JP2900500B2 - Method for producing chlorosulfonated polyolefin - Google Patents

Description

The present invention relates to a method for producing a chlorosulfonated polyolefin. More specifically, the present invention relates to a method for producing a chlorosulfonated polyolefin by dissolving or suspending a polyolefin in chloroform and performing a chlorination and chlorosulfonation reaction.

[Background Art] It is known to produce a chlorosulfonated polyolefin by dissolving or suspending a polyolefin in a solvent. It is also known to use a halogenated solvent such as carbon tetrachloride, chloroform, methylene chloride or fluorinated benzene as the solvent.

Of these, carbon tetrachloride is the most suitable solvent and is often used industrially. However, the use of carbon tetrachloride has been less than desirable since it has recently been raised as a substance that destroys ozone in the Earth's stratosphere.

On the other hand, it is possible to obtain a chlorosulfonated polyolefin even if chloroform is used as a solvent, but this product has a practical problem such that the product is colored yellow and the compound is apt to cause scorch.

For example, chlorosulfonated polyolefins are used for escalator handrails, LP gas hoses, light-colored electric wires, leisure boats, and the like. Such coloring is a fatal defect because of its beautiful color. Further, the short scorch time of the compound and the tendency of scorch to occur tend to impair the processing safety when processing the chlorosulfonated polyolefin into final products such as hoses and electric wires. That is, a chlorosulfonated polyolefin obtained by a conventional reaction with a chloroform solvent was of low commercial value.

Chloroform is generally 0.5 to 1.0% ethyl alcohol added as a stabilizer in commercial products, whether it is a research reagent for industrial use. This is intended to suppress harmful phosgene because chloroform is an unstable substance and easily generates harmful phosgene. (For example, Iwanami Rikagaku Dictionary
That is, refer to the third edition of Iwanami Shoten) In other words, what is generally called chloroform means automatically containing this alcohol compound. Here, chloroform containing an alcohol compound and chloroform not containing this are clearly defined. To distinguish. Further, the alcohol compound referred to herein is a compound having an -OH group, and examples thereof include ethyl alcohol and methyl alcohol.

Previously, the present inventors have found that a chlorosulfonated polyolefin synthesized using chloroform as a solvent from which the alcohol compound of the stabilizer has been removed is pure white, has no coloration, and is a product with excellent scorch stability. I understood. Moreover, it was found that there was no difference between the two in the strength, elongation, hardness, etc. after vulcanization, and that there was no characteristic distinguishing the two from the aspect of vulcanization properties (Japanese Patent Application No. 2-4628).

However, chloroform containing no stabilizer was unstable and liable to generate highly toxic phosgene. For example, highly toxic phosgene may be generated in a tank storing chloroform, in a reactor for performing chlorination and chlorosulfonation reactions, and during drying.

Therefore, it does not color like a chlorosulfonated polyolefin synthesized using chloroform to which an alcohol compound is added as a solvent, and its composition does not cause scorch, and during storage of chloroform or during chlorination and chlorosulfonation reaction. There has been a strong need for a stabilizer that suppresses the production of highly toxic phosgene.

[Problems to be Solved by the Invention] An object of the present invention is to provide an industrial method for producing chlorosulfonated polyolefin, which solves such a problem that occurs when chloroform is used as a solvent.

[Means for Solving the Problems] As a result of the present inventors' eager opinion, when performing a chlorination or chlorosulfonation reaction by dissolving or suspending a polyolefin in a solvent, alcohol-free chloroform is added to C 4 -carbon. ~ 10 compounds having at least one double bond in the molecule thereof are added in an amount of 0.0
The present inventors have found that the use of chloroform added as a solvent in an amount of 005 to 15 parts by weight is a method for producing a chlorosulfonated polyolefin which solves such a problem, and has led to the present invention.

 The details will be described below.

