JPS5812281B2 - Kouritsutaikisokuseipori -A- Olefuinno Seizouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing α-olefins using a supported catalyst, which can produce highly stereoregular α-olefin polymers in high yields over a long period of time.

Conventionally, a combination system of a solid titanium halide and an organoaluminum compound has been widely used as a catalyst for producing a highly stereoregular polymer of α-olefin.

Polymerization using this catalyst system yields polymers with high stereoregularity, but the polymer yield per titanium catalyst component remains at a low level, and as a result, catalyst residues in the resulting polymer are removed. It requires a process.

Proposals for polymerizing olefins with high polymerization activity and eliminating the need for the step of removing catalyst residues from the resulting polymer include, for example, Japanese Patent Publication Nos. 46-34092 and 3 published earlier.
There are methods described in each patent publication No. 4093.

These methods involve polymerizing olefins by supporting titanium halide on a compound prepared by pretreating a divalent metal halide with alcohol or water, and combining this with an alkyl aluminum. In the case of polymerizing α-olefin containing more than one carbon atom, such as propylene, the stereoregularity of the polymer is very low, around 40°, and considering the yield as a method for obtaining a crystalline polymer, it is not suitable for industrial use. This is not an advantageous method.

The present invention solves the problems that still remain in conventional methods and proposals for solving them, and achieves high activity and high stereoregularity (
The object of the present invention is to provide a polymerization method using an excellent catalyst that can produce a highly crystalline polymer over a long period of time.

To explain in detail, the advantages of using the catalyst of the present invention are as follows.

(1) Since α-olefin containing three or more carbon atoms is polymerized with high polymerization activity, the step of removing catalyst residues from the resulting polymer can be omitted.

(2) When an α-olefin containing three or more carbon atoms, such as propylene, is polymerized, the stereoregularity of the polymer can be around 90%.

(3) The catalyst of the present invention is a catalyst system capable of producing a highly active, highly stereoregular (highly crystalline) α-olefin polymer over a long period of time.

Therefore, the method of the present invention is an industrially advantageous method for obtaining crystalline poly-α-olefins in combination with a high yield.

In the present invention, the term "polymerization of α-olefin" refers not only to its homopolymerization but also to the case where a non-rubber-like copolymer is produced by copolymerizing α-olefin with ethylene or other α-olefin or diolefin. nothing.

Here, α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-nibutene, etc., and diolefins include conjugated diolefins such as butadiene, cyclopentadiene, ethylidene norbornene, and 1,5- Examples include non-conjugated dienes such as quizadiene.

The present invention was obtained by (a) treating a titanium compound supported on a magnesium compound with an aromatic carboxylic acid ester, and washing the treated solid portion with an inert solvent.

The present invention relates to a method for polymerizing olefins, which comprises polymerizing α-olefins containing three or more carbon atoms in the presence of a catalyst derived from a titanium-containing solid catalyst component and an organic aluminum compound catalyst component.

The catalyst (a) component used in the present invention is usually prepared as follows.

First, the following method is recommended as a method for producing a titanium compound supported on magnesium halide.

(1) A method in which anhydrous magnesium halide is brought into close contact with a titanium compound by mechanical crushing means.

The mechanical contact treatment with the titanium compound must be carried out until the half-value width of the magnesium halide as measured by X-ray diffraction becomes larger than the half-value width before treatment.

The degree of increase in half width is preferably 5 times or more, more preferably 10 times or more, than the half width before treatment.

The measurement was performed using a Cu generated from a 50KV, 100mA X-ray device.
Magnesium halide crystal (10
4) Do this on the surface.

(2) A method of bringing a titanium compound into contact with an electron donor pretreated product of anhydrous magnesium halide.

This pretreatment is carried out to treat magnesium halide, usually at room temperature to 200°C.
．． Contact with 0.01 to 6 mol of electron donor or its inert solvent solution for usually 5 minutes to 5 hours (hereinafter referred to as chemical contact), or contact with magnesium halide and 0.01 to 6 mol of electrons, usually for about 5 minutes to 5 hours. This can be suitably carried out by bringing the donor into mechanical contact.

