JPS58101104A - Olefin polymerization method - Google Patents

Abstract

PURPOSE:To accomplish, under specific conditions, a selective rapid polymerization of 1-butene, i.e. a componenet of a C-4 fraction comprising, other than the 1-butene, isobutylene, trans-2-butene and cis-2-butene, by the use of a catalytic system specifically composed of a Ti-contg. catalyst, an organoaluminum compound etc. CONSTITUTION:The objective polymerization can be performed in the following manner: a C-4 fraction comprising isobutylene, 1-butene, trans-2-butene and cis- 2-butene is subjected to a polymerization, at 20-100 deg.C under a pressure <=30kg/ cm<2> in the presence of a catalytic system comprising (A) a titanium-contg. catalyst, (B) an organoaluminum compound of formula AlR3 CR is a 1-12C hydro carbon residue) (e.g. triisobutylaluminum and, if required. (C) a metal chloride of formula MCln (M is metal atom such as of Ni, Co, Cr, Mn, Fe, Mo, n is a valence of the M) under conditions expressed by equationsIand II, thus effecting a selective polymerization of the above 1-butene.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) 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 a 1-butene polymer substantially as an uncurved monomer. This invention relates to a method for polymerizing σ-containing olefins to recover high-purity isobutylene.

As awareness 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 it is produced as C4-1j, while a considerable amount of C4t'4 is produced as a by-product from the 4, catalytic cracking, and catalytic reforming processes in petroleum fine sacs. . Nine of these C4 fractions contain a mixture of various saturated and unsaturated hydrocarbons, but an economical separation method for them has not yet been fully established, so the effective use of C4 fractions is insufficient. The current situation is that we are far from progressing.

In Japan, butadiene, which contains nearly 40% in the C4 fraction, is extracted and used as a raw material for rubber and resin. Its utilization rate as a chemical raw material is said to be low, with an addendum of about 5, and the remainder is mainly consumed as fuel. However, many of its components are extremely important as chemical raw materials, and poly 1-
Butene, methyl ethyl ketone, maleic anhydride (and above,
Raw materials are 1-butene), butyl rubber, polyinobutylene,
A large number of chemical products such as isozolene, butylated hydroxytoluene, diisobutylene, methyl methacrylate, and methyl tert-butyl ether (hereinafter referred to as raw material imbutylene) are derived. The reason why Spen) B-B has a low effective utilization rate even though it contains many useful components is that there is no method for separating the main components, isobutane/1-butene, with high purity. This is because the boiling points of isobutylene and 1-butene are extremely close [and cannot be separated by simple distillation, so sulfuric acid extraction and isomerization separation methods are used.

This is because relatively expensive methods such as adsorption separation method and t-butyl alcohol method have to be used.

In view of this situation, the present inventors have developed a new method for effective utilization of Spen)B-B.
We focused on developing a method to directly convert isobutylene into 1-butene polymer and to recover isobutylene in a composition substantially free of 1-butene.

According to this method, 1-butene is itself a plastic material and not only is it converted into a useful polymer, but also the unreacted material, which consists mainly of isobutylene, is substantially free of 1-butene, so that isobutane/butene can be extracted from it itself. Separation with high purity is also possible by ordinary distillation. However, unlike the case of obtaining high-purity 1-buty/1-butene polymer, spent B@B contains unsaturated hydrocarbons such as isobutylene, trans- and cis-2-butene, and butadiene. and
These active compounds contain low purity 1-butene.
- There is no known method for quantitatively converting butene into polymers.

The present inventors used Spen) B-B as a raw material and converted the 1-butene contained therein into a polymer useful as a plastic material at a high reaction rate and quantitatively, while converting mainly isobutylene as an unreacted product. As a result of extensive research into a method for recovering a mixture which is 1-butene-free and substantially free of 1-butene, the present invention has been completed.

(6) Summary of the invention The method for polymerizing olefins according to the present invention includes inzotylene,
C4 cut containing l-butene, trans-2-butene, cis-2-butene, titanium-containing catalyst, general formula AIR
An organoaluminum compound represented by , (wherein R
is C□~, about 2 hydrocarbon residues) and, if necessary, a metal chloride represented by the general formula MCln (wherein, M is N1, C01Cr.

A catalyst system consisting of a metal atom selected from Mn, F's or MO (n is the valence of gold W4M) was prepared under the following conditions 1≦A1/
It is characterized in that it acts on Ti (molar ratio)≦10 and 0≦M/Ti (molar ratio)<1.

DETAILED DESCRIPTION OF THE INVENTION Raw Material The raw material used in the method of the present invention is obtained by extracting the butadiene contained therein from the C4 fraction that is piled up in the process of naphtha cracking in the petrochemical industry and catalytic cracking or catalytic reforming in the oil refining industry. The remaining fraction after most of it has been extracted and separated is a fraction called Spen) B.B, butadiene raffinate, etc. 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 usually inbutylene is the most abundant, followed by 1-butene. Contains a lot. The total content of both accounts for more than 50% of the total, and 70
It reaches around %. The next most abundant is trans-
2-butene, cis-2-butene, n-butane, 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%. About 0.5% of 1°3-butadiene, which could not be removed by extraction, is contained. Other minor components include isobutane, 1,2-butadiene,
Acetylenes, c5 components, etc. may be included.

Among these, the spent B-B used in the method of the present invention is at least inbutylene, 1-butene, trans-2-
It shall contain butene and cis-2-butene.

Although it is contrary to the spirit of the present invention to use raw materials lacking any of these components, 1,3-butadiene that could not be removed in spent B-B and monomers that are not substantially contained in the original, For example, it is permissible to add α-olefins such as ethylene and propylene to the raw materials for the reaction.

Catalyst The catalyst system used in the method of the invention comprises a titanium-containing catalyst,
An organoaluminum compound represented by the general formula AI R3 (wherein R is a hydrocarbon residue of approximately C1 to □2) and optionally N1, Cr, Mo, Mn%Fe, (
: Consists of chlorides of metals such as o.

As the titanium-containing catalyst, α-, β-, r- or a-type titanium trichloride, a carrier such as magnesium chloride (a supported titanium compound, etc.) may be used. Titanium trichloride obtained by reducing titanium trichloride with organoaluminium (the main component is thought to be a eutectic compound of titanium trichloride and aluminum chloride) using an emulsifier to extract and remove pigeonified aluminum. When using a titanium component prepared by activating it by an appropriate method as the titanium component of the catalyst, it is possible to obtain a higher yield of titanium χ with respect to the catalyst than when using other titanium trianide. can.

Even when titanium trichloride or titanium tetrachloride supported on magnesium chloride or the like is used, a polymer can be obtained with a high catalyst yield.

Suitable organic aluminum compounds have the general formula AlR3
(However, in the formula, R is a hydrocarbon residue of approximately 1 to 1 □). Specific examples of R include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-methyl, n-hexyl, 2-methylpentyl, n
-octyl, n-decyl, n-dodecyl and the like. Of the above, C□ to 4 hydrocarbon residues are preferred.

As the organic Al<=Rum compound, ^IR8 as mentioned above
In addition to type compounds, KAIR, , is effective, but cannot be said to be effective in the method of the present invention. This is because when these organoaluminiums are used, the molecular weight of the monomer obtained may not be high enough, or they may act as cationic polymerization catalysts, causing the electrolysis reaction of imbutylene to proceed. .

Gold gR chloride is not an essential catalyst component, but when this component is added in a specific ratio to T1, it becomes tertiary-2-
The isomerization of butene and cis-2-butene to 1-butene and active polymerization are promoted, resulting in the effect of increasing the content of inbutylene in unreacted monomers. This effect is particularly strong when the 2-butene content in the raw material is high. A preferred metal chloride is nickel chloride.

The quantitative ratio between the catalyst components should be as follows.

