JPS608004B2 - Catalyst for polyolefin production - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly active catalyst for stereoregular polymerization of olefins. In particular, the present invention provides propylene, butene-1, bentene-1
It is suitable for stereoregularly polymerizing olefins such as , 4-methylbentene-1, and 3-methylbutene-1, and for copolymerizing the above olefins with ethylene or other olefins. A stereoregular polymer can be obtained by contacting an olefin with a Ziegler-Natta catalyst system consisting of a transition metal compound of Groups W to WA of the Periodic Table of the Elements and an organometallic compound of Groups 1 to M of the Periodic Table of the Elements. In particular, titanium halides in combination with organoaluminum compounds such as triethylaluminum or diethylaluminum chloride are used industrially as catalysts for the production of stereoregular polyolefins. using this catalyst. When olefins such as pyrene are polymerized, the polymerization activity is unsatisfactory (the proportion of butane-insoluble polymers (i.e., stereoregular polymers is quite high), and the process of removing the catalyst residue from the resulting polymer. is necessary. recent years,
As highly active catalysts for ethylene polymerization, many catalyst systems comprising reaction products of inorganic or organic magnesium compounds and titanium or vanadium compounds, and organic aluminum compounds have been proposed. Although these catalyst systems exhibit remarkable activity for the polymerization of propylene, the proportion of stereoregular polymers in the total polymer is low, making them difficult to use in industry for the production of stereoregular polymers of olefins such as propylene. That is extremely difficult. (For example, JP-A-47-19342, JP-A-43-130
5pi No. 5) As these improvements, Special Publication No. 52-39431
No. 52-36153 and Japanese Unexamined Patent Publication No. 1698-1983
The method described in No. 8 has been proposed. These methods involve using a solid catalyst component obtained by co-pulverizing a tsuba compound of a titanium halide compound and an electron donor and anhydrous magnesium halide, and an addition reaction product of trialkyl aluminum and an electron donor. It is a catalyst system consisting of However, even with these methods, the proportion of stereoregular polymer in the produced polymer is still not sufficiently high, the polymer yield per solid catalyst component is insufficient, and the catalyst residue during polymerization is In particular, the high content of halogen causes problems such as corrosion of manufacturing process equipment and molding machines, and the physical properties of the product are not fully satisfactory. The present inventors should improve these points.
As a result of extensive studies, we found that organic magnesium components soluble in an inert hydrocarbon medium, or those obtained by reacting them with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or their derivatives, alcohols, and amines, were found. A component obtained by reacting a chlorosilane compound containing a Si bond with a component obtained by reacting with a component containing an alkyl group-containing magnesium compound, and reacting and/or pulverizing this solid with a titanium compound and a sulfur-containing enomoto ring carboxylic acid ester. , or a catalyst obtained by combining a solid treated with a tetravalent titanium compound with a sulfur- or oxygen-containing polycyclic carboxylic acid ester and an organometallic compound has extremely excellent performance as an olefin polymerization catalyst. Heading, we arrived at the present invention. That is, the present invention provides: [A]'1) (i), {a} general formula MQMg8RIPR
2q (wherein M is an element selected from aluminum, zinc, boron or beryllium, R1 and R2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, Q≧0, 8>0,
a hydrocarbon-soluble organomagnesium component represented by p, q>0, m is the valence of M, and has the relationship p+q=mQ+23, or 'a}

[b] A component obtained by reacting an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or their derivatives, or alcohols, thioalcohols, and amines, and (ii) General formula ratio S
