JPS58117206A - Production of catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a high-activity catalytic component for producing stereoregular olefin polymers, by mixing a magnesium halide with a specified organic acid ester, an alkoxy compound of titanium or born, and a halide of titanium. CONSTITUTION:The purpose titanium-containing solid catalytic component is obtained by mixing a magnesium halide (e.g., magnesium chloride) with an alpha- branched carboxylic acid ester of formulaI(wherein R<1> is H or a 1-12C hydrocarbyl and R<2>-R<4> are 1-12C hydrocarbyls), e.g., isobutyrate ester, a titanium or boron compound of formula II (wherein M is titanium or boron, R is a 1- 20C hydrocarbyl, X is a halogen, 1<=m<=n and n is the valence of M) and a titanium halide (e.g., titanium tetrachloride). This catalytic component is combined with an organoaluminum compound and then used as a catalyst for alpha- olefin polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION [11 Background of the Invention The present invention relates to a method for producing a titanium-containing solid catalyst component for olefin polymerization. More specifically, the present invention includes:
The present invention relates to a method for producing a so-called carrier-type titanium-containing solid catalyst component having a high degree of activity for producing an α-olefin polymer having stereoregularity. The carrier-type titanium-containing solid catalyst component according to the present invention is further used in combination with an organoaluminium compound as a catalyst for polymerization of α-olefins.

It is well known that a magnesium compound is included in the transition metal catalyst component of the Ziegler type catalyst in order to significantly increase the activity of the olefin polymerization catalyst (! #public i1839-1
No. 2105, see Japanese Patent Publication No. 47-41676].

However, when α-olefins such as propylene are polymerized using catalysts produced by these methods, although the bulk yield is high, the stereoregularity of the resulting polymer is significantly low.
It is also widely known to add various electron-donating compounds to catalyst systems with the aim of improving the stereoregularity of polymers (J, Polym@r 5cien
ce, Polym@r L@tters.

3, 855 (1965)).

In recent years, a large number of catalyst production methods related to these have been proposed, and in particular, it has been proposed to use compounds such as esters, amines, ketones, and ethers with respect to electron-donating compounds. Among these compounds, esters and 4IK aromatic carboxylic acid esters have been shown to have a significantly superior effect in obtaining stereoregular polymers (% 126590/1986, JP 53/19892). -25
No. 80, JP-A-55-104303, JP-A-56-8
11 publications). That is, these publications specify that aromatic carboxylic acid esters are particularly preferred as electron-donating compounds, and in many of the disclosed examples, aromatic carboxylic acids are mainly used. Therefore, it appears that the use of organic acid esters other than aromatic carboxylic acids, such as fatty acid esters such as acetic acid esters, generally results in a decrease in catalytic performance.

Furthermore, in the production of titanium-supported catalyst components, it has been proposed to improve the catalyst performance by adding certain components in addition to the electron-donating compounds such as the esters mentioned above. .

By the way, the inventors of the present invention have filed an earlier patent application (%
No. 07273), a catalyst was prepared using an organic acid ester having a specific molecular structure. 41i, it is possible to obtain a catalyst component that exhibits better catalytic activity than when using generally well-known aromatic carboxylic acid esters in which a carboxylate group is bonded to an aromatic ring. . The present inventors have discovered that by adding a specific component in addition to the organic acid ester having the above specific structure, the titanium-containing solid is significantly superior to the catalyst component disclosed in the patent application. It was discovered that a catalyst component could be obtained, and the present invention was completed.

Furthermore, by introducing an organic acid ester into the titanium-containing solid catalyst component, it is possible to improve the catalytic activity and the stereoregularity of the produced polymer, but the produced polymer does not easily decompose the organic acid ester. Although it has the disadvantage of having a possible odor, this problem is also solved by the present invention.

l] Summary of the Invention The purpose of the present invention is to provide a method for producing a carrier-type titanium-containing solid catalyst component having a high degree of activity for producing an α-olefin polymer having stereoregularity. Components (A), (B), (C) and component (D
), a carrier-type titanium-containing solid catalyst component is obtained.

