JP3286857B2 - Method for producing chlorosulfonated polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 having excellent low-temperature properties and lightness, characterized in that a polyolefin is dissolved or suspended in 1,1,2-trichloroethane to perform chlorination and chlorosulfonation reactions. Things.

[0002]

2. Description of the Related Art Chlorosulfonated polyolefins are produced by dissolving or suspending a polyolefin in a solvent and chlorinating and chlorosulfonating it. ~ 3.0% by weight
included. This chlorosulfonated polyolefin is easily vulcanized together with a metal oxide and a vulcanization accelerator, and is used as an elastomer having excellent weather resistance, ozone resistance, heat resistance, chemical resistance, and bright color.

However, one of the drawbacks of chlorosulfonated polyolefin is that it has poor cold resistance. Therefore, for the purpose of remedying such drawbacks, we have submitted a process for producing a chlorosulfonated polyolefin having excellent low-temperature properties by using an aromatic compound as a solvent (Japanese Patent Application Laid-Open No. 60-144306). However, there has been a problem that chlorosulfonated polyolefin produced using an aromatic compound as a solvent tends to be colored during heat aging.

On the other hand, the solution after the chlorination and chlorosulfonation reactions contains hydrogen chloride gas by-produced during the reaction and / or
Alternatively, sulfur dioxide is included. The hydrogen chloride gas and the sulfurous acid gas are corrosive substances, and it is not preferable in terms of production formula to isolate chlorosulfonated polyolefin from a solution containing these corrosive substances. Therefore, after removing these corrosive substances out of the reaction system, the chlorosulfonated polyolefin is isolated. Conventionally, in order to remove hydrogen chloride gas and / or sulfurous acid gas by-produced during the reaction to the outside of the reaction system, a method of blowing nitrogen at a boiling point temperature of a solvent used has been performed. However, when a chlorosulfonated polyolefin is produced using a solvent having a high boiling point (eg, a solvent having a boiling point of 100 ° C. or higher),
When hydrogen chloride and / or sulfurous acid gas by-produced at the boiling point of the solvent is removed from the reaction system, there has been a problem that the obtained chlorosulfonated polyolefin is colored.

[0005] The coloring problem as described above significantly impairs the lightness characteristic of chlorosulfonated polyolefins, and a solution to this problem has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention relates to 1,1,2
-An object of the present invention is to provide a process for producing a commercially valuable chlorosulfonated polyolefin having excellent low-temperature properties and lightness using trichloroethane as a solvent.

[0007]

That is, the present invention provides a polyolefin dissolved or suspended in a solvent, using a radical generator as a catalyst, chlorine and sulfur dioxide gas, chlorine and sulfuryl chloride,
In the reaction of chlorination using sulfuryl chloride alone or chlorine and sulfurous acid gas and sulfuryl chloride, or sulfuryl chloride and sulfurous acid gas, or chlorination and chlorosulfonation,
In the step of using 1,1,2-trichloroethane as a solvent and removing hydrogen chloride gas and / or sulfur dioxide gas by-produced during the reaction to the outside of the reaction system, the temperature during the process was set at 9%.
The present invention relates to a method for producing a chlorosulfonated polyolefin excellent in low-temperature characteristics and lightness by controlling the temperature to 0 ° C. or lower. The details will be described below.

[0008]

The solvent used in the present invention is 1,1,2-trichloroethane.

In the reaction for chlorination and chlorosulfonation, a radical generator is used as a catalyst to convert chlorine and sulfur dioxide, chlorine and sulfuryl chloride, sulfuryl chloride alone, or chlorine and sulfur dioxide and sulfuryl chloride, sulfuryl chloride and sulfur dioxide, It is reacted with a polyolefin dissolved or suspended in 1,1,2-trichloroethane. 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 to 150 ° C., preferably 60 to 130 ° C., and the reaction pressure is 0 to 10 kg / cm ² , preferably 0 to 10 kg / cm ² .
7 kg / cm ² .

