JP5991941B2 - 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 cocondensation resin containing a coumarone resin 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 them, p-octylphenol sulfur chloride co-condensation resins are known to have excellent processing performance and adhesiveness. Yes. (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) is attracting attention, and this value is being reduced. (For example, Patent Documents 2 and 3) In these patent documents, in order to reduce tan δ, an alkylphenol / sulfur chloride cocondensation resin is used as a crosslinking agent instead of sulfur.・ After confirming the physical properties of rubber using sulfur chloride co-condensation resin, the scorch time (the time required to start vulcanization of unvulcanized rubber), which is one of the indicators of processing performance, is short and vulcanized. It has been confirmed that stable product production may be difficult because it takes a long time to start.

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

In the present invention, when added to a rubber as a crosslinking agent for rubber, the scorch time is longer than that of a conventionally known p-octylphenol sulfur chloride cocondensation resin, and viscoelastic properties are not deteriorated. The basic performance of rubber as a crosslinking agent for rubber is similar to that of hitherto known ones, and the residual amount of volatile organic compounds that has become a problem in recent years is greatly reduced. An object of the present invention is to provide a rubber crosslinking agent mainly comprising a condensation resin and a method for producing the same.

As a result of various investigations focusing on the production method of a conventionally known p-octylphenol sulfur chloride cocondensation resin, the use ratio of sulfur monochloride used in producing the p-octylphenol sulfur chloride cocondensation resin is increased. It has been found that the scorch time can be made longer than that of conventionally known p-octylphenol sulfur chloride cocondensation resins by increasing the sulfur content of the resin. However, the p-octylphenol sulfur chloride cocondensation resin obtained has a very high softening point, and when it is intended to be produced industrially, the solvent used in the reaction, that is, a large amount of volatile organic compounds must be left industrially. Since it was also found that it was difficult to produce, in order to reduce the volatile organic compounds without reducing the performance of the rubber crosslinking agent such as blocking resistance and dispersibility, add coumarone resin in the production process, Then, it was found that these problems can be solved by removing the residual solvent. Specifically, the following invention is included.
[1]
In the presence of a solvent, 1.2 to 1.5 mol of sulfur monochloride is reacted with 1 mol of p-tert-octylphenol. After the reaction, 5 to 50 parts by weight of coumarone resin is added to 1 part by weight of p-tert-octylphenol. A method for producing a p-tert-octylphenol sulfur chloride cocondensation resin composition containing coumarone resin, wherein the solvent is removed after the addition.
[2]
The composition of p-tert-octylphenol sulfur chloride cocondensation resin containing coumarone resin according to [1], wherein the softening point is 70 to 140 ° C. and the content of coumarone resin is 5 to 50% by weight object.
[3]
[2] A rubber composition comprising 0.5 to 50 parts by weight of a p-tert-octylphenol sulfur chloride cocondensation resin composition containing the coumarone resin according to [2].

According to the present invention, when added to rubber as a crosslinking agent for rubber, the scorch time is longer than that of a conventionally known p-octylphenol sulfur chloride cocondensation resin, viscoelastic properties are not deteriorated, and further, blocking resistance is improved. P-octylphenol chloride, which has the same basic performance as a known crosslinking agent for rubber, such as glycerin and dispersibility, and further has greatly reduced the residual amount of volatile organic compounds, which has recently become a problem. It is possible to provide a rubber crosslinking agent mainly comprising a sulfur co-condensation resin and a method for producing the same.

The present invention is described in detail below. Octylphenol used in the present invention refers to p-tert-octylphenol in the presence of various isomers. In the case of 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.

Sulfur chloride used in the present invention refers to sulfur monochloride (S ₂ Cl ₂ ). When sulfur dichloride (SCl ₂ ) is used, the resulting p-tert-octylphenol sulfur chloride co-condensation resin has a low sulfur content, and the scorch time, which is the effect of the present application, cannot be lengthened. In addition, sulfur monochloride is used in an amount of 1.2 to 1.5 mol, preferably 1.2 to 1.4 mol, per 1 mol of p-tert-octylphenol. When the amount is less than 1.2 mol, the scorch time cannot be increased even when the obtained co-condensation resin composition is used as a crosslinking agent, and when the amount is more than 1.5 mol, the viscoelastic properties are deteriorated.

