JP4175705B2 - Method for producing silylated polysulfide polymer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is a vulcanizing agent for rubber having a double bond, the average number of bonds of the repeating units sulfur at 6 or less than 2, relates to the production how silylated polysulfide polymer is a liquid at room temperature .
[0002]
[Prior art]
The use of silicate as a reinforcing agent for rubber having a double bond is widely used in the industrial field. When hydrophilic silica is blended with hydrophobic rubber, the rubber and silica are not compatible, and various problems are derived. As one of the solutions, bis (3-triethoxysilylpropyl) tetrasulfide which is a binder between rubber and silica is used. However, since this has a low molecular weight, it is difficult for rubber and silica to bond uniformly. Increasing the molecular weight is advantageous because the dispersion becomes uniform and the contact efficiency between silica and rubber increases. Japanese Patent Application Laid-Open No. 9-3248 responds to this need by including a method for synthesizing a silylated polysulfide polymer from mercaptosilane, dithiol and sulfur dichloride with an anhydrous solvent, and silylated alkyl halide and dihalogenated alkyl. And a method for synthesizing a silylated polysulfide polymer from a metal polysulfide in an anhydrous solvent. However, these methods have problems such as the need to react in a completely anhydrous state, the need for a large amount of solvent, and the high viscosity of the product, making it difficult to separate from the by-product metal halide. It was. Japanese Examined Patent Publication No. 6-25284 discloses a silylated polysulfide compound which is a low molecular compound having a thiocarbamyl group, and this compound has a fracture strength in a system using silica as a reinforcing agent for rubber having a double bond. It is described that it has the characteristic of lowering Mooney viscosity (workability) than bis (3-triethoxysilylpropyl) tetrasulfide. However, since this compound has a low molecular weight, it is necessary to use it in a large amount.
[0003]
[Problems to be solved by the invention]
The object of the present invention is not only to solve the above-mentioned conventional drawbacks, but also to have a function as a vulcanizing agent for rubber having a double bond by including a repetition of the number of sulfur bonds exceeding the disulfide in the main chain. A silylated polysulfide polymer having a required chemical structure, such as a benzothiazole group or a thiocarbamyl group, which necessarily contains an alcoholyl group having a bonding property to silica by hydrolysis, and in some cases has an effect of accelerating rubber vulcanization. to provide how to readily synthesized.
[0004]
[Means for Solving the Problems]
As a result of intensive studies by the inventors, the object of the present invention has been achieved industrially advantageously by the following present invention.
[0005]
[1] A compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or a compound represented by the general formula R ⁸ Sy (R ¹ Sy) nR ¹ SyR ⁸ and the general formula R ² SyR a compound represented by ^2, characterized in that to sulfur exchange reaction, a vulcanizing agent of rubber having a double bond, represented by the general formula ^{R 2 (SxR 1) nSxR 2} , is liquid at room temperature A method for producing a silylated polysulfide polymer.
[0006]
However, in the above general formula:
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, its ester or polyoxyalkylene Group, benzyl group, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (where R ⁶ and R ⁷ are any of methyl group, ethyl group and butyl group ) Alkyl group, benzyl group) Thiocarbamyl group showing a _{forming, (CH 3) 2 CHO (} CS) - xanthate showing the structure of a _morpholine shown benzothiazole group, and _OC 4 _H 8 N-structure showing the structure of a C ₆ H 4 SNC- A group selected from the group,
R ⁸ may even R ² that is different may be the same R ² in R ² SxR ^2,
x represents a value from 2 to 6;
y represents a numerical value of 2 or more, and n is an integer representing 1 to 100.
[0007]
[2] A compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and a compound represented by the general formula R ² SyR ² Is a rubber vulcanizing agent having a double bond, characterized by a sulfur exchange reaction in the presence of sulfur , and is represented by the general formula R ² (SxR ¹ ) nSxR ² and is a liquid at room temperature A method for producing a polysulfide polymer.
