JPH08301943A - Production of petroleum resin - Google Patents

Abstract

PURPOSE: To obtain a high-quality petroleum resin in a shortened oil/water separation time by treating a liquid polymerization mixture with water and/or an alkaline aqueous solution. CONSTITUTION: The production process comprises the step of treating the liquid reaction mixture obtained by polymerizing a petroleum distillate containing unsaturated hydrocarbons in the presence of a Friedel-Crafts catalyst with water and/or an alkaline aqueous solution in the presence of 5-70ppm of a polyoxyalkylene copolymer represented by the formula (wherein R1 and R2 are each alkyl; PO is a propylene oxide unit; and EO is an ethylene oxide unit).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing a petroleum resin, and more particularly, to a fraction containing an unsaturated hydrocarbon obtained by cracking and / or reforming petroleum as a Friedel-Crafts catalyst. It relates to an improvement in a method for producing a petroleum resin, which comprises a step of removing a catalyst residue by treating a liquid polymerization reaction product mixture obtained by polymerization in the presence of water with water and / or an alkaline aqueous solution.

[0002]

BACKGROUND OF THE INVENTION Petroleum resins are obtained by polymerizing, in the presence of Friedel-Crafts catalyst, a fraction containing unsaturated hydrocarbons obtained by cracking and / or reforming naphtha and other petroleum fractions of petroleum. The catalyst residue is removed by washing the liquid polymerization reaction product mixture produced by this polymerization with water and / or an aqueous alkali solution. The most typical method of removing the catalyst residue is to treat the liquid polymerization reaction product mixture with an alkaline aqueous solution such as caustic soda, sodium carbonate or ammonia to decompose the polymerization catalyst,
Neutralization, followed by washing treatment with water to remove waste alkali and decomposition products of polymerization catalyst.

In the above method for removing catalyst residues, a stable emulsion is produced when the liquid polymerization reaction product mixture is washed with water and / or an alkaline aqueous solution,
Oil phase (polymer phase) and water phase (waste water) in the next stationary step
As a result, the cleaning process takes an extremely long time, the polymerization product is lost, and the yield of the product resin is reduced. There is a problem that is damaged.

In order to solve the above problems, shorten the oil-water separation time in the washing step during the production of petroleum resin, and further reduce the amount of ash such as residual catalyst residue to obtain a high quality product resin, liquid polymerization It is known to treat the reaction product mixture with water and / or an aqueous alkaline solution in the presence of an emulsion breaker. As the emulsion breaker, for example, the following have been proposed. (I) A polyoxyethylene or propylene derivative of an alkylphenol formalin condensate represented by the following general formula (2) (JP-A-5-86113).

[0005]

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(Wherein R ₁ is an alkyl group, X is H, an alkyl group or an aminomethyl group, m is an integer of 8 to 20 and n is an integer of 0 to 8), (ii) poly Oxyethylene or polyoxyethylene oxypropylene
Alkyl ester or alkyl ether of block polymer (JP-A-57-195715, JP-A-61-1)
52712, Japanese Examined Patent Publication No. 4-56845), (iii)
Aryl monoether of polyoxyethylene oxypropylene glycol (Japanese Patent Publication No. 59-14487). However, according to these proposals, although the oil-water separation time is shortened as compared with the case where the emulsion breaker is not added, it is not sufficiently shortened.

As another method for solving the above problems,
When washing the liquid polymerization reaction product mixture with water, a method has been proposed in which the liquid polymerization product is boiled in the presence of a hydrocarbon having a boiling point lower than that of water during and / or after contact with the cleaning liquid. (Japanese Patent Publication Sho 56-39336
issue). However, this method does not provide rapid emulsion breakage, and the ash residue in the product resin is relatively large.

