KR20060017075A - Hybrid vulcanizing agent and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a hybrid rubber vulcanizing agent and a manufacturing method thereof.

Rubber based on 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane produced by the reaction of sodium dibenzyldithiocarbamate and 1,6-bis (sodiumthiosulfato) hexane By preparing the vulcanizing agent,

While conventional conventional or semi-eves maintain good mechanical properties in the vulcanization system, the low heat aging resistance and degradability, which are disadvantages of the system, can be significantly increased.

Hybrid vulcanizing agent, 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane, heat aging resistance, vulcanizing agent, lower version.

Description

Hybrid rubber vulcanizing agent and its manufacturing method {Hybrid vulcanizing agent and manufacturing method

The present invention relates to a hybrid rubber vulcanizing agent that can improve the heat aging characteristics and reversion characteristics of various rubber products manufactured using natural rubber and synthetic rubber, and more particularly, The present invention relates to a rubber vulcanizing agent mainly containing 1,6-bis (N, N-dibenzylthiocarbamoyldithiohexane) and a method for producing the same.

The vulcanizing agents used in the manufacture of tires and other rubber products include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S) and colloidal sulfur, TMTD (tetramethylthiuram disulfide), It is classified into organic vulcanizing agents such as tetraethyltriuramdisulfide (TETD) and dithiodimorpholine (dithiodimorpholine). In the manufacture of actual rubber products using these vulcanizing agents, vulcanization accelerators are used together to improve the quality and productivity of rubber molded products.

Currently used vulcanization accelerators include sulfenamide vulcanization accelerators, dithiocarbamate vulcanization accelerators, guanidine vulcanization accelerators, thiouurea vulcanization accelerators, thiazole compounds Vulcanization accelerators and the like.

The vulcanization systems are generally classified into three types according to the mixing ratio of sulfur and vulcanization accelerators, which are conventional systems (CV) having a mixing ratio of sulfur and vulcanization accelerators of at least 2: 1, and semi-eves having a mixing ratio of 1: 1. semi-EV) systems, EV systems where the content of vulcanization accelerators is greater than that of sulfur.

The characteristics of molded rubber products vary greatly according to each vulcanization system. Conventional and semi-eve systems have improved mechanical properties such as tensile strength and repulsion, while deteriorating heat aging and degradation. .

This is due to the difference in the number of sulfur (S) bonded between the rubber molecules, when using a lot of sulfur (S), the mechanical properties of the molded rubber product is improved as the crosslinking density increases, while a large amount of sulfur (S) ) The use of polysulfide (Sx: x = 3 ~ 4 or more) bonds with low dissociation energy is also generated due to the use.

On the other hand, there is also a process to vulcanize at a high temperature for a long time in order to obtain a high crosslinking density while using less sulfur, but not only the productivity is lowered but also the risk of scorch generation is not applied.

SUMMARY OF THE INVENTION The present invention has been made in view of such a conventional problem, and while the conventional or semi-vehicle maintains good mechanical properties in the vulcanization system, it fundamentally solves the problems of low heat aging and deversionability which are disadvantages of the system. It is an object of the present invention to provide a rubber vulcanizing agent and a method for producing the same.

The hybrid rubber vulcanizing agent of the present invention for achieving the above object, 1,6-bis (which can form a rubber intermolecular hybrid (hybrid) type crosslinked structure (Rubber-Sx- (CH) y-Sx-Rubber) It is characterized by having N, N-dibenzylthiocarbamoyldithio) hexane as a main component.

The molecular structure of the 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane as the main component of the rubber vulcanizing agent according to the present invention is as follows.

Hereinafter, the rubber vulcanizing agent of the embodiment of the present invention and a manufacturing method thereof will be described in detail.

The 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane constituting the main component of the rubber vulcanizing agent according to the present invention is sodium dibenzyl represented by the following Chemical Formula 1 and Chemical Formula 2, respectively. Dithiocarbamate (sodiumdibenzyl dithiocarbamate) and 1,6-bis (sodiumthiosulfato) hexane is made by reacting at a molar ratio of 1 mole: 0.1 to 10 moles.

(Formula 1)

Sodiumdibenzyldithiocarbamate

(Formula 2)

1,6-bis (sodiumthiosulfato) hexane

In the reaction of the two components (Formula 1) and (Formula 2), the reaction temperature is 10 ℃ to 200 ℃, the reaction catalyst is used sulfuric acid, nitric acid, acetic acid, hydrochloric acid, oxalic acid and the like.

In addition, acetaldehyde, formaldehyde and the like can be used as a reaction stabilizer, and additives such as fatty acids and oils may be used to supplement the physical properties.

In order to separate the salt which arises in reaction from a product, organic solvents, such as toluene and methylene chloride, are used.

A rubber vulcanizing agent according to an embodiment of the present invention containing the sodium dibenzyldithiocarbamate of the formula (1) and 1,6-bis (sodiumthiosulfato) hexane of the formula (2) according to the following process sequence Then, the physical properties were tested and confirmed.

(Process order)

1) 354 g of 1,6-bis (sodiumthiosulfato) hexane is added to a reactor, and 1000 g of water is injected to melt.

2) 300 g of sodium dibenzyldithiocarbamate is added, and 25 g of 37% -formalin and 65 g of 10% -hydrochloric acid are added.

3) The temperature is raised to 75 ° C., and then stirred / maintained for 2 hours.

4) After cooling to room temperature, 500 g of toluene was added and the layers were separated.

5) The layer separated solution is degassed to 135 ° C and taken out in a high viscosity liquid phase.

The results of testing the effect of the rubber vulcanizing agent of the present invention prepared by the above process sequence are shown in Table 1 below.

According to Table 1, the rubber molded products in the case of using only the conventional rubber vulcanizing agent and the case in which the rubber vulcanizing agent of the present invention is added are divided into Comparative Examples and Examples, and the respective physical property values are compared with each other.

In the Table 1, the rubber vulcanizing agent according to the present invention was referred to as "composite".

 Table 1Effect Test Result Table of Rubber Vulcanizer

As shown in Table 1, the rubber vulcanizing agent of the present invention, which contains 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane as a main component, has a mechanical strength such as tensile strength in molded rubber products. While maintaining the physical properties in a normal state in a good state, it brings about a significant increase in heat aging resistance and degradation.

In other words, according to the present invention, even in the conventional conventional or semi-vulcanized system using a large amount of sulfur (S) for the purpose of increasing the crosslinking density and securing good mechanical properties, heat resistance, which has been a disadvantage or problem of the system, A very large effect can be obtained that completely solves the problem of deterioration of aging and degradability.

Claims (4)

A hybrid rubber vulcanizing agent comprising sodium dibenzyldithiocarbamate and 1,6-bis (sodiumthiosulfato) hexane represented by the following formulas (1) and (2), respectively. (Formula 1)

(Formula 2)

The hybrid rubber vulcanizing agent according to claim 1, wherein the composition ratio of sodium dibenzyldithiocarbamate and 1,6-bis (sodiumthiosulfato) hexane is 1 mol: 0.1 to 10 mol. A hybrid rubber comprising a step of reacting sodium dibenzyldithiocarbamate and 1,6-bis (sodiumthiosulfato) hexane represented by the following Chemical Formula 1 and Chemical Formula 2, respectively Vulcanizing agent manufacturing method. (Formula 1)

(Formula 2)

According to claim 3, In addition to the reaction of sodium dibenzyldithiocarbamate and 1,6-bis (sodium thiosulfato) hexane, the step of removing the high viscosity liquid product by layer separation by a separation solvent and high temperature degassing Hybrid rubber vulcanizing agent manufacturing method characterized in that the addition.