JPS603322B2 - Method for manufacturing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the polymerization or copolymerization of olefins using a novel catalyst, and in particular to the polymerization or copolymerization of Q-olefins with good stereoregularity using a novel high-performance supported catalyst. The present invention relates to a method for producing a characteristic polyolefin.

Conventionally, a catalyst comprising a titanium halide and an organoaluminum compound has been known as a highly stereoregular polymerization catalyst for Q-olefin.

However, in polymerization using this catalyst system, although a highly stereoregular polymer can be obtained, the yield per titanium catalyst component is still insufficient, and a step is required to remove the catalyst dipping in the produced polymer. In order to solve this technical issue, several high-performance catalysts using magnesium halide as a carrier have been proposed in recent years (Japanese Unexamined Patent Publication No. 48-16, No. 6, Samurai Seki No. 48-11).
6 Job No. 7, Tokukan Sho 48-116988, etc.).
-However, clearly the polymerization activity is as high as possible;
It is also desirable that the stereoregularity is as high as possible, and that the resulting polymer has good powder properties.

The present invention relates to a method for producing extremely highly active and highly stereoregular polyolefins using a novel catalyst system, and the resulting polymer has a high bulk specific gravity and good powder properties.

Another feature is that the halogen content in the polymer is lower than that of a catalyst system using magnesium chloride as a carrier, so there is less concern about destabilization of the polymer due to halogen contamination and corrosion of equipment. Thus, the present invention provides a method for producing polyolefins that is extremely economical overall, since the catalyst removal step can be omitted in the polyolefin production process and the amount of atactic moieties produced in the polymer obtained during parenthesis is extremely small. It is something. That is, the present invention provides a hydroxy compound represented by [A]'1} magnesium oxide, '2) aluminum halide, {3} general formula ROH (where R represents an organic residue having 1 to 20 carbon atoms). and '41 a solid component obtained by contacting a titanium halide and/or an adduct of a titanium halide and an aromatic carboxylic acid ester, and [B] an organometallic compound and/or an organometallic compound and an aromatic carbonate. This invention relates to a method for polymerizing or copolymerizing olefins using an adduct with an acid ester as a catalyst, or a catalyst further comprising [C] aromatic carboxylic acid ester. The fact that polyolefins with highly stereoregular activity could be produced was completely unexpected and surprising.

The present invention will be explained in detail below. Specifically, the method for preparing the solid components of the present invention includes (i) magnesium oxide as component '1}, aluminum halide as component (■), and component t3.
} A method for simultaneously co-pulverizing a hydroxy compound represented by the general formula ROH and a component [41] of a titanium halide and/or an adduct of a titanium halide and an aromatic carboxylic acid ester.

(ii) A method in which components '1}, ■ and '3' are co-pulverized, and then component '4} is added and further co-pulverized.

(iii) A method of co-pulverizing components {1-, [2- and '3'] and then contacting them with component (2) in a liquid phase or gas phase.M A method of further contacting the obtained product with component {41 in a liquid phase.

can be mentioned. The above solid component preparation method (ii
) and (iii), a solid carrier is first synthesized by pulverizing components '1', '21 and the paste.

At this time, the order of addition of each component '1} to {3' is not particularly limited. The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and conditions such as grinding temperature and grinding time can be easily determined by those skilled in the art depending on the grinding method. be.

Generally, the grinding temperature may be about 0° C. to 50 qo, and the grinding time is 0.5 to 50 hours, preferably 1 to 3 field hours. In addition, in method oii) or M, components ■
When contacting with the liquid titanium halide, the liquid titanium halide is brought into contact as it is or in an inert solvent such as hexane or heptane at a reaction temperature of 0 to 15,000 ℃, and the solid component is separated and washed with an inert solvent. It can be a solid component of the invention. When preparing the solid component of the present invention, the components may be brought into contact in the absence of the aromatic carboxylic acid ester, but a method of bringing each component into contact in the presence of the aromatic carboxylic acid ester is also preferably employed.

When an aromatic carboxylic acid ester is coexisting, the amount of the aromatic carboxylic acid ester added is usually 1 mol (M
(based on g atoms), preferably 1 mol or less.

Of course, the aromatic carboxylic acid ester used to coexist during the preparation of the solid catalyst component described above and the aromatic carboxylic acid ester used as an adduct in component (1) may be the same or different, or two or more may be used in combination. Good too.

In the present invention, the amount of each component used when synthesizing the solid component is 1) 1 mol of magnesium oxide, 2' aluminum halide from 0.001 to 10 mol, preferably 0.01 to 5 mol; '3} The hydroxy compound represented by the general formula ROH is 0.001 to 5 mol, preferably 0.
．． 01 to 1 mole is used.

