JPS61138603A - Production of chlorosulfonated polyethylene - Google Patents

Abstract

PURPOSE:To obtain a chlorosulfonated polyethylene having excellent low- temperature characteristics, by carrying out the chlorination and chlorosulfonation reaction of polyethylene introducing a chlorination and chlorosulfonation agents uniformly to the reaction solution at two or more parts of the liquid phase of the solution. CONSTITUTION:A polyethylene is dissolved in a halogenated hydrocarbon, and chlorinated and chlorosulfonated in the presence of a radical reaction catalyst such as alpha,alpha'-azobisisobutyronitrile. In the above process, the chlorination and chlorosulfonation agents (e.g. chlorine gas, sulfur dioxide gas, etc.) are added to the reaction solution dividedly from two or more parts of the liquid phase of the solution. USE:various industrial material, paint, adhesive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing chlorosulfonated polyethylene having excellent low-temperature properties.

(Prior art) Chlorosulfonated polyethylene, which is produced by digesting polyethylene into a 7-lodenated hydrocarbon and reacting it with a chlorination and chlorosulfonation reagent in the presence of a radical reaction catalyst, has good heat resistance and weather resistance. It has excellent ozone resistance and is used in various industrial materials, paints, adhesives, etc.

However, conventional chlorosulfonated polyethylene has drawbacks in its low-temperature properties, which limits its use in places where cold resistance is required. Methods to improve this drawback include a method using linear low-density polyethylene as a raw material (Japanese Patent Application Laid-Open No. 58-201805), and a method of carefully controlling temperature conditions during the reaction of polyethylene (Japanese Patent Application Laid-open No. 59-1
8708) etc. have been proposed.

(Problems to be Solved by the Invention) The present inventor has conducted research on the development of a method for producing chlorosulfonated polyethylene with excellent low-temperature properties.

(Means for solving the problem) As a result, during the chlorination and chlorosulfonation reaction of polyethylene, the chlorination and chlorosulfonation agent is divided into two or more locations from the liquid phase of the reaction solution and dissolved. The present invention was accomplished by discovering that chlorosulfonated polyethylene produced by uniformly adding chlorosulfonated polyethylene has excellent low-temperature properties.

That is, the present invention provides a method for producing chlorosulfonated polyethylene by dissolving polyethylene in a halogenated hydrocarbon and subjecting it to chlorination and chlorosulfonation reactions in the presence of a radical reaction catalyst. This is a method for producing chlorosulfonated polyethylene with excellent low-temperature properties by adding the agent uniformly to the liquid phase of the reaction solution from two or more locations and causing the reaction.

Details regarding the reaction in the present invention are described below. The reaction proceeds by dissolving polyethylene in a halogenated hydrocarbon, adding a radical reaction catalyst, and continuously adding a chlorination and chlorosulfonation reagent to the reaction system. The reaction temperature is higher than the temperature at which the polyethylene is dissolved in the solvent used, and varies depending on the density of the polyethylene, but 60 to 120''C is usually suitable.

Chlorination and chlorosulfonation reaction agents include chlorine gas, sulfite, sulfuryl chloride, etc., but they have great industrial value, such as being able to carry out chlorination and chlorosulfonation reactions simultaneously and increasing the polyethylene concentration. For this reason, it is suitable to use sulfuryl chloride, which is in liquid form.

When sulfuryl chloride is used, the reactant can be added to the reaction solution either in the gas phase or in the liquid phase, but liquid phase addition is preferred from the viewpoint of homogeneous mixing of the reactant into the reaction solution. In the present invention, when this addition is carried out, it is divided into two or more locations separated from each other and added to the reaction solution. Simply adding from one place is not suitable for producing the chlorosulfonated polyethylene with excellent low-temperature properties as referred to in the present invention.

The amount of chlorination reactant used is determined by the amount of chlorine introduced into the chlorosulfonated polyethylene.

Usually, when high-density polyethylene is used as a raw material, the amount used is determined so that the chlorine content in the chlorosulfonated polyethylene is about 66 to 37% by weight. When high-density polyethylene is used as a raw material, if the chlorine content is less than 33% by weight, crystallinity remains in the resulting lorosulfonated polyethylene, resulting in poor low-temperature properties, and if it is more than 67% by weight, the glass transition temperature increases. As a result, low-temperature characteristics deteriorate.

The amount of sulfur in chlorosulfonated polyethylene is usually 0.6
~1.5% by weight is preferable from the viewpoint of the balance of physical properties of the vulcanizate.

As radical reaction catalysts, azo catalysts such as α,α'-adebisindeconitrile and a-dobiscyclohexanecarbinitrile, and organic peroxide catalysts such as pen-doyl peroxide are used. Preferably α,α'-azogisodethylonitrile is used. Moreover, light, especially ultraviolet light, can also be used instead of the radical generator. Further, in this reaction, in order to control the sulfur content in the chlorosulfonated polyethylene, a small amount of an amine compound such as pyridine, quinoline, or tri-n-butylamine may be added as a cocatalyst, if necessary. In particular, when using sul7lyl chloride, an amine compound is often used.

The halogenated hydrocarbon solvent used in the reaction is one that is inert to the chlorosulfonation reaction, such as carbon tetrachloride, chloroform, ethane tetrachloride, ethane trichloride, ethylene tetrachloride, chlorobenzene, fluorobenzene, I- Lichloro 70 lomethane or the like is used. Preferably carbon tetrachloride is used.

The polyethylene used in the present invention is high density polyethylene,
It includes not only low-density polyethylene, but also copolymers with other monomers copolymerizable with ethylene, such as propylene, butene-14-methylpentene-1, vinyl acetate, and the like. However, in consideration of the mechanical properties of the product, it is preferable to use high-density polyethylene. These polyethylenes are usually used in a concentration of 2 to 40 weight percent relative to the solvent during the reaction.

