JPH11322931A - Polysulfide polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer which functions as a vulcanizer having double bonds and has an effect of accelerating the vulcanization of rubber or compatibility with a mineral oil by using a normally liquid polysulfide polymer having a specified chemical structure. SOLUTION: This polymer is represented by the formula: R<2> (SxR<1> )n Sx R<2> (wherein R<1> is a 2-10C alkylene, a 2-10C oxyalkylene, a polyoxyalkylene having 2-20 oxygen atoms, or a 3-12C hydroxyalkylene; R<2> is a 1-20C alkyl, an ester thereof, a polyoxyalkylene, benzyl, a resorcinol group, a 2-18C hydroxyalkyl, a hydroxypolyoxyalkylene, thiocarbamyl, a xanthogenic acid group, a benzothiazole group, or a morpholine group; (x) is 2-6; and (n) is 2-100). The polymer is obtained by subjecting a compound represented by the formula: R<8> S(R<1> Sy)n RSR<8> (wherein (y) is 2 or greater; and (n) is 2-100) and a compound represented by the formula: R<2> SyR<2> to a sulfur exchange reaction in the presence of sulfur.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysulfide polymer which is liquid at ordinary temperature and has an average number of sulfur bonds of the repeating unit of more than 2 and 6 or less, and a method for producing the same.
The present invention also relates to a polysulfide polymer suitable as a vulcanization accelerator, a vulcanizing agent and an extreme pressure agent, and a method for producing the same.

[0002]

2. Description of the Related Art A polysulfide polymer is commercially available in a liquid form in which the number of sulfur bonds in a repeating unit is 2, and in a case where the number of sulfur bonds in a repeating unit is 2 or more, a solid form at room temperature exceeding 10.000 in solid temperature. Have been. Liquids at room temperature, in which the number of sulfur bonds in the repeating unit exceeds 2, are difficult to produce, and none of them are industrially effective. According to JP-B-63-42927, the number of sulfur bonds in the repeating unit obtained by the reaction between sulfur chloride and dithiol is 2;
A method is described in which a polysulfide polymer which is liquid at room temperature is used as a rubber flushing agent. In this method, it is necessary to use an expensive dithiol as a raw material and to carry out the reaction in a large amount of an anhydrous solvent, so that the production cost is industrially high and its use is difficult. In addition, the polysulfide polymer obtained by this method has a disadvantage that the terminal group is -SH and lacks storage stability.

According to Japanese Patent Application Laid-Open No. Sho 62-10054, the following formula is used.

[0004]

A method for obtaining a desired product by a synthesis route of the formula 1 is described. However, this method uses -SH or -S
A method of reacting with -SH S- and in the -SCl with chlorine (Cl _2), the synthetic route is a difficult way to considerably industrialization costly case of industrialization. Moreover, the number of sulfur bonds in the repeating unit of the obtained polysulfide polymer is 2, and therefore, the vulcanization accelerator has an effect but the vulcanization agent has no effect.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional drawbacks and to add a rubber having a double bond to the main chain by repeating the number of sulfur bonds exceeding disulfide in the main chain. A polysulfide polymer having a required chemical structure, such as a benzothiazole group having a rubber vulcanization accelerating effect, a thiocarbamyl group, and an alkyl group that increases compatibility with mineral oil, as well as having a function as a flow agent. An object of the present invention is to provide a method for easily synthesizing and a novel specific polysulfide polymer which can be obtained by the method.

[0006]

As a result of intensive studies by the present inventors, the objects of the present invention have been industrially and conveniently achieved by the following present invention. [1] A polysulfide polymer represented by the following general formula (1) that is liquid at normal temperature.

