JPS59221312A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To polymerize an olefin, by using a catalyst consisting of a catalytic component comprising titanium trichloride as a main component, a specific chlorine-containing organoaluminum, and an organic acid ester, subjecting a 4C fraction containing isobutylene and 1-butene to polymerization condition. CONSTITUTION:4C fraction containing isobutylene and 1-butene is subjected to polymeriation condition by using a catalyst consisting of a catalytic component comprising titanium trichloride as a main component, a chlorine-containing organoaluminum(e.g., diethylaluminum chloride, etc.) shown by the formula (R is 1-12C alkyl, preferably ethyl; n is 0.8-1.5, preferably 0.9-1.3), and an organic acid ester(preferably aromatic carboxylic acid), cationic polymerization of isobutyl is suppressed, and 1-butene is polymerized, to give a polymer like polybutene-1. USE:A pipe, bag for heavy packaging, improver for quality, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION ■ Background of the Invention The present invention is directed to obtaining a 1-butene polymer directly from the so-called Spen) B-B fraction (or butadiene raffinate), as well as obtaining substantially high purity as unreacted monomer. The present invention relates to a method for polymerizing olefins to recover inbutylene.

As recognition of the finite nature of petroleum resources increases year by year, there is a strong demand for advanced resource utilization in the petrochemical industry. Until now, the petrochemical industry has been dominated by C2 and C3 fractions, BTX, and their derivatives.

During naphtha cracking, about 10% of naphtha is produced as a C4 fraction, and on the other hand, from the catalytic cracking and catalytic reforming processes in petroleum refining, a small amount of C4 fraction is produced as a by-product. Various saturated and unsaturated hydrocarbons coexist in these C4 fractions, but an economical separation method for them has not yet been fully established, so the effective use of C4 fractions is insufficient. At present, it is difficult to say that progress is being made.

In Japan, butadiene, which contains nearly 40% in the C4 fraction, is extracted and used as a raw material for rubber and resin, but the distillate after extraction (spent B/B or butadiene raffinate) is used as a chemical raw material. The usage rate is low, 20
It is said that the amount is only a few inches, and the rest is mainly consumed as fuel.

However, many of its components are very important as chemical raw materials, and these components include poly 1-butene, methyl ethyl ketone, maleic anhydride (all raw materials are 1-butene), butyl rubber, polyisobutylene, isoprene,
A large number of chemical products are derived, such as butylated hydroxytoluene, diisobutylene, and methinopemethyl tertiary butylene methacrylate (hereinafter referred to as raw material imbutylene).

The reason why the effective utilization rate of Spen)B is low is because it does not contain many useful components, and the main component is inbutylene and 1.
- This is because there is no method to separate butene with high purity. Since the boiling points of imbutylene and 1-butene are very close to each other, they cannot be separated by simple distillation, so they are often divided into sulfuric acid extraction methods, isomerization separation methods, adsorption separation methods, and t-butyl alcohol methods. This is because they have no choice but to rely on it.

In view of this situation, as a new method for effective utilization of Spent B-B, the present inventors directly converted the 1-butene in Spent B-B into l-butene polymer, and simultaneously converted the inbutylene into substantially Focusing on the development of a method for recovering with a composition that does not contain 1-butene, he filed a patent application (Japanese Patent Application No. 56-1
99738).

According to this method, not only is 1-butene itself converted into a polymer useful as a plastic material, but also the unreacted material, which is mainly composed of isobutylene, is substantially free of 1-butene, and therefore imbutylene can be highly converted from it. Purity separation can also be achieved by conventional distillation.

However, the catalyst used for polymerization in this method is
A titanium-containing catalyst component and an organoaluminum compound represented by the general formula A, tR (wherein R is 01 to 1.
Although this catalyst system suppresses cationic polymerization, the resulting polymer contains a large amount of ether-soluble matter, making it unsatisfactory in terms of strength and rigidity as a plastic material.

Also, if pure 1-butene is used as a starting material, this problem can be avoided by using a catalyst system consisting of titanium trichloride and diethylaluminum chloride, but mixed monomers such as Spen) B-H This is not preferable since cationic polymerization of isobutylene also occurs.

As a result of intensive research to improve this point, the inventors of the present invention found that
By using a specific electron-donating compound in combination with a catalyst system consisting of a combination of titanium trichloride and a chlorine-containing organic aluminum, the cationic polymerization of inbutylene is suppressed and the conversion rate of 1-butene to polymer is increased. Furthermore, it was discovered that a polymer having a low content of ether-soluble matter could be obtained, and the present invention was completed based on this finding.

Summary of the Invention The method for polymerizing olefins according to the present invention comprises
-n C1n (0,8≦n≦15) A method for polymerizing olefins, characterized by contacting with a catalyst system consisting of a chlorine-containing organoaluminum represented by the formula -n C1n (0,8≦n≦15) and an organic acid ester, and subjecting it to polymerization conditions.

