JPS62115004A - Storage of catalyst component for polymerization of olefin - Google Patents

Abstract

PURPOSE:To give a highly active stable catalytic performance to a solid component containing Ti, Mg and a halogen, by prepolymerizing an olefin in the presence of the solid component and storing this catalyst component in an inert solvent. CONSTITUTION:A catalyst component for polymerization of an olefin, obtained by prepolymerizing a small amount of an olefin in the presence of a solid component containing titanium, magnesium and a halogen as components is stored in an inert solvent. An example of the source of Ti is a titanium compound of the formula (wherein R<1> is a hydrocarbon residue, X is a halogen and 0<=n<=4). Examples of the source of Mg include magnesium compounds such as magnesium halides and alkoxymagnesium halides. As the source of a halogen, choline is particularly desirable. As an organometallic compound which can be used as a cocatalyst, an organoaluminum compound is particularly desirable and it is added in an amount of, preferably, 0.01-10wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for preserving catalyst components for olefin 1 synthesis.

According to the present invention, a method is provided that does not reduce the activity of an olefin polymerization catalyst component that is immersed in polymer properties and exhibits high stereoregularity, but rather increases the activity and allows storage for a long period of time.

According to prior art Japanese Patent Publication No. 57-45244, a method is proposed in which "prepolymerization" is carried out using a catalyst system consisting of a solid catalyst component formed from a magnesium compound, a titanium compound, and an electron donor, and an organic aluminum. There is. In this method, approximately 100
The α-olefin having 3 or more moles of carbon atoms is t-prepolymerized.

However, in order to carry out such a pre-coating, a separate polymerization tank is required, which would require investment in equipment on an industrial scale.

Similar prepolymerization techniques have been proposed in Japanese Patent Publications No. 39-11085 and No. 47-32312, but both methods require a large amount of prepolymerization and are considered disadvantageous on an industrial scale. It will be done.

According to JP-A-57-15160, a method is proposed in which 0.01 to 1 gram of preliminary polymerization is carried out per solid catalyst component and then continuous polymerization is carried out. 0 Japanese Patent Publication No. 56-136806 which seems to be
The publication proposes a method in which a highly active magnesium-containing solid titanium catalyst component is prepolymerized and then stored in a dry state under an inert gas atmosphere.

Although the prepolymerization jf[f is an effective method as described above, prepolymerization often leads to a decrease in catalyst performance.

Therefore, it is desirable to be able to use prepolymerized or precombined catalyst components without deteriorating catalyst performance.

Summary of the Invention The present invention provides a catalyst component for olefin polymerization, characterized in that the catalyst component for olefin polymerization is prepared by prepolymerizing a small amount of olefin to a solid component containing titanium, magnesium, and halogen as essential components, and is stored in an inert solvent. This provides a method for preserving.

Effects of the Invention When olefin polymerization is performed using a melting medium component prepolymerized and stored according to the preservation method of the present invention, the activity of the catalyst component for olefin polymerization, which has excellent polymer properties and high stereoregularity, is reduced. Rather, it exhibits highly active and stable catalytic performance.

It was completely unexpected that using catalyst components preserved by the method of the present invention, catalyst activity would increase rather than decrease.

The solid catalyst component containing titanium, magnesium and halogen as essential components used in the present invention is not particularly limited as long as it contains titanium, magnesium and halogen, and is a known catalyst component.

Examples of materials containing titanium, magnesium and halogen include JP-A-53-45688, JP-A-54-3894, JP-A-54-31092, and JP-A-54-3.
No. 9483, No. 54-94591, No. 54-1184
No. 84, No. 54-131589, No. 55-75411
No. 55-90510, No. 55-90511, No. 55-127405, No. 55-147507, No. 55-155003, No. 56-18609, No. 56
-70005, 56-72001, 56-86
No. 905, No. 56-90807, No. 56-15520
No. 6, No. 57-3803, No. 57-34103, No. 57-92007, No. 57-121003, No. 58
-5309, 58-5310, 58-5311
No. 58-8706, No. 58-27732, No. 5
No. 8-32604, No. 58-32605, No. 58-6
No. 7703, No. 58-117206, No. 58-127
No. 708, No. 58-183708, No. 58-1837
No. 09, No. 59-149905, No. 59-14990
Prior art such as No. 5 publications can be exemplified.

