JPH01207302A - Production of chlorinated ethylene-based copolymer - Google Patents

Abstract

PURPOSE:To obtain the title readily vulcanizable copolymer, excellent in resistance to heat, cold, oils and weather, by chlorinating an ethylene-based copolymer in an aqueous suspension in two steps under each specified condition. CONSTITUTION:An ethylene-based copolymer consisting of ethylene and an alpha,beta-unsaturated dicarboxylic acid and/or anhydride thereof (e.g., fumaric acid or maleic anhydride) and having a melt flow index of 0.1-100g/10min and a copolymerization ratio of the total of the alpha,beta-unsaturated dicarboxylic acid and the anhydride thereof of 0.5-25mol% is contacted with gaseous chlorine in an aqueous suspension. In this case, the first step chlorination is carried out so as to be 20-60% of the total chlorination at such temperatures as to be at least 25 deg.C lower than the melting point of said copolymer and >=50 deg.C followed by, in the second step, the remaining chlorination at such temperatures as to be 10 deg.C or more higher than those in the first chlorination and 5-15 deg.C lower than the melting point of said copolymer to provide the objective copolymer containing 5-45wt.% of chlorine and giving Mooney viscosity (ML1+4, 100 deg.C) of >=5.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing chlorinated ethylene copolymers by chlorinating the ethylene copolymers in two stages in an aqueous suspension. More specifically, it not only has good heat resistance and cold resistance, but also excellent oil resistance, weather resistance and ozone resistance, and also has excellent adhesion to metal and synthetic fiber base fabrics. and
The present invention also relates to a method for producing a chlorinated ethylene copolymer that not only allows crosslinking but also relatively simple vulcanization.

BACKGROUND OF THE INVENTION Chlorinated elastomers and resins have been commercially produced and used in a wide range of applications. These obtained kPIB compounds are #-like.

It is well known that it is used as parts for automobiles, electric machines, electronic equipment, industrial equipment, etc. due to its excellent solubility, chemical resistance, heat aging resistance, and oil resistance.

Among the chlorinated products, chlorinating a copolymer of ethylene and alkyl (meth)acrylate or a copolymer of ethylene, alkyl (meth)acrylate, and (meth)acrylic acid or (anhydride) maleic acid. A chlorinated product obtained by
No. 9205), the resulting chlorinated product is transparent, oil-resistant, and flexible, and is known to be useful as an adhesive.

(Problems to be Solved by the Invention) The chlorinated product is produced by dissolving a copolymer in a solvent such as carbon tetrachloride and chlorinating the copolymer in the solution at a relatively high temperature. In order to produce chlorinated products using this method, the vapor pressure of the solvent in the two reaction systems is high, a high-temperature and pressure-resistant reactor is required, and the thermal stability of the resulting polymer (chlorinated product) becomes a problem. Monochemical or not powdered (
In addition, it is difficult to remove the solvent used from the chlorinated product after chlorination because the chlorinated product is in the form of lumps.

From the above, the present invention does not have these drawbacks (problems), that is, it not only has excellent heat resistance and cold resistance, but also has good oil resistance, weather resistance, and ozone resistance.
In addition, chlorination is possible at relatively low temperatures, and the resulting chlorinated product does not clump, and it can be crosslinked with organic peroxides as well as vulcanized with sulfur or sulfur-containing compounds (sulfur-releasing compounds). This is a method for obtaining a chlorinated ethylene copolymer.

(Means and effects for solving the problems) According to the present invention, these problems can be solved by melt flow index (
JIS 721O, measured under condition 4, hereinafter referred to as rIIIFRJ) or 0°1 to 100 g/1
0 minutes, and the copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride is 0.5 to 25 mol% in total amount of ethylene and α, β-unsaturated dicarboxylic acid and/or its anhydride. This is a method for producing a chlorinated ethylene copolymer by contacting an ethylene copolymer with chlorine gas in an aqueous suspension, and in the first step, the temperature is at least 25 ℃ lower temperature, but at a temperature higher than 50℃, 20 to 60 of the total chlorination amount
% is chlorinated, and in the second stage, the temperature is 10°C or more higher than the chlorination temperature in the first stage, but 5 to 5% higher than the melting point of the ethylene copolymer. The remaining chlorination is carried out at a temperature 5℃ lower, and the chlorine content is 5-45% by weight.
A method for producing a chlorinated 1+4 tyrenic copolymer having a Mooney viscosity (ML, 100° C.) of 5 or more.

It can be solved by The present invention will be explained in detail below.

(8) Ethylene-based copolymer In producing the chlorinated ethylene-based copolymer of the present invention, the ethylene-based copolymer as a raw material is at least ethylene and "α,β-unsaturated dicarboxylic acid and/or its anhydride." ” (hereinafter referred to as “comonomer (1)”). The copolymer may be a copolymer of ethylene and comonomer (1), and may be a copolymer of ethylene and comonomer (1).
In addition to the 2nd and 3rd copolymerization components, [a comonomer having at least one double bond selected from the group consisting of unsaturated carboxylic esters, alkoxyalkyl acrylates, and vinyl esters] (hereinafter referred to as ``comonomers'') It may also be a multi-component combination consisting of

Among the comonomers (1), the α,β-unsaturated dicarboxylic acid usually has at most 20 carbon atoms, especially 4 to 1 carbon atoms.
Six pieces are preferred. Representative examples of the dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, 3.6-nindomethylene-1.2. and 6-titrahydrosis-phthalic acid (Nadei Sokyou @).

Among the α,β-unsaturated dicarboxylic acid components of the present invention, anhydrides of the α,β-unsaturated dicarboxylic acids are preferred, and maleic anhydride is particularly preferred.

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, particularly preferably 4 to 20 carbon atoms. Representative examples include methyl (meth)acrylate, ethyl (meth)acrylate, Preferably, those with good thermal stability such as

Furthermore, the number of carbon atoms in the alkoxyalkyl platform acrylate is usually at most 20. Further, the alkyl group has 1 to 8 carbon atoms (preferably).

It is preferable that the alkoxy group has 1 to 4 carbon atoms, and it is more preferable that the alkoxy group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). Representative examples of preferred alkoxy[alkyl acrylates] include methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate.

Furthermore, the number of carbon atoms in vinyl ester is generally at most 2.
Representative examples of suitable vinyl esters having 0 (preferably 4 to 16) vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate, with vinyl acetate being particularly preferred.

In the ethylene copolymer of the present invention, the comonomer (1
) copolymerization ratio is 0.5 to 25 mol%, and 1.0 to 25 mol%.
25 mol% is preferred, and 1.0 to 20 mol% is particularly preferred. Copolymerization ratio of comonomer (1) or 0.1 mol%
If less than 20% of the ethylene copolymer is used, the effect of the resulting chlorinated product will not be exhibited.

On the other hand, an ethylene copolymer containing more than 25 mol % poses problems in terms of cost and construction when industrially produced.

In addition, the copolymerization ratio of comonomer (2) is generally at most 25 mol%, and 0.5
~25 mol% is preferable, especially 1.0~25 mol%
Mol% is preferred.

The MFR of the ethylene copolymer is 0.1 to 200 g/l
0.5 to 0.0 g/10 minutes is preferable, and 1.0 to 200 g/In is particularly preferable. If an ethylene copolymer with an MFR of less than 0.1 g/10 min is used, the resulting ethylene copolymer will not have good moldability or crosstalk.
If you use an ethylene copolymer that has been used for more than 10 minutes.

The mechanical properties of the resulting chlorinated ethylene copolymer are poor.

The ethylene copolymer is composed of ethylene and comonomer (1) or ethylene, comonomer (1) and comonomer (2).
) under ultra-high pressure of 50 to 2500 kg/crn'.

It is manufactured by radical polymerization in the presence of a chain transfer agent at a temperature of 100 to 280°C. This copolymer is industrially produced and used in a wide variety of fields, and its production method and physical properties are well known.

In producing the chlorinated ethylene copolymer of the present invention, a copolymer consisting of ethylene and the comonomer (1) may be used as the ethylene copolymer, but especially a copolymer consisting of ethylene, the comonomer (1), and the comonomer (2)
By using a ternary copolymer consisting of the following, blocking does not occur during chlorination and it can be carried out easily. Moreover, the obtained chlorinated ethylene copolymer is preferable because it has excellent rubber elasticity and heat resistance.

The chlorinated ethylene copolymer of the present invention can be produced by subjecting the above ethylene copolymer to the first-stage chlorination and second-stage chlorination described below.

The first and second stage chlorination is carried out in aqueous suspension. To carry out the chlorination in the form of an aqueous suspension, the ethylene copolymer in particulate or powder form is suspended in an aqueous medium. In order to maintain this aqueous suspension, it is preferable to add a small amount of emulsifying agent or suspending agent. At this time, if necessary, radical generating agents such as benzoyl peroxide, azobisisobutyronitrile and hydrogen peroxide are added. Antifoaming agents, light silicone oil, and other additives may be added.

(B) First Stage Chlorination In the first stage, chlorination is carried out at a temperature at least 25°C lower than the melting point of the ethylene copolymer used. In particular, 30 to 60°C above the melting point of the copolymer.
It is preferable to carry out the chlorination at a low temperature; if the chlorination is carried out at a temperature at least 25°C below the melting point of the copolymer, no agglomeration of the particles occurs during the reaction, and no Chlorination can be easily carried out. On the other hand, when chlorination is carried out at a low temperature below 25°C, particles tend to aggregate during one reaction, making it difficult to continue the reaction, and the resulting product is also non-uniform. It has a chlorination degree distribution.

The chlorination in the first stage is carried out at a temperature above 50°C.

In addition, in this first stage, 20 to 60 of the total chlorination amount
% chlorination (for example, the chlorine content is 30%
When producing the chlorinated ethylene-based copolymer of the present invention, which is a chlorinated ethylene copolymer, it is preferable to carry out chlorination in this first step. If less than 20% of the total chlorination amount is chlorinated at this stage, particles tend to aggregate in the subsequent second stage chlorination reaction.

On the other hand, if chlorination exceeds 60%, the chlorination will proceed unevenly and the resulting product will have poor heat resistance and processability.

After carrying out the chlorination in the first stage in this way,
The chlorinated ethylene copolymer of the present invention can be produced by carrying out the second stage of chlorination under the following conditions. When moving from the first stage chlorination to the second stage chlorination, the second stage chlorination may be carried out by changing the conditions in the reactor used in the first stage chlorination, or the second stage chlorination may be carried out in advance. The aqueous suspension containing the chlorinated ethylene-propylene copolymer produced by the first stage chlorination may be transferred to another reactor controlled to the conditions of the second stage chlorination.

(C) Second stage chlorination The second stage chlorination is 10°C higher than the first stage chlorination temperature.
This can be achieved by carrying out the remaining chlorination at a temperature higher than or equal to 5 DEG C. or at a temperature 5 to 15 DEG C. lower than the melting point of the ethylene copolymer used. In particular, it is desirable to carry out the reaction at a temperature that is 0° C. or more higher than the chlorination temperature in the first step or 5 to 1° C. lower than the melting point of the copolymer. If the second stage chlorination is carried out at a temperature 5° C. or more below the melting point of the copolymer, the product will have a uniform tm chlorination degree distribution and will have poor processability and heat resistance.

On the other hand, if this stage of chlorination is carried out at a temperature lower than the melting point of the copolymer used by more than 15°C, the product will not have a non-uniform chlorination degree distribution and will have poor processability and heat resistance. Inferior.

In the above first and second stage chlorination, chlorine can be used alone in gaseous form or diluted with a suitable inert gas. In this case, the chlorine introduction pressure is usually 5 g.
/crrf or less. The progress of chlorination can be determined by measuring the weight loss of the supplied chlorine, or the degree of chlorination can be determined by measuring the amount of hydrogen chloride produced.

The chlorinated ethylene copolymer thus obtained is
After washing with water to remove attached hydrochloric acid, emulsifier, etc.
The chlorinated ethylene copolymer of the present invention can be produced by drying.

(D) Physical properties and mechanical properties of the chlorinated ethylene copolymer The chlorine content of the chlorinated ethylene copolymer thus obtained is 5 to 45% by weight (preferably 5 to 40% by weight, Suitably, it is 10-35%). If the chlorine content of this chlorinated ethylene copolymer is less than 5% by weight,
There are problems in recovering and purifying the resulting chlorinated ethylene copolymer.

Moreover, the chlorinated ethylene copolymer has poor solubility resistance, and on the other hand, the chlorinated ethylene copolymer produced when the amount exceeds 45% by weight is undesirable because the thermal stability and heat resistance are significantly reduced.

The Mooney viscosity of the chlorinated ethylene copolymer obtained as described above is 5 or more points in a large rotor at a temperature of 100 DEG C., preferably 5 to 150 points, particularly preferably 10 to 150 points.

Furthermore, the melt flow index of the chlorinated ethylene copolymer of the present invention (measured according to JIS K-7210, condition 7, hereinafter referred to as rMFR(2) J)
is generally 0.1 to 100 g/10 minutes, and 0.
2 to 100 g/10 minutes is preferred, especially 0.5 to
80g/10 minutes is suitable.

Typical properties of the chlorinated ethylene copolymer of the present invention are shown below.

Density is 1.00-1. :lOg/cm'.

In addition, in a tensile test measured according to JISK-6:101, the tensile breaking strength was 5 to 70 kg/cr.
It is n'.

The tensile elongation at break is 800-2500%. Furthermore, the hardness (Shore A) is 30-70.

(E) Processing and molding method In processing and molding the chlorinated ethylene copolymer of the present invention, lubricants, colorants, antistatic agents, fillers, and oxygen commonly added to chlorinated polyethylene are used. Additives such as stabilizers against light and heat may be added.Also, commonly used chlorinated polyethylene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene and propylene Rubber products such as binary or tertiary copolymer rubber, chloroprene rubber, chlorosulfonated botethylene rubber, butadiene homopolymer rubber and natural rubber, as well as polyvinyl chloride, ethylene and/or propylene as main components. Graft polymerization of at least one vinyl compound such as styrene, acrylonitrile, and methyl methacrylate to an olefin resin, a methyl methacrylate resin containing methyl methacrylate as a main component, an acrylonitrile-styrene copolymer resin, and the rubbery material. A resinous material such as a graft polymer obtained by the above method may also be blended.

When producing these compositions, the blending (mixing) method may be to use a mixer commonly used in the art, such as an open roll, dry blender, Banbury mixer, and Nigoo mixer. ,
Among these mixing methods, two or more of these mixing methods may be applied in order to obtain a layer-uniform composition (for example, after mixing with a dry blender in advance.

method of mixing the mixture using an open roll),
Among these mixing methods, in order to mix the chlorinated ethylene copolymer and the rubbery material, the mixing temperature is 30 to 120°C.
The temperature is usually 50 to 100°C. In particular, during mixing, since the rubbery material generates heat due to cohesive force, it is desirable to control the mixing temperature to 150° C. or lower. In addition, in order to mix the chlorinated ethylene copolymer and the resinous material,
It is above the temperature at which they melt, but 1 liter (1'c
It is preferable to carry out the following.

The chlorinated ethylene copolymers of the present invention and their compositions can be used in molding machines such as extrusion molding machines, injection molding machines, compression molding machines, and calender molding machines that are commonly used in the rubber and resin industries. It is used after being molded into a desired shape. In addition, when molding only the chlorinated ethylene copolymer, the molding temperature is 70 to 130°C.
℃, generally 90 to 120℃.

(Examples and Comparative Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the tensile test was conducted according to JIS
According to K-5:101, tensile speed is 500mm
/ minute condition (dumbbells are JIS No.
No. 3 dumbbells were used), and the hardness was JIS hardness (Shore A), and the test piece was JIS -6301.
The hardness was measured using a hardness meter by stacking three JIS No. 3 dumbbells. Furthermore, the Mooney viscosity is J
The 4-minute values were measured according to IS K-6101 using a large rotor at a temperature of 100° C. and a preheat of 1 minute. In addition, in the adhesion test, specimens (4 mm thick) of each of the obtained chlorinated ethylene copolymers were attached to an aluminum plate (
Glued to a thickness of about 1v++), according to JISK63 old,
Evaluation was made by peeling in a 90 degree direction at a tensile speed of 50 mm.

Example 1 In a 100 JJ glass-lined autoclave, 80 g of water, 80 g of sodium laurate, and ethylene-methyl methacrylate having an MFR (1) or too g of 710 minutes as an ethylene copolymer and a melting point of 108°C were placed in a 100 JJ glass-lined autoclave. -Maleic anhydride terpolymer [copolymerization ratio of methyl methacrylate 18.5 mol%, copolymerization ratio of m-maleic acid hydroxide 1.5 mol%, hereinafter rEMMA (1
) J) Pour 10kg and add 50kg while stirring.
The copolymer was chlorinated in a temperature range of ~85°C until the chlorine content was 5.0% by weight (first stage chlorination).
Then, the reaction system was heated to 90 to 103°C, and in this temperature range, the chlorine content was reduced to 13.5% by weight. rc1.EEA (A) J) was produced.

Example 2 Chlorination was carried out in the same manner as in Example 1, except that the chlorine content of the chlorinated ethylene copolymer finally obtained was 30.1% by weight. An ethylene-based copolymer (hereinafter referred to as rCLEMMA (B)) was produced.

Example 3 Instead of EMMA (1) used in Example 1, M
FR(1) or 50g/10min, and melting point is 120
ethylene-methyl methacrylate-maleic anhydride terpolymer (copolymerization ratio of methyl methacrylate: 9.6 mol%, copolymerization ratio of maleic anhydride: 1.2
mol%, hereinafter referred to as rEMMA (2) J),
The first stage chlorination was carried out in the same manner as in Example 1 at a temperature range of 50 to 90°C. The chlorine content of the chlorinated product obtained at this stage is g/. 8% by weight. about,
This reaction system was heated and chlorinated in a temperature range of 5 to 106°C until the chlorine content reached 35.6% by weight, producing a chlorinated ethylene copolymer (r CLEMMA (C)).
J) was manufactured.

Comparative example 1 Instead of EMMA (1) used in the example, MF
R(1): 100g/10min, and melting point is 50
Ethylene-methyl methacrylate-maleic anhydride terpolymer (copolymerization ratio of methyl methacrylate: 21.4 mol%, copolymerization ratio of maleic anhydride: 3.
The first stage chlorination and second stage chlorination were carried out in the same manner as in Example 1, except that 8 mol %) was used. Obtained IM
Hydrogenated ethylene copolymer C or below CLEMMA (D)
The chlorine content of the sample (referred to as J) was 31.3% by weight.

Comparative Examples 2 to 5 EMMA (1) used in Example 1 was chlorinated in the temperature range shown in Table 1 until the chlorine content was shown in Table 1, and each first stage chlorination was carried out. Next, each of the chlorinated products thus obtained was immediately chlorinated in the temperature range shown in Table 1 (second stage chlorination) to obtain a chlorinated ethylene system having the chlorine content shown in Table 1. A copolymer was produced.

Table 1 1) Chlorine content of each chlorinated ethylene copolymer after second-stage chlorination Note that in the first-stage chlorination of Comparative Examples 1 and 5, agglomeration occurred and the chlorine distribution was uneven. there were. Furthermore, in the first stage chlorination of Comparative Example 2, the distribution of 111 elements was non-uniform. Furthermore, in Comparative Examples 3 and 4, agglomeration occurred in the second stage chlorination, and the chlorine distribution was uneven.

The physical properties of each of the chlorinated ethylene copolymers obtained in Examples 3 to 3 and Comparative Example 2 were measured. The results are shown in Table 2.

Table 2 Note that adhesiveness tests were conducted on each of the chlorinated ethylene copolymers obtained in Examples 1 to 3 and Comparative Example 2. In each case, specimens of chlorinated ethylene copolymer were cut.

(Reference Example) The vulcanizability of the chlorinated ethylene copolymer obtained by the present invention and commonly available chlorinated polyethylene will be compared and studied.

Reference Example l CLEMMA(A) 10 obtained by Example 1
0 parts by weight, 10 parts by weight of magnesium oxide as an acid acceptor, and carbon black as a filler (manufactured by Asahi Carbon Black Co., Ltd., SRF 50. Average particle size 94n) 50
Part by weight, trioctyl trimellitate 30 as plasticizer
A sheet was prepared by thoroughly kneading 0.5 parts by weight of sulfur as a vulcanizing agent and 4.5 parts by weight of diethylthiourea as a vulcanization accelerator at room temperature using an oven roll for 20 minutes.

Reference Example 2 Instead of CLEMMA (A) used in Reference Example 1, the molecular weight is approximately 200,000, and 'f: degree or 0.
The Mooney viscosity (ML, 100° C.) obtained by chlorinating high-density polyethylene (950 g/cm) by an aqueous suspension method is 70.

1+4 A sheet was prepared by kneading in the same manner as in Reference Example 1, except that chlorinated polyethylene having a chlorine content of 30.3% by weight was used.

The vulcanization state of each sheet of Reference Example 1 (a) and Reference Example 2 (b) thus obtained was examined using a rheometer tester at a temperature of 165°C and an angle of 3 degrees. . These vulcanization curves are shown in the first UA.

(Effect of the invention) The chlorinated ethylene copolymer obtained by the present invention is
From Figure 1, it is clear that it is vulcanizable or normal Ill! It is not only superior to J-bodethylene, but also exhibits the following effects.

(1) Good ozone resistance.

(2) Excellent repellency.

(3) It also has good flame retardancy.

(4) Excellent weather resistance and durability.

(5) Tearability and other mechanical strengths are also good.

(6) #Excellent oiliness.

(7) It also has good heat resistance and low temperature properties.

(8) Excellent adhesion to metals, etc.

Since the chlorinated ethylene copolymer of the present invention has the above-mentioned excellent properties, it can be used in a wide variety of fields. Typical application examples are shown above.

(+) If only the flame retardance of these resins is improved by blending them with polypropylene, acrylonitrile-butadiene-styrene terpolymer resin (ABS resin), high-density polyethylene, low-density polyethylene, vinyl chloride resin, etc. First, mechanical properties (for example, impact resistance) can be improved.

(2) By incorporating commonly used flame retardants, it can be used as a more advanced flame retardant material.

(3) Various parts for automobiles (e.g., hoses, tube materials) (4) Covering materials for electric wires (5) Adhesives (6) Parts for electronic equipment, electric machine bases, etc.

[Brief explanation of the drawing]

FIG. 1 is a vulcanization curve diagram of each sheet (composition) obtained in Reference Example 1 and Reference Example 2, measured using a disc rheometer. In this figure, the vertical axis is the torque (
Kg-cm), and the horizontal axis shows vulcanization time (minutes). Note that a and b are the vulcanization curves of each composition obtained in Reference Example 1 and Reference Example 2, respectively. .

Claims (1)

[Claims] Ethylene and α, β having a melt flow index of 0.1 to 100 g/10 min and a copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride in a total amount of 0.5 to 25 mol%. - A method for producing a chlorinated ethylene copolymer by contacting an ethylene copolymer with an unsaturated dicarboxylic acid and/or its anhydride with chlorine gas in an aqueous suspension, in which ethylene The temperature is at least 25°C lower than the melting point of the system copolymer, but 20 to 60% of the total chlorination amount at a temperature higher than 50°C.
% is chlorinated, and in the second step, the remaining chlorination is carried out at a temperature that is at least 10°C higher than the chlorination temperature in the first step, but 5 to 15°C lower than the melting point of the ethylene copolymer. The chlorine content is 5-45% by weight.
and Mooney viscosity (ML_1_+_4, 100
℃) is 5 or more.