[Action] Compounds having 4 to 10 carbon atoms and one or more double bonds in the molecule used in the present invention include, for example, 2-
Butene, 2-methyl-2-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-pentene, 2-methyl-2-pentene, 4-methyl-1-pentene, 2-
Methyl-1-pentene, 3-methyl-2-pentene, 2
-Hexene, 2-methyl-1-hexene, 3-methyl
There are 1-hexene, 1-heptene, 1-octene, 2-nonene and the like.

This stabilizer is used in an amount of 0.0
Use 005 to 15 parts by weight. Preferably, it is 0.0008 to 10 parts by weight.

Chloroform containing less than 0.0005 parts by weight of this stabilizer was unstable, and generation of highly toxic haogen during storage and reaction was observed. On the other hand, the chlorosulfonated polyolefin synthesized using chloroform as a solvent containing more than 15 parts by weight of this stabilizer was colored brown, and the compound showed a tendency to scorch.

In the present invention, the chlorination and chlorosulfonation reactions are performed by dissolving three reagents of chlorine and sulfurous gas, chlorine and sulfuryl chloride, chlorine, sulfurous acid gas and sulfuryl chloride, or sulfuryl chloride in chloroform, using light or a radical generator as a catalyst. The reaction is carried out by reacting with the suspended polyolefin. When sulfuryl chloride is added, an amine compound such as pyridine or quinoline is added as a cocatalyst, if necessary. The reaction temperature is 40-150 ° C., preferably 60
110110 ° C., and the reaction pressure is 0-10 kg / cm ² , preferably 2-7 kg / cm ² .

Radical generators include, for example, α, α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide or acetyl peroxide. Among them, azo compounds are preferred.

Examples of the raw material polyolefin include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-constant-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), Ethylene-based homopolymers and copolymers such as ethylene-propylene copolymer (EPM) are exemplified.

As a method for separating the product polymer from the solvent after completion of the reaction, steam distillation, a drum dryer, and a vented extruder are known, and both are separated by these methods.

The chlorosulfonated polyolefin referred to in the present invention includes, for example, chlorosulfonated polyethylene, chlorosulfonated ethylene / propylene copolymer, chlorosulfonated ethylene / butene copolymer according to the raw materials described above,
Chlorosulfonated ethylene / hexene copolymers and chlorosulfonated ethylene / vinyl acetate copolymers are exemplified.

The obtained product is compounded and kneaded in the same manner as a conventional rubber or resin, and is used as a vulcanized product or an unvulcanized product.
Compounding agents include vulcanizing agents such as magnesia and calcium hydroxide, reinforcing agents such as carbon black and white carbon, fillers such as calcium carbonate and talc, plasticizers,
Compounding agents for rubbers or resins such as processing aids, anti-aging agents or vulcanization accelerators. Vulcanization is steam vulcanization, UH
Examples include F vulcanization, hot air vulcanization, injection, molding, and roto curing.

For end use, similar to existing chlorosulfonated polyolefins, automotive hoses, gas hoses, industrial hoses,
Escalator handrails, wires, pleasure boats, roofing, pond liners, rolls, belts, boots, packings, sheets, drawn cloths, adhesives, paints and sealants.

[Effects of the Invention] The chlorosulfonated polyolefin obtained by the present invention has improved coloring and scorch stability of a product which is a problem when a conventional chloroform solvent is used, and enhances its commercial value, In addition, an industrial production process for preventing generation of phosgene is established.

[Examples] Next, the present invention will be described in more detail based on examples, but these are examples for assisting the present invention, and the present invention is not limited at all by these examples.

The values used in these examples were obtained in accordance with the following measurement methods.

Chlorine and sulfur content: Combustion flask method Unvulcanized rubber properties: JIS K 6300 Vulcanized rubber properties: JIS K 6301 Hue of product: visual Stability of product hue by accelerated test: 70 ° C gear oven method, visual chloroform Stabilizer content in gas: Gas chromatography phosgene gas detection: GS-MS (Hitachi: M-80B),
Hazardous Gas Monitor 7100 (manufactured by Shibata Kagaku) Example 1 Prior to the reaction, ethyl alcohol contained in chloroform was removed by the following method.

