WO1999060047A1

WO1999060047A1 - Polysulfide polymers and process for the preparation thereof

Info

Publication number: WO1999060047A1
Application number: PCT/JP1999/002581
Authority: WO
Inventors: Tatsuro Matsui; Kazuhisa Sakae
Original assignee: Toray Thiokol Co., Ltd.
Priority date: 1998-05-18
Filing date: 1999-05-18
Publication date: 1999-11-25
Also published as: JPH11322931A; JP3978736B2

Abstract

A process for easily preparing a polysulfide polymer which contains in the main chain repeating polysulfide units exceeding disulfide in the number of constituent sulfur atoms to therefore function as the vulcanizing agent for rubbers having double bonds and which is terminated with groups effective in accelerating the vulcanization of rubbers, e.g., benzothiazolyl or thiocarbamyl, alkyl groups effective in enhancing the compatibility with mineral oils, or other necessary chemical structures; and novel specific polysulfide polymers prepared by the process. The polysulfide polymers are ones which are represented by the general formula (1): R2(SxR1)nSxR2 and are liquid at ordinary temperatures.

Description

Specification

POLYSULFIDE POLYMER AND PROCESS FOR PRODUCING THE SAME

Technical field

The present invention relates to a polysulfide polymer which is liquid at ordinary temperature and has a mean sulfur number of repeating units of more than 2 and not more than 6 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.

The polysulfide polymer is a liquid one in which the number of sulfur bonds in the repeating unit of the polysulfide polymer is 2, or a solid at room temperature in which the molecular weight exceeds 10 000 when the number of sulfur bonds in the repeating unit is 2 or more. Things are traded commercially. Polysulfide polymers that are liquid at room temperature and have more than two sulfur bonds in the repeating units are difficult to produce and there are no industrially effective ones. According to Japanese Patent Publication No. 63-42929, Japanese Patent Application Laid-Open (JP-A) No. 63-42929 states that a polysulfide polymer which is liquid at room temperature and has a repeating unit sulfur bond number of more than 2 obtained by the reaction of sulfur chloride and dithiol is a rubber. It describes a method of using as a filler. In this method, it is necessary to use expensive dithiol as a raw material and to carry out the reaction in a large amount of anhydrous solvent, and the production cost is high industrially, which makes it difficult to use. In addition, the polysulfide polymer obtained by this method has a drawback that the terminal group is 1 SH and lacks storage stability.

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

α Ν

SCI + n [HS (CH ₂ CH ₂ 0) _x CH ₂ CH ₂ SH

. S

The method for obtaining the desired product is described in the synthesis route of the compound indicated by. You. However, this method, once one SH or - SS- a chlorine (C 1 ₂₎ - after the SC 1, a method of reacting with one SH, synthetic route takes considerable costs if the industrialization, industrialization This is a difficult method to do. Moreover, the obtained polysulfide polymer has a sulfur bond number of 2 in the repeating unit of the polysulfide polymer, and thus has an effect of a vulcanization accelerator but has no effect of a vulcanizing agent.

Disclosure of the invention

An object of the present invention is to eliminate the above-mentioned conventional drawbacks and to provide a main chain having a repetition number of sulfur bonds exceeding disulfide, so that it can function only as a rubber flowing agent having a double bond. Instead, easily synthesize a polysulfide polymer having the required chemical structure, such as an alkyl group that increases the compatibility with mineral oil, such as a benzothiazol group or a thiocarbamyl group, which has a rubber vulcanization accelerating effect. An object of the present invention is to provide a method and a novel specific polysulfide polymer which can be obtained by the method.

As a result of intensive studies by the present inventors, the above object of the present invention has been industrially and conveniently achieved by the present invention described below.

[1] A polysulfide polymer represented by the following general formula (1) and being liquid at normal temperature.

R ² (S xR ¹ ) n S xR ² (1) However, in the general formula (1) R ² (S xR ¹ ) n S xR ² ,

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 a hydroxyalkylene group having 3 to 12 carbon atoms. At least one group selected,

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, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS ) — (Where R ⁶ and R ⁷ are methyl, ethyl, butyl, or any alkyl or benzyl group of C ₅ H.) thiocarbamyl, (CH ₃ ) ₂ CH〇 ( At least one group selected from the group consisting of a xanthate group showing a structure of CS), a benzothiazole group showing a structure of C ₆ H ₄ SNC—, and a morpholine group showing a structure of OC ₄ H ₈ N—,

X indicates a value from 2 to 6; and n represents an integer of 2 to 100.

