JPH05178925A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular polyolefin without retarding the polymerization reaction. CONSTITUTION:An alpha-olefin is polymerized in the presence of a catalyst comprising a titanium-containing solid catalyst component (one comprising a solid titanium trichloride or one essentially consisting of Mg, Ti and halogen), an organoaluminum compound and a compound selected from among sulfonic, sulfinic and sulfenic acids) (one having an aromatic group or a linear or branched bulky hydrocarbon group) (e.g. dodecylbenzenesulfonic acid).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing α-olefins. More specifically, it relates to a method for producing an α-olefin polymer having high stereoregularity.

[0002]

Polymerization of olefins using a catalyst composed of a solid catalyst component containing titanium and an organoaluminum compound,
In particular, it is well known to use an electron-donating compound as the third component in the stereoregular polymerization of α-olefin. That is, by using the electron-donating compound as the third component, the stereoregularity of the produced polymer is improved, and the yield of the crystalline polymer is improved by reducing the amount of the amorphous polymer produced as a by-product. And achieving high stereoregularity generally improves physical properties such as rigidity and heat resistance of products.

[0003]

On the other hand, due to a change in the polymerization process, a process which does not include a separation / removal step of an amorphous polymer has been widely used recently, and higher stereoregularity is desired. There is. However, when the conventionally proposed electron-donating compound is used as the third component, the stereoregularity of the produced polymer is improved, but the polymerization rate is largely decreased, which is not always satisfactory. .. Under these circumstances, it is an object of the present invention to provide a method for producing an α-olefin polymer, which uses a novel catalyst system excellent in both polymerization activity and stereoregularity. ..

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors for the purpose of searching for a third component which minimizes the decrease in the polymerization rate and improves the stereoregularity, the present inventors found that a special structure was formed. They have found that the compounds they possess have a surprising effect with the addition of very small amounts and have reached the present invention. That is, the present invention provides (1) (a) a titanium-containing solid catalyst component (b) an organoaluminum compound (c) a catalyst containing a compound selected from sulfonic acid, sulfinic acid, and sulfenic acid, in the presence of α -A method for polymerizing an α-olefin characterized by polymerizing an olefin.

The present invention will be described in detail below. Examples of the titanium-containing solid catalyst component of the polymerization catalyst used in the present invention include a solid catalyst component containing titanium trichloride as a main component or a carrier-supporting solid catalyst component containing Mg, Ti, and halogen.

As titanium trichloride as a main component, conventionally known titanium trichloride can be used. For example,
Titanium trichloride activated by ball milling, and titanium trichloride and β-titanium trichloride obtained by solvent extraction thereof are treated with a chain-forming agent such as ethers and further treated with titanium tetrachloride to form aluminum (A1 ) Titanium tetrachloride is treated with an organoaluminum compound in the presence of titanium trichloride whose content is 0.15 or less in atomic ratio to Ti, ethers or thioethers to form a liquid, which is further heated to 150 Precipitated as a solid at a temperature below ℃,
Examples thereof include titanium trichloride and the like, the content of 1 of which is 0.15 or less in atomic ratio to Ti.

Among these titanium trichloride, it is particularly preferable that the aluminum content is 0.15 or less, preferably 0.1 or less in terms of atomic ratio of aluminum to titanium.
It is more preferably 0.02 or less and contains a chain-forming agent such as ethers. Specific examples of the method for producing these titanium trichlorides include JP-B-55-8452.
No. 55, No. 55-8451, No. 55-8003, No. 54
No. 41040, No. 55-8931, JP-A-58-3
No. 6928, No. 59-12905, No. 59-1363.
No. 0 etc. are mentioned.

As the carrier-supporting solid catalyst component containing Mg, Ti, and halogen as essential components, a conventionally known carrier-supporting solid catalyst component can be used. For example, Mg
Examples of the solid catalyst component include a solid catalyst component obtained by ball-milling the contained compound and treating with titanium tetrachloride, and a solid catalyst component obtained by contacting the Mg-containing compound with alcohol or metal alkoxide to obtain a homogeneous solution, and then treating with titanium tetrachloride. .. Further, in the production of the solid catalyst component, it is desirable to coexist with an electron donating compound such as an aromatic carboxylic acid ester or a carboxylic acid metal salt.

