JPS5857408A - Production of catalytic component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To produce the titled catalytic component having high activity and providing stereoregular polymers in high yields, by contacting a fatty acid magnesium salt with an electron-donating substance in an organic solvent and then reacting the product with a titanium halide. CONSTITUTION:A solid composition is obtained by contacting 1mol of a fatty acid magnesium salt (A) having the lowest possible moisture content, with 0.01- 50mol of an electron-donating substance (B) (e.g., ethyl acetate) in an organic solvent (C) which is liquid at 0 deg.C and 1 atm (e.g., n-pentane) at a temperature above 10 deg.C and below the b.p. of component C for 1min-100hr and then removing the organic solvent. Then, this solid composition is contacted with a titanium halide (D) of the formula: TiX4 (where X is a halogen) at a temperature above room temperature and below the b.p. of component D for 10min-10hr and then washing the product with an organic solvent to obtain a catalytic component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a high-performance catalyst component that exhibits high activity when subjected to the polymerization of α-olefins and is capable of obtaining a stereoregular polymer in high yield. More specifically, a method for polymerizing α-olefins, which comprises contacting fatty acid magnesium with an electron-donating substance in an organic solvent, and then contacting the obtained solid composition with a titanium compound. The present invention relates to a method for producing a catalyst component.

Conventionally, solid titanium halides have been well known and widely used as catalyst components for the polymerization of α-olefins. Due to the low polymerization activity of titanium in the components, a so-called deashing process to remove the catalyst residue was unavoidable.The deashing process uses a large amount of alcohol or chelating agent. Such recovery equipment or regeneration equipment is indispensable, and there are many problems related to resources, energy, etc., and it is an important issue that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity of titanium in the catalyst component and the sieving catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of α-olefins, the polymerization activity of titanium in the catalyst component is reduced. There are many proposals that have dramatically improved this.

For example, in JP-A-50-126590, magnesium chloride as a carrier material is brought into contact with an aromatic carbic acid ester by mechanical means, and titanium tetra-lodenide is added to the resulting solid composition in a liquid phase. A method of contacting catalyst components is disclosed.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the produced polymer, and therefore requires high activity to the extent that the influence of chlorine can be virtually ignored. However, there remained unresolved issues such as the need to keep the concentration of magnesium chloride low or the concentration of magnesium chloride itself low.

Attempts have therefore been made to use substances other than magnesium chloride that can effectively act as carrier materials. However, the methods proposed so far can not only increase the polymerization activity of the catalyst component but also fully satisfy the requirements of the technical field for maintaining a high yield of stereoregular polymers. Nothing has been proposed.

For example, in JP-A-49-120980, a catalyst component is obtained by reacting magnesium acetate with an aluminum compound and then contacting the reaction product with titanium tetrahalide in a liquid phase. , a method for polymerizing α-olefins is disclosed, but judging from the description of the publication, especially from the examples, the catalyst component obtained by the method is used only for ethylene polymerization. However, it is not suitable for zolopyrene polymerization, which requires a high yield of stereoregular polymers, as in the present invention.

This fact is also demonstrated in the comparative examples described below.

The inventors of the present invention have arrived at the present invention as a result of intensive research to solve the problems remaining in the prior art, and propose it to Tsuzumi.

That is, the feature of the present invention is that (a) fatty acid magnesium and (b) an electron-donating substance are brought into contact in (C) an organic solvent, and then the obtained solid composition is (d) It is used as a catalyst component for the polymerization of α-olefins in contact with a titanium halide represented by the general formula T1X4 (wherein X is a haloke9 element).

According to the present invention, the chlorine content, which is a problem that remains in the catalyst component with a magnesium chloride support, which has been the mainstream in this technical field, can be suppressed to a much lower level, and...
...by bringing fatty acid magnesium and an electron-donating substance into contact in an organic solvent instead of dry co-pulverization),
This makes it possible to omit the pulverization process using a ball mill or vibration mill, which is commonly used as a contact means during the catalyst component preparation process, which simplifies the process and reduces manufacturing costs. can.

Of course, it has been demonstrated that the method has extremely excellent effects on the yield of stereoregular polymers without sacrificing the intended purpose of polymerization activity.