Taking a rotary ball mill as an example of a mechanical contact method, 100 balls made of stainless steel (SUS32) with a diameter of 15 mm are housed in a ball mill cylinder made of stainless steel (SU.S32) with an inner volume of 800 ml and an inner diameter of 1007 n@. Rotation speed 125r when the amount is 20 to 40g
The grinding process may be carried out for a period equivalent to a grinding process of usually 48 hours or more, preferably 72 hours or more.

In addition, the temperature of the grinding process should normally be selected around room temperature;
If the heat generation is significant, it is preferable to carry out the grinding contact at room temperature or below with appropriate cooling.

The contact between the pretreated product and the titanium compound may be carried out by mechanical means or by immersing the pretreated product in a liquid titanium compound or a liquid phase containing a titanium compound.

The molar ratio of the electron donor and the titanium compound is usually 1:0.
01 to 20).

Further, it is preferable that the pretreated material be brought into contact with the titanium compound at a temperature ranging from room temperature to 200° C. for 5 minutes to 5 hours.

(3) 0.1 to 1.5 with respect to the alcohol pretreated product of anhydrous magnesium halide and the hydroxyl group of the alcohol.
A method in which a reaction product with an aluminum alkyl in an amount equivalent to twice the mole of organic groups is brought into contact with a halogen compound of titanium.

When the titanium compound is liquid, such as titanium tetrachloride, the method of bringing the pre-treated carrier into contact with a titanium compound includes, for example, immersing the pre-treated or reduced carrier in a liquid phase made of the titanium compound; Although there are no particular limitations, a general method may include heating at 80 to -150°C for 30 minutes to 5 hours.

This dipping treatment may be carried out in a liquid phase in which the titanium compound is dissolved in a suitable inert solvent.

Furthermore, if the electron donor used in the pretreatment is something other than alcohol, the coexistence of alcohol in the inert solvent solution of the titanium compound can increase the amount of the titanium compound. Activity improves.

(4) Anhydrous magnesium halide is brought into mechanical contact with an organic acid ester and a silicon compound such as silicon tetrachloride simultaneously or sequentially, and the resulting activated magnesium halide is combined with the titanium compound itself or a liquid containing it. Examples include methods for supporting a titanium compound on magnesium halide by immersion in a phase, contact with vapor of a titanium compound or a gas phase containing it, or further mechanical contact with a titanium compound. I can do it.

In this case, magnesium halide, organic acid ester,
The silicon tetrachloride and titanium compounds can also be subjected to mechanical contact at the same time.

Further, the magnesium halide may be pretreated with an organic acid ester.

Examples of mechanical means for effecting contact under pulverization conditions include rotary ball mills, vibrating ball mills, impact mills, and the like.

The method for producing a titanium-containing solid catalyst component obtained by treating a titanium compound supported on magnesium halide with an aromatic carboxylic acid ester and washing the treated solid part with an inert solvent is preferably a method for producing a titanium-containing solid catalyst component by treating a titanium compound supported on a magnesium halide with an aromatic carboxylic acid ester, and washing the treated solid part with an inert solvent. The process consists of contacting the group carboxylic acid ester in the liquid phase and washing the resulting treated solid with an inert solvent.

In this case, the amount of aromatic carboxylic acid ester used is preferably selected within the range of 164 to 104 mm01 per gram of titanium compound supported on magnesium halide.

This reaction is preferably carried out in an inert solvent.

In addition, there is no particular restriction on the reaction time, but it ranges from 1 minute to 10 minutes.
You can choose an appropriate time between 0 hours.

There is no particular restriction on the reaction temperature, but it may be selected at an appropriate temperature within the range of 0 to 300°C.

In addition, as a method for obtaining a titanium-containing solid catalyst component by treating a titanium compound supported on magnesium halide with an aromatic carboxylic acid ester, a titanium compound supported on magnesium halide and an aromatic carboxylic acid ester are mechanically processed. A method of contacting using a pulverizing means can also be mentioned as a preferable example.

