JPH0456845B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing petroleum resin. More specifically, the present invention relates to a method for effectively removing inclusions such as ash from a polymerization reaction product obtained by polymerizing a polymerizable unsaturated hydrocarbon obtained from a petroleum fraction, and for significantly improving its operation. Conventionally, petroleum resins are produced by converting a fraction containing polymerizable unsaturated hydrocarbons obtained by thermal decomposition of petroleum products, usually in the presence of a Friedel-Crafts type catalyst such as aluminum trichloride or boron trifluoride. It is produced by polymerizing. However, petroleum resins produced in this way often contain ash from the catalyst used for polymerization, alkaline content from polymerization termination or catalyst removal, and these may affect the physical properties of the product resin. This is the cause of the decline. Such inclusions in the resin are usually removed by washing the fraction containing the resin with water. However, when washing a fraction containing resin with water, it becomes extremely difficult to separate the washed fraction (oil phase) from the washed aqueous phase due to the formation of an emulsion between the two phases, which poses major operational problems. This is often the case.
The present inventors have completed the present invention as a result of various studies aimed at solving the above-mentioned difficulty in separating oil and water phases when washing petroleum resins with water. That is, the present invention involves polymerizing a polymerizable unsaturated hydrocarbon of a petroleum fraction using a Friedel-Crafts type catalyst, and adding a polymerization reaction product to a certain type of surfactant, that is, a dibasic acid, and a polyoxygenate. It is characterized in that it is brought into contact with an aqueous phase in the presence of a polyester obtained by adding ethylene to remove contaminants in the polymerization reaction product. According to the present invention, an oil phase containing a mixture of polymerization reaction products of petroleum resins and an aqueous phase can be separated well, and emulsion formation does not occur during the separation operation as described above, and ash, etc. It is possible to obtain petroleum resin with less inclusions. Furthermore, the present invention can significantly reduce the time required to separate the oil and aqueous phases, allowing for a significant increase in resin production capacity in commercial production. The raw material for petroleum resin polymerization used in the present invention has a boiling point of -
Any fraction containing unsaturated hydrocarbons with a temperature of 20 to 280°C. In the present invention, the aforementioned raw material, the fraction containing unsaturated hydrocarbons, is polymerized in the presence of a Friedel-Crafts type catalyst. Examples of Friedel-Crafts type catalysts include aluminum halides or their complexes such as anhydrous aluminum trichloride, boron trifluoride or its complexes, and tin halides such as tin tetrachloride. Aluminum chloride, boron trifluoride, or complexes thereof. Conditions such as polymerization temperature, polymerization time, and amount of catalyst used in polymerization may be the same as those used in ordinary petroleum resin polymerization, that is, 10 to 100°C, 0.5 to 6 hours, and 0.1 to 1 wt% based on the raw material. However, it is of course not limited to this range. In the present invention, after the completion of the polymerization reaction described above, the oil phase containing the polymerization reaction mixture is brought into contact with water or an aqueous alkaline solution in the presence of a surfactant, and the aqueous phase is further separated to terminate polymerization, decatalyze, and deash. . The surfactant used at this time is a surfactant having a polyoxyalkylene chain, specifically,
It is (1) or a mixture of (1) and (2) represented by the following general formula. Here, R is an alkyl group selected from natural fatty acids, purified fatty acids, and synthetic fatty acids. R1 to R6 are H or an alkyl group. a and b are numbers selected so that the polyoxyalkylene copolymer has an average molecular weight of 1000 or more and ethylene oxide units of 40% to 100%. c, d, f, g, h are polyoxyalkylene copolymers with an average molecular weight of 1000 or more and 40% to 100%
of ethylene oxide units. e represents 2 to 4, respectively. The mixing ratio of (1) and (2) above is (1)/(2)=3/7~7/
The range is 3. The amount of such surfactant to be used is 0.1 to 200 ppm based on the aqueous phase used. In the above, if it is less than 0.1 ppm, the emulsion will not be broken enough, and if it exceeds 200 ppm, emulsion will be more likely to form. The method of adding the surfactant is not particularly limited, and may be injected alone, dispersed in water or an alkaline aqueous solution, or dissolved in diluent oil used to reduce the viscosity of the oil phase. This method is usually used. When using the water or alkaline aqueous solution, the amount used is not particularly limited, but usually 100% of the oil phase is used.
20 to 200 parts per part are used. The temperature at which decatalyst and deashing operations are carried out is not particularly limited, but is usually carried out under slight heating, i.e. from 50°C.
Preferably, the temperature is 100°C. By carrying out the decatalyst and deashing operations using the method described above, a resin with sufficiently low ash content can be obtained.
If necessary, the oil phase obtained by the above method may be further washed with water in the presence or absence of the surfactant. In the present invention, separation of an oil phase and an aqueous phase can be carried out in an extremely short time, particularly during decatalyst and deashing operations. After decatalyzing and deashing, unreacted oil is distilled off from the oil phase by a conventional method, such as distillation, to obtain a petroleum resin. Next, the method of the present invention will be specifically explained using Examples and Comparative Examples. Comparative Example 1 A four-neck separable flask with an internal volume of 2 has a boiling point range of 140 to 280°C obtained by thermal decomposition of petroleum.
500 g of a fraction containing aromatic unsaturated hydrocarbons was charged. After thoroughly purging the inside of the flask with nitrogen,
While stirring, 2.5 g of boron trifluoride phenol complex was added dropwise over 30 minutes at a reaction temperature of 30°C. After the dropwise addition was completed, the reaction was continued at 30°C for an additional hour. After the reaction, 250g of 1wt% caustic soda aqueous solution,
After adding 250 g of xylene and polymerizing by stirring at 60°C for 30 minutes, the mixture was further allowed to stand at 60°C for 30 minutes. The oil and water phases formed an emulsion, making it difficult to separate the oil and water phases, and the separated oil phase was cloudy. Unreacted oil was distilled off from the separated oil phase by steam distillation to obtain a resin. The table shows the water content of the oil phase after separating the water phase, the physical properties of the resin produced, and the time required to separate the oil phase and water phase. Examples 1 to 4 The same operation as in Comparative Example 1 was carried out except that the surfactants shown in the table were added in the amounts shown in the table at the time of termination of the polymerization after completion of the polymerization. The table shows the water content of the oil phase after separating the water phase, the physical properties of the resin produced, and the time required to separate the oil phase and water phase. Comparative examples 2 to 5

【table】

[Table] The same operation as in Example 1 was performed except that the amounts added were changed to 0.05 ppm and 250 ppm. The table shows the water content of the oil phase after the water phase has been separated, the physical properties of the resin produced, and the time required to separate the oil phase and water phase. From the above results, it can be seen that the petroleum resin produced according to the present invention has a very low ash content and can significantly shorten the time for separating the oil phase and the aqueous phase.

Claims (1)

[Claims] 1. An oil phase fraction containing a polymerization reaction product obtained by polymerizing a fraction containing unsaturated hydrocarbons obtained by thermal decomposition of petroleum in the presence of a Friedel-Crafts catalyst. in the presence of (1), or (1) and (2) represented by the following general formula (Here, R is an alkyl group selected depending on the natural fatty acid, purified fatty acid, or synthetic fatty acid. R1 to 6 are H or an alkyl group. a and b are the average molecular weight of the polyoxyalkylene copolymer of 1000 or more and 40 % to 100% of ethylene oxide units. c, d, f, g, h are the average molecular weight of the polyoxyalkylene copolymer of 1000 or more and 40% to 100%.
number chosen to be ethylene oxide units. e represents 2-4. ) A method for producing a petroleum resin, which comprises obtaining a polymer from the oil phase fraction after contacting with water or an aqueous alkaline solution. 2. The method according to claim 1, wherein (1) or (1) and (2) are used in an amount of 0.1 to 200 ppm relative to the aqueous phase used for contact with the oil phase. 3. The method according to claim 2, wherein the dibasic acid constituting the substance of general formula (1) is succinic acid or glutaric acid.