JPH0772214B2 - Method for producing chlorinated ethylene-propylene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention involves chlorinating an ethylene-propylene copolymer in an aqueous suspension in the first and third stages,
The second step relates to a method for producing a chlorinated ethylene-propylene-based copolymer by annealing without introducing chlorine at a temperature higher than the melting point of the ethylene-propylene-based copolymer, and relates to heat resistance and cold resistance. Chlorinated ethylene, which has not only good properties but also excellent oil resistance, good weather resistance and ozone resistance, is not only crosslinkable, but is relatively easy to vulcanize. It is intended to provide a propylene-based copolymer.

It has been known for a long time that chlorinated ethylene-propylene copolymers are generally useful as paints and adhesives because they are excellent in oil resistance and flame retardancy. 59-122503). However, as a method of chlorinating the ethylene-propylene copolymer, the ethylene-propylene copolymer is less than 50 ° C in the first step in an aqueous medium containing no suspending agent (for example, 20 to 45 ° C). Chlorinated to 2% by weight or more (for example, 2 to 15% by weight), and at the second stage
(For example, 70 to 100 ° C.), and at this temperature, the chlorine content is chlorinated up to 18% by weight (eg 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, and a high temperature pressure resistant reactor is required,
Moreover, the thermal stability of the produced polymer becomes a problem. On the other hand, in the case of chlorinating with the above-mentioned aqueous medium, there is a problem that the chlorinated product becomes agglomerated when 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, not only is it excellent in heat resistance and cold resistance, but also oil resistance, weather resistance and ozone resistance. Good,
Also, chlorination is possible at a relatively low temperature, the obtained chlorinated product does not agglomerate, and not only crosslinking by organic peroxide but also vulcanization by sulfur or a sulfur-containing compound (sulfur-releasing compound) is possible. Chlorinated ethylene
This is a method for obtaining a propylene-based copolymer.

Means and Actions for Solving Problems According to the present invention, these problems are that the content of propylene is 15 to 40% by weight, the melt flow index (JIS K7210, according to conditions, measured at 14). , MF below
R ”) is 0.01 to 5.0 g / 10 minutes and Mooney viscosity (ML _{1 + 4} , 100 ° C) is 10 to 180.
A method for producing a chlorinated ethylene-propylene-based copolymer by contacting a propylene-based copolymer with chlorine gas in an aqueous suspension, which is at least higher than the melting point of the ethylene-propylene-based copolymer in the first step. It is 25 ℃ lower, but 20-60% of the total chlorination amount at a temperature higher than 50 ℃.
Chlorination, and in the second stage, the temperature is raised to a temperature 1 to 7 ° C. higher than the melting point of the ethylene-propylene copolymer,
It is annealed at this temperature for 10 to 60 minutes without introducing chlorine, and in the third step, the remaining chlorination is carried out at a temperature 2 to 25 ° C. lower than the melting point of the ethylene-propylene copolymer, and the chlorine content is 20-45% by weight,
In addition, the problem can be solved by a method for producing a chlorinated ethylene-propylene copolymer having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 10 to 150. Hereinafter, the present invention will be specifically described.

(A) Ethylene-Propylene-Based Copolymer In producing the chlorinated ethylene-propylene-based copolymer of the present invention, the content of propylene in the ethylene-propylene-based copolymer as a raw material is 15 to 40% by weight. , 18 ~
40% by weight is preferable, and 20 to 38% by weight is particularly preferable.
When chlorinated with an ethylene-propylene-based copolymer having a propylene content of 15% by weight, the resulting chlorinated ethylene-propylene-based copolymer has poor rubber-like elasticity and is rather plastic-like in products. is there.
On the other hand, when chlorination is performed using an ethylene-propylene-based copolymer in excess of 40% by weight, the particles of the chlorinated ethylene-propylene-based copolymer obtained during chlorination become large and become agglomerated in the reaction system. Is not preferable.

The MFR of the ethylene-propylene copolymer is 0.01
˜5.0 g / 10 minutes, preferably 0.02 to 5.0 g / 10 minutes, and particularly preferably 0.05 to 5.0 g / 10 minutes. If chlorination is performed using an ethylene-propylene copolymer having an MFR of less than 0.01 g / 10 min, the processability of the obtained chlorinated ethylene-propylene copolymer will be poor. On the other hand, when chlorination is performed using an ethylene-propylene-based copolymer that exceeds 5.0 g / 10 minutes, the reaction efficiency during the production of the chlorinated ethylene-propylene-based copolymer is poor, and the chlorinated product is severely agglomerated. .

Further, 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 the Mooney viscosity of less than 10 ethylene-propylene copolymer is chlorinated,
Aggregation of chlorinated compounds is intense during chlorination. On the other hand, when an ethylene-propylene copolymer having a ratio of more than 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 is obtained by copolymerizing ethylene and propylene by using a so-called Ziegler catalyst so that the propylene content is within the respective ranges of MFR and Mooney viscosity. It is industrially produced and used in various fields.

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

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

(B) First Step Chlorination In the first step, chlorination is carried out at a temperature at least 25 ° C lower than the melting point of the ethylene-propylene copolymer used. In particular, the melting point of the copolymer is 30
It is desirable to carry out chlorination at a temperature lower by ~ 60 ° C. When the chlorination is carried out at a temperature at least 25 ° C. lower than the melting point of the copolymer, no agglomeration of particles occurs during the reaction, and the chlorination in the subsequent second step can be easily carried out. On the other hand, when chlorination is carried out at a low temperature of less than 25 ° C, agglomeration of particles is likely to occur during the reaction, it may be difficult to continue the reaction, and the product obtained may be non-uniform. It has a chlorination degree distribution. The chlorination in the first stage is carried out at a temperature above 50 ° C.

Also, in this first stage, it is necessary to chlorinate 20 to 60% of the total chlorination amount (for example, the chlorine content is 30% by weight).
When the chlorinated ethylene-propylene-based copolymer of the present invention is produced, the chlorine content in the first step is 8
-20% by weight of chlorinated ethylene-propylene copolymers have to be produced), in particular 20-70% chlorination is preferred. If chlorination of less than 20% of the total chlorination amount is carried out at this stage, agglomeration of particles is likely to occur in the subsequent second stage chlorination reaction.

On the other hand, if the chlorination is carried out in excess of 60%, non-uniform chlorination will proceed, 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-based copolymer of the present invention can be produced by performing the second stage annealing under the following conditions. Upon transitioning from the first-stage chlorination to the second-stage anneal, the second-stage anneal may be performed by changing the conditions in the reactor used in the first-stage chlorination. The aqueous suspension containing the chlorinated ethylene-propylene copolymer produced by the first stage chlorination may be transferred to another reactor controlled by the conditions of the second stage annealing.

(C) Second Stage Annealing The second stage annealing is performed by raising the temperature to a temperature 1 to 7 ° C. higher than the melting point of the ethylene-propylene-based copolymer, and at this temperature 10 to 60 without introducing chlorine. It can be achieved by annealing for a minute.
In particular, it is desirable to carry out at a temperature 1 to 6 ° C. (preferably 1 to 5 ° C.) higher than the melting point of the ethylene-propylene copolymer. Also, the time required for annealing is 10 ~
It is 60 minutes, preferably 10 to 50 minutes, particularly preferably 10 to 40 minutes. When the annealing is performed at a temperature lower than the melting point of the ethylene-propylene-based copolymer by less than 1 ° C., the product obtained by carrying out the chlorination in the third step described below (chlorinated ethylene-propylene-based copolymer) ) Does not have a uniform distribution of chlorination degree. On the other hand, when it is carried out at a temperature higher than the melting point by 7 ° C., the product obtained by carrying out the chlorination in the third step is likely to agglomerate and a good product cannot be obtained. In addition, the annealing is 10
If it is less than a minute, the annealing is insufficient and the finally obtained chlorinated ethylene-propylene copolymer is not good. On the other hand, even if annealing is performed for more than 60 minutes, not only cannot the chlorinated ethylene-propylene copolymer finally obtained be further improved,
There is a cost problem.