[0008]
However, in the above general formula:
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Thiocarbamyl group represented _{by, (CH 3) 2 CHO (} CS) - xanthate showing the structure _of, C ₆ H 4 SNC- benzothiazole showing the structure of, and _OC 4 _H 8 N-morpholine group showing the structure of A group selected from
R ⁸ may even R ² that is different may be the same R ² in R ² SyR ^2,
x represents a value from 2 to 6;
y represents a numerical value exceeding 1, and n is an integer representing 1 to 100.
[0009]
[3] the general formula HS (R ¹ Sy) nR compound represented by ¹ SH, the formula R ² compound represented by SYR ^2, and is characterized by causing a polymerization reaction causes the sulfur exchange reaction of sulfur, two A process for producing a silylated polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² , which is a rubber vulcanizing agent having a heavy bond, and which is liquid at room temperature.
[0010]
However, in the above general formula:
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Shown thiocarbamyl _{group, (CH 3) 2 CHO (} CS) - xanthate showing a structure _of, C ₆ H 4 SNC- benzothiazole group showing the structure of, and _OC 4 _H 8 N-morpholine group showing the structure of is a group selected from,
x represents a value from 2 to 6;
y represents a number greater than 1, and
n is an integer representing 1 to 100.
[0011]
[4] the general formula HS (R ¹ Sy) nR compound represented by ¹ SH, general formula R compounds represented by ² SH, and is characterized by causing a polymerization reaction causes the sulfur exchange reaction of sulfur, double A process for producing a silylated polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² , which is a rubber vulcanizing agent having a bond, and which is liquid at room temperature.
[0012]
However, in the above general formula:
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are a methyl group, an ethyl group, a butyl group, C ₅ H ₁₀₎ Any alkyl group of Thiocarbamyl group of the structure of the _{group), (CH 3) 2 CHO} (CS) - xanthate showing the structure of a benzothiazole group showing the structure of a C ₆ H ₄ SNC-, and OC ₄ H ₈ N-structural A morpholine group selected from
x represents a value from 2 to 6;
y represents a numerical value exceeding 1, and n is an integer representing 1 to 100.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a vulcanizing agent for rubber having a double bond, the average number of bonds of the repeating units sulfur at 6 or less than 2, relates to the production how silylated polysulfide polymer is a liquid at room temperature .
[0018]
The compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ used in the present invention can be obtained from the compound represented by the general formula HS (R ¹ Sy) nR ¹ SH. This HS (R ¹ Sy) nR ¹ SH is selected from the compounds described in Patrick et al. US Pat. No. 2,466,963 and JP-A-4-363325. This polysulfide polymer usually has a sulfur bond number y of 2.
[0019]
The compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ is a compound represented by the general formula HS (R ¹ Sy) nR ¹ SH in addition to an oxygen atom-containing cyclic ether compound such as ethylene oxide or propylene oxide. Can be easily obtained. It can be easily obtained by reacting with an unsaturated group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. It can also be obtained by subjecting a polysulfide polymer having terminal SH groups to addition reaction of glycidyl ethers such as allyl, butyl, phenyl, methyl, 2-ethylhexyl, stearyl group glycidyl ether and the like. Further, as described in JP-B-41-19514, it can also be obtained by reacting an aldehyde or ketone with terminal SH of a polysulfide polymer under an amine catalyst.
[0020]
R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ whose terminal group is a silyl group is an addition reaction of isocyanate silane, epoxy silane, vinyl silane or the like having a silyl group to a polysulfide polymer whose terminal group is SH group or OH group. Can be easily obtained. Those in which x exceeds 2 can be obtained by adding sulfur under an amine catalyst to a polysulfide polymer obtained by carrying out these addition reactions.