(Example) In order to explain the present invention in more detail, examples are shown below. Parts and parts are based on weight.

Example 1 A 1001 glass-lined reaction vessel shown schematically in Figure 1 was filled with 90% carbon tetrachloride and high-density polyethylene (density 0).
．． 9659/CC, melt index 7.3.9/1
0) Prepare 10 yu and add 6.5kl with nitrogen? /cT
After pressurizing to rL2 (dage), the internal temperature was raised to 100°C to dissolve the polyethylene. After adding 0.5 g of pynodine to this solution, 23 g of α, α'-adebis isodethyronitrile was added.
A solution of 6 ml of carbon tetrachloride was added to the reactor at a flow rate of 1.2 ml/hour. At the same time, sulfuryl chloride 21.
6kl? The mixture was divided into equal amounts from 1.302 addition ports at the bottom of the reaction vessel and added into the liquid phase over 5 hours to allow the reaction to proceed. During this reaction, the temperature is 100°C, the pressure is 3.5k
g/cm” (/f-zo).

The contents of chlorine and sulfur in the polymer at the end of the reaction were 65.0% and 1.04%, respectively.

After the reaction, the internal pressure was increased to 3.5'9/cm for 2 hours.
Dissolved acid gases were removed by decreasing the pressure linearly from 400 mx Hgabe to 400 mx Hgabe.

After degassing, 150 I of 2,2'-bis(4-glycidyloxyphenyl)propane was added as a stabilizer, and the product was separated in a drum dryer in a conventional manner.

This chlorosulfonated polyethylene was blended according to the following formulation, then vulcanized at 160'C for 20 minutes, and its physical properties were measured. The results are shown in Table-1. The physical properties were measured according to n5x-6301.

Chlorosulfonated polyethylene 1°00 stearic acid
3 magnesia
20 Example-2 Same 100 as used in Example-1! 85 kg of carbon tetrachloride and high density polyethylene (density 0.96011/CC-, melt index 9
．． 75'/10 minutes) Add 9 to 10 and heat for 30k with nitrogen.
After pressurizing to g/(7)2(p, --di), the internal temperature was increased to 95℃
Then, the polyethylene was dissolved. This solution contains 0.0% hyridine.
After adding 59, a solution of peroxide pen-toil 351 dissolved in 4 ml of carbon tetrachloride was added to the reaction vessel at a flow rate of 1 to 7 ml. At the same time, 21 kg of sulfuryl chloride was divided into equal amounts from the three points 1, 2, and 3 at the addition port 1, 2, and 3 into the liquid phase of the reaction vessel.
The reaction was allowed to proceed. During this reaction, the temperature was 95°C and the pressure was 3.0 kg/cm” (Dage)
It was operated so that The contents of chlorine and sulfur in the polymer at the end of the reaction were 34.5%, i, and iis, respectively.

After the reaction, the internal pressure was reduced to 3.0 kg/an in 2 hours.
After removing the dissolved acidic gas by linearly lowering the pressure from (gauge) to 600 mz Hgabe,
2. As a stabilizer. z-bis(4-glycidyloxyphenyl)propane 150. ! i' was added, and the product was separated in a drum dryer in a conventional manner.

The obtained chlorosulfonated polyethylene was compounded and vulcanized in the same manner as in Example 1, and its physical properties were measured.

These results are also shown in Table-1.

Comparative Example 1 In the same reaction vessel as in Example 1, a reaction was carried out in exactly the same manner as in Example 1, except that sulfur chloride was added only from 101 addition ports at the bottom of the reaction vessel. The contents of chlorine and sulfur in the polymer at the end of the reaction were 35 and 35, respectively.
11 It was 1.07%.

After the reaction was completed, removal and finishing were carried out in the same manner as in Example 1, and the product was dried.

The obtained chlorosulfonated polyethylene was also blended and vulcanized in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table-1.

In this comparative example, since sul7lyl chloride was added at one location, the value of compression set at low temperature was large and the low temperature properties were poor.

(Effects of the Invention) According to the method for producing chlorosulfonated polyethylene of the present invention, the method of adding the reactant to the reaction solution is improved (by this, chlorosulfonated polyethylene with better low-temperature properties than before can be produced). be able to.

[Brief explanation of the drawing]

FIG. 1 is a side view of a reaction vessel used in the reactions of Examples and Comparative Examples. In Example-1, sulfuryl chloride was added through addition port 1.3, in Example-2, sulfuryl chloride was added through addition ports 1.2 and 3, and in Comparative Example-1, sulfuryl chloride was added only through addition port 1. Patent Applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendment/Written January 17, 1985 Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case 1982 Patent Application No. 261408 2. Name of the invention Process for producing chlorosulfonated I-lyethylene 3 Relationship with the person making the amendment Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Contents of the 5th amendment to the detailed description of the invention in the specification (1) Page 5, line 5 of the specification Chlorsulfonation (
2) "Chlorosulfo/polyethylene" in line 14-15 of section 5m of the specification is corrected to "chlorosulfo/polyethylene." (3) "Buty/-14-methylpentene-1" on page 6, line 10 of the specification is corrected to "buty:/-1,4-methylpentene-1."

Claims (1)

[Claims] In a method for producing chlorosulfonated polyethylene by dissolving polyethylene in a halogenated hydrocarbon and subjecting it to chlorination and chlorosulfonation reactions in the presence of a radical reaction catalyst, the chlorination and chlorosulfonation reactants are added to the reaction solution. A method for producing chlorosulfonated polyethylene, which is characterized in that it is added to the phase in parts from two or more locations.