manufactured by extruding a rubber composition in accordance with the carcass shape of a tire and attaching the rubber composition to the top and bottom of a carcass fiber cord. The carcass fiber cord is usually used in a state of being aligned in parallel. As the carcass fiber cord, preferred is an inexpensive polyester that has good elastic modulus and fatigue resistance and excellent creep resistance. One or more of these are laminated and used as a tire reinforcing material.
A pneumatic tire can be produced from the rubber composition by a usual production method. For example, a rubber composition is extruded to obtain a tire member, and the obtained tire member is attached and molded to another tire member by a normal method on a tire molding machine, and heated and pressurized in a vulcanizer. Thus, a tire is obtained.

The present invention will be specifically described with reference to examples. Unless otherwise indicated, the part and% of an Example mean a basis of weight.
The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin were determined by the GPC area percentage method.
In GPC analysis, the compound represented by formula (IV) and its isomer are represented by the first elution peak, and the compound represented by formula (III) and its isomer are represented by the second elution peak by formula (I). And the compound represented by the formula (II) and the isomer thereof were detected as the third elution peak.
The softening point was measured according to JIS K 6220-1.
<GPC analysis conditions>
Column: TOSOH TSGel Super HZ2000 (4.6 mmφ × 150 cm) and two TOSOH TSGel Super HZ1000 (4.6 mmφx150 cm) connection temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Detector: RI
Example 1A
A 1000 ml separable flask equipped with a thermometer, a stirrer, and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 65.0 g (1.12 mol) of acetone and 44. 0 g was charged and heated to 40 ° C. Thereto was charged 0.40 g of 98% sulfuric acid, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 3 hours.
Thereafter, 132 g of toluene was charged at an internal temperature of 60 ° C. and neutralized with a 10% aqueous sodium hydroxide solution, and then the inside of the flask was depressurized and heated to an internal temperature of 80 ° C. to remove water from the reaction system. After cooling to an internal temperature of 60 ° C., 0.88 g of 98% sulfuric acid was charged and kept at an internal temperature of 60 ° C. for 2 hours. Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution, heated to an internal temperature of 80 ° C., and then charged with 55.8 g (1.20 mol) of acetone to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 80 ° C., and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 110 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 43.6%
Resorcin: 0.8%
First eluting peak: 16.6%
Weight average molecular weight of first elution peak: 1164
Second eluting peak: 16.2%
Third elution peak: 22.3%
Softening point 124 ° C
Example 2A
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 55.1 g (0.88 mol) of acetone and 223 g of toluene were added. Charge and heat to 40 ° C. Thereto was charged 0.60 g of 98% sulfuric acid, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 3 hours.
Then, after neutralizing with a 10% aqueous sodium hydroxide solution at an internal temperature of 60 ° C., the inside of the flask was depressurized and heated to an internal temperature of 80 ° C. to remove water from the reaction system. After cooling to an internal temperature of 60 ° C., 79.0 g (1.36 mol) of acetone and 0.80 g of 98% sulfuric acid were charged and kept at an internal temperature of 60 ° C. for 3 hours. Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution, heated to an internal temperature of 80 ° C., and charged with 23.2 g (0.50 mol) of acetone to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 80 ° C., and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 121 g of a resorcin-acetone condensate. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 45.3%
Resorcin: 0.9%
First eluting peak: 15.1%
Weight average molecular weight of first elution peak: 1161
Second eluting peak: 14.4%
Third elution peak: 23.2%
Example 3A
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen, and then 69.7 g (1.20 mol) of acetone and 26.26 mol of toluene. 4 g was charged and heated to 40 ° C. Thereto was charged 0.60 g of 98% sulfuric acid, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 4 hours.