[0021]
Examples of the compound represented by the general formula R ² SyR ² used in the present invention include dimethyl disulfide, diphenyl disulfide, di-t-dodecyl polysulfide, di-t-nonyl polysulfide, di-t-butyl disulfide, bis (3 -Trimethoxysilylpropyl) polysulfide, bis (3-triethoxysilylpropyl) polysulfide, bis (3-trimethoxysilyltolylene) polysulfide, bis (3-triethoxysilyltolylene) polysulfide, tetramethylthiuram disulfide, tetraethyl Thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dibenzothiazyl disulfide, 2- (4′-morpholine nodithio) benzothiazole, di Examples thereof include thiodimorpholine, perisopropylxanthogen disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, o, o′dibenzamide diphenyl disulfide, and the like.
[0022]
Examples of the compound represented by the general formula R ² SH include mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and mercaptans such as 2-mercaptobenzothiazole.
[0023]
In the present invention, in order to obtain a polysulfide polymer R ² Sx (R ¹ Sx) nR ² , a method of producing R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and R ² SyR ² , R ⁸ S (R ¹ Sy) a method of producing from nR ¹ SR ⁸ and R ² SyR ² and sulfur, a method of producing from HS (R ¹ Sy) nR ¹ SH, R ² SyR ² and sulfur, and HS (R ¹ Sy) nR ¹ SH There is a method of producing from R ² SH and sulfur. In either case, the alkali catalyst can be used under the conditions of 0 to 10% by weight, a reaction temperature of 20 to 150 ° C., and a reaction time of 5 minutes to 30 hours. When an alkali catalyst is used, an amine catalyst, particularly triethylamine, has a large catalytic effect and has a relatively low boiling point. More preferably, the reaction temperature is 30 ° C. to 100 ° C., the reaction time is 10 minutes to 5 hours, and the catalyst amount is 0.01% to 3% by weight. R ² SyR ² and / or R ² SH to be added is ¹ to 1000 parts by weight based on 100 parts by weight of raw material polysulfide polymer R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or HS (R ¹ Sy) nR ¹ SH. The amount is preferably 2 to 500 parts by weight. The sulfur added is stoichiometrically determined by the target x of the target polysulfide polymer R ² Sx (R ¹ Sx) nR ² .
[0024]
In the polysulfide polymer R ² (SxR ¹ ) nSxR ² obtained by this production method, R ² is R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ A group (wherein R ³ represents an alkyl group having 1 to ⁴ carbon atoms, R ⁴ is an alkoxy group having 1 to 8 carbon atoms, R ⁵ is a divalent alkylene group having 2 to 12 carbon atoms, or an ester, an amide thereof, In the case of an ether or a divalent C2-C12 alkylene group having a hydroxyl group, or an ester, amide, or ether thereof, it can be used as a binder in a rubber having a double bond and a silicate filler.
[0025]
The silylated polysulfide polymer obtained by this production method can be expected not only as a vulcanizing agent for rubber itself by blending when producing rubber or thermoplastic elastomer, but also glass and rubber, glass and thermoplastic elastomer, It can also be expected to improve the adhesion.
[0026]
It can also be used as a vulcanizing agent for rubber having a double bond, and since it is a polymer vulcanizing agent, it does not have bloom, has good heat resistance and stress relaxation, and is suitable for rubber, rubber / rubber, and rubber / resin. Stabilization of quality and improvement of quality can be expected by uniform dispersion of the vulcanizing agent.
[0027]
Here, as rubber having a double bond, natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber and hydrogenated rubber thereof, butyl rubber, halogenated butyl rubber, epichlorohydrin rubber, ethylene- Examples include propylene-copolymer, ethylene-vinyl acetate copolymer, carboxy rubber, epoxide rubber, chloroprene rubber, acrylic rubber, and millable urethane rubber. These rubbers can be used not only for single systems but also for blend systems. Further, it does not preclude the use of the rubber having a double bond for dynamic crosslinking used as a thermoplastic elastomer. These uses include tire parts for automobiles, bicycles, trucks, buses, motorcycles, various belts, various rollers, shoe materials, various hoses, sheets, packing, vibration damping materials, seismic isolation materials, golf balls, electric wire insulation, Examples include coating materials, buffer elements, cables, gaskets, home appliance parts, and interior / exterior surface materials for civil engineering and construction.