R ² (SxR ¹ ) nSxR ² (1) wherein, in R ² (SxR ¹ ) nSxR ² , R ¹ is an alkylene group having 2 to 10 carbon atoms, an oxyalkylene group having 2 to 10 carbon atoms, an oxygen number Is at least one group selected from a polyoxyalkylene group having 2 to 20 carbon atoms and a hydroxyalkylene group having 3 to 12 carbon atoms, and R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, or a polyoxyalkylene. group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( where R ^6, R ⁷ is a methyl group,
A thiocarbamyl group having a structure of any of an ethyl group, a butyl group, an alkyl group of C ₅ H ₁₀ and a benzyl group),
A xanthate group showing a structure of H ₃ ) ₂ CHO (CS) —, a benzothiazole group showing a structure of C ₆ H ₄ SNC—,
And at least one group selected from morpholine groups having the structure of OC ₄ H ₈ N—, wherein x represents a value of from 2 to 6 and n represents an integer of 2 to 100. [2] The polysulfide polymer according to the above [1], represented by the general formula C ₆ H ₄ SNC (SxR ¹ ) nSxR ² or the general formula R ⁶ R ⁷ N (CS) (SxR ¹ ) nSxR ² .

Wherein R ¹ is at least CH ₂ CH ₂ OCH ₂
OCH ₂ CH ₂ or CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂
Or a group containing one or more CH ₂ CH (OH) CH ₂ . [3] In the general formula (1), R ¹ is at least CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ or CH ₂ CH ₂ OCH ₂
A group containing one or more CH ₂ OCH ₂ CH ₂ or CH ₂ CH (OH) CH ₂ , wherein R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, a resorcinol, The polysulfide polymer according to the above [1], which is a group selected from a hydroxyalkyl group having 2 to 18 carbon atoms and a hydroxypolyoxyarylene group. [4] General formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and general formula R ²
Formula R ² (SxR ¹⁾ method for producing a polysulfide polymer which is liquid at room temperature, represented by NSxR ^2, characterized in that to sulfur exchange reaction and SYR ^2.

However, in the above general formula, R ¹ is 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 carbon atoms, and 3 to 12 carbon atoms. at least one group selected from hydroxy alkylene group, R ² is C 1 -C
20 alkyl group, esters thereof, polyoxyalkylene group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( where R ^6, R ⁷ is a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ ,
A thiocarbamyl group having the structure of
A xanthate group showing a structure of H ₃ ) ₂ CHO (CS) —, a benzothiazole group showing a structure of C ₆ H ₄ SNC—,
And at least one group selected from morpholine groups having the structure of OC ₄ H ₈ N—, wherein x represents a value exceeding 2 and up to 6, and R ⁸ may be the same R ² in R ² SxR ² . R ² may be different, y represents a numerical value of 2 or more, and n is an integer of 2 to 100. [5] A compound characterized by performing a sulfur exchange reaction between a compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and a compound represented by the general formula R ² SyR ² in the presence of sulfur. Formula R
^{2 A} method for producing a polysulfide polymer which is liquid at room temperature and represented by (SxR ¹ ) nSxR ² .

In the above general formula, R ¹ is 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 3 to 12 carbon atoms. at least one group selected from hydroxy alkylene group, R ² is C 1 -C
20 alkyl group, esters thereof, polyoxyalkylene group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( where R ^6, R ⁷ is a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ ,
A thiocarbamyl group having the structure of
A xanthate group showing a structure of H ₃ ) ₂ CHO (CS) —, a benzothiazole group showing a structure of C ₆ H ₄ SNC—,
And at least one group selected from morpholine groups having the structure of OC ₄ H ₈ N—, wherein x represents a value exceeding 2 and up to 6, and R ⁸ may be the same R ² in R ² SxR ² . May be different R ² , y is a number greater than 1,
And n is an integer representing 2 to 100. [6] A compound represented by the general formula HS (R ¹ Sy) nR ¹ SH is subjected to a sulfur exchange reaction with a compound represented by the general formula R ² SyR ² and sulfur. A method for producing a polysulfide polymer which is a liquid at ordinary temperature and represented by the general formula R ² (SxR ¹ ) nSxR ² , wherein the polysulfide polymer is subjected to a polymerization reaction with the polymer.

