JP6341612B2 - p-tert-octylphenol sulfur chloride co-condensation resin composition and method for producing the same - Google Patents

Description

The present invention relates to a p-tert-octylphenol sulfur chloride co-condensation resin composition that can be used as a rubber resin cross-linking agent and its application.

Alkylphenol / sulfur chloride co-condensation resins have been used as conventional rubber cross-linking agents to replace sulfur. Among these, p-tert-octylphenol sulfur chloride co-condensation resins are known to have excellent processing performance and adhesiveness. It has been. (Patent Document 1)

In recent years, from the viewpoint of environmental protection, there has been a demand for improvement in fuel consumption (that is, reduction in fuel consumption) of automobiles. Various methods are known for improving the fuel efficiency of automobiles, and one of them is to change the characteristics of tires. To that end, it is necessary to improve the viscoelastic characteristics of rubber used in tires. Among them, a value called loss tangent (tan δ) has attracted attention, and this value has been reduced (for example, Patent Documents 2 and 3).

In the above document, an alkylphenol / sulfur chloride cocondensation resin is used instead of sulfur as a cross-linking agent in order to reduce tan δ. As a result, it was found that there was a problem that the breaking characteristics deteriorated, and as a means to solve these problems, when manufacturing alkylphenol-sulfur chloride cocondensation resin, use of sulfur monochloride used during the manufacturing The amount is higher than that of conventionally known methods, and 1.2 to 1.8 mol of sulfur monochloride is reacted with 1 mol of p-tert-octylphenol, which is a kind of alkylphenol, to increase the sulfur content in the resin. It was proposed that it could be solved. (Patent Document 4)

However, as described above, when an excess amount of sulfur monochloride is reacted with p-tert-octylphenol, when the solvent used in the reaction is concentrated after the reaction is completed, particularly when the residual solvent amount is to be greatly reduced. The obtained p-tert-octylphenol sulfur chloride co-condensation resin has a very high softening point and has been found to be unsuitable for use as a rubber crosslinking agent.

JP 58-13648 A JP 2009-138148 A JP 2010-95670 A JP2013-203742A

The present invention contains a p-tert-octylphenol sulfur chloride cocondensate that is suitably used as a rubber resin cross-linking agent as a main component, and has a low volatile organic compound in the cocondensate, a high sulfur content, A p-tert-octylphenol sulfur chloride co-condensation resin composition having a softening point comparable to that of a conventionally known alkylphenol-sulfur chloride cocondensation resin can be produced industrially.

As a result of various investigations focusing on the production method of a conventionally known p-tert-octylphenol sulfur chloride cocondensation resin, p-tert-octylphenol sulfur chloride cocondensation is carried out by reacting p-tert-octylphenol with sulfur monochloride in the presence of a solvent. After obtaining the resin, before removing the solvent used by concentration, 5 to 50 parts by weight of a fatty acid having 12 or more carbon atoms is added to 1 part by weight of p-tert-octylphenol, and then mixed and concentrated. The present inventors have found that the softening point of the obtained p-tert-octylphenol sulfur chloride cocondensation resin composition containing the cocondensation resin as a main component can be reduced. Specifically, the following invention is included.

[1] A p-tert-octylphenol sulfur chloride cocondensation resin composition having a softening point of 70 to 140 ° C. and a content of fatty acids having 12 or more carbon atoms of 5 to 50% by weight.

[2] A reaction step of reacting p-tert-octylphenol with sulfur monochloride in the presence of a solvent to obtain a p-tert-octylphenol sulfur chloride cocondensation resin;
After the reaction step, 5 to 50 parts by weight of a fatty acid having 12 or more carbon atoms is added to 1 part by weight of p-tert-octylphenol, and then the solvent is removed to obtain a p-tert-octylphenol sulfur chloride cocondensation resin composition. To obtain a mixed concentration step,
The manufacturing method of the p-tert- octyl phenol sulfur chloride cocondensation resin composition of Claim 1 containing these.

[3] The p-tert-octylphenol sulfur chloride cocondensation resin according to claim 2, wherein the amount of sulfur monochloride used in the reaction step is 1.2 to 1.5 mol per mol of p-tert-octylphenol. A method for producing the composition.

[4]
A rubber composition comprising 0.5 to 50 parts by weight of the p-tert-octylphenol sulfur chloride co-condensation resin composition according to claim 1.

According to the present invention, a p-tert-octylphenol sulfur chloride cocondensate that is suitably used as a resin cross-linking agent for rubber is contained in the main component, the volatile organic compound in the cocondensate is small, the sulfur content is high, Furthermore, a p-tert-octylphenol sulfur chloride co-condensed resin composition having a softening point similar to that of conventionally known alkylphenol-sulfur chloride cocondensation resins can be produced industrially.