When α-olefins are polymerized using the catalyst component obtained according to the present invention, the amount of catalyst residue in the resulting polymer is extremely small, and the chlorine content is low, making it possible to omit the deashing step. By obtaining this, it is possible to achieve a polymerization system that is advantageous in terms of cost, and furthermore, it has shown extremely excellent effects in terms of the yield of stereoregular polymers.

The fatty acid magnesium used in the present invention includes: magnesium glumitate, magnesium stearate, magnesium behenate, magnesium acrylate, magnesium adipate, magnesium acetylenedicaldate, magnesium acetoacetate, magnesium aceate, oxalic acid. Magnesium, Magnesium citrate, Magnesium glyoxylate, Magnesium glutaraldehyde, Magnesium glutarate, Magnesium crotonate, Magnesium succinate, Magnesium isovalerate, Magnesium isobutyrate, Magnesium octoate, Magnesium valerate, Magnesium decanoate, Nonanoic acid Magnesium, magnesium tocosenate, magnesium undecenoate, magnesium elaidate,
Magnesium crotonate, magnesium lyrunate, magnesium hexanoate, magnesium heptanoate, magnesium myristate, magnesium laurate acetate, magnesium butyrate, magnesium oxalate, magnesium tartrate, magnesium perate, magnesium sepacate, magnesium sorbate, magnesium tetrolate, Magnesium human acrylate, magnesium biparate, magnesium pimelate, magnesium pyruvate, magnesium fumarate, magnesium zolopiolate,
Examples include magnesium maleate, magnesium malonaldehyde, magnesium malonate, and the like, with magnesium stearate being preferred.

Note that it is preferable to use the fatty acid magnesium in a form with as much moisture removed as possible.

The electron-donating substance used in the present invention is selected from organic compounds containing at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus in its molecule, such as ether, ester, ketone, amine, phosphine,
Phosphinamide etc. can be used. More specifically, aliphatic ethers such as diacetyl ether, aromatic ethers such as anisole, aliphatic carboxylic acid esters such as ethyl acetate and methyl methacrylate, ethyl toluate, ethyl anisate, ethyl benzoate, etc. aromatic carbo/acid esters, ketones such as acetone, phosphines such as ) IJ phenylphosphine, bosphinamides such as hexaphosphine amide, etc.
Among these, aromatic caldefic acid esters are preferred.

The organic solvent used in the present invention is selected from organic compounds that are liquid at 10° C. and 1 atm, and preferred are aliphatic and aromatic hydrocarbons having 5 to 1 carbon atoms. More specifically, n-pentane, n-hexane, n-
- Examples include hebutane, benzene, toluene, etc.

Titanium hao)y' represented by the general formula T1X4 (in the formula, X is a halogen element) used in the present invention
The compounds include T i C64, T i B r 4
, T i I 4, etc., among which TiCl4 is preferable. Furthermore, this titanium halide may be used in the form of a complex with the electron donating substance.

It is also possible to further enhance the effects of the present invention by further washing with an organic solvent such as n-hebutane after contacting the solid composition produced in the present invention with the titanium locide.

The ratio of each of these components to be used is arbitrary as long as it does not adversely affect the performance of the catalyst component produced, and is not particularly limited, but the amount of electron donating substance is usually 0.00% per 1 mole of fatty acid magnesium. 01-50 mol, preferably 0
．． It is used in a range of 1 to 10 moles.

In the present invention, the contact between the fatty acid magnesium and the electron donating substance is usually carried out in an organic solvent, and then the solvent is removed to obtain a solid composition, but the removal of the solvent is not necessarily required. .

The contact time in the organic solvent is not particularly limited, but is usually 1 minute to 100 hours, preferably 10 minutes to 1 hour.
The contact temperature is not particularly limited as long as the solvent used is in liquid form, and a temperature of usually 10° C. to the boiling point of the organic solvent used is suitable. Also,
Any method such as distillation under reduced pressure or filtration can be freely selected for solvent removal.

The catalyst component of the present invention is obtained by contacting the thus obtained solid composition with a titanium halide and washing with an organic solvent.

The titanium halide and the solid composition are brought into contact with each other using a container equipped with a stirrer, usually at room temperature up to the boiling point of the titanium halide used.

The slurry composition obtained after the treatment is washed using an organic solvent such as n-hebutane. At this time, the cleaning is considered complete when no log 7 elements are detected in the cleaning solution, and the solid and liquid are separated and dried, or an appropriate amount of organic solvent is added to form a slurry, and the main product is used as is. alpha of invention
-Used as a catalyst component for polymerization of olefins.

These series of operations in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

The catalyst component produced as described above has the general formula AtRrn
In the formula X5-, R is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is a halide element, and m is an integer of 1 to 3. ) to form a catalyst for polymerizing α-olefins. The organoaluminum compound used is used in a range of 1 to 1000 degrees, preferably 1 to 300 degrees, in terms of molar equivalent simole ratio of titanium atoms in the catalyst component. Further, it is not prohibited to add and use a third component such as an electron-donating substance during the polymerization.

Polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 to 9/ffl・G or less, preferably 50kl? /c
rl-G or less.

The olefins homopolymerized using the catalyst component produced by the method of the present invention include globylene, 1-p-thene, 4-
Olefins copolymerized with methyl-1-pentene and the like include ethylene, globylene, 1-f-tene, 4-methyl-1-pentene, and the like.

The present invention will be specifically described below using Examples and Comparative Examples.

Example 1 [Preparation of catalyst component] Commercially available magnesium stearate was vacuum-calcined at 110°C for 7 hours, 60F, 15.8 g of ethyl benzoate, and 135 m/n-hebutane were mixed in an internal volume of 30 m/m under a nitrogen atmosphere.
The mixture was placed in a 0 ml glass container, stirred at room temperature for 1 hour, and then dried under reduced pressure to obtain a solid composition.

Capacity 20, fully purged with nitrogen gas and equipped with a stirrer
A 0 ml round bottom flask was charged with 450 ml of TiCl and the solid composition 10F, and a stirring reaction was carried out at 65° C. for 2 hours. After the reaction was completed, the mixture was cooled to 45° C., left to stand, and the supernatant liquid was removed by decantation. Then n-
Washing with hebutane 1001i/Nyor was repeated, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst was used as a catalyst component.

At this time, when the solid and liquid in the catalyst component was separated and the titanium content in the solid was measured, it was found to be 2.64% by weight.

[Overlapping]

500 ml of n-hebutane was charged into an autoclave with an internal volume of 1.5 t and equipped with a stirrer, which was completely purged with nitrogen gas, and 1 ml of triethylaluminum was added while maintaining the nitrogen gas atmosphere.
3.6~, then 1. with titanium atoms as the catalyst component.
411Rg was charged. Thereafter, the temperature was raised to 60°C, and while propylene gas was introduced, a pressure of 4 kg/crl-a was maintained, and polymerization was carried out for 2 hours.

After the polymerization was completed, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after concentrating the F solution is set as (4), and the amount of solid polymer is CB
). Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hemethane, and this amount was set as (0).

Polymerization activity of catalyst components! 1. Expressing (b) as a formula and the yield of crystalline polymer (6) as a formula, the yield of total crystalline polymer (g) was determined using the formula. Further, residual chlorine (G) in the produced polymer was measured by the Genbu combustion method. The results obtained are shown in Table 1.

Example 2゜ Triethylaluminum was added to ios, s■, P- during polymerization.
) An experiment was carried out in the same manner as in Example 1, except that 44.8 μm of ethyl ruylate and 1.13 to 1.13 Ti atoms were used as the catalyst component. The results obtained are shown in Table 1.

Example 3 20 g of commercially available magnesium stearate vacuum-calcined at 110° C. for 7 hours, 3.3 g of ethyl benzoate and 47 m of n-pentane were mixed in an internal volume of 300 m/m under a nitrogen atmosphere.
A solid composition was obtained by charging the mixture into a ml glass container, stirring it at room temperature for 1 hour, heating it to 40° C., and distilling off the solvent.