[0028]
In the polysulfide polymer R ² (SxR ¹ ) nSxR ² obtained by this production method, R ² is R ⁶ R ⁷ N (CS) — (where R ⁶ and R ⁷ are any of methyl group, ethyl group, and butyl group) A thiocarbamyl group representing the structure of such an alkyl group, a benzyl group), a xanthogenic acid group representing the structure of (CH ₃ ) ₂ CHO (CS) —, a benzothiazole group representing the structure of C ₆ H ₄ SNC—, and OC ₄ H _In the case of a morpholine group having a structure of ₈ N-, it is more advantageous because it can have not only the effect as a vulcanizing agent of rubber having a double bond but also the effect of a vulcanization accelerator. Without bloom, heat resistance and stress relaxation are good, and stabilization of quality and improvement of quality can be expected by uniform dispersion of the vulcanizing agent in rubber, rubber / rubber and rubber / resin.
[0030]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[0031]
[Example 1]
Ethylene oxide was added to a thiocol LP3 having a molecular weight of 1,000 (manufactured by Toraythiol Co., Ltd.) in a molar amount 1.4 times that of SH to obtain a polysulfide polymer having an OH terminal. The OH group of this polymer was reacted with an equimolar amount of 3-isocyanatopropyltriethoxysilane in the presence of an amine catalyst, and it was confirmed that IR infrared absorption light of OH disappeared. Next, powder sulfur commensurate with the sulfur rank 2.0 of the silylated polysulfide polymer being 4.0 was added and reacted under an amine catalyst. 40 g of this polymer and 10 g of bis (3-triethoxysilylpropyl) tetrasulfide were placed in a 200 cc volumetric flask, 0.5 g of triethylamine was further added, and the mixture was mixed for 30 minutes in an N 2 stream at 80 ° C. and degassed at the same temperature for 30 minutes. The bis (3-triethoxysilylpropyl) tetrasulfide in the polymer obtained was 14% immediately before mixing as measured by liquid chromatography, but decreased to 4% after completion of the reaction, and the desired polysulfide polymer. It was confirmed that This substance has an n of about 3 and a number average molecular weight of 1280. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0032]
[Example 2]
In a 300 cc volumetric flask, 50 g of thiocol LP23 having a molecular weight of 2200 (SH 2.9 wt%, manufactured by Toraythiol Co., Ltd.), 18 g of powdered sulfur, 23.4 g of bis (3-triethoxysilylpropyl) tetrasulfide, and triethylamine as a catalyst After 0.2 g was added and mixed for 2 hours at 80 ° C. under N 2 stream, the mixture was degassed under reduced pressure at the same temperature for 1 hour. When the obtained product was measured by IR infrared absorption light, the absorption of SH completely disappeared and the odor was almost odorless. The viscosity of this product at 25 ° C. was 68 poise, and the desired polysulfide polymer was obtained. After placing the substance in a glass bottle and leaving it to stand at 90 ° C. for 4 days, the viscosity at 25 ° C. was 68 poise and was excellent in storage stability. This substance has an n of about 7 and a number average molecular weight of 2100. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0033]
[Example 3]
50 g of thiocol LP23 (SH 2.9 wt%, manufactured by Toraythiol Co., Ltd.) with a molecular weight of 2200, 18 g of powdered sulfur, 15 g of γ-mercaptopropyltrimethoxysilane and 0.2 g of triethylamine as a catalyst are added to a 300 cc volumetric flask. After mixing in an N2 stream at 80 ° C. for an hour, the mixture was further degassed at the same temperature for 1 hour. When the obtained product was measured by IR infrared absorption light, the absorption of SH completely disappeared and the odor was almost odorless. The product had a viscosity of 90 poise at 25 ° C., and the desired polysulfide polymer was obtained. This substance has an n of about 9 and a number average molecular weight of 2630. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0034]