Of these, preferred are those obtained by treating a homogeneous solution of a Mg-containing compound with titanium tetrachloride. Specific examples of the method for producing such a solid catalyst component include JP-A-64-54007 and JP-A-3-72.
No. 503 etc. are mentioned. The organoaluminum compound used as a cocatalyst for the titanium-containing solid catalyst component has the general formula A1R ¹ mX _3-m (wherein R ¹ has 1 to ¹ carbon atoms).
20 hydrocarbon groups, X represents halogen, and m is 3 ≧ m>
The number is 1.5. ).

Of the organoaluminum compounds represented by the above general formula, when the titanium-containing solid catalyst component has titanium trichloride as the main component, it is preferable to use A1R ¹ ₂ X, and the titanium-containing solid catalyst component. but, Mg, Ti, and in the case of solid catalyst components of the carrier supported type to halogen as essential components is preferably used A1R ¹ _3.

Specifically, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum chloride, di-n-octyl aluminum chloride, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, Examples thereof include trihexyl aluminum and tri-n-octyl aluminum. The titanium-containing solid catalyst component and the organoaluminum compound shown above are generally used in a molar ratio of organoaluminum compound / titanium of 1 to 300, preferably 2 to 150.

In the present invention, the above catalyst may be used as it is, but as a pretreatment, a small amount of α-olefin is preliminarily polymerized with a catalyst comprising a titanium-containing solid catalyst component and an organoaluminum compound. Preferably. In the above method, a titanium-containing solid catalyst component and an organoaluminum compound are added to an inert catalyst such as hexane, heptane, and toluene, and propylene,
Α-, such as ethylene, 1-butene, 3-methyl-1 butene
An olefin or a mixture thereof is supplied for polymerization.

As the prepolymerization conditions, known conditions can be adopted. The polymerization temperature may be in the range of 15 to 70 ° C. The polymerization rate is 0.1 to 100 per 1 g of the catalyst.
g / g-CAT, preferably 0.5-10 g / g-CA
It is performed in the range of T. A molecular weight modifier such as hydrogen may coexist during the preliminary polymerization. Further, the compound (c) and a known electron donating compound can be coexistent. Further, it is preferable that the preliminary polymerization is carried out uniformly in a batch system.

The obtained prepolymerization catalyst component may be used for polymerization after washing with an inert hydrocarbon such as n-hexane, or may be used as it is without washing. In producing the α-olefin polymer, a catalyst system composed of the above titanium-containing solid catalyst component and an organoaluminum compound,
As the stereoregularity improving component, a compound represented by the compound (c) selected from sulfonic acid, sulfinic acid and sulfenic acid is added. The compound preferably has an aromatic group or a linear or branched bulky hydrocarbon group.

Specifically, as the sulfonic acid, benzenesulfonic acid, 1-naphthylbenzenesulfonic acid, 2-
Aromatic sulfonic acids such as naphthylbenzenesulfonic acid, p-methylbenzenesulfonic acid, p-ethylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid, p-
t-Butylbenzenesulfonic acid, m-methylbenzenesulfonic acid, m-ethylbenzenesulfonic acid, m-t-butylbenzenesulfonic acid, o-methylbenzenesulfonic acid, o-ethylbenzenesulfonic acid, ot-butylbenzenesulfonic acid , N-substituted sulfonic acids such as 2,4-dimethylbenzenesulfonic acid, n-butylsulfonic acid, n-pentylsulfonic acid, n-hexylsulfonic acid, n-heptylsulfonic acid, n-octylsulfonic acid, n -Sulfonic acid having a linear hydrocarbon group such as decyl sulfonic acid and n-dodecyl sulfonic acid, carbonization having a branch such as isobutyl sulfonic acid, t-butyl sulfonic acid and 2,4-dimethylhexyl sulfonic acid Examples thereof include sulfonic acid having a hydrogen group. In addition, as specific examples of sulfinic acid, aromatic sulfinic acids such as benzenesulfinic acid, 1-naphthylbenzenesulfinic acid, and 2-naphthylbenzenesulfinic acid, p-methylbenzenesulfinic acid, p-ethylbenzenesulfinic acid,
p-dodecylbenzenesulfinic acid, pt-butylbenzenesulfinic acid, m-methylbenzenesulfinic acid, m-ethylbenzenesulfinic acid, m-t-butylbenzenesulfinic acid, o-methylbenzenesulfinic acid, o-ethylbenzenesulfinic acid , N-butylsulfinic acid, n-hexylsulfinic acid, n-heptylsulfinic acid, n-butylsulfinic acid, n-pentylsulfinic acid, n-hexylsulfinic acid, n-heptylsphine Acid, n-octylsulfinic acid, n-decylsulfinic acid, sulfinic acid having a linear hydrocarbon group such as n-dodecylsulfinic acid, isobutylsulfinic acid, t-butylsulfinic acid, 2,4-dimethylhexyl Has a branch like sulfinic acid Include sulfinic acid having a hydrocarbon group.

Specific examples of sulfenic acid include aromatic sulfenic acids such as benzenesulfenic acid, 1-naphthylbenzenesulfenic acid and 2-naphthylbenzenesulfenic acid, p-methylbenzenesulfenic acid, p-
Ethylbenzenesulfenic acid, p-dodecylbenzenesulfenic acid, pt-butylbenzenesulfenic acid, m
-Methylbenzenesulfenic acid, m-ethylbenzenesulfenic acid, m-t-butylbenzenesulfenic acid, o
-Methylbenzenesulfenic acid, o-ethylbenzenesulfenic acid, ot-butylbenzenesulfenic acid,
Nuclear-substituted aromatic sulfenic acid such as 2,4-dimethylbenzenesulfenic acid, n-butylsulfenic acid, n-pentylsulfenic acid, n-hexylsulfenic acid, n-
Heptylsulfenic acid, n-octylsulfenic acid, n
-Sulfenic acid having a linear hydrocarbon group such as decylsulfenic acid and n-dodecylsulfenic acid, isobutylsulfenic acid, t-butylsulfenic acid, 2,4-
Examples thereof include sulfenic acid having a branched hydrocarbon group such as dimethylhexylsulfenic acid.

Of these, preferred are sulfonic acid having 4 or more carbon atoms, sulfinic acid, or sulfenic acid. The amount of addition is generally selected from the range of 0.001 to 100 mol, preferably 0.01 to 50 mol per mol of titanium. In addition to the stereoregularity improving component shown in (c) above, N, O, P or Si can be incorporated into the molecule.
A known electron-donating compound containing an atom can be allowed to coexist.

Specific examples of these electron-donating compounds include ethers, polyethers, alkylene oxides, furans, amines, trialkylphosphines, triarylphosphines, phosphoric acid esters, phosphoric acid amides, phosphine oxides, trialkylphosphines. Examples include phyto, triaryl phosphite, ketone, carboxylic acid ester, carboxylic acid amide, alkoxysilane, aryloxysilane, alkylalkoxysilane, arylalkoxysilane, and alkylarylsilane.

Of these, preferred are carboxylic acid esters, and particularly preferred are methyl benzoate, methyl toluate, methyl anisate, phenyl acetate, methyl methacrylate and the like. Further, alkoxysilane, aryloxysilane, alkylalkoxysilane, arylalkoxysilane, and alkylarylsilane are also preferably used, and as particularly preferable ones,
Examples thereof include phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, phenyl-t-butyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane and the like.

When adding these stereoregularity improving components, generally, benzene, toluene, n-hexane and n are added.
An inert hydrocarbon such as heptane is used as solvent. Known processes can be used for the polymerization. That is, slurry polymerization using an inert hydrocarbon such as n-hexane as a solvent, bulk polymerization using a monomer itself such as liquid propylene as a solvent, and liquid phase such as inert hydrocarbon or liquid propylene are substantially A gas phase polymerization that does not exist is used. Further, these processes can be used in combination. The reaction system may be either a batch system or a continuous system.

As the monomer, α-olefins such as propylene, ethylene, 1-butene, 1-hexene and 3-methyl-1-butene are used. Moreover, these can also be mixed and used. The reaction conditions are usually 1 to 10
50 to 90 at a pressure of 0 atm, preferably 5 to 40 atm
C., preferably in the range of 60-80.degree. As a method for adjusting the molecular weight of the produced polymer, a known molecular weight adjusting agent such as hydrogen or diethylzinc can be appropriately used.

[0022]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto without departing from the gist thereof. In the following examples and comparative examples, the amount of xylene-insoluble component (IIXY) as a measure of stereoregularity.
L) was measured by the following method. About 1g of polypropylene powder sample was precisely weighed in an eggplant-shaped flask, and 200m
l xylene was added, and the mixture was heated to boiling and completely dissolved. Then, this was rapidly cooled in a water bath, the precipitated solid portion was filtered, and 50 ml of the filtrate was evaporated to dryness in a platinum dish and further dried under reduced pressure, and the weight was weighed. II _XYL was calculated as the amount of xylene-insoluble component in the polypropylene powder sample.
The polymerization activity (indicated as K) is 1 g of the solid catalyst component per 1 kgf / cm ^{2 of} α-olefin pressure.
Polymer production amount (g).

Example 1 (A) Preparation of Solid Titanium Trichloride Catalyst Chain An autoclave having a capacity of 10 L, which was sufficiently replaced with nitrogen, was charged with 5.0 L of purified toluene and 5.0 mol of titanium tetrachloride, and further di-n- 5.0 mol of butyl ether was added. 2.38 mol of diethylaluminum chloride was added dropwise while maintaining the temperature at 25 to 30 ° C. under stirring to obtain a uniform solution of blackish brown titanium trichloride. Then, the uniform solution of titanium trichloride was heated to 40 ° C. and kept for 2 hours. During this process, precipitation of purple titanium trichloride was observed.

At this point, 1.6 mol of titanium tetrachloride and 0.57 mol of tridecyl methacrylate were further added, and 9 mol
The temperature was raised to 8 ° C. and stirring was continued for 2 hours. Thereafter, the precipitate was separated by filtration and washed repeatedly with n-hexane to obtain a fine-grained purple solid titanium trichloride catalyst chain. (B) Production of Titanium Trichloride Containing Propylene Polymer: Purified n-hexane (5 L) was placed in a 10 L autoclave sufficiently replaced with dry nitrogen, 195 g of diethylaluminum chloride and the solid titanium trichloride catalyst chain obtained in (A) above. Was charged as TiCl _{3 in an amount} of 250 g, and then 4
Keep the temperature at 0 ° C and stir 250 g of propylene gas to about 60 with stirring.
The liquid phase was blown into the liquid phase for a contact treatment. Then, the solid components are allowed to settle and the supernatant is removed by decantation.
-Washing with hexane several times to obtain propylene polymer-containing titanium trichloride.

(C) Production of Propylene Polymer To a 2 L induction stirring autoclave sufficiently substituted with purified nitrogen, 0.8 mmol of diethylaluminum chloride and 0.04 mmol of dodecylbenzenesulfonic acid were added at room temperature under a nitrogen blanket. , 0.5 more hydrogen at room temperature
After tensioning at kgf / cm ² , 750 g of liquid propylene was charged. Then, the temperature of the autoclave was raised to 70 ° C., 25 mg of the above propylene polymer-containing titanium trichloride was added as titanium trichloride, and polymerization was carried out at 70 ° C. for 3 hours. Then, excess propylene was purged to obtain 300 g of powder polypropylene. Polymerization activity K is 133, II
_XYL was 97.9%.

Comparative Example 1 Except that no dodecylbenzene sulfonic acid was added,
Polymerization was carried out in the same manner as in Example 1. Polymerization activity K is 15
0, II _XYL was 95.0%.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the addition amount of dodecylbenzenesulfonic acid was changed to 0.08 mmol.
Polymerization activity K was 133 and II _XYL was 97.4%.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that t-butylsulfonic acid was used instead of dodecylbenzenesulfonic acid. Polymerization activity K was 144 and II _XYL was 96.5%.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that dodecylbenzenesulfinic acid was used instead of dodecylbenzenesulfonic acid. Polymerization activity K is 133, II _{XY L} is 9
It was 7.1%.

Example 5 (A) Manufacture of Mg-supported catalyst component A 500 ml flask equipped with a stirrer and a thermometer was sufficiently replaced with purified nitrogen, and then 5 g of commercially available diethoxymagnesium was collected under a purified nitrogen seal. Butoxy titanium 7.
4 g and tetraethoxysilane 4.6 g were added, and the temperature was raised with stirring. When the temperature reached 130 ° C., a toluene solution of 8.2 g of phenol was added, and the mixture was reacted at 130 ° C. for 1 hour to obtain a yellow slurry-like reaction product.

After the reaction, purified toluene was added so as to have a magnesium concentration of 0.5 mol / L-toluene, cooled to -20 ° C., and 25 g of titanium tetrachloride was added. After the addition, the whole solution became a uniform solution. After the addition, the temperature was gradually raised, and after the temperature was raised to 110 ° C., titanium phthalate (IV) salt synthesized by the reaction of phthalic acid and titanium tetrachloride was added to M
It was added so as to have a molar ratio of 0.1 to g, and the mixture was kept at the same temperature for 1 hour. Then, it was washed with purified toluene to obtain a solid product. Then add 42 g of titanium tetrachloride,
The solid product was treated at 110 ° C. for 1 hour and then thoroughly washed with purified toluene to obtain 4.3 g of a solid catalyst component.

(B) Polymerization of Propylene In a 2 L induction-stirring autoclave sufficiently replaced with purified nitrogen, 0.5 mmol of triethylaluminum and 0.05 of dodecylbenzenesulfonic acid were added at room temperature under a nitrogen blanket.
Mmol at room temperature and 0.3 kgf / hydrogen at room temperature.
750 g of liquid propylene was charged in such a manner that the content became cm ² . Next, after adding 9 mg of the above solid catalyst component, the temperature was raised to 70 ° C. and polymerization was carried out for 1 hour. After that, excess propylene was purged and powder polypropylene 235 g
Got Polymerization activity K was 870 and II _{XY L} was 95.2%.

Comparative Example 2 Except that no dodecylbenzene sulfonic acid was added,
Polymerization was carried out in the same manner as in Example 5. Polymerization activity K is 73
0, II _XYL was 82.1%.

Example 6 (A) Manufacture of Mg-supported catalyst component A 500 ml flask equipped with a stirrer and a thermometer was sufficiently replaced with purified nitrogen, and then 5 g of commercially available diethoxymagnesium was collected under a purified nitrogen seal and tetra- Butoxy titanium 7.
4 g and tetraethoxysilane 4.6 g were added, and the temperature was raised with stirring. When the temperature reached 130 ° C., a toluene solution of 8.2 g of phenol was added, and the mixture was reacted at 130 ° C. for 1 hour to obtain a yellow slurry-like reaction product. After the reaction, purified toluene was used as a magnesium concentration of 0.5 mol / L-
After adding so that it becomes toluene, it is cooled to -20 ° C,
25 g of titanium tetrachloride was added. After the addition, the whole solution became a uniform solution. After the addition, the temperature is gradually raised to 80 ° C.,
1.3 g of ethyl benzoate was added, and the mixture was kept at the same temperature for 1 hour. Then, it was washed with purified toluene to obtain a solid product. The solid product obtained is then added with titanium tetrachloride 82
g and 1.3 g of ethyl benzoate were added, and the mixture was treated at 80 ° C. for 1 hour and then sufficiently washed with purified toluene to obtain 4.8 g of a solid catalyst component.

(B) Polymerization of Propylene To a 2 L induction-stirring autoclave sufficiently replaced with purified nitrogen, 1.0 mmol of triethylaluminum and 0.3 mmol of dodecylbenzenesulfonic acid were added at room temperature under a nitrogen blanket, and the temperature was further increased to room temperature. 1.0 kgf / c of hydrogen
added to a m ^2, was charged with liquid propylene 750 g. Next, after adding 15 mg of the above solid catalyst component, the temperature was raised to 70 ° C. and polymerization was carried out for 1 hour. After that, excess propylene was purged and powdered polypropylene 315 g
Got Polymerization activity K is 700, IIXYL is 96.4%
Met.

Comparative Example 3 Except that no dodecylbenzene sulfonic acid was added,
Polymerization was carried out in the same manner as in Example 6. Polymerization activity K is 12
60 and II _XYL were 73.1%.

[0037]

EFFECT OF THE INVENTION By polymerizing an α-olefin in the presence of a catalyst using the third component defined in the present invention, it is possible to produce a polyolefin having a small decrease in polymerization rate and high stereoregularity. it can.

Claims (1)

[Claims] 1. An α-olefin in the presence of a catalyst comprising (a) a titanium-containing solid catalyst component, (b) an organoaluminum compound, (c) a compound selected from sulfonic acid, sulfinic acid, and sulfenic acid. A method for polymerizing an α-olefin, which comprises polymerizing