A Si-day bond-containing chlorosilane compound represented by IC1bR4-(a+b) (wherein a and b are numbers larger than 0, a+b≦4, and R represents a hydrocarbon group having 1 to 20 carbon atoms) A solid formed by the reaction, {2) at least one C. A titanium compound containing a gen atom, a glue, a sulfur-containing heterocyclic carboxylic acid ester, a solid catalyst obtained by reacting and/or pulverizing the above [1], '2), and [3'], and [B] an organometallic compound. This is a catalyst for producing polyolefin, which is a component consisting of a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester, and is composed of [A] and [B]. The first feature of the present invention is that the catalyst efficiency per titanium metal and per catalyst solid component is extremely high. As is clear from the examples below, in the case of polymerization of propylene in liquid propylene, the catalyst efficiency is 330,000 evening-pp notar titanium component/hour, and 7,600 evening-pp/night-solid catalyst/hour or more. The second feature of the present invention is
In addition to the high activity described above, high stereoregularity can be obtained. The value of the present invention is 94.6%. The third feature of the present invention is that when hydrogen is used as a molecular weight regulator during polymer production, only a small amount of hydrogen is required. The fourth feature of the present invention is that there is little scale adhesion to the reactor and other parts during polymer production. The fifth feature of the present invention is that the particle size of the polymer is good, and large polymer particles with high density can be produced. The raw material components and reaction conditions used for preparing the catalyst of the present invention will be explained. '1' single-prong type MQMgPR1pR (Q, B, p in the formula
, q, M, R1, R2 have the above-mentioned meanings). This organomagnesium component is shown as a tsuba compound of organomagnesium, but R2Mg and these with other metals This includes all types of bodies with compounds. In the above formula, the hydrocarbon group represented by RI to R2 is
An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as methyl, ethyl, propyl,
Butyl, amyl, hexyl, decyl, cyclohexyl,
Examples include a phenyl group, and it is particularly preferable that RI is an alkyl group. As M, aluminum, zinc, boron, or beryllium atoms are preferable because they facilitate the formation of a hydrocarbon-soluble organomagnesium body. When used as a catalyst component in the present invention, an organomagnesium rust body or compound that is soluble in an inert hydrocarbon solvent is preferred. In the case of the above formula Q>0, this organomagnesium rust body has a ratio of magnesium to metal atom M of 8/Q' or 0.
．． 1 or more, preferably 0.5 or more, particularly preferably 1 to
It is 10. These organomagnesium compounds have the general formula RIMgQ, R Mg (RI has the above-mentioned meaning,
Q represents halogen) and the general formula MR2m, MR2m-, day (M, R2,
m is the above-mentioned meaning) in an inert hydrocarbon solvent such as hexane, heptanecyclohexane, benzene, toluene, etc. at room temperature to 150°C. Furthermore, MgX2, RIMgX and MR can also be expressed as MR Young, Day, or RIMgX, MgR Kei and R2nMXmm (where M, R1, and R2 are as described above, × represents halogen, and n is 0 to m). can be synthesized by reaction with Generally, organomagnesium compounds are insoluble in inert hydrocarbon media, but organomagnesium armor bodies are soluble when Q>0, and in the present invention, hydrocarbon-soluble rust bodies are preferred. Give results. As the organic magnesium component, when Q=0 in the above formula, that is, MgR1bR2q (in the formula, R1, R2
, p, and q have the above-mentioned meanings). In the above formula, R1 and R2 are assumed to be in any of the following three cases. {i} When at least one of R1 and R2 is a secondary to tertiary alkyl group having 4 to 6 carbon atoms. [〇- When RI and R2 are alkyl groups with different numbers of carbon atoms. (1) When at least one of RI and R2 is a hydrocarbon group having 6 or more carbon atoms. Preferably, R1 and R2 are in any of the following three cases. When R1 and R2 both have 4 to 6 carbon atoms, and at least one of them is a secondary to tertiary alkyl group. (2) When RI is an alkyl group having 2 to 3 carbon atoms and R2 is an alkyl group having 4 or more carbon atoms. If RI and R2 are both alkyl groups having 6 or more carbon atoms. These groups will be specifically shown below. In 'A] and (A'), the secondary or tertiary alkyl group having 4 to 6 carbon atoms is sec-C4day9
, tert-C4 ratio, one CH(C2 day 5)2, one C(C