[Example 4]
In a 300 cc volumetric flask, 50 g of thiocol LP23 (SH 2.9 wt%, manufactured by Toraythiol Co., Ltd.) with a molecular weight of 2200, 18 g of powdered sulfur, 4 g of tetramethylthiuram disulfide, and 23 g of bis (3-triethoxysilylpropyl) tetrasulfide Further, 0.5 g of triethylamine as a catalyst and 25 g of toluene as a solvent were added, mixed for 2 hours at 80 ° C. in a N 2 stream, and then degassed under reduced pressure at the same temperature for 1 hour. When the obtained product was measured by IR infrared absorption light, the absorption of SH completely disappeared and the odor was almost odorless. The viscosity of this product at 25 ° C. was 63 poise. When this product was measured by liquid chromatography, tetramethylthiuram disulfide and bis (3-triethoxysilylpropyl) tetrasulfide, which are the raw materials of this substance, were produced. It was confirmed that the target polysulfide polymer was obtained because it decreased in the product. This substance has an n of about 5 and a number average molecular weight of 1600. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0035]
[Example 5]
In a 300 cc volumetric flask, 50 g of thiocol LP23 (SH 2.9 wt%, manufactured by Toraythiol Co., Ltd.) with a molecular weight of 2200, 18 g of powdered sulfur, 5 g of dibenzothiazyl disulfide, and 23 g of bis (3-triethoxysilylpropyl) tetrasulfide Further, 0.3 g of triethylamine as a catalyst and 25 g of toluene as a solvent were added, mixed for 1 hour at 80 ° C. in an N 2 stream, and then degassed under reduced pressure at the same temperature for 0.5 hour. When the obtained product was measured by IR infrared absorption light, the absorption of SH completely disappeared and the odor was almost odorless. The viscosity of this product at 25 ° C. was 69 poise. When this product was measured by liquid chromatography, dibenzothiazyl disulfide and bis (3-triethoxysilylpropyl) tetrasulfide, which are the raw materials of this substance, were produced. It was confirmed that the target polysulfide polymer was obtained because it decreased in the product. This substance has an n of about 5 and a number average molecular weight of 1560. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0036]
[Example 6]
In a 300 cc volumetric flask, 50 g of thiocol LP23 having a molecular weight of 2200 (SH 2.9 wt%, manufactured by Toraythiol Co., Ltd.), 18 g of powdered sulfur, 4 g of dithiodimorpholine, and 23 g of bis (3-triethoxysilylpropyl) tetrasulfide Further, 0.4 g of triethylamine as a catalyst and 24 g of toluene as a solvent were added, mixed for 1 hour in a stream of N2 at 80 ° C., and further degassed under reduced pressure at the same temperature for 0.5 hour. When the obtained product was measured by IR infrared absorption light, the absorption of SH completely disappeared and the odor was almost odorless. The viscosity of this product at 25 ° C. was 60 poise, and when this product was measured by liquid chromatography, dithiodimorpholine and bis (3-triethoxysilylpropyl) tetrasulfide, which are the raw materials of this substance, were obtained. It was confirmed that the target polysulfide polymer was obtained. This substance has an n of about 5 and a number average molecular weight of 1600. According to Raman analysis, the disulfide bond of the raw polysulfide polymer was a tri-, tetra-, and penta-bond in this substance, and the average rank x was 4.
[0037]
【The invention's effect】
The silylated polysulfide polymer having a number of sulfur bonds in the repeating unit of more than 2 and not more than 6 produced according to the present invention is not only excellent as a rubber vulcanizing agent having a double bond, but also has a double bond. It is an excellent binder of rubber / silica having bonds.