[0008]

The object of the present invention is to significantly reduce the oil-water separation time of a liquid polymerization reaction product mixture treated with water or an aqueous alkaline solution, and to obtain a high-quality petroleum resin with very little ash residue. It is to provide a manufacturing method capable of

[0009]

[Means for Solving the Problems] The above object is a liquid polymerization reaction obtained by polymerizing a fraction containing an unsaturated hydrocarbon obtained by cracking and / or reforming petroleum in the presence of a Friedel-Crafts catalyst. In a method for producing a petroleum resin, which comprises a step of removing a catalyst residue by treating a product mixture with water and / or an aqueous alkali solution, the following general formula (1) of 5 to 70 ppm based on the weight of the liquid polymerization reaction product mixture is used.

[0010]

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(Wherein R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ may be the same or different, PO represents a propylene oxide unit, and EO
Represents an ethylene oxide unit, a, b, c and d
Represents a number in the range of 5 to 20, which may be the same as or different from each other. The method for producing a petroleum resin is characterized in that the liquid polymerization reaction product mixture is treated with water and / or an alkaline aqueous solution in the presence of the polyoxyalkylene copolymer represented by the formula (1).

The starting material used in the production method of the present invention is a fraction containing unsaturated hydrocarbons obtained by cracking and / or reforming petroleum, and usually has a boiling point range of -20 ° C to 280 ° C. Any fraction is used.
Specifically, as a raw material of the aliphatic petroleum resin, a boiling point of a cracked oil having a boiling point range of −20 ° C. to 280 ° C. separated by distillation is 1
Examples thereof include a C ₅ fraction at a temperature of 00 ° C. or lower, or a fraction obtained by mixing the C ₅ fraction with another aliphatic olefin, diolefin or the like. Further, as a raw material of the aromatic petroleum resin, a C ₉ fraction having a boiling point range of cracked oil of 140 to 220 ° C. can be mentioned. Further, as a raw material of the aliphatic / aromatic copolymer petroleum resin, a fraction of a cracked oil having a boiling range of 10 ° C. to 280 ° C. or a mixture of the above-mentioned raw material for producing an aliphatic petroleum resin and a raw material for producing an aromatic petroleum resin is used. Can be mentioned.

In the production method of the present invention, the above-mentioned unsaturated hydrocarbon-containing petroleum fraction is polymerized in the presence of a Friedel-Crafts type catalyst. Examples of Friedel-Crafts type catalysts include anhydrous aluminum halides such as anhydrous aluminum trichloride and anhydrous aluminum tribromide or their complexes; boron trifluoride, or boron trifluoride and phenols, ethers, organic carvone. Examples thereof include complexes with acids and alcohols; tin halides such as tin tetrachloride and tin tetrabromide; titanium halides such as titanium tetrachloride and titanium tetrabromide. Preferred Friedel
The Kraft's type catalyst is anhydrous aluminum halide, boron trifluoride or a complex thereof. Especially when the anhydrous aluminum halide such as anhydrous aluminum trichloride or its complex is used, the above-mentioned effects of the present invention are particularly remarkable. In the production method of the present invention, the amount of the Friedel-Crafts catalyst used is not particularly limited, but is usually 0.05 to 20 relative to the polymerizable component in the unsaturated hydrocarbon-containing fraction. %, Preferably 0.1 to 10% by weight.

In the production method of the present invention, the polymerization reaction can be carried out in the absence of a solvent, but it is usually carried out in the presence of a solvent. As the reaction solvent, saturated aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, kerosene, benzene, toluene and xylene are used. When the polymerization raw material contains these saturated hydrocarbon components, it can be used as it is as a reaction solvent. In the production method of the present invention, a mixture of the above-mentioned unsaturated hydrocarbon-containing fraction, Friedel-Crafts type catalyst and, if necessary, a solvent is stirred at a temperature of usually -20 to 200 ° C, preferably 0 to 150 ° C. By doing so, the polymerization reaction proceeds.