However, in the above general formula, R ¹ has 2 carbon atoms.
An alkylene group having 10 to 10, an oxyalkylene group having 2 to 10 carbon atoms, a polyoxyalkylene group having 2 to 20 oxygen atoms,
And at least one group selected from hydroxyalkylene groups having 3 to 12 carbon atoms, and R ² has 1 to 1 carbon atoms.
20 alkyl group, their esters, polyoxyethylene alkyl group, a benzyl group, resorcinol, hydroxyalkylene group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( provided that R ^5, R ⁶ is a methyl group, an ethyl group, butyl group, or an alkyl group C ₅ H ₁₀₎
A thiocarbamyl group having the structure of (CH ₃ ) ₂ CHO (C
S) - xanthate showing the structure of, C ₆ H ₄ SNC-
Benzothiazole showing the structure of, and OC ₄ H ₈ N-
At least one group selected from morpholine groups having the structure of x, wherein x represents a value exceeding 2 to 6 and y represents 1
And n represents an integer of 2 to 100. [7] 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 a sulfur-exchange reaction of sulfur and a polymerization reaction of the general formula R ² (SxR ¹ ) A method for producing a polysulfide polymer which is liquid at normal temperature and represented by nSxR ² .

However, in the above general formula, R ¹ is 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 3 to 12 carbon atoms. at least one group selected from hydroxy alkylene group, R ² is an alkyl group having 1 to 20 carbon atoms, esters thereof, polyoxyalkylene group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, A hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS) — (where R ⁶ and R ⁷ are methyl groups,
A thiocarbamyl group having a structure of any of an ethyl group, a butyl group, an alkyl group of C ₅ H ₁₀ and a benzyl group),
A xanthate group showing a structure of H ₃ ) ₂ CHO (CS) —, a benzothiazole group showing a structure of C ₆ H ₄ SNC—,
And at least one group selected from morpholine groups having the structure of OC ₄ H ₈ N—, wherein x represents a value exceeding 2 to 6, y represents a value greater than 1, and n represents 2
Shows an integer of ~ 100.

The most important feature of the present invention is the above [4] to
The present invention provides a novel and excellent method for producing a polysulfide represented by [7], which is suitable for use as a vulcanizing agent and a vulcanization accelerator. The point is that we have been able to provide a coalescence.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The HS (R ¹ S
y) nR ¹ SH is disclosed in US Pat.
No. 63 and compounds described in JP-A-4-363325. This polysulfide polymer usually has a sulfur bond number y of 2.

R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ is HS (R ¹
Sy) It can be easily obtained by adding an oxygen atom-containing cyclic ether compound such as ethylene oxide or propylene oxide to nR ¹ SH. It can also be easily obtained by reacting with an unsaturated group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. Glycidyl ethers such as allyl, butyl, phenyl, methyl,
It can also be obtained by adding 2-ethylhexyl, stearyl glycidyl ether and the like. In addition, Shoko 4
As described in 1-19514, it can also be obtained by reacting an aldehyde or ketone with a terminal SH of a polysulfide polymer under an amine catalyst.

R ² SyR ² is dimethyl disulfide, diphenyl disulfide, di-t-dodecyl polysulfide, di-t-nonyl polysulfide, di-t-
Butyl disulfide, resorcinol polysulfide,
Bis (3-trimethoxysilylpropyl) polysulfide, bis (3-triethoxysilylpropyl) polysulfide, bis (3-trimethoxysilyltolylene)
Polysulfide, bis (3-triethoxysilyltolylene) polysulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dibenzothiazyl disulfide, 2- (4'- Morpholine nodithio) benzothiazole, dithiodimorpholine, peroxypropylxanthogen disulfide, tetrakis (2-ethylhexyl)
Thiuram disulfide, o, o'dibenzamide diphenyl disulfide and the like.