2 days 5) (C melon) 2, 1 CH (CH3) (C4 days 9),
1CH (C2 day 5) (C3 day 7>, -C(CH3)2(
C3day7), monoC(CH3)(C2day5)2, etc. are used, and are preferably secondary alkyl groups, sec-C4
Day 7 is particularly preferred. (B'), carbon number 2-3
Examples of the alkyl group include ethyl and propyl,
Ethyl is particularly preferred. As the alkyl group having 4 or more carbon atoms, butyl, amyl,
Examples include hexyl and octyl, with butyl and hexyl being particularly preferred. In 1 and (c'), carbon number is 6
Examples of the above hydrocarbon groups include hexyl, octyl, decyl, phenyl groups, etc., with alkyl groups being preferred, and hexyl groups being particularly preferred. Examples of such organomagnesium compounds include (sec-C4)2
Mg, (rt-C4 melon)2Mg, n-C4&-Mg-
C2 戊, n-C4日91 Mg-sec-Mr. C4, n-C
4 days 91 Mg- to 91 C4 horses, n-C 6 days, 3 Mg 1 C
2 days 5, n-C 8 days, 7-1 Mg-C 2 days 5, (n-C6
Day. 3) 2Mg, (n -C8 days, 7) 2Mg, (n
-C, Niji 2, ) 2M history, etc. The electron donor to be reacted with the hydrocarbon-soluble organomagnesium component will be explained. For ethers of the general formula KORI, R and RI are aliphatic, aromatic and alicyclic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl, cyclohexyl. , phenyl, benzyl, and other hydrocarbon groups. Also for thioether RSRI, R and RI are aliphatic, aromatic and cycloaliphatic hydrocarbons, for example methyl, ethyl, propyl, butyl, amyl, hexyl,
Examples include hydrocarbon groups such as cyclohexyl and phenyl. For ketone RCORI, R and RI are aliphatic,
Aromatic and alicyclic hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl and the like may be mentioned, with dimethyl ketone, jetyl ketone and the like being particularly preferred. When it comes to aldehydes, aliphatic, aromatic and cycloaliphatic aldehydes are used. As the carboxylic acid or its derivative, a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid ester, a carboxylic acid halide, or a carboxylic acid amide can be used. Examples of carboxylic acids include formic acid, acetic acid, propiosic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid,
Examples include maleic acid, acrylic acid, benzoic acid, toluic acid, terephthalic acid, and the like. Examples of carponic acid anhydride include acetic anhydride,
Examples include propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, and the like.
Examples of carboxylic acid esters include methyl formate and ethyl formate, methyl acetate, ethyl, propyl, methyl propionate, ethyl, propyl, butyl, ethyl butyrate, ethyl valerate, and cap. Ethyl phosphate, ethyl n-hebutanoate, dibutyl oxalate, ethyl succinate, ethyl malonate, dibutyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl, propyl, butyl, tolyl Methyl, ethyl, propyl, butyl, amyl, p-ethylbenzoate, methyl and ethyl anisate, ethyl, propyl and butyl p-ethoxybenzoate, methyl and ethyl p-ethoxybenzoate. Carboxylic acid halides include acid chloride. Preferably, acetyl chloride,
Examples include propionyl chloride, butyryl chloride, succinyl chloride, penzoyl chloride, and tolyl chloride. Examples of the carboxylic acid amide include dimethylformamide, dimethylacetamide, dimethylpropionamide, and the like. Examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, phenol, cresol, etc. Lopyl alcohol, sec-butyl alcohol, upper
t-butyl alcohol, SeC-amyl alcohol, t
Secondary, tertiary or aromatic alcohols such as e-amyl alcohol, SeC-hexyl alcohol, phenol, o-, m-, p-cresol are preferred. Examples of thioalcohols include methyl mercaptan, ethyl mercaptan, propyl mercaptan, propyl mercaptan, Examples include butyl mercaptan, amyl mercaptan, hexyl mercaptan, phenyl mercaptan, etc., but secondary, tertiary or aromatic thioalcohols are preferred.As the amines, aliphatic,
Examples include alicyclic or aromatic amines, but secondary to tertiary amines such as trialkylamine, triphenylamine hepyridine, etc. give preferable results. Regarding the reaction between hydrocarbon-soluble organomagnesium components and electron donors The reaction is carried out in an inert reaction medium, such as aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane,
The reaction can be carried out in an alicyclic hydrocarbon such as methylcyclohexane or a mixed solvent thereof. Regarding the reaction order, there is a method in which the electron donor is added to the organomagnesium component (■), a method in which the organomagnesium component is added in the electron donor (■), and a method in which both are added at the same time (■).