Asahi Glass's chloroform and distilled water are placed in a large separating funnel at a ratio of 1: 1 (volume ratio) and vigorously shaken. This operation was repeated three times to extract ethyl alcohol as a stabilizer into water. Further, water mixed in by distillation under a nitrogen stream was dehydrated.

In a 30-liter glass-lined autoclave, chloroform excluding ethanol: 28 kg, 2-methyl-2
-Butene: 0.28 g was added and stirred. The content of the stabilizer in the chloroform was determined by gas chromatography and found to be 0.0012 parts by weight based on 100 parts by weight of chloroorm. Melt index 5.2g / 10min, density 0.964
4.2 kg of g / cc high density polyethylene was charged.

1.12 pyridine as co-catalyst for chlorosulfonation reaction
After adding g, pass steam through the jacket of the reactor,
For 30 minutes to uniformly dissolve the polyethylene.
During this time, nitrogen gas was introduced into the reactor at a flow rate of 15 liters / min to eliminate air that had entered.

5.67 g of α, α'-azobisisobuironitrile was added to the reactor as a radical initiator. The reaction is 9.01
kg of sulfuryl chloride was added to the reactor from another inlet. During this time, the temperature of the reactor
It was kept at 3.5 kg / cm ² .

After the reaction is completed, the pressure is returned to normal pressure and the temperature of the reactor is raised to 60 ° C.
, Sulfuric acid gas and hydrogen chloride gas remaining in the reaction solution were removed by introducing nitrogen.

After adding 72.2 g of bis (4-glycidyloxyphenyl) propane as a stabilizer, the solution was fed to a drum dryer heated to 140 ° C. to separate the chlorosulfonated polyethylene as a product from the solvent.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 34.6 wt% chlorine and 1.0 wt%.
% Of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 56.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When phosgene contained in the waste gas during the reaction was checked, no phosgene gas was detected.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of unvulcanized products represented by scorch time and vulcanized physical properties such as tensile strength were measured.

The obtained values are summarized in Table 2.

Example 2 2-methyl-2-butene: 2.8 g was added to 28 kg of chloroform excluding ethanol, and the mixture was stirred. The content of the stabilizer in the chloroform was determined by gas chromatography, and was found to be 0.011 part by weight based on 100 parts by weight of chloroform. Raw material polyolefin melt index 0.85
The reaction was carried out in the same manner as in Example 1 except that the density was changed to high density polyethylene having a density of 0.969 g / cc at g / 10 minutes, and then the product was separated.

The product had a pure white hue, and analysis showed that the chlorosulfonated polyethylene contained 35.5 wt% chlorine and 1.0 wt%.
% Of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 98.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When phosgene contained in the waste gas during the reaction was checked, no phosgene gas was detected.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

Example 3 2-pentene: 1.4 g was added to chloroform: 28 kg excluding ethanol, and the mixture was stirred. When the content of the stabilizer in this chloroform was determined by gas chromatography, it was 0.0049 parts by weight based on 100 parts by weight of chloroform. Raw material polyolefin melt index 6.0g / 10 minutes,
The reaction was carried out in the same manner as in Example 1 except that the density was changed to ultra low density polyethylene (VLDPE) having a density of 0.900 g / cc and the amount of sulfuryl chloride added was changed to 8.4 kg, and then the product was separated.

The product has a pure white hue and analysis shows that the chlorosulfonated polyethylene is 29.9 wt% chlorine and 1.0 wt%
% Of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 57.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When phosgene contained in the waste gas during the reaction was checked, no phosgene gas was detected.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

Example 4 3-methyl / 1-butene: 0.84 g was added to 28 kg of chloroform excluding ethanol, and the mixture was stirred. When the content of the stabilizer in this chloroform was determined by gas chromatography, it was 0.0031 parts by weight based on 100 parts by weight of chloroform. Melt index 5.
Reaction was carried out in the same manner as in Example 1 except that linear low-density polyethylene (ethylene / butene 1 copolymer) was changed to 0 g / 10 min and density 0.922 g / cc, and the amount of sulfuryl chloride added was changed to 5.9 kg. And the product was subsequently separated.