[2] The above-mentioned [1] represented by the general formula C ₆ H ₄ SNC (S xR ¹ ) n S x R ² or the general formula R ⁶ R ⁷ N (CS) (S xR ¹ ) n S xR ² Polysulfide polymer. Where R ¹ is a group containing at least one CH ₂ CH ₂ 〇CH ₂ 〇CH ₂ CH ₂ , CH ₂ CH ₂ 〇CH ₂ CH ₂ 〇CH ₂ CH ₂ , or CH ₂ CH (OH) CH ₂ is there.

[3] In the above general formula (1), R ¹ is at least CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH ₂ or CH ₂ CH ₂ 〇CH 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 hydroxypolyoxy group. The polysulfide polymer according to the above [1], which is a group selected from an allene group.

[4] A general formula R ² (S xR ¹ ) n S xR ² characterized by performing a sulfur exchange reaction between the general formula R ⁸ S (R'S y) nR'SR ⁸ and the general formula R ² S yR ² A method for producing a polysulfide polymer which is liquid at normal temperature.

However, in the above general formula,

R ′ is 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 At least one group,

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, a resorsi 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, ethyl, butyl, CsH !, any alkyl group or benzyl group), thiol bamyl group, (CH ₃ ) ₂ CH〇 (CS) At least one group selected from a xanthate group having a structure of —, a benzothiazol group having a structure of C 6 H 4 SNC—, and a morpholine group having a structure of OC ₄ H ₈ N—

X indicates a value between 2 and 6,

R ⁸ is R ² S may be the same R ² in the xR ² well even different R ^2,

y is a number greater than or equal to 2, and

n is an integer representing 2 to 100. [5] a compound represented by the general formula R ⁸ S (R'S y) nR'SR ⁸ and a compound represented by the general formula R ² S.yR ² are subjected to a sulfur exchange reaction in the presence of sulfur A method for producing a polysulfide polymer which is a liquid at room temperature and represented by the general formula R ² (S xR ¹ ) SXR ² .

However, in the above general formula,

R ′ 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 a hydroxyalkylene group having 3 to 12 carbon atoms. At least one group selected,

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, resorcinol, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxy polyoxyalkylene group, R ⁶ R ⁷ N (CS) -(However, R ⁶ and R ⁷ are methyl, ethyl, butyl, CsH !. any alkyl group or benzyl group), a rubamyl group, (CH ₃ ) ₂ CHO ( At least one group selected from the group consisting of a xanthogenic acid group having the structure of (CS) —, a benzothiazole group having the structure of C ₆ H ₄ S NC—, and a morpholine group having the structure of OC ₄ H ₈ N—. ,

X indicates a value between 2 and 6,

R ⁸ ttR ² S may be the same R ² in the xR ² well even different R ^2,

y indicates a number greater than 1, and

n is an integer representing 2 to 100

[6] — characterized by a sulfur exchange reaction and a polymerization reaction between a compound represented by the general formula HS (R'S y) nR 'SH and a compound represented by the general formula R ² S yR ² and sulfur A method for producing a polysulfide polymer represented by the general formula R ² (SXR ′) n SXR ² that is liquid at normal temperature.

However, in the above general formula,

R ¹ is 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. At least one group

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkyl group, a benzyl group, a hydroxyalkylene group having 2 to 18 carbon atoms, hydroxypolyoxy Alkylene group, R ⁶ R ⁷ N (CS)-(where R ^fi and R ⁷ are any alkyl groups of methyl group, ethyl group, butyl group and CsH), thiocarbamyl group showing the structure of (CH ₃ ) ₂ CHO (CS) At least one selected from a xanthate group showing a single structure, a benzothiazole group showing a C ₆ H ₄ SNC— structure, and a morpholine group showing a 〇C ₄ H ₈ N— structure Group,

X indicates a value between 2 and 6,

y indicates a number greater than 1,

n represents an integer of 2 to L00.