) can be used. Regarding the reaction ratio between the hydrocarbon-soluble organomagnesium component and the electron donor, per 1 mol of the organomagnesium component, 1 mol or less of the electron donor,
Preferably it is 0.05 to 0.8 mol. Next, the general formula HasiC1bR4-(a+b) (wherein,
The Si-day bond-containing chlorosilane compound represented by (a, b, and R have the above-mentioned meanings) will be explained. The hydrocarbon group represented by R in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as "methyl, ethyl, propyl, butyl, amyl, hexyl, deJyl , cyclohexyl, phenyl, etc., preferably alkyl groups having 1 to 10 carbon atoms, and lower alkyl groups such as methyl, ethyl, and propyl are particularly preferred.The values of a and b are a, b>0, a ten b
S4, preferably 0<aS2. These compounds include HSiC13, HSiC12CH3,
HSiC12C 2 days 3, HSiC12n-C 3 days 7
, HSiC12i-C3 day 7 "HSiC12n-C4
Day 9, HSiC12C6 Day 5, HSiC12 (4-CI
-C6 day 4), HSiC12CH=CH2, HSiC1
2CH2C6& , HSiC12(1-C,oH
7), HSiC12CH2CH = CH2, ratio SICICH3, day 2SICIC2 day 5, HSiC1
(CH3)2, HSiCICH3 (i-C3 day 7), H
SiCICH3 (C6 ratio), HSiC1 (C2 day 5)2
, HSiC1 (C6day5)2, etc., and chlorosilane compounds consisting of these compounds and mixtures with compounds selected from these compounds are used, including trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, etc. Chlorosilane and the like are preferred, and trichlorosilane and monomethyldichlorosilane are particularly preferred. As is clear from the Examples and Comparative Examples described later, when a silicon compound containing no Si bond is used, favorable results cannot be obtained. The reaction between the organomagnesium component (i) and the chlorosilane compound (ii) will be described below. The reaction of the organomagnesium compound or organomagnesium complex with the chlorosilane compound can be carried out using an inert reaction medium, such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, or the like. The reaction can be carried out in an alicyclic hydrocarbon such as hexane or methylcyclohexane, an ether medium such as ether or tetrahydrofuran, or a mixed medium thereof. In terms of catalyst performance, aliphatic hydrocarbon media are preferred.
Although there is no particular restriction on the reaction temperature, it is preferably carried out at a temperature of 4,000 or higher in view of the progress of the reaction. Although there is no particular restriction on the reaction ratio of the two components, it is preferable to use o. The range is from ol to loo mol, particularly preferably from 0.1 mol to 10 mol. Regarding the reaction method, two types of components are introduced into the reaction zone at the same time (method 2), or the chlorosilane component is charged into the reaction zone in advance, and then the organomagnesium collar component is introduced into the reaction zone. Sh) A method of reacting (Method @), or a method of preparing the organomagnesium body component in advance and adding the chlorosilane component (Method Q)
However, the latter two are preferred, and method @ gives particularly favorable results. When the organomagnesium compound is insoluble, it is also possible to use a chlorosilane compound as a reaction agent in a heterogeneous treatment reaction in the reaction zone. In this case as well, the conditions described above are preferred regarding temperature, molar ratio, and reaction ratio. The composition and structure of the solid substance (corresponding to '1} above) obtained by the above reaction may vary depending on the type of starting material and reaction conditions, but from the composition analysis value, the stiffness of solid substance 1 is approximately 0.1 It is estimated to be a halogenated magnesium compound containing an alkyl group with ~2.5 mmol of Mg-C bonds. This solid substance has an extremely large specific surface area, and B
．． E.T. When measured by the method, it shows extremely high values in the range of 100 to 300. Compared to conventional magnesium halide solids, the solid material of the present invention is characterized in that it is an active magnesium-containing solid that has a very high surface area and contains an alkyl group with reducing power. Next, a tetravalent titanium compound containing at least one halogen atom {2
I will explain. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, ethoxytitanium trichloride,
Proboxy titanium trichloride, butoxy titanium trichloride, dibutoxy titanium dichloride, tributoxy titanium monochrome. A single or a mixture of titanium halides and alkoxy halides, such as lido, can be used. Preferred compounds are those containing three or more halogens, and titanium tetrachloride is particularly preferred. Next, the trivalent titanium halide 2' will be explained. Examples of trivalent titanium halides include titanium trichloride,
Examples include titanium tribromide and titanium triiodide, but a solid solution containing these as one component may also be used. As solid melts, solid solutions of titanium trichloride and aluminum trichloride, solid solutions of titanium tribromide and aluminum tribromide,
Examples include solid solutions of titanium trichloride and vanadium trichloride, solid solutions of titanium trichloride and iron trichloride, and solid solutions of titanium trichloride and zirconium trichloride. Among these, preferred are titanium trichloride and a solid solution of titanium trichloride and aluminum trichloride (TIC13.1'3NC13). Next, the sulfur-containing heterocyclic carbonester will be explained. Examples of sulfur-containing double ring carboxylic acid esters include thiophene carboxylic acid esters, thianaphthene carboxylic acid esters, isothianaphthene carboxylic acid esters, benzothiophene carboxylic acid esters, phenoxathin carboxylic acid esters, benzothiane carboxylic acid esters, and thiaxanthene. Examples include esters of thiophene-2-carboxylic acids, esters of thioindoxyl-type carboxylic acids, and more specifically, methyl, ethyl, propyl, butyl and amyl thiophene-2-carboxylate, and thiophene-3-carboxylate.
