JPS5980413A - Preparation of copolymer - Google Patents

Abstract

PURPOSE:To prepare a copolymer having high activity, stereoregularity and bulk density, and useful as a film and other molded article, by copolymerizing an olefin with a complex compound of a Lewis acid and a polar vinyl monomer in the presence of a specific catalyst. CONSTITUTION:A copolymer of an olefin and a polar vinyl monomer is prepared by copolymerizing an olefin (e.g. ethylene, styrene, etc.) with a complex compound derived from a polar vinyl monomer (e.g. 10-undecenoic acid, methyl 8- noneate, etc.) and more than equimolar amount of a Lewis acid (e.g. ethyl alminum dichloride, methyl tin trichloride, etc.) in the presence of a catalyst composed of an organoaluminum compound (e.g. triethyl aluminum) and a catalyst component containing Mg, Ti, halogen and an electron donor.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a copolymer of a polar vinyl monomer such as an unsaturated ester and an olefin.

BACKGROUND ART In general, polyolefins have excellent mechanical strength and elastic properties, so they are extremely advantageous as materials for films and various molded products.

However, as expected from its chemical structure, it is chemically inert because it does not have a polar group (1), and therefore its properties such as adhesiveness, printability, and dyeability are extremely poor. The downside is that. To improve this, a method involves directly polymerizing olefins and unsaturated carboxylic acid esters using a catalyst consisting of a complex containing magnesium, titanium, halogen, and an electron donor, and an organometallic compound of Group 1 to Group II metals. is known from Japanese Patent Application Laid-open No. 118905/1983.

However, to the extent that the present inventors have investigated, the polymerization method disclosed in the above-mentioned publication has a low yield of copolymer using a catalyst, and the resulting copolymer has low stereoregularity. There are problems and it is not practical.

The present invention has been made to improve the above-mentioned prior art, and its purpose is to produce a copolymer of an olefin and a polar vinyl monomer that has catalytic efficiency and stereoregularity that can be put to practical use. The purpose is to provide a method.

The present inventors achieved the object of the present invention by copolymerizing an olefin with a complex compound obtained by complexing a polar vinyl monomer with a Lewis acid having higher Lewis acidity than the cocatalyst used during polymerization. They discovered this and completed the present invention.

In other words, the present invention is a method for producing a copolymer of an olefin and a polar vinyl monomer, in which a complex compound formed from a polar vinyl monomer and a Lewis acid in an amount equal to or more than equimolar to the polar vinyl monomer, The gist of this invention is a method for producing a copolymer, which is characterized by copolymerizing with an olefin in the presence of a catalyst consisting of a composite catalyst component rich in magnesium, titanium, halogen, and an electron donor and an organoaluminum compound.

Copolymerization method In the present invention, substances with high Lewis acidity and Lewis acids capable of being used in this copolymerization include compounds with the general formula RrnMXn.
Hail to you.

R; hydrocarbon group (alkyl, cycloalkyl, aryl, etc.) m ≦ 1.5 M; B r At + 8 nX; halogen,
■, Br, (3tn≧1.5 Specifically, ethylaluminum dichloride, methylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, aluminum chloride, poron pentachloride, methylporone dibromide, chloride Examples include Lewis acids such as tin and methyltin trichloride. Two or more types of these Lewis acids can be used.