(D) Third Stage Chlorination The third stage chlorination can be achieved by carrying out the remaining chlorination at a temperature 2 to 25 ° C. lower than the melting point of the ethylene-propylene copolymer used. In particular, it is desirable to carry out at a temperature lower by 2 to 23 ° C, and it is preferable to carry out at a temperature lower than 2 to 20 ° C. If this third-stage chlorination is carried out at a temperature lower than 2 ° C. lower than the melting point of the ethylene-propylene copolymer used, the product tends to agglomerate and a good product cannot be obtained.
On the other hand, when chlorination is performed at a low temperature exceeding 25 ° C, the chlorinated ethylene-propylene copolymer obtained has a non-uniform chlorination distribution, and a product having excellent heat resistance cannot be obtained. .

In the above-mentioned chlorination in the first step and the third step, chlorine can be used in a gaseous state alone or diluted with a suitable inert gas. The chlorine introduction pressure in this case is usually 5 Kg / cm
² or less. The progress of chlorination can be known by measuring the weight loss of chlorine supplied, but the degree of chlorination can also be known by measuring the amount of hydrogen chloride produced.

The chlorinated ethylene-propylene-based copolymer thus obtained is washed with water to remove the attached hydrochloric acid, emulsifier, etc., and then dried to obtain the chlorinated ethylene-propylene-based copolymer of the present invention. Can be manufactured.

(E) Physical properties of chlorinated ethylene-propylene copolymer,
Mechanical properties, etc. The chlorine content of the chlorinated ethylene-propylene-based copolymer thus obtained is 20 to 45% by weight (preferably 20 to 45% by weight).
˜42 wt%, preferably 25-42 wt%). The chlorine content of this chlorinated ethylene-propylene-based copolymer is 20
If it is less than wt%, there is a problem in recovering and purifying the obtained chlorinated ethylene-propylene-based copolymer. Moreover, flame resistance is poor. On the other hand, a chlorinated ethylene-propylene-based copolymer produced when it exceeds 45% by weight is not preferable because it is significantly deteriorated in thermal stability and heat resistance.

The Mooney viscosity of the chlorinated ethylene-propylene-based copolymer obtained as described above is 10 to 150 points, preferably 10 to 120 points, and particularly preferably 15 to 100 points on a large rotor at a temperature of 100 ° C. is there.

Furthermore, the melt flow index of the chlorinated ethylene-propylene-based copolymer of the present invention (measured according to JIS K-7210, condition 7; hereinafter referred to as "FR") is generally 1 to 100 g / 10 minutes. Yes, 3 to 50 g / 10 minutes is preferable, and 5 to 30 g / 10 minutes is particularly preferable.

Typical characteristics of the chlorinated ethylene-propylene copolymer of the present invention are shown below.

The density is 1.00 to 1.30 g / cm ³ . Also, in the tensile test measured according to JIS K-6301, the tensile breaking strength is 5
~ 70 Kg / cm ² , and the tensile elongation at break is 800-2500%. Further, the hardness (Shore A) is 30 to 70.

(F) Processing and molding method When processing and molding the chlorinated ethylene-propylene-based copolymer of the present invention, a lubricant, a colorant, an antistatic agent, a filler, which is added to chlorinated polyethylene that is generally used, In addition, additives such as stabilizers against oxygen, light and heat may be added. In addition, commonly used chlorinated polyethylene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber,
Binary or ternary copolymer rubbers containing ethylene and propylene as main components, chloroprene rubbers, chlorosulphonated polyethylene rubbers, rubbers such as butadiene homopolymer rubbers and natural rubbers, and polyvinyl chloride, ethylene and / or Or olefin resin containing propylene as a main component, methyl methacrylate resin containing methyl methacrylate as a main component, acrylonitrile-styrene copolymer resin and styrene in the rubber-like material, at least vinyl compound such as acrylonitrile and methyl methacrylate. A resinous material such as a graft polymer obtained by graft-polymerizing one kind may be blended.

When manufacturing these compositions, the mixing (mixing) method may be carried out by using a mixer such as an open roll, a dry blender, a Banbury mixer and a kneader generally used in the art.
Of these mixing methods, two or more of these mixing methods may be applied in order to obtain a more uniform composition (for example, after mixing in a dry blender in advance, this mixture is mixed using an open roll). how to). Among these mixing methods, in order to mix the chlorinated ethylene-propylene-based copolymer and the rubber-like material, the mixing temperature is 30 to 12
The temperature is 0 ° C, usually 50 to 100 ° C. In particular, it is desirable to control the mixing temperature to 150 ° C. or less because the rubber-like material generates heat due to cohesive force during mixing. Further, in order to mix the chlorinated ethylene-propylene-based copolymer and the resinous material, it is preferable to carry out at 180 ° C. or lower, though the temperature is higher than the melting temperature of them.

The chlorinated ethylene-propylene-based copolymer of the present invention and the composition thereof are molded into an extruder, an injection molding machine, a compression molding machine, and a calender molding machine which are commonly used in the general rubber industry and resin industry. It is used after being molded into a desired shape using a machine. When molding only the chlorinated ethylene-propylene copolymer, the molding temperature is 70 to 130 ° C, and generally 90 to 120 ° C.

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

In the examples and comparative examples, the tensile test is JIS K.
According to −6301, the tensile speed was measured under the condition of 500 mm / min (the dumbbell was JIS No. 3 dumbbell). Also,
JIS hardness (Shore A) is used for the hardness, and the test piece is JIS
According to K-6301, three JIS No. 3 dumbbells were overlaid and measured with a hardness tester. Furthermore, Mooney viscosity is JIS
According to K-6301, the temperature was 100 ° C., the preheating was 1 minute, and the value at 4 minutes was measured using a large rotor.

Example 1 100 glass lined autoclave with 80 water, 8
0 g sodium laurate and propylene content 22
% By weight and has a Mooney viscosity (ML _{1 + 4} , 100 ° C) of 11
5 ethylene-propylene copolymer [MFR 1.0g / 1
0 minutes, melting point 120 ° C., hereinafter referred to as “FPR (1)”] 10 kg was charged and chlorinated with stirring in the temperature range of 50 to 90 ° C. until the chlorine content of the copolymer reached 18.2% by weight. (First stage chlorination). Then, raise the temperature of the reaction system to 121-125 ° C and stop the introduction of chlorine within this temperature range.
Annealing was performed for 30 minutes (second stage annealing).
Then, the reaction system is cooled and chlorinated in the temperature range of 95 to 118 ° C. until the chlorine content becomes 30.4% by weight (third stage chlorination), and the chlorinated ethylene-propylene copolymer [hereinafter referred to as “CIEPR (A ) ”] Is manufactured.

Example 2 Instead of the EPR (1) used in Example 1, the propylene content was 24.5 wt% and the Mooney viscosity (ML
_{1 + 4} , 100 ° C.) is 34, and an ethylene-propylene copolymer (MFR 4.8 g / 10 min, melting point 80 ° C.) is used, and the temperature range is 50 to 55 ° C. Staged chlorination was performed. The chlorine content of the chlorinated product obtained at this stage was 18.2% by weight. Then, the temperature of this reaction system was raised, and second-stage annealing was performed in the temperature range of 85 to 87 ° C. in the same manner as in Example 1. Then, cool the reaction system,
In the temperature range of 55 to 78 ° C., the third step chlorination was carried out until the chlorine content reached 30.5% by weight to produce a chlorinated ethylene-propylene copolymer (hereinafter referred to as “CIEPR (B)”).

Example 3 Using the EPR (1) used in Example 1, Example 1
The first stage chlorination was carried out under the same conditions as above until the chlorine content reached 21.5% by weight. Then, the second step annealing and the third step chlorination were carried out in the same manner as in Example 1 to give a chlorinated ethylene-propylene copolymer having a chlorine content of 40.3% by weight [hereinafter referred to as "CIEPR (C)"]. Was manufactured.

Comparative Example 1 Instead of the EPR (1) used in the examples, the propylene content was 31.8% by weight, and the Mooney viscosity (ML
_{1 + 4} , 100 ° C.) 58.7% by weight of ethylene-propylene copolymer (MFR 8.2 g / 10 min, melting point 35 ° C.) except that the first step chlorination and Second stage chlorination was performed (no second stage anneal). The chlorine content of the obtained chlorinated ethylene-propylene copolymer [hereinafter referred to as "CLEPR (D)"] was 31.5% by weight.