In the reaction of p-tert-octylphenol and sulfur monochloride, the reaction is performed using a solvent. Any organic solvent may be used as long as it does not cause side reactions 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. When the amount is less than 0.5 parts by weight, the viscosity of the reaction system becomes too high to produce a p-tert-octylphenol sulfur chloride co-condensation resin. When the amount exceeds 2 parts by weight, the p-tert-octylphenol sulfur chloride of the present invention is used. Although a cocondensation resin can be produced, the volumetric efficiency is deteriorated, or after the reaction is completed, it is necessary for a long time to remove the solvent. Therefore, the p-tert-octylphenol sulfur chloride cocondensation resin is economically advantageous. It cannot be manufactured and is not preferable.

The reaction between p-tert-octylphenol and sulfur monochloride is usually performed after (1) p-tert-octylphenol and (2) solvent are charged into the reaction vessel, and (3) to the reaction vessel while adding sulfur monochloride over a certain period of time. (4) After that, it is carried out by stirring for a certain period of time. 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 reaction proceeds slowly, which is economically disadvantageous. If the temperature is higher than 180 ° C, decomposition tends to 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 reaction proceeds slowly, which is economically disadvantageous. If the temperature is higher than 180 ° C, decomposition tends to 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 adding the coumarone resin to the p-tert-octylphenol sulfur chloride cocondensation resin containing the solvent thus obtained, the solvent used in the reaction is removed. Before entering the solvent removal step, if necessary, an operation of removing impurities and the like in the p-tert-octylphenol sulfur chloride cocondensation resin, such as water washing and neutralization, may be performed. Coumarone resin as used herein refers to a copolymer having an average degree of polymerization of 4 to 8 containing coumarone residues in its skeleton structure, and those having indene and styrene residues in addition to coumarone residues. It is common. Specific examples of such a coumarone resin include a knit resin coumarone manufactured by Nikkiso Chemical Co., Ltd., a process resin manufactured by Kobe Oil Chemical Co., Ltd., and Novares C series manufactured by Rutgers.

The softening point of coumarone resin varies depending on the degree of polymerization and the structure, but those having a temperature of 5 to 150 ° C., preferably 5 to 120 ° C. are usually used. When a temperature higher than 150 ° C is used, the viscosity of the reaction mass may become too high in the process of removing the solvent, making it impossible to manufacture industrially. When a temperature lower than 5 ° C is used, the resulting coumarone The p-tert-octylphenol sulfur chloride cocondensation resin containing the resin may be blocked (melted and fixed) during storage, which is not preferable. The coumarone resin is usually used in an amount of 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 20% by weight in the resin crosslinking agent. If it is less than 5% by weight, the reaction mass may become too viscous in the process of removing the solvent, making it impossible to produce industrially. If it is more than 50% by weight, p-tert containing the resulting coumarone resin may be used. -The octylphenol sulfur chloride cocondensation resin is not preferred because it may block (melt and fix) during storage.

The solvent removal step can be performed by a method generally performed in accordance with the boiling point of the solvent after adding the coumarone resin described above. Examples of such a method include a method in which a p-tert-octylphenol sulfur chloride co-condensation resin and a coumarone resin containing a solvent are introduced into the reactor, and the solvent is removed from the reactor at an internal temperature equal to or higher than the boiling point of the solvent. . At this time, the reactor may be a reduced pressure system if necessary, and the solvent may be removed at a lower temperature. 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 solvent removal step is determined by the amount of residual solvent in the p-tert-octylphenol sulfur chloride cocondensation resin containing coumarone resin. 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. If it is more than 5% by weight, the solvent may affect the environment as a volatile organic compound.

The p-tert-octylphenol sulfur chloride cocondensation resin containing the coumarone resin thus obtained is further added and mixed so that the softening point is 70 to 140 ° C, preferably 80 to 130 ° C. It is possible to adjust. 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 cross-linking 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 JIS * K5902.

As a result of adjusting the resin composition in the present invention to have the aforementioned softening point range, the coumarone resin contained in the p-tert-octylphenol sulfur chloride cocondensation resin composition containing coumarone resin is usually 5 to 50% by weight. And preferably 5 to 40% by weight, more preferably 5 to 20% by weight. The coumarone resin has a very low vapor pressure and is usually hardly removed in the solvent removal step. Therefore, the coumarone resin added in the solvent removal step and the coumarone added as needed after the solvent removal step are used. The total amount of the resin used becomes the coumarone resin content in the resin composition of the present invention as it is.

