JPS6155103A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin excellent in heat resistance and light fastness, by polymerizing a 3C or higher alpha-olefin in the presence of additives such as an antioxidant, an ultraviolet absorber and an aliphatic carboxylic acid metal salt and a specified highly active catalyst. CONSTITUTION:A catalyst is prepared by combining (A) a solid catalyst component consisting essentially of Mg, a halogen, titanium and an electron donor with (B) a trialkoxyaluminum and (C) a compound selected from among a silicon compound of formula I (wherein R<1> and R<2> are each a hydrocarbon and n is 0, 1 or 2), an aromatic carboxylate ester and a nitrogen-containing compound of formula II (wherein R<3> is a hydrocarbon and R<4>, R<5>, R<6> and R<7> are each H or a hydrocarbon). A 3C or higher alpha-olefin (e.g., propylene) is polymerized with the aid of said catalyst in the presence of additives selected from among an antioxidant, an ultarviolet absorber and an aliphatic carboxylic acid salt to obtain the aimed polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing polyolefins, and particularly to a method for producing polyoleins having excellent heat resistance and light resistance.

(Prior art) An α-olefin having 3 or more carbon atoms is produced in the presence of a highly active catalyst obtained from a solid catalyst component containing magnesium, halogen, titanium, and an electron donor as essential constituents, a trialkylaluminium, and an electron donor. Many proposals have been made regarding how to polymerize to obtain polyolefins with significantly higher yields per catalyst used. A feature of the proposed process is that the polyolefin produced can be used without removing the catalyst remaining therein. However, it is known that the produced polyolefin is susceptible to deterioration due to the influence of oxygen in the air if left as is. Therefore, it is essential to stabilize the polyolefin obtained by polymerization by adding an antioxidant, an ultraviolet absorber, and an acid neutralizer such as an aliphatic carboxylic acid metal salt.

(Problems to be Solved by the Invention) The present invention provides excellent results by adding antioxidants, ultraviolet absorbers, acid neutralizers, etc. when polymerizing α-olefins using highly active catalysts. The present invention provides a method for producing a polyolefin having high heat resistance and light resistance. in general,
It is known that the presence of antioxidants, ultraviolet absorbers, acid neutralizers, etc. during the polymerization of α-olefins using Ziegler catalysts significantly reduces the polymerization activity or reduces the stereoregularity of the resulting polyolefin. ing. However, when polymerizing α-olefins using highly active catalysts,
Contrary to expectations, it was found that the polymerization activity and the stereoregularity of the polyolefin produced were not adversely affected.

(Means for Solving the Problems) The present invention provides an α-olefin having 3 or more carbon atoms in the presence of an additive selected from the group consisting of an antioxidant, an ultraviolet absorber, and an aliphatic carboxylic acid metal salt. , is a method for producing polyolefin characterized by polymerization using a catalyst obtained from the following components.

A solid catalyst component containing magnesium, halogen, titanium, and an electron donor as essential components.

Upright JIL Trialkyl aluminum.

Aru”! mouth Σ set RnS i (OR)4-IL [3 (in the formula, R
and R are hydrocarbon groups, n is Oll, 2 or 3, and R is hydrogen or a hydrocarbon group; At least one of R and R is a hydrocarbon group.

) A compound selected from the group consisting of M-containing compounds represented by

Component [A] is a solid catalyst component containing magnesium, halogen, titanium, and an electron donor as essential components. The solid catalyst component can be obtained, for example, by a method of co-pulverizing magnesium halide, titanium halide and an electron donor such as an ester, ether or amine, or by a reaction product of an organomagnesium compound and an aluminum halide or a silicon halide compound. can be prepared by contacting titanium halides in the presence of an electron donor.

In the present invention, the solid catalyst component is aluminum halide and the formula Shima 5t (OR) Gin-4 [■] (wherein R and R- are a hydrocarbon group, and n is 0.1.
2 or 3. ) A Grignard compound is reacted with the reaction product with a silicon compound, and the resulting carrier is
A solid catalyst component obtained by reacting titanium tetrahalide and an aromatic carboxylic acid ester and reacting the resulting reaction solid with titanium tetrahalide again is preferably used.

Specific examples of aluminum halides include aluminum chloride, aluminum bromide, and aluminum iodide.