R ² SH is a mercaptosilane such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, n-octyl mercaptan, t-nonyl mercaptan. Alkyl mercaptans such as dodecyl mercaptan, hexadodecyl mercaptan, n-octadecyl mercaptan, 2-mercaptoethanol, 2-ethylhexyl thioglycolate, octyl β-mercapsipropionate, methoxybutyl β-mercapsipropionate, 2-mercaptobenzothiazole And other mercaptans.

In the present invention, to obtain a polysulfide polymer R ² Sx (R ¹ Sx) nR ² , R ⁷ S (R ¹ S
y) When manufactured from nR ¹ SR ⁷ and R ² SyR ² , R ⁷ S
(R ¹ Sy) nR ^{1 When} produced from SR ⁷ and R ² SyR ² and sulfur, HS (R ¹ Sy) nR ¹ SH and when produced from R ² SyR ² and sulfur, HS (R ¹ Sy) nR ¹ SH and R
² For both cases of production from SH and sulfur,
The reaction can be performed under the conditions of 0 to 10% by weight of an alkali catalyst, a reaction temperature of 20 ° C. to 150 ° C., and a reaction time of 5 minutes to 30 hours. When an alkali catalyst is used, an amine catalyst, particularly triethylamine, is preferred because it has a large catalytic effect and has a relatively low boiling point, so that it can be easily removed in a subsequent step. The reaction temperature is preferably from 30 ° C. to 100 ° C., the reaction time is from 10 minutes to 5 hours, and the amount of the catalyst is more preferably from 0.01 wt% to 3 wt%. The added R ² SyR ² and / or R ² SH is a raw material polysulfide polymer R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and / or
Or ^{1 to} 100 parts by weight of HS (R ¹ Sy) nR ¹ SH
-1000 parts by weight, preferably 2-500 parts by weight. The sulfur to be added is the target polysulfide polymer R ² S
It is stoichiometrically determined by the target x of x (R ¹ Sx) nR ² .

In the polysulfide polymer R ² (SxR ¹ ) nSxR ² obtained by this production method, when R ² is an alkyl group, a polyoxyalkylene group, a hydroxyl group, a hydroxyalkyl group or a hydroxypolyoxyalkylene group, lubricating oil, cutting It can be used for extreme pressure agents such as oil. In particular, a surfactant is required for uniform dispersion without dissolving in mineral oil or water, but a stable emulsion can be formed by selecting an appropriate R ² . It can also be used as a vulcanizing agent for rubber having double bonds,
Because it is a polymer vulcanizing agent, it has no heat,
Good stress relaxation can be expected to stabilize quality and improve quality by uniform dispersion of vulcanizing agent in rubber, rubber / rubber, rubber / resin.

The rubber having a double bond includes natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber and / or its hydrogenated rubber, butyl rubber, halogenated butyl rubber, epichlorohydrid Rubber, ethylene-propylene-copolymer, ethylene-vinyl acetate copolymer,
Carboxy rubber, epoxide rubber, chloroprene rubber,
Acrylic rubber, millable urethane rubber and the like can be mentioned.
These rubbers can be used not only for a single system but also for a blend system. It does not preclude the use of a rubber having a double bond for dynamic crosslinking used as a thermoplastic elastomer. These applications include tire parts for automobiles, bicycles, trucks, buses, motorcycles, etc., various belts, various rollers, shoe materials, various hoses, seats, packing, vibration damping materials, seismic isolation materials, golf balls, wire insulation, Examples include coating materials, shock-absorbing elements, cables, gaskets, interior / exterior surface materials for automobiles, home appliances, civil engineering, and parts thereof.

The polysulfide polymer obtained by the present invention can be used not only as a vulcanizing agent for rubber itself but also as a vulcanizing agent for rubber itself by blending in the production of rubber or thermoplastic elastomer. The effect can be expected.

