CN112079959A

CN112079959A - Aluminum trichloride complex catalyst, preparation method and application

Info

Publication number: CN112079959A
Application number: CN201910506169.7A
Authority: CN
Inventors: 马忠林
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2019-06-12
Filing date: 2019-06-12
Publication date: 2020-12-15

Abstract

The invention belongs to the technical field of petroleum resin synthesis, and particularly relates to an aluminum trichloride complex catalyst, a preparation method and application thereof. The aluminum trichloride complex catalyst comprises the following raw materials in parts by weight: 10 parts of anhydrous aluminum trichloride, 2-10 parts of ethylbenzene, 5-15 parts of dimethylbenzene and 0.5-2 parts of co-initiator. The aluminum trichloride complex catalyst can be used for polymerization reaction, can ensure that the reaction is stable, is easy to operate, further improves the polymerization yield, the petroleum resin yield and the softening point, reduces the color and luster of products and improves the quality of the products.

Description

Aluminum trichloride complex catalyst, preparation method and application

Technical Field

The invention belongs to the technical field of petroleum resin synthesis, and particularly relates to an aluminum trichloride complex catalyst, a preparation method and application thereof.

Background

At present, C5 petroleum resin is prepared by catalytic polymerization process, which has the same and different flow path, and the difference lies mainly in the selection and removal method of catalyst. Catalysts for the cationic polymerization are generally used which are of the Friedel-Crafts type. The different catalysts are not identical in reactivity. Using AlCl₃Specific BF₃The resin with high molecular weight and high softening point can be more easily obtained. AlCl₃When used in conjugated diolefins, cyclization is caused to reduce the degree of unsaturation, and the resulting resin has a relatively high softening point. When BF₃When used in the C5 conjugated diene, linear polymerization occurs and the resulting resin has a low softening point or is liquid. In fact, most of C5 olefin polymerization is carried out by using AlCl₃Or other halides. Directly using AlCl₃The dry powder is used as a catalyst for petroleum resin production, and has a plurality of problems. Firstly, a part of AlCl needs to be consumed₃Reacting with trace water in the raw material to generate HCl, further reacting with AlCl₃Formation of HAlCl₄Thus, on the one hand, the catalyst consumption is increased and, on the other hand, the water content of the feed must be strictly controlled. Secondly, the catalytic activity of the anhydrous aluminum trichloride is too high, and the cationic catalytic polymerization reaction is an exothermic reaction, so that the reaction temperature is too high, the reaction rate is increased, the operation is not easy, a large amount of gel is easy to generate, the yield and the softening point of the petroleum resin are reduced, the color is deep, and the product quality is poor. Thirdly, adding the dry powder AlCl during production₃It is very inconvenient. Mixing AlCl₃The catalyst is prepared into a liquid compound with an organic compound for use, such as CN1088850A and CN1197808A, and the catalyst has moderate activity and is more convenient to use. The compound used for complexing is phenol, ether, aliphatic carboxylic acid, aldehyde, alkyl halide, alkyl aluminum and other compounds.

Disclosure of Invention

The invention aims to provide an aluminum trichloride complex catalyst, a preparation method and application, wherein the aluminum trichloride complex catalyst is used for polymerization reaction, can ensure that the reaction is stable, is easy to operate, further improves the polymerization yield, the petroleum resin yield and the softening point, reduces the color and luster of products, and improves the quality of the products.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

an aluminum trichloride complex catalyst comprises the following raw materials in parts by weight: 10 parts of anhydrous aluminum trichloride, 2-10 parts of ethylbenzene, 5-15 parts of dimethylbenzene and 0.5-2 parts of co-initiator.

Preferably, the coinitiator is acetic anhydride.

Acetic anhydride is used as a coinitiator, and is complexed with anhydrous AlCl3 to properly reduce the activity of carbocation, stabilize the main reaction, reduce the color of the product, and improve the yield, softening point and quality of the petroleum resin. On the other hand, acetic anhydride reacts with water in the C5 raw material to generate acetic acid, and the acetic acid is used as a proton donor to be complexed with AlCl3 to form an initiator system. Meanwhile, the method avoids the reaction of excess water in the raw materials and AlCl3 to generate ineffective aluminum hydroxide, and reduces the dosage of AlCl 3.

Preferably, the catalyst comprises the following raw materials in parts by weight: 10 parts of anhydrous aluminum trichloride, 3-6 parts of ethylbenzene, 8-12 parts of dimethylbenzene and 0.7-1.5 parts of co-initiator.

Preferably, the preparation method comprises the following steps: and adding the ethylbenzene, the xylene and the acetic anhydride into a reaction container, adding anhydrous aluminum trichloride under the protection of inert gas at the temperature of 60-130 ℃ until the anhydrous aluminum trichloride is completely dissolved, and discharging under the protection of the inert gas.

Preferably, the inert gas is nitrogen or argon.

Preferably, the preparation temperature is 80-110 ℃.

Preferably, the preparation temperature is 85-100 ℃.

Preferably, the composition of the complex catalyst comprises 10 parts of anhydrous aluminum trichloride, 5 parts of ethylbenzene, 8 parts of xylene and 1 part of coinitiator, and the complexing temperature is 85 ℃.

The catalyst is applied to the polymerization of hydrocarbon-modified petroleum resin.

The application comprises the following specific steps: adding the cyclopentadiene C5-removed fraction, comonomer styrene and solvent benzene which are less than 70 ℃ into a polymerization kettle, then adding an aluminum trichloride complex catalyst, carrying out polymerization at the temperature of 30-50 ℃, then carrying out alkali washing and water washing on a polymerization solution to be neutral, and distilling to obtain the C-V petroleum resin.

The invention has the following beneficial effects:

the invention introduces acetic anhydride into the aluminum trichloride complex catalyst system to be compounded into the liquid complex catalyst, thereby avoiding the problems of high consumption and difficult control and operation caused by directly using anhydrous aluminum trichloride as the catalyst, correspondingly reducing the using amount of the catalyst and lowering the operation cost. When the anhydrous aluminum trichloride catalyst complexed by the method is used in polymerization reaction, the active components of the anhydrous aluminum trichloride catalyst can be more fully and uniformly dispersed in a reaction system by adding ethylbenzene, dimethylbenzene and acetic anhydride in the complexing process, so that the polymerization reaction is stable, the operation is easy, the polymerization yield, the petroleum resin yield and the softening point are greatly improved, the color of the product is reduced, and the product quality is improved.

Detailed Description

(I) preparation of aluminum trichloride Complex catalyst

Example 1

20g of ethylbenzene, 50g of xylene and 5g of acetic anhydride are added into a reaction kettle. Under the stirring state and the protection of nitrogen, adding 100g of anhydrous aluminum trichloride into a reaction kettle in 5 batches at 60 ℃ until solid aluminum trichloride is completely dissolved, and discharging under the protection of nitrogen to obtain 175g of the aluminum trichloride complex catalyst 1.

Example 2

30g of ethylbenzene, 60g of xylene and 7g of acetic anhydride are added into a reaction kettle. Under the stirring state and the protection of nitrogen, 100g of anhydrous aluminum trichloride is added into a reaction kettle in 5 batches at 75 ℃ until the solid aluminum trichloride is completely dissolved, and the solid aluminum trichloride is discharged under the protection of nitrogen, so that the yield of the aluminum trichloride complex catalyst 2 is 197 g.

Example 3

The dosage of the raw materials in the embodiment 2 is changed to 40g of ethylbenzene, 70g of dimethylbenzene, 8g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature is changed to 80 ℃, other conditions and steps are kept unchanged, and the yield of the aluminum trichloride complex catalyst 3 is 218 g.

Example 4

The dosage of the raw materials in the embodiment 2 is changed to 50g of ethylbenzene, 80g of dimethylbenzene, 10g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature is changed to 85 ℃, other conditions and steps are kept unchanged, and the yield of the prepared aluminum trichloride complex catalyst 4 is 240 g.

Example 5

The raw materials in the example 2 were replaced with 60g of ethylbenzene, 90g of xylene, 10g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature was replaced with 90 ℃, other conditions and steps were kept unchanged, and the yield of the aluminum trichloride complex catalyst 5 was 260 g.

Example 6

The raw materials in the example 2 were replaced by 70g of ethylbenzene, 100g of xylene, 14g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature was replaced by 95 ℃, other conditions and steps were kept unchanged, and the yield of the aluminum trichloride complex catalyst 6 was 284 g.

Example 7

The raw materials in the example 2 were replaced with 80g of ethylbenzene, 110g of xylene, 15g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature was replaced with 100 ℃, other conditions and steps were kept unchanged, and the yield of the aluminum trichloride complex catalyst 7 was 305 g.

Example 8

The raw materials in the example 2 were replaced with 90g of ethylbenzene, 120g of xylene, 16g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature was replaced with 110 ℃, other conditions and steps were kept unchanged, and the yield of the aluminum trichloride complex catalyst 8 was 326 g.

Example 9

The raw materials in the example 2 were replaced by 95g of ethylbenzene, 130g of xylene, 18g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature was replaced by 120 ℃, other conditions and steps were kept unchanged, and the yield of the aluminum trichloride complex catalyst 9 was 343 g.

Example 10

The dosage of the raw materials in the embodiment 2 is changed to 100g of ethylbenzene, 150g of dimethylbenzene, 20g of acetic anhydride and 100g of anhydrous aluminum trichloride, the reaction temperature is changed to 130 ℃, other conditions and steps are kept unchanged, and the yield of the prepared aluminum trichloride complex catalyst 10 is 370 g.

(di) aluminum trichloride Complex catalyst polymerization test

The following polymerization reactions were carried out using the complexed anhydrous aluminum trichloride catalysts obtained in examples 1 to 10 (the same amount of aluminum trichloride) respectively, and the polymerization process was as follows: adding 570g of fraction of which the temperature is less than 70 ℃ and which is subjected to cyclopentadiene C5 removal, 30g of comonomer styrene and 300g of solvent benzene into a polymerization kettle, slowly adding an aluminum trichloride complex catalyst while stirring, polymerizing at the temperature of 40 ℃ for 3 hours to obtain a polymerization solution, washing the polymerization solution with alkali and water for multiple times to be neutral, distilling under reduced pressure after normal pressure, wherein distillates at the top of the tower are unreacted components, solvents and oligomers, and obtaining petroleum resin at the bottom of the kettle. The analysis of the resins produced at the bottom of the kettle gave the following results:

TABLE 1 summary of the effects of aluminum trichloride Complex catalyst on Carbonic penta Petroleum resins

In the table, comparative example 1 has 23.9g of anhydrous aluminum trichloride in place of the complex catalyst of the present invention, and other polymerization conditions were not changed. Comparative example 2 an aluminum trichloride chloroalkane complex catalyst (containing 23.9g of anhydrous aluminum trichloride, 120g of toluene and 12g of dichloroethane) was used in place of the complex catalyst of the present invention, and other polymerization conditions were unchanged.

As can be seen from Table 1, the color of the product is effectively reduced by adopting the aluminum trichloride complex catalyst for polymerization, the softening point and the yield of the obtained petroleum resin are greatly improved, and the effect is very obvious.

Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.

Claims

1. The aluminum trichloride complex catalyst is characterized by comprising the following raw materials in parts by weight: 10 parts of anhydrous aluminum trichloride, 2-10 parts of ethylbenzene, 5-15 parts of dimethylbenzene and 0.5-2 parts of co-initiator.

2. The complex catalyst according to claim 1, characterized in that the catalyst comprises the following raw materials in parts by weight: 10 parts of anhydrous aluminum trichloride, 3-6 parts of ethylbenzene, 8-12 parts of dimethylbenzene and 0.7-1.5 parts of co-initiator.

3. The complex catalyst according to claim 2 wherein the co-initiator is acetic anhydride.

4. A method for preparing the complex catalyst according to any one of claims 1 to 3, comprising the steps of: and adding the ethylbenzene, the xylene and the co-initiator into a reaction container, adding anhydrous aluminum trichloride under the protection of inert gas at the temperature of 60-130 ℃ until the anhydrous aluminum trichloride is dissolved, and discharging under the protection of inert gas.

5. The complex catalyst according to claim 4 wherein the inert gas is nitrogen or argon.

6. The complex catalyst according to claim 5, wherein the preparation temperature of the complex catalyst is 80-110 ℃.

7. The complex catalyst according to claim 6, wherein the preparation temperature of the complex catalyst is 85-100 ℃.

8. The complex catalyst according to claim 7, wherein the composition of the complex catalyst comprises 10 parts of anhydrous aluminum trichloride, 5 parts of ethylbenzene, 8 parts of xylene and 1 part of co-initiator, and the temperature of the complex is 85 ℃.

9. Use of the catalyst of any one of claims 1-8 in the polymerization of hydrocarbon-five petroleum resins.

10. The specific steps of the application of claim 9 are: adding the cyclopentadiene C5-removed fraction, comonomer styrene and solvent benzene which are less than 70 ℃ into a polymerization kettle, then adding an aluminum trichloride complex catalyst, carrying out polymerization at the temperature of 30-50 ℃, then carrying out alkali washing and water washing on a polymerization solution to be neutral, and distilling to obtain the C-V petroleum resin.