[7] A compound represented by the general formula HS (R'S y) n R ¹ SH, a compound represented by the general formula R ² SH and a general formula R characterized by a sulfur exchange reaction and a polymerization reaction of sulfur. ² (S xR ¹ ) n SXR ²

A method for producing a rufide polymer.

However, in the above general formula,

R ¹ is 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 At least one group,

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, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS )-(Where R ^s and R ⁷ are methyl, ethyl, butyl, CsH, any of alkyl or benzyl) thiocarbamyl, (CH ₃ ) ₂ CHO (CS) — At least one group selected from a xanthate group showing a structure, a benzothiazole group showing a structure of C ₆ H ₄ SNC—, and a morpholine group showing a structure of 〇C ₄ H ₈ N—,

X indicates a value between 2 and 6,

y indicates a number greater than 1, and

n represents an integer of 2 to 100.

The most important feature of the present invention is to provide a novel and excellent method for producing polysulfide represented by the above-mentioned [4] to [7], which is suitable as a vulcanizing agent and a vulcanization accelerator. The polysulfide polymer shown in [1] to [3] above is provided. It is in the point that we can offer.

BEST MODE FOR CARRYING OUT THE INVENTION

The polysulfide polymer represented by the general formula HS (R ¹ Sy) nR′SH used in the present invention is described in US Pat.No. 2,669,633 of Nodrick et al. And Japanese Patent Application Laid-Open No. 4-363325. Selected from such compounds. In this polysulfide polymer, the number of sulfur bonds y is usually two.

Further, the polysulfide polymer represented by the general formula R ₈ S (R ¹ S y) nR'S R ₈ is obtained by adding an oxygen atom such as ethylene oxide or propylene oxide to the compound represented by the general formula HS (R'S y) nR 'SH. It is easily obtained by adding a cyclic ether compound. Further, by reacting a compound represented by the general formula HS (R'Sy) n R ¹ SH with an unsaturated group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. Can also be easily obtained. It can also be obtained by adding a glycidyl ether such as aryl, butyl, phenyl, methyl, 2-ethylhexyl, stearyl glycidyl ether, etc. to a polysulfide polymer having a terminal SH group. . Further, as described in JP-B-41-19514, it can be obtained by reacting an aldehyde or ketone with a terminal SH of a polysulfide polymer in the presence of an amine catalyst.

Examples of the compound represented by the formula R ² S y R ² include dimethyl disulfide, diphenyl disulfide, di-t-dodecyl polysulfide, di-t-nonyl polysulfide, di-t-butyl disulfide, resorcinol polysulfide, and bis (3-trimethoxysilylpropyl) polysulfide, bis (3-triethoxysilylpropyl) polysulfide, bis (3-trimethoxysilyltolylene) polysulfide, bis (3-triethoxysilyltolylene) polysulfide

Fido, dibenzothiazyl disulfide, 2- (4 'morpholine nodithio) benzothiazol, dithiodimorpholine, peroxypropyl xanthogen disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, o, o' And dibenzamido diphenyl disulfide. Examples of the compound represented by the formula R ² SH include mercaptosilanes such as amercaptopropyltrimethoxysilane and amercaptopropyltriethoxysilane, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, and n Alkyl mercaptans such as octyl mercaptan, t-noyl mercaptan, dodecyl mercaptan, hexadodecyl mercaptan, noctadecyl mercaptan, 2-mercaptoethanol, 2-ethylhexyl thioglycolate, 3-mercapsipropion And mercaptans such as octyl acid, methoxybutyl monomercapsipropionate, and 2-mercaptobenzothiazole.

In the present invention, in order to obtain a polysulfide polymer R ² SX (R ¹ S x) nR ² , when R ⁷ S (R ¹ S y) nR ¹ SR ⁷ and R ² S y R ² ⁷ S (R ¹ S y) nR'S Alkaline for both R ⁷ and R ² S yR ² and sulfur or HS (R'S y) n R ¹ SH and R ² SH and sulfur The catalyst can be carried out at 0 to 10 wt%, 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 preferable 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 to 100 ° (:, the reaction time is from 10 minutes to 5 hours, and the amount of the catalyst is more preferably from 0.0 lwt% to 3 wt%. R ² S y R ² to be added And Z or R ² SH are preferably from 1 to 10 parts by weight of the raw material polysulfide polymer R ⁸ S (R'S y) n R ¹ SR ⁸ and / or HS (R 'S y) n R' SH 100 parts by weight. 100 parts by weight, more preferably 2 to 500 parts by weight The added sulfur is stoichiometric depending on the target x of the target polysulfide polymer R ² SX (R ′ S x) nR ^2. Can be decided.