In addition, the amount of {4' titanium halide and/or adduct of titanium halide and aromatic carboxyl ester used is determined when the amount of titanium contained in the produced solid component is 0.
．． It is preferably adjusted within the range of 5 to 1% by weight, and particularly preferably 1 to 8% by weight in order to obtain a well-balanced activity per titanium and activity per solid.

The present invention also provides [A] '1' magnesium oxide, (2) aluminum halide, [3' hydroxy compound represented by the general formula ROH (where R represents an organic residue having 1 to 20 carbon atoms), and [4 -Titanium halides and/or
Or a solid component obtained by contacting an adduct of a titanium halide and an aromatic carboxylic acid ester, [B]
It also relates to a method of polymerizing or copolymerizing an olefin using an organometallic compound and/or an adduct of an organometallic compound and an aromatic carboxylic ester, and a catalyst further comprising [C] an aromatic carboxylic ester, At this time, the amount of aromatic carboxylic acid ester added as component [C] is such that the molar ratio of aromatic carboxylic acid ester/organometallic compound is 1.5 or less, for example, 0.05 to 1.5, preferably 0.05 to 1.5.
It can be selected within the range of 1 to 0.7.

Of course, the aromatic carboxylic acid esters used in components [A], [B] and [C] may be the same or different.

There is no particular restriction on the type of magnesium oxide used in the component [1 liter] in the present invention, and a commercially available product may be used as it is or may be used after being fired as appropriate.

As the aluminum halide of component (1), aluminum chloride, aluminum bromide, and aluminum chloride are used, and aluminum chloride is particularly preferred. The hydroxy compound represented by the general formula ROH (where R represents an organic residue having 1 to 20 carbon atoms) of component [3} includes various monovalent or polyvalent aliphatic alcohols, alicyclic alcohols,
One or more compounds selected from the group consisting of aromatic alcohols and phenols are used.

Specific examples of these include alcohols such as methanol, ethanol, n-propanol, n-butanol, hexanol, cyclohexanol, 2,6-dimethylhexanol, menthol, benzyl alcohol, phenethyl alcohol, cumyl alcohol, phenol, and cresol. , xylenol, butylphenol, octylphenol, nonylphenol, dibutylphenol,
Examples include phenols such as naphthol, cumylphenol, and chlorophenol, various polyols such as ethylene glycol, propylene glycol, and resorcinol, and various substituted derivatives thereof.

The titanium halide used as component '41 of the present invention is not particularly limited, but examples of tetravalent titanium halides include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxytrichlorotitanium, diethoxydichlorotitanium. Examples include titanium, triethoxymonochlorotitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, a reaction product of silicon tetrachloride and titanium alkoxide, and mixtures thereof.

The trivalent titanium halide used in the present invention is not particularly limited, and includes various titanium trihalides obtained by reducing titanium tetrahalide with hydrogen, aluminum, titanium, or an organometallic compound, and Examples include compounds obtained by reducing various tetravalent alkoxy titanium halides with organometallic compounds.

In the present invention, tetravalent titanium halides are particularly preferably used.

The adducts of titanium halides and aromatic carboxylic acid esters used in the present invention include addition compounds of the titanium halides and the various aromatic carboxylic acid esters, such as aromatic carboxylic acid esters. The molar ratio of acid ester: titanium halide is 1:1 or 2:
1 is preferred.

Examples of these adducts include, for example, TIC14.
C6 day 5 COOC2 day 5, TIC14
・2C Niji 5 COOC 2nd 5, TIC14
pC cucumber OC6 WCOOC2 day 5, TIC13・C6
I can give 5 COOC 2 days 5th grade. A mixture of a titanium halide and an adduct of a titanium halide and an aromatic carboxylic acid ester can also be preferably used.

The aromatic carboxylic acid ester used in the present invention is a compound containing one or more carboxylic acid ester groups directly connected to a monocyclic or polycyclic aromatic ring, and as long as the aromatic ring does not adversely affect the reaction, It may have other substituents such as an alkyl group, an aryl group, and a halogen. Typical examples of such esters include the following: Furkyl benzoates such as methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoate, cycloalkyl benzoates such as cyclobentyl benzoate, cyclohexyl benzoate, benzoic acid phenyl,
Aryl benzoates such as 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, cyclohexyl p-oxybenzoate, pendyl salicylate, ethyl Q-resorcinate, etc. Oxybenzoic acid esters, methyl anisate, ethyl anisate, phenyl anisate, penzyl anisate, ethyl o-methoxybenzoate, alkoxybenzoic acid esters such as methyl p-ethoxybenzoate, methyl p-toluate, p-toluic acid Alkylbenzoic acid esters such as ethyl, p-phenyl p-tolylate, o-ethyl tolylate, m-ethyl tolylate, methyl p-aminobenzoate, p-aminobenzoate, etc.
Amino group-containing benzoic acid esters such as ethyl benzoate; other benzoic acid esters such as vinyl benzoate, allyl benzoate, and pendyl benzoate; and naphthoic acid esters such as methyl naphthoate and ethyl naphthoate.