Capacity 20, fully purged with nitrogen gas and equipped with a stirrer
6450 ml of TiC and 10.9 ml of the solid composition were placed in a 0 m/2 round bottom flask, and a stirring reaction was carried out at 65° C. for 2 hours. After the reaction was completed, the mixture was cooled to 45° C., left to stand, and the supernatant gold was removed by decantation. Next, washing with 100 ml of n-hebutane was performed repeatedly, and when chlorine was no longer detected in the washing liquid, the washing was completed and the catalyst component was used. At this time, when the solid and liquid in the catalyst component was separated and the titanium content in the solid content was measured, it was 2.3.7
% by weight.

The polymerization was carried out in the same manner as in Example 1, and the results obtained are shown in Table 1.

Example 4 An experiment was carried out in the same manner as in Example 1, except that TiC64 was added and the reaction temperature after Δ was set at 50°C. Note that the titanium content in the solid content at this time was 2.32% by weight. The results obtained are as shown in Table 1.

Example 5 An experiment was carried out in the same manner as in Example 1 except that the reaction temperature after adding T i C14 was changed to 80'C. The titanium content in the solid content at this time was 2.47% by weight. The results obtained are as shown in Table 1.

Example 6 Magnesium stearate 30.9. Ethyl benzoate 5
．． An experiment was conducted in the same manner as in Example 1 except that 7 g and 70 ml of n-hezotane were used. Note that the titanium content in the solid content at this time was 2.44% by weight. The results obtained are as shown in Table 1.

Comparative Example 1 [Preparation of catalyst components] MgCl2100 #, ethyl benzoate 31.5.9
is ground for 18 hours under a nitrogen gas atmosphere. Thereafter, the pulverized composition 100.9 was collected and charged into a glass container with an internal volume of 2000 ml under a nitrogen gas atmosphere.
00m was added thereto, and a stirring reaction was carried out at 65°C for 2 hours.

After the reaction was completed, the mixture was cooled to 40° C., left to stand, and the supernatant liquid was removed by decantation.

Next, washing with n-hebutane 10001/ was performed repeatedly, and when chlorine was no longer detected in the washing liquid, the washing was completed and the catalyst component was used.

At this time, the solid and liquid in the catalyst component was separated and the titanium content of the solid component was measured and found to be 1.28% by weight.

[Overlapping]

The same procedure as in Example 1 was carried out except that 20.4 mm of triethylaluminum and 0.71 mm of the above catalyst component were used as titanium sources. The results obtained are as shown in Table 1.

Comparative Example 2 14.2 Ii of anhydrous magnesium acetate, 40.8 # of aluminum triisozolopoxide, and 50 ml of decalin were placed in a 200 ml round bottom flask under a nitrogen atmosphere, and heated at 170 to 230°C for 10 hours. A stirring reaction was performed. Thereafter, the solvent was removed and drying was performed under reduced pressure to obtain a solid powder. The obtained solid powder was dehydrated with n~hebutane 100
After washing with m1 was repeated 10 times, the solvent was removed in the same manner, and drying under reduced pressure was further performed to obtain a solid powder. After the reaction was completed, the mixture was cooled to room temperature, left to stand, and the supernatant liquid was removed by decantation. Next, washing with 100 ml of dehydrated n-hebutane was carried out repeatedly, and the washing was completed when chlorine was no longer detected in the washing solution, which was used as a catalyst component. At this time, the solid and liquid in the catalyst component were separated and the titanium content in the solid was measured and found to be 1.22% by weight.

During polymerization, the obtained catalyst component is 1 as a titanium atom.
．． An experiment was conducted in the same manner as in Example 1 by charging 62 ay, 109 ~ of triethylaluminum, and 35 ~ of p-ethyl toluate. The results are as shown in Table 1, but no polymer was obtained that was sufficient to substantially measure polymerization characteristics.

Procedural amendment April 19, 1980 Commissioner of the Japan Patent Office Shima 1) Indication of Haruki Tono1 case 1982 Patent Application No. 156162 2 Title of the invention Process for producing a catalyst component for olefin polymerization 3 Amendments made Patent applicant address: 1-26-5 Toranomon, Minato-ku, Tokyo Name: Toho Titanium Co., Ltd. Representative: Tadao Negishi 4, Agent: 107 Address: 4-3-1-6, Akasaka, Minato-ku, Tokyo Amended The title of the invention column of the subject application, the title of the invention column of the specification, the scope of claims column of the specification, and the column of specification 1 and title of the invention of the application will be amended as follows: - The production capacity of catalyst components for polymerization of olefins is corrected to [Method for manufacturing catalyst components for polymerization of olefins].

2. The column for the title of the invention in the specification will be amended as follows.

[Method for producing a catalyst component for polymerizing α-olefins] will be amended to “Process for producing a catalyst component for polymerizing olefins.”

3. Amend the claims section of the specification as shown in the attached sheet.

4. The detailed description of the invention section of the specification is amended as follows.

(1) Page 1, lines 13 and 19; Page 2, lines 1 and 17; 4
Pages 5 and 20 lines; page 10 line 17; page 11 line 5: “α-
” to be deleted.

(2) Page 4, line 14: ``...The results of intensive research to solve the problem...'' This is the result of intensive research aimed at reducing the residual chlorine in the produced polymer while maintaining the same level of chlorine."

(3) Page 6, lines 8-9: "Magnesium oxalate" is deleted.

(4) Page 6, lines 10-11: "Magnesium glutaraldehyde" is deleted.

(5) Page 6, lines 17-18: “Magnesium chlorate”
Delete.

(6) Page 6, line 20 to page 7, line 1: "Magnesium laurate acetate" is corrected to "magnesium laurate."

(7) Page 7, line 5: Delete “magnesium biparate”.

(8) Page 7, lines 10-11: "Magnesium stearate is preferred." is corrected to "Saturated fatty acid magnesium is preferred, and magnesium stearate, magnesium octane, magnesium decanoate, and magnesium laurate are particularly preferred."

(9) Page 7, lines 17-18 = “ester, ketone,”
Corrects esters, alcohols, ketones, etc.

αQ Page 8, line 8: "..." is corrected to "...among them, ethyl benzoate, p-ethyl anisate, and p-)ethyl ruylate are particularly preferred."

0]) Page 9, line 9: "...in the range of 0.1 to 10 mol...
..." is "...0.1 to 5 mol, particularly preferably 0.1 to 5 mol.
3 to 2 moles, titanium halogen (ln'io, in the range of 01 mole or more, preferably 1 mole or more...").

αBu, page 9, line 19: Correct “10℃” to “room temperature”・
0bori Page 10, lines 6-7: Change “…to the boiling point” to “…
・Up to the boiling point, preferably 20 to 100°C.”

α Page 49, line 12: “…Contact is in an organic solvent…”
amend it to "...contact is carried out in an organic solvent using, for example, a container equipped with a stirrer..." 〇αli Page 18 1
4th line =: Correct r 1.22 J to r12.2 J.

cIllG Comparative Example 2) Description (page 17, line 1'6 to page 18, 2)
0 line), add the following message.

Example 7 An experiment was conducted in the same manner as in Example 1, except that 20 g of magnesium octoate vacuum-calcined at 70°C for 7 hours, 7,5 F ethyl benzoate, and 45 rnl of n-heptane were used. The titanium content in solid 9 at this time was 2.63% by weight.

During polymerization, triethylaluminum 108.8W
An experiment was carried out in the same manner as in Example 1, except that 39.2 rn9 of ethyl I9, p-toluyVate, and the catalyst component were each charged as a titanium atom of 0.91 η. The results obtained are shown in Table 1. ” αf) Table 1 on page 19 is corrected as shown in the table below.

2 Claims (1) After (a) fatty acid magnesium and (b) an electron-donating substance are brought into contact in (C) an organic solvent, the obtained solid composition is formed by (d) the general formula T1X4 (titanium halo represented by the formula, where X is a halogen element) l'/
1. A method for producing a catalyst component for polymerizing olefins, the method comprising contacting the catalyst component with a compound.

Claims (1)

[Claims] (1) After bringing (a) fatty acid magnesium and (b) an electron-donating substance into contact in (c) an organic solvent, the obtained solid composition is mixed with (d) the general formula TjX4 (in the formula teeth·
・It is a Rogon element. 1. A method for producing a catalyst component for polymerizing α-olefins, which comprises bringing the catalyst component into contact with a titanium rognide represented by