JPS6289715A - Petroleum resin manufacturing method - Google Patents

Abstract

PURPOSE:To readily carry out catalyst removal in a very short time and facilitate the subsequent filtering operation and discarding treatment of filter cake, etc., by using calcium hydroxide and an aliphatic alcohol together as a catalyst removing agent for boron trifluoride catalyst used for producing petroleum resin. CONSTITUTION:A fraction having within 20-280 deg.C boiling point range in a thermal decomposition product of a petroleum fraction is first polymerized in the presence of boron trifluoride and/or a complex compound thereof as a catalyst. Calcium hydroxide and an aliphatic alcohol, preferably methanol as a catalyst removing agent are then added to the above-mentioned polymerization solution to remove the catalyst and afford the aimed petroleum resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for easily removing a boron trifluoride catalyst in a petroleum resin manufacturing process.

Conventionally, when producing petroleum resin using a boron trifluoride catalyst (hereinafter referred to as catalyst, including boron trifluoride gas and boron difluoride complex compound), caustic soda was used as a method to remove the catalyst after the polymerization reaction. , a method using an alkaline aqueous solution such as caustic potash, a method using calcium hydroxide and a small amount of water (Japanese Patent Publication No. 39-12101), a method using ammonia gas (Japanese Patent Publication No. 40-20274), etc. are known. There is.

However, the method using an aqueous alkali solution has disadvantages in that an emulsion is often formed and its separation takes a long time, and that alkali is mixed into the resin, degrading the quality of the resin. In the method using calcium hydroxide and a small amount of water, the dispersion of calcium hydroxide and water in the polymerization solution is poor and it takes a long time, and a considerably large amount of calcium hydroxide is required (approximately 10 times the amount of catalyst). So did you filter it? A: A large amount of slag is generated, and it is sticky due to water, making it difficult to dispose of the slag.Also, the method using ammonia gas generates fine particles, making the filtration operation difficult, and the disposal of slag and K. There will be another national crisis.

As a result of intensive research to overcome the above-mentioned problems, the present inventors have discovered that by using calcium hydroxide and aliphatic alcohol together, the catalyst can be removed in an extremely short time with a small amount of calcium hydroxide, and It has also been found that filtration is easy and the resulting filtrate is also easy to dispose of.

A known method for deactivating the boron trifluoride catalyst is to add L water or methanol to the polymerization solution, but this method is not sufficient for removing the catalyst and is not suitable for industrial use. has not been carried out.

The present inventors arrived at the present invention while researching the effects of aliphatic alcohols on catalysts. That is, it has been found that when calcium hydroxide and aliphatic alcohol are used in combination, an IB2 catalyst can be produced in a short time with an extremely small amount of addition.

The type of aliphatic alcohol is not particularly limited, but in practice alcohols with large molecular weights and high boiling points may remain in the fat after decatalyzing and when unreacted oil is removed by distillation. Therefore, alcohols having 1 to 8 carbon atoms are preferable, and methanol is particularly preferable. Polyols also have a high boiling point and cannot be used practically.

The following examples will demonstrate the usefulness of the present invention, in which the following combinations 1 to 1, B, and C were used in the polymerization of oil deposits;
395 parts (parts by weight, same hereinafter) of thermally decomposed oil with a boiling point of 20 to 100°C (hereinafter referred to as C5 fraction) and a boiling point of 140 to 28°C
A mixture of 2,100 parts of pyrolysis oil (hereinafter referred to as C5 fraction) at 0'C and 2.9 parts of boron trifluoride gas was used at 30°C.
(0.12% by weight of boron trifluoride)
) Polymerization solution Using 5.5 parts of boron trifluoride (30%) in a mixed oil of 900 parts of BCS fraction and 1689 parts of C3 fraction, polymerization 21
Polymerized under the same conditions as &A (boron trifluoride 0.1
6%) Polymerization liquid C: 790 parts of C fraction and 164 parts of C3 fraction
Example: 3 parts of mixed oil, 4 parts of boron trifluoride gas, 6.6 parts of trifluoride phenol ε1), and polymerized under the same conditions to a polymerization solution (0.25% boron trifluoride) ].

