JPS6357607A - Production of chlorosulfonated polyethylene - Google Patents

Abstract

PURPOSE:To obtain the title PE excellent in oil resistance and extrudability and low in compression set at low temperature, by chlorinating and low temperature, by chlorinating and chlorosulfonating a mixture of medium to low-pressure PE with high-pressure PE. CONSTITUTION:Mixed PE is obtained by mixing medium to low-pressure PE (a) of a density of 0.948-0.965g/cc and an MI of 0.01-300g/10min with a high- pressure PE (b) of a density of 0.910-0.930g/cc and an MI of 0.1-300g/10min at a weight ratio of 80-30/20-70. This mixed PE is dissolved in a solvent (e.g., CCl4) and chlorinated and chlorosulfonated by the addition of sulfuryl chloride in the presence of a radical generator (e.g., alpha,alpha'-azobisisobutyronitrile) as a catalyst and, optionally a promotor (e.g., pyridine), and the title PE of a chlorine content of 32-29wt% and sulfur content of 0.4-1.6wt% is separated from the solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to chlorosulfonated polyethylene.

More specifically, it relates to rollosulfonated polyethylene, which is characterized by high oil resistance and low compression set at low temperatures, and also has good extrusion processability.

[Conventional technology]

Chlorosulfonated polyethylene is a halogenated elastomer that does not have two TCTj bonds and is weather resistant.

Due to its excellent ozone resistance, heat resistance, oil resistance, and bright color compatibility, it is used for automobile hoses, gas hoses, electric wires,
It is used for hanging cloth, etc.

However, one of the drawbacks of chlorosulfonated polyethylene is that it has poor cold resistance.

In particular, the large compression set at low temperatures leads to the phenomenon that, for example, when commercialized as a hose, the caulked portion of one metal fitting sometimes loosens at low temperatures.

Therefore, in order to improve the compression set at low temperatures, we
JP-A-61-145204 is proposed.

However, the chlorosulfonated polymer disclosed in JP-A-61-145204 is a low chlorinated chlorosulfonated product with a chlorine content of 1[lLO to 3αOwt4], and is therefore unsuitable for application to parts requiring high oil resistance.

Generally, oil resistance and cold resistance are contradictory properties.

Therefore, it has high oil resistance equivalent to TO8O-CEM T8-530 and Hypalon 40, which are representative grades of commercially available chlorosulfonated polyethylene, and also has low compression set at low temperatures and good extrusion processability. Polyethylene was requested.

[Problem that the invention seeks to solve]

That is, an object of the present invention is to provide a method for producing lolosulfonated polyethylene, which is characterized by high oil resistance and low compression set at low temperatures, and also has good extrusion processability.

[Means to solve the problem]

That is, the present invention resides in a method for producing chlorosulfonated polyethylene, which is characterized by chlorinating and chlorosulfonating mixed polyethylene consisting of medium-low pressure polyethylene and high-pressure polyethylene as a raw material.

[Effect]

The medium-low pressure polyethylene referred to in this specification has a density of α94
8~(L 9659/cc, melt index α0
It is 300% polyethylene.

The high-pressure polyethylene referred to in this specification has a density of 1910~
(L 9 3 0 9 /cc, melt index α
It is a low density branched polyethylene with a ratio of 1 to 3009/10 minutes.

The raw material polyethylene is a mixed polyethylene consisting of medium-low pressure polyethylene and high-pressure polyethylene, and the weight ratio of this mixture is 98/2 to 2/98, more preferably 80/20 to 30/70.

Even if chlorosulfonated polyethylene is obtained using mixed polyethylene in which the proportion of medium-low pressure polyethylene exceeds 98 wt% as a raw material, the compression set at low temperatures cannot be reduced.

On the other hand, if the proportion of medium-low pressure polyethylene is less than 2 wt%, it is difficult to obtain good processability. In particular, the surface texture during extrusion processing is not smooth and becomes uneven. For this reason, medium-low pressure polyethylene is 9 8
It is desirable to contain 2 wt% or more of wtl or less.

Particularly preferably, mixed polyethylene with a weight ratio of medium-low pressure polyethylene and high-pressure polyethylene of 80/20 to 30/70 is used as a raw material, and chlorosulfone has excellent processability and low compression set at low temperatures. Add polyethylene.

The amount of chlorine contained in chlorosulfonated polyethylene is 10
~60 wt%, but the oil resistance of chlorosulfonated polyethylene largely depends on the amount of chlorine contained. Therefore, if a particularly high degree of oil resistance is required, the amount of chlorine should be 32v.
rt% or more is desirable.

However, since an excessive increase in the amount of chlorine increases the compression set at low temperatures, a particularly preferred chlorosulfonated polyethylene has a chlorine amount of 32 to 59 wt%.

The amount of sulfur contained in chlorosulfonated polyethylene is α
2 to 5 weights, preferably α4 to 1.6 weights.

The amount of sulfur is a measure of the amount of chlorosulfone groups contained in chlorosulfonated polyethylene, and is a factor that controls vulcanization behavior such as vulcanization rate and vulcanization density.

A method of chlorinating and chlorosulfonating polyethylene to obtain chlorosulfonated polyethylene is, for example, dissolving polyethylene in a solvent, and adding chlorine, sulfur dioxide gas, and/or sulfuryl chloride, or sulfuryl chloride alone using a radical generator as a catalyst, as necessary. Depending on the situation, a method of producing using a co-catalyst may be mentioned.

In this case, as a solvent, carbon tetrachloride, chloroform, tetrachloroethane, monochlorobenzene, benzene, etc., which are inert to the halogenation reaction, are used.

As the radical generator, an azo radical initiator such as α, d-azobisisobutyronitrile or azobiscyclohexanecarbonitrile, a peroxide such as benzoyl peroxide or acetyl peroxide, or ultraviolet rays is used.

Examples of cocatalysts include amine compounds such as pyridine and quinoline.

After the reaction, the solution contains hydrogen chloride gas remaining in the solution,
Removes acids such as sulfur dioxide gas.

After this, an epoxy stabilizer is added.

2.27-bis(4-glycidyloxyphenyl)propane is preferred.

Methods for separating and drying chlorosulfonated polyethylene from the resulting solution include: 1) Steam distillation method A method in which a polymer solution is fed into hot water, the solvent is separated by steam distillation method, and then dried. (For example, US Patent 2
592814) 2) Drum Drying Method A method in which a polymer solution is fed onto the surface of a heated rotating drum and the polymer is taken out as a film. (See, for example, US Pat. No. 2,925g/9) 3) Extrusion drying method A method in which the polymer solution is preconcentrated or directly dried using an extrusion dryer.

(For example, see Japanese Patent Laid-Open No. 57-47305.).

However, in carrying out the present invention, the manufacturing process is preferably a solution method as described above, but is not limited to the above-mentioned method.

It is also possible to carry out the reaction by a method in which the reaction is carried out by suspending it in a solvent, a method in which the reaction is carried out in a gas phase, and the like.

The obtained chlorosulfonated polyethylene can be made into a vulcanized product by adding compounds such as a vulcanizing agent, a vulcanization accelerator, a reinforcing agent, a filler, a plasticizer, a softener, and an anti-aging agent and vulcanizing it. Used as an unvulcanized product.

In general, chlorosulfonated polyethylene is prepared using metal oxides such as magnesia, litharge, tribasic lead maleate, calcium hydroxide, and calcium oxide, epoxy resins, and polyhydric alcohols as vulcanizing agents.

Polyvalent amines and the like are used.

Examples of vulcanization accelerators include sulfur-based vulcanization accelerators such as TRA (dipentamethylenethiuram tetrasulfide), TT (tetramethylthiuram disulfide), and ethylene thiourea, peroxides such as DCP (dicumyl oxide), and PM. (N, N'-m -7 Any Range! Reimido)
Maleimides such as

Carbon black is used as a reinforcing agent and filler.

Examples include clay, talc, silica, calcium carbonate, titanium oxide, and the like.

Examples of plasticizers and softeners include phthalic acid esters, sebacic acid esters, and various oils.

Also, NBC! (dibutyldithiocarbamic acid, nickel), amine type, and phenol type anti-aging agents are used, but these compounding agents are not limited to the above.

Rubber compounds containing these compounding agents are used as unvulcanized products or are vulcanized into various products by press vulcanization, steam vulcanization, UHF vulcanization, electron beam vulcanization, or the like.

〔Effect of the invention〕

The chlorosulfonated polyethylene produced by Sukanmei Trap is characterized by high oil resistance and low compression set at low temperatures, and also has good extrusion processability.

Therefore, it is particularly suitable for the field of extruded products such as cold-resistant hoses and cold-resistant electric wires.

Examples include automobile hoses such as fuel oil hoses and cooler hoses; gas hoses such as LP gas hoses and city gas hoses; electric wires and cables.

Of course, there are other products in which conventional chlorosulfonated polyethylene is used, such as raincoats and bags.

Windbreaker, belt, packing, gasket,
It can also be used for escalator handrails, sponges, and wetsuits.

〔Example〕

Next, the present invention will be explained in more detail based on Examples, but these are examples to help understand the present invention, and
The present invention is not limited in any way by these Examples.

Note that the values used in these Examples were obtained in accordance with the following measurement method.

<About polyethylene> Melt index: JIS K 7210 density
: JIS K 7112 <For chlorosulfonated polyethylene> Analysis of chlorine and sulfur content Dual combustion flask method Mooney viscosity : J
IS K 6300 Vulcanized rubber physical properties: JIS
K 6301 extrusion processing conditions: Imanaka Machine ■
50flIφL/D-10 extruder, cylinder part 5
0°C head 50°C, shaft rotation speed 30 rpm Example-1 Melt index 6.59/10 minutes in a 30t glass-lined autoclave with a stirrer.

1400 g of medium-low pressure polyethylene with a density (L 9599/cc) and a melt index of 1.6 g for 710 minutes.

1400 ml of high-pressure polyethylene with a density α9209/cc was charged.

Solvent: carbon tetrachloride 28J19 and cocatalyst: pyridine 0.2
After charging 89, the temperature was raised to 110° C. under pressure to dissolve the polyethylene.

Subsequently, the temperature was lowered to 100°C, and a carbon tetrachloride solution containing 5 g of α, d-azobisisobutyronitrile as a radical generator was dissolved. The reaction was carried out by adding sulfuryl chloride S, g/09, while adding 9 to 2.5.

It took 120 minutes to add sulfuryl chloride, during which time the reaction temperature was increased to 100°C and the reaction pressure was increased to 53 to 9/c! i
I kept it.

After the reaction was completed, the internal temperature of the polymer was lowered to 70° C., and the residue remaining in the solution was removed by blowing nitrogen under reflux of the solvent.

After adding 55 g of 2,2'-bis(4-glycidyloxyphenyl)propane as a stabilizer, the product was separated from the solvent by feeding into a drum dryer.

As a result of analysis, this chlorosulfonated polyethylene has 3
a 7 wt% chlorine and 1. It was found that it contained Owt% of sulfur.

Mooney viscosity was 59.

The formulations shown in Table 1 were prepared using a 10-inch open roll.

A portion of the blend was extruded in the form of a round bar using an extruder with a diameter of 50 mm.

The surface texture of the extrudate was smooth and good.

The remaining formulation was press cured for 40 minutes at 150'C.

The physical properties of the vulcanizate were measured, and these results were summarized as follows.
It is shown in Table-2.

Table-1 Chlorosulfonated polyethylene 10
0 (parts by weight) Magnesia
5SRF carbon black
50 dioctyl sebacate ester
20AC polyethylene 617h
5 suntight
2 Splendor R-3002 Pentaerythritol, Ru
3 Accelerator TRA 2 Dibutyldithiocarbami 4 Tips Nickel
3N, NLm-7 engineering nimberimite 3 total
193 Example-2 Regarding the raw material mixed polyethylene chain, the reaction was carried out in the same manner as in Example-1, except that the medium-low pressure polyethylene charge was changed to 16809 and the high-pressure process polyethylene charge was changed to 11209, to produce chlorosulfonated polyethylene. Obtained.

As a result of analysis, this chlorosulfonated polyethylene has 5
a 5 Wtes of chlorine and 1. It was found that it contained Owt% sulfur.

Mooney viscosity was 58.

Mixing was performed using rolls using the same formulation as in Example-1.

A portion of the blend was extruded under the same conditions as Example-1. The surface texture of the extrudate was good.

On the other hand, the remaining formulations were vulcanized in the same manner as in Example 1, and the physical properties of the vulcanized products were measured.The results are summarized in Table 1.
Shown in 2.

Example 3 Mixed polyethylene used as a raw material was mixed with medium and low pressure polyethylene 14009 having a melt index Q of 99/10 minutes and a density (L958 g/cc) and a melt index of 55 M.
The reaction was carried out under the same conditions as in Example 1, except that 1400 g of high-pressure polyethylene with a density (L9219/cc) was used for 710 minutes.

As a result of analysis, this chlorosulfonated polyethylene has a concentration of 35
．． It was found to contain 3 wt% chlorine and 1.1 wt% sulfur.

Mooney viscosity was 77.

Mixing was performed using rolls using the same formulation as in Example-1.

A portion of the blend was extruded under the same conditions as Example-1. The surface texture of the extrudate was good.

On the other hand, the remaining formulations were vulcanized in the same manner as in Example 1, and the physical properties of the vulcanized products were measured.The results are summarized in Table 1.
Shown in 2.

Example-4 Mixed polyethylene used as a raw material was mixed with a melt index of 11 l/10 minutes, a medium-low pressure polyethylene 16809 with a density Q of 960 l/cc, and a melt index of 52.
The reaction was carried out under the same conditions as in Example 1, except that high-pressure polyethylene 1120F having a density of α9249/cc and a density of α9249/cc was used.

As a result of analysis, this chlorosulfonated polyethylene was found to be 5a
It was found to contain 7wt% chlorine and α9wt% sulfur.

Mooney viscosity was 48.

The same formulation as in Example 1 was used for kneading using rolls.

A portion of the blend was extruded under the same conditions as Example-1. The surface texture of the extrudate was good.

On the other hand, the remaining formulations were vulcanized in the same manner as in Example 1, and the physical properties of the vulcanized products were measured.The results are summarized in Table 2.
Shown below.

Comparative Example 1 A reaction was carried out under the same conditions as in Example 1, except that the polyethylene used as a raw material was the medium-low pressure polyethylene 280051 used in Example 1 alone.

As a result of analysis, this chlorosulfonated polyethylene has a concentration of 35
．． It was found to contain 8 wt% chlorine and t o wt% sulfur.

Mooney viscosity was 57.

Mixing was performed using rolls using the same formulation as in Example-1.

A portion of the blend was extruded under the same conditions as Example-1. The surface texture of the extrudate was good.

On the other hand, the remaining formulations were vulcanized in the same manner as in Example 1, and the physical properties of the vulcanized products were measured.The results are summarized in Table 1.
Shown in 2.

Comparative Example 2 A reaction was carried out under the same conditions as in Example 1, except that the polyethylene used as a raw material was the high pressure polyethylene 28009 used in Example 1.

As a result of analysis, 'this chlorosulfonated polyethylene is 3
It was found to contain chlorine of 5.4 vrt9J and sulfur of α9 wt4.

Mooney viscosity was 61.

Mixing was performed using rolls using the same formulation as in Example-1.

A portion of the blend was extruded under the same conditions as in Example-1.

The surface of the extrudate was uneven, and the extrusion surface texture was poor.

On the other hand, the remaining formulations were vulcanized in the same manner as in Example 1, and the physical properties of the vulcanized products were measured.The results are summarized in Table 1.
Shown in 2.

Comparative Example 3 TO8O-O8MTS-530, a representative grade of chlorosulfonated polyethylene manufactured by Toyo Soda Kogyo ■, was blended in the same manner as in Example 1, and an extrusion test and measurement of the physical properties of the vulcanizate were conducted.

These results are shown in Table 2 along with the analytical values and Mooney viscosity.

Comparative Example 4 Hypalon 40, a representative grade of chlorosulfonated polyethylene manufactured by Typon, USA, was blended in the same manner as in Example 1, and extrusion tests and physical properties of the vulcanizate were measured.

The analytical values, Mooney viscosity, and K results are shown in Table 2.

The chlorosulfonated polyethylenes obtained in Examples 1 to 4 have good extrusion surface texture, low compression set at low temperatures, and oil resistance comparable to commercially available chlorosulfonated polyethylenes. .

From the above Examples and Comparative Examples, it is clear that the present invention is an excellent production method that provides chlorosulfonated polyethylene that has high oil resistance and low compression set at low temperatures.

Claims (1)

[Claims] 1) A method for producing chlorosulfonated polyethylene, which comprises chlorinating and chlorosulfonating mixed polyethylene consisting of medium-low pressure polyethylene and high-pressure polyethylene as a raw material. 2) Medium and low pressure polyethylene has a density of 0.948 to 0.96
5g/cc, melt index 0.01-300g/
The manufacturing method according to claim 1, which takes 10 minutes. 3) High-pressure polyethylene has a density of 0.910 to 0.930
g/cc, melt index 0.1-300g/10
The manufacturing method according to claim 1 or 2, which is a method for manufacturing. 4) The manufacturing method according to claim 1, 2 or 3, wherein the weight ratio of medium-low pressure polyethylene and high pressure polyethylene in the mixed polyethylene is 80/20 to 30/70. 5) The amount of chlorine in the chlorosulfonated polyethylene is 32 to 3
9 wt%, and the sulfur content is 0.4 to 1.6 wt%.