JPS598704A - Preparation of chlorosulfonated polyethylene - Google Patents

Abstract

PURPOSE:To obtain the titled polyethylene having excellent weatherability, heat resistance, etc., economically, by separating the carbon tetrachloride used as a reaction solvent for the reaction of polyethylene with sulfuryl chloride, contacting the solvent with zeolite to remove amine compounds, and reusing the purified solvent to the reaction. CONSTITUTION:Polyethylene is dissolved in carbon tetrachloride and made to react with sulfuryl chloride in the presence of a radical generating agent (e.g., alpha,alpha'-azobisisobutyronitrile) and an amine compound (e.g. pyridine) as a cocatalyst. After the completion of the reaction, the reaction mixture is fed to a drum drier, etc., and the separated carbon tetrachloride is made to contact with zeolite to remove the amine compound and water selectively therefrom. The purified carbon tetrachloride is reused as the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 00 sulfonated polyethylene by reacting polyethylene with sulnoryl chloride using carbon tetrachloride as a solvent.

Chlorosulfonated polyethylene has 20% chlorine in its molecule.
~60 t% (preferably 25-45 wt%), sulfur α6-50 wt% (preferably (18-1.5 wt%)
) It is chlorinated and chlorosulfonated to contain it, and is easily vulcanized with reinforcing agents such as metal oxides, accelerators, or carbon black, and has weather resistance and ozone resistance.

Used as an elastomer with excellent heat resistance and chemical resistance.

As a method for producing chlorosulfonated polyethylene, a method is known in which polyethylene bath-dissolved in carbon tetrachloride is reacted with sulfuryl chloride using a radical generator as a catalyst (
Tokuko Sho 39-12M3).

This method is a reaction method using chlorine gas and fluorosulfuric acid gas as reagents for chlorination and chlorosulfonation (Japanese Patent Publication No. 33-7
Unlike the reaction method using 838L or chlorine gas and monovalent sulfuryl (JP-A-56-76406), this method is attractive in that it performs -shield K tM and chlorosulfonation with a single reagent (sulfuryl chloride). This is a great method. Furthermore, it is possible to increase the degree of polyethylene in the reaction solution, which has great industrial advantages such as shortening the reaction time.

However, since sulfuryl chloride contributes to both chlorosulfonation and chlorosulfonation of polyethylene, this reaction method is a reaction product, and a certain amount of sulfuryl chloride for the purpose of chlorosulfonation of sulfonated polyethylene. It has the disadvantage that it is difficult to control the value of nl.

Chlorosulfonated polyethylene has physical properties of 1 barium,
This is a major industrial point of view for this reaction method, since it is highly praised for its sulfur content.

As a result of our extensive research into solving this problem, we found that the addition of chlorine and sulfur by sururyl Pfi
The screen base of l11 was added with 7J of amine compound as co-catalyst (
I discovered that I can control and serve by I m.

-tt (i.e., if no amine compound is present during refrigeration, almost no sulfur is added to the chlorine and sulfonyl polyethylene produced, but only a small amount of sulfur is added.

When the amine compound was added, the amount of sulfur added increased in proportion to the amount added. However, in order to control the amount of amine compound added to chlorosulfonated polyethylene, it is necessary to precisely add 1 amine compound to the reaction solution.

The sulfur needles contained in chlorosulfonated polyethylene are
This indicates the inclusion of a sulfonyl chloride group that acts as a crosslinking point, and controlling this is extremely important as a manufacturing issue.

On the other hand, the polymer bath solution after the reaction is dried by extrusion drying using a trowel or a vent type, in which acidic components such as hydrogen chloride and submerged gas remaining in the bath solution are removed by blowing nitrogen gas under reflux of an electric medium. It is fed to a rock or drum dryer, where the carbon tetrachloride is vaporized and separated from the product. However, carbon tetrachloride, which has been phase-separated by drying, contains the co-catalyst amine compound used in the reaction. Quite a lot of + is mixed in.

This is extremely inconvenient when carbon tetrachloride is to be repeatedly used industrially. This is because if carbon tetrachloride mixed with an amine compound is used for the next chlorosulfonation reaction, the amount of the cocatalyst amine compound added will not be changed, and the amount of sulfur in the product will not be able to be controlled. It's for a reason. Therefore, it is important to remove one part of the amine compound from the recovered carbon tetrachloride.