In the polysulfide polymer R ² (SxR ¹ ) nSxR ² obtained by this production method, R ² is R ⁵ R ⁶ N (C
S)-(where R ⁵ and R ⁶ are a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ and a benzyl group), a thiocarbamyl group, and (CH ₃ ) ₂ CHO (C
S) - xanthate showing the structure of, C ₆ H ₄ SNC-
In the case of a benzothiazole group having the structure of the formula and a morpholine group having the structure of OC ₄ H ₈ N-, not only the effect as the vulcanizing agent of the rubber having the double bond but also the effect of the vulcanization accelerator are combined. Is more advantageous because It is expected that the stabilization of the quality and the improvement of the quality by uniform dispersion of the vulcanizing agent in rubber, rubber / rubber, and rubber / resin can be expected without the bloom, and having good heat resistance and stress relaxation property. Recently, the Rubber Chemical Industry Association has been taking measures against nitrosamines, and the emergence of polymer vulcanizing agents and polymer vulcanizing accelerators is expected (Akiha:
Polymer digest, 1991.11, p21-2
The substance obtained by the method 9) can answer this.

[0023]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. [Example 1] Thiokol LP2 having a number average molecular weight of 2200
3 (manufactured by Toray Thiokol Co., Ltd., n = approximately 12), ethylene oxide was added at a 1.5-fold molar amount to the SH group, and the terminal was changed to O-terminal.
A polysulfide polymer having a number average molecular weight of 2300, which is H, was synthesized. 91 g of this polymer, 26 g of dibenzothiazyl disulfide, 33 g of powdered sulfur, 0.4 g of triethylamine, and 45 g of toluene using a solvent as a solvent.
The mixture was placed in a 00 cc volumetric flask and mixed for 1 hour at 80 ° C. in a stream of N 2, and then the solvent was removed at the same temperature for 1 hour. This product had a viscosity at 25 ° C. of 182 poise. When this product was measured by liquid chromatography, it was confirmed that the product was shifted to a lower molecular weight region than the molecular weight distribution of the terminal OH polysulfide polymer as a raw material, indicating that the product was the present material. This substance has n of about 4, and a number average molecular weight of 1280. According to Raman analysis, the disulfide bonds of the starting polysulfide polymer were tri-, tetra-, and penta-bonds in this substance, and the average rank x was 4. [Example 2] Thiokol LP2 having a number average molecular weight of 2200
3 (Toraythiol Co., Ltd., n = approximately 12) was added with 1.5 times mol of ethylene oxide based on SH groups, and the terminal was OH
Was synthesized, a polysulfide polymer having a number average molecular weight of about 2360. 92 g of this polymer, 18 g of tetramethylthiuram disulfide, 34 g of powdered sulfur, 0.8 g of triethylamine, and 45 g of toluene as a solvent
g, put into a 300 cc volumetric flask and put at 80 ° C for 3 hours.
After mixing under two streams, the solvent was removed under reduced pressure at the same temperature for an additional hour. The viscosity of the product at 25 ° C. was 158 poise. When this product was measured by liquid chromatography, it was confirmed that the product was shifted to a lower molecular weight region than the molecular weight distribution of the terminal OH polysulfide polymer as a raw material, indicating that the product was the present material. This substance has n of about 4 and a number average molecular weight of 1250. According to Raman analysis, the disulfide bonds of the starting polysulfide polymer were tri-, tetra-, and penta-bonds in this substance, and the average rank x was 4. Example 3 It was examined whether the polysulfide polymer obtained in Example 1 had the effect of a vulcanizing agent and a vulcanization accelerator for rubber having a double bond.