Thereafter, 106 g of toluene was charged at an internal temperature of 60 ° C. and neutralized with a 10% aqueous sodium hydroxide solution, and then the interior of the flask was depressurized and heated to an internal temperature of 80 ° C. to remove water from the reaction system. After cooling to an internal temperature of 60 ° C., 18.6 g (0.40 mol) of acetone and 0.80 g of 98% sulfuric acid were charged and kept at an internal temperature of 60 ° C. for 1 hour. Furthermore, 18.6 g (0.40 mol) of acetone was additionally charged at an internal temperature of 60 ° C., and the temperature was kept for 1 hour. Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution, heated to an internal temperature of 80 ° C., and then charged with 46.5 g (1.00 mol) of acetone to completely dissolve the reaction product. Furthermore, 132 g of hot water was added at an internal temperature of 80 ° C., and the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and then unreacted resorcin was removed by liquid separation washing. Thereafter, it was dried at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 131 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 42.6%
Resorcin: 0.9%
First eluting peak: 29.3%
Weight average molecular weight of first elution peak: 1340
Second eluting peak: 13.1%
Third elution peak: 13.5%
Softening point 139 ° C
Example 1B
A 500 ml four-necked flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and after the inside of the flask was purged with nitrogen, 69.7 g (1.20 mol) of acetone was charged. Heated to 35 ° C. Thereto was charged 1.20 g of 98% sulfuric acid, and the resulting mixture was kept at an internal temperature of 35 ° C. for 5 hours. Thereafter, 132 g of toluene was charged at an internal temperature of 35 ° C., and neutralized with a 10% aqueous sodium hydroxide solution.
After the reaction solution was transferred to a 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser, 69.7 g (1.20 mol) of acetone was charged and heated to an internal temperature of 60 ° C. to completely dissolve the reaction product. I let you. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 88 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 38.6%
Resorcin: 0.3%
First eluting peak: 13.4%
Weight average molecular weight of first eluting peak: 995
Second eluting peak: 17.9%
Third elution peak: 29.7%
Softening point 114 ° C
Example 2B
A 500 ml four-necked flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and after the inside of the flask was purged with nitrogen, 69.7 g (1.20 mol) of acetone was charged. Heated to 35 ° C. Thereto was charged 4.00 g of 98% sulfuric acid, and the resulting mixture was kept at an internal temperature of 35 ° C. for 3 hours. Thereafter, 132 g of toluene was charged at an internal temperature of 35 ° C. and stirred for 15 minutes, and then heated to an internal temperature of 60 ° C. and further kept warm for 6 hours.
Thereafter, the reaction solution was neutralized with a 10% aqueous sodium hydroxide solution.
After the reaction solution was transferred to a 1000 ml separable flask equipped with a thermometer, stirrer and condenser, 83.6 g (1.44 mol) of acetone was charged and heated to an internal temperature of 60 ° C. to completely dissolve the reaction product. I let you. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 110 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 42.6%
Resorcin: 0.3%
First eluting peak: 16.4%
Weight average molecular weight of first elution peak: 1054
Second eluting peak: 17.6%
Third elution peak: 22.8%
Softening point 115 ° C
Example 3B
A 500 ml four-necked flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin while cooling in an ice bath, and the inside of the flask was purged with nitrogen, followed by 69.7 g of acetone (1. 20 mol) was charged and kept at 0 ° C. Thereto was charged 4.00 g of 98% sulfuric acid, and the resulting mixture was kept at 0 ° C. for 4 hours. Subsequently, 132 g of toluene was charged at an internal temperature of 0 ° C., stirred for 15 minutes, heated to an internal temperature of 60 ° C., and further kept warm for 4 hours. Thereafter, the reaction solution was neutralized with a 10% aqueous sodium hydroxide solution.