■Detailed explanation of the invention Raw material The C4 fraction used as the raw material of the present invention is derived from the C4 fraction produced in the process of naphtha cracking in the petrochemical industry and catalytic cracking or catalytic reforming in the oil refining industry. The remaining part after extracting and separating 5 parts of Butadien to be used is 1-B.
-B, butadiene raffinate, etc. are preferred.

The composition of B-B varies depending on the composition of crude oil and naphtha, their processing conditions, etc., so it is difficult to express it uniformly, but it usually contains imbutylene, followed by 1-butene. .

The total content of both accounts for more than 50% of the total, reaching around 70 mangoes. The next most abundant is trans-2-
Butene, cis-2-butene, normal-butene, etc., each of which is usually contained in an amount of about 5 to 10%. Isobutane, C3 component, etc. account for the next largest content, which is usually about 1 to 2%. The amount of 1,3-butadiene that could not be removed by extraction is usually about 5%.

In addition, inbutane, 1,2-butadiene, acetylenes, C5 components, etc. may be included as trace components.

The C4 fraction used in the present invention is one containing inbutylene and 1-butene, and it is contrary to the spirit of the present invention to use a portion lacking at least one of them as a raw material. The presence of components normally contained in B-13, or the presence of 1,3-butadiene that could not be removed, or monomers that are essentially not included, such as α-olefins such as ethylene and propylene. It is permissible to add these to the raw materials and subject them to the reaction.

Catalyst The catalyst used in the method of the present invention is a catalyst component containing titanium trichloride as a main component, a chlorine-containing organoaluminium, and an organic acid ester.

The catalyst component whose main component is titanium trichloride is titanium trichloride obtained by reducing titanium tetrachloride with organoaluminium (the main component is thought to be a eutectic composite of titanium trichloride and aluminum chloride). It is preferable to use titanium trichloride obtained by extracting and removing aluminum chloride using a complexing agent and activating it by an appropriate method, since the polymer can be obtained with a high catalyst yield.

As the chlorine-containing organoaluminum, the composition of the compound is single, or the composition of the entire mixture is AI-Ra-nC1n (where R has 1 to 12 carbon atoms). Preferably it is an alkyl group of 2 to 4, particularly preferably an ethyl group, and n is 0.8
-1.5, preferably 0.9-1.3) is used.

Generally, diethylaluminum chloride can be used, and triethylaluminum, ethylaluminum dichloride, etc. can also be mixed and used in proportions falling within the range represented by the above general formula.

Examples of organic acid esters include methyl formate, propyl acetate,
Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl methacrylate methinecrotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, metinope toluate, ethyl toluate, amyl toluate, ethyl benzoate, etinopeanisate, ethyl benzoate, ethyl benzoate, benzoyl ethyl benzoate, etc. 2 to 18 organic acid esters are used, but aromatic carboxylic acid esters are particularly preferred.

Further, these organic acid esters are essential components used together with a catalyst consisting of a combination of titanium trichloride and a chlorine-containing organic aluminum.

When these electron-donating compounds are not used, although 1-butene itself provides a polymer with a low content of ether-soluble components, cationic polymerization of inbutylene occurs simultaneously, resulting in a decrease in the ether-soluble content of the entire resulting polymer. The content ratio of the components increases. In addition, it has been found that the addition of an electron donor increases the polymer conversion rate of 1-butene in Spen)B B, which has an advantageous effect on improving the efficiency of polymerization and separation of imbutylene. .

The quantitative ratios between the catalyst components are as follows.

For titanium trichloride and chlorine-containing organic aluminum 9-miniram in the solid component, the At/TI molar ratio is 1 to 10,
Preferably it is set between 1.5 and 8, more preferably between 2 and 6. When the amount is below the above range, an amorphous polymer composed of isobutylene units is produced as a by-product. On the other hand, when the amount exceeds the above range, there are no particular problems in terms of polymer properties and polymerization activity, but there is no advantage from using an excessive amount of the aluminum compound.

Regarding the organic acid ester and titanium trichloride, the organic acid ester/T1 molar ratio is set between 0.25 and less than 2, preferably between 0.5 and 1.0, and more preferably between 0.5 and 0.75. . During this period, the 1-butene conversion rate,
If the content of inbutylene in the unreacted monomer is high,
The polymer ether soluble content is also lower.

Polymerization Method Except for the use of specific monomers and catalysts, the olefin polymerization method according to the present invention is essentially the same as general olefin polymerization using a Ziegler type polymerization catalyst. That is, polymerization can be carried out in the presence of a diluent such as inert-10=hydrocarbon, or suspension polymerization using B-B itself as a medium without using an additional inert medium. can. Examples of diluents when using diluents include TEHA, hexane, heptane, cyclohexane, benzene, toluene, refined kerosene, and the like. It is also possible to polymerize without the use of diluents and under conditions where the raw materials are present in gaseous form.

Although the polymerization temperature can usually be selected from the range of 0 to 200°C, it is preferably carried out at a temperature of 20 to 100°C.

The polymerization pressure is usually from atmospheric pressure to 50 kp/CJ or less, preferably from atmospheric pressure to 30 ky/cr! -, more preferably atmospheric pressure to 15ky/cr& (all above gauge pressure)
selected from the range.

The polymerization method may be either a batch method or a continuous method, but the batch method is preferable in order to quantitatively convert 1-butene into a polymer.

The resulting polymer has physical properties similar to polybutene-1. Therefore, it can be used in the same applications as polybutene-1, such as pipes and heavy packaging bags. It can also be added to polyethylene and the like as a quality improving agent.

Moreover, the spent B-B that has undergone the polymerization process is substantially 1-
Since it does not contain butene, inbutylene can be separated by distillation or the like, and inbutylene can be supplied as a raw material for producing methyl methacrylate, methyl-1-butyl ether, and polyisobutylene.

Examples Examples 1 to 6 Internal volume approximately 25m7 with vacuum system and connection! After sufficiently purging the inside of the glass tube with nitrogen, add 3rnl of n-hebutane! .

0.32 m mot of titanium trichloride and 0.96 m mat of diethylaluminum chloride were added in this order. After aging this mixture at room temperature (approximately 25°C) for 30 minutes, ethyl benzoate (EB) was added to
Add the specified amount of ``m mo7'' and further stir at room temperature for 3
After reacting for 0 minutes, a mixture of -butene and inbutylene (1=1 (molar ratio)) was added so that the concentration of the mixture was 2.0 mol/l, and the glass tube was melt-sealed.

Polymerization was carried out by immersing the glass tube in a constant temperature bath kept at 60° C. and shaking it for 4 hours.

After the polymerization was completed, the glass tube was opened, the unreacted olefin was recovered by distillation, and its composition was analyzed by gas chromatography.

The remaining contents after recovering the unreacted olefin were poured into methanol acidified with hydrochloric acid to precipitate the produced polymer. The polymer was filtered and dried under vacuum. The polymerization yield was calculated as the polymerization ratio of the dry polymer to the charged olefin.

The produced polymer was analyzed by each method described below.

The composition of 1-butene and imbutylene is I i (or "
A calibration curve was created from a homopolymer mixture whose multicomponents are known by C-NMR, and calculations were made using the calibration curve.

The viscosity of the polymer was measured at 30°C using an Usoberohde viscometer.
, n-heptane.

13- Ether soluble content was extracted by boiling point extraction with diethyl ether.

The results are shown in Table 1.

Examples 7 to 10 Polymerization was carried out under the same conditions as in Example 2, except that the polymerization time was set to a predetermined time between 1 and 8 hours.

The results are shown in Table 1.

Examples 11 to 14 As a polymerization solvent, benzene was used instead of n-hebutane, and ortho-
Ethyl benzoyl benzoate (EOBB) from 0.08 to 0
．． Polymerization was carried out under the same conditions as in Examples 1 to 4, except that a predetermined amount between 32 m mot 0 was used.

The results are shown in Table 1.

Comparative Example 1 Polymerization was carried out under the same conditions as in Example 1, except that no organic acid ester was used.

As a result, cationic polymerization occurs, resulting in low 1-butene 14- Only a small amount of polymer was obtained.

The results are shown in Table 1.

Comparative Example 2 Polymerization was carried out under the same conditions as in Example 11, except that no organic acid ester was used.

As a result, similar to Comparative Example 1, cationic polymerization occurred, resulting in low
- Only polymers with a butene content were obtained.

The results are shown in Table 1.

Comparative Examples 3 to 8 Polymerization was carried out under the same conditions as Examples 1 to 6, except that acetophenone (AP) was used in place of EB.

As a result, with electron-donating substances such as ketones, cationic polymerization occurred simultaneously, and only polymers with a low 1-butene content were obtained.

The results are shown in Table 1.

Comparative Example 9 Polymerization was carried out under the same conditions as in Comparative Example 1, except that 0.96 m mot of triethylaluminum was used in place of diethylaluminum chloride.

As a result, cationic polymerization did not occur, but only a polymer containing a large amount of ether soluble material was obtained.

(Margin below)

Claims (1)

[Claims] A C4 fraction containing inbutylene and 1-butene is combined with a catalyst component containing titanium trichloride as a main component, an organoaluminum containing a general formula %, and an organic acid ester. A method for polymerizing olefins, which comprises bringing the system into contact with the system and subjecting it to polymerization conditions.