A rubber composition having the following composition was prepared using a two-roll mill, and the vulcanization characteristics were examined. (Curastometer Type III
(Amplitude ± 1 ゜ frequency 100 cpm) Natural rubber 94 parts The substance of Example 3 6 parts Zinc oxide 5 parts Stearic acid 2 parts The vulcanization characteristics at 150 ° C. and 170 ° C. were as follows. 150 ° C Minimum value (kgf · cm) 0.2 Maximum value (kgf · cm) 5.4 T10 (min) 3.4 T50 (min) 5.8 T90 (min) 22.6 170 ° C Minimum value (kgf · cm) cm) 0.2 Maximum value (kgf · cm) 4.5 T10 (min) 1.2 T50 (min) 1.8 T90 (min) 5.0 Vulcanization rate at 150 ° C is slightly slow, but vulcanization is accelerated This substance is sufficiently vulcanized without any chemicals or vulcanizing agents. Vulcanization at 170 ° C. is rapid and little re-vulcanization is observed. [Example 4] A test was conducted in the same manner as in Example 3, except that the amount of this substance was further reduced. As a shortage of the excipient, sulfur was added at 0.
5 parts were added.

[0025] The vulcanization characteristics at 150 ° C. and 170 ° C., together with Example 3, were as follows. 150 ° C. Case 1 Case 2 Example 3 Minimum value (kgf · cm) 0.4 0.8 0.2 Maximum value (kgf · cm) 4.6 3.4 5.4 5.4 T10 (min) 3.2 7 3.4 T50 (min) 5.8 9.0 5.8 T90 (min) 15.0 20.0 22.6 170 ° C Minimum (kgf · cm) 0.4 0.7 0.2 Maximum (kgf · cm) 4.0 2.9 4.5 T10 (min) 1.2 1.3 1.2 T50 (min) 2.0 2.2 1.8 T90 (min) 3.8 5.1 5.0 The result was almost the same as in Example 3. Example 5 It was examined whether or not the polysulfide polymer obtained in Example 2 had the effect of a vulcanizing agent and a vulcanization accelerator for a rubber having a double bond.

A rubber composition having the following composition was prepared using a two-roll mill, and the vulcanization characteristics were examined. (Curastometer Type III
(Amplitude ± 1 ゜ frequency 100 cpm) Formulation 1 Formulation 2 NBR 95 parts 98 parts The substance of Example 4 5 parts Zinc oxide 5 parts 5 parts Stearic acid 1 part 1 part Sulfur -0.5 part Heating at 160 ° C. The vulcanization properties were as follows, and the substance was sufficiently vulcanized without a vulcanization accelerator or vulcanizing agent.

Formulation 1 Formulation 2 Minimum value (kgf · cm) 0.6 0.8 Maximum value (kgf · cm) 10.0 7.0 T10 (min) 1.9 2.5 T50 (min) 3.1 3.8 T90 (min) 16.3 20.6 [Example 6] In a 300 cc volumetric flask, thiochol LP23 having a number average molecular weight of 2200 (Toray Thiokol Co., SH content 2.9 wt%, n = about 12) was placed. 88
g, powdered sulfur 33 g, dimethyl disulfide 8 g
Further, 0.4 g of triethylamine was added as a catalyst, mixed for 1 hour in a stream of N2 at 80 ° C., and 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 was completely eliminated, and the odor was almost odorless. The viscosity of the product at 25 ° C. was 118 poise, and the target polysulfide polymer was obtained. This substance has n of about 6, and a number average molecular weight of 1520. According to Raman analysis, the disulfide bonds of the starting polysulfide polymer were tri-, tetra-, and penta-bonds in this substance, and the average rank x was 4. Example 7 In a 500 cc volumetric flask, 50 thiocol LP23 (Toray Thiokol, SH content: 2.9 wt%, n = about 12) having a number average molecular weight of 2,200 was added.
g, powdered sulfur 18 g, t-dodecyl mercaptan 1
5 g, 0.2 g of triethylamine was further added as a catalyst, and 30 g of toluene was added as a solvent. After mixing for 1 hour under a stream of N2 at 80 ° C., 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 was completely eliminated, and the odor was almost odorless. The viscosity of the product at 25 ° C. was 180 poise, and the target polysulfide polymer was obtained. This substance has n of about 8 and a number average molecular weight of 2240. According to Raman analysis, the disulfide bonds of the starting polysulfide polymer were tri-, tetra-, and penta-bonds in this substance, and the average rank x was 4. Example 8 In a 300 cc volumetric flask, 46 thiochol LP23 (Toray Thiokol Co., SH content 2.9 wt%, n = about 12) having a number average molecular weight of 2200 was added 46.
g, 17 g of powdered sulfur, 13 g of dibenzothiazyl disulfide and 0.8 g of triethylamine with further catalyst.
g, 25 g of toluene as a solvent and 80 ° C. for 2 hours
After mixing under two air streams, 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 was completely eliminated, and the odor was almost odorless.
The viscosity of this product at 50 ° C. was 242 poise, and the target polysulfide polymer was obtained. This substance has n of about 7 and a number average molecular weight of 1940. According to Raman analysis, the disulfide bonds of the starting polysulfide polymer were tri-, tetra-, and penta-bonds in this substance, and the average rank x was 4.