As the radical generator, an azo compound or an organic peroxide is used. Examples of the azo compound include α, α′-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and the like. Examples include benzoyl oxide, acetyl peroxide, t-butyl peroxide, t-butyl perbenzoate and the like. An azo compound is preferred, and α, α'-azobisisobutyronitrile is particularly preferred.

Examples of the polyolefin as a raw material include high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDP).
E), ethylene homopolymers and copolymers such as very low density polyethylene (VLDPE), ethylene vinyl acetate copolymer (EVA), and ethylene / propylene copolymer (EPM).

After completion of the reaction, hydrogen chloride gas and sulfur dioxide gas remaining in the reaction solution are removed by introducing nitrogen. There is no problem even if the hydrogen chloride gas and the sulfurous acid gas are removed under reduced pressure. At that time, it is important that the temperature in the reaction system is 90 ° C. or less. When the hydrogen chloride gas and the sulfurous acid gas are removed at a temperature in the reaction system exceeding 90 ° C., the obtained chlorosulfonated polyolefin is colored.

After removing the hydrogen chloride gas and the sulfurous acid gas,
Add stabilizers as needed. 2,2'-
Epoxy compounds such as bis (4-glycidyloxyphenyl) propane are preferred.

As methods for separating the product polymer from the solvent, 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, 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,
Compounding agents for rubbers or resins such as plasticizers, processing aids, anti-aging agents or vulcanization accelerators such as TRA and TT. Vulcanization methods include steam vulcanization, UHF vulcanization, hot air vulcanization,
General techniques such as injection, mold, and roto-cure are exemplified.

For end use, similar to existing chlorosulfonated polyolefins, automotive hoses, gas hoses, industrial hoses, escalator handrails, electric wires, leisure boats, roofing, pond liners, rolls, belts,
Examples include boots, packings, sheets, draw cloths, adhesives, paints and sealants.

[0018]

Next, the present invention will be described in more detail with reference to examples, but these are examples for assisting the present invention, and the present invention is not limited by these examples.

The values used in these examples were obtained according to the following measuring methods.

Chlorine and sulfur content: Combustion flask method Unvulcanized rubber properties: JIS K 6300 Vulcanized rubber properties: JIS K 6301 Low temperature properties (low temperature torsion test): JIS K 6301 Color of product: Visually determined. Color stability of the product by accelerated aging: 70 ° C. gear oven method, visual.

Example 1 A 30-liter glass-lined autoclave was charged with 28 kg of 1,1,2-trichloroethane and 2.8 kg of high-density polyethylene having a melt index of 6.2 g / 10 min and a density of 0.95 g / cc. .

After 0.3 g of pyridine was added as a co-catalyst for the chlorosulfonation reaction, steam was passed through the jacket of the reactor and kept at 120 ° C. for 2 hours to uniformly dissolve the polyethylene. During this time, nitrogen gas was introduced into the reactor at a flow rate of 15 liters / minute to eliminate air mixed in the reactor.

As a radical initiator, 14 g of α, α'-
Azobisisobutyronitrile was prepared using 1-butanol and 1,
It was dissolved in 2.9 kg of 1,1,2-trichloroethane from which 2-epoxybutane had been removed. While continuously adding this solution to the reactor, the reaction was carried out by adding 5.9 kg of sulfuryl chloride to the reactor from another inlet.
During this time, 3 hours were required, but the pressure of the reactor was increased to 2.0 kg /
cm ² .

After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was reduced to 70 ° C., and nitrogen was introduced while maintaining the temperature at 70 ° C. to remove sulfurous acid gas and hydrogen chloride gas remaining in the reaction solution. .

As a stabilizer, 43 g of 2,2'-bis (4
-Glycidyloxyphenyl) propane,
This solution was fed to a drum dryer heated to 155 ° C. to separate chlorosulfonated polyethylene as a product from the solvent.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 35.5% chlorine and 1.0% sulfur. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the raw rubber was 59.