The thus obtained p-tert-octylphenol sulfur chloride co-condensation resin composition containing coumarone resin is applicable to all rubbers capable of sulfur crosslinking, such as natural rubber (NR), styrene butadiene rubber (SBR), and polybutadiene rubber. (BR), polyisoprene rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene-isobutylene copolymer rubber (IIR), ethylene-propylene terpolymer (EPDM), etc. The Of these, natural rubber (NR), styrene butadiene rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and polybutadiene rubber (BR) are preferably used. The amount of p-tert-octylphenol sulfur chloride cocondensation resin composition containing coumarone resin used in rubber is p-tert- containing the coumarone resin of the present invention relative to 100 parts by weight of rubber. The octylphenol sulfur chloride cocondensation resin composition is usually used in an amount of 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the amount is less than 0.5 part by weight, the crosslink density tends to be low and the viscoelastic properties tend to be deteriorated. When the amount is more than 50 parts by weight, the breaking property and wear resistance tend to be deteriorated.

When the p-tert-octylphenol sulfur chloride cocondensation resin composition containing the coumarone resin of the present invention is blended and used in rubber, a compounding agent usually used in the rubber industry, for example, a filler such as carbon black, Zinc oxide, stearic acid, oils and the like can be appropriately selected and blended within a range not impairing the object of the present invention, and commercially available products can be suitably used as these blending agents.

The rubber composition containing 0.5 to 50 parts by weight of the p-tert-octylphenol sulfur chloride co-condensation resin composition containing coumarone resin in the present invention is a rubber used for tires, hoses, tubes, gaskets, home appliance parts, etc. It is suitably used for products.

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 K5902.

<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 4-necked flask equipped with a reflux condenser and a thermometer was charged with 800 g (3.8 mol) of p-tert-octylphenol and 500 g of toluene, and 630 g (4.7 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution was added dropwise over 5 hours, and after completion of the addition, the internal temperature was raised to 120 ° C and kept warm for 3 hours. After adding 94 g of Rutgers Novares C10 as a coumarone resin to the resulting reaction solution, the solvent and unreacted monomer were removed under reduced pressure, and 1170 g of p-tert-octylphenol sulfur chloride co-condensation resin composition (referred to as resin A). Got. Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

Example 2 Synthesis of Resin B
A 4-necked flask equipped with a reflux condenser and a thermometer was charged with 1000 g (4.8 mol) of p-tert-octylphenol and 1000 g of toluene, and 864 g (6.4 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution is added dropwise in 5 hours, and after completion of the addition, the internal temperature is increased to 120 ° C and kept for 3 hours. After adding Ruggers Novares C100, 173 g as a coumarone resin to the resulting reaction solution, the solvent and unreacted monomer were removed under reduced pressure, and p-tert-octylphenol sulfur chloride co-condensation resin composition (referred to as Resin B) 1530 g Got. 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 4-necked flask equipped with a reflux condenser and a thermometer was charged with 800 g (3.8 mol) of p-tert-octylphenol and 500 g of toluene, and 630 g (4.67 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution was added dropwise over 5 hours, and after completion of the addition, the internal temperature was raised to 120 ° C and kept warm for 3 hours. After 94 g of paraffinic process oil was added to the resulting reaction solution, the solvent and unreacted monomers were removed under reduced pressure to obtain 1190 g of p-tert-octylphenol sulfur chloride cocondensation resin (referred to as resin D). Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

<Comparative Example 2 Synthesis of Resin D>
A four-necked flask equipped with a reflux condenser and a thermometer was charged with 800 g (3.9 mol) of p-tert-octylphenol and 470 g of toluene, and 970 g (7.2 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution was added dropwise over 5 hours, and after completion of the addition, the internal temperature was raised to 120 ° C and kept warm for 3 hours. The solvent and unreacted monomer were removed under reduced pressure without adding coumarone resin to the resulting reaction solution, to obtain 1250 g of p-tert-octylphenol sulfur chloride cocondensation resin (referred to as resin E). Table 1 shows the softening point, residual solvent amount, and residual monomer amount of the obtained resin.

<Comparative Example 3 Synthesis of Resin E>
A 4-necked flask equipped with a reflux condenser and a thermometer was charged with 800 g (3.8 mol) of p-tert-octylphenol and 500 g of toluene, and 630 g (4.67 mol) of sulfur monochloride was adjusted to an internal temperature of 70%. While maintaining at -80 ° C, the solution was added dropwise over 5 hours, and after completion of the addition, the internal temperature was raised to 120 ° C and kept warm for 3 hours. Thereafter, when the solvent and unreacted monomer were to be removed under reduced pressure, the reaction mass solidified during the removal and could not be completed.