After the reaction solution was transferred to a 1000 ml separable flask equipped with a thermometer, stirrer and condenser, 83.6 g (1.44 mol) of acetone was charged and heated to an internal temperature of 60 ° C. to completely dissolve the reaction product. I let you. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 101 g of a resorcin-acetone condensate. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 40.2%
Resorcin: 0.4%
First eluting peak: 12.3%
Weight average molecular weight of first elution peak: 984
Second eluting peak: 17.3%
Third elution peak: 29.6%
Softening point 117 ° C
Example 1C
A 1000 ml separable flask equipped with a thermometer, a stirrer, and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen, and then 79.0 g (1.36 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 3.34 g of 35% hydrochloric acid, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 8 hours. Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution at an internal temperature of 60 ° C., and 74.3 g (1.28 mol) of acetone was added to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 118 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 40.4%
Resorcin: 0.4%
First eluting peak: 17.6%
Weight average molecular weight of first elution peak: 1006
Second eluting peak: 16.9%
Third elution peak: 23.6%
Softening point 119 ℃
Example 2C
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen, and then 74.3 g (1.28 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 6.67 g of 35% hydrochloric acid, and the resulting mixture was heated to an internal temperature of 50 ° C. and kept warm for 7 hours.
Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution, heated to an internal temperature of 60 ° C., and then charged with 74.3 g (1.28 mol) of acetone to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 122 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 43.8%
Resorcin: 0.2%
First eluting peak: 18.6%
Weight average molecular weight of first elution peak: 1034
Second eluting peak: 15.6%
Third elution peak: 21.2%
Softening point 118 ° C
Example 3C
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen, and then 74.3 g (1.28 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.92 g of 35% hydrochloric acid, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 8 hours.
Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution at an internal temperature of 60 ° C., and 74.3 g (1.28 mol) of acetone was added to completely dissolve the reaction product. Furthermore, after adjusting the pH to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 120 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2′4′7-trihydroxyflavan: 49.3%
Resorcin: 0.6%
First eluting peak: 13.1%
Weight average molecular weight of first eluting peak: 996
Second eluting peak: 14.4%
Third elution peak: 22.1%
Softening point 116 ° C
Example 1D
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 65 ° C. and kept for 7 hours.
Then, after cooling to an internal temperature of 60 ° C., the mixture was neutralized with a 10% aqueous sodium hydroxide solution and charged with 58.1 g (1.00 mol) of acetone to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 113 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 31.1%
Resorcin: 0.5%
First eluting peak: 16.3%
Weight average molecular weight of first elution peak: 1030
Second eluting peak: 19.7%
Third elution peak: 30.2%
Softening point 116 ° C
Example 2D
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 7 hours. Thereafter, 55.8 g (0.96 mol) of acetone was charged at an internal temperature of 60 ° C., and the temperature was further maintained at 60 ° C. for 6 hours.
Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution, and 13.9 g (0.24 mol) of acetone was charged at an internal temperature of 60 ° C. to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 112 g of a resorcin-acetone condensate. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 33.9%
Resorcin: 0.3%
First eluting peak: 19.2%
Weight average molecular weight of first elution peak: 1059
Second eluting peak: 19.5%
Third elution peak: 25.8%
Softening point 119 ℃
Example 3D
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept warm for 7 hours. Thereafter, 46.5 g (0.80 mol) of acetone was charged at an internal temperature of 60 ° C., and the mixture was further incubated at the internal temperature of 60 ° C. for two and a half hours.
Thereafter, the mixture was neutralized with a 10% aqueous sodium hydroxide solution and charged with 20.9 g (0.36 mol) of acetone at an internal temperature of 60 ° C. to completely dissolve the reaction product. Furthermore, 220 g of hot water was charged at an internal temperature of 60 ° C., the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. under reduced pressure of 1 KPa or less for 12 hours to obtain 112 g of a resorcin-acetone condensate. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the resulting condensate were as follows.
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 39.4%
Resorcin: 0.7%
First eluting peak: 16.0%
Weight average molecular weight of first elution peak: 1051
Second eluting peak: 17.1%
Third elution peak: 24.6%
Softening point 124 ° C
Example 4 (Production of rubber composition)
Using a 0.6 liter lab plast mill, the initial system temperature was 110 ° C., and natural rubber (RSS # 1) was added and masticated for 3 minutes, followed by carbon black (N330), hydrous silica, Stearic acid, zinc white, anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline condensate) and the condensate obtained in Example 1D were added, kneaded for 5 minutes and discharged. The obtained composition was transferred to an open roll, the initial product temperature was 60 ° C., sulfur, vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazylsulfenamide), methoxylated methylol melamine resin (Sumicanol 507AP). (Manufactured by Sumitomo Chemical Co., Ltd.)) and cobalt naphthenate were added, and a rubber composition was obtained by kneading while controlling the temperature of the rubber to 80 ° C. or lower.
