JPS60163904A - Production of chlorosulfonated polymer - Google Patents

Abstract

PURPOSE:To produce the titled polymer of excellent oil resistance without detriment to rubber elasticity, by chlorinating and chlorosulfonating a polymer comprising PE and a specified ethylene copolymer. CONSTITUTION:A polymer comprising PE (preferably medium to low-pressure process PE or linear low-density PE when excellent processability and rubber elasticity are desired) and a copolymer of ethylene with a compound of formula I or II (wherein R1, R2, R3, and R4 are each H, or a substituent), e.g., ethylene/vinyl acetate copolymer or ethylene/ethyl acrylate copolymer, is chlorinated and chlorosulfonated. A method for performing the above reaction usually comprises dissolving the above polymer in a solvent and reacting this solution in the presence of a radical generator as a catalyst by adding both of chlorine and sulfur dioxide gas, both of chlorine and sulfuryl chloride or sulfuryl chloride alone. It is possible to improve the oil resistance of chlorosulfonated polyethylene without detriment to its rubber elasticity.

Description

[Detailed description of the invention] It is something to do.

More specifically, the present invention relates to a method for producing a chlorosulfonated polymer that improves the oil resistance of chlorosulfonated polyethylene.

Conventional chlorosulfonated polyethylene is weather resistant.

Taking advantage of its excellent ozone resistance, heat resistance, and oil resistance,
Used for automotive hoses and automotive wiring cord coatings.

On the other hand, in recent years, it has become a challenge to further improve the oil resistance of elastomers used in automobiles, as represented by sour oil resistance and sour gasoline resistance. , it is strongly desired to improve gasoline resistance.

Since the oil resistance of chlorosulfonated polyethylene depends on the amount of chlorine, it is possible to improve the oil resistance of chlorosulfonated polyethylene by increasing the amount of chlorine.

However, the rubber elasticity of chlorosulfonated polyethylene is highly dependent on its chlorine content, and the one with the lowest chlorine content, which destroys the polyethylene crystals and becomes amorphous through chlorination, has the most rubber-like properties. (This is called the optimal chlorine amount. Polymer processing, Vot32, Black 6, Plo(1
985). ) Therefore, it is not appropriate to change the amount of chlorine for the purpose of improving the oil resistance of chlorosulfonated polyethylene, as this results in a loss of rubber elasticity or 'rubber-likeness'.

From this, it is possible to use chlorosulfonated polyethylene without impairing its original rubber elasticity or ``rubber-likeness''.
It is important to improve the oil resistance of chlorosulfonated polyethylene.

The present invention aims to solve these problems and to produce a chlorosulfonated polymer with improved oil resistance.

That is, the present invention provides a polymer comprising polyethylene and an ethylene copolymer in which the copolymer components are represented by either of the following structural formulas R, R4 (where RIs R2+ R8r ``4 is hydrogen or a substituent). This is a method for producing a chlorosulfonated polymer, characterized by chlorinating and chlorosulfonating the polymer.

The polyethylene used in the present invention is an ethylene polymer having a density of 188 to 0.96 and containing an ethylene homopolymer as well as a copolymer with an α-olefin mainly composed of ethylene.

Here, the α-olefins copolymerized with ethylene include propylene, butene-1, pentene-1, hexene-1,
octene-1, decene-1,4-methylpentene-1,
Examples include 3-methylpentene-1.

Specifically speaking, the polyethylene used in the present invention includes medium and low pressure polyethylene, linear low density polyethylene, and high pressure polyethylene.

However, in order to expect better processability and rubber elasticity, it is desirable to select medium-low pressure polyethylene or linear low-density polyethylene as the polyethylene.

The copolymer component of the ethylene copolymer constituting the raw material polymer together with this polyethylene must have one of the following structural formulas.

1 -0 1 R,R.

However, RIs R2* RBe R4 is hydrogen or a substituent.

Types of substituents include alkyl groups such as methyl, ethyl, propyl, and butyl groups, and glycidyl groups, but there are no particular restrictions as long as the chemical structure permits.

Ethylene copolymers having the copolymerization component shown by the structural formula on the left above include ethylene-vinyl acetate copolymers.

The ethylene copolymer having the copolymerization component shown by the structural formula on the right above includes ethylene-ethyl acrylate copolymer,
Examples include ethylene-methyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer.

Particularly preferred ethylene copolymers are ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer.

The content of copolymerized components copolymerized with ethylene is 1 to 70wt
It is preferable that the weight is 3 to 50 wt.
I am in charge.

The chlorosulfonated ethylene copolymer obtained by chlorinating and chlorosulfonating this ethylene copolymer alone has excellent oil resistance as a vulcanizate, but when compounded by roll, it sticks to the roll surface and the rubber sticks to the front and back rolls. The workability of the rolls is poor due to the so-called roll separation phenomenon in which the rolls are separated.

Furthermore, because the rubber elasticity of vulcanized products is inferior, automobile hoses,
K is not suitable for use in industrial products such as molds.

It is important to chlorinate and chlorosulfonate the blend of polyethylene and ethylene copolymer.

The reason why the oil resistance of the chlorosulfonated polymer is improved by the present invention is not clear, but since polar groups such as ester groups and carboxylic acid groups are introduced into the chlorosulfonated polymer, it is difficult to interact with oil. It is presumed that the affinity decreases and the oil resistance improves.

In the present invention, there is no particular restriction on the mixing ratio of polyethylene and the polymer made of ethylene copolymer, and the mixing ratio of polyethylene:ethylene copolymer can be set arbitrarily from 99:1 to 1:99.

However, if the mixing ratio of polyethylene:ethylene copolymer is 99
:1 to 60:40, more preferably 95:5 to 70:3
0 is highly effective in improving oil resistance without impairing the original processability and rubber elasticity of chlorosulfonated polyethylene.

The chlorine and sulfur content of the chlorosulfonated polymer obtained by chlorinating and chlorosulfonating these polymers composed of polyethylene and ethylene copolymer is the same as that of conventional chlorosulfonated polyethylene. , a sulfur content of 0.5 to 5 Owt is preferable.

However, if you are looking for better rubber elasticity or rubber-like properties, the amount of chlorine should be approximately 35wt1 when medium-low pressure polyethylene is used as the polyethylene, and approximately 30wt1 when linear low-density polyethylene is used. 53wt
'lr, approximately s o when using high pressure polyethylene
Preferably, it is wtl.

This means that the optimum amount of chlorine for each type of polyethylene is approximately 35 wtl for medium-low pressure polyethylene, approximately 30 to 33 wt% for linear low density polyethylene, and approximately 5 wt% for high pressure polyethylene.
G wtl, while the optimum chlorine content of the ethylene copolymer is about 27-50 wtl.

That is, in the raw material polymer used in the present invention, the optimum chlorine content for the polymer made of medium-low pressure polyethylene and ethylene copolymer is about 35 wt%, and the optimum chlorine content for the polymer made of linear low density polyethylene and ethylene copolymer is about 35 wt%. The amount is about 30
This is because the optimum amount of chlorine for a polymer made of high-pressure polyethylene and ethylene copolymer is approximately 30 wt%.

These optimum amounts of chlorine can be obtained by measuring the amount of hemp (1 = 1 - 1 - hemp) using a differential scanning calorimeter (DgC).

Here, in order to improve the workability or rubber elasticity of the chlorosulfonated polymer roll, it is desirable to select medium-low pressure polyethylene or linear low-density polyethylene as the polyethylene; however, linear low-density polyethylene The optimum amount of chlorine for ethylene copolymer and ethylene copolymer is about 60
~33 wtl and about 27-50 wtl, which are close to each other.

For this reason, obtaining a chlorosulfonated polymer by chlorinating and chlorosulfonating a polymer consisting of linear low-density polyethylene and ethylene copolymer to approximately 30 to 33 wt% yields a product with excellent rubber elasticity. It is particularly effective when

Furthermore, chlorosulfonated polyethylene made from linear low-density polyethylene has a lower optimal chlorine content than that of chlorosulfonated polyethylene made from medium-low pressure polyethylene, so although it has excellent rubber elasticity, it has poor oil resistance. This is a drawback, and improving this drawback has great industrial value.

However, the present invention is not limited to these amounts of chlorine or types of polyethylene.

The amount of sulfur is the vulcanization rate of the chlorosulfonated polymer.

Although it affects vulcanized density and stability, C
At less than L 5 wtl, vulcanization will not be sufficiently performed.

On the other hand, if the sulfur content exceeds h o wt %, the vulcanization is too fast, causing scorch, discoloration, etc., and also having an adverse effect on the storage stability of the unvulcanized product.

Preferably the sulfur content is 0.7 to 1.5 wt4.

Mooney viscosity W of chlorosulfonated polymer (ML1+4
(1100°C) is 10-150, preferably 20-130.

In carrying out the present invention, the reaction of chlorosulfonating the polymer to chlorinated Rahi to form a chlorosulfonated polymer may be the same as known methods for producing chlorosulfonated polyethylene.

Although there are no particular restrictions as long as the intent of the present invention is not impaired, a method in which the reaction is carried out by uniformly dissolving the polymer in a solvent (solution method) is a particularly preferred method for obtaining the effects of the present invention.

A general method for synthesizing a chlorosulfonated polymer using a solution method is shown below.

A polymer consisting of polyethylene and ethylene copolymer is dissolved in a solvent to form a homogeneous solution, and then 1) chlorine and sulfur dioxide gas, 2) chlorine and sulfuryl chloride, or 3) sulfuryl chloride are reacted alone using a radical generator as a catalyst. The reaction is carried out by adding it to the liquid.

The reaction temperature is 50 to 180°C, and the reaction pressure is suitably normal pressure to 8.97 m (gauge pressure). During the reaction, gases such as hydrogen chloride are continuously purged out of the system.

The solvent used in the reaction is carbon tetrachloride, chloroform, dichloroethane, and trichloroethane.

A halogenated hydrocarbon solvent inert to the chlorination reaction is used, such as tetrachloroethane, monochlorobenzene, dichlorobenzene, fluorobenzene, dichloroschiff methane, and trichlorofluoromethane. Preferably it is carbon tetrachloride.

Examples of radical generators that serve as catalysts include azo radical initiators such as α, d-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and 2,2′-azobis(2,4-dimethylvaleronitrile); Benzoyl peroxide, t-butyl peroxide.

There are organic peroxide radical initiators such as acetyl peroxide. Preferably it is α,d-azobisisobutyronitrile.

Instead of using a radical initiator, ultraviolet rays may be irradiated.

As mentioned above, the reaction reagents for chlorination and chlorosulfonation are: 1) Chlorine and sulfur dioxide gas (for example, Japanese Patent Publication No. 33-7838
).

2) Chlorine and sulfuryl chloride (e.g., JP-A-56-76
406).

3) Sulfuryl chloride (e.g., Japanese Patent Publication No. 59-12113
).

3) are known, but 2) or 3) is industrially preferred.

When sulfuryl chloride is used, an amine compound such as pyridine, quinoline, dimethylaniline, nicotine, or piperidine is used as a cocatalyst in order to add sulfur.

The amount of the polymer to be dissolved may be arbitrary, but it is preferably 5 to 20% by weight in terms of reaction since the viscosity of the reaction becomes high.

Hydrogen chloride remaining in solution after the end of the reaction.

Sulfur dioxide gas is removed from the system by blowing inert gas such as nitrogen while the solvent is refluxing. Add an epoxy compound as a stabilizer if necessary.

2.2'-bis(4-glycidyloxyphenyl)furopane is preferred.

The obtained solution of the chlorosulfonated polymer is subjected to 1) steam distillation, 2) drum drying, 3) extrusion drying, etc. to separate the rubber and the solvent.

1) is a method of feeding a polymer solution into hot water (see US Pat. No. 2,592,814).

2) is 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 US Pat. No. 2,923,979).

3) is a method in which the reaction solution is preconcentrated and then separated by feeding it into an extrusion dryer with a vent (Japanese Patent Laid-Open No. 57-475).
05).

In the present invention, separation and drying can be performed by any of the above processes.

The chlorosulfonated polymer referred to in the present invention is similar to conventional chlorosulfonated polyethylene, either as an unvulcanized product or as a vulcanized product that is vulcanized with a vulcanizing agent, a vulcanization accelerator, a filler, a stabilizer, etc. used as. As the vulcanizing agent, vulcanization accelerator, filler, stabilizer, etc., those currently used for chlorosulfonated polyethylene are used.

As the vulcanizing agent, metal oxides such as magnesia and litharge, small amounts of sulfur, and organic peroxides are known. As a vulcanization accelerator, dipentamethylene lentithuram/
Hexasulfide (TRA).

Examples include 2-mercaptoimidacillin (S22). Fillers include charcoal, clay, and silica.

Oil softeners, carbon black, etc. Stabilizers include Robo NBC and the like.

Like chlorosulfonated polyethylene, these are blended using rolls or a Banbury mixer.

After kneading, press vulcanization, steam vulcanization, UHF vulcanization, electron beam vulcanization, etc. are performed.

The chlorosulfonated polymer obtained by the present invention has excellent oil resistance.

Therefore, by taking advantage of its excellent oil resistance, it is suitable for automotive parts such as various fuel system hoses, lubricating oil system hoses, brake system hoses, radiator hoses, cooler hoses, ignition cables, and various wiring cord coverings.

On the other hand, since ester bonds are introduced into the molecules of the chlorosulfonated polymer, its adhesion to fibers, metals, etc. is improved, so it can be used in fabrics, electric wire coverings, escalator handrails, tarpaulins, and various gas hoses.

It is also suitable for use in roof ink adhesives, paints, etc.

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 numerical values used in the present invention were obtained based on the following measurement method.

Melt index: ASTM D 123B
Degree: ASTM 1) 1505 Vinyl acetate content: , He K 6730 Chlorine, sulfur content: Combustion flask method Mooney viscosity (M'LI +4, 100'C):
JIS K 6300 vulcanized rubber physical properties: , rIEI
K 6301 oil resistance: Based on J Engineering EI K 65rJj immersion test. Conditions: J Engineering S3 oil, 120"CX. Volume change rate after 70 hours (determination of rust).

Example-1 Melt index 4.09710 minutes, density G, 921 in a 30t glass-lined autoclave with a stirrer
9/cJ, the copolymerization component α-olefin is butene-
1, linear low-density polyethylene 22409 and ethylene-vinyl acetate copolymer mu634 (manufactured by Toyo Soda Kogyo ■)
Melt index 4.09710 minutes, density 0.949
97tri, vinyl acetate content 2/+wt%) 5609 was charged to obtain a raw material polymer.

The solvent carbon tetrachloride 2a (19) and the cocatalyst pyridine 0.3
After charging 81g, the temperature was raised to 110°C under pressure.
The polymer was dissolved.

Subsequently, the temperature was lowered at 100 °ct, and Z 2/-azobisisobutyronitrile 7,5 as a radical generator
Carbon tetrachloride solution in which 9 was dissolved 2. ．． The reaction was carried out by adding sulfuryl chloride 46509 while adding 9 to 86.

It took 180 minutes to add sul7lyl chloride, during which time the reaction temperature was increased to 100°C and the reaction pressure was increased to 3-3 kgl.
C1 & (Casing pressure) K hold*.

After the reaction was completed, the internal temperature of the boria solution was lowered to 70°C, and hydrogen chloride and sulfur dioxide gas remaining in the solution were discharged from the system by blowing nitrogen under reflux of the solvent.

After adding 47 g of Z 2/-bis(4-glycidyloxyphenyl)propane as a stabilizer, it was fed to a drum dryer to separate the product from the solvent.

As a result of analysis, this chlorosulfonated polymer has a concentration of 50.1
wtl chlorine and 1. It was found that it contains sulfur (o wtll).

Mooney viscosity was 49.

The following formulation was carried out using a 10-inch open roll heated to 50°C.

(Composition) Chlorosulfonated polymer 100 parts by weight Magnesium oxide 101 parts (Kyowa Kagaku Kogyo ■'s Kyowa Mag 15o) Pentaerythritol 3 parts by weight Dipentamethylene lentithurum hexasulfide 2 parts by weight (Omukai Shinko Chemical Industry ■ Tsukusela) Workability using the TRA) roll was good.

The compound was press-vulcanized at 150°C for 140 minutes, and the physical properties of the vulcanized product were measured.

These results are summarized in Table-1.

Example 2 In the autoclave used in Example 1, medium and low pressure polyethylene 25209 with a melt index of 0/10 minutes and a density α9589/di and ethylene manufactured by Nippon Unicar were added.
Ethyl acrylate copolymer DPD, r-6169 (melt index 69/10 original density 0.931 r/al
) 2809 was charged to obtain a raw material polymer.

Carbon tetrachloride 2ELOIc9 as a solvent and pyridine Q as a promoter
, 5059, the temperature was raised to 110°C under pressure to dissolve the polymer.

Subsequently, the temperature was lowered to 100°Cf, and 2.2'-azobisisobutyronitrile was added as a radical generator7.
The reaction was carried out by adding 5955 g of sulfuryl chloride while adding 2.8119 g of a carbon tetrachloride solution in which 59 was dissolved.

It took 230 minutes to add nurfuryl chloride, during which time the reaction temperature was 100°C and the reaction pressure was 5.31c9/min.
cI/l (gauge pressure) K was maintained.

After the reaction was completed, hydrogen chloride and sulfur dioxide gas remaining in the solution were discharged from the system in the same manner as in Example-1.

After adding 53 g of 2,2'-bis(4-glycidyloxyphenyl)propane as a stabilizer, it was fed to a drum dryer to separate the product from the solvent.

As a result of analysis, this chlorosulfonated polymer has a s 5.7
wtl chlorine and 1. It was found to contain o wtl sulfur.

Mooney viscosity was 55.

Blending was carried out using rolls in the same manner as in Example 1, and the workability was good.

It was vulcanized in the same manner as in Example-1 and its physical properties were measured.
These results are summarized in Table-1.

Example-3 The autoclave used in Example-1 had a melt index of 11. Og/l 0 min, density αq 22 q/l:
RL's high pressure polyethylene 19609 and Toyo Soda Kogyo■
Ethylene-vinyl acetate copolymer UB625 (melt index 149/10 min, density 0, 9349/ct
/l, vinyl acetate content 15 wt%) was charged to obtain a raw material polymer.

The reaction was carried out under the same conditions as in Example 1, except that the amount of pyridine used as a cocatalyst was changed to [1,4589], and the product was separated.

As a result of analysis, this chlorosulfonated polymer has 3α5 v
It was found to contain t'4 chlorine and 1.4 wt'J sulfur.

Mooney viscosity was 27.

Blending was carried out using a roll in the same manner as in Example-1.

Although the rubber stuck to the roll surface and the roll separation phenomenon was observed, and the workability of the roll was poor, it was possible to blend it.

It was vulcanized in the same manner as in Example-1 and its physical properties were measured.
These results are summarized in Table-1.・Comparative Example-1 Linear low-density polyethylene 28009 used in Example-1
Example-1 except that polyethylene was used as the raw material alone
The product was obtained after separation and drying.

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

Mooney viscosity was 49.

Blending was carried out in the same manner as in Example-1, but workability with a roll was good.

The compound was vulcanized and its physical properties were measured in the same manner as in Example 1, and the results are summarized in Table 1.

Comparative Example 2 A reaction was carried out in the same manner as in Example 2, except that 2800 g of medium-low pressure polyethylene used in Example 2 was used as the raw material polyethylene, and a product was obtained after separation and drying.

As a result of analysis, this chlorosulfonated polyethylene has a
．． 8 wtqb of chlorine and 1. It was found to contain Ow14 sulfur.

Mooney viscosity was 55.

The blending was carried out in the same manner as in Example 2, but the workability with the roll was good.

The compound was vulcanized in the same manner as in Example 2, and its physical properties were measured, and the results are summarized in Table 1.

Comparative Example 3 A reaction was carried out in the same manner as in Example 3, except that 2800 g of the high-pressure polyethylene used in Example 5 was used alone as the raw material polyethylene, and a product was obtained after separation and drying.

As a result of analysis, this chlorosulfonated polyethylene is
It was found to contain a s wt% chlorine and 1.4 wt% sulfur.

Mooney viscosity was 2 days.

Although the formulation was carried out in the same manner as in Example 3, a phenomenon of roll separation due to adhesion to the rolls was observed.

Although the workability of the roll was poor, blending was possible.

The compound was vulcanized and its physical properties were measured in the same manner as in Example 3. These results are summarized in Table 1. According to the above example, the chlorosulfonated polymer obtained by the present invention was It has the property of improved oil resistance. It is clear that the present invention provides a method for producing chlorosulfonated polymers having excellent oil resistance properties.

Patent Applicant Toyo Soda Kogyo Co., Ltd. Procedural Amendment May 23, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1 Description of Case 1989 Patent Application No. 19346 2 Name of Invention Process for Producing Chlorosulfonated Polymer Relationship with the case of the person making the amendment Patent applicant address 4560 Oaza Tomita, Shinnanyo City, Yamaro Prefecture 746 Phone number (585) 3311 4 Date of amendment order April 4, 1980 (Shipping date April 1982) April 24th) Table 1 on page 25 of the detailed description of the invention column 6 of the specification subject to the amendment is corrected as shown in the attached sheet.

7 List of Attached Documents (1) A document in which the entire text of page 25 of the specification is printed in No. 4 brackets.

Claims (1)

[Claims] 1) A polymer consisting of polyethylene and an ethylene copolymer whose copolymerization component is represented by one of the following structural formulas (wherein Rs+Rt+R31R4 is hydrogen or a substituent) , a method for producing a chlorosulfonated polymer, characterized by chlorination and chlorosulfonation. 2) The method for producing a chlorosulfonated polymer according to claim 1), wherein the polyethylene is linear low density polyethylene. 3) The method for producing a chlorosulfonated polymer according to claim 1) or 2), wherein the ethylene copolymer is an ethylene-vinyl acetate copolymer. 4) The method for producing a chlorosulfonated polymer according to claim 1) or 2), wherein the ethylene copolymer is an ethylene-ethyl acrylate copolymer.