<Reference Example Resin F>
As a commercially available p-tert-octylphenol sulfur chloride cocondensation resin, Taoka Chemical Co., Ltd. V-200 was used as resin F as it was.

<Evaluation of blocking properties>
In the blocking test, the solid resin obtained in each Example, Comparative Example, and Reference Example was crushed into a flake powder of about 0.5 cm each, and the sample was filled so that it would be about 1 cm from the bottom of the polyethylene container. Then, the container was opened for 168 hours under the conditions of a temperature of 40 ° C. and a humidity of 95% RH with the container lid opened, and evaluation was performed based on the following evaluation criteria.

<Blocking evaluation criteria>
The blocking state between the resin fine powders was visually observed, and the blocking property was evaluated based on the following evaluation criteria. The results are shown in Table 1.
(Double-circle): No blocking, (circle): Blocking of the grade which can be loosened easily if it crushes with a fingertip, (triangle | delta): Partial blocking is recognized, X: Blocking is recognized as a whole.

<Creation of unvulcanized rubber sheet for evaluation>
A rubber compound (400 g) having the following composition was prepared by kneading at a set temperature of 0 ° C. for 10 minutes using a 6-inch open roll manufactured by Kansai Roll.
<Combination>
Styrene butadiene rubber (SBR) (JSR 1502 made by JSR) 70 parts by weight butadiene rubber (BR) (Ube Industries BR150B) 30 parts by weight silica (Tosoh Silica VN3) 50 parts by weight carbon black (Showa Cabot) N330) 5 parts by weight silane coupling agent (Si69, manufactured by Degusa) 5 parts by weight anti-aging agent (Nocrack 6C, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 2 parts by weight zinc oxide (manufactured by Sakai Chemical) 3 parts by weight stearic acid (Japan) 2 parts by weight vulcanization accelerator (CZ-G made by Ouchi Shinsei Chemical Co., Ltd.) 3 parts by weight insoluble sulfur (Crytex HS OT-20 made by Flexis) 2 parts by weight p-tert-octylphenol sulfur chloride cocondensation 2 parts by weight of resin (resins A to F)

<Scorch time>
At Toyo Seiki Seisakusho Ltd. Mooney viscometer (L rotor), and the t ₅ at 130 ° C. of the unvulcanized rubber sheet for evaluation was measured as scorch time.

<Rubber physical property evaluation method>
(Rolling resistance; tan δ (70 ° C))
A vulcanized test piece for evaluating rubber properties was prepared by cutting 50 mm × 5 mm from a vulcanized rubber sheet having a thickness of 2 mm prepared by pressing at 160 ° C. for 20 minutes.
The dynamic viscoelasticity of the vulcanized specimen is measured with a dynamic viscoelasticity measuring device manufactured by Seiko Instruments Inc. at an initial strain of 1%, an amplitude of ± 0.2%, and a frequency of 10 Hz, and a temperature of 70 ° C. (temperature increase) Tan δ at a rate of 2 ° C./min) was determined.

<Rubber properties evaluation criteria>
For each evaluation result of resin F, which is a reference example, the evaluation result when using each resin crosslinking agent was evaluated relative to the evaluation result based on the following evaluation criteria.
tan δ (value relating to viscoelastic properties. The lower the value, the better the viscoelastic properties)
Increased compared to the reference example: ×
Less than 5% decrease: ○
Reduction of 5% or more: ◎

Claims (2)

In the presence of a solvent, 1 to 1.5 mol of sulfur monochloride is reacted with 1 mol of p-tert-octylphenol, and coumarone resin is added to p-tert-octylphenol sulfur chloride cocondensate with p-tert-octylphenol. p-tert-octylphenol sulfur chloride containing coumarone resin, characterized in that the solvent is removed after adding to a mixture of tert-octylphenol sulfur chloride cocondensation resin and coumarone resin so as to contain 5 to 50 wt% A method for producing a co-condensation resin composition. The p-tert-octylphenol sulfur chloride cocondensation resin composition containing the coumarone resin produced by the production method according to claim 1 is used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of rubber. A method for producing a rubber composition .