Porisarufai de polymer ^{^{R 2 (S xR 1) n}} S xR 2 obtained by the production method of the present invention, R ² is an alkyl group, polyoxyalkylene group, a hydroxyl group, a hydroxyalkyl group, if the hydroxy polyoxyalkylene group, It can be particularly suitably used for extreme pressure agents such as lubricating oil and cutting oil. In particular, in the case of dispersing uniformly in a mineral oil or water system without dissolving, a surfactant is usually required, but a stable emulsion can be formed by selecting an appropriate. Further, the polysulfide polymer obtained by the production method of the present invention can also be used as a vulcanizing agent for rubber having a double bond, and is a polymer vulcanizing agent. It has good heat resistance and good stress relaxation, and can be expected to stabilize quality and improve quality by uniform dispersion of vulcanizing agent in rubber, rubber / rubber, and rubber Z resin.

Here, rubbers having a double bond include natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber and / or its hydrogenated rubber, butyl rubber, halogenated butyl rubber, epichlorohydrin rubber, ethylene —Propylene-copolymer, ethylene-vinyl acetate copolymer, carboxy rubber, epoxide rubber, chloroprene rubber, acrylic rubber, millable urethane rubber and the like. These rubbers can be used not only for a single system but also for a blend system. Further, the use of the polysulfide polymer of the present invention in rubber having a double bond for dynamic crosslinking used as a thermoplastic elastomer does not preclude its use. 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 , Electric wire insulation • coating materials, cushioning elements, cables, gaskets, automobiles, home appliances, civil and architectural interior and exterior exterior materials and their parts.

The polysulfide polymer obtained in the present invention can be expected not only as a vulcanizing agent for the rubber itself by being compounded when producing a rubber or a thermoplastic elastomer, but also as an adhesive between glass and rubber, or between a glass and a thermoplastic elastomer. The effect can be expected. Porisarufai de polymer R ² (S xR ¹⁾ Oite to n S xR ² obtained by the production method of the present invention, R ² ^{^{is, R 5 R 6 N (CS}} ) - ( where, R ^5, R ⁶ is methyl A thiocarbamyl group having the structure of any of the following groups: an alkyl group, a benzyl group, an ethyl group, a butyl group, and a C ₅ H group; a xanthate group having a structure of (CH ₃ ) ₂ CHO (CS) — In the case of a benzothiazole group showing the structure of C ₆ H ₄ S NC— and a morpholine group showing the structure of 〇C ₄ H ₈ N—, not only the effect as a vulcanizing agent for rubber having a double bond but also vulcanization This is more advantageous because the effect of the accelerator can be combined. By using the polysulfide polymer obtained by the production method of the present invention, it is free of bloom, has good heat resistance and stress relaxation properties, and is obtained by uniform dispersion of a vulcanizing agent in rubber, rubber / rubber, and rubber Z resin. Can be expected to stabilize and improve quality. In recent years, the Japan 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, 1999.11.11) , P21-29), the polysulfide polymer obtained by the present invention can meet this problem.

Example

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[Example 1]

Thiokol LP 23 with a number average molecular weight of 2200 (Structural formula: HS— (CH ₂ CH ₂ 〇CH ₂ OCH ₂ CH ₂ -S ₂ ) ₁₂ — CH ₂ CH ₂ 〇CH ₂ 〇CH ₂ CH ₂ — SH) (Toraychi N = about 12), a 1.5-fold mole of ethylene oxide added to the SH group to synthesize a polysulfide polymer with a number-average molecular weight of 2300 and OH-terminated. . 91 g of this polymer, 26 g of dibenzothiazyl disulfide, 33 g of powdered sulfur, 0.4 g of tritylamine, and 45 g of toluene as a solvent were put into a 300 cc three-necked flask and charged at 80 ° for 1 hour. After mixing under a nitrogen stream, the solvent was removed under reduced pressure at the same temperature for an additional hour. The viscosity of the product at 25 ° C. was 182 boise. When this product was measured by liquid chromatography, it was found 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, and the target substance (polysulfide polymer, structural formula: H ◦— CH ₂ CH ₂ —S— (CH ₂ CH ₂ 〇CH ₂ 〇CH ₂ CH ₂ —SX) ₄ — CH ₂ CH ₂ OCH2OCH2CH2-S-CH2CH2-OH) This substance had n of about 4 and a number average molecular weight of 1,280. According to Raman analysis, the disulfide bonding force of the starting polysulfide polymer was found to be tri-, tetra-, and pen-bonded with this substance, and the average rank X was 4.