<Reaction process>
First, the reaction step of reacting p-tert-octylphenol and sulfur monochloride to obtain a p-tert-octylphenol sulfur chloride cocondensation resin will be described in detail. Hereinafter, the p-tert-octylphenol sulfur chloride cocondensation resin is simply referred to as a cocondensation resin, and the resin composition containing the p-tert-octylphenol sulfur chloride cocondensation resin and a fatty acid having 12 or more carbon atoms is referred to as a cocondensation resin composition. is there.

In the present invention, -p-substituted octylphenol is used among tert-octylphenols in which three kinds of -o, -m, and -p-substituted products exist. In the case of tert-octylphenol substituted at the o-position and m-position, even if it does not react with sulfur monochloride or reacts, the co-condensation resin targeted by the present invention cannot be obtained, which is not preferable.

In the present invention, sulfur monochloride (S ₂ Cl ₂ ) is used. When sulfur dichloride (SCl ₂ ) is used, the sulfur content in the obtained p-tert-octylphenol sulfur chloride co-condensation resin cannot be increased, which is not preferable. The sulfur monochloride is usually used in an amount of 0.8 to 2.0 mol, preferably 1.2 to 1.5 mol, more preferably 1.2 to 1.4 mol, per 1 mol of p-tert-octylphenol. use. If the amount is less than 0.8 mol, the effect as a crosslinking agent is not expressed, and if it is between 0.8 and 1.2 mol, the effect as a crosslinking agent is expressed, but the sulfur content in the co-condensation resin composition is reduced. It cannot be increased. Moreover, when more than 1.5 mol, the viscoelastic property of the rubber | gum obtained when using as a crosslinking agent may fall.

When carrying out the reaction step, it is necessary to carry out the reaction using a solvent. The solvent used at this time may be any solvent as long as it does not cause side reaction with p-tert-octylphenol or sulfur monochloride and does not inhibit the reaction. For example, benzene, toluene, xylene, mesitylene, heptane, Cyclohexane, tetrahydrofuran and the like can be used, and preferably toluene and xylene are used. Moreover, the usage-amount is 0.5-2 weight part with respect to 1 weight part of p-tert- octylphenol, Preferably it uses 0.5-1.8 weight part. If the amount is less than 0.5 parts by weight, the viscosity of the reaction system becomes too high to produce a cocondensation resin. If the amount is more than 2 parts by weight, the cocondensation resin can be produced, but the volumetric efficiency becomes poor. In some cases, the cocondensation resin cannot be produced in an economically advantageous manner because it takes a long time to remove the solvent after completion of the reaction.

In general, the reaction between p-tert-octylphenol and sulfur monochloride is carried out by adding p-tert-octylphenol and a solvent to the reaction vessel, adding sulfur monochloride to the reaction vessel over a certain period of time, and then keeping the mixture stirred for a certain period of time. It is carried out by doing. Hereinafter, these reaction conditions and procedures will be described in detail.

The temperature at which sulfur monochloride is added is usually 40 to 180 ° C, preferably 70 to 120 ° C. If the temperature is lower than 40 ° C., the progress of the reaction may be slow, which may be economically disadvantageous. If the temperature is higher than 180 ° C., decomposition may occur. Moreover, the addition mentioned here includes both an operation of intermittently charging into the reaction system such as dropping, and an operation of continuously charging into the reaction system while controlling the flow rate. Although the addition time varies depending on the reaction scale, it usually takes 0.1 to 12 hours. The addition time can be easily set by those skilled in the art by sequentially confirming the temperature change during the addition.

The reaction after addition of sulfur monochloride is usually carried out at 40 to 180 ° C, preferably 70 to 120 ° C. If the temperature is lower than 40 ° C., the progress of the reaction may be slow, which may be economically disadvantageous. If the temperature is higher than 180 ° C., decomposition may occur. Although reaction time changes with temperature, it is 1 to 10 hours normally. The reaction time can be easily set by those skilled in the art by measuring the remaining amount of unreacted p-tert-octylphenol or measuring the viscosity change of the reaction system.

After completion of the reaction step, if necessary, operations such as washing with water or neutralization may be performed to remove impurities in the p-tert-octylphenol sulfur chloride cocondensation resin. This operation may be performed before the fatty acid having 12 or more carbon atoms is added to the reaction product containing the cocondensation resin obtained in the reaction step, or after the addition and before the concentration step described later. .

<Mixed concentration step>
Subsequently, a mixing and concentration step in which a fatty acid having 12 or more carbon atoms is added to the reaction product containing the cocondensation resin obtained in the reaction step, and then the solvent is removed will be described in detail.

The fatty acid having 12 or more carbon atoms to be added may be linear or branched as long as the carbon number is 12 or more, and may have an unsaturated bond. Among these, it is preferable that carbon number is 14-18.

Examples of the fatty acid having 12 or more carbon atoms as described above include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and the like. Among these, stearic acid is preferable.