Possible methods for removing amine compounds include distillation, extraction with acid, and the like. However, 1. performing mu-distillation requires a huge amount of thermal energy, and performing acid extraction poses problems in removing water or acid from the extracted tetrachloride odor. It cannot be said that this is a suitable method.

The object of the present invention is to eliminate such industrial inconveniences and to provide an excellent method for producing chlorosulfonated polyethylene.

That is, in the method for producing chlorosulfonated polyethylene, polyethylene is reacted with an amine compound using sulfuryl tetrachloride as a catalyst and a radical generator as a catalyst. This is a method for producing chlorosulfonated polyethylene, which is characterized by bringing carbon tetrachloride separated from the product into contact with zeolite, selectively removing the co-catalyst amine compound and water contained in the liquid, and reusing it. .

The amine compound used includes, for example, pyridine.

Quinoline, isoquinoline, naphthoquinoline, aniline,
Examples include dimethylaniline, butylamine, nicotine, and piperidine.

Since zeolite produces a molecular sieving effect due to the pores in its network structure, it is desirable to select a zeolite having a pore diameter larger than the molecular diameter of the amine used. The zeolite container to be used varies depending on the amount of carbon tetrachloride treated, the treatment rate, and the treatment method, and is not particularly limited. Furthermore, various shapes of zeolite are used, such as spherical or cylindrical.

If carbon tetrachloride separated from the dryer is treated with zeolite, the concentration of amine compounds in carbon tetrachloride can be reduced to 0.1.
It can be set to 11111 or less. When [j of the mixed amine compound is set to 01 pH 1 or less, the effect of the residual amine compound on the next reaction can be ignored. In addition, it is particularly preferable for the production of chlorosulfonated polyethylene that moisture mixed in carbon tetrachloride can be removed together with the amine compound in the separation and drying step from the reaction step. If possible, use tetrahedral carbon containing a large amount of water, since it is difficult to remove residual acid in the polymer bath solution by blowing nitrogen after the reaction is completed. This is because not only does it cause corrosion of the reactor, but it also has a significant negative impact on the quality of the product, such as discoloration.

Although amine compounds and water are removed from carbon tetrachloride treated with zeolite, carbon tetrachloride itself does not undergo any chemical or physical changes.

The raw material polyethylene used in the present invention has a high percentage of
Nipolyethylene 7 (HDpg) for °, low density boy (L-L
DPK), ethylene-vinyl acetate copolymer (EVA)
), including ethylene copolymers such as

In the reaction, polyethylene is bath-dissolved in carbon tetrachloride to form a homogeneous bath solution, and then Cχ, α′-azobisinopteronitrile,
Azobiscyclohexanecarbonitrile.

This is carried out by introducing sulfuryl chloride while adding a radical generator such as benzoyl peroxide or t-butyl peroxide and an amine compound serving as a promoter at a constant flow rate. The amount of the amine compound to be added varies depending on the amount of polyethylene or the amount of sulfur added, but in order to bottom out chlorosulfonated polyethylene containing about 1.0% by weight of sulfur, it is necessary to add it to carbon tetrachloride. It is about 1.0 to 10 [LOplo.

The addition tank for sulsuril chloride is calculated from the reaction rate of chlorine and the targeted amount of chlorine in the chlorosulfonated polyethylene raw material bIi. After the addition of a given sulthuryl chloride, residual hydrogen chloride from bubbling nitrogen into the polymer bath solution;
Acid components such as sulfur dioxide gas are removed (.Next, the polymer bath liquid is fed to a dryer such as a vent type extrusion dryer or a drum dryer by a conventional method.

The carbon tetrachloride separated in the drying tank is treated with zeolite to remove amine compounds and water.

As a treatment method using zeolite, for example, there is a method in which carbon tetrachloride is passed through a column filled with zeolite. The production of carbon tetrachloride by zeolite treatment eliminates the need for complicated purification steps such as distillation and extraction, making it an extremely economically advantageous method.

The present invention will be specifically described and explained below with examples, but these are examples to help understand the present invention, and the present invention is not limited in any way by these examples.

Example 1 Melt index 7.0r710 minutes in a 100t glass lined autoclave, density α960? /(L
10 parts of polyethylene and 100 parts of carbon tetrachloride as a solvent were added, and the polyethylene was bath-dissolved at a temperature of 1,100 degrees Celsius under pressure.

