JPS596204A - Production of olefin polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a solid catalyst for α-olefin polymerization. More specifically, the present invention relates to a solid catalyst preferably used for the polymerization of ethylene, propylene, butene-114-methylpentene-1, etc., which is composed of a supported catalyst component having high polymerization activity and an organoaluminum compound.

Conventionally, as a supported catalyst suitable for the stereoregular polymerization of α-olefins having carbon Ji3 or more, JP-A-48-169 has been proposed.
No. 86, JP-A-49-86482, JP-A-50-10
No. 8385, JP-A-50-126590, JP-A-51
Many methods have been proposed for producing a titanium-containing catalyst using a halogenated magnesium compound, preferably magnesium chloride, as the carrier piece 11, including No. 28189.

Further, the general formula used in the present invention and R2 may be the same or different. n indicates 2≧n≧0. ) regarding the polymerization of olefins using titanium-containing catalysts as carriers, Japanese Patent Publications No. 46-34098, Japanese Patent Publication No. 47-1768,! Although some proposals have been made, such as in Japanese Patent Application Publication No. 47-42137, none have been found suitable for the highly stereoregular polymerization of olefins having 3 or more carbon atoms.

Various attempts have been made to improve the stereoregularity using a carrier represented by the general formula (11).
Including No. 52-9F1076, JP-A-53-
No. 2580, JP-A-53-43094, I-Kokai No. 1987
-152710,'r! Although JP-A-56-26904 and the like have been proposed, they have not been fully satisfactory. The present inventors have diligently studied a method for producing a titanium-containing solid catalyst using a carrier represented by the general formula (1) and a polymerization method using the catalyst, and have thus arrived at the present invention.

That is, the present invention is based on the general formula Mg(OR'')n(OR2)
2-n (wherein R' and R2 represent an alkyl group, an aryl group, or an aralkyl group that differs by four dimensions, and n(d:2
Indicates ≧n≧0. ) with a compound of three families consisting of an electron-donating compound, a halogen-containing silicon compound, and a titanium compound repeatedly at least twice; This is a method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an organometallic compound (b) of a metal of Groups 1 to 3 of the Table of Contents.

The above-mentioned halogen-containing magnesium has the property of being hygroscopic or reacting with moisture, and therefore the use of the carrier represented by the general formula (1) has great advantages in the catalyst production process.

To explain the present invention in detail, (5) a magnesium compound represented by the general formula ill (
A solid catalyst component (a) obtained by repeating the treatment at least twice with a three-barrel compound consisting of a silicon electrodynamic compound, (C) a halogen-containing silicon compound, and a titanium compound, and It is characterized by polymerization or copolymerization of olefins using a titanium-containing catalyst containing an organometallic compound (b) of a metal of Groups 1 to 3 as an essential component and further appropriately combining an electron-donating compound (C). 1) A method for producing olefin.

Specifically, the magnesilano compound (a) represented by the general formula (1) used in the present invention is Mg(OCHs)2
.

Mg(OCiHs)z, Mg(OCsIb)*
, Mg(OCiHs) snow.

Mg(OCd(s)!, Mg(QC)I2CeH
s ) 21Mg (OC!Hs ) (OC4H11)
.

Mg(OCtHs)(OCslb) -Mg((JC4
Examples include dialkoxymagnesium, diaryloxymagnesium, dialkyloxymagnesium, and alkyloxyaryloxymagnesium such as HsC)is)*. In addition, it is necessary to sufficiently remove moisture and air trapped in a magnesium compound before use.

The 1h child-donating compound 03) generally includes phosphorus-containing compounds, acid-containing non-compounds, sulfur-containing compounds, and nitrogen-containing compounds.

Among these, the phosphorus-containing compound has the following general formula % formula %) (In the formula, R3 represents hydrogen, a hydrocarbon group, an amine group, or an alkylamino group, Y represents oxygen or sulfur, and m1l-t
Indicates the number of θ to 3. ),
Specific examples include triphenylphosphine oxide, trimethylphosphine, triphenylphosphate, triphenylphosphite, hexamethylphosphoric triamide, triphenylthiophosphite, and the like.