The product had a pure white hue and analysis showed that the chlorosulfonated ethylene / butene 1 copolymer contained 26% by weight of chlorine and 1.0% by weight of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 42.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When phosgene contained in the waste gas during the reaction was checked, no phosgene gas was detected.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

Comparative Example 1 2-methyl / 2-butene: 0.056 g was added to 28 kg of chloroform excluding ethanol, followed by stirring. When the content of the stabilizer in this chloroform was determined by gas chromatography, it was 0.0002 parts by weight based on 100 parts by weight of chloroform. Hereinafter, the reaction was carried out in the same manner as in Example 1,
Subsequently, the product was separated.

The product had a pure white hue, and analysis showed that the chlorosulfonated polyethylene contained 34.9 wt% chlorine and 1.0 wt%.
% Of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 56.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When the waste gas during the reaction was checked, phosgene gas was detected, and the generation of highly toxic phosgene could not be suppressed.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

Comparative Example 2 2-pentene: 0.080 g was added to 28 kg of chloroform excluding ethanol, followed by stirring. When the content of the stabilizer in this chloroform was determined by gas chromatography, it was 0.0003 parts by weight based on 100 parts by weight of chloroform.
Thereafter, the reaction was carried out in the same manner as in Example 3, and then the product was separated.

The reaction was carried out in the same manner as in Example 3 except that a commercially available product in which ethanol as a stabilizer was added to chloroform as a solvent was used, and then the product was separated.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 30.0 wt% chlorine and 1.0 wt%.
% Of sulfur. The Mooney viscosity (ML1 + 4,100 ° C.) of the raw rubber was 57.

The hue stability of the product was tested by a heat acceleration test, but no change was observed in the hue after 10 days at 70 ° C.

When the waste gas during the reaction was checked, phosgene gas was detected, and the generation of highly toxic osgen could not be suppressed.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

Comparative Example 3 2-methyl-2-butene: 4.5 kg was added to 28 kg of chloroform excluding ethanol, followed by stirring. When the content of the stabilizer in this chloroform was determined by gas chromatography, it was 16 parts by weight based on 100 parts by weight of chloroform. Thereafter, the reaction was carried out in the same manner as in Example 4, and then the product was separated.

The product was colored yellow and analysis showed that the chlorosulfonated polyethylene contained 25.0 wt% chlorine and 0.9 wt% sulfur. Mooney viscosity of raw rubber (ML
(1 + 4,100 ° C.) was 42.

The hue stability of the product was examined by a heat acceleration test, but after 70 days at 70 ° C., the product turned browner.

When phosgene contained in the waste gas during the reaction was checked, no phosgene gas was detected.

Further, the product was kneaded according to the composition shown in Table 1, and the physical properties of the unvulcanized product and the vulcanized physical properties were measured.

 This is summarized in Table-2.

The scorch time is short, indicating that it is easy to scorch.

As is clear from the above Examples and Comparative Examples, the chlorosulfonated polyethylene obtained in the present invention has a pure white hue, has an excellent effect on scorch stability, and at the same time, is highly toxic phosgene. The occurrence of is suppressed.

Claims (1)

(57) [Claims] (1) When performing chlorination or chlorosulfonation reaction by dissolving or suspending a polyolefin in a solvent, chloroform containing no alcohol has 4 to 10 carbon atoms and one double bond in the molecule. A method for producing a chlorosulfonated polyolefin, comprising using, as a solvent, chloroform obtained by adding 0.0005 to 15 parts by weight of the above compound to 100 parts by weight of chloroform.