The amount of each component used is as follows.
<Amount used>
・ Natural rubber (RSS # 1) 100 parts ・ Carbon black (N330) 45 parts ・ Water-containing silica (Nippil AQ manufactured by Tosoh Silica Co., Ltd.) 10 parts ・ Stearic acid 3 parts ・ Zinc flower 5 parts ・ Anti-aging agent (2 , 2,4-trimethyl-1,2-dihydroquinoline condensate) 2 parts • condensate obtained in Example 1D 2 parts • sulfur 5 parts • vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazyl) Sulfenamide) 0.7 parts / Methoxylated methylol melamine resin (Sumikanol 507AP (manufactured by Sumitomo Chemical Co.)) 4 parts (2.6 parts active ingredient)
・ Cobalt naphthenate 2 parts (cobalt content 0.2 parts)
Example 5 (Production of rubber composition)
In Example 4, a rubber composition was obtained in the same manner as in Example 4 except that the condensate obtained in Example 2D was used instead of the condensate obtained in Example 1D.
Example 6 (Production of rubber composition)
In Example 4, a rubber composition was obtained in the same manner as in Example 4 except that the condensate obtained in Example 3D was used instead of the condensate obtained in Example 1D.
Example 7 (Production of tire belt and tire using the same)
A belt is obtained by covering the steel cord subjected to the brass plating treatment with the rubber composition obtained in Example 4. Using the resulting belt, a green tire is formed according to a normal production method, and the resulting green tire is heated and pressurized in a vulcanizer to obtain a tire.
Example 8 (Production of tire carcass and tire using the same)
By extruding the rubber composition obtained in Example 4, a rubber composition having a shape corresponding to the carcass shape is prepared, and carcass is obtained by applying the rubber composition on top and bottom of a polyester carcass fiber cord. Using the obtained carcass, a tire is obtained by molding a green tire according to a normal production method and heating and pressing the resulting green tire in a vulcanizer.
Example 9 (Tire Cap Tread and Manufacturing of Tire Using This)
The rubber composition obtained in Example 4 is extruded to obtain a cap tread. Using the obtained cap tread, a tire is obtained by molding a green tire according to a normal production method and heating and pressing the resulting green tire in a vulcanizer.
Example 10 (Production of tire undertread and tire using the same)
The rubber composition obtained in Example 4 is extruded to obtain an undertread. Using the obtained undertread, a tire is obtained by molding a green tire according to a normal production method and heating and pressing the resulting green tire in a vulcanizer.

According to the production method of the present invention, the content of unreacted resorcin contained in the condensate of resorcin and acetone can be reduced.
The condensate of resorcin and acetone obtained by the production method of the present invention is excellent in performance as a reinforcing agent of the rubber composition, and can prevent deterioration of the working environment due to transpiration of resorcin during processing of the rubber composition, Industrially advantageous.

Claims

Step 1A of reacting resorcin and acetone in the presence of an acid;
A second A step of mixing the mixture obtained in the first A step and a base;
A 3A step of removing water from the mixture obtained by the 2A step;
4A process which mixes the mixture and acid which were obtained by 3A process,
A method for producing a condensate of resorcin and acetone satisfying the following (1a), (2a) and (3a):
(1a) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as measured by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2a) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 30% (3a) of the first elution peak The weight average molecular weight is 800 or more
Step 1A of reacting resorcin and acetone in the presence of an acid;
A second A step of mixing the mixture obtained in the first A step and a base;
A 3A step of removing water from the mixture obtained by the 2A step;
4A process which mixes the mixture and acid which were obtained by 3A process,
Step 5A for mixing the mixture obtained in Step 4A with a base;
A 6A step of washing the mixture obtained in the 5A step with water;
The manufacturing method of Claim 1 containing this.