Among the solid catalyst components mentioned above, the following are preferably used as the solid catalyst components used in the present invention.

f tough i21 L'-'l; t, general formula T i (OR
) 4-, Xn (here, R1 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, and n represents a number of O≦n≦4) Examples include titanium compounds represented by Specific examples include TiC4, ']'1Br4, T 1 (OC2Hs
) Cta, Ti (OC2R5) 2C4, Ti (o
c2Hs )3CL, Ti (0-i C3H,)C
43, T i (0-nC4He) Cl3, T t
(OHC4He) 2Ct2,Ti (OC2H5
) Br3, T I (OC2R5) (OC4Ho)
2 C4,TI (0-nC4H0)3C6,Tt (
OC6H6) C43, Ti(0-ic4H6) 2
C42,Ti (OC6Hll) C2s,Ti(Q
Cs HI3 ) C23, Ti (OC2Hs)4, T
t (0-n C3”?) 4, Ti (0-nC
4H,)4, Ti (0-1C4H0),, Ti (o
-nc6HI3)4,Ti (0-rlc8E(17)
, 1, Ti(OCH2CH(C2H5)C4H9)4, etc.

Alternatively, a molecular compound obtained by reacting TiX,' (where X' represents a halogen) with an electron donor described later may be used.

Specific examples include TiC64・CH3COC2H5, T
lC6411CH3CO2C2H5, T i C10・
C, II (, NO2, TiCt4・CH3C0CL,
TiC4, aC6F (5COC4, TiC44-Cs
R5CO2C2R5, TiCt, ・CjCOC,,R
5, TiCt4.C4H, O, etc.

Examples of the magnesium source include magnesium compounds such as magnesium halide, dialkoxymagnesium, alkoxymagnesilahalide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate.

As a halogen source, 710 gen atoms contained in the titanium compound and/or magnesium compound mentioned above are sufficient, and among the halogens, chlorine is particularly preferable.

When producing the solid catalyst component used in the present invention, an electron donor can be added and used.

Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides and acid anhydrides; ammonia, amine,
Examples include nitrogen-containing electron donors such as nitrile and incyanate.

More specifically, those having 1 to 1 carbon atoms, such as methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc.
Alcohols of 8; phenols with alkyl bases such as phenol, cresol, xylenol, ethylphenol, flobylphenol, cumylphenol, nonylphenol, naphthol, etc., phenols with prime numbers 6 to 25; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones having 3 to 15 carbon atoms such as , acetophenone and benzophenone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and nathaldehyde; methyl formate, methyl acetate, ethyl acetate, Vinyl acetate, propyl acetate, octyl acetate,
Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate , butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, x-f ethyl benzoate, methyl anisate, ethyl anisate, ethoxy Ethyl benzoate, diethyl phthalate, dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, α
- Organic acid esters having 2 to 20 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; Inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane; acetyl chloride, benzoyl chloride, toluic acid chloride,
Acid hydrides having 2 to 15 carbon atoms, such as anisyl chloride, phthaloyl chloride, and isophthaloyl chloride: 54 acids having 2 to 15 carbon atoms, such as methyl ether, ethyl ether, isopropyl nityl, butyl ether, aluminum ether, tetrahydrofuran, anisole, and diphenyl ether. 2
0 ethers; acetic acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine ; Nitriles such as acetonitrile, benzonitrile, and tolnitrile; and the like. Two or more types of these electron donors can be used.

The solid catalyst component used in the present invention is produced using the above-mentioned essential components and, if necessary, the above-mentioned electron donor, but in addition to these, it is also possible to use other components such as silicon, aluminum, and boron. It is also possible for the solid catalyst component to remain in the solid catalyst component.

Examples of methods for producing the solid component containing titanium, magnesium and halogen as essential components used in the present invention include the following methods.

(a) A method in which a magnesium halide, an electron donor, and a titanium-containing compound are co-pulverized and treated with a specific solvent.

(b) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and then brought into contact with a magnesium halide, an electron donor, and a titanium/halogen-containing compound.

(c) A method of contacting an electron donor, a titanium...halogen compound, and/or a silicon halogen compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound.

B) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound.

The content of each component in the solid component produced as described above may be arbitrary as long as the effects of the present invention are observed, but generally it is preferably within the following range. Titanium content is 0.1-20% by weight, magnesium content is
1-20 weight percent, including halokene, to-75
The content of the electron donor is from o, i to 30 weight percent, and it is also possible to contain other components such as silicon in a total weight percent of 1 to 20 weight percent.

A small amount of olefin is prepolymerized to the thus obtained solid component containing titanium, magnesium, and halogen as essential components. Although there are no particular restrictions on the conditions for the small amount of olefin polymerization, the following conditions are generally preferred. The polymerization temperature is 0 to 80°C, preferably 10 to 60°C. The amount of polymerization is 0.001 to 5 per gram of the solid component.
It is preferred to polymerize 0 grams of olefin, more preferably 1 to 10 grams of olefin.

As the organoaluminum component used in this prepolymerization, commonly known components can be used.

As a specific example, At(C2H5)3, ノS, t(1s
oc4He)s, At(CaHts)a, At(Ca
H17) s, At(C,.H2□)8, ht (C2
r(S)2CA, At(isOc4H9)2C2,A
t(C2H,)2H, At(iso C41-I,)2
H, AtfczHs)2(OCqHs), etc.

Among these, At(CzHs)3, At(
is.

C, Ho)3. Further, a combination of trialkylaluminum and alkyl aluminum halide, a combination of trialkylaluminum, alkyl aluminum halide, and alkyl aluminum ethoxide, etc. are also effective.

To give a specific example, At(C2H5)3 and At(C,,H
5) Combination of 2Ct, At(iso C4H9)3 and At
(iso C4Hg)2C1-, At(C2Hs
)3 and At(C2H5), 5C4,5 combination, At
(C2Hs) 3 and ht (C2H5)2Ct and At
(C2H6)2(OC2H5) may be used in combination.

The amount of the organoaluminum component used during prepolymerization is 1 to 20, preferably 2 to 10, in terms of ht/Ti (mole ratio), based on the titanium component in the solid component. Also the third
Electron donors such as the same alcohols, esters, ketones, etc. as mentioned above can also be added as components.

Examples of olefins specifically used in the prepolymerization include ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-pentene-1. It is also possible to coexist hydrogen during prepolymerization.

The catalyst component for olefin polymerization obtained as described above is stored in an inert solvent.

The inert solvent used here does not react with the catalyst component for olefin polymerization, and is one from which impurities such as water and oxygen contained in the solvent have been thoroughly removed. Specific examples include aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, and the like. For example, pentane, isopentane, hexane, heptane, octane, decane,
Benzene, toluene, cyclohexane, n-butyl chloride, n-butyl bromide, octyl chloride, chlorobenzene, 0
-chlorotoluene, 1,2-dichloroethane, carbon tetrachloride, etc. Among these, aliphatic hydrocarbons are preferred.

The storage conditions in the present invention may be arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferred.

The catalyst concentration in the solvent may be from 1 to 1000 grams/liter solvent, preferably from 10 to 500 grams/liter solvent.

The atmosphere at that time is preferably an inert gas such as nitrogen or argon, or hydrogen. As for storage time,
It is preferably about 1 day to 1 year, more preferably about 5 days to 6 months. Storage temperature: 0 to 100
The temperature may be within the temperature range of 10 to 50 °C, preferably 10 to 50 °C.

Furthermore, it is also possible to store the product in the presence of an organoaluminum compound. As the organoaluminum compound at that time, it is possible to use any organoaluminum compound, but as a specific example, general formula R3-nAt
X- or Rj-mAz (of))m (where Ro, R
o is a hydrocarbon residue having 1 to 20 carbon atoms or hydrogen, which may be the same or different; Ro is a hydrocarbon residue having 1 to 20 carbon atoms;
≦n (a number of 2,0≦m≦1).

Specifically, the same organoaluminum as used as a cocatalyst described below can be used (details will be described later). The amount added is 0.01 to 1 in molar ratio to the titanium component in the catalyst.
0. Preferably it is within the range of 0.1 to 1.0.

The olefin polymerization catalyst component stored as described above can be used in olefin polymerization in combination with a known organometallic compound as a cocatalyst.