Claims (4)

A compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or a compound represented by R ⁸ Sy (R ¹ Sy) nR ¹ SyR ⁸ and the general formula R ² SyR ² A silylated polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² , which is a rubber vulcanizing agent having a double bond, which is a liquid at room temperature, characterized by sulfur exchange reaction with a compound Manufacturing method.
However, in the above general formula:
R ¹ is at least one selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. Group,
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Shown thiocarbamyl _{group, (CH 3) 2 CHO (} CS) - xanthate showing the structure _of, C ₆ H 4 SNC- benzothiazole showing the structure of, and _OC 4 _H 8 N-morpholine group showing a structure of A group selected from
R ⁸ may even R ² that is different may be the same R ² in R ² SxR ^2,
x represents a value from 2 to 6;
y represents a numerical value of 2 or more, and n is an integer representing 1 to 100. A compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and a compound represented by the general formula R ² SyR ² A silylated polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² , which is a rubber vulcanizing agent having a double bond, and is liquid at room temperature, characterized by performing a sulfur exchange reaction in the presence of Manufacturing method.
However, in the above general formula:
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Shown thiocarbamyl _{group, (CH 3) 2 CHO (} CS) - xanthate showing the structure _of, C ₆ H 4 SNC- benzothiazole showing the structure of, and _OC 4 _H 8 N-morpholine group showing the structure of A group selected from
R ⁸ may even R ² that is different may be the same R ² in R ² SyR ^2,
x represents a value from 2 to 6;
y represents a numerical value exceeding 1, and n is an integer representing 1 to 100. A compound represented by the general formula HS (R ¹ Sy) nR ¹ SH, a compound represented by the general formula R ² SyR ² , and sulfur undergoing a sulfur exchange reaction and a polymerization reaction, A method for producing a silylated polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² , which is a vulcanizing agent for rubber having a liquid at room temperature.
However, in the above general formula,
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Shown thiocarbamyl _{group, (CH 3) 2 CHO (} CS) - xanthate showing the structure _of, C ₆ H 4 SNC- benzothiazole showing the structure of, and _OC 4 _H 8 N-morpholine group showing the structure of is a group selected from,
x represents a value from 2 to 6;
y represents a number greater than 1, and
n is an integer representing 1 to 100. A compound represented by the general formula HS (R ¹ Sy) nR ¹ SH, a compound represented by the general formula R ² SH, and having a double bond characterized by causing sulfur to undergo sulfur exchange reaction and polymerization reaction A process for producing a silylated polysulfide polymer, which is a rubber vulcanizing agent, represented by the general formula R ² (SxR ¹ ) nSxR ² and is liquid at room temperature.
However, in the above general formula,
R ¹ is at least one group selected from an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms. And
R ^2, at least one of R ² in the general formula, R ³ R ³ R ⁴ SiR ⁵ group or R ³ R ⁴ R ⁴ SiR ⁵ group or R ⁴ R ⁴ R ⁴ SiR ⁵ group (wherein R ³ is carbon Represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkoxy group having 1 to 8 carbon atoms, R ⁵ represents a divalent alkylene group having 2 to 12 carbon atoms, or an ester, amide, ether or hydroxyl group thereof. A valent alkylene group having 2 to 12 carbon atoms, or an ester, amide or ether thereof), and when R ² is not the above, an alkyl group having 1 to 20 carbon atoms, an ester or a polyoxyalkylene group , A benzyl group, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkyl group, R ⁶ R ⁷ N (CS) — (wherein R ⁶ and R ⁷ are any alkyl of a methyl group, an ethyl group, and a butyl group) Group, benzyl group) Shown thiocarbamyl _{group, (CH 3) 2 CHO (} CS) - xanthate showing the structure _of, C ₆ H 4 SNC- benzothiazole showing the structure of, and _OC 4 _H 8 N-morpholine group showing the structure of A group selected from
x represents a value from 2 to 6;
y represents a numerical value exceeding 1, and n is an integer representing 1 to 100.