3. The production method according to claim 1, wherein the step 3A is a step of removing water by-produced by the reaction between the resorcin and acetone in the presence of an organic solvent.
The method according to any one of claims 1 to 3, wherein the step 3A is a step of removing water by-produced by the reaction of resorcin and acetone by azeotropic distillation in the presence of an organic solvent. .
A method for producing a condensate of resorcin and acetone satisfying the following (1b), (2b) and (3b), comprising a first step B in which resorcin and acetone are reacted in the presence of an acid and in the absence of a solvent.
(1b) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2b) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3b) of the first elution peak The weight average molecular weight is 800 or more
6. The process according to claim 5, wherein step 1B is a step of reacting resorcin and acetone at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent.
Step 1B, in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
A second B step of mixing the mixture obtained in the first B step and the organic solvent;
A third B step of heating the mixture obtained in the second B step to 50-70 ° C;
The manufacturing method of Claim 5 or 6 containing.
Step 1B, in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
Step 4B for mixing the mixture obtained in Step 1B and the base;
A 5B step of washing the mixture obtained in the 4B step with water;
The production method according to any one of claims 5 to 7, comprising:
Step 1B, in which resorcin and acetone are reacted at −5 to 45 ° C. in the presence of an acid and in the absence of a solvent;
A second B step of mixing the mixture obtained in the first B step and the organic solvent;
A third B step of heating the mixture obtained in the second B step to 50-70 ° C;
Step 4B for mixing the mixture obtained in Step 3B and the base;
A 5B step of washing the mixture obtained in the 4B step with water;
The production method according to any one of claims 5 to 8, comprising:
Including the step 1C of reacting resorcin and acetone in the presence of hydrochloric acid,
A method for producing a condensate of resorcin and acetone satisfying the following (1c), (2c) and (3c).
(1c) The ratio of the peak area of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks determined by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2c) The area ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3c) of the first elution peak The weight average molecular weight is 800 or more
The manufacturing method according to claim 10, wherein step 1C is a step of reacting resorcin and acetone in the presence of hydrochloric acid and an organic solvent.
Step 1C of reacting resorcin and acetone in the presence of hydrochloric acid;
A second C step of mixing the mixture obtained in the first C step with a base;
Step 3C for washing the mixture obtained in Step 2C with water;
The manufacturing method of Claim 10 or 11 containing.
Including a first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate,
The amount of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate with respect to resorcin is 0.1 to 10 mol%,
A method for producing a condensate of resorcin and acetone satisfying the following (1d), (2d) and (3d).
(1d) The area ratio of the peak of 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks as measured by gel permeation chromatography (differential refractive index detection) is 25 to 55. (2d) The ratio of the first elution peak to the total area of all peaks by gel permeation chromatography (differential refractive index detection) measurement is 10 to 25% (3d) of the first elution peak The weight average molecular weight is 800 or more
14. The first step D is a step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate and an organic solvent. Manufacturing method.
A first D step in which resorcin and acetone are reacted in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate;
A second D step of mixing the mixture obtained in the first D step with a base;
A 3D step of washing the mixture obtained in the 2D step with water;
The manufacturing method of Claim 13 or 14 containing.
A condensate obtained by the production method according to any one of claims 1 to 15.
A rubber composition comprising a condensate obtained by the production method according to any one of claims 1 to 15, a rubber component, a filler, and a sulfur component.
A tire belt comprising a steel cord coated with the rubber composition according to claim 17.
A carcass for a tire comprising a carcass fiber cord coated with the rubber composition according to claim 17.
A tire tread or a tire undertread comprising the rubber composition according to claim 17.
A pneumatic tire produced by processing the rubber composition according to claim 17.