[Example 2]

A 1.5-fold molar addition of ethylene oxide to SH groups to Thocol LP 23 (Toray Reticor Corp., n = about 12) with a number-average molecular weight of 2200 to give a polyhydric polymer having a number-average molecular weight of about 2360 with OH at the end. Sulfide volima was synthesized. This poly 92 g of the polymer, 18 g of tetramethylthiuram disulfide, 34 g of powdered sulfur, 0.8 g of trieuramine, and 45 g of toluene as a solvent were put into a 300 cc three-necked flask for 3 hours. ^D C under a nitrogen gas stream after mixing, under reduced pressure solvent removal further 1 hour at the same temperature. The viscosity of the product at 25 ° C. was 158 boise. When this product was measured by liquid chromatography, it was found 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, and the target substance (polysulfide polymer, Formula: HO—CH ₂ CH ₂ —S— (CH ₂ CH ₂ OCH ₂ OCH ₂ CH2-S) _4— CH ₂ CH ₂ OCH ₂ CH ₂ -S x-(CS) N (CH ₃ ) ₂ ) I was able to confirm that. This substance had 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 pen-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.

Using two rolls, a rubber composition having the following composition was prepared and the vulcanization characteristics were examined. (Kyulastometer type III amplitude ± frequency 100 cpm)

94 parts of natural rubber

6 parts of the substance of Example 1

Zinc oxide 5 parts

Stearic acid 2 parts

The vulcanization characteristics at 150 ° C and 170 ° C were as follows, respectively.

(1 50 ° C)

Minimum value (k g f c m) 0 2

Maximum value (kg gcm) 5 4

T 1 0 (min) 3 4

T50 (min) 5 8

T 90 (min) 22 6

(170 ° C) Minimum value (kgf · cm) 0.2

Maximum value (kgfcm) 4.5

T 1 0 (min) 1.

T 5 0 (min) 1.8

T 9 0 (min) 5.0

From the above results, although the vulcanization rate at 150 ° C is somewhat slow, the vulcanization was sufficiently performed with the poly → nal sulfide polymer obtained in the present invention even without the vulcanization accelerator and vulcanizing agent. You can see this. In addition, vulcanization at 170 ° C is rapid and almost no reversion is observed.

[Example 4]

The test was conducted in the same manner as in Example 3 except that the amount of the polysulfide polymer of the present invention was reduced. 0.5 part of sulfur was added as a shortage of the vulcanizing agent.

Case 1 Case 2

Natural rubber 97 parts 9 9 parts

The substance of Example 1 3 parts 1 part

Zinc oxide 5 parts 5 parts

Stearic acid 2 parts 2 parts

Sulfur 0.5 part 0.5 part

The vulcanization characteristics at 150 ° C and 170 ° C were as follows. The results of Example 3 are also shown.

(150 ° C) Case 1 Case 2 Example:

Minimum value (kgf • cm) 0.40., 80.2 Maximum value (kgf • cm) 4.6.3, 45.4

T 1 0 (min) 3. 2 3., 7 3. 4

T 50 (min) 5. 8 9., 0 5.8

T 9 0 (min) 1 5.0 0 2 .. 0 22.6

(170 ° C)

Minimum value (kgf • cm) 0.4 0 · 7 0.2 Maximum value (kgf • cm) 4.0 2. 9 4.5 T 10 (min) 1. 2 1. 3 1. 2

Τ 50 (min) 2. 0 2. 2 1. 8

Τ 90 (min) 3.85.15.0 The result was almost the same as that of Example 3.