1 1 In formula [I], examples of the hydrocarbon group substituted by R and R include an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a benzyl group. Specific examples of silicon compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-isopentoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyltriethoxysilane.
-butoxysilane, ethyltriethoxysilane, ethyltriisopentoxysilane, n-butyltriethoxysilane, dimethyljethoxysilane, dimethyldi-n-butoxysilane, diethyljethoxysilane, trimethylmethoxysilane, triethylethoxysilane 1, phenyl Examples include triethoxysilane, methylphenyldimethoxysilane, phenyltriisobutoxysilane, diphenyljethoxysilane, triphenylmethoxysilane, benzyltriethoxysilane, and benzyltriptoxysilane.

The proportion of aluminum halide used in the reaction is 0.1 to 10 mol, especially O0'3 to 1 mol of silicon compound.
Preferably it is 2 moles.

The reaction between an aluminum halide and a silicon compound is usually carried out by preparing both compounds in an inert organic solvent at -52, O to 100
The reaction product is subjected to the reaction with the Grignard compound as a solution in an inert organic solvent.

Specific examples of Grignard compounds include methylmagnesium chloride, ethylmagnesium chloride, n-
Examples include butylmagnesium chloride, n-hexylmagnesium chloride, methylmagnesium bromide, and methylmagnesium iodite. The amount of Grignard compound used is 0.05 to 4 mol per mol of aluminum halide used for the preparation of the reaction product;
In particular, it is preferably 1 to 3 mol.

There is no particular restriction on the method of reacting the reaction product and the Grignard compound, but it may be done by gradually adding an ether solution of the Grignard compound to a solution of the reaction product in an inert organic solvent, or in the reverse order. It is convenient to do this by adding . The reaction temperature is usually -5
The temperature is 0 to 100°C, preferably -20 to 25°C. There is no particular restriction on the reaction time, but it is usually 5 minutes or more.

As the reaction progresses, the carrier precipitates out.

Specific examples of titanium tetrahalide include titanium tetrachloride,
Titanium tetrabromide and titanium tetramorphide are mentioned. The amount of titanium tetrahalide used is 1 mol or more, especially 2 to 10 mol, per 1 mol of Grignard compound used in preparing the carrier.
Preferably it is 0 mol.

As the aromatic carboxylic acid ester, an aromatic monocarboxylic acid ester and an aromatic radical mono- or diester can be used. Specific examples of aromatic monocarboxylic acid esters include methyl benzoate, ethyl benzoate, butyl benzoate, ethyl toluate, propyl toluate, methyl anisate, ethyl anisate, and butyl anisate. Specific examples of mono- or diesters of aromatic dicarboxylic acids include monomethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, and diheptyl phthalate. The amount of aromatic carboxylic acid ester used is preferably 0.1 to 10 mmol per finger.

The method of reacting the carrier with titanium tetrahalide and aromatic carboxylic acid ester includes, for example, (1) a method of adding titanium tetrahalide and then aromatic carboxylic acid ester to an inert organic solvent slurry of the carrier and reacting; (2
) A method in which an aromatic carboxylic acid ester and then titanium tetrahalide are added to an inert organic solvent slurry of the carrier and reacted, or a gluing method can be employed, and among them, the method (1) above is preferred. In the method (1) above, it is also possible to bring the carrier into contact with titanium tetrahalide, then separate and wash the contact solid, and then react the contact solid with an aromatic carboxylic acid ester.

The reaction temperature is preferably 0 to 200°C, particularly 5 to 150°C, and the reaction time is not particularly limited and is usually 5 minutes or more.

A solid catalyst component is obtained by reacting the reaction solid thus obtained with titanium halide again. Conditions such as the amount of titanium tetrahalide used, contact temperature, and contact time are the same as those used in preparing the reaction solid.

Specific examples of trialkylaluminum as component [B] include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, and trioctylaluminum. The amount of trialkylaluminum used is usually from 1 to 1000 moles per gram atom of titanium in the solid catalyst component.

As the silicon compound and aromatic carboxylic acid ester of component [C], the same silicon compounds and aromatic carboxylic acid esters mentioned above can be used. Specific examples of R in formula [1] include alkylene groups having 2 or 3 carbon atoms;

Specific examples of hydrocarbon groups in R and R include carbon atoms of 1
-4 alkyl groups are mentioned. Specific examples of nitrogen-containing compounds include 2,2,6,6-titramethylpiperidine,
2,2,6,6-titraethylpiperidine, 2,2-dimethyl-6-methylpiperidine, 2,6-diisopropylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, 2゜5-diisopropylpyrrolidine, 2 , 2-dimethyl-5-methylpyrrolidine. Component [C]
The amount used is preferably 0.01 to 1 mol, particularly 0.05 to 1.5 mol, per 1 mol of component [B].

In the present invention, as the antioxidant, amine-based, phenol-based, sulfur-based, and phosphorus-based antioxidants that are known per se can be used. Specific examples include phenyl-α-naphthylamine, phenyl-β-naphthylamine, diphenylamine, N,N-diphenyl-p-)echolenediamine, N,N-di-β-naphthyl-p-phenylenediamine, 2, 6-di-tert-butyl-4-methylphenol, 3-tert-butyl-4-hydroxyanisole, tetrakis-[methylene-(3,5-di-tert-
butyl-4-hydroxy-hydrocinnamate)]butane, 2,2-methylene-bis(6-i3-7'thyl-4
-ethylphenol), distearylthiodipropionate, trilauryltrithiophosphite, triotadecylphosphite, and trisnonylphenylphosphite.

Specific examples of ultraviolet absorbers include 2-hydroxy-4-
n-octoxybenzophenone, 2-hydroxy-4-
Benzophenones such as dobukoshibenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-(2-
hydroxy-3-tert-butyl-5-methylphenyl)
- triazoles such as 5-chlorobenzotriazole, salicylic acid esters such as 4-tert-butylphenyl salicylate, p-octylphenyl salicylate, l'LNi-bis(p-tert-octylphenyl)-
Examples include metal chelates such as monosulfides.

Specific examples of aliphatic carboxylic acid metal salts include zinc stearate, calcium stearate, and barium stearate.

The amount of these additives used is usually 100! The amount is 0.001 to 0.5 parts by weight per part ffi.

In the present invention, component [A]
, [B] and [C] are used to polymerize an α-olefin having 3 or more carbon atoms.

Specific examples of α-olefins having 3 or more carbon atoms include propylene, butene-1,4-methylpentene-1, and hexene-1. In the present invention, the α-olefin described above can be used alone or copolymerized, and the α-olefin described above and ethylene can also be copolymerized.

The polymerization reaction is carried out using an ordinary Ziegler-Natsuta type catalyst.
It can be carried out in the same manner as the polymerization reaction of olefins.

The polymerization reaction can be carried out in liquid phase or gas phase.

When the polymerization reaction is carried out in a liquid phase, an inert organic solvent may be used as the polymerization solvent, or the liquid α-olefin itself may be used as the polymerization solvent. The polymerization reaction is carried out in a state substantially free of moisture and oxygen.

The polymerization temperature is usually 30 to 100°C, and the polymerization pressure is usually 1 to 80 kg/cnf. The molecular weight of the resulting polyolefin can be easily controlled by the presence of hydrogen in the polymerization system.

(Example) Next, Examples and Comparative Examples will be shown. In the following, "polymerization activity" is the number i (g) of polymers per gram of solid catalyst component used in the polymerization reaction, and "Hl" is the number of polymers i (g) produced per gram of solid catalyst component used in the polymerization reaction, and "Hl" is the number of polymers produced by extraction with boiling n-hebutane for 20 hours. This is the weight percentage of the extraction residue based on the total polymer. rMIJ is 2.16 kg according to ASTM D1238.
Melt index of polyolefin measured at 230°C under a load of /c++t.

Example 1-'1. 2.I To 30 ml of a toluene slurry containing 2 g of aluminum chloride, 10 ml of a toluene solution containing 3.7 rrl of phenyltriethoxysilane was added dropwise at 20°C, and the mixture was stirred at room temperature for 1 hour and then at 60°C for 1 hour.Reaction product was allowed to cool and then cooled to -70°C.A solution of 27 mmol of n-butylmagnesium chloride in diisopropyl ether 18
．． 5 ml was added dropwise to the reaction product at -70 to -65°C over 30 minutes, and then the temperature was raised to room temperature at a rate of 30°C/hour.
The carrier was precipitated. The carrier was separated by filtration, and each 30 mJ of toluene was added.
Washed 3 times with

Add 15 ml of titanium tetrachloride and 0.9 ml of diheptyl phthalate to 30 ml of toluene slurry of the carrier at room temperature.
The mixture was stirred at 90°C for 1 hour. The resulting solid was filtered off at the same temperature and washed three times with 30 ml each of n-hebutane. Add 15 ml of titanium tetrachloride to 30 ml of this solid toluene slurry at room temperature.
mj+ was added and then stirred at 90°C for 1 hour. The obtained solid catalyst component was filtered at the same temperature, and 30 ml each of toluene was added.
Washed 5 times with 80ml of n-hebutane as solid catalyst component
was added to prepare a slurry. The titanium content of the solid catalyst component was 3.55% by weight. Its particle size is 15-20
It was μ.

Tetrakis-[methylene-(3,5-di-tert-butyl-4-
After charging 45 cm of cobutane (hydroxy-hydrocinnamate), 15 nv of distearyl thiodipropionate, and 23 cm of calcium stearate, and attaching a glass ampoule containing a slurry of the solid catalyst component (7.7 cm as the solid catalyst component), The inside of the autoclave was purged with nitrogen.

2. 0.19 mmol of 2,6,6-tetramethylpiperidine and 1.14 mmol of triethylaluminum in n-hebutane solution 5. 2 ml was charged into an autoclave.

Hydrogen was charged into the autoclave until the pressure reached 0.1 kg/cnl, 1200 ml of liquid propylene was added, and the autoclave was shaken.

The contents of the autoclave were heated to 65°C, stirring was started, and the glass ampoule was crushed to start the polymerization reaction.
The polymerization reaction was carried out at 5°C for 1 hour.

After the polymerization reaction is complete, unreacted propylene is released, glass ampoule fragments are removed, and the resulting polypropylene is heated at 50°C.
It was dried for 20 hours. White powdered polypropylene 25
6g was obtained. Polymerization activity is 33250, Hl is 94.
It was 0%. The polypropylene produced has good fluidity,
80% of them have a particle size of 0.25 m1 or more in diameter, and a bulk specific gravity of 0.41. MI was 3.4 g/10 minutes.

In order to investigate the heat resistance of the obtained polypropylene, the thermal decomposition onset temperature was measured using a thermogravimetric analyzer.
The temperature was 230°C under conditions of an air flow rate of 60 mJ/min and a temperature increase rate of 10°C/min.

During polymerization, tetrakis-[methylene-(3.5-di-tertiary
-butyl-4-hydroxy-hydrocinnamate)] When cobutane distearyl thiodipropionate and calcium stearate were not used, the thermal decomposition onset temperature of the obtained polypropylene was 218°C.

Example 2 Example 1 except that 135 mg of 2,6-di-tert-butyl-4-methylphenol was further used as an additive.
The same method was repeated.

Polymerization activity is 31,800, HI is 94.2%, M1 is 3.
It was 2g/l and 0 minutes. The polypropylene produced had good fluidity, 80% of which had a particle size of 0.25 mm or more in diameter, and a bulk specific gravity of 0.42. The thermal decomposition initiation temperature of this polypropylene was 232°C.

Example 3 The same method as in Example 1 was repeated, except that 15 μm of 2-hydroxy-4-n-octoxybenzophenone was further used as an additive.

Polymerization activity is 32,200, HI is 94.0%, MI is 2.
It was 8g/10 minutes. The polypropylene produced has good fluidity, with 80% of it having a diameter of 0. It had a particle size of 25 mm or more, and a bulk specific gravity of 0.42. The thermal decomposition initiation temperature of this polypropylene was 232°C.

Example 4 The same method as Example 1 was repeated, except that 0.19 mmol of methylphenyldimethoxysilane was used instead of 2,2,6,6-titramethylpiperidine.

Polymerization activity is 25,200, HI is 94.4%, MI is 4.
It was 1g/10 minutes. The produced polypropylene had good fluidity, 80% of which had a particle size of 0.25 mm or more in diameter, and a bulk specific gravity of 0.40. The thermal decomposition initiation temperature of this polypropylene was 230°C.

During polymerization, tetrakis-[methylene-(3,5-di-tertiary
-butyl-4-hydroxy-hydrocinnamate)] butane, distearyl thiodipropionate and calcium stearate were not used, the thermal decomposition onset temperature of the obtained polypropylene was 216°C.

Example 5 A solid catalyst component was prepared in the same manner as in Example 1, except that 15 mmol of methyltriethoxysilane was used instead of phenyltriethoxysilane. Its titanium content was 3.21% by weight, and its particle size was 15-20μ.

A propylene polymerization reaction was carried out in the same manner as in Example 1 except that the n-hebutane slurry containing 7.0 μ of the obtained solid catalyst component was used.

Polymerization activity is 31,700, Hl is 94.2%, Ml is 3.
It was 8g/10 minutes. The produced polypropylene had good fluidity, 80% of it had a particle size of 0.25 In or more in diameter, and the bulk specific gravity was 0.41. The thermal decomposition initiation temperature of this polypropylene was 231°C. When no additives were used during polymerization, the thermal decomposition onset temperature of the polypropylene produced was 218°C.

Example 6 Using 7.0 cm of the solid catalyst component obtained in Example 5,
A polymerization reaction was carried out in the same manner as in Example 3.
' Polymerization activity is 30,500, HI is 94.2%, MI is 3.
It was 0g/10 minutes. The polypropylene produced has good fluidity, and 80% of it is directly produced! ! It had a particle size of 0.25I1m or more, and a bulk specific gravity of 0.41. The thermal decomposition initiation temperature of this polypropylene was 235°C.

Example 7 - 30ml of toluene slurry containing 2.0g of aluminum chloride
3.0 mff of methyltriethoxysilane in toluene solution I Qmj! was added dropwise at 20°C. After completion of the dropwise addition, the reaction product was stirred at room temperature for 1 hour and then at 60°C for 1 hour, then allowed to cool, and then cooled to -70°C. 17 ml of a solution of 27 mmol of n-butylmagnesium chloride in diisoamyl ether was added dropwise to the reaction product over 30 minutes at -70 to -65°C. The reaction product mixture was heated to room temperature to precipitate the carrier. The carrier was filtered off and washed three times with 30 ml each of toluene.

10 ml of titanium tetrachloride was added to 23 ml of toluene slurry containing 3.4 g of carrier, and the mixture was stirred at 90° C. for 1 hour. The obtained titanium-containing solid was filtered at the same temperature, and 30% each of n-hebutane was added.
ml! Washed 3 times with Add 0.0 ml of ethyl benzoate to 30 ml of toluene slurry of titanium-containing solid. Add 65mf,
The mixture was stirred at 90°C for 1 hour. The resulting ester-containing solid was filtered off at the same temperature and treated twice with 3 Q ml each of n-hebutane, then tolu.

En 30mj! Washed once with Toluene slurry of ester-containing solid 3 Q m A to titanium tetrachloride 10 ml
was added and stirred at 90°C for 1 hour. The obtained solid catalyst component was filtered at the same temperature and washed five times with 30 mJ each of n-hebutane. 70 m of n-hebutane was added to this solid catalyst component.
1 was added to form a slurry. The titanium content of the solid catalyst component is 2.72% by weight, most of which is 15-20μ
It had a particle size of

-1- Internal volume 2I with a coalescing stirrer! Trisnonylphenyl phosphite 15, 2゜6-di 3 in an autoclave.
-Butyl-4-methylphenol 45μ and calcium stearate 23μ were charged, and after attaching a glass ampoule sealed with the slurry of the solid catalyst component (13.8μ as solid catalyst component), the inside of the autoclave was purged with nitrogen. .

'p-'t-)L/Itv#)un, 50e1. engineering)
I, = (D. - ~ Butane solution 5.' 1 ml, then triethyl aluminum 1, and 52 mmol n-hebutane solution 6° 4 ml were charged into the autoclave. Hydrogen was added until the pressure reached 0.9 kg/c- In addition, liquid propylene 1
200 mJ was introduced into the autoclave and the autoclave was shaken. Thereafter, a propylene polymerization reaction was carried out in the same manner as in Example 1.

Polymerization activity is 94.5% for 14800SH1, and MI is 3.
2 g/10 minutes, bulk specific gravity was 0.43. The produced polypropylene had good fluidity, and more than 80% of it had a particle size of 0.25 mm or more.

The thermal decomposition initiation temperature was 229°C. Note that the thermal decomposition initiation temperature of polypropylene obtained without using any additives during polymerization was 216°C.

Claims (1)

[Claims] A catalyst obtained from the following components is added to an α-olefin having 3 or more carbon atoms in the presence of an additive selected from the group consisting of an antioxidant, an ultraviolet absorber, and an aliphatic carboxylic acid metal salt. 1. A method for producing a polyolefin, which comprises polymerizing using a polyolefin. Component [A] A solid catalyst component containing magnesium, halogen, titanium, and an electron donor as essential components. ¥ Component [B] ¥ Trialkyl aluminum. ¥Component [C]¥ Formula R^1nSi(OR^2)_4_-_n (In the formula, R^1 and R^2 are hydrocarbon groups, and n is 0
, 1, 2 or 3. ), and there are silicon compounds, aromatic carboxylic acid esters, and formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a hydrocarbon group, R^4, R^5, R^
6 and R^7 are hydrogen or hydrocarbon groups, and R^4 and R
At least one of each of ^5, R^6, and R^7 is a hydrocarbon group. ) A compound selected from the group consisting of nitrogen-containing compounds.