Catalyst α,α'-azobisisobutyronitrile 50? and 0.94 Of of pyridine as a co-catalyst were dissolved in 8 Kp of carbon tetrachloride and added dropwise to the reactor at a flow rate of 2.0 to 9.7 hours. At the same time, addition of 21.5 Kp of sulfuryl chloride was started, but the addition took 4 hours.

The temperature of the reactor was lowered to 75° C. and nitrogen was blown at a flow rate of 30 t/h to remove any remaining hydrogen chloride in the polymer bath.
Sulfur dioxide gas was discharged from the system.

After adding 2,2'-bis(4glycidyloxyphenyl)propane 1502 as a stabilizer, the mixture was fed to a drum dryer in a conventional manner to separate the product and carbon tetrachloride.

Elemental analysis of the product showed that the chlorosulfonated polyethylene contained 658 g of chlorine and 1.0 gb of sulfur. On the other hand, the separated carbon tetrachloride is 6.2
It contained pln pyridine and 85 pharyngeal water.

This carbon tetrachloride is Zeorum F- manufactured by Toyo Soda Kogyo a) J.
9 (10X type) 100rd to column filled with 9 in 1
It flowed down at a flow rate of /min. Analysis of the carbon tetrachloride that passed through the column showed that pyridine was less than 0.111111, and water content had decreased to 8.

Pyridine analysis was carried out using HCL-806D manufactured by Toyo Soda Kogyo ■, and moisture analysis was carried out by the Karl Fischier method.

Example 2 A chlorosulfonation reaction was carried out according to the same reaction recipe as in Example 1 using carbon tetrachloride that had been used in the reaction in Example 1 and then treated with zeolite. The polymer bath solution after the reaction was fed to a drum dryer in the same manner as in Example 1 to separate the product and carbon tetrachloride.

Elemental analysis of the product showed 659% by weight of chlorine and 1.0% by weight of sulfur. On the other hand, the separated carbon tetrachloride contains 6-. It contained 1p+8 pyridine and 81pro water.

When this carbon tetrachloride is treated with Zeolum F-9 in the same manner as in Example 1, the pyridine content is 0.19 tM or less, and the water content is 6 tM.
The pH was 12.

Example 6 In a 100 t autoclave made of glass linen, melt index 1.0r 710 minutes, dense cooking α959 f/
9 was added to Hiromu's Polyethylene 7 K9 and 100% carbon tetrachloride as a solvent, and polyethylene was heated under pressure at a hot water temperature of 110°C.

The catalyst is α'-azobis-imbutyronitrile 30V
and cocatalyst quinoline were added dropwise to 8 Kp of carbon tetrachloride at a flow rate of 2.0 Kg into the reactor at a flow rate of 7 hours. At the same time, 15. The I Kf addition day started and the addition took 4 hours. The temperature of the reactor was lowered to 75° C., nitrogen was blown in at a flow rate of 500° C., and the chloride water and 1° sulfur dioxide gas remaining in the polymer bath were discharged from the system.

After adding 2,2'-bis(4-glycidyloxyphenyl)propane 1052 as a stabilizer, the mixture was fed to a drum dryer in a conventional manner to separate the product and carbon tetrachloride.

Analysis of the product revealed that this chlorosulfonite polyethylene contained 360% by weight of chlorine and 1.0% by weight of sulfur. On the other hand, the separated carbon tetrachloride is 4.9
It contained pea's quinoline and 781-'s water. This carbon tetrachloride is produced by Toyo Soda Industrial Co., Ltd.) Zeorum F-9 (1
02 type) was flowed down to a column packed with 1 and 2 at a flow rate of 100 m/min.

When the carbon tetrachloride that passed through the column was analyzed, quinoline was found to be 0.
It was less than 1w, and the water content had decreased to 7 watts.

Looking at this example, it is clear that the present invention is an excellent method for simultaneously removing water and an amine compound as a co-catalyst contained in carbon tetrachloride, and provides a more excellent method for producing chlorosulfonated polyethylene. It is clear that this is the case.

Patent source: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] 1. In a method for producing chlorosulfonated polyethylene by reacting polyethylene bath-dissolved in carbon tetrachloride with sulfuryl smoke using a radical generator as a catalyst and an amine compound as a co-catalyst, after the completion of the reaction,
The carbon tetrachloride separated from the chlorosulfonated polyethylene by vaporization is brought into contact with zeolite to selectively remove the co-catalyst amine compound and water contained in the carbon tetrachloride and reuse it. A method for producing chlorosulfonated polyethylene.