JPS6259730B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a sulfur-containing phenolic resin. More specifically, the present invention provides improvements in the production of sulfur-containing phenolic resins, which are useful primarily as heat resistance improvers for rubber, by reacting phenols with sulfur monochloride and then reacting formaldehyde and phenols simultaneously or sequentially. Regarding the law. Truck/bus tires (TB tires) or off-the-road tires (OR tires) for construction vehicles.
It is well known that the rubber quality of the tread portion of tires is required to be of a higher quality than that of passenger tires because of the harsh operating conditions. For example, TB tires or OR tires often have thick rubber layers due to their structure, and in these cases, the heat generated in the tread area during driving increases heat accumulation inside the tire, which can lead to repeated large deformations, especially on rough, bumpy roads. As a result, there have been problems such as failures inside the tire, such as peeling between the tread layer and the carcass or player layer, as well as cracks in the surface layer of the tread portion due to bending. In addition, especially in the case of OR tires, as they are often driven on rough roads with protruding crushed stones and rocks, as well as other construction sites such as civil engineering work, the tires may chip or cut, eventually becoming unusable. In terms of performance, there were some very undesirable problems. As a method to improve these drawbacks, it has been proposed to use a rubber composition containing a sulfur-containing phenolic resin (Japanese Patent Laid-Open Publication No.
54−86542). The present inventors have carefully studied the relationship between the manufacturing conditions of such sulfur-containing phenolic resins and their performance on rubber physical properties, and found that in the reaction between phenols and sulfur monochloride, sulfur monochloride reacts with Therefore, we discovered that the use of alcohols, which have not been conventionally used in the reaction between phenols and sulfur monochloride, gave surprisingly good results.
The present invention has now been completed. That is, the present invention is based on the following formula [Here, R ₁ and R ₂ represent a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an aryl group, a C ₁ to C ₁₈ alkyl group, a cycloalkyl group, a cycloalkenyl group, and a C ₇ to _{C 12} aralkyl group. , R ₃ represents a hydrogen atom, an acetyl group, or a methyl group. ] Component (A) shown in is reacted with sulfur monochloride as component B, and then formaldehyde and the following formula as component (C) are reacted.

[expression] and/or

[Formula] [Here, R ₄ is −OR ₇ , −NHR ₇ , −COOR ₇ , −
_OCOR7 , aryl group, _C1 - _C18 alkyl group, cycloalkyl group, cycloalkenyl group, _C7 - _C12
means aralkyl, R ₅ and R ₆ are hydrogen atoms, −
_OR7 , _-NHR7 , _-COOR7 , _-OCOR7 , aryl group, _C1 - _C18 alkyl group, cycloalkyl group,
It means a cycloalkenyl group, a _C7 - _C12 aralkyl group, and _R7 means a hydrogen atom, _{a C1-C14 alkyl} group. ] In the method for producing a sulfur-containing phenolic resin by reacting the (D) components shown in the formula simultaneously or sequentially, the reaction between the (A) component and the (B) component is carried out using a monohydric alcohol. The present invention provides a method for producing a sulfur-containing phenolic resin. The present invention will be explained in detail below. Component (A) used in the present invention includes phenol, cresol, ethylphenol, dimethylphenol, propylphenol, propenylphenol, methylethylphenol, butylphenol, methylpropylphenol, diethylphenol, amylphenol, methylbutylphenol, and ethylphenol. Propylphenol, cyclopentylphenol, cyclopentenylphenol, hexylphenol, phenylphenol, methylamylphenol, ethylbutylphenol, diisopropylphenol, cyclohexylphenol, heptylphenol, tolylphenol, octylphenol, xylylphenol,
Each isomer of alkyl-, cycloalkyl-, alkenyl-, aryl- and aralkyl-substituted phenol such as nonylphenol, decylphenol, dodecylphenol, and their acetates and methyl ethers; resorcinol, methylresorcinol, ethylresorcinol, propylresorcinol, butylresorcinol, Isomers of alkyl-substituted resorcinols such as amylresorcinol, hexylresorcinol, cashew, and urushiol, their acetates and methyl ethers; isomers of aromatic carboxylic acids such as oxybenzoic acid, methyloxybenzoic acid, and ethyloxybenzoic acid. Examples thereof include acetates, methyl ethers, and the like. As component (B), sulfur monochloride is used. The formaldehyde used as component (C) may be one that substantially supplies formaldehyde into the system, such as an aqueous formalin solution, a formaldehyde polymer (paraform), or trioxane. Component (D) includes m-cresol, m-ethylphenol, m-propylphenol, m-propenylphenol, m-butylphenol, m-
amylphenol, m-hexylphenol, m
-Heptylphenol, m-octylphenol, m-nonylphenol, m-decylphenol, m-dodecylphenol, m-cyclopentylphenol, m-cyclopentenylphenol, m-cyclohexylphenol, m-tolylphenol, m-xylylphenol Monosubstituted phenols of alkyl, cycloalkyl, alkenyl, aryl and aralkyl, their acetates and methyl ethers; dimethylphenol, methylethylphenol, methylpropylphenol, diethylphenol, methylbutylphenol, ethylpropylphenol,
Disubstituted phenols such as methylamylphenol, ethylbutylphenol, diisopropylphenol, etc., in which one of the substituents is substituted at the meta position relative to the hydroxyl group, their acetates and methyl ethers; resorcinol, methylresorcinol , each isomer of alkyl-substituted resorcinol such as ethylresorcinol, propylresorcinol, butylresorcinol, amylresorcinol, hexylresorcinol, cashew, urushiol, their acetates and methyl ethers; m-
Aromatic carboxylic acids such as hydroxybenzoic acid, methylhydroxybenzoic acid, and ethylhydroxybenzoic acid in which either substituent is substituted at the meta position relative to the hydroxyl group, their acetates and methyl ethers; naphthol , each isomer of alkyl-substituted naphthols such as methylnaphthol, dimethylnaphthol, ethylnaphthol, diethylnaphthol, propylnaphthol, methylethylnaphthol, butylnaphthol, methylpropylnaphthol, diethylnaphthol,
Their acetates and methyl ethers;
Examples include isomers of dihydroxynaphthol, their acetates, and methyl ethers. Each of the components (A) and (D) may be used alone or in a mixture of two or more. The monohydric alcohols used in the method of the present invention are saturated aliphatic monohydric alcohols or saturated alicyclic monohydric alcohols, specifically methanol,
Ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-
Examples include butanol, t-butanol, n-amyl alcohol, sec-amyl alcohol, iso-amyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, cyclopentyl carbinol, n-octanol, and 2-ethylhexyl alcohol. Ru. When producing the sulfur-containing phenolic resin of the present invention, the molar ratio of each component used is preferably (A)
Component: (B) component: (C) component: (D) component = 1: (0.2 ~
0.9): (0.1~0.2): (0.1~1.2) range. The amount of monohydric alcohol used is 100% of component (A).
It is about 10 to 1000 parts by weight, preferably about 50 to about 300 parts by weight. The method of the present invention includes: 1. A method in which component (A) is reacted with component (B), then component (C) is reacted, and then component (D) is reacted. 2 A method in which component (A) is reacted with component (B), and then component (C) and (D) are reacted simultaneously. It is carried out by either method, but method 2 is more preferably adopted. The temperature in the reaction of component (A) and component (B) is below the boiling point of the monohydric alcohol used, preferably in the range of about 10°C to about 80°C, and the reaction time is not particularly limited. do not have. The sulfur-containing phenolic resin produced by the method of the present invention described above can be used for desired purposes as is or after acetylating or methyl etherifying some or all of the hydroxyl groups in the resin, if necessary. be. EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples. Example 1 206 g (1.0 mol) of pt-octylphenol and 200 g of iso-propanol are placed in a flask equipped with a stirrer, thermometer, dropping funnel, and condenser, and heated to 55°C to dissolve them. Here 67.6g (0.5mol) of sulfur monochloride
is added dropwise over 2 hours while keeping the temperature inside the flask at 55-60°C. Thereafter, the internal temperature was maintained at 55 to 60°C for 1 hour to complete the reaction. 100 g of water and 128 g of a 30% aqueous solution of caustic soda are added thereto to neutralize the hydrogen chloride dissolved in the system, and the resulting brine layer is separated from the flask and removed. Add 34.1 g (1 mol) of 88% paraformaldehyde to the reaction product in the flask, maintain the internal temperature of the flask at 60-65°C, and add 30% aqueous sodium hydroxide solution 67
g was added dropwise over 30 minutes, and then heating was continued for 6 hours while keeping the internal temperature at 60-65°C. Next, 100 g of iso-propanol is added, and the caustic soda in the system is further neutralized with 52.1 g of 35% hydrochloric acid, and the resulting brine layer is separated and removed from the flask. After adding 2 g of oxalic acid monohydrate to make the system slightly acidic, 99 g (0.9 mol) of resorcinol was charged. After heating at an internal temperature of 75 to 80℃ for 5 hours, the internal temperature is reduced to normal pressure.
After heating and concentrating to 130°C to distill off the solvent, the solvent is further removed under reduced pressure. 46g of acetic anhydride was added dropwise over 30 minutes while keeping the internal temperature at 120-125°C, heated at 120-125°C for 1 hour, and the liberated acetic acid was distilled off under reduced pressure, resulting in 377g of reddish brown resin. is obtained. (Softening point: 83°C) This resin is referred to as sulfur-containing phenolic resin (a). Example 2 150 g (1.0 mol) of pt-butylphenol and 200 g of iso-amyl alcohol were placed in the same flask as in Example 1, heated to an internal temperature of 65°C,
Let it dissolve. Here is 90.5g of sulfur monochloride (0.67
The reaction is completed by keeping the internal temperature of the flask at 65-70°C for 1 hour. 100 g of water and 170 g of a 30% caustic soda aqueous solution are added thereto to neutralize the hydrogen chloride dissolved in the system, and the resulting brine layer is separated and extracted from the flask. Add 25.6 g (0.75 mol) of 88% paraformaldehyde to the reaction product in the flask, keep the internal temperature of the flask at 60 to 65°C, and add 67 g of 30% caustic soda aqueous solution dropwise over 30 minutes. 60~65℃
Continue heating for 4 hours. After finishing, add 100g of iso-amyl alcohol and add 35% hydrochloric acid.
The caustic soda in the system is neutralized with 51.8 g, and the resulting brine layer is separated and removed from the flask. After adding 2 g of oxalic acid monohydrate to make the system weakly acidic, 74.4 g of resorcin monomethyl ether was added.
(0.6 mol). After heating at an internal temperature of 95 to 100°C for 2 hours, the solvent is distilled off by heating at normal pressure until the internal temperature reaches 130°C, and then the solvent is further removed under reduced pressure.
61.2g of acetic anhydride was added dropwise over 30 minutes while keeping the internal temperature at 125-130°C, heated at 125-130°C for 1 hour, and the liberated acetic acid was distilled off under reduced pressure. 301g of product is obtained. (Softening point: 105°C) This resin is referred to as sulfur-containing phenolic resin (b). Example 3 206 g (1.0 mol) of pt-octylphenol and 200 g of iso-butanol were placed in a flask similar to that of Example 1, and heated to 55°C to dissolve them. 90.5 g (0.67 mol) of sulfur monochloride was added dropwise thereto over 2 hours while keeping the internal temperature of the flask at 55-60°C. Thereafter, the internal temperature was maintained at 55 to 60°C for 1 hour to complete the reaction. 100 g of water and 171 g of a 30% caustic soda aqueous solution are added thereto to neutralize the hydrogen chloride dissolved in the system, and the resulting brine layer is separated and extracted from the flask. 88% paraformaldehyde 25.6g (0.75mol)
Add to the reaction product in the flask, keep the internal temperature of the flask at 60-65℃, and add 30% caustic soda aqueous solution 67
g over 30 minutes, then continue heating for 4 hours while keeping the internal temperature at 60-65°C. After completion, 100 g of iso-butanol is added, and the caustic soda in the system is neutralized with 52 g of 35% hydrochloric acid, and the resulting brine layer is separated and drained. After adding 2 g of oxalic acid monohydrate to make the system slightly acidic, 66 g (0.6 mol) of resorcin was added, and after heating at an internal temperature of 95 to 100°C for 3 hours, the internal temperature was reduced to normal pressure.
After heating to 130°C to distill off the solvent, the solvent is further removed under reduced pressure. The resin thus obtained is referred to as sulfur-containing phenolic resin (c). (Softening point: 110°C) Example 4 The same operation as in Example 3 was repeated, and after removing the solvent under reduced pressure, 61.2g of acetic anhydride was added dropwise over 30 minutes while keeping the internal temperature at 125-130°C. After heating for 1 hour, liberated acetic acid was distilled off under reduced pressure to obtain 349 g of a reddish-brown resinous substance. (Softening point: 100℃) The resin obtained here is used as a sulfur-containing phenolic resin.
(d). Comparative Example 1 206 gr (1 mol) of pt-octylphenol and 150 ml of ethyl acetate were placed in a flask equipped with a stirrer, thermometer, dropping funnel, and condenser, and dissolved by heating at 70°C. Add 67.6 g (0.5 mol) of sulfur monochloride to the flask and
Drop it while keeping it at 70-80℃, and after finishing, reduce the internal temperature to 90-90℃.
Raise the temperature to 100℃ and heat for 6 hours. Hydrogen chloride generated during this time is released outside the system. After finishing, water
After adding 15 ml and neutralizing with 15% caustic soda water, ethyl acetate was distilled off under reduced pressure. Dissolve the obtained residue in 150 ml of toluene, add 34 g (1 mol) of 88% paraformaldehyde, and add 13.4 g of 15% caustic soda water while keeping the internal temperature of the flask at 60-65°C.
Drop in for 1 hour. After completion, the internal temperature was raised to 85-90°C and heated for 4 hours. After cooling to 40-45°C, 110 g (1.0 mol) of resorcin and oxalic acid dihydrate
After adding 3.2g and gradually raising the internal temperature,
Water is azeotropically dehydrated with toluene, and the dehydration is completed at an internal temperature of 85 to 115°C over 5 hours. After the reaction is complete, add 200 ml of toluene, dissolve the inorganic substances in the system in 20 ml of water, and remove them from the system by liquid separation. If necessary, perform liquid separation again. The obtained toluene layer was concentrated under reduced pressure (160℃/degree of vacuum)
50mmHg), 308g of reddish-brown residue was obtained (Japanese Patent Application Laid-open No. 1983
-86542, method described in Reference Example 1). This is referred to as sulfur-containing phenolic resin (e). Comparative Example 2 206 g (1 mol) of pt-octylphenol and 280 ml of toluene were placed in a flask equipped with a stirrer, thermometer, dropping funnel, and condenser.
Prepare and heat to dissolve at 70℃. 67.6 g (0.5 mol) of sulfur monochloride was added dropwise to this while maintaining the internal temperature of the flask at 70-80°C, and after the completion of the dropwise addition, the internal temperature was raised to 90-100°C and heated for 6 hours. During this time, hydrogen chloride generated by the reaction is released outside the system. After the reaction is completed, 15 ml of water is added, and after neutralization with a 15% aqueous sodium hydroxide solution, 34.1 g (1 mole) of 88% paraformaldehyde is charged into the flask. Keeping the internal temperature of the flask at 60-65℃, drop 67g of 30% caustic soda aqueous solution over 1 hour, and after 60℃
110g (1 mol) of resorcinol and 3.2g of oxalic acid dihydrate were charged at ~65°C, and the internal temperature was gradually raised.The water was distilled off together with toluene to reduce the internal temperature.
Complete dehydration at 85-115℃. (The above is a reaction of formaldehyde using 30% caustic soda, 60 ~
(Same as the method described in Reference Example 1 of JP-A-55-125137, except that the temperature is 65°C) Thereafter, the solvent is distilled off by heating to 130°C, and further the solvent is removed under reduced pressure. here
61.2g of acetic anhydride was heated for 30 minutes while keeping the internal temperature at 125-130℃.
It was added dropwise for 1 minute, heated at 125-130℃ for 1 hour, and the liberated acetic acid was distilled off under reduced pressure, resulting in a reddish-brown resin.
387 g are obtained (softening point 97°C). This is referred to as sulfur-containing phenolic resin (f). Reference Example 1 Using a 1.8 B-type Banbury mixer, the sulfur-containing resins (a) to (f) produced in Examples and Comparative Examples were
Combined with other compounding agents based on the following prescription,
A rubber composition was prepared. Thereafter, a test piece with a predetermined shape was prepared at 145°C for 30 minutes. These rubber compositions were tested using a tensile test (JIS-K-6301), a tear test (JIS-K-6301, Type A), a Gutdoritsu flexometer, and a heat generation test (ASTM-D
-623), a flexural cracking test (JIS-K-6301) was conducted using a Dematschia testing machine. The results are shown in Table 1. (Composition) Natural rubber (RSS#1) 100.0 parts by weight HAF Black 45.0 Stearic acid 3.0 Process oil 3.0 Zinc white 5.0 Sulfur 2.0 Soccinol CZ* ¹ 1.0 Sulfur-containing resin 2.0 Bonding agent M-3* ² 1.0 Hydrous silica* ³ 10.0 *1 N-cyclohexylbenzothiazilsphenamide (Sumitomo Chemical brand name) *2 Oxazolidine derivative (Uniroyal brand name) *3 Nibcil VN3 (Nippon Silica brand name)

【table】

Claims (1)

[Claims] 1. The following formula [Here, R ₁ and R ₂ represent a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an aryl group, a C ₁ to C ₁₈ alkyl group, a cycloalkyl group, a cycloalkenyl group, and a C ₇ to _{C 12} aralkyl group. , R ₃ represents a hydrogen atom, an acetyl group, or a methyl group. [Here, R ₄ is − OR ₇ , −NHR ₇ , −COOR ₇ , −
_OCOR7 , aryl group, _C1 - _C18 alkyl group, cycloalkyl group, cycloalkenyl group, _C7 - _C12
means an aralkyl group, R ₅ and R ₆ are hydrogen atoms, -
_OR7 , _-NHR7 , _-COOR7 , _-OCOR7 , aryl group, _C1 - _C18 alkyl group, cycloalkyl group,
It means a cycloalkenyl group, a _C7 - _C12 aralkyl group, and _R7 means a hydrogen atom, _{a C1-C14 alkyl} group. ] In the method for producing a sulfur-containing phenolic resin by simultaneously or sequentially reacting components (D), the reaction between components (A) and (B) may be carried out using a monohydric alcohol. Characteristic method for producing sulfur-containing phenolic resin.