An oil phase containing a mixture of polymerization reaction products obtained by the above-mentioned polymerization (hereinafter sometimes referred to as polymerized oil)
Is washed with water and / or an aqueous solution of an alkali aqueous solution in the presence of a specific polymer to carry out a washing and deashing operation. That is, in the production method of the present invention, the contact between the oil phase containing the polymerization reaction product mixture and the water phase consisting of water and / or an alkaline aqueous solution is carried out to obtain the polyoxyalkylene copolymer represented by the general formula (1). The feature is that it is performed in the presence. In the general formula (1), R ₁ and R ₂ have 1 to 20 carbon atoms, preferably 4 to
16, more preferably 7 to 15 alkyl groups,
R ₁ and R ₂ may be the same or different. Specific examples of R ₁ and R ₂ include n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, Cyclohexyl group, heptyl group,
Examples thereof include an octyl group, a nonyl group, a decyl group, a dodecyl group, a lauryl group, a cetyl group, a stearyl group and an oleyl group. Among these, nonyl group is preferable. A, b, c and d representing the number of moles of the propylene oxide unit (PO) and the ethylene oxide unit (EO) in the formula
Is a number in the range of 5 to 20, which may be the same or different from each other.

The ratio (a + d) :( b + c) of PO and EO in the copolymer is preferably 40:60 to 60:40. If the proportion of PO in the copolymer is too low, the hydrophilicity of the copolymer will increase excessively, and if it is too high, the hydrophilicity of the copolymer will extremely decrease. In either case, a satisfactory oil-water separation effect cannot be obtained, which is not preferable. The number average molecular weight of the polyoxyalkylene copolymer is preferably 1,000 or more, and 1,000 to
More preferably, it is in the range of 6,000.

The amount of polyoxyalkylene copolymer based on the oil phase containing the polymerization reaction product mixture is 5 to 70 ppm, preferably 20 to 60 ppm, based on the weight of the oil phase. If the amount of the polyoxyalkylene copolymer is too small, the emulsion is not sufficiently destroyed, and a large amount of sludge is generated at the interface between the oil and water phases. The phase becomes cloudier,
In any case, it becomes difficult to achieve the object of the present invention. The method for adding the polyoxyalkylene copolymer is not particularly limited, and the polyoxyalkylene copolymer is added as it is or after being dissolved in a suitable solvent and then added to either the oil phase or the water phase, preferably the oil phase.

The polyoxyalkylene copolymer used in the present invention is produced by a conventionally known method. For example, it can be synthesized by addition-polymerizing propylene oxide to ρ-alkylphenol in the presence of an alkali catalyst, then addition-polymerizing ethylene oxide, and further applying a suitable terminal group modification technique.

The amount of water and / or alkaline aqueous solution used for the washing treatment of the oil phase containing the mixture of the polymerization reaction products is not particularly limited, but it is usually 2 per 100 parts by weight of the oil phase.
0 to 200 parts by weight are used. The contact between the oil phase and the water phase may be performed by any of batch, semi-batch and continuous operation methods, and is not particularly limited. The operating temperature is generally 50 to 100 ° C., and the operating time is about 5 minutes to 3 hours.

After the contact treatment of the oil phase and the water phase as described above, the mixture is allowed to stand for 5 minutes to 3 hours to cause phase separation, and then the oil phase and the water phase are separated. If necessary, water is added to the oil phase again for 5 minutes to 1 minute.
After stirring for about an hour and allowing to stand, the oil phase and the water phase are separated. Such water washing-static separation can be repeated multiple times. After decatalyzing and deashing as described above, unreacted oil is distilled off according to need and other conventional methods such as distillation, and then concentrated and dried to obtain a product.

[0021]

EXAMPLES Next, the production method of the present invention will be specifically described with reference to Examples and Comparative Examples. Comparative Example 1 A pressure-resistant glass autoclave having an internal volume of 1 liter was purged with nitrogen, and then 600 g of a fraction containing an unsaturated hydrocarbon having a boiling point of 40 to 50 ° C. obtained by thermal decomposition of petroleum and 400 g of benzene were charged. The main unsaturated hydrocarbons contained in this fraction were 1,3-pentadiene, cyclopentene, cyclopentadiene and the like. Further, 5 g of aluminum trichloride was added, and the contents were reacted with stirring for 1 hour while maintaining the polymerization temperature at 80 ° C.
After completion of the reaction, 300 g of a 3% caustic soda aqueous solution (6 times mol of caustic soda based on aluminum trichloride) was added to stop the polymerization, and the catalyst residue was extracted by stirring at 80 ° C. for 30 minutes. Further, the mixture was allowed to stand at the same temperature for 20 minutes to separate oil and water, and the aqueous phase was removed. Furthermore, 0.3 times the weight of warm water was added to the oil phase, and the mixture was stirred for 30 minutes and allowed to stand for 20 minutes. This series of operations of adding warm water, stirring, and allowing to stand still is repeated once, and then the oil phase is distilled to distill off unreacted oil and low-polymerization products, and then concentrated and dried to obtain 400 g of petroleum resin.
I got

In the above operation, after the polymerization reaction, an aqueous caustic soda solution was added, and after stirring, the time until the bubbles of the emulsion disappeared and the boundary surface between the oil and water phases became clear, and the condition of the boundary surface was observed. Further, the chlorine content and the ash content in the obtained petroleum resin were measured. The results are shown in Table 1.

Example 1 A petroleum resin was produced in the same manner as in Comparative Example 1 from a distillate at 40 to 50 ° C. However, after the completion of the polymerization reaction, prior to adding the caustic soda aqueous solution to the oil phase, the polyoxyalkylene copolymer represented by the formula (1) is added to the oil phase [manufactured by Kurita Kogyo,
"Tretrite DS-651", R ₁ and R ₂ in the formula (1)
= C ₉ C ₁₉ , (a + d) / (b + c) = 56/46, number average molecular weight 4000, viscosity 240 cst (15 ° C.)] was added at 50 ppm based on the weight of the oil phase. Table 1 shows the results of evaluation of the oil-water separation state and the chlorine content and ash content in the petroleum resin.

Comparative Example 2 A petroleum resin was produced in the same manner as in Comparative Example 1 from the fraction at 40 to 50 ° C. However, after the completion of the polymerization reaction and prior to the addition of caustic soda aqueous solution to the oil phase, the oxyalkylated phenol formaldehyde resin represented by the formula (2) described in JP-A-5-86113 is added to the oil phase. [Kurita Kogyo's "Tretrite DS-656", viscosity 12
2 cst (15 ° C.)] was added at 50 ppm based on the weight of the oil phase. Table 1 shows the results of evaluation of the oil-water separation state and the chlorine content and ash content in the petroleum resin.

Comparative Example 3 A petroleum resin was produced in the same manner as in Comparative Example 1 from the fraction at 40 to 50 ° C. However, after the completion of the polymerization reaction, prior to adding a caustic soda aqueous solution to the oil phase, a condensate of an alkylphenol alkylene oxide adduct [Hakuto Kagaku, Hakuto E-531, viscosity 25 cps (38
C)]] was added at 50 ppm based on the weight of the oil phase. Table 1 shows the results of the separation of oil and water and the amounts of chlorine and ash in the petroleum resin.

[0026]

[Table 1]

Example 2 (A) Boiling range -10 to 10 by the same method as in Example 1.
From a fraction having a C ₅ / C ₄ / C ₉ component as a main component at 150 ° C. and (B) a fraction having a C ₅ / C ₄ component as a main component at a boiling range of −10 to 50 ° C., a petroleum resin A and a Petroleum resin B was produced. However, a polyoxyalkylene copolymer to be added to the oil phase after completion of the polymerization reaction (manufactured by Kurita Kogyo,
The addition amount of "Tretrite DS-651"] was variously changed as shown in Table 2. The amount of sludge (weight ratio based on the weight of the water phase) formed at the interface between the oil and water phases was measured, and the turbidity of the water phase was observed. Table 2 shows the results.