[0028]

According to the present invention, the polysulfide polymer in which the number of sulfur bonds in the repeating unit is more than 2 and 6 or less is a vulcanizing agent for rubber having an excellent double bond by having a terminal having a specific chemical structure. , An extreme pressure agent, a vulcanizing agent / vulcanization accelerator and a binder for rubber / silica fillers.

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Claims (7)

[Claims] 1. A polysulfide polymer represented by the following general formula (1) that is liquid at normal temperature. R ² (SxR ¹ ) nSxR ² (1) wherein, in R ² (SxR ¹ ) nSxR ² , R ¹ is an alkylene group having 2 to 10 carbon atoms;
0 is an oxyalkylene group, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms, and R ² is an alkyl group having 1 to 20 carbon atoms. Group, its ester,
Polyoxyalkylene group, benzyl group, resorcinol, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS)-(where R ⁶ ,
R ⁷ is a thiocarbamyl group having a structure of a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ and a benzyl group), and a xanthate group having a structure of (CH ₃ ) ₂ CHO (CS) —. , A benzothiazole group having a structure of C ₆ H ₄ SNC— and a morpholine group having a structure of OC ₄ H ₈ N—, wherein x is a value exceeding 2 and up to 6. And n is 2-10
Indicates an integer of 0. 2. The general formula C ₆ H ₄ SNC (SxR ¹ ) nSxR ²
Or the general formula ^{R 6 R 7 N (CS)} (SxR 1) nSxR polysulfide polymer of claim 1 wherein is represented by ^2. Where R
¹ is at least CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ , CH
₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ or CH ₂ CH (O
H) A group containing one or more CH ₂ . 3. In the general formula (1), R ¹ is at least CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ or CH ₂ CH ₂
OCH ₂ CH ₂ OCH ₂ CH ₂ or CH ₂ CH (OH) CH ₂
Wherein R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, a resorcinol, a hydroxyalkyl group having 2 to 18 carbon atoms, and a hydroxypolyoxyalkyl group. The polysulfide polymer according to claim 1, wherein the polysulfide polymer is a group selected from a len group. 4. A compound represented by the general formula R ² (SxR ¹ ) nSxR ² , wherein a sulfur exchange reaction is performed between the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and the general formula R ² SyR ^2. A method for producing a polysulfide polymer which is liquid at room temperature. However, in the above general formula, R ¹ is an alkylene group having 2 to 10 carbon atoms, 2 to 10 carbon atoms.
Oxyalkylene group, a polyoxyalkylene group having 2 to 20 oxygen atoms, and at least one group selected from hydroxyalkylene groups having 3 to 12 carbon atoms, wherein R ² is an alkyl group having 1 to 20 carbon atoms, esters, polyoxyalkylene group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( where R ^6, R ⁷
Represents a thiocarbamyl group having a structure of a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ and a benzyl group), a xanthate group having a structure of (CH ₃ ) ₂ CHO (CS) —, A benzothiazole group having a structure of ₆ H ₄ SNC- and a morpholine group having a structure of OC ₄ H ₈ N-, wherein x represents a value exceeding 2 to 6; ⁸ may be the same R ² in R ² SxR ^{2 or} different R ^2