Component (A) Magnesium halide component (B) Organic acid esterification. However, this organic acid ester is an ester of α-position branched carboxylic acid represented by the following formula.

2 ■ R'-C-COOR' A. (where R1 is a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, and R-R each represents a hydrocarbon residue having 1 to 12 carbon atoms) component ( C) General formula M(OR)mXn-m
(M is titanium or boron atom, R has 1 to 2 carbon atoms
o is a hydrocarbon residue, X is a halogen, m and n are each 1
≦m≦n, and n is an integer satisfying the condition that n is equal to the valence number of M. When an organic acid ester having a specific molecular structure (a-position branched structure) is used as an electron-donating compound, only alkoxy or allyloxy compounds of titanium or boron exhibit excellent effects.
JP-A-51-20297, JP-A-52-8748
No. 9, JP-A-52-100596 and JP-A-55-82103, etc. Polysiloxanes, alkoxyaluminum compounds, which are recognized to be effective in supported catalyst component systems containing aromatic carboxylic acid esters, It is unexpected that when compounds such as alkoxysilicon compounds and siloxyaluminum compounds are used in place of component (C) of the present invention, their effects do not appear at all or their performance deteriorates. and
This fact suggests the specificity of each catalyst component based on the specificity of the organic acid ester of the present invention.

In this way, in the present invention, the catalyst performance is not improved in all cases by introducing an additive component that has conventionally been known to be used in combination with an aromatic carboxylic acid ester; In the case of components, it is even observed that the catalytic performance deteriorates. A significantly superior effect is exhibited only when the titanium or boron compound component (0) specified in the present invention is introduced.The difference in such effects is due to the organic acid ester component (0) used in the present invention.
One reason is thought to be that B) has different properties compared to conventionally used esters such as aromatic carboxylic acid esters.

Therefore, the present invention provides a novel bonding mode between an organic acid ester component (B) having a specific molecular structure different from conventionally used aromatic carboxylic acid esters and a specific donor component (C). It has a significant effect on the performance of the catalyst, and its bonding mode can be considered as one of the constituent elements of the present invention.

In addition, the organic acid ester having a branched structure at the α-position used in the present invention is more effective than the organic aluminum used in combination with component i in this invention, compared to an organic acid ester that does not have a branched structure at the α-position. For example, the fact that it has the specificity of forming a thermally or temporally stable complex with triethylaluminum means that organic acid esters with an α-branched structure are different from conventionally used aromatic carboxylic acid esters. supports the fact that they are different.

Furthermore, in the present invention, in addition to the organic acid ester component (B) having a specific structure, a specific titanium or boron compound component (C) is used. Since the ester content is at least good compared to the solid catalyst component, the above-mentioned problem of odor of the produced polymer is also solved.

[llll] Detailed description of the invention The titanium-containing solid catalyst component of the present invention is component (A).

It is produced by bringing (B), (C) and component (D) into contact.

1) Component (A) Component (A) is a magnesium halide. NoSc1
Preferably, the magnesium genide is anhydrous.

Fluorine, chlorine, and bromine can be used as the chemical, and among these, chlorine is preferred.

2) Component (B) Component (B) is an ester of a-position branched carboxylic acid represented by the following formula.

2 3 (Here, R1 is a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, and B2-R4 each represents a hydrocarbon residue having 1 to 12 carbon atoms.) As is clear from this formula, the carboxylate group The carbon atom to which is bonded, that is, the carbon atom at the α-position, is an aliphatic atom having a branch and is a saturated carbon atom. Therefore, the organic acid ester represented by this formula does not include aromatic carboxylic acids, especially benzoic acid esters, and α,β-unsaturated carboxylic acid esters, especially methacrylic acid esters, which have been proposed as preferred in the past.

R1-R4 are each defined as described above, but if they are hydrocarbon residues, they may be aliphatic, fatty acid residues (including fatty acid residues), saturated and It may be unsaturated.

Specific examples of such organic acid esters include ethyl isobutyrate, ethyl isobutyrate, isoglobil isobutyrate, butyl isobutyrate, phenyl isobutyrate, ethyl α-ethylbutyrate, and ethyl α-ethylbutyrate. , α-ethylvaleric acid ethyl, α-ethylcaproate ethyl, α-phenylbutyrate ethyl, pivalate ethyl, and the like. Among these, ethyl isobutyrate, ethyl -monophenyl@acid, etc. are preferred.

3) Component (C) Component (C) is a titanium or boron alkoxy or allyloxic compound represented by the following general formula.

M (OR) mX rho m (M is a titanium or boron atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, Specific examples of titanium compounds include tetraethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, tetrahexyl titanate, tetra 2-ethylhexyl titanate, and tetraoctadecyl. titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate and mixed alkyl orthoesters thereof, i710 Genated alkoxides include triptoxy titanium chloride, triphenoxy titanium chloride, dibutoxy titanium dichloride, butoxy titanium chloride , triethoxytitanium fluoride, ethoxytitanium trifluoride, and the like. Among these, ortho titanate, especially tetrabutoxy titanate,
Tetraphenoxy titanate is preferred.

In addition, as a specific example of a boron compound, B(OCR,)
3, B (OC2H5) 3, B (QC, H7) 3,
n(0-isoc3H7)3,B (0-C4H,)
3, B(0-1fiOc, H,)8, B(0(cu2)
,7C)13']3,B(QC6)15)3,B(Q
C6f(5cH8)3,B (0-CH2C6H5)
3,B (QC,H6) □Cl5B(OC6H,G(
3) 2C1.

B(OC6H5)C1, etc. Among these compounds, B(QC2H,)3, B(QC,H,)3,
Triacollade compounds such as B(QC, H4CH, 33) are preferred.

Of course, the above titanium compounds and boron compounds can also be used in combination.

Seasonal ingredients (D) Component - is a halogen compound of titanium.

Suitable titanium halogen compounds include trivalent and tetravalent titanium halogen compounds, particularly preferably tetravalent titanium halogen compounds. Chlorine, bromine, and iodine can be used as the gas, but chlorine is preferred.

Preferred titanium halogen compounds have the general formula rt (OR
) nc14-H (R is a hydrocarbon residue of cm to c6) where H=Q or 1. Specific examples include titanium tetrachloride and titanium trichlorobutoxy.

5) Auxiliary Components The titanium-containing solid catalyst component of the present invention has four components (4) to (4) as essential components, but may additionally contain auxiliary components as the case may be.

Examples of auxiliary ingredients are aluminum chloride, phosphorus pentachloride,
Examples include inorganic halides such as silicon tetrachloride, and inorganic oxides such as silica, alumina, titania, and magnesia.

6) Amount ratio The component ratio of the four components (A) to (tin) is arbitrary and not critical as long as the effects of the present invention are recognized.

Generally, the molar ratio of (B)/(A) is used in a ratio of 0.05 to 1, preferably 0.1 to 0.5. Component (C) has a molar ratio of (C)/container of 0
．． It is used in a ratio of 0.005 to 1, preferably 0.005 to 1.
It is used in a ratio of 0.01 to 0.5. Component (D) can be used in a wider range of proportions, but generally the amount of titanium atoms contained in the titanium-containing solid catalyst component produced by various methods is 0.5 to 15% by weight, preferably 0.5% by weight. ~1of
It is preferable to set Kv14 so that it is within the range of t%.

7) Cleavage of the titanium-containing solid catalyst component The titanium-containing solid catalyst component of the present invention comprises components (A) to
It is obtained by subjecting (b) to a contact treatment and can be obtained by various preparation methods. Some specific preparation methods are listed below.

1) Component (A) and (Q) are mixed and pulverized, and then component (B) is mixed and pulverized.
) is added and pulverization is continued, and the resulting mixture and component (D) are brought into contact with each other in a liquid phase.

m) After mixing and pulverizing components (A) and (B), the resulting mixture is contacted with components (C) and (b) in a four-component liquid phase.

ll1) After mixing and pulverizing component (Q), the resulting mixture and components (B) and (D) are brought into contact with each other in a four-component liquid phase.

iV) Components (A), (B), (C) and (parrot) are simultaneously mixed and ground.

■) Components (A), (B), (C) and (D) are simultaneously mixed and pulverized, and the resulting mixed pulverized product is mixed with a soluble substance in titanium % cf genide in the liquid phase or in an inert solvent. Bamboo extraction process.

Vl) Components (B) and (C) are dissolved in a dissolving agent to prepare a homogeneous solution, and titanium is added to this solution.
A 0-gen compound or a halogenating agent is added to precipitate a solid, and in some cases, the precipitated solid is treated again with a titanium halide in a liquid phase or an inert solvent.

8) Polymerization of olefins The titanium-containing solid catalyst component of the present invention can be used in the polymerization of olefins by combining it with an organoaluminium compound. The organoaluminum compound is a compound represented by the general formula AlRnX3-n (where R is a hydrocarbon residue having 1 to 12 carbon atoms, X is) rogene, and n is 0 (indicating n≦3).

Specifically, for example, triethylaluminum,)
Thor n-propyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, )! j, 7.
Examples include tt-hexylaluminum, triisohexylaluminum, diethylaluminum monochloride, diisobutylmonochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride. Of course, two or more kinds of these aluminum compounds can also be used.

The olefins used for polymerization include ethylene, propylene, 1-butene, l-hex*y, 4-1 thylpentene-
There are at least one type of polymer, and these can be used not only for homopolymerization, but also for random copolymerization and block copolymerization with each other. Regarding copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes, polar unsaturated compounds such as acrylates and acrylates, etc. can also be used as copolymerization components.

When carrying out the polymerization reaction of α-olefins having 3 or more carbon atoms, the titanium-containing solid catalyst component according to the present invention may contain α-olefins specified in the present invention in order to further improve the stereoregularity of the resulting polymer. It is preferable to further add an electron-donating compound in addition to the position-branched carboxylic acid ester. Such electron-donating compounds have been proposed for use in Ziegler polymerization catalysts, and may be any electron-donating compounds that have an effect on stereoregularity. These usually contain at least one atom selected from 0, NSS and P atoms in the molecule. Examples of such compounds include ethers, esters, ketones, amines, phosphorus compounds, etc. Among these, carboxylic acid esters are preferred, and aromatic carboxylic acid esters, specifically methyl benzoate, benzoic acid Preference is given to using ether, methyl toluate, ethyl toluate, ethyl anisate, ethyl salicylate and the like.

The ratio of the titanium-containing diagonal catalyst component to the organoaluminum compound used can vary over a wide range, but is generally 1 to 600, preferably 10 to 400 (molar ratio) per titanium atom contained in the solid catalyst component. It is possible to use organoaluminum compounds in the sleep.

The electron donating compound used for the purpose of improving the stereoregularity of α-olefin polymerization is usually used at a ratio of 0.01 to 2 mol, preferably 0.1 to 1 mol, per 1 mol of the organoaluminum compound. used in

The order of contacting or mixing the titanium-containing solid catalyst component, the organoaluminum compound, and the electron-donating compound is arbitrary, but the electron-donating compound is already present when the titanium component and the organoaluonium compound come into contact with each other. It is preferable.

Except that the catalyst used is as above.
The olefin polymerization method using the titanium-containing solid catalyst component of the present invention is essentially the same as the conventional olefin polymerization method using a so-called Ziegler type catalyst. Polymerization methods include the so-called slurry electrolysis method using an inert hydrocarbon such as hexane or hegetane as a solvent, the liquid phase polymerization method using a liquefied polymer as a solvent, and the gas-phase polymerization method where the monomer exists as a gas phase. is possible. The polymerization temperature is generally 20
The polymerization pressure is from atmospheric pressure to about 100 atm, preferably about 50 atm. The molecular weight of the polymer is mainly controlled by a method using hydrogen or the like.

9) Examples Hereinafter, the present invention will be specifically explained with reference to Examples.

Example-1 l) Production of titanium-containing solid catalyst component In an argon atmosphere, 20 g of anhydrous MgC12 (magnesium chloride) and B(OEt)3 (triethyl borate) 3.19 (B(OEt)3/Mgc12=
0.1 (The molar ratio is filled in a vibrating mill pot with an internal volume of 1 liter. Approximately 800 cc (apparent volume) of stainless steel balls with a diameter of 2511 m are placed in the pot.), 16
Time grinding, ethyl α-phenylbutyrate 12.1.9 (
α-phenylbutyric acid ether/MgC12=o, 3 (molar ratio) was added in equal 2-millimeter portions for 6 hours and 1 ml, respectively.
The mixing and pulverizing process was continued for 6 hours to obtain a pulverized solid composition.

Approximately 6 g of the obtained crushed solid was divided into 2001 flasks, and 50 rILl of 1,2-dichloroethane and TiC as a titanium halide compound were added thereto as a solvent.
14 (titanium tetrachloride) 50- was added, contact treatment was performed at 80° C. for 2 hours, and after removing the superposition liquid, contact treatment with TiC14 was performed again under the same conditions. After this treatment, the solids were washed by decantation (n-hebutane 100%
6 times) to obtain the desired titanium-containing solid catalyst component slurry. When a part of this slurry was sampled and analyzed for n-hbutane by evaporation drying, it was found that the solid contained 3.91 weight of titanium, and 7.2 weight of titanium.
It was found that 0 weight of ethyl α-phenylbutyrate was contained.

2) Polymerization-1 Dry and degassed heptane 500-1 TIBA (
) 1821Q ('rIBA
/'rt = 110 (Molar dead eye, EASC (ethyl aluminum sesquichloride) 114 WIg (E
ASC/l'1 = 55 (molar ratio)), PMT(p-)methyl ruylate)44~()'MT/Tl = 35 (
molar ratio)) and from 0.4 to 0.4 in terms of T1 atom from the solid catalyst component slurry were introduced in this order under a propylene atmosphere, and 100 d of hydrogen was added to initiate polymerization. Polymerization was carried out at a propylene pressure of 9/cdG/7/2 hours. After the polymerization was completed, the remaining monomer was purged, the polymer slurry was separated, and the amount of each produced polymer was determined by drying the powdered polymer and concentrating the liquid f.

The stereoregularity of this powder polymer (hereinafter referred to as product II) was determined by a boiling hebutane extraction test. In addition, the total II (ratio of the amount of boiling heptan-insoluble polymer to the total amount of polymer produced) is: total II = amount of powdered polymer x Illi product II/'
(Determined using the relational expression: powder polymer + r-liquid concentrated polymer 11. These results are shown in Table IK.

Polymerization-2 (TIBA/Ti=130 molar ratio, EASC/Ti=
50 molar ratio, PMT/Ti = 33 molar ratio) Table 1 shows the results of propylene polymerization similar to Polymerization-1 under the following conditions.
It is written in

Table-1 Polymerization results of Example-1 Appetizer Attack generation rate = r liquid concentrated polymer/all produced polymer cut o.

Examples 2 to 7 During the production of titanium-containing solid catalyst components, solid catalyst components were prepared under the same conditions and method as in Example 1, except that component (C) was replaced with various titanium or boron compounds.

However, as a solvent during contact treatment with TiCl4, 1
．． Toluene was used instead of 2-dichloroethane.

Propylene polymerization was carried out under the conditions of Polymerization-1.

The results are shown in Table-2.

Comparative Examples 1 to 5 Comparative examples will be described here, including JP-A-51-20297, JP-A-52-87489, and JP-A-52-10.
No. 0596, Japanese Patent Application Laid-open No. 55-82103, etc., when producing a solid catalyst component using an aromatic carboxylic acid ester as an organic acid ester by a method similar to the present invention, the effect of the added component is known. The polysiloxanes, alkoxyaluminum compounds, alkoxysilicone compounds, and siloxyaluminum compounds shown in Table 1 do not have the effect of component (C) of the present invention at all.

That is, in Comparative Example-1, a solid catalyst component was prepared under the same conditions and method as in Example-1 except that the component (0) of the present invention was not used, and Comparative Examples 2 to 5L were prepared in place of the component (C) of the present invention. All conditions are the same as in Example-1 except for using the above compound,
The solid catalyst component was prepared by the method.

Fi-3 shows the results of propylene polymerization using these solid catalyst components.

As is clear from Table 3, the introduction of these compounds:
In terms of the balance between the activity and stereoregularity of the solid catalyst component, the introduction effect is rarely recognized, and the performance may even be degraded. When a new specified organic acid ester is used as in the present invention, only the component (Q) of the present invention has the effect of its introduction (Comparative Example-1 and Examples 1 to 8).
reference).

Comparative Examples-6~''0 and Example-8 Here, 1) Specificity of α-position branched organic acid ester, U)
+ Even if the organic acid ester has an aromatic ring, the aromatic ring must have a substituent at the α-position and have a branched structure; and ■) The organic acid ester of the present invention generally has It is shown to be superior to the well-known nine aromatic carboxylic acid esters.

Comparative Examples 6-toe, 9 solid catalyst components were prepared under the same conditions and method as in Example-1 using the components of the present invention (without using odor and using other various esters), and Example-8 is B
(OE t ), /Mg C1! A titanium-containing solid catalyst component was produced under exactly the same conditions and method as in Example 1, except that B(OEt)3 was used in a molar ratio of =0-05 (molar ratio). The results of these proprene polymerizations are shown in Table 4.

Comparing Comparative Examples 1 and 6, Comparative Examples 7 to 9, etc., α
The specificity of the organic acid ester having a branched structure at the - position is clear, and Comparative Example-6 has an aromatic ring. l!
# This shows that even esters may have inferior performance depending on their molecular structure. Furthermore, comparing Example 8 and Comparative Example 10, the 4T organic acid ester of the present invention is superior to the aromatic carboxylic acid ester, which is generally recognized to be effective for seed-supported solid catalysts. is also clear.

Examples 9 to 12 In the production of titanium-containing solid catalyst components, tetrabutoxytitanium/MgC1, (molar content TiCl
The solid catalyst component was added to 1!4#! under the same conditions and method except that the number of times of contact treatment with 4 and the polymerization 1 conditions were changed.
Polymerization was performed. These results are shown in Table-5.

Example-9 was carried out in the same manner as in Example-3 except that the number of times of contact between the pulverized solid composition and TiC1 was changed to three times, and in Example-1O, tetrabutoxytitanium/MgCl2
All the same methods as in Example 3 except for changing the ratio,
And Example-11 is TiCl4 in Example-10.
The titanium-containing solid catalyst component was obtained in the same manner as in Example 10 except that the number of times of contact with was changed from 2 times to 3 times. In Example 12, propylene polymerization was carried out under the conditions of Polymerization-3 using the solid catalyst component of Example ELL-10.

Claims (1)

[Claims] The following components (A), (B)I (C) and component (D
1. A method for producing a titanium-containing solid catalyst component for olefin polymerization, the method comprising producing a titanium-containing solid catalyst component by contacting J. (A) C1'-ionized magnesium (B) organic acid ester. This organic acid ester is an ester of an α-position branched carboxylic acid represented by the following formula. 2 3 (Here, R1 is a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, and R2-R4 each represents a hydrocarbon residue having 1 to 12 carbon atoms.) (C) General formula M(OR)mXn-m (Ma titanium or boron atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, X is halogen, m and n are each l≦m≦n,
Moreover, a titanium or boron compound (DJ titanium halogen compound