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

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

The values obtained are summarized in Table 2 below.

Example 2 0.09 g of a melt index was used as the raw material polyolefin.
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 0.955 g / cc and the product was subsequently separated.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 35.2% chlorine and 1.0% sulfur. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the raw rubber was 99.

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

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 A raw material polyolefin was melted at a melt index of 4.3 g /
The reaction was carried out in the same manner as in Example 1 except that the low-density polyethylene (ethylene-butene 1 copolymer) was changed to a linear low-density polyethylene having a density of 0.922 g / cc and the amount of sulfuryl chloride was changed to 4.0 kg. This was followed by separation of the product.

The product had a pure white hue and analysis showed that the chlorosulfonated ethylene / butene 1 copolymer contained 29.7% chlorine and 0.9% sulfur. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the raw rubber was 38.

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

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 In the step of removing hydrogen chloride and / or sulfurous acid gas by-produced during the reaction out of the reaction system, the temperature during the step was adjusted to 113, the boiling point of 1,1,2-trichloroethane as the solvent.
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at ℃, and the product was subsequently separated.

The product had a brown hue and analysis showed that the chlorosulfonated polyethylene contained 35.1% chlorine and 1.0% sulfur. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the raw rubber was 58.

The hue stability of the product was examined by a heat acceleration test, and no change was observed in the hue even after 10 days at 70.degree.

Further, the product was kneaded according to the formulation 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.

This indicates that the light color is inferior.

Comparative Example 2 In the step of using carbon tetrachloride as a solvent and removing hydrogen chloride and / or sulfurous acid gas by-produced during the reaction out of the reaction system, the temperature during the process was determined by the boiling point of carbon tetrachloride as the solvent. The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at 76.8 ° C., and the product was subsequently separated.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 35.4% chlorine and 1.0% sulfur. The Mooney viscosity (ML1 + 4, 100 ° C.) of the raw rubber was 59.

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

Further, the product was kneaded according to the formulation 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.

This indicates that the low temperature characteristics are inferior.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that monochlorobenzene was used as a solvent, and then the product was separated.

The product had a pure white hue and analysis showed that the chlorosulfonated polyethylene contained 35.5% chlorine and 1.0% sulfur. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the raw rubber was 54.

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

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.

This indicates that the light color is inferior.

Comparative Example 4 In the step of removing hydrogen chloride and / or sulfurous acid gas by-produced during the reaction from the reaction system by using carbon tetrachloride as a solvent, the temperature during the process was determined by the boiling point of carbon tetrachloride as a solvent. The reaction was carried out in the same manner as in Example 3 except that the reaction was carried out at 76.8 ° C., and the product was subsequently separated.

The product had a pure white hue and analysis showed that the chlorosulfonated ethylene / butene 1 copolymer contained 29.9% chlorine and 0.9% sulfur. . Mooney viscosity of raw rubber (ML _{1 + 4} , 100 ℃)
Was 39.

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

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.

This indicates that the low-temperature characteristics are inferior.

As is apparent from the above Examples and Comparative Examples, the chlorosulfonated polyolefin obtained in the present invention has excellent low-temperature characteristics and a high commercial value having a pure white hue. I understand.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

According to the present invention, a process for producing a chlorosulfonated polyolefin by using 1,1,2-trichloroethane as a solvent is established. It has excellent color properties, and can increase its commercial value.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (1)

(57) [Claims] 1. A polyolefin dissolved or suspended in a solvent, using a radical generator as a catalyst, chlorine and sulfurous gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, or chlorine and sulfurous acid gas and sulfuryl chloride, sulfuryl chloride and sulfurous acid. In the reaction for chlorination and chlorosulfonation using gas, 1,1,2-trichloroethane is used as a solvent, and hydrogen chloride and / or sulfurous acid gas produced as a by-product during the reaction is removed from the reaction system. A method for producing a chlorosulfonated polyolefin having excellent low-temperature properties and lightness, characterized in that the temperature is controlled to 90 ° C. or lower.