Methyl carboxylate, ethyl, propyl, butyl and amyl, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl,
2-thhenylacetate methyl, ethyl, propyl, butyl,
Methyl 2-chenyl acrylate, ethyl, methyl 2-chenylpyruvate, ethyl, methyl thianaphthene-2-carboxylate, ethyl, methyl thianaphthene-3-carboxylate, ethyl, methyl thianaphthene-2,3-dicarboxylate, ethyl, 3 -Methyl oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, methyl 3-thianaphthenyl acetate, ethyl, benzothiophene-2-carboxylate, ethyl, benzothiophene-3-carboxylate methyl, ethyl, benzothiophene Examples thereof include methyl phenoxathiine-4-carboxylate, ethyl, methyl phenoxathiine-1-carboxylate, ethyl, methyl phenoxathiine-2-carboxylate, ethyl, methyl phenoxathiine-3-carboxylate, ethyl, and the like. More preferred are methyl thiophene-2-carboxylate, ethyl, propyl and butyl, methyl thiophene-3-carboxylate, ethyl, methyl 2-thhenylacetate, ethyl, methyl 2-thhenylacrylate, ethyl, methyl thianaphthene-2-carboxylate. , ethyl, etc. The reaction with the above-mentioned solid substance 1}, titanium compound 2', and sulfur-containing double ring carboxylic acid ester [3} can be carried out by the method [1] of reacting the titanium compound or sulfur-containing carboxylic ester in a liquid phase or gas phase, Any method can be employed, such as the method [2] that combines phase or gas phase reaction and pulverization reaction. Regarding method [1], a method in which a solid substance, a titanium compound, and a sulfur-containing heterocyclic carboxylic acid ester are simultaneously reacted (
(■), or a method in which a solid substance and a titanium compound are first reacted, and then a combined yellow heterocyclic carboxylic acid ester is reacted (■), or a method in which a solid substance and a sulfur-containing heterocyclic carboxylic acid ester are first reacted, and then There is a method (■) in which titanium compounds are reacted. Although either method is possible, the latter two methods are preferred, and method (2) is particularly preferred. For method [2], when the titanium compound is (1) tetravalent, (0) trivalent,
(m) The case where tetravalent and trivalent are used together will be described. In the case of (1), the above solid substance, a titanium compound, and a sulfur-containing double ring carboxylic acid ester are simultaneously reacted and the resulting solid is pulverized (synthesis method ■), or the above solid substance and a titanium compound are first reacted. , a method in which the solid obtained by further reacting with a sulfur-containing heterocyclic carboxylic acid ester is pulverized (synthesis method ■), or the solid substance and the sulfur-containing heterocyclic carboxylic acid ester are first reacted, and then a titanium compound is reacted. There is a method (synthesis method ■) in which the solid obtained is pulverized. Although either method is possible, the latter two methods are more preferable, and particularly synthesis method (1) gives preferable results. In the case of (b), various methods are possible for synthesizing the solid component from the three components of the above solid substance, trivalent titanium halide, and sulfur-containing double ring carboxylic acid ester, but the following three methods are particularly possible. give favorable results. That is, a method in which the three components are co-pulverized (synthesis method ■), a method in which the solid component and the sulfur-containing polycyclic carboxylic acid ester are brought into contact in advance, and then a trivalent titanium halide is added and mechanically crushed ( Synthesis method ①) or a method in which a solid component and a trivalent titanium halide are brought into mechanical crushing contact and then treated with a sulfur-containing polycyclic carboxylic acid ester (synthesis method ①). In the case of (m), the solid substance m
, Method of simultaneously crushing a tetravalent titanium compound (2-1), a trivalent titanium compound (2-2), and a sulfur-containing heterocyclic carboxylic acid ester leg (synthesis method ■), '1} Toku 2-1
) is treated with [3- and (2-2) and ) are crushed together (synthesis method ■), and the solid obtained by reacting '1' with glue is treated with (2- 1) and (2-
2) and) method of crushing both (synthesis method ■), (1} and (2)
Examples include a method of adding (2-2) and glue to a solid obtained by reacting -1) and pulverizing it (synthesis method ①), but synthesis method ① is preferable. The first feature of the present invention can be achieved by further treating the solid catalyst synthesized by the above method [1] and method [2] with a tetravalent titanium compound (4) containing at least one halogen atom. A further increase in catalytic efficiency is achieved.Firstly, a method in which the solid catalyst synthesized by method [1] is further treated with the above-mentioned tetravalent titanium halide, the above-mentioned solid material, titanium A method in which a compound and a sulfur-containing heterocyclic carboxylic acid ester are simultaneously reacted, and then further treated with a tetravalent titanium halide (synthesis method ■); a method in which the above solid substance and a titanium compound are reacted, and then a sulfur-containing ester is reacted with a titanium compound; A method of reacting a ring carboxylic acid ester and then further treating with a tetravalent titanium halide (synthesis method ■), reacting the above solid substance with a sulfur-containing enomoto ring carboxylic acid ester, and then reacting with a titanium compound. After that, there is a method (synthesis method ■) in which the solid catalyst synthesized by method [2] is further treated with a tetravalent titanium halide. In this section, we will explain (1), (b), and (m). In the case of (1), synthesis method [2]-(1)-■, [2]-(
Although it is possible to treat the solid catalyst synthesized by 1)-■ or [2]-(1)-■ with a tetravalent titanium halide, the latter two methods are more preferred. In the case of (b), “Synthesis method [2]-(D) 1■, [2]-(
0) 1■, [2]-(b)1■ or [2]-(b)-
A possible method is to treat the solid catalyst synthesized by (1) with a tetravalent titanium halide. In the case of (m), basic solid 01, tetravalent titanium compound (2
-1), trivalent titanium compound (2-2), and sulfur-containing heterocyclic carboxylic acid ester {3},
Treatment method with tetravalent titanium halide (synthesis method ■),
The solid obtained by reacting [1} and (2-1) is [3'
(2-2) and pulverization, followed by treatment with a small group of titanium halide (synthesis method ■), [1
) and [3} are reacted, the solid obtained is treated with (2-1), both (2-2) and ) are pulverized, and then further treated with a tetravalent titanium halide (synthesis method) Law■),'
In the solid obtained by reacting 11 and (2-1), (2-2
) and (3) are added and pulverized, and then further treated with a tetravalent titanium halide (synthesis method ■), but method ■■■ is preferable.Next, the various reactions and The pulverization operation will be explained in detail. (i) A solid material obtained by reacting an organomagnesium component and a chlorosilane compound, or a reaction product of this solid material and a fused yellow heterocyclic carboxylic acid ester, and a titanium compound. The reaction is described. The reaction is carried out using an inert reaction medium or without an inert reaction medium, using the undiluted titanium compound itself as the reaction medium. Examples of inert reaction medium include hexane, heptane, etc. Examples include aliphatic hydrocarbons such as benzene, toluene, aromatic hydrocarbons such as xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, among which aliphatic hydrocarbons are preferred. There is no particular limit to the concentration, but preferably 80
The reaction is carried out at a temperature of 0.00 or higher and a titanium compound concentration of 2 mol/liter or higher, or using the undiluted titanium compound itself as a reaction medium. Regarding the reaction molar ratio, preferred results are obtained when the reaction is carried out in the presence of a sufficient excess amount of the titanium compound relative to the magnesium component in the solid substance. (ii) The reaction between a solid substance obtained by reacting an organomagnesium component and a chlorosilane compound, or a reaction product of this solid substance and a titanium compound, and a sulfur-containing double Qin ring carboxylic acid ester will be explained. The reaction is carried out using an inert reaction medium. As the inert reaction medium, any of the aforementioned aliphatic, aromatic, and alicyclic hydrocarbons may be used. The temperature during the reaction is not particularly limited, but is preferably in the range of room temperature to 100°C. When reacting a solid substance with a sulfur-containing heterocyclic carboxylic acid ester, there is no particular restriction on the reaction ratio of the two components, but preferably the sulfur-containing heterocyclic carboxylic acid ester is The recommended amount of ring carboxylic acid ester is 0.001 mol to 50 mol, particularly preferably 0.005 mol to 10 mol. When a reaction product of a solid substance and a titanium compound is reacted with a sulfur-containing compound ring carboxylic acid ester, the reaction ratio of the two components is 1 mole of titanium atom in the organomagnesium solid component. Ring carboxylic acid ester is 0.01 mol ~
A range of 100 mol, particularly preferably from 0.1 mol to 10 mol, is recommended. (lii) A method of pulverizing the solid produced by the above (i) to (in the presence or absence of a reaction reagent) will be explained. As a pulverizing method, a rotary ball mill, a vibrating ball mill,
Known mechanical grinding means such as impact ball mills can be employed. The grinding time is 0.5 to 10 field hours, preferably 1 to 3 feeding hours, and the grinding temperature is 0 to 200 qo, preferably 10 to 15
It is 0qo. A case will be described in which the solid component obtained from the (i) side of G is treated with a tetravalent titanium halide. The reaction is carried out using an inert reaction medium or using the titanium compound itself as the reaction medium. Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. is preferred. Regarding the concentration of titanium compound, 2 mol/
The titanium compound itself is preferably used as a reaction medium for the reaction. There is no particular restriction on the temperature of the reaction, but preferably the reaction is carried out at a temperature of 80°C or higher. The composition and structure of the solid catalyst component obtained by the above (i) mountain reaction will vary depending on the type of starting materials and reaction conditions, but
From the compositional analysis values, it was found that the solid catalyst contained about 1 to 1% by weight of titanium and had a surface area of 50 to 300. Next, each substance used as a solid catalyst component according to the present invention will be explained with specific examples. [B] As the organometallic compound used as the component,
Among the compounds of Groups 1 to M of the periodic table, organic aluminum compounds are particularly preferred. As organoaluminum compounds,
General formula YamaRteoZ3-t (in the formula, Rio has 1 carbon atom
~20 hydrocarbon groups, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy groups, and t is a number from 2 to 3) are used alone or as a mixture. In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R1o includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminium, trin-butylaluminum, triisoptylaluminium, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum , trihexadecylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethyl Hydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminumisoprenyl, etc., and mixtures thereof are recommended. A highly active catalyst can be obtained by combining these alkylaluminum compounds with the solid catalyst described above, and trialkylaluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity.
As the sulfur-containing heterocyclic carboxylic acid ester to be added to the organometallic compound, a sulfur-containing heterocyclic carboxylic acid ester of [A]'3' can be used. Next, the oxygen-containing polycyclic carboxylic acid ester will be explained. Examples of oxygen-containing heterocyclic carboxylic acid esters include furan carboxylic esters, dihydrofuran carboxylic esters, benzofuran carboxylic esters, coumaran carboxylic esters, pyran carboxylic esters, pyrone carboxylic esters, and coumarins. Examples include carboxylic acid esters, ink marine carboxylic acid esters, and the like. For example, methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate, ethyl, propyl, butyl, methyl furan-2,3-dicarboxylate, methyl furan-2,4-dicarboxylate, Methyl furan-2,5-dicarboxylate, methyl furan-3,4-dicarboxylate, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, methyl tetrahydrofuran-2-carboxylate, methyl coumarate (benzofuran-2 -methyl carboxylate), ethyl coumaran-2-carboxylate,
Methyl coumarate, