JPS6339901A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which has good retentivity of a polymerization activity and high catalytic activity and gives a polymer of excellent streoregularity, by combining a specified solid component with an organoaluminum compound. CONSTITUTION:A complex of formula III is obtained by contacting a titanium compound of formula I (wherein R<1> is a 1-10C hydrocarbon residue, X is a halogen and 1 <= n <= 4) with a silicon compound of formula II (wherein R<2> is a branched hydrocarbon residue, R<3> and R<2> are the same or different hydrocarbon residues, R<4> is a hydrocarbon residue and m is in the range of 1 <= m <=3) at -50-100 deg.C in the presence of an inert diluent. A solid component obtained by contacting this complex with a magnesiumn compound (e.g., magnesium halide) at -50-200 deg.C is combined with an organoaluminum compound (e.g., trimethylaluminum).

Description

[Detailed description of the invention] Technical field The present invention relates to an olefin polymerization catalyst.

More specifically, in the present invention, the transition metal component of the Ziegler catalyst contains a specific complex of a titanium compound and a silicon compound formed in advance.

When olefins are polymerized using the catalyst of the present invention, the polymerization activity is long-lasting and the polymerization temperature can be set high, resulting in excellent productivity. Furthermore, the molecular weight of the resulting polymer can be easily controlled. An excellent method is provided.

Prior Art In recent years, solid components containing titanium, magnesium and halogen as essential components have been used to produce
Many proposals have been made to produce highly stereoregular polymers of olefins.

According to these methods, in addition to the above-mentioned solid components and organic aluminum compounds, an electron-donating compound (external donor) is added during polymerization in order to increase the stereoregularity of the product polymer. needed to be used.

Using an electron-donating compound as the third component in this way complicates the catalyst system, making it difficult to control product performance. In addition, due to the reaction between the organoaluminum compound and the electron-donating compound as the third component, there are problems such as low sustainability of the polymerization rate, inability to increase the polymerization temperature, and difficulty in controlling the molecular weight of the polymer. be.

A catalyst system that does not use a third component as described above is disclosed in Japanese Unexamined Patent Publication No. 57
Although it has been proposed in Japanese Patent No. 63312, it is still not at a sufficient level in terms of catalytic activity and stereoregularity of the resulting polymer, and further improvements have been desired.

SUMMARY OF THE INVENTION The present invention provides an olefin polymerization catalyst comprising a combination of component (A) and component (1) below.

Component magnesium compound and general formula, TICOR"J 4-nXn# R"R', -ms:
(OR'3m (where R1 is a hydrocarbon residue, R'' is a branched hydrocarbon residue, R3 is a hydrocarbon residue that is the same as or different from R2, R' is a hydrocarbon residue, and X is]) Component (B): a solid component contained as a complex essential component represented by a logen atom, n is a number where l≦n≦4, and m is a number where 1≦m≦3.

Effects of the Invention The catalyst of the present invention has good sustainability of polymerization activity and can increase the polymerization temperature, resulting in excellent productivity. Furthermore, a polymer with high catalytic activity and high stereoregularity can be produced without using a third component, the molecular weight of the resulting polymer can be easily controlled, and a polymer without odor problems can be obtained. .

Detailed Description of the Invention (Catalyst) Component (4) The components of the catalyst of the present invention are a magnesium compound and the general formula: Ti(OR1)4-total 4·h"g's: (oR1)
□! -m (However, R" is a hydrocarbon residue, R" is a branched hydrocarbon residue, R3 is a hydrocarbon residue that is the same as or different from R2, R4 is a hydrocarbon residue, X is a halogen atom, n is 1≦n
It is a solid component containing as an essential component a complex represented by a number of ≦4, m is a number of 1≦n≦3, respectively.

Here, the complex represented by the above general formula is obtained by previously contacting a titanium compound and a silicon compound, which will be described later, and is further contacted with a magnesium compound, etc., and remains in the component list. The complex of the titanium compound and the silicon compound may undergo a structural change within the range of the above general formula by the above two contacts.

Magnesium compounds used to produce the above component (4) include magnesium halide, dialkoxymagnesium, alkoxymagnesicum halide, magnesium oxyhalide, dialkylmagnesium,
Examples include magnesium compounds such as magnesium oxide, magnesium hydroxide, and carboxylate of magnesium hydroxide.

Another essential component constituting the component is a complex of titanium compounds and silicon compounds. The titanium compound for forming the complex has the general formula Ti(OR1)4-
11Xn (here, R1 is a hydrocarbon residue, preferably one having about 1 to 10 carbon atoms, X represents a halogen,
n represents a number satisfying l≦n≦4. ) are titanium compounds represented by: Specific examples include Ttcz4, TiB
r,,Ti(QC2H,>ctt,,Ti(nC2H6
)2C12,Ti (nC2H5)3cz%'rt(o
-1c, H? )C13,Ti(0-nC4H,>cz,
, Tt (0-nC4H,), CI, , Ti (QC2
H,)Br,,Ti(OC2H3](OC4H9J2C
11T 凰 (0-uc, H,), CJ, Ti (0
-C,R3)C1,,rt(o=c,攬)2C12,r
i (QC,H,,)ct, %rt (QC,Hl
, )C13, Ti(nC8H17)2C12, Ti(O
Cl. H2□)C1, etc. are mentioned.

As a silicon compound for forming a complex, general 2R
"s -m Sl("' 3m (however, R2 is a branched hydrocarbon residue, R" is the same or different hydrocarbon residue as R2, R4 is a hydrocarbon residue, n is 1≦ m≦3
) is a silicon compound represented by the number of .

Here, R2 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example,
A phenyl group or a methyl-substituted phenyl group) is preferable. More preferably, R2 is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom, is secondary or tertiary.
It is a carbon atom of class.

In particular, the number of carbon atoms in silicon atom I: OR'', in which the bonded carbon atom is preferably tertiary, is usually 3 to 20, preferably 4 to 1O1. nj is 1 to 20 carbon atoms, preferably 1- 10, is usually a branched or straight chain aliphatic hydrocarbon group.R4 is an aliphatic hydrocarbon group, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms,
It is normal that

Specific examples of silicon compounds are shown below.

C out CH.

(CHsJ, C-8i (OCH, J3, (CH3)3C
-S i (QC, H,).

CH, OH.

etc. The conditions for producing the complex represented by the above general formula by contacting the titanium compound and the silicon compound in advance are arbitrary as long as the effects of the present invention are recognized, but generally they are within the following range. is preferred.

The contact temperature is -50 to 100°C, more preferably 0 to 50°C.

Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, etc., and a method of contacting by stirring in the presence of an inert diluent.

Inert diluents used at this time include aliphatic hydrocarbons such as n-hexane, n-hebutane, n-octane, n-decane, iso-pentane, and paraffin; L) toluene;
Aromatic hydrocarbons A such as benzene, ortho-xylene and para-xylene, R2-dichloroethylene, n-salt 4F, halohydrocarbons such as butyl and chlorobenzene, dimethylpolysiloxane, methylethylpolysiloxane, methylphenylsiloxane, etc. can give.

The molar ratio of the silicon compound to the titanium compound to the titanium compound may be in the range of 1×1O to 1O, preferably in the range of 0.1 to 5.

Electron donors may be used in preparing this component. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. child donor, ammonia,
Examples include nitrogen-containing electron donors such as amines, nitriles, and isocyanates.

More specifically, those having 1 to 1 carbon atoms, such as methanol, ethanol, gropanol, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc.
Alcohols of 8; phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphtholnato; acetone, methyl ethyl ketone, methyl isobutyl ketone, 3 carbon atoms such as acetophenone and benzophenone
to 15 ketones; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
Aldehydes having 2 to 15 carbon atoms such as tolualdehyde and nathaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, butyrate;
Methyl ether, ethyl ether, inglobil ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, etc. with 2 carbon atoms
to 20 ethers; acetic acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine,
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Examples include amines such as picoline and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile. Two or more types of these electron donors can be used.

In addition to the above-mentioned essential components, the two-phase component (4) of the present invention C includes silicon compounds such as di5icz4, cH3sict, alkylhydrodiene polysiloxane, AI (OiC
,H7)1,AI (QC,H,),,AlcOcH,
), CI, hlct, , AnoBr, etc., and B<ocHl)s, B(QC2H
It is also possible to use other components such as boron compounds such as .

The amount of each of the above compounds to be used may be arbitrary as long as the effects of the present invention are observed, but generally (: is preferably within the following range).

The amount of the complex of titanium and silicon compound used is I x 1 in molar ratio with respect to the amount of magnesium compound used.
May be within the range of 0-2 to Zoo, preferably 0.1 to 1
It is within the range of 0.

When using the electron donating compound, the amount used is IXI O to the amount of the above magnesium compound used in molar ratio.
It may be within the range of 10, preferably within the range of 0.01 to 5.

Component (4) is produced using the above-mentioned magnesium compound, a complex of a titanium compound and a silicon compound, and, if necessary, other components such as an electron-donating compound, for example, by the following production method.

(a) A method of contacting a complex of a magnesium halide, a titanium compound, and a silicon compound (hereinafter sometimes abbreviated as a titanium-silicon complex) and, if necessary, an electron-donating compound.

(b) A method in which alumina or magnesia is treated with a phosphorus halide compound, and then brought into contact with a magnesium halide, a titanium-silicon complex, and, if necessary, an electron-donating compound.

→ A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then brought into contact with a titanium-silicon complex.

B) A method of contacting an alkoxymagnesium compound with a halogenating agent, and then contacting the titanium-silicon complex and, if necessary, an electron-donating compound.

The contact conditions for the magnesium compound, titanium-silicon complex, and other components used in combination when producing component (4) may be arbitrary as long as the effects of the present invention are recognized, but generally The following conditions are preferable. The contact temperature is about -50 to 200°C, preferably 0 to 200°C.
The temperature is 100°C.

Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include the inert diluents described as those used in the production of titanium-silicon complexes, that is, aliphatic or aromatic hydrocarbons, octopus hydrocarbons, polysiloxanes, and the like.

Ingredients (intestinal component (B) is an organoaluminum compound 0 Specific examples include IC''s -p l'JI Xp or R'
, -qAJ(OR1)9 (where R' and R' are hydrocarbon residues or hydrogens having about 1 to 20 carbon atoms, which may be the same or different, R7 is a hydrocarbon residue, X is a halogen, p and Each q is expressed as 0≦p (3, o<q<3).

Specifically, ke) triethylaluminum, triethylaluminum, triimbutylaluminum, trihexylaluminum, trioctyl 7, miniram, tridecylaluminum, and other trialkylaluminum;
(b) Diethylaluminium 9-monochloride, cyinobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride,
Alkyl aluminum halides such as (c) diethylaluminium hydride, diisobutyl aluminum hydride, (c) diethylaluminium ethoxide, aluminum alkoxides such as diethylaluminium phenoxytonato, and the like.

Other organometallic compounds may be added to these organoaluminum compounds (a) to (c), such as R8, -1V (OR'
).

For example, triethyl aluminum and diethylaluminum ethoxide, combination of diethylaluminum monochloride and diethylaluminum ethoxide, combination of ethylaluminum dichloride and ethylaluminum jetoxide, and combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride. It will be done.

(Polymerization) The catalyst system of the present invention can be applied not only to ordinary slurry polymerization, but also to liquid-phase solventless polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. Ru. It is also applicable to continuous polymerization, batch polymerization or preliminary polymerization.

As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures.

The polymerization temperature is from room temperature to about 200°C, preferably from 50°C to
iso°C, and hydrogen can be used as an auxiliary molecular weight regulator at that time.

Further, although the amounts of component (A) and component (B) to be used are not particularly limited, the following ranges are generally preferred. The weight ratio of component (B) to component prisoner is 0.1 to 10
00, preferably lO~500. In addition to component (4) and component (B), a known electron donor can also be used as a third component.

(Olefin) The olefins polymerized by the catalyst system of the present invention are general
CH=CH2 (where R is a hydrogen atom or has 1 to 1 carbon atoms
0 hydrocarbon residue and may have a branched group). Specifically, there are olefins such as ethylene, propylene, butene-11pentene-11hexene-1,4-methylpentene-1. Preferred are ethylene and propylene.

In these polymerizations, it is possible to carry out copolymerizations with up to 50% by weight, preferably 20% by weight, based on ethylene, of the abovementioned olefins, and up to 30% by weight, based on propylene, of the abovementioned olefins, especially ethylene. can be copolymerized with

Furthermore, the above olefins and other copolymerizable monomers (
For example, copolymerization with vinyl acetate, diolefin] can also be carried out.

Experimental Examples Example 1 (Synthesis of titanium-silicon complex) Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- 100 ml of hebutane is introduced, then (cH
3) 0.1 mol of c-si(OCH3) (hereinafter abbreviated as a-1) was introduced. Then TiCJ, 0.
1 mol was introduced over 30 minutes and reacted at 30°C for 3 hours. After the reaction was completed, it was washed with n-hebutane. When I took out a part and analyzed its composition, I found that it was 'rlc/4・0.86 (
a-1).

(Production of composition diagram) A thoroughly dried and nitrogen-substituted 0.41 J millimeter ball mill was filled with 40 12 m9 stainless steel balls, and 202 moles of F#CJ2 and 0.02 mol of the above complex were introduced therein. , and ground in a rotating ball mill for 48 hours. After the pulverization was completed, the pulverized composition was taken out from the mill and used as component (4).

(Polymerization of proprene) In a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 500 ml of thoroughly dehydrated and deoxygenated n-hebutane was added, and the components (
As B), 75 mg of triethylaluminum and 15 mg of the catalyst composition diagram synthesized above were introduced. Next, 60 milliliters of H4 was introduced, the temperature and pressure were increased, and polymerization was carried out under the conditions of polymerization pressure = 5 h/crnGs, polymerization temperature = 70°C, and polymerization time = 2 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried. 96 grams of polymer was obtained, and from the boiling hebutane extraction test, the total weight of Zenfuhinko, 1 (hereinafter abbreviated as T-1, I) was 94.1 weight percent, and MFR = 7.8.
Yllo minute, polymer bulk specific gravity = 0.35 t/C
Comparative Example 1 A composition diagram was produced in the same manner as in Example 1 except that TlCl was used instead of the titanium-silicon complex in the production of the composition diagram in Example 1, and this component (4) was Polymerization of propylene was carried out in the same manner as in Example 1 except for using the following. As a result, 58
grams of polymer were obtained, 'l'-1.1=48.6
weight percent, MFR = 29.6 r/10
The bulk specific gravity of the polymer was 0.31 f/C.

Example 2 (Production of composition diagram) Into a flask that had been sufficiently purified in the same manner as in Example 1, 50 milliliters of n-hebutane purified in the same manner was introduced, and further M
20.05 mol of P(QC,H,) was introduced.

Then 5 sct, o, t mol were introduced at 30 °C and 90
The reaction was carried out at ℃ for 4 hours. After the reaction was completed, the mixture was thoroughly washed with n-hebutane.

Next, TiC4e synthesized in the same manner as in Example 1 was added to this.
0.02 mol of O,86(a-1) was introduced and reacted at 40°C for 6 hours. After the reaction was completed, it was washed with n-heptane to obtain component (4).

(Polymerization of propylene) Polymerization was carried out in the same manner as in Example 1, except that the composition diagram was as obtained above and 145 milligrams of triisobutylaluminum was used instead of triethylaluminum under the polymerization conditions of Example 1.

101 grams of polymer were obtained, T −1,I =9
3.8 weight percent, Mf1)l=7.7t7
10 minutes, polymer bulk specific gravity = 0.36 f/cc.

Examples 3 to 5 In producing the composition diagram of Example 1, a composition diagram was prepared in the same manner as in Example 1 except that the titanium-silicon complex shown in Table 1 was used, and the composition diagram was prepared in the same manner as in Example 1. Polymerization of propylene was carried out in the same manner as in the example. The results are shown in Table-1.

Claims (1)

[Claims] (1) An olefin polymerization catalyst comprising a combination of the following components (A) and (B). ¥Component (A)¥ Magnesium compound and general formula, Ti (OR^1)_4_-_nX_n・R^2R^3_
3_-_mSi(OR^4)_m (where, R^1 is a hydrocarbon residue, R^2 is a branched hydrocarbon residue, R^3 is R
^2 is the same or different hydrocarbon residue, R^4 is a hydrocarbon residue, X is a halogen atom, n is a number of 1≦n≦4, m is a number of 1≦m≦3) A solid component containing a complex represented by the following as an essential component, ¥Component (B)¥ Organoaluminum compound.