Further, as the oxygen-containing compound, for example, the following general formula (in the formula R
', R' represents a hydrocarbon group which may be substituted with an alkoxy group, and may be bonded to each other to form a cyclic group. fck indicates a number from 1 to 3. ) can be mentioned. Specifically, diethyl ether, dipropyl ether, diethylene glycol, polypropylene glycol, ethylene oxide, propionmexide,
Ethers such as furan: ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, phenylpropyl ketone; ethyl acetate, methyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenyl acetate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, furovir toluate, butyl toluate, methyl ethylbenzoate, ethyl benzoate, ethyl frate, ethyl xylene carboxylate, Examples include esters of carboxylic acids such as methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxylate, and ethyl cinnamate, and cyclic esters such as γ-butyllactone.

Also included are silicon-containing carboxylic acid esters such as β-trimethoxysilylethyl benzoate and β-trimethoxysilylethyl acetate.

Examples of nitrogen-containing compounds include amines or their derivatives such as triethylamine, tetramethylethylenediamine, piperazine, pyridine, and piperidine; nitroso compounds such as tertiary amines, pyridines, and N-oxides of quinolines; urea or its derivatives. , urethanes,
Examples include fatty acid amides, lactams, imides, carbamate esters, glycine esters, and alanine esters.

Examples of the sulfur-containing compound include thioethers such as diethyl thioether and dibutyl thioether, and metal salts of sulfonic acids such as sodium benzenesulfonate and sodium toluenesulfonate.

Among them, trialkyl, trialkoxy, triaryl or triaryloxyphosphine, carboxylic acid ester; N-substituted phosphoric acid amide; N-substituted diamine; trialkylamine; triarylphosphine oxide is preferred, and particularly preferred is carboxylic acid It is an ester, and more preferably an aromatic carboxylic acid ester.

Examples of the halogen-containing silicon compound (k) include tetrachlorosilane, tetrabromosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, and diphenyldichlorosilane%)! Examples include J/f lepo/l/silane and other similar compounds thereof, including tetrachlorosilane,
Phenyltrichlorosilane and the like are preferably used.

In the method of the present invention, the above (4), CB), C)
, Q)) component may be subjected to techniques such as mechanical grinding techniques or contacting in the presence or absence of a hydrocarbon solvent.

For example, components (2), (6), C), and Q)l are mechanically pulverized and mixed, washed with an inert hydrocarbon solvent, the solvent is separated, and the following steps are repeated at least once on the dried product. Get the catalyst by returning it. That is, (υ, 0.I is added and further mechanically crushed or Q3), L”),
A method of contact-mixing (6) under heating and washing with an inert hydrocarbon solvent.

Or, add components (6), (C), Q)) to (4), mix them under heating, and then wash repeatedly with an inert hydrocarbon solvent, and then dry in the presence of a solvent or dry it in the absence of CB).
, C) , A method of adding the component (L) and repeating the above operation.

Although the reason why the catalyst performance is improved by repeated treatments with components (6), C), and (D) is currently unknown, the improvement in stereoregularity and polymerization activity is very useful industrially.

Further, the amount of each component used in the catalyst manufacturing process in one process is expressed in molar ratio as in the usual method.

Mg(OR)n(OR)2-n1 Electron-donating compound 10-0.01, preferably 1-(1,1 halogen-containing silicon compound 20-
0.1, preferably 5-0.5 titanium compound
100 to 0.11, preferably 40 to 1, and usually the amount of each of the above components used is adjusted so that the amount of titanium in the product is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Mechanical pulverization in each of the above methods may be performed by conventionally commonly used methods such as a ball mill, an impact mill, and a vibration mill. The pulverization temperature may normally be around room temperature, and heating and cooling are not particularly required. The pulverization processing time depends on the type of pulverizer used, but is usually 200 hours from fi waiting time.

In addition, the reaction in the presence or absence of an inert hydrocarbon solvent is usually carried out at room temperature to 200°C, preferably 80 to 150°C.
Yes, the reaction time is about 0.5 to 4 hours.

In the present invention, the anti-1b product qqed as described above is then washed with an inert hydrocarbon solvent to remove components soluble in the solvent. And the catalyst component thus obtained (
Organometallic compounds of ω and metals from Groups I to III of the periodic table (b)
A polyolefin is produced by polymerizing or copolymerizing the olefin using a catalyst system in which an electron-donating compound (c) is further mixed as required. On this occasion(
a) (b) (c) There is no particular restriction on the order of addition of each component.

Next, as the organometallic compound of a metal of Groups 1 to 3 of the periodic table (component (b)) used in this tactile system, a compound represented by the general formula AtRnXa -n is preferably mentioned. In the above formula, l( is a hydrogen hydride group having 1 to 20 carbon atoms, especially an aliphatic hydrocarbon group, X is a halogen, and n is a number of 2 to 3. Specific examples of this organoaluminum compound include , triethylaluminum, tripropylaluminum, trioctylaluminum, trioctylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethyl-f-luminium monochloride, etc., but preferably trialkylaluminum alone or a mixture with dialkylaluminum monohalide. is used.

Further, as the catalyst system component (c), component 03) used in the production of the solid catalyst component (a) described above is used, preferably a carboxylic acid ester, and particularly preferably an aromatic carboxylic acid ester.

The ratio of the catalyst components used is titanium in the catalyst component (a), aluminum compound in the catalyst component (middle), and 'f(f) in the catalyst component (c).
, the molar ratio of the child compound is 1=3-500: (1
-100 preferably l:20-200:3-50
chosen to be.

As olefins, ethylene, propylene, butene
Preferably, α-olefins having 3 or more carbon atoms, particularly propylene, are mentioned. Further, the polymerization can be applied not only to homopolymerization but also to random polymerization or block copolymerization.

The polymerization reaction is preferably carried out in a slurry polymerization method using an inert hydrocarbon such as hexane, heptane, cyclohexane, benzene, toluene, pentane, butane or a mixture thereof, or a liquefied product of an α-olefin to be polymerized. , it is also possible to carry out the polymerization in the gas phase. The temperature is 50 to 100°C, preferably 60 to 90°C, and the pressure is not particularly limited, but usually atmospheric pressure to ioo
Selected from within the atmospheric pressure range.

If hydrogen can also be present in the polymerization system as a molecularization regulator, this increases the melt flow index (MF
I, measured according to ASTM-D 1238) from 50 to 0.
1 polymer can be easily produced. Other methods commonly used in the polymerization and copolymerization of α-olefins can also be applied to the method of the present invention. For example, the three catalyst components (a).

(b), (e) or (a), (b) A method of pretreating with an α-olefin using two components.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by these embodiments unless it departs from the gist thereof.

In the examples, polymerization activity (denoted as K) lIj
α-olefin pressure per hour (I K9/IM)
, the amount of polymer produced per 1y of titanium (2), and the catalyst efficiency (denoted as CE) is the production of polymer M'(f) per 1y of titanium as a catalyst component. Isotactic index (denoted as II) is the residual volume (by weight) after extraction with boiling n-hebutane in a modified Soxhlet extractor for a certain period of time. II indicates the yield of crystalline polymer since the amorphous polymer is soluble in boiling n-hebutane. Bulk density (expressed as ρB, unit f/cc) is JI
Measured according to S-K-6721. Melt flow index (expressed as MFI) is ASTM-1)
123B.

Example 1 Commercially available Mg(OC*)Is)! was sufficiently dried and 51.5% was collected in a 300ml flask at room temperature, and 79.9% of phenyltrichlorosilica was collected. ．． 2 f, k f k Hayshade 1.32, 'l'i (: 1480 g) was added under a purified nitrogen seal, and the temperature was gradually raised while stirring. After raising the temperature to 120 °C, After holding for .5 hours, the mixture was thoroughly washed with purified n-heptane, and the supernatant was separated and dried to obtain the catalyst precursor of Example 1.

Next, 9.2 f of itequenyltrichlorosilane and 1-39 s of ethyl benzoate and 1480 f of TlC were added under a seal of purified N3, and the temperature was gradually raised while stirring at 120°C for 1.
The mixture was held for 5 hours, thoroughly washed with n-hebutane, and the supernatant liquid was separated and dried to obtain a solid catalyst. The amount of supported Ti was 2.1% by weight M%.

Polymerization of propylene was carried out using a 2-ton induction stirring autoclave. 2.5 mmol of triethylaluminum and 0.77 mmol of rose methyl methyl benzoate were added to an autoclave at room temperature under a seal of purified N2, and further, at room temperature, H, x, 4 kg/cn? After adding 70 of liquid propylene, the temperature was raised with stirring, and at 70° C., 26.7 rng of the above solid catalyst was added to initiate polymerization.

After holding at 70° C. for 1 hour, excess propylene was removed to obtain 274 g of white powder polypropylene including all atactic polypropylene.

The catalyst efficiency CE was 489--PP/g#Ti, and the undercarriage activity was 16.300. ρB is 0.41 f/cc
Adashi, II was 95.3%. MF1=5.7
Met.

Comparative Example 1 In Example 1, the same polymerization as in Example 1 was carried out using 27.4~ of solid catalyst precursors. In addition, T of this precursor
The amount of i supported was 2.3% by weight. White powdered polypropylene 10 (lr was obtained. Catalyst efficiency CE was 173 Kg
-pp/g-TI and polymerization activity was 5,760. ρB is 0.37 f/cc, II is 90.
In 8th grade, the MFI was 6.1.

Examples 2 and 3 Comparative Examples 2 and 3 In Examples 2 and 3, the catalyst of Example 1 was used, and in Comparative Example 2゜3, the catalyst of Comparative Example 1 was used. The changes were made as shown in -1. The results are shown in Table-1.

Table-1 Example 2 0.60 B20 27,300
0.41 92.4 5.9 Example 3 1.00
290 9,670 0.42 96.1
5.6 Comparative Example 2 0.60 680 22,
670 0.35 Bt, 3 6.3 Comparative Example 3
1.00 76 2,530 0.3B 92
．． 6 5.7*a; Paramethylmethylbenzoate Example 4 Comparative Example 4 Phenyltrichlorosilane 13.8?
, ethyl benzoate 1.32, TiCl4 ctOr
A catalyst was produced in exactly the same manner as in Example 1 except that . Example 4 was polymerized using a catalyst and a catalyst precursor, respectively.
The results are shown in Table 2 as Comparative Example 4.

Table-2 Example 4 0.77 425 14,170
(1,4094,83,8 ratio @Example 4 0.77
157 5,230 0.36 90.1
4.1 Examples 5 to 7 Polymerization was carried out using the catalyst of Example 1 and the Nisdels shown in Table 3 in place of the paramethyl methyl benzoate used in the polymerization of Example 1.

The results are shown in Table-3.

Table-3 Ace Example 6 Paramethoxy 329 11,000
0.4296.2 7.6 Ethyl benzoate implementation 1+! 17 C3PB*565 18,80
0 o, 5o94. s 5.1*benzoic acid-3-
Trichlorosilylpropyl ester comparative example 5 When producing the catalyst precursor of Example 1, the reaction time was 1.
5 hours was changed to 3.0 hours. Next, polymerization was carried out in the same manner as in Example 1 using this precursor, and the catalyst efficiency was found to be C.
E is 226 Kg-pp/g-Ti, and polymerization activity is 7
,500,ρBij O,36f/cc %II is 9
1.8%, MFI = 5.2.

Claims (1)

[Claims] (1) General formula Mg(OR')n(OR")z-n(
In the formula, R''tR2 represents the same or different alkyl group, aryl group or aralkyl group, and n represents 2≧n≧0. A titanium-containing solid catalyst component (a) obtained by repeated treatment at least twice with three types of compounds, and an organometallic compound (b) of a metal from Groups 1 to 3 of the periodic table. A method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst. i21?ii, polymerizing or copolymerizing an olefin in the presence of a child-donating compound A method according to claim E(1), characterized in that: