JPH0329242B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a chlorinated ethylene-propylene copolymer by chlorinating the ethylene-propylene copolymer in three stages in an aqueous suspension. Chlorine not only has good water resistance and cold resistance, but also has excellent oil resistance, weather resistance and ozone resistance, and is not only crosslinkable but also relatively easy to vulcanize. The object of the present invention is to provide a modified ethylene-propylene copolymer. Prior Art It has been known for a long time that chlorinated ethylene-propylene copolymers are useful as paints and adhesives because they generally have excellent oil resistance and flame retardancy (Japanese Patent Laid-Open Publication No. No. 59-122503). but,
A method for chlorinating an ethylene-propylene copolymer is to chlorinate the ethylene-propylene copolymer in an aqueous medium containing no suspending agent at a temperature of less than 50°C (for example, 20 to 45°C) for 2 hours in the first step. Chlorinate to more than 2% by weight (e.g. 2 to 15% by weight), and in the second stage 50% by weight.
℃ (for example, 70 to 100 degrees Celsius), and chlorine is carried out at this temperature to a chlorine content of 18% by weight (for example, 18 to 50% by weight). A method has also been proposed in which an ethylene-propylene copolymer is dissolved in a solvent such as carbon tetrachloride and chlorinated in the solution at a relatively high temperature (150° C. or lower). However, in this method, the vapor pressure of the solvent in the reaction system is high, a high-temperature and pressure-resistant reactor is required, and the thermal stability of the produced polymer becomes a problem. On the other hand, when chlorinating with an aqueous medium, there was a problem that the chlorinated product formed into lumps when the chlorinated product was washed with water after chlorination. Problems to be Solved by the Invention 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 oil resistance, weather resistance, and ozone resistance. chlorination is possible at relatively low temperatures, the resulting chlorinated product does not aggregate, and is not only crosslinked by organic peroxides but also crosslinked by sulfur or sulfur-containing compounds (sulfur-releasing compounds). This is a method for obtaining a chlorinated ethylene-propylene copolymer that can be vulcanized. Means and Effects for Solving the Problems According to the present invention, these problems are solved when the propylene content is 15 to 40% by weight and the melt flow index (according to JIS K7210, conditions are 14). measurement (hereinafter referred to as "MFR") is 0.01 to 5.0
g/10 min, and Mooney viscosity (ML ₁₊₄ ,
This is a method for producing a chlorinated ethylene-propylene copolymer by contacting a chlorinated ethylene-propylene copolymer with a temperature of 10 to 180 (100℃) in an aqueous suspension with chlorine gas, and the first step is at least lower than the melting point of the ethylene-propylene copolymer at
The temperature is 25°C lower, but 20-60% of the total chlorination amount is chlorinated at a temperature higher than 50°C, and the chlorination temperature in the second stage is 10°C lower than the chlorination temperature in the first stage.
However, at a temperature 5 to 15 degrees Celsius lower than the melting point of the ethylene-propylene copolymer, at least 30% of the remaining chlorination amount is obtained, and by this stage, 60 to 90% of the total chlorination amount is % chlorination and then in a third step at a temperature lower than the melting point of the ethylene-propylene copolymer, but 2°C above the melting point.
A chlorinated ethylene-propylene copolymer with a chlorine content of 20 to 45% by weight and a Mooney viscosity (ML ₁₊₄ , 100°C) of 10 to 150, with the remaining chlorination carried out at a temperature as low as: This can be solved by the manufacturing method. The present invention will be specifically explained below. (A) Ethylene-propylene copolymer In producing the chlorinated ethylene-propylene copolymer of the present invention, the propylene content of the ethylene-propylene copolymer as a raw material is 15 to 15%.
40% by weight, preferably 18-40% by weight, especially
20-38% by weight is preferred. When an ethylene-propylene copolymer with a propylene content of 15% by weight is used for chlorination, the resulting chlorinated ethylene-propylene copolymer has poor rubber-like elasticity and is rather plastic-like in the product. be. On the other hand, when chlorinating with more than 40% by weight of ethylene-propylene copolymer, the particles of the chlorinated ethylene-propylene copolymer obtained during chlorination become large and form nodules in the reaction system. Unfavorable for becoming. In addition, the ethylene-propylene copolymer
MFR is 0.01-5.0g/10 min, 0.02-5.0g/
10 minutes is desirable, and 0.05 to 5.0 g/10 minutes is particularly suitable. If an ethylene-propylene copolymer having an MFR of less than 0.01 g/10 minutes is used for chlorination, the processability of the resulting chlorinated ethylene-propylene copolymer is poor. On the other hand, 5.0g/10
When chlorinating an ethylene-propylene copolymer in excess of 20%, the reaction efficiency during production of the chlorinated ethylene-propylene copolymer is poor, and moreover, the chlorinated product forms agglomerates. Furthermore, the Mooney viscosity (ML ₁₊₄ , 100°C) of the ethylene-propylene copolymer is 10 to 180, preferably 10 to 170, and particularly preferably 10 to 150. If an ethylene-propylene copolymer having a Mooney viscosity of less than 10 is chlorinated, the chlorinated product will be severely aggregated during chlorination. On the other hand, when an ethylene-propylene copolymer with a molecular weight exceeding 180 is used, the resulting chlorinated product has excellent mechanical properties, but has poor rubber-like elasticity and is rather plastic-like. The ethylene-propylene copolymer contains ethylene and propylene in the above propylene content,
It is obtained through copolymerization using a so-called Ziegler catalyst so that the MFR and Mooney viscosity are in the respective ranges, and it is industrially produced and used in a wide variety of fields. . The chlorinated ethylene-propylene copolymer of the present invention can be produced by subjecting the above ethylene-propylene 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 this aqueous suspension, the above-mentioned ethylene in granular or powdered form is
A propylene-based copolymer is suspended in an aqueous medium. In order to maintain this aqueous suspension state, it is preferable to add a small amount of emulsifying agent or suspending agent. At this time, if necessary, benzoyl peroxide,
Radical generators such as azobisisobutyronitrile and hydrogen peroxide, antifoam agents such as light silicone oil, and other additives may also be added. (B) First stage chlorination In the first stage chlorination is the ethylene used -
At least 25% higher than the melting point of the propylene copolymer
It is carried out at a lower temperature. In particular, it is desirable to carry out the chlorination at a temperature 30 to 60°C lower than the melting point of the copolymer. When the chlorination is carried out at a temperature at least 25° C. lower than the melting point of the copolymer, no agglomeration of the particles occurs during the reaction, and the subsequent chlorination in the second stage can be carried out easily. On the other hand, when chlorination is carried out at a low temperature below 25°C, particles tend to aggregate during the reaction, making it difficult to continue the reaction, and the resulting product is also non-uniform. It has a chlorination degree distribution. Chlorination in the first stage is at 50℃
carried out at higher temperatures. In addition, in this first stage, 20% of the total chlorination amount is
~60% chlorination (e.g., the chlorinated ethylene of the present invention with a chlorine content of 30% by weight)
When producing propylene copolymers, this first step must produce a chlorinated ethylene-propylene copolymer with a chlorine content of 8 to 20% by weight), especially 20 to 55% chlorination. It is preferable. If less than 20% of the total chlorination amount is chlorinated at this stage, agglomeration of particles is likely to occur 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-propylene copolymer of the present invention can be produced by carrying out the chlorination in the second stage under the following conditions. can. 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 performed at a temperature 10°C or more higher than the first-stage chlorination temperature.
This can be achieved by carrying out the chlorination at a temperature 5 to 15°C lower than the melting point of the propylene copolymer. In particular, it is preferably carried out at a temperature that is 10°C or more higher than the chlorination temperature in the first stage, but 5 to 10°C lower than the melting point of the copolymer. If the second stage chlorination is carried out at a temperature 5°C or more lower than the melting point of the copolymer, the product will not have a uniform degree of chlorination distribution and will have poor processability and heat resistance. On the other hand, if this stage of chlorination is carried out at a temperature more than 15°C below the melting point of the copolymer used, the product will not have a non-uniform chlorination degree distribution and will have poor processability and heat resistance. is inferior. In the first and second stages, 60 to 90% (preferably 65 to 90%, preferably 65 to 90%, preferably
70-90%) must be chlorinated. For example, when producing the chlorinated ethylene-propylene copolymer of the present invention with a chlorine content of 30% by weight, the chlorine content is preferably 21 to 27% by weight in the first and second stages. , 24 to 27% by weight) of a chlorinated ethylene-propylene copolymer. In this second step, it is necessary to chlorinate at least 30% of the total chlorination amount. At this stage, chlorination accounts for 30% of the total chlorination amount.
If less than that, non-uniform chlorination will proceed during the subsequent third stage of chlorination, and the resulting product (chlorinated ethylene-propylene copolymer) will have poor heat resistance. In addition, if chlorination is carried out until this second stage exceeds 90% of the total chlorination amount,
This is not preferred because the product may form lumps. After carrying out the chlorination in the second stage in this way, the chlorinated ethylene-propylene copolymer of the present invention can be produced by carrying out the chlorination in the third stage under the following conditions. can. When moving from the second stage chlorination to the third stage chlorination, the third stage chlorination may be carried out by changing the conditions in the reactor used in the second stage chlorination, or the third stage chlorination may be carried out in advance. The aqueous suspension containing the chlorinated ethylene-propylene copolymer produced by the second stage chlorination may be transferred to another reactor controlled to the conditions of the third stage chlorination. (D) Third stage chlorination The chlorination in this third stage is carried out at a temperature lower than the melting point of the ethylene-propylene copolymer used, but at a temperature lower than 2°C, at least 10% of the total chlorination amount is This can be achieved by chlorination. If the third stage chlorination is carried out at a temperature more than 2 °C below the melting point of the copolymer, the product does not have a uniform chlorination distribution;
Moreover, it has poor heat resistance. On the other hand, when chlorinated at a temperature higher than the melting point, the product tends to aggregate, resulting in poor processability. Furthermore, in the third stage, 10% of the total chlorination amount
If the chlorination is carried out in excess of 10%, chlorine can be used alone in gaseous form or diluted with a suitable inert gas in the above first to third stages of chlorination. In this case, the chlorine introduction pressure is usually 5
Kg/ ^cm2 or less. The progress of chlorination can be determined by measuring the weight loss of the supplied chlorine, but the degree of chlorination can also be determined by measuring the amount of hydrogen chloride produced. The chlorinated ethylene-propylene copolymer thus obtained is washed with water to remove adhering hydrochloric acid, emulsifiers, etc., and then dried. Polymers can be produced. (E) Physical properties, mechanical properties, etc. of chlorinated ethylene-propylene copolymer The chlorine content of the chlorinated ethylene-propylene copolymer thus obtained is 20 to 45% by weight.
(preferably 20-42% by weight, preferably 25-42% by weight)
weight%). If the chlorine content of this chlorinated ethylene-propylene copolymer is less than 20% by weight,
There are problems in recovering and purifying the resulting chlorinated ethylene-propylene copolymer. On top of that,
Poor flame resistance. On the other hand, when the amount exceeds 45% by weight, the chlorinated ethylene-propylene copolymer produced is unfavorable because its thermal stability and heat resistance are significantly reduced. The Mooney viscosity of the chlorinated ethylene-propylene copolymer obtained as described above is 10 to 150 points in a large rotor at a temperature of 100°C, preferably 10 to 120 points, particularly 15 to 120 points.
100 points is preferred. Furthermore, the melt flow index (JIS K
−7210, measured under conditions 7, hereinafter referred to as “FR”
) is generally 1 to 100g/10 minutes,
3 to 50 g/10 minutes is preferred, especially 5 to 30 g/10 min.
10 minutes is suitable. Typical properties of the chlorinated ethylene-propylene copolymer of the present invention are shown below. The density is 1.00-1.30 g/ ^cm3 . Also, JIS K
In a tensile test measured according to -6301,
The tensile strength at break is 5 to 70 Kg/cm ² and the elongation at break is 800 to 2500%. Furthermore, the hardness (Shoer A) is 30-70. (F) Processing and molding method When processing and molding the chlorinated ethylene-propylene copolymer of the present invention, lubricants, colorants, antistatic agents, fillers, which are generally added to chlorinated polyethylene, Additionally, additives such as oxygen, light and heat stabilizers may be included. In addition, commonly used chlorinated polyethylene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, binary or tertiary copolymer rubber containing ethylene and propylene as main components, chloroprene rubber, chloroprene rubber, etc. Rubbery products such as sulfonated polyethylene rubbers, butadiene homopolymer rubber and natural rubber, as well as polyvinyl chloride, olefin resins based on ethylene and/or propylene, and methyl methacrylates based on methyl methacrylate. A resin-like material such as a graft polymer obtained by graft-polymerizing at least one of vinyl compounds such as styrene, acrylonitrile, and methyl methacrylate to the resin, acrylonitrile-styrene copolymer resin, and the rubber-like material is blended. It's okay. When producing these compositions, mixing may be carried out using mixers commonly used in the art, such as open rolls, dry blenders, Banbury mixers, and kneaders. Among these mixing methods, two or more of these mixing methods may be applied in order to obtain a more uniform composition (for example,
A method in which the mixture is mixed in advance with a dry blender and then mixed using an open roll).
Among these mixing methods, to mix the chlorinated ethylene-propylene copolymer and the rubbery material,
The mixing temperature is 30-120°C, usually 50-100°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, chlorinated ethylene
In order to mix the propylene copolymer and the resinous material, the temperature is higher than the temperature at which they melt, but the temperature is 180°C.
It is preferable to carry out the following. The chlorinated ethylene-propylene copolymers of the present invention and their compositions can be molded using extrusion molding machines, injection molding machines, compression molding machines, and calender molding machines commonly used in the general rubber industry and resin industry. It is used after being molded into a desired shape using a machine. In addition, when molding only the chlorinated ethylene-propylene copolymer, the molding temperature is 70 to 130°C, generally 90 to 120°C. EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail with reference to Examples. In addition, in the examples and comparative examples, the tensile test was conducted in accordance with JIS K-6301, and the tensile speed was 500 mm/
Measurements were made under the following conditions (JIS No. 3 dumbbells were used). The hardness was determined using JIS hardness (Shor A), and the test piece was measured using a hardness meter using three JIS No. 3 dumbbells stacked on top of each other in accordance with JIS K-6301. Furthermore, Mooney viscosity is JIS K-
6301 at a temperature of 100° C. and a preheat of 1 minute using a large rotor, the 4-minute value was measured. Example 1 80 in a 100 glass-lined autoclave
water, 80 g of sodium laurate and an ethylene-propylene copolymer with a propylene content of 22% by weight and a Mooney viscosity (ML ₁₊₄ , 100°C) of 115 [MFR 1.0 g/10 min, Melting point 120
℃, 10 kg of "EPR (1)" was charged and chlorinated with stirring in the temperature range of 50 to 90 ℃ until the chlorine content of the copolymer became 18.2% by weight (first stage chlorination). ). Then, the reaction system was heated to 105-115℃.
The chlorine content decreases within this temperature range.
It was chlorinated to 27.1% by weight (second stage chlorination). Then, it is chlorinated in a temperature range of 118 to 120°C until the chlorine content becomes 30.2% by weight (third stage chlorination), resulting in a chlorinated ethylene-propylene copolymer [hereinafter referred to as "CLEPR(A)"]. was manufactured. Example 2 The first stage chlorination was carried out under the same conditions as in Example 1. The reaction system was then heated to 105 to 115°C, and chlorinated in this temperature range until the chlorine content became 36.1% by weight (second stage chlorination). Then 118
Chlorinated in the temperature range of ~120°C until the chlorine content was 41.1% by weight (third stage chlorination). Chlorinated ethylene-propylene copolymer (hereinafter referred to as “CLEPR”)
(B)" was manufactured. Example 3 Instead of EPR(1) used in Example 1,
Ethylene _- propylene copolymer (MFR4.8g/
The first stage chlorination was carried out in the temperature range 50-55°C using 10 minutes (melting point 80°C) until the chlorine content was 17.6% by weight. A second stage chlorination was then carried out at a temperature range of 65-75°C until the chlorine content was 26.8% by weight. Furthermore, chlorination is performed in the temperature range of 78 to 80℃ (third stage chlorination), and the chlorine content is reduced.
A 31.3% by weight chlorinated ethylene-propylene copolymer (hereinafter referred to as "CLEPR(C)") was produced. Comparative Example 1 Instead of EPR(1) used in Example 1,
Ethylene with a propylene content of 31.8% by weight and a Mooney viscosity (ML ₁₊₄ at 100°C) of 58.7.
Propylene copolymer (MFR8.2g/10min, melting point
The first to third stages of chlorination were carried out under the same conditions as in Example 1, except that a temperature of 35°C was used. The chlorine content of the obtained chlorinated ethylene-propylene copolymer [hereinafter referred to as "CLEPR(D)"] was 30.3% by weight.
It was hot. Comparative Examples 2 to 7 EPR (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 produce chlorinated products. Further, chlorination was carried out as shown in Table 1 (third stage chlorination) to produce a chlorinated ethylene-propylene copolymer having the chlorine content shown in Table 1.

[Table] Note that in the first stage chlorination of Comparative Examples 1, 2 and 5, agglomeration occurred and good products could not be obtained. Furthermore, in the second stage chlorination of Comparative Example 3, the chlorine distribution was non-uniform. Furthermore, in Comparative Example 4, agglomeration occurred in the second stage chlorination, the chlorine distribution was non-uniform, and a good chlorine ethylene-propylene copolymer could not be obtained. The physical properties of each of the chlorinated ethylene-propylene copolymers obtained in Examples 1 to 3 and Comparative Examples 6 and 7 were measured. The results are shown in Table 2.

[Table] Reference Example The vulcanizability of the chlorinated ethylene-propylene copolymer obtained according to the present invention and commercially available chlorinated polyethylene will be compared and studied. Reference Example 1 For 100 parts by weight of CLEPR(A) obtained in Reference Example 1, 10 parts by weight of magnesium oxide was used as an acid acceptor, and carbon black (manufactured by Asahi Carbon Black Co., Ltd., SRF#50, average grain) was used as a filler. diameter 94 nm) 50 parts by weight, trioctyl trimellitate as plasticizer
A sheet was prepared by sufficiently kneading 30 parts by weight of sulfur as a vulcanizing agent, 0.5 parts by weight of sulfur as a vulcanizing agent, and 4.5 parts by weight of diethylthiourea as a vulcanization accelerator for 20 minutes at room temperature using an open roll. Reference example 2 Instead of CLEPR(A) used in reference example 1,
The molecular weight is approximately 200,000 and the density is 0.950.
Chlorine with a Mooney viscosity (ML ₁₊₄ , 100°C) of 70 and a chlorine content of 30.3% by weight obtained by chlorinating high-density polyethylene with a concentration of g/cm ³ by an aqueous suspension method. A sheet was prepared by kneading in the same manner as in Reference Example 1, except that polyethylene was used. The sheets of Reference Example 1(a) and Reference Example 2(b) thus obtained were heated to 165°C and at an angle of 3.
The vulcanization state was observed using a rheometer tester under the following conditions: These vulcanization curves are shown in FIG. Effects of the Invention As is clear from FIG. 1, the chlorinated ethylene-propylene copolymer obtained by the present invention not only has superior vulcanizability compared to ordinary chlorinated polyethylene, but also has the following properties. be effective. (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 oil resistance. (7) Furthermore, it has good heat resistance and low temperature resistance. Since the chlorinated ethylene-propylene copolymer of the present invention has the excellent properties described above, it can be used in a wide variety of fields. Typical application examples are shown below. (1) Polypropylene, acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin),
By blending resins with high-density polyethylene, low-density polyethylene, vinyl chloride resin, etc., it is possible to not only improve the flame retardance of these resins, but also improve the mechanical properties (for example, impact resistance). . (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, electrical equipment, 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 disk rheometer. In this figure, the vertical axis shows 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] 1 The content of propylene is 15 to 40% by weight,
The melt flow index is 0.01 to 5.0 g/10 min, and the Mooney viscosity (ML ₁₊₄ , 100℃) is
This is a method for producing a chlorinated ethylene-propylene copolymer by contacting an ethylene-propylene copolymer with a molecular weight of 10 to 180 with chlorine gas in an aqueous suspension. At a temperature at least 25°C below the melting point of the polymer, but above 50°C, the total amount of chlorination is reduced.
20 to 60% of the ethylene-propylene copolymer 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 15 °C lower than the melting point of the ethylene-propylene copolymer. at least 30% of the remaining chlorinated amount, by this stage 60 to 90% of the total chlorinated amount is chlorinated, and then in a third step at a temperature lower than the melting point of the ethylene-propylene copolymer. , the remaining chlorination is carried out at a temperature below 2°C below the melting point, and the chlorine content is 20°C.
~45% by weight, and Mooney viscosity (ML ₁₊₄ ,
100°C) is 10 to 150.