[Example 5]

It was examined whether the polysulfide polymer obtained in Example 2 had the effect of a vulcanizing agent and a vulcanization accelerator for a rubber having a heavy bond.

A rubber composition having the following composition was prepared at one outlet, and the vulcanization characteristics were examined (Curastome Ichiichi Type III Amplitude ± 1 ° Frequency 100 cpm)

Formula 1 Formula 2

NB R 95 copies 98 copies

5 parts of the substance of Example 2 2 parts

Zinc oxide 5 parts 5 parts

Stearic acid 1 part 1 part

0.5 parts of sulfur

The vulcanization characteristics at 160 ° C. are as follows, and the polysulfide polymer of the present invention was sufficiently vulcanized even without a vulcanization accelerator or a vulcanizing agent.

Formula 1 Formula 2

Minimum value (kgf.cm) 0.6 0.8

Maximum value (kgf · cm) 1 0.0 7.0

T 10 (min) 1. 9 2. 5

T 50 (min) 3.1 3.8

T 90 (min) 1 6. 3 20.6

[Example 6]

In a 300 cc three-necked flask, 88 g of Thiokol LP 23 with a number average molecular weight of 2200 (Toray Reticor Co., Ltd., SH content 2.9 wt%, n = about 12), 33 g of powdered sulfuric acid, 33 g of dimethyl disulphide 8 g and 0.4 g of triethylamine as a catalyst were added, mixed for 1 hour under a nitrogen stream at 80 ° C., and further 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 complete. It had completely disappeared and the odor was almost odorless. This product has a viscosity at 118 ° C. of 18 boise at 25 ° C. and is a desired polysulfide polymer (structural formula: CH ₃ — SX— (CH2CH2OCH2OCH2CH2-SX) ₆ — CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH ₂ — S x — CH ₃ ) was obtained. This substance had n of about 6 and a number average molecular weight of 1520. According to the Raman analysis, the disulfide bonds of the raw polysulfide polymer were converted into tri-, tetra-, and pen-bonds with this substance, and the average rank X was 4.

[Example 7]

In a 500 cc three-necked flask, 50 g of Thiokol LP 23 with a number average molecular weight of 2200 (Toray Reticor Co., Ltd., SH content 2.9 wt%, n = about 12), 50 g of powdered sulfur, 18 g of powdered sulfur, Then, 15 g of toluene, 0.2 g of triethylamine as a catalyst and 30 g of toluene as a solvent were added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour, 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 was completely eliminated, and the odor was almost odorless. The viscosity of this product at 25 ° C is 180 boise, and the desired polysulfide polymer (structural formula: C ₁₂ H ₂₅ — S x— (CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH 2-S x) ₈ — CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH ₂ —S x—C ₁₂ H ₂₅ ) was obtained. This substance had n of about 8 and a number average molecular weight of 2240. According to Raman analysis, the disulfide bond of the raw material polysulfide polymer was changed to tri-, tetra-, and cyanine bonds in this substance, and the average rank X was 4.

[Example 8]

In a 300 cc three-necked flask, 46 g of Thiokol LP 23 with a number average molecular weight of 2200 (Toray Reticor Co., Ltd., SH content 2.9 wt%, n = about 12), 46 g of powdered sulfur, 17 g of dibenzothiazyldis 13 g of sulfide, 0.8 g of triethylamine as a catalyst, and 25 g of toluene as a solvent were added, and the mixture was mixed for 2 hours under a nitrogen stream at 80 ° C., and further degassed under reduced pressure at the same temperature for 1 hour. When the obtained product was measured by IR infrared absorption light, it was found that the SH absorption had completely disappeared and the odor was almost odorless. The viscosity of this product at 50 ° C is 242 boises, and the desired polysulfide polymer (structural formula: C ₆ H ₄ SNC_S x— (CH ₂ CH ₂ 〇CH ₂ 〇C H 2 CH 2 -S) ₇ -CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ -S x— CNS C ₆ H ₄ ) Force S This substance has n of about 7 and a number average molecular weight of 1940. According to Raman analysis, the disulphide bond of the starting polysulphide polymer was tri-, tetra-, and pen-bonded with this substance, and the average rank X was 4.

[Example 9]

In a 50-Occ three-necked flask, Tiocol LP 56 with a number average molecular weight of 2900 (Structural formula: HS— (CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH ₂ —S ₂ ), ₆ -CH ₂ CH ₂ CH ₂ O CH2CH2 -SH) (manufactured by Toray Recoal Co., SH content 2.3 wt%, n = about 16) 125 g, powdered sulfur 51 g, t-decyl mercaptan 11.8 g, and triethylamine as catalyst After charging 0.6 g and toluene 40 g as a solvent, the mixture was stirred in a nitrogen stream at 80 ° C for 5 hours, and then the solvent was removed under reduced pressure at 80 ° C. When the obtained product was measured by FT-IR, the absorption of the SH group completely disappeared, the odor became almost odorless, and a sulfide polymer having a t-dodecyl group at the terminal (structural formula: C ₁₂ H ₂₅ — SX— (CH ₂ CH ₂ 〇CH ₂ OCH ₂ CH ₂ —SX) ₂₄ — CH ₂ CH ₂ OCH ₂ 〇CH ₂ CH ₂ —S x— C ₁₂ H ₂₅ ) was obtained. The viscosity of the product is 2600 e. Isno is 23 ° C, 1 is about 24, and the number average molecular weight is 6,500. From the Raman analysis, the disulfide bond of the starting polysulfide polymer was a tri-, tetra-, and pen-bond in this substance, and the average rank X was 4.

Industrial applicability

The polysulfide polymer in which the number of sulfur bonds in the repeating unit of the present invention is more than 2 and not more than 6 is a rubber vulcanizing agent having an excellent double bond, It serves as a binder for the pressure agent, vulcanizing agent and vulcanization accelerator and rubber / silica filler. The polysulfide polymer obtained by the production method of the present invention can also be used as a vulcanizing agent for a rubber having a double bond. It has good stress relaxation and can be expected to stabilize quality and improve quality by uniform dispersion of vulcanizing agent in rubber, rubber / rubber, and rubber / resin. Further, polysulfide polymer ^{^{R 2 (S xR 1) n}} S xR 2 of the present invention, R ² Gaa alkyl group, polyoxyalkylene group, a hydroxyl group, a hydroxyalkyl group, if the hydroxy polyoxyalkylenated groups, the lubricant Particularly suitable for extreme pressure agents such as cutting oil. Can be used.

Further, the polysulfide polymer of the present invention can also be used for 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 mouthpieces, shoe materials, various hoses, seats, packing, vibration damping materials, seismic isolation materials. , Golf balls, electric wire insulation and coating materials, cushioning elements, cables, gaskets, interior and exterior surfaces for automobiles, home appliances, civil engineering construction, and parts thereof.

Claims

The scope of the claims

1. A polysulfide polymer represented by the following general formula (1) that is liquid at normal temperature.

R ² (SXR ') n S xR ² (1) However, in general formula (1) R ² (SX R') n S xR ²

R ¹ represents 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. At least one group selected,

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, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS ) — (Provided that R ⁶ and R ⁷ are methyl, ethyl, butyl, CsH, any alkyl group or benzyl group) thiocarbamyl group, (CH ₃ ) ₂ CHO (CS) At least one group selected from a xanthate group having the structure of, a benzothiazole group having a structure of C ₆ H ₄ SNC—, and a morpholine group having a structure of 〇 C ₄ H ₈ N—,

X indicates a value from 2 to 6; and

n represents an integer from 2 to: L00.

2. The polysulfide polymer according to claim 1, which is represented by the general formula C ₆ H ₄ SNC (SXR ⁾ ) n SX or the general formula R ⁶ R ⁷ N (CS) (S x R ¹ ) n S x R ^2. .

Here, R ¹ is a group containing at least one or more CH ₂ CH ₂ 〇CH ₂ 〇CH ₂ CH ₂ , CH ₂ CH ₂ 〇CH ₂ CH ₂ OCH CH ₂ , or CH ₂ CH (OH) CH ₂ .

3. In the above general formula (1), R ¹ represents at least CH ₂ CH ₂ 〇CH ₂ OCH ₂ CH ₂ or CH ₂ CH ₂ OCH ₂ CH ₂ 〇CH ₂ CH ₂ or CH ₂ CH (OH) CH ₂ 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 hydroxypolyoxy group. The polysulfide polymer according to claim 1, wherein the polysulfide polymer is a group selected from an allene group.

4. Room temperature represented by the general formula R ² (S xR ¹ ) n S xR ² , which is characterized by performing a sulfur exchange reaction between the general formula R ⁸ S (R'S y) nR'SR ⁸ and the general formula R ² Sy The method for producing a polysulfide polymer which is a liquid at room temperature. However, in the above general formula,

R ¹ is 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. At least one group,

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, resorcinol, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS ) — (However, R 6 and R ⁷ are methyl, ethyl, butyl, or any alkyl or benzyl group of CsH i), and the structure is (CH ₃ ) ₂ CHO (CS At least one group selected from a xanthate group having a structure of —, a benzothiazole group having a structure of C 6H4SNC—, and a morpholine group having a structure of OC ₄ H ₈ N—

X indicates a value between 2 and 6,

R ^ R ² S xR ² may be the same R ² or different R ² ,

y is a number greater than or equal to 2, and

n is an integer indicating 2 to: L00.

5. General formula R characterized by subjecting a compound represented by the general formula R ⁸ S (R'S y) nR'SR ⁸ to a compound represented by the general formula R ² SyR ² to undergo a sulfur exchange reaction in the presence of sulfur ² (SXR ¹ ) n A method for producing a liquid polysulfide polymer represented by SXR ² at room temperature.

However, in the above general formula,

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkylene group, a benzyl group, resorcinol, a hydroxyalkyl group having 2 to 18 carbon atoms, a hydroxy polyoxyalkylene group, R ⁶ R ⁷ N (CS) - (wherein R ^6, R ⁷ is a methyl group, E Ji group, butyl group, C ₅ H ₁ or an alkyl group _U, a benzyl group) Chi Sairyoku Rubamiru group showing the structure of a, (CH ₃₎ ₂ The xanthate group showing the structure of CHO (CS) —, the benzothiazole group showing the structure of C ₆ H ₄ S NC—, and the structure of 〇C ₄ H ₈ N— At least one group selected from the morpholine groups shown,

X indicates a value exceeding 2 up to 6,

R ⁸ is R ² S may be the same R ² in the xR ² well even different R ^2,

y indicates a number greater than 1, and

n is an integer representing 2 to 100

6. The compound represented by the general formula HS (I ^ S y) n R ¹ SH is characterized by the sulfur exchange reaction and the polymerization reaction of the compound represented by the general formula R ² S yR ² and sulfur. A method for producing a polysulfide polymer which is a liquid at room temperature and represented by the general formula R ² (S xR ¹ ) n S xR ² .

However, in the above general formula,

R ² is an alkyl group having 1 to 20 carbon atoms, an ester thereof, a polyoxyalkyl group, a benzyl group, a hydroxyalkylene group having 2 to 18 carbon atoms, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS) — (However, R ⁶ and R ⁷ are alkyl groups of any of methyl group, ethyl group, butyl group and C ₅ H !.) The structure of thiocarbamyl group and (CH ₃ ) ₂ CHO (CS) — At least one group selected from the group consisting of a xanthate group shown in the following, a benzothiazole group showing the structure of C ₆ H ₄ SNC—, and a morpholine group showing the structure of OC ₄ H _s N—

X indicates a value between 2 and 6,

y indicates a number greater than 1, and

n represents an integer of 2 to L00.

7. A general formula characterized by a sulfur exchange reaction and a polymerization reaction of a compound represented by the general formula HS (R ¹ Sy) n R ¹ SH, a compound represented by the general formula R ² SH and sulfur. R ² (S xR ¹ ) n SXR ²

A method for producing a rufide polymer.

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 at least one group selected from a hydroxyalkylene group having 3 to 12 carbon atoms,

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, a hydroxypolyoxyalkylene group, R ⁶ R ⁷ N (CS ) — (Provided that R ⁶ and R ⁷ are methyl, ethyl, butyl, or an alkyl or benzyl group of C ₅ H !.), thiocarbamyl, (CH ₃ ) ₂ CHO (CS At least one group selected from a xanthate group having a structure of —, 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—,

X indicates a value between 2 and 6,

y indicates a number greater than 1, and

n represents an integer of 2 to 100.