It may be 2, y represents a numerical value of 2 or more, and n is an integer representing 2 to 100. 5. A sulfur exchange reaction between a compound represented by the general formula R ⁸ S (R ¹ Sy) nR ¹ SR ⁸ and a compound represented by the general formula R ² SyR ² in the presence of sulfur. A method for producing a polysulfide polymer which is liquid at ordinary temperature and represented by the general formula R ² (SxR ¹ ) nSxR ² . However, in the above general formula, R ¹ is an alkylene group having 2 to 10 carbon atoms, 2 to 10 carbon atoms.
Oxyalkylene group, a polyoxyalkylene group having 2 to 20 oxygen atoms, and at least one group selected from hydroxyalkylene groups having 3 to 12 carbon atoms, wherein R ² is an alkyl group having 1 to 20 carbon atoms, esters, polyoxyalkylene group, a benzyl group, resorcin, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxy polyoxyalkylene ^{group, R 6 R 7 N (CS} ) - ( where R ^6, R ⁷
Represents a thiocarbamyl group having a structure of a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ and a benzyl group), a xanthate group having a structure of (CH ₃ ) ₂ CHO (CS) —, ₆ is at least one group selected from a benzothiazole group having a structure of ₆ H ₄ SNC- and a morpholine group having a structure of OC ₄ H ₈ N-; ⁸ may also R ² that is different may be the same R ² in R ² SXR ^2, y represents a numerical value of greater than 1, and n is an integer indicating the 2-100 6. 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 are subjected to a sulfur exchange reaction and a polymerization reaction. A method for producing a polysulfide polymer represented by the general formula R ² (SxR ¹ ) nSxR ² which is liquid at ordinary temperature. However, in the above general formula, R ¹ is an alkylene group having 2 to 10 carbon atoms, 2 to 10 carbon atoms.
Oxyalkylene group, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms, wherein R ² is an alkyl group having 1 to 20 carbon atoms , Its esters,
A polyoxyalkyl group, a benzyl group, a hydroxyalkylene group having 2 to 18 carbon atoms, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS) — (where R ⁵ and R ⁶ are a methyl group, an ethyl group, a butyl group, A thiocarbamyl group having the structure of (C ₅ H ₁₀ any alkyl group), (CH ₃ ) ₂ CH
A xanthate group showing the structure of O (CS)-, C ₆ H ₄ S
A benzothiazole group showing the structure of NC-, and OC ₄
At least one group selected from a morpholine group having the structure of H ₈ N—, x represents a value exceeding 2 to 6, y represents a value exceeding 1 and n is an integer of 2 to 100 Is shown. 7. 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 sulfur being subjected to a sulfur exchange reaction and a polymerization reaction. A method for producing a polysulfide polymer which is liquid at room temperature and represented by R ² (SxR ¹ ) nSxR ² . However, in the above general formula, R ¹ is an alkylene group having 2 to 10 carbon atoms, 2 to 1 carbon atoms.
0 is an oxyalkylene group, a polyoxyalkylene group having 2 to 20 oxygen atoms, and a hydroxyalkylene group having 3 to 12 carbon atoms, and R ² is an alkyl group having 1 to 20 carbon atoms. , Its esters,
Polyoxyalkylene group, benzyl group, resorcinol, hydroxyalkyl group having 2 to 18 carbon atoms, hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS)-(where R ⁶ ,
R ⁷ is a thiocarbamyl group having a structure of a methyl group, an ethyl group, a butyl group, an alkyl group of any of C ₅ H ₁₀ and a benzyl group), and a xanthate group having a structure of (CH ₃ ) ₂ CHO (CS) —. , A benzothiazole group having a structure of C ₆ H ₄ SNC— and a morpholine group having a structure of OC ₄ H ₈ N—, wherein x is a value exceeding 2 and up to 6. , Y represents a number greater than 1, and n represents an integer from 2 to 100.