Any of the organometallic compounds of metals from Groups 1 to 2 of the periodic table, which are known as cocatalysts, can be used.

Particularly preferred are organic aluminum compounds.

Specific examples of organoaluminum compounds include the general formula Rj
, AtX- or R? '-mAt(OR force m (where Ro, Ro is a hydrocarbon residue with about 1 to 20 carbon atoms or hydrogen, which may be the same or different, Ro is a hydrocarbon residue with about 1 to 20 carbon atoms, X is a halogen, and n and m are each represented by 0≦n (a number satisfying 2, 0≦m≦1).

Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl Alkylaluminum halides such as aluminum sesquichloride, ethylaluminum dichloride, dialkylaluminum nohydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, diethylaluminium phenoxide, etc. etc. can be mentioned.

In addition to these organoaluminum compounds (A) to 0J, other organometallic compounds such as R3-aAt(OR0)a(1
≦a≦3, and Ro and Ro are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different.) Alkylaluminum alkoxides can also be used together. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminium ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminium chloride, Can be used in combination with

The amount of these organometallic compounds to be used is not particularly limited, but the weight ratio is 0.5 to 1 with respect to the solid catalyst component of the present invention.
It is preferably within the range of 000.

In order to improve the stereoregularity of olefin polymers having 3 or more carbon atoms, it is effective to add and coexist known electron-donating compounds such as ethers, esters, amines, and silane compounds during polymerization. The amount of the electron-donating compound used for this purpose is o, o o t to 2 mol, preferably 0.01 to 1 mol, per 1 mol of the organoaluminum compound.
It is a mole.

The olefin polymerized using the preserved catalyst in the method of the present invention has the general formula R-CH=CH2 (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms and has a branched group). ). in particular,
There are olefins such as ethylene, propylene, butene-1, pentene-1, and hexene-1,4-methylpentene-1.

Preferred are ethylene and propylene.

In the case of these polymerizations, copolymerizations can be carried out with up to 50xL weight percent, preferably 2ON weight percent, based on ethylene, of the above-mentioned olefins, e.g. Copolymerization can be carried out. Copolymerization of other copolymerizable monomers (eg vinyl acetate, diolefins) can also be carried out.

This polymerization is carried out by a method such as liquid-phase solventless polymerization, solution polymerization, or gas-phase polymerization, which does not substantially use a solvent, in addition to usual slurry polymerization. It is also applicable to continuous polymerization, batch polymerization, and even 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. 1 rationality is from room temperature to about 200°C, preferably from 50°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at that time. Experimental Example 1 (Production of solid component) Sufficient 40 stainless steel balls of 12 m9 were filled in a 0.4 liter ball mill that was dried and purged with nitrogen, and was filled with M'/Cl2k 20 ? , 15.5 milliliters of diheptyl phthalate was introduced, and 48 milliliters of diheptyl phthalate was
Time crushed. After the pulverization was completed, the mixed pulverized composition was taken out from the mill in a dry box. Subsequently, a total of 8.8 grams of the pulverized composition was introduced into a flask that had been sufficiently purged with nitrogen.
Furthermore, 25 ml of n-hebutane and TLC1425
Milliliter was introduced and the reaction was carried out at 100°C for 3 hours.

After the reaction was completed, it was thoroughly washed with n-hebutane. When a part of the obtained solid component was taken out and analyzed for composition, it was found that T
1 content was 3.01% by weight, and the content of diheptyl heptatalate was 20.7% by weight.

(Small amount polymerization of olefin) In a 1.5 liter stainless steel stirring tank with stirring and temperature control length fit, 500 milliliters of sufficiently dehydrated and deoxidized n-hebutane, 4.2 grams of triethylaluminum, 20 grams of each of the above solid components were introduced. The temperature inside the stirring tank was set at 20° C., propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes.

After the polymerization was completed, it was thoroughly washed with n-hebutane. When a portion was taken out and the amount of propylene polymerized was examined, it was found to be 0.89 grams of propylene per gram of solid component.

(Storage of Prepolymerized Catalyst Component) The prepolymerized catalyst synthesized above was placed in a nitrogen-substituted flask and stored in 100 grams of prepolymerized catalyst/liter of n-hebutane at 0 degrees and 25° C. for one week.

(Polymerization of propylene) In a 1.5 liter stainless steel autoclave equipped with a stirring and temperature control device, 500 milliliters of thoroughly dehydrated and deoxygenated n-hegetane were added, 125 milligrams of triethylaluminum, and diphenyldimethoxysilane i 26. 8 milligrams, and a total of 15 milligrams of the catalyst components synthesized above were introduced. Then,
60 ml of H2'i was introduced, and the temperature and pressure were increased to a polymerization pressure of 5 kp/cm G.

Polymerization was carried out at a polymerization temperature of 75° C. and a polymerization time of 22 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried.

151.7 g of polymer was obtained. 1.4 g of polymer was obtained from one filtrate. From the boiling hebutane extraction test, all products 1. I (hereinafter referred to as T-I).

) was 97.7% by weight.

MFR=3.9 ylx o min, polymer bulk specific gravity=0
．． It was 372/head.

Comparative Example 1 Without storing the prepolymerized catalyst synthesized in Example 1,
Immediately after the synthesis, polymerization was carried out under exactly the same conditions as in Example 1. 136.2 grams of polymer were obtained, M F R=
4.8 rpm/10 minutes, T-1, I = 97° 1% by weight, polymer bulk specific gravity = 0.37P/■.

Examples 2 to 3 Polymerization was carried out under exactly the same conditions as in Example 1, except that the storage conditions for the prepolymerized catalyst synthesized in Example 1 were changed as shown in Table 1. The results are shown on the table.

Comparative Example 2 The prepolymerized catalyst synthesized in Example 1 was dried to substantially eliminate the solvent in the catalyst and stored for 7 days.

Table 1 shows the polymerization results of the catalyst.

(Left below) Example 4 (Production of solid component) 100 ml of dehydrated and deoxidized it, n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then My
Cl, 0.2 mol, T 1 (0-n Ca H,)
4 was introduced in an amount of 0.4 mol, and the mixture was reacted at 95° C. for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 24 mIJ IJ liter of methylhydropolysiloxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane.

50 milliliters of n-hebutane purified in the same manner as described above was introduced into a flask which had been sufficiently purged with nitrogen by adding nitrogen, and 0.06 mol of the solid component synthesized above was introduced in terms of M1 atom. Then add 5I (J) to 25 ml of n-hebutane.
1 mol of O was mixed and introduced into the flask at 30°C for 30 minutes, and reacted at 70°C for 1 hour. After the reaction was completed, it was washed with n-hebutane. Next, 7 mol of diethyl 7-talate was mixed with 25 ml of n-hebutane.
The mixture was introduced into the flask at 0°C for 30 minutes, and reacted at 70°C for 1 hour. After the reaction was completed, it was washed with n-hebutane. Next, 450 ml of Ti (J) was introduced and reacted at 100° C. for 3 hours. After the reaction was completed, the mixture was thoroughly washed with n-hebutane. The Ti content was 2.561%.

(Small amount polymerization of olefin) In a stainless steel stirring tank purified in the same manner as in Example 1, n
500 ml of hebutane, 1.2 g of triethylaluminum and 10 g of the above solid components were each introduced. The temperature inside the tank was set at 25°C, propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the polymerization was completed, it was thoroughly washed with n-hebutane. When a portion was taken out and the amount of propylene polymerized was examined, it was found that 1 gram of solid component was 0.63 grams of propylene.

(Storage of Prepolymerized Catalyst Component) The prepolymerized catalyst synthesized above was placed in a flask in which the atmosphere was replaced with nitrogen, and the concentration was adjusted to 125 g of prepolymerized catalyst/liter n-hebutane.

Next, triisobutylaluminum was added at a molar ratio of 0.25 to the titanium component in the prepolymerized catalyst, stirred at 20° C. for 2 hours, and then stored. The polymerization results of the catalyst are shown in Table 2.

Claims (2)

[Claims] (1) A method for preserving an olefin polymerization catalyst component, which comprises storing in an inert solvent an olefin polymerization catalyst component obtained by prepolymerizing a small amount of olefin to a solid component containing titanium, magnesium, and halogen as essential components. (2) The method according to claim 1, wherein the inert solvent contains 0.01 to 10% by weight of organic aluminum.