[0028]

[Table 2]

[0029]

According to the method of the present invention, in the step of producing a petroleum resin, when the polymerization reaction product mixture is washed with water and / or an aqueous alkaline solution after the polymerization, the polyoxyalkylene copolymer represented by the above formula (1) is added. By adding the coalescence, the generation of emulsion is suppressed, and the time required for the stationary separation of the oil phase and the aqueous phase containing the mixture can be significantly shortened. Moreover, the amount of ash and the amount of chlorine in the obtained petroleum resin product are very low, and the quality of the product resin is good.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION A method for producing a petroleum resin according to the present invention, that is, a fraction containing an unsaturated hydrocarbon obtained by cracking and / or reforming petroleum is polymerized in the presence of a Friedel-Crafts catalyst. In the method for producing a petroleum resin, which comprises a step of removing a catalyst residue by treating the obtained liquid polymerization reaction product mixture with water and / or an aqueous alkali solution, the following general amount of 5 to 70 ppm based on the weight of the liquid polymerization reaction product mixture is used. Formula (1)

[0031]

[Chemical 4]

(In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ may be the same or different, PO represents a propylene oxide unit, and EO
Represents an ethylene oxide unit, a, b, c and d
Represents a number in the range of 5 to 20, which may be the same as or different from each other. The following is a summary of preferred embodiments of the method for producing a petroleum resin, which comprises treating the liquid polymerization reaction product mixture with water and / or an aqueous alkali solution in the presence of a polyoxyalkylene copolymer represented by Is.

(1) The Friedel-Crafts catalyst is anhydrous aluminum halide or its complex. (2) The amount of Friedel-Crafts catalyst is in the range of 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on the polymerizable components in the unsaturated hydrocarbon-containing fraction. (3) The polymerization reaction is carried out in a solvent composed of saturated hydrocarbon.

(4) The polymerization reaction is carried out at a temperature of -20 to 200 ° C, more preferably 0 to 150 ° C. (5) In the general formula (1), R ₁ and R ₂ have 4 to 4 carbon atoms.
16 alkyl groups. (6) The number average molecular weight of the polyoxyalkylene copolymer represented by the general formula (1) is 1,000 to 6,000.

(7) The amount of the polyoxyalkylene copolymer represented by the general formula (1) is 20 to 60 ppm based on the weight of the oil phase containing the polymerization reaction product mixture. (8) The amount of water and / or alkaline aqueous solution used is 20 with respect to 100 parts by weight of the oil phase containing the polymerization reaction product mixture.
~ 200 parts by weight. (9) Treatment with water and / or alkaline aqueous solution is 5
It is carried out at 0 to 100 ° C.

(10) After treatment with water and / or an alkaline aqueous solution, the mixture is left standing for 5 minutes to 3 hours to separate oil and water. (11) After the treatment of the oil phase containing the polymerization reaction product mixture with the alkaline aqueous solution and the standing oil-water separation, the washing process of the oil phase containing the polymerization reaction product mixture-the standing oil-water separation is performed at least once.

Claims (1)

[Claims] 1. A liquid polymerization reaction product mixture obtained by polymerizing an unsaturated hydrocarbon-containing fraction obtained by cracking and / or reforming petroleum in the presence of a Friedel-Crafts catalyst, and water and / or an aqueous alkali solution. In the method for producing a petroleum resin, which comprises a step of removing a catalyst residue by treating with the above-mentioned compound, the following general formula (1): (In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ may be the same or different, and PO
Represents a propylene oxide unit, EO represents an ethylene oxide unit, and a, b, c and d represent 5 to 20.
Represents the number of the range, and these may be the same or different from each other. ) In the presence of the polyoxyalkylene copolymer represented by
Alternatively, a method for producing a petroleum resin, which comprises treating with an alkaline aqueous solution.