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. did. Then, each of the chlorinated products thus obtained is immediately subjected to the second step in the temperature range shown in Table 1, and further chlorinated in the temperature range shown in Table 1 (the third step chlorination). ), And a chlorinated ethylene-propylene copolymer having the chlorine content shown in Table 1 was produced.

In the first-stage chlorination of Comparative Examples 1, 2 and 5, nodules were formed and good products could not be obtained. In Comparative Examples 3 and 4, in the second stage chlorination,
No agglomeration occurred, but the chlorine distribution was non-uniform.

The physical properties 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.

Reference Example The vulcanizability of the chlorinated ethylene-propylene-based copolymer obtained by the present invention and chlorinated polyethylene which is generally commercially available is compared and examined.

Reference Example 1 With respect to 100 parts by weight of CLEPR (A) obtained in Example 1, 10 parts by weight of magnesium oxide as an acid acceptor and carbon black as a filler (SRF manufactured by Asahi Carbon Black Co., Ltd.
^# 50, average particle size 94nm) 50 parts by weight, trioctyl trimellitate 30 parts by weight as a plasticizer, sulfur 0.5 as a vulcanizing agent
A sheet was prepared by sufficiently kneading parts by weight and 4.5 parts by weight of diethyl thiourea as a vulcanization accelerator using an open roll at room temperature for 20 minutes.

Reference Example 2 Instead of CLEPR (A) used in Reference Example 1, a high-density polyethylene having a molecular weight of about 200,000 and a density of 0.950 g / cm ³ was obtained by chlorinating by an aqueous suspension method. The Mooney viscosity (MS _{1 + 4} , 100 ℃) is 70.
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.

Reference Example 1 (a) and Reference Example 2 thus obtained
The vulcanized state of each sheet (b) was observed with a rheometer tester under the conditions of a temperature of 165 ° C. and an angle of 3 degrees. These vulcanization curves are shown in FIG.

EFFECTS OF THE INVENTION The chlorinated ethylene-propylene-based copolymer obtained according to the present invention not only has excellent vulcanizability as compared with ordinary chlorinated polyethylene as shown in FIG. 1, but also has the following effects. Demonstrate.

(1) Ozone resistance is good.

(2) Excellent resilience.

(3) The flame retardancy is also good.

(4) Excellent weather resistance and durability.

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

(6) Excellent oil resistance.

(7) Further, it has good heat resistance and low temperature resistance.

(8) In addition, it has excellent adhesiveness.

Since the chlorinated ethylene-propylene-based copolymer of the present invention has the excellent properties as described above, it can be used in various fields. A typical application example is shown below.

(1) To improve the flame retardancy of polypropylene, acrylonitrile-butadiene-styrene terpolymer resin (ABS resin), high density polyethylene, low density polyethylene, vinyl chloride resin, etc. Mechanical properties (eg impact resistance)
Can be improved.

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

(3) Various parts for automobiles (for example, hoses and tube materials) (4) Electric wire covering materials (5) Adhesives (6) Parts for electronic devices, electric devices, etc.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A propylene content of 15-40% by weight, a melt flow index of 0.01-5.0 g / 10 minutes, and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 10-180. It is a method of producing a chlorinated ethylene-propylene-based copolymer by contacting an ethylene-propylene-based copolymer with chlorine gas in an aqueous suspension, and in the first step, from the melting point of the ethylene-propylene-based copolymer. Is at least 25 ° C lower, but 20-60% of the total chlorination amount is chlorinated at a temperature higher than 50 ° C, and the ethylene-
The temperature is raised to a temperature 1 to 7 ° C higher than the melting point of the propylene-based copolymer, and chlorine is not introduced at this temperature.
Anneal for 10 to 60 minutes, and in the third step, the remaining chlorination is performed at a temperature 2 to 25 ° C lower than the melting point of the ethylene-propylene copolymer, and the chlorine content is 20 to 45% by weight, and Mooney viscosity (ML _{1 + 4} , 100 ℃) is 10 ~
A method for producing a chlorinated ethylene-propylene copolymer which is 150.