When 5 g of calcium hydroxide and 5 g of methanol were added to J (f combined m/\1000 g and stirred at room temperature, the color of the liquid changed from dark brown to bright yellow after 5 minutes, indicating the completion of the catalyst). The powder was easy to filter and had a smooth texture.

Example 2゜! To 1000 g of R'i'i liquid B, 4 g of calcium hydroxide + 4 g of methanol was added and stirred. After 5 minutes, the color changed from dark brown to bright yellow, and the catalytic power was removed. It was easy to filter, and it was smooth.

Example 3: Calcium hydroxide' for polymerized rfflclooog
After adding g + 4 g of methanol and stirring, the color of the liquid changed to bright yellow after 5 minutes, indicating that the 1112 catalyst had finished.Filtration was easy (1M7 was a smooth t fraction. there were.

Example /1゜・R i&A] 6 g of calcium hydroxide in ooog, n-
When 3 g of butanol f was added and stirred, the color of the liquid changed to bright yellow after 10 minutes, indicating that decatalyst was completed.It was easy to filter, and the birth chamber was a smooth powder.

Example 5゜Polymerization 1ffl A I OOOg to 6 calcium hydroxide
When 5 g of g, n-octanol was added and stirred, the color of the liquid changed to bright yellow after 10 minutes, indicating that the decatalyst was completed. It was easy to filter, and the powder had a smooth texture.

Specific gravity bite example l.

20 g of calcium hydroxide was added to 1000 g of polymerization solution A and stirred, but the color of the solution finally changed to bright yellow after 2 hours.

Ratio f bite example 2゜ Add 1.00 g of calcium hydroxide to 000 g of polymerization solution CI. og.

1 g of water was added and stirred, but after 2 hours the color of the liquid finally changed to bright yellow. Although filtration was easy, the birth chamber was sticky.

Comparative Example 3. To 1000 g of polymerization solution A, 1000 g of water in which 1.2 g of caustic soda was dissolved was added, stirred vigorously for 15 minutes, and left to stand. However, an emulsion was formed at the boundary between the oil phase and the water phase, and an emulsion phase remained even after 2 hours. did not disappear.

As shown in the above Examples and Comparative Examples, it is clear that the present invention achieves one-time catalysis with a smaller addition amount and in a shorter time than the conventional method.

Examples and comparative examples are collectively shown in the table.

The purity of my death! ) (No change in content) Table-1 *1. The time it takes for the hue of the ff1 mixture to change from dark red to bright yellow.

*2. An emulsion phase remains between the oil and water phases.

*3. viI fat after removing unreacted and bottom-type compounds by steam distillation.

*4. Gardner color number.

*5. Hue after 5 hours of air at 220℃.

Procedural City Authorization (Spontaneous) September λφ, 1986 Director-General of the Patent Office Black 1) Akio Yu Tono 1, Indication of the case 1985 Patent Application No. 222803 3, Patent Applicant Address Nihonbashi Kakigara, Chuo-ku, Tokyo Town 1-14-94, the full text of the "specification" subject to amendment 5, contents of the amendment As shown in the appendix, there is no change in the "scope of claims" due to the correction of errors and unclear parts. , 2--In ('1
°, full text correction E old thread lIr book ■1 Name of invention Process for manufacturing petroleum resin 2, special + T'F
j+7 range l) 20 to 280°C of oil produced by thermal decomposition of petroleum fractions
Calcium hydroxide and fat are used as a decatalyst when producing petroleum resin by polymerizing a fraction having an arbitrary boiling point within the range of boron trifluoride and/or a complex compound of boron trifluoride as a catalyst. A method for producing petroleum resin characterized by adding a group alcohol.