Among these, particularly preferred are alkyl esters of benzoic acid, o- or p-tolylic acid, or p-anisic acid, and methyl esters and ethyl esters thereof are particularly preferred.

As the organometallic compound used in the present invention, organometallic compounds belonging to Groups 1 to W of the periodic table, which are known as one of the components of zigular soot, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred.

Specific examples include general formulas R3A1, R2AIX, RN
X2, R2NOR, RN(OR)X and R3AI2×
3 (where R is an alkyl group or aryl group having 1 to 20 carbon atoms, X is a halogen atom, and R may be the same or different), including triethylaluminum, triisobutylaluminum, Examples include trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. The adduct of an organometallic compound and an aromatic carboxylic acid ester used in the present invention is an adduct of the above-mentioned organometallic compound and the various aromatic carboxylic esters, such as an aromatic carboxylic ester: Those in which the molar ratio of the organometallic compound is 1:2 to 2:1 are preferably employed.

Also preferably used is a mixture of an organometallic compound and an adduct of the organometallic compound and an aromatic carboxylic acid ester.

In the present invention, the amount of the organometallic compound to be used is not particularly limited, but is usually 0.1 to 0.1 to the amount of titanium halide.
It can be used in an amount of 1000 moles.

In the present invention, when components [A] and [B] are used as a catalyst, and when components [A], [B] and [C] are used as a catalyst, in either case, the aromatic carboxylic acid ester present in the catalyst The total amount of is 0.05 mol or more based on the amount of Mg (gram atom) in the catalyst system, preferably . 0.05-10 mol, most preferably 0.2-10 mol
It is 10 moles. The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst.

That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, or in the presence of an inert solvent or with the monomer itself as the solvent. The polymerization conditions for olefin are temperature of 20 to 300°C, preferably 40 to 180 qo, and pressure of normal pressure to 70 kg/G.
, preferably without 2, and 60k9/G. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-stage or more multi-stage polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler catalysts, such as ethylene, propylene, 1-butene,
It is suitably used for the homopolymerization of Q-olefins such as 4-methylbentene-1, and the random and block copolymerization of ethylene and propylene, ethylene and 1-butene, propylene and 1-butene, and the like.

In addition, copolymerization with genes for the purpose of modifying polyolefins, such as copolymerization of ethylene and butadiene, ethylene and 1,4-hexadiene, etc., is also preferably carried out. In the present invention, it can be particularly effectively used to polymerize or copolymerize olefins having 3 to 8 carbon atoms with good stereoregularity.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 'a' Synthesis of group catalyst component Magnesium oxide 5.7 vacuum dried at 400°C for 4 hours
Aluminum trichloride: 13.0%, methanol: 1.0%
The powder was placed in a stainless steel pot with an internal volume of 400 cm containing 28 stainless steel balls with a diameter of 1'2 inches, and after ball milling was carried out at room temperature for 1 hour under a nitrogen atmosphere, titanium tetrachloride was further added. 3.4 hours were added and ball milling was performed for 1 hour at room temperature under a nitrogen atmosphere.

The solid powder obtained after ball milling contained 39 pieces of titanium. 'b} Polymerization 2 The stainless steel autoclave equipped with an induction mill was purged with nitrogen and 1000 g of hexane was added, 2 mmol of triethylaluminum, and 0.56 ethyl benzoate.
mmol and 9 of 80 of the solid powder described above were added, and the temperature was raised to 50q0 while stirring.

The vapor pressure of hexane brought the system to 0.5k9'·G, and then propylene was added to the system until the total pressure reached 7k9/d·G to start polymerization. Polymerization was carried out for 1 hour by continuously introducing propylene so that the total pressure was 7k9/G.G. After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried to obtain white polypropylene.

This is the total amount of the product, including the amorphous material. Catalyst activity: 92 Tapolypropylene/Yellow solid, hr, C3 days, 6 Mr., 2
3702 polypropylene/Ti.hr.C3HB pressure, and the total extraction residue rate with N-hebutane, including the solvent-soluble polymer, was 80.1%.

Comparative Example 1 When a catalyst was synthesized and polymerized in the same manner as in Example 1 except that methanol was not used, only 1 ta of polypropylene was obtained.

Comparative Example 2 In Example 1, a collective catalyst component was synthesized and polymerized in the same manner as in Example 1 except that aluminum chloride was not used, but no polypropylene was obtained.

Example 2 A solid catalyst component was synthesized in the same manner as in Example 1 except that one portion of n-butanol was used instead of methanol in Example 1. A solid containing 36 parts of titanium in 1 part of the solid was obtained. A powder was obtained.

Polymerization of propylene was carried out in the same manner as in Example 1, except that the solid powder 80:2 was used, and white polypropylene 35 was obtained. The catalytic activity was 67% polypropylene/3 solids/hr/C3 day 6 pressure, 1870% polypropylene/3days/hr/C3 pressure, and the total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was The rate is 83
．． It was 0%. Example 3 Polymerization was carried out in the same manner as in Example 1 except that 0.56 mmol of p-ethyl anisate was used instead of ethyl benzoate, and 41 mmol of white polypropylene was obtained.

Catalytic activity is 79 polypropylene/solid solid/hr/C
3 days 6 pressure, 2020 tap polypropylene nota Ti・hr・
C3 day 6 pressure, boiling n including solvent soluble polymer
-The total extraction residue rate with heptane was 83.0%. Example 4 Magnesium oxide vacuum dried at 40030 for 4 hours4.
5 days, aluminum trichloride 17.3 days, methanol 2 days.
0' was placed in a tabletop stainless steel pot with an internal volume of 400 and containing 29 stainless steel balls with a diameter of 1'2 inches, and after ball milling was performed at room temperature for 1 hour under a nitrogen atmosphere, it was further mixed with tetrachloride. After adding 4.1 kg of titanium, ball milling was carried out at room temperature for 16 hours under a nitrogen atmosphere.

One solid powder obtained after ball milling contained 40 particles of titanium. Polymerization was carried out in the same manner as in Example 1 using 80% of the solid powder, and 52% of white polypropylene was obtained. The catalyst activity was 100% polypropylene solid/hr/C3 day 6 sho, 2500% polypropylene/temperature/hr/C3 horsepower, and the total extraction residue with boiling n-heptane including the solvent-soluble polymer was 7
It was 9%. Example 5 In Example 1, 1 of titanium tetrachloride and ethyl benzoate:
A solid powder was synthesized in the same manner as in Example 1, except that 4.7 molar adducts of 1 (molar ratio) were used.
The resulting solid powder contained 36 parts and 9 parts of titanium.

Using the above solid powder 80-9, polymerization was carried out for 1 hour in the same manner as in Example 1, resulting in white polypropylene 3.
0 evening was obtained.

Catalytic activity is solid, hr, C3 days, 6 pressure, 1600
The total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was 88.0%. Example 6 80% of the solid powder synthesized in Example 1, 1% of n-hexane
000', 1 mmol of an adduct of 1 mol of triethylaluminum and 0.5 mol of ethyl benzoate, and 1 mmol of triethylaluminum, 50°C, Zensho 7k.
Polymerization of propylene was carried out for 1 hour at 9/G, yielding white polypropylene 55%.

Claims (1)

[Scope of Claims] 1 [A] (1) magnesium oxide, (2) aluminum halide, (3) hydroxy represented by the general formula ROH (where R represents an organic residue having 1 to 20 carbon atoms) A compound and (4) a solid component obtained by contacting a titanium halide and/or an adduct of a titanium halide and an aromatic carboxylic acid ester, and [B] an organoaluminum compound and/or an organoaluminum compound and an aromatic consisting of an adduct with a group carboxylic acid ester,
A method of polymerizing or copolymerizing olefin using a catalyst in which the total amount of aromatic carboxylic acid ester is 0.05 mol or more based on the amount of Mg (gram atom). 2 [A] (1) Magnesium oxide, (2) aluminum halide, (3) hydroxy compound represented by the general formula ROH (where R represents an organic residue having 1 to 20 carbon atoms), and (4) titanium A solid component obtained by contacting a halide of titanium and/or an adduct of a titanium halide and an aromatic carboxylic ester, [B] an organoaluminum compound and/or an addition of an organoaluminum compound and an aromatic carboxylic ester and [C] aromatic carboxylic acid ester, and the total amount of aromatic carboxylic acid ester is 0.0 based on the amount of Mg (gram atom).
A method of polymerizing or copolymerizing olefin using a catalyst present in an amount of 5 moles or more.