Polar vinyl monomers, which are complexed with these Lewis acids! l
Examples include 6-pentenyl acetate, 3-butenyl acetate, 4-pentenyl acetate), 5-hexenyl acetate, 6-hephthynylacetate, 7-octynylacetate, 10-undecenyl acetate, 2- Methyl-4-pentenyl acetate, 1o-undecenylpropionate, octa-2,7-diphenylacetate,
3-butenyl-10-undecenoate, 4-pentenyl-10-undecenyl-), 5-hekymonyl-10-
undecenoate, 6-hebutenyl-10-undecenoate, 7-octenyl-10-undecenoate, 1
Esters of unsaturated alcohols and organic acids such as ゜-undecenyl-1o-undecenoate, 1゜-undecenyl acrylate, 1o-undecenyl allyl acetate, ethyl acrylate, methyl 3-butenoate, methyl 4-pentenoate, Unsaturated carboxylic acid ester of ethyl 6-heptenoate, methyl 8-nonenoate, methyl 10-undecenoate, propyl 1o-undecenoate, butyl 10-undecenoate, hexyl 1°-undecenoate, ethyl natate 13-tetrathecenate, 3 - Unsaturated alcohols such as 1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hebuten-1-ol, 10-undecen-1-ol, and 4-penten-1-ol. 1-carboxylic acid, 5-hexene-1-carboxylic acid, 6-hebutene-1
Examples include unsaturated carboxylic acids such as -carboxylic acid and 10-undecenoic acid. Note that two or more types of these polar vinyl monomers may be used in combination.

The synthesis of a complex compound between a Lewis acid and a polar vinyl monomer is
It can be prepared by contacting a polar vinyl monomer and a Lewis acid with stirring, usually under heating, in the presence of a solvent, if necessary, so that the molar ratio of the Lewis acid is 1 or more.

Suitable solvents include aliphatic, alicyclic, and aromatic hydrocarbons having 5 to 18 carbon atoms, and chlorinated hydrocarbons, and may be mixed as appropriate depending on the solubility of the complex compound. It is possible.

Examples include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, benzyl chloride, monochlorobenzene, and dichloroethane.

The catalyst component containing magnesium, titanium, halogen, and an electron donor as used in the present invention is one obtained by bringing magnesium or a magnesium compound, a titanium compound, and an electron donor into contact with each other by means such as heating or co-pulverization. As the magnesium compound, it is preferable to use magnesium halides, particularly magnesium chloride, and when these do not contain halogens, it is preferable to use halogen-containing compounds such as hydrogen halides and halogenated hydrocarbons.

Here, the halogen and titanium contained in the catalyst component are those whose halogen/titanium molar ratio preferably exceeds about 4 and which do not substantially eliminate the titanium compound by simple means such as washing with hexane at room temperature. Although its chemical structure is unknown, it is thought that the magnesium and titanium atoms share a halogen atom and are strongly bound together. Depending on the manufacturing method, it may also contain other metal atoms such as aluminum, silicon, tin, boron, germanium, calcium, and zinc. Furthermore, organic or inorganic inert diluents such as Li0A, 0aO
03, BaO12°Na2 (!03. 5r04.
It may contain B2O3,8102, TiO2,0a3(PO4)2°Oa OAt + polyethylene, polypropylene, etc. As the electron donor, one containing a fluoric acid ester or an ether is suitable.

A good catalyst component has a halogen/titanium (mole ratio) greater than about 4, preferably greater than about 5, and more preferably about 8.
The magnesium/titanium (molar ratio) is about 3 or more, preferably about 5 to about 50, and the electron donor/titanium (molar ratio) is about 1.2 to about 6, preferably about [14 to about 5, more Preferably about α8 to about 2, and the specific surface area is about 3 rn2/S' or more, more preferably about 40 m''/S' or more, and still more preferably about 100
In addition, the X-ray spectrum of the catalyst component shows poor quality irrespective of the starting magnesium compound, or is extremely amorphous compared to that of ordinary commercially available magnesium cybaride. It is desirable that the equipment be in the same condition as before.

As a means for producing the catalyst component, for example,
-108385, 50-126590, 51-
28189, No. 51-64586, No. 51-9288
No. 5, No. 52-87489, No. 52-104593, No. 53-2580, No. 54 +, No. 135691, No. 55-118905, No. 56-54707, No. 57-70104, No. 57-70105 This is disclosed in publications such as No. Among these, preferred manufacturing methods include JP-A-56-34707 and JP-A-57-7.
This method is described in each publication of No. 0105. To give a specific example, a magnesium-rich solid obtained by contacting metallic magnesium with a halogenated hydrocarbon and an orthoacid ester (ethyl orthoformate, etc.) described in JP-A No. 56-34707 is combined with a titanium compound (tetraformate). A method of contacting magnesium chloride, an electron donor (ethyl benzoate, etc.), a silicon compound (methylpolysiloxane) as a reaction accelerator, and a titanium compound ( (Japanese Unexamined Patent Publication No. 118905/1983).