2) The method for producing a petroleum resin according to claim 1, wherein the aliphatic alcohol is an aliphatic alcohol having 1 to 8 carbon atoms.

3) The method for producing a petroleum resin according to claim 1, wherein the aliphatic alcohol #J is methanol.

3. Detailed Description of the Invention The present invention relates to a method for easily removing a boron trifluoride catalyst in a petroleum resin manufacturing process.

Conventionally, when producing petroleum resin using a boron trifluoride catalyst (hereinafter referred to as catalyst, including boron trifluoride gas and boron trifluoride complex compound), caustic soda was used as a method to remove the catalyst after one polymerization reaction. , a method using an alkaline aqueous solution such as caustic potash, a method using calcium hydroxide and a small amount of water (Japanese Patent Publication No. 39-12101), a method using ammonia gas (Japanese Patent Publication No. 40-20274), etc. are known. .

However, the method using an aqueous alkali solution has disadvantages in that an emulsion is often formed and its separation takes a long time, and that alkali is mixed into the resin, degrading the quality of the resin. In the method using calcium hydroxide and a small amount of water, dispersion of calcium hydroxide and water in the polymerization solution is poor and it takes a long time, and a considerably large amount of calcium hydroxide is required (approximately 10 times the amount of catalyst). Therefore, a large amount of filtration dregs is produced, and the dregs are sticky due to water, making it difficult to dispose of the dregs.Also, the method using ammonia gas generates fine particles, making the filtration operation difficult and the dregs being sticky. In order to overcome the above-mentioned difficulties, the present inventors conducted intensive research and found that by using calcium hydroxide and aliphatic alcohol together, a small amount of calcium hydroxide can be used in an extremely short period of time. The catalyst can be removed, and
It has also been found that filtration is easy and the resulting filter dregs can be easily disposed of.

A known method for deactivating boron trifluoride catalysts is to add a large amount of water or methanol to the polymerization solution, but this method is not sufficient to remove the catalyst and is not used industrially. Not yet.

The present inventors arrived at the present invention while researching the effects of aliphatic alcohols on catalysts. That is, it has been found that when calcium hydroxide and aliphatic alcohol are used together, decatalyst can be removed in a very small amount and in a short time.

The type of aliphatic alcohol is not particularly limited, but in practice alcohols with large molecular weights and high boiling points may remain in the resin when unreacted oil is removed by distillation after decatalyst. , charcoal.

Alcohols having a prime number of 1 to 8 are preferred, and methanol is particularly preferred. Polyols also have high boiling points and cannot be used practically.

The following Examples will demonstrate the usefulness of the present invention by using the following petroleum resin polymerization solutions A, B, and C.

Polymerization liquid A: boiling point 20. 395 parts (by weight, the same below) of pyrolysis product oil at ~100°C (hereinafter referred to as C1 fraction) and pyrolysis oil with a boiling point of 140 to 280°C (hereinafter referred to as C, fraction) 2
Using 100 parts of mixed oil and 2.9 parts of boron trifluoride gas,
Polymerized at 30'C for 2 hours (boron trifluoride 0.1
2% by weight).

Polymerization liquid B: 2.5 parts of boron trifluoride gas and 5.5 parts of boron trifluoride phenol complex (30% boron trifluoride) were added to a mixed oil of 900 parts of C fraction and 1689 parts of C9 fraction. , polymerized under the same conditions as polymerization solution A (boron trifluoride 0.16
%).

Polymerization liquid C: 1 Polymerize under the same conditions as polymerization liquid A using 4 parts of boron trifluoride gas and 6.6 parts of boron trifluoride phenol complex in a mixed oil of 790 parts of C, fraction and 1643 parts of C1 fraction. (Boron trifluoride 0.25%) Example 1° Polymerization tli, Calcium hydroxide 5% for 1000g of A
After adding g and 5 g of methanol and stirring at room temperature, the color of the liquid changed from dark reddish brown to bright yellow after 5 minutes, indicating that the decatalyst had been completed. Filtration was easy, and the filter cake was a smooth powder.

Example 2 To 81,000 g of polymerization solution, 5 g of calcium hydroxide and 4 g of methanol were added and stirred. After 5 minutes, the color of the solution changed from dark reddish brown to bright yellow, indicating that decatalyst was completed. Filtration was easy and the filter cake was a smooth powder.

Example 3 To 1000 g of polymerization solution C, 6 g of calcium hydroxide and 4 g of methanol were added and stirred. After 5 minutes, the color of the solution changed from dark reddish brown to bright yellow, indicating that decatalyst was completed. Filtration was easy and the filter cake was a smooth powder.

Example 4 When 6 g of calcium hydroxide and 6 g of n-butanol were added to 1000 g of polymerization liquid A and stirred, the color of the liquid changed from dark reddish brown to bright yellow after 10 minutes, indicating that decatalyst was completed. +! ! Filtration was easy and the filter cake was a smooth powder.

Example 5 When 6 g of calcium hydroxide and 5 g of n-octatool were added to 1000 g of polymerization solution A and stirred, the color of the liquid changed from dark reddish brown to bright yellow after 10 minutes, indicating that decatalyst was completed. Filtration was easy and the filter cake was a smooth powder.

Comparative Example 1° 20 g of calcium hydroxide was added to 000 g of Al polymerization solution and stirred, but after 2 hours the color of the liquid finally changed to bright yellow.

Comparative example 2゜ Add 10 g of calcium hydroxide to 1000 g of polymerization solution C.

1 g of water was added and stirred, but after 2 hours the color of the liquid finally changed to bright yellow. It was easy to pass through the filter, but the filter cake was sticky.

Comparative example 3゜Polymerization liquid A 1000g: Added 1000g of water in which 1.2g of caustic soda was dissolved, stirred vigorously for 15 minutes, and then allowed to stand, but an emulsion was formed at the boundary between the oil phase and the water phase.
The emulsion phase did not disappear even after hours.

As shown in the above Examples and Comparative Examples, it is clear that the present invention can remove the catalyst in a smaller amount and in a shorter time than the conventional method.

Table 1 shows examples and comparative examples.

Note 1. Calcium soda was used instead of calcium hydroxide.

Note 2. n-butanol was used instead of methanol.

Note 3. N-octatool was used instead of methanol.

Note 46: Time required for the hue of the polymerization solution to change from dark red to bright yellow Note 5. An emulsion phase remained between the oil and water phases.

Note 6. Note 7. Resin after removing unreacted oil and low polymers by steam distillation. Gardner color number.

Note: Hue after air bath at 220°C for 5 hours.

Patent Applicant: Toho Oil Resin Co., Ltd. - J-I, Adne City 03 (Method) November 13, 1985 Commissioner of the Patent Office Kuro 1) Akio Tono 1, Indication of Case 1985 Special Revision Application No. 222803 No. 2, Title of invention: Process for producing petroleum resin 3, Patent applicant: 4, Date of amendment order (shipment date) 2) Engraving of table 1 on page 8 of specification 6, List of attached documents 1) Amendment of application Statement of reasons 2) Certified copy of the register

Claims (1)

[Scope of Claims] 1) Among oils produced by thermal decomposition of petroleum fractions, a fraction having an arbitrary boiling point within the range of 20 to 280°C is converted into boron trifluoride and/or a complex compound of boron trifluoride. A method for producing petroleum resin, which comprises adding calcium hydroxide and an aliphatic alcohol as decatalysts during the production of petroleum resin by polymerization using as a catalyst. 2) The method for producing a petroleum resin according to claim 1, wherein the aliphatic alcohol is an aliphatic alcohol having 1 to 8 carbon atoms. 3) The method for producing a petroleum resin according to claim 2, wherein the aliphatic alcohol is methanol.