Fatty acids having 12 or more carbon atoms are usually used 5 to 50 times by weight, preferably 5 to 30 times by weight, based on 1 part by weight of p-tert-octylphenol. When the amount is less than 5 parts by weight, the effect of lowering the viscosity and the softening point is small, and it may be difficult to produce or the dispersibility may be deteriorated when blended with rubber. Is not preferable because it may block (melt and fix) during storage.

The mixing and concentration step can be performed by a method generally performed in accordance with the boiling point of the solvent after adding the above-described fatty acid having 12 or more carbon atoms. As such a method, for example, the reaction product containing the co-condensation resin obtained in the above reaction step and a fatty acid having 12 or more carbon atoms are charged into the reactor, and the solvent is removed from the reactor with the internal temperature being higher than the boiling point of the solvent. A method is illustrated. At this time, the reactor may be a reduced pressure system if necessary, and the solvent may be removed at a lower temperature. When adding the above-mentioned fatty acid having 12 or more carbon atoms, a part of the predetermined amount may be added to the reactor before the concentration step, and the remainder may be divided or continuously added during the concentration step. . The internal temperature and pressure at the time of solvent removal can be appropriately selected by those skilled in the art depending on the type of solvent.

The end point of the mixing and concentration step is determined by the amount of residual solvent in the cocondensation resin composition. The amount of residual solvent varies depending on the desired performance, but is usually 5% by weight or less, preferably 1% by weight or less. When the amount is more than 5% by weight, the solvent may affect the environment as a volatile organic compound.

<P-tert-octylphenol sulfur chloride cocondensation resin composition>
The physical properties of the p-tert-octylphenol sulfur chloride cocondensation resin composition produced by the above method will be described in detail.

The content of the fatty acid having 12 or more carbon atoms in the cocondensation resin composition needs to be 5 to 50% by weight, preferably 5 to 30% by weight. When the amount is less than 5% by weight, the softening point is not sufficiently lowered and the effect of the present application is not exhibited. On the other hand, when the amount is more than 50% by weight, the softening point becomes very low, blocking during storage (melt fixing), and bleed out fatty acids having 12 or more carbon atoms (exuded from the surface of the co-condensation resin composition). There is a case.

The softening point of the cocondensation resin composition is 70 to 140 ° C, preferably 80 to 130 ° C. When the softening point of the obtained resin is lower than 70 ° C., there is a risk of blocking (melting and fixing) during storage, and when it is higher than 140 ° C., when added to rubber as a resin crosslinking agent, poor dispersibility is exhibited. As a result, a rubber composition having sufficient performance cannot be obtained. In addition, the softening point said by this invention shows the softening point measured by the ring and ball method based on JISK2207.

In the cocondensation resin composition, the content of the solvent used in the reaction step described above varies depending on the desired performance, but is usually 5% by weight or less, preferably 1% by weight or less. When the amount is more than 5% by weight, the solvent may affect the environment as a volatile organic compound. In particular, when an organic compound such as a solvent whose boiling point is lower than 190 ° C., which is a general rubber kneading temperature, remains more than 5% by weight, it volatilizes and evaporates when the co-condensation resin composition is used. There may be a problem in the working environment such as an organic compound (VOC) causing a suspended particulate matter and a photochemical oxidant, and an odor.

The cocondensation resin composition thus obtained can be applied to all rubbers capable of sulfur crosslinking, such as natural rubber (NR), styrene butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), chloroprene. Examples include rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene-isobutylene copolymer rubber (IIR), ethylene-propylene terpolymer (EPDM), and the like. Of these, natural rubber (NR), styrene butadiene rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and polybutadiene rubber (BR) are preferably used. The amount of the cocondensation resin composition used for rubber is usually 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of rubber. Preferably 1-20 weight part is used. When the amount is less than 0.5 part by weight, the crosslink density may be lowered and the viscoelastic properties may be deteriorated. When the amount is more than 50 parts by weight, the breaking property and the wear resistance may be deteriorated.

When the co-condensation resin composition is blended with rubber and used, a compounding agent usually used in the rubber industry, for example, a filler such as carbon black, zinc oxide, stearic acid, oils, etc. In the range which does not inhibit this, it can select and mix | blend suitably, As a compounding agent, a commercial item can be used conveniently.

The rubber composition containing 0.5 to 50 parts by weight of the co-condensation resin composition is suitably used for rubber products used for tires, hoses, tubes, gaskets, home appliance parts and the like.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these.

(Manufacture of each resin)
In the production of each resin, analysis was performed based on the following analysis conditions.

<Softening point>
The softening point was measured by the ring and ball method based on JIS K2207.

<Residual solvent>
"Measurement of residual monomer and solvent"
The residual monomer and residual solvent were quantified by gas chromatography based on the following conditions.
Equipment used: Gas chromatograph GC-14B manufactured by Shimadzu Corporation
Column: Glass column outer diameter 5 mm x inner diameter 3.2 mm x length 3.1 m
Filler: Filler Silicone OV-17 10% Chromosorb WHP 80/100 mesh, max. temp. 340 ° C
Column temperature: 80 ° C → 280 ° C
Vaporization chamber temperature: 250 ° C
Detector temperature: 280 ° C
Detector: FID
Carrier: N ₂ (40 ml / min)
Combustion gas: Hydrogen (60 kPa), Air (60 kPa)
Injection volume: 2 μL
1 g of a resin crosslinking agent and 0.05 g of anisole as a sample were dissolved in 10 mL of acetone and analyzed under the above conditions. Residual solvent content and residual monomer content (%) in the resin were measured by an internal standard method (GC-IS method).
In addition, content (%) described in the text of Examples and Comparative Examples is expressed as weight percent unless otherwise specified.

<Synthesis of Example 1 Resin A>
A four-necked flask equipped with a reflux condenser and a thermometer was charged with 700 g (3.4 mol) of p-tert-octylphenol and 740 g of toluene, and 605 g (4.5 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution was dropped in 9 hours, and after completion of the dropping, the internal temperature was raised to 100-110 ° C and kept for 5 hours. After adding 86 g of stearic acid to the obtained reaction liquid, the mixture was concentrated at 130 to 135 ° C. under reduced pressure with an internal pressure of 9.3 kPa with stirring to obtain a p-tert-octylphenol sulfur chloride co-condensation resin composition (resin A 1072 g). Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

Example 2 Synthesis of Resin B
The same operation as in Example 1 was carried out except that stearic acid was changed to oleic acid to obtain 1043 g of a p-tert-octylphenol sulfur chloride cocondensation resin composition (referred to as resin B). Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

<Comparative Example 1 Synthesis of Resin C>
A four-necked flask equipped with a reflux condenser and a thermometer was charged with 700 g (3.4 mol) of p-tert-octylphenol and 740 g of toluene, and 605 g (4.5 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. The solution was added dropwise in 7 hours while maintaining at -80 ° C, and the internal temperature was raised to 110-120 ° C after completion of the addition, and the temperature was kept for 5 hours. Then, when the concentration operation was performed under the same conditions as described in Example 1, since the reaction mass was solidified during the concentration operation, the concentration was completed when solidified, and the resin solidified from the flask was used with a spatula. Scraped.

<Reference Example 1 Synthesis of Resin D>
A four-necked flask equipped with a reflux condenser and a thermometer was charged with 700 g (3.4 mol) of p-tert-octylphenol and 740 g of toluene, and 605 g (4.5 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. The solution was added dropwise in 9 hours while maintaining at -80 ° C, and the internal temperature was raised to 110-120 ° C after completion of the addition, and the temperature was kept for 5 hours. By adding 86 g of coumarone resin (Novares C10 manufactured by Rutgers) to the resulting reaction solution and performing a concentration operation under the same conditions as described in Example 1, a p-tert-octylphenol sulfur chloride co-condensation resin composition (resin 1020 g) was obtained. The obtained cocondensation resin composition had a specific odor. Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

<Odor evaluation criteria>
The odor of the cocondensation resin composition obtained in Examples 1 and 2 was evaluated relative to the odor of the resin D obtained in Reference Example 1 according to the following criteria.
An odor equivalent to or higher than that of Resin D was confirmed. : ×
The odor was improved compared to Resin D. : ○

＊：測定不可（２００℃以上）

*: Measurement not possible (200 ° C or higher)

Claims (4)

A p-tert-octylphenol sulfur chloride co-condensation resin composition having a softening point of 70 to 140 ° C. and a content of fatty acids having 14 to 18 carbon atoms of 5 to 50% by weight. A reaction step of reacting p-tert-octylphenol with sulfur monochloride in the presence of a solvent to obtain a p-tert-octylphenol sulfur chloride co-condensation resin;
After the reaction step, 5 to 50 parts by weight of a fatty acid having 14 to 18 carbon atoms is added to 1 part by weight of p-tert-octylphenol, and then the solvent is removed, whereby a p-tert-octylphenol sulfur chloride cocondensation resin composition is obtained. To obtain a mixed concentration step,
The manufacturing method of the p-tert- octyl phenol sulfur chloride cocondensation resin composition of Claim 1 containing these. The p-tert-octylphenol sulfur chloride co-condensation resin composition according to claim 2, wherein the amount of sulfur monochloride used in the reaction step is 1.2 to 1.5 mol with respect to 1 mol of p-tert-octylphenol. Production method. A rubber composition comprising 0.5 to 50 parts by weight of the p-tert-octylphenol sulfur chloride co-condensation resin composition according to claim 1.