A method of contacting a magnesium halide, an electron donor (ethyl benzoate, etc.), an aromatic carboxylic acid or its derivative (benzoic anhydride, etc.), an organoaluminum compound, and a titanium compound, as described in JP-A-57-70104. It is. Particularly desirable is the above-mentioned Japanese Patent Application Publication No. 57
This is the method described in Publication No.-70104.

In the present invention, the organoaluminum compound as a co-catalyst used together with the catalyst component has the general formula %. Examples of these include diethylaluminum chloride, triethylaluminum, triisobutylaluminum, and the like. Note that alumoxane compounds synthesized by reacting these organoaluminum compounds with a small amount of water can also be effectively used.

The olefins related to the present invention include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-
Examples include α-olefins such as methyl-1-butene and styrene, but two or more of these olefins may be used.

In the present invention, copolymerization may be carried out by bringing a catalyst into contact with liquefied olefin or gaseous olefin, or copolymerization may be carried out in an inert solvent. Hydrocarbons and chlorinated hydrocarbons are suitable as inert solvents.

For example, saturated aliphatic hydrocarbons such as pentane, hexane, benzene, octane, decane, cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, decahydronaphthalene, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetrahydronaphthalene. , chlorinated hydrocarbons such as benzene chloride and ethylene dichloride. Hydrocarbon mixtures such as kerosene, petroleum benzene, petroleum ether, etc. can also be used.

In addition to the two components, the catalyst component and the organoaluminum compound, a third component that increases the activity of the catalyst or increases the crystallinity of the produced copolymer, such as esters such as ethyl benzoate, n-butyl ether, etc. It is permissible to include ethers such as, organic phosphorus compounds such as triphenyl phosphite, etc., as long as they do not adversely affect the copolymerization reaction. Furthermore, hydrogen, alkyl halide, and the like, which are known as molecular weight regulators during olefin polymerization, can also be present in the copolymerization system.

The conditions during polymerization are generally the same as those for olefin polymerization using a coordination catalyst; for example, temperature and pressure can be arbitrarily selected depending on the type of monomer to be polymerized, the concentration of catalyst, and the desired degree of polymerization. Usually, a temperature range of 150° C. to 150° C. and a pressurized condition of 50 to 50 atm are suitable.

The concentration of titanium in the catalyst component during liquid phase polymerization is 0.
．． 01-200 mmol/1. Preferably α is in the range of 1 to 10 mmol/l. The molar ratio of the organoaluminum compound as a promoter to titanium in the catalyst component is 5 to 5.
00, preferably 50-200.

The amount of complex compound of polar vinyl monomer and Lewis acid used is:
The amount is 5 to 500 mol, preferably 50 to 150 mol, based on the titanium in the catalyst component. The conversion rate of this complex compound is 10
The content of the polar vinyl monomer in the polymer is at least 0.01 molar, preferably at least α1 molar.

In this copolymerization, various methods can be employed for adding the catalyst component, organoaluminum compound, and polymerization components (olefin and complex compound). For example, a method in which a complex compound of a Lewis acid and a polar vinyl monomer and an organoaluminium compound are premixed and then copolymerized with an olefin, or a method in which a catalyst component and a polymerization component are simultaneously fed to a polymerization system without premixing. Can be adopted. Of course, the copolymerization is not limited to random copolymerization, but may also be sequential polymerization in which the polymer components and ratios are changed during the polymerization. Polymerization or copolymerization can be conducted in a continuous manner, a batchwise manner, a semi-continuous manner, etc. as appropriate.

The copolymer obtained by the method of the present invention can be used alone or in combination with other polymers as adhesives, coatings, molded articles, etc. Various other functional groups can also be added to these by the same reaction as with compounds having low molecular weight polar groups.

Effects of the Invention By copolymerizing a complex compound of a Lewis acid and a polar vinyl monomer with an olefin, the poisoning effect of the polar vinyl monomer on the catalyst component can be suppressed, resulting in a highly active and highly steric compound. A copolymer with regularity and high bulk density can be obtained.

Hereinafter, the present invention will be explained in detail using specific examples.

Note that percentages in specific examples are based on weight unless otherwise specified. Copolymer melt index (
M engineering) in accordance with ASTM-D 123B, temperature 230
℃ and a load of 2.16 Kf. The heptane insoluble content (H), which indicates the proportion of the crystalline polymer in the copolymer, is the residual amount when extracted with boiling n-hebutane using an improved Soxhlet extractor. Also, the bulk density is ASTM-D
1895-69 Measured according to Method A.

Example 1 Preparation of catalyst components Ball 10 made of stainless steel (5Us32) with a diameter of 10 m
Stainless steel (SUB
! +2) Anhydrous magnesium chloride 2 & 1f and ethyl benzoate 5.5 t in a mill pot made of aluminum under nitrogen gas atmosphere.
d (5a 5 mmol) and benzoyl chloride (39
This mill pot was attached to a shaker and kept in contact for 15 hours by vibration to obtain a pulverized solid.

7.2 f of the obtained pulverized solid was placed in a 300-mm glass container equipped with a stirrer under a nitrogen gas atmosphere, and 1.
After adding 2-dichloroethane 110-, ethylaluminum dichloride α81 m/(7,7 mmol)
A mixed solution of 1,2-dichloroethane 10- and 1,2-dichloroethane was added dropwise at 32° C. over 15 minutes with stirring, and the mixture was further stirred at 70° C. for 2 hours.

The obtained solid material was separated at 70°C and washed five times with 150°C of n-hexane at 65°C.

Next, 120-titanium tetrachloride was added to this solid substance,
The mixture was stirred at 120°C for 2 hours. The obtained solid substance was
The mixture was separated in a furnace at 0°C, washed with 26,150 m of n-hexane at 65°C seven times, and then dried at 50°C under reduced pressure for 1 hour to obtain catalyst component (1).

This catalyst component (1) contained 24 titanium atoms.

Co-electrode A of undecene propylene Under a nitrogen gas atmosphere, &25 mmol of 10-undecenoic acid and 15 mmol of ethylaluminum dichloride (
KADO) in heptane at room temperature to form a complex. This solution was converted into the catalyst component (1) synthesized as described above.
A glass ampoule containing 151 mg of triethyl aluminum (TEAL) 86 was placed in a 1 ton autoclave under a nitrogen gas atmosphere.
49 mol (At/Ti == 100-F: to/-E:
k) was added. After charging hydrogen in gaseous form and propylene in liquid form at 60°C, the autoclave was heated to 70°C.
The glass ampoule was broken with a stirrer to initiate polymerization. After copolymerization for 2 hours, unreacted propylene was purged, and the copolymerized polymer was taken out and vacuum dried day and night to obtain 6 tons of copolymer. From this yield, the catalyst efficiency was 501 t/l (catalyst component), indicating high activity.

The 10-undecenoic acid content in the copolymer is 0.
At 12 molti, the compound (1) exhibited high stereospecificity with 92.59 IJ. The bulk density was relatively high at α36f/cC.

Also, the M work was 2.3F/10 minutes.

Comparative Example 1 Copolymerization was carried out in the same manner as in Example 1, except that the catalyst component (1) was 110 mg, 1o-undecenoic acid was 6.25 mmol, and TEAL was 172 mmol, and IADO as the Lewis acid was not used. went. In this case, the amount of polymer produced was only a trace.

Comparative Example 2 Example 1 except that 11iADO was not brought into contact with 1o-undecenoic acid in advance and was used mixed with TEfAL.
Copolymerization was carried out in exactly the same manner. Copolymer yield is 12
．． At 8F, the catalyst efficiency was low at 84.89/Ta1 catalyst component.
The organic acid content was also as low as 0.04 mol. In addition, M work was 1.8 f/10 minutes.

Example 2 10-f) Endecenoic acid 25 mm%/I/, iAD.

Polymerization was carried out in exactly the same manner as in Example 1, except that 27.5 mmol of TEAL, 115 mmol of TEAL, and 148 mg of catalyst component (1) were used. Copolymer yield 61.5f
The catalyst efficiency was 420 f/f-catalyst component. In addition,
The content of organic acid in the polymer was α21-f:ruti. The H-work was 950cm and the bulk density was 11569/Cr. Moreover, Ml was 2.09710 minutes.

Example! , 4,5.6 Except for using 10-undecenyl acetate, methyl 8-nonenoate, methyl 10-undecenoate, and 10-undecen-1-ol in place of 10-undecenoic acid.
Copolymerization was carried out in exactly the same manner as in Example 1. The results are shown in Table 1.

Example 7 Copolymerization was carried out in exactly the same manner as in Example 1, except that aluminum trichloride was used as the base of 1jADo and toluene was added to dissolve the complex compound. The copolymer yield was 82.31, the catalyst efficiency was 545 f/f-catalyst component, and the unsaturated carboxylic acid content was 113 mol. The H work was 92.3 inches and the bulk density L was 56t/Cr. Also, MI was 2.4f710min.

Example 8 Copolymerization was carried out in exactly the same manner as in Example 1, except that methyltin trichloride was used as the IADO glue. Copolymer yield was 67.5 f, catalyst efficiency was 447? /f-catalyst component, unsaturated carboxylic acid content 111 mol%, 111
Engineering 951cm, bulk density α37f/CC, MI 2.3
F/10 minutes later.

Example 9 Preparation of catalyst components
c, e, (25℃)) in a nitrogen gas atmosphere with a diameter of 12 m.
A stainless steel (EIUS !1) with an internal volume of 30 rows that accommodates 100 stainless steel (SUB 316) balls.
16) under a nitrogen gas atmosphere, the mill pot was attached to a shaker, and the mixture was shaken and brought into contact for 20 hours to obtain a pulverized solid.

10 f of the obtained crushed solid was placed in a Saa* glass container equipped with a stirrer under a nitrogen gas atmosphere, and 100-
After adding titanium tetrachloride, the mixture was stirred at 80° C. for 2 hours. After the treatment, the product was washed with 150-hexane until titanium was no longer eluted into the washing solution, and dried to obtain catalyst component (2). This catalyst component (2) contains 1.9 titanium.
It contained polymeric acid.

Copolymerization of undecenoic acid and probile Copolymerization was carried out in exactly the same manner as in Example 1, except that the catalyst component (2) synthesized as described above was used, and 51,5 fO
A copolymer was obtained. From this yield, the catalyst efficiency is 541 f/
f-catalyst component, the organic acid content in the copolymer is
From α10 morchi, H engineering was 9α5 rice cake. Note that the bulk density was α34f/CC. Also, M type is 2.1 f/
It was 10 minutes.

Comparative Example 3 Catalyst component (2) was used in place of catalyst component (1), diethylaluminum chloride (Dwha) was used in place of TEAL, and 31! ! Copolymerization was carried out in the same manner as in Example 1 except that ADO was not used.

Copolymer yield is 11.5 f and catalyst efficiency is 76.1 f/f.
- It was a catalyst component, and the organic acid content was α09 molar. In addition, the M work was 1.9 f/10 min.

Agent: 1) Akira Agent Ryo Hagi Hara - 129-

Claims (1)

[Claims] ( ]) In a method for producing a copolymer of olein and a polar vinyl monomer, a complex compound formed from a polar vinyl monomer and a Lewis acid in an amount equal to or more than the same mole relative to the polar vinyl monomer is mixed with magnesium, titanium, halogen, and electrons. A method for producing a copolymer, which comprises copolymerizing with an olefin in the presence of a catalyst comprising a catalyst component carrying a donor and an organoaluminum compound.