Each raw material for preparing the catalyst (a) JtE component will be explained below.

The magnesium halide used as a carrier is MgX
2 (where X represents a halogen), such as magnesium chloride, magnesium bromide, magnesium iodide, etc.
Among them, magnesium chloride is preferred.

It is preferable to use commercially available magnesium halides prepared by adjusting them to an appropriate particle state and, if necessary, drying them.

However, the general hydrate represented by MgX2/IH20 (where X is a halogen and 1 is 1σ6≦1≦6),
Treatment of alcohol or phenol adducts with the general formula MgX2·mROH (X is halogen, ROH is alcohol or phenol, m is 10-6≦m≦6) or other electron donors of magnesium halide It can also be used in the form of objects.

Examples of the above ROH are saturated aliphatic alcohols containing usually 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, n-butanol, and usually 6 to 10 carbon atoms. phenols, preferably 6 to 8, including phenol, O-, m- and p-cresol, 2,6-
Xylenol such as xylenol and naphthol.

Examples of the electron donor include various organic acids and their esters, as well as ethers, ketones, amines, nitrile and phosphorus compounds, preferably primary alkyl esters of haloaliphatic carboxylic acids and primary aromatic monocarboxylic acids. It is an alkyl ester.

(a) Various organic acids have 1 to 12 carbon atoms.
aliphatic carboxylic acids containing 7 or 8 carbon atoms, aromatic carboxylic acids containing 7 or 8 carbon atoms, such as formic acid, acetic acid, propionic acid, benzoic acid, (b) as esters containing 1 to 12 carbon atoms and halogen substituted Esters of aliphatic monocarboxylic acids, which may be monocarboxylated, with saturated or unsaturated aliphatic primary alcohols containing 5 to 12 carbon atoms, such as ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate and ethyl monochloroacetate. and esters of aromatic monocarboxylic acids containing 5 to 12 carbon atoms, preferably 7 or 8, with saturated aliphatic primary alcohols containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl benzoate. , ethyl benzoate, benzoic acid-n
- proyl, n- and -1-butyl benzoate, mono-n- and -1-octyl benzoate, 2-ethylhexyl benzoate, (c) as ethers, aliphatic ethers containing 2 to 12 carbon atoms; , for example diethyl ether, di(1
-propyl) ether, di(n-butyl) ether, ethylene glycol monomethyl ether, (a) Ketones include aliphatic ketones containing 2 to 13 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, (e) Amines include aliphatic amines containing 1 to 12 carbon atoms, aromatic amines containing 6 to 10 carbon atoms and heterocyclic amines containing 5 to 10 carbon atoms, such as methylamine, ethylamine, diethylamine, tributylamine. , aniline, naphthylamine,
pyridine, picoline, quinoline, quinaldine; (f) Nitriles include aliphatic nitriles containing 2 to 12 carbon atoms and aromatic nitriles containing 7 to 12 carbon atoms, such as acetonitrile, valeronitrile, acrylonitrile, penzonitrile; , tolnitrile, (g) As a phosphorus compound, carbon atoms 3 to 18
aliphatic phosphine containing 6 to 21 carbon atoms
Aromatic phosphine containing, for example trimethylphosphine, triethylphosphine, triphenylphosphine, tribenzylphosphine and from 3 to 1 carbon atoms
aliphatic phosphines containing 8 and aromatic phosphites containing 6 to 21 carbon atoms, such as trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, tribenzyl phosphite, (2) An example of a titanium halogen compound supported on a carrier or a pretreated carrier has the general formula TI(OR) Among them, chlorine-containing compounds are preferred, and titanium tetrachloride is particularly preferred.

(3) The organic acid ester for treating the magnesium halide supporting the titanium compound may be the same as the aromatic carboxylic acid ester included in the electron donor, but for example, the following may be used. .

For example, usually 7 to 12 carbon atoms, preferably 7
aromatic carboxylic acids containing from 1 to 10 carbon atoms, usually 1
Saturated or unsaturated aliphatic primary alcohols containing from 1 to 8, preferably 1 to 4, phenols containing usually 3 to 8, preferably 6 to 8 carbon atoms, usually 3 to 10 carbon atoms is an ester with an aliphatic saturated or unsaturated primary alcohol containing usually 1 to 4 carbon atoms bonded to an alicyclic or aromatic ring.

These esters will be specifically explained below.

Methyl benzoate, ethyl benzoate, mono-n-propyl benzoate, 101 or -1-butyl benzoate, -benzoate
Primary alkyl benzoates such as n- and -i-amyl, mono-n-hexyl benzoate, mono-n-octyl benzoate or -2-ethylhexyl benzoate, methyl toluate, ethyl toluate, -n- or -1- toluate. Butyl, primary alkyl toluate such as 2-ethylhexyl toluate, methyl anisate, ethyl anisate, anisate-n
- Primary alkynole anisate such as propyl, methyl naphthoate, n-propyl naphthoate, n-naphthoate
Primary alkyl naphthoates such as butyl and 2-ethylhexyl naphthoate.

Preferred among these are alkyl esters of benzoic acid containing 5 to 4 carbon atoms, with methyl benzoate and ethyl benzoate being particularly preferred.

The organoaluminum compound which is the catalyst (b) component has the general formula RnAlX3-n (where R is an alkyl group,
represents hydrogen and halogen, and n is a number of 2≦n≦3) and combinations thereof, and those having an average composition within the above range are preferred.

Examples include trialkylaluminums such as triethylaluminum, triprobylaluminum, tributylaluminum and mixtures thereof, dialkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide, dibutylaluminum chloride and mixtures thereof, dialkylaluminum hydrides such as diethylaluminum hydride. Among the hydrides, preferred is trialkylaluminium.

The inert solvent that may be used in the catalyst preparation reaction and polymerization reaction of the present invention refers to a solvent that is generally recognized as having no adverse effect on the polymerization reaction of olefins using a Ziegler catalyst, and is usually used for saturated fatty acids. group hydrocarbons such as pentane, hexane, heptane, isooctane and kerosene.

The polymerization reaction of the present invention can be carried out in the presence or absence of a liquid inert solvent, ie, in the presence of a liquid olefin monomer.

The polymerization temperature may be selected within the range conventionally used for the polymerization of α-olefins using Ziegler catalysts.
Usually, room temperature to 200°C is used.

The polymerization pressure may be selected within an appropriate range, usually from normal pressure to about 50%.

The concentration of the catalyst charged into the polymerization system for the polymerization reaction is such that (a) component is usually 0.0001 to 1.0 mmol/l in terms of titanium atoms, and (b) The components may be selected so that the aluminum atom/titanium atom ratio is usually 1/1 to 100/1, preferably 1/1 to 30/1.

In order to reduce the molecular weight of the produced polymer (increase the melt index), it is effective to include hydrogen in the polymerization system.

Of course, other known molecular weight reduction methods can also be used.

Actual example 1 ≧Preparation of catalyst (a) component> 19 g (200 mmol) of commercially available anhydrous magnesium chloride
was suspended in 200 ml of purified hexane at room temperature, and 1.8 g (100 mmol) of water was added with stirring.
l) Added.

After continued stirring for 30 minutes, it was filtered and the hexane was removed in vacuo.

According to elemental analysis, the reaction product of magnesium chloride and water obtained was Mgcl20. It had a composition of 5H20.

MgCl2・0.5H2020 synthesized in this way
g was suspended in 150 ml of titanium tetrachloride, and heat-treated at 130° C. with stirring.

Thereafter, the reaction suspension was filtered while still hot, and washed with purified hexane until the presence of chlorine was no longer recognized in the washing solution, thereby obtaining a titanium compound supported on magnesium chloride.

The component is titanium 3. Owt% and chlorine 75
Including wt%.

Titanium compound 10 supported on magnesium chloride
g was suspended in 100 mA of purified kerosene, 15 mmol of ethyl benzoate was added, and the mixture was stirred at 85°C for 1 hour. After cooling, the mixture was separated in a furnace and washed with purified hexane to obtain the catalyst (a) component.

The components are titanium 2.0wt% and chlorine 62% in terms of atoms.
．． Contains 1wt%.

<Polymerization> Add sufficient oxygen to an autoclave with an internal volume of 2 liters. and 750 ml of refined kerosene from which water has been removed, and triethylaluminum 0.016 mA (0.016 mA) as component (b).
12 mmol) and 47.9 mmol of component (a) in the previous section (
0.02 mmol (calculated as titanium atom) is charged.

When the temperature of the polymerization system reached 70°C, propylene was introduced and the total pressure was reduced to 7. Polymerization begins at the c floor.

After polymerizing at 70°C for 5 hours, the introduction of propylene was stopped, the inside of the autoclave was cooled to room temperature, and the solid components were collected by filtration, yielding white powdery polypropylene 140.
Obtain 1g.

The residual rate after extraction with boiling n-hebutane was 97.4%.

On the other hand, by concentrating the liquid phase, 8.3 g of solvent-soluble polymer was obtained.
get.

The average polymerization specific activity per titanium of this catalyst is 212 p p
g/T i -mM ゜n r-a tm.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 31.9 mg of the titanium compound supported on magnesium chloride prepared in Example 1 was used. When the entire amount of the polymer was precipitated with methanol, a rubber-like 95 g of polypropylene was obtained.

Only 40.8% remained after extraction with boiling n-hebutane.

Comparative Example 2 10 g of the titanium compound supported on magnesium chloride prepared in Example 1 was suspended in 100 ml of refined kerosene, and while stirring, 15 mmol of ethanol was added, and the mixture was stirred at 85° C. for 1 hour, cooled, and subjected to filtration separation for purification. A titanium-containing solid catalyst component was obtained by washing with hexane.

The components are titanium 1.9wt% and chlorine 61% in terms of atoms.
．． It included 8wt staff.

Propylene polymerization was carried out in the same manner as in Example (2) using the solid catalyst component 50~, but no polymer was obtained.

Examples 2 to 6 In Example 1, ethyl benzoate is used as the organic acid ester when preparing the catalyst (a) Jff component, and the number of mmol of the ester used per 10 g of the titanium compound supported on magnesium chloride is The catalyst (a) component was prepared under the same conditions as in Example 1, except that , and the catalyst (a) component was polymerized in the same manner as in Example 1. Table 1 shows the results.

Examples 7 to 13 Same as Example 1 except that the reaction temperature and reaction time between ethyl benzoate and the titanium compound supported on magnesium chloride were changed when preparing the catalyst (a) component. The catalyst (a) component was prepared under the following conditions and polymerization was carried out using this in the same manner as in Example 1. The results are also shown in Table 1.

Examples 14 to 22 Preparation of catalyst (a) component> Titanium supported on magnesium chloride using the magnesium chlorine compound obtained by changing the amount of water added in Example 1 or using alcohol instead of water. Catalyst (a) component was prepared in the same manner except that the compound was prepared.

<Polymerization> Example 1 except that the catalyst (a) component prepared in the previous section was used.
Table 2 shows the results of polymerizing propylene in the same manner as above.

Example 23 <Preparation of catalyst (a) component> 20 g of commercially available anhydrous magnesium chloride and titanium tetrachloride 1.
Inner volume 8 containing 100 stainless steel (SUS-32) balls with a diameter of 15 mm and 2 ml in a nitrogen atmosphere.
00mA, inner diameter 100M stainless steel (SUS-3
2) was charged into a ball mill cylinder manufactured by Co., Ltd., and the ball mill was rotated at 1 2 5 rpm for contact for 48 hours.

The obtained solid treated product was washed with purified hexane, and the washing was repeated until the presence of chlorine was no longer recognized in the washing solution, thereby obtaining a titanium compound supported on magnesium chloride.

The components are titanium 2.5wt% and chlorine 69% in terms of atoms.
Including wt%.

10 g of the titanium compound supported on magnesium chloride thus prepared was suspended in 100 ml of refined kerosene, 15 mmol of ethyl benzoate was added, stirred at 85° C. for 1 hour, cooled, and subjected to furnace separation. The catalyst (a) component was obtained by washing with purified hexane.

The components are titanium 1.6wt% and chlorine 6% in terms of atoms.
Contains 7 wt%.

<Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 except that 60 m9 of the catalyst (a) component mentioned above was used, and 124.5 g of white powdery polypropylene was obtained.

The residual rate after extraction with boiling n-hebutane was 97.2%.

On the other hand, by concentrating the liquid phase, 10.5% of the solvent-soluble polymer
get g.

In addition, the average polymerization specific activity is 193PP g/Ti mM-
Corresponds to hr-atm.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 using 38.3 m9 of the titanium compound supported on magnesium chloride prepared in Example 23, and the entire amount of the polymer was precipitated with methanol.
108 g of rubbery polypropylene was obtained.

Only 42.4% remained after extraction with boiling n-hebutane.

Example 24 <Preparation of catalyst (a) component> 500 ml of kerosene purified from 20 g of anhydrous magnesium chloride
70 ml of ethanol was added dropwise to this at room temperature over 1 hour.

After the addition was completed, stirring was continued for 1 hour, and then 72 ml of diethylaluminum chloride was added dropwise over 1 hour at room temperature, producing a precipitate.

After the reaction was completed, the supernatant was washed several times with 500 ml of kerosene each time.

Next, 1.5 mol of titanium tetrachloride was added, and while stirring, the
It was heated to 0.degree. C. and reacted with the precipitate for 1 hour.

The solid reaction product was washed with purified kerosene until no chlorine was detected in the washing solution, to obtain magnesium chloride supported on a titanium compound.

The components are 4.3wt% titanium and 58% chlorine in terms of atoms.
．． Contains 3wt%.

10g of magnesium chloride supporting the above titanium compound
was suspended in 100 ml of refined kerosene, and ethyl benzoate 1
5 mmol was added and the mixture was stirred at 85° C. for 1 hour. After cooling, the solids were separated by filtration and washed with purified hexane to obtain the catalyst (a) component.

The component is titanium 3. swt%, chlorine 60.7
Including wt%.

<Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 except that 25.2 cm of the catalyst (a) component described in the previous section was used, and 130.2 g of white powdery polypropylene was obtained.

The residual rate after extraction with boiling n-hebutane was 96.8%.

On the other hand, by concentrating the liquid phase, 9.7 g of solvent-soluble polymer was obtained.
get.

Note that the average polymerization specific activity is 200P P g/Ti −
Corresponds to mK-hr-at m.

Comparative Example 4 Magnesium chloride supported on a titanium compound was synthesized in the same manner as in Example 24.

Magnesium chloride Log supporting the above titanium compound
was suspended in 100 m6 of n-decane, 15 mmol of ethyl benzoate was added, and the mixture was stirred at 85°C for 1 hour.

The reaction product thus obtained was used in the same manner as in Example 1 except that it was used in place of the catalyst <a) of Example 1 in the same manner as in Example 24 above, without washing. When polymerization was carried out, white powdery polypropylene 8
3.2g was obtained.

The residual rate after extraction with boiling n-hebutane was 96.0%.

On the other hand, 5.4 g of a solvent-soluble polymer was obtained by concentrating the liquid phase.

The average polymerization specific activity is 127PP-g/Ti-mM-hr-
It is ATM.

Claims (1)

[Claims] 1(a) A titanium-containing solid catalyst component obtained by treating a titanium compound supported on magnesium halide with an aromatic carboxylic acid ester and washing the treated solid part with an inert solvent. A method for polymerizing olefins, comprising polymerizing an α-olefin containing three or more carbon atoms in the presence of a catalyst derived from an organoaluminum compound catalyst component.