In other words, for organic aluminum and titanium compounds 9, A
The l/Ti molar ratio is 1 to 10. Preferably it is set between 1.5 and 8, more preferably between 2 and 60. When the amount is below the above range, an anatomical remer consisting of inbutylene is produced as a by-product. On the other hand, when the above range is exceeded, there is no particular problem in terms of polymer properties and binding activity, but the advantage of using an aluminum compound is that (1) the stereoregularity of the resulting polymer is improved. The conversion rate of 01-butene to 1-butene polymer is improved. ■Cation binding of inbutylene is suppressed. The effects will not extend any further.

The molar ratio of the metal chloride and the titanium compound is 0 or more and less than 1,
Preferably 0.1-0.8, more preferably 0.2-0
．． It is set at the 7th Seki. During this time, the content of inbutylene in the unreacted upper layer increases as the temperature increases.

Polymerization Method Except for the use of specific polymers and catalysts, the method for polymerizing olefins according to the present invention is essentially the same as general olefin synthesis using Ziegler type polymerization catalysts. That is, the polymerization can be carried out in the presence of a diluent such as an inert hydrocarbon or in the presence of a diluent used in the polymerization (B-B itself), and suspension polymerization can be carried out substantially without additional use of an inert medium. I'll be staying there. Examples of diluents when using diluents include hexane, heptane, cyclohexane, benzene, toluene, refined kerosene, and the like. It is also possible to combine the raw materials in a gaseous state without using a diluent.

The joining temperature is usually within the range of 20 to 100℃, but
Preferably, it is carried out at a temperature in the range of 85"C to 85"C.

The polymerization pressure is usually 30 KI/(X" or less, preferably atmospheric pressure to 2 o/cm", more preferably atmospheric pressure to 15 K
It is selected from the range of p/m2 (all of the above are gauge pressures).

The polymerization method may be either a batch method or a continuous method, but the batch method is preferable in order to quantitatively convert l-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 Ave and heavy packaging bags. It can also be added to polyethylene and the like as a quality improving agent.

In addition, Spen) B-B that has passed the polymerization process is 1
Since it does not contain -butene, isobutylene can be separated by distillation or the like, and isobutylene can be supplied as a raw material for producing methyl methacrylate, methyl-1-butyl ether, and polyisobutylene.

Experimental Examples Examples 1 to 4 After replacing molecules with nitrogen in a glass tube 1 with an internal volume of about 25 mm and connected to a vacuum system, 3 volumes of n-hebutane, 0.32 mm of titanium trichloride, and triethylaluminum (T
EA) 0.64 mmol! t were added in this order.

After aging this mixture for one hour at room temperature (approximately 27"C), approximately 1:1 of 1-zote/, 2-buty/(trans/cis isomer molar ratio = 1.7) and imbutylene:
1 (molar ratio) mixture was added so that the concentration of the mixture was 3.0 mol/l, and the glass tube was melt-sealed.

The lath tube was immersed in a constant temperature bath kept at 80℃, and the temperature was 4.0℃.
Polymerization was carried out by shaking for a specified period of time between ˜20.0 hours.

After the polymerization was completed, the glass tube was opened, and 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. After the polymer was separated from P, it was dried under vacuum. The polymerization yield was calculated as the weight of the dry polymer relative to the charged olefin.

The results are shown in Table 1.

Incidentally, according to infrared absorption spectrum analysis, the produced polymer consisted only of l-butene units.

Examples 5 to 7 Bonding temperature Y: Bonding was carried out under the same conditions as in Example 3, except that the temperature was set at a predetermined temperature between 40 and 60°C.

Results vh: Shown in Table 1.

Example 8.9 Adjusting the Al/Ti molar ratio of the catalyst to a predetermined value (1,0 or 5.0
) Polymerization was carried out under the same conditions as in Example 3, except that the addition tv of K TEA was changed.

The results are shown in Table 1.

Example 10.11 Triisobutylaluminum (TIBA) instead of TEA
) or trimethylaluminum (TMA) was used, but the polymerization was carried out under the same conditions as in Example 3.

The results are shown in Table IK.

Comparative Example I Polymerization was carried out under the same conditions as in Example 3, except that the Al/Ti molar ratio was YO, 5, and the polymerization time was u hours.

The results are shown in Table 1.

Comparative Example 2 Diethylaluminum chloride (DE
AC) was used, and the polymerization time was set to S time.
Polymerization was carried out under the same conditions as wm Example 3.

The results are shown in Table 1.

Example 12.13 Polymerization was carried out under the same conditions as in Example 3, except that spent B@B having the composition shown below was used as a raw material, and the polymerization time '4I was 30 hours or 8 hours. .

Raw material composition Mordiyne butylene 60.3 1-butene 26.8 n-butane 4.3 tertiary-2-butene 4.2 cis-2-butene 2.4 i-butane 1.6 1.3-citadiene 0.4 Result 1! are shown in Table 2.

Example 14 Example 13 except that nickel chloride was further added as a catalyst component so that the Ni/Ti molar ratio was 0.5.
Polymerization was carried out under the same conditions.

The results are shown in Table 2.

Comparative Example 3 Polymerization was carried out under the same conditions as in Example 13, except that Ni was added so that the Ni/74 molar ratio was 1.0.

The results are shown in Table 2.

Example 15 Polymerization was carried out under the same conditions as in Example 13, except that KTMA was used instead of TEA and the polymerization time was 24 hours.

The results are shown in Table 2.

Example 16 Polymerization was carried out under the same conditions as in Example Minoru, except that TIBA was used instead of TEA.

The results are shown in Table 2.

Comparative Example 4 Polymerization was carried out under the same conditions as in Example 13, except that KDEAC4' was used instead of TEA, the temperature was 40° C., and the time was 10 hours.

The results are shown in Table 2.

Comparative Example 5 Polymerization was carried out under the same conditions as in Example 13, except that the AI/T1 molar ratio was 0.5, the temperature was 40° C., and the time was 10 hours.

The results are shown in Table 2.

Comparative Example 6 Polymerization was carried out under the same conditions as in Example 12, except that vanadium trichloride was used instead of titanium trichloride and the polymerization time was 24 hours.

The results are shown in Table 2.

Comparative Example 7 Comparative Example 6 except that KTIBA was used instead of TEA
Polymerization was carried out under the same conditions.

The results are shown in Table 2.

Examples 17 to 20 Polymerization was carried out under the same conditions as in Example 12, except that time 1 was 10 hours and the temperature was 30°C, 40°C, or 1°C.

The results are shown in Table 3.

Examples 21-24 Polymerization was carried out under the same conditions as Examples 17-20 except that triisobutylaluminum was used instead of triethylaluminum.

The results are shown in Table 3.

Example 6 Polymerization was carried out under the same conditions as in Example 17, except that the temperature was set to 1:40° C. and the time was changed to 3.0 or 24.0 hours.

The results are shown in Table 3.

Example n: Polymerization was carried out under the same conditions as in Example 21, except that the temperature was set to 0.degree. C. and the time was set to 3.0 or 24.0 hours.

The results are shown in Table 3.

Claims (1)

[Claims] A C4 fraction containing isozotylene, 1-butene, trans-2-buty/and cis-2-butene is heated at a temperature of 20 to
titanium-containing catalyst at Zoo°C and pressure below 30 Kp/m;
An organoaluminum compound represented by the general formula AlR8 (
However, in the formula, R is a hydrocarbon residue of about C to □2) and, if necessary, a metal chloride represented by the general formula MC1n (however, in the formula, M is Ni, Co, CrlMn, Fe or M
A catalyst system consisting of a metal atom selected from O, n is the valence of metal M) is allowed to act under the following conditions: 1≦Al/Ti (molar ratio)≦10 0≦M/Ti (molar ratio)<1 1. A method for polymerizing olefins, which comprises selectively polymerizing l-butene.