JPH0372092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an olefin-diene copolymer, and more particularly to an efficient method for producing an olefin-diene copolymer with a high yield and a low degree of unsaturation within a specific temperature range. Conventionally, it has been known to copolymerize an olefin such as isobutylene and a diene compound such as butadiene in the presence of a Friedel-Crafts type catalyst to produce an olefin-diene copolymer. However, in conventional methods, in order to suppress the formation of gel-like polymers, the polymerization temperature was kept low, from about -35°C to room temperature, and a large amount of diene was used. Therefore, the conversion rate of olefin was low and the degree of unsaturation was also relatively high. Therefore, as a result of intensive research to develop a production method that eliminates these problems, the present inventor discovered that the purpose could be achieved by carrying out copolymerization in a specific amount and within a specific temperature range. The present invention was completed based on this knowledge. That is, the present invention uses a butane-butene fraction obtained by removing butadiene from a 4-carbon fraction obtained by thermal decomposition of petroleum as an olefin, uses isoprene as a diene compound, and produces an olefin.
Production of an olefin-diene copolymer characterized by adding a diene compound at a ratio of 5 to 30 parts by weight per 100 parts by weight and copolymerizing at a temperature of 66 to 150°C in the presence of a Friedel-Crafts type catalyst. The present invention provides a method. As the olefin which is a raw material of the present invention, a butane-butene fraction whose main component is isobutylene obtained by removing butadiene from a C4 fraction obtained by thermal decomposition of petroleum is used. Note that the raw material olefin may be diluted with a butane-butene fraction containing butadiene, and the concentration may be adjusted before use. Further, isoprene is used as the diene compound. There are no particular restrictions on the amount of olefin and diene compound used, but in general, olefin
The amount of the diene compound is 5 to 30 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight. If the amount of the diene compound used is less than 5 parts by weight, the properties as a copolymer will be insufficient, and if it exceeds 30 parts by weight, a large amount of gel-like material will be produced in the copolymerization reaction, which is not preferable. The Friedel-Crafts type catalyst used in the present invention is not particularly limited as long as it is commonly used. Specific examples include aluminum chloride, iron chloride, tin chloride, titanium chloride, and zinc chloride, with aluminum chloride being particularly preferred. The amount used is usually 0.2 to 1.0 mol%, preferably 0.5 to 0.6 mol%, based on the olefin. In the method for producing a copolymer of the present invention, the reaction proceeds even without a solvent, but it is preferable to use a solvent. As the solvent, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, etc. can be used. In the present invention, the above raw materials are copolymerized in the presence of a catalyst using a solvent or in the absence of a solvent. The copolymerization reaction is carried out at a reaction temperature of 66-150℃, preferably
Perform at 70-110°C. By carrying out the copolymerization reaction in this temperature range, an olefin-diene copolymer with a high conversion rate and a low degree of unsaturation can be obtained. There are no particular restrictions on other reaction conditions, including olefin,
It may be determined as appropriate depending on the type of diene compound, etc. Usually, the reaction pressure is 1.0 to 30.0 Kg/cm ² , preferably 5 to 25 Kg/cm ² , and the reaction time is 5 to 120 minutes, preferably 20 to 60 minutes. After the reaction is completed, necessary post-treatments such as removal of the catalyst and unreacted raw materials are carried out to produce the desired olefin.
A diene copolymer is obtained. The method of the present invention yields an olefin-diene copolymer with a high conversion rate, has a lower degree of unsaturation than those obtained by conventional methods, and can be used as an additive for tackifiers, softeners, etc. for resins or rubbers. It can be suitably used. Therefore, the present invention is extremely practical as a method for producing an olefin-diene copolymer. Next, the present invention will be explained in detail with reference to examples. Example 1 An autoclave having a thermometer, a stirrer, a raw material inlet, and a catalyst inlet was purged with dry nitrogen, and then the pressure was reduced using a vacuum pump. Next, butane-
100 g of butene fraction and 12 g of butadiene were charged. polybutene with a molecular weight of 500 while stirring.
1.00 g of aluminum chloride dispersed in 30 ml was added dropwise over 10 minutes, and the reaction was carried out at 70°C for 60 minutes. After the reaction was completed, the contents were washed with water, followed by 5
% aqueous sodium hydroxide solution to completely decompose and remove aluminum chloride, 10 g of anhydrous sodium sulfate was added to the obtained oil layer and dried for 24 hours. Thereafter, light components were removed by distillation at 20 mmHg and 100°C to obtain 62.0 g of a liquid copolymer. The yield, conversion rate, average molecular weight and bromine number of this product are shown in Table 1. The composition of the butane-butene fraction used is as follows. Isobutane 5.2% by weight Normal butane 18.8% by weight 1-Butene 17.3% by weight Isobutene 42.9% by weight Tras-2-butene 9.8% by weight Cis-2-butene 5.6% by weight Comparative Example 1 In Example 1, the reaction temperature was set to 0°C. 76.8 g of a copolymer was obtained in the same manner as in Example 1, except that the amount of butadiene used was 45 g.
The results are shown in Table 1. Example 2 An autoclave similar to Example 1 was purged with dry nitrogen, and then the pressure was reduced using a vacuum pump. Next, 100 g of butane-butene fraction (same as Example 1) was added to this.
and 12.0 g of isoprene were charged. While stirring, 1.00 g of aluminum chloride dispersed in 30 ml of polybutene having a molecular weight of 500 was added dropwise over 10 minutes, followed by a reaction at 100° C. for 60 minutes. Thereafter, it was treated in the same manner as in Example 1 to obtain 60.1 g of a liquid copolymer. The yield, conversion rate, average molecular weight and bromine number of this product are shown in Table 2. Comparative Example 2 69.0 g of a copolymer was obtained in the same manner as in Example 2, except that the reaction temperature was 0° C. and the amount of isoprene used was 45.0 g. The results are shown in Table 1.

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Claims (1)

[Claims] 1 As the olefin, a butane-butene fraction obtained by removing butadiene from a fraction with a carbon number of 4 obtained by thermal decomposition of petroleum is used, and isoprene is used as the diene compound, and 5 to 30 parts of the diene compound is added per 100 parts by weight of the olefin. Olefins are added in parts by weight and copolymerized at a temperature of 66 to 150°C in the presence of a Friedel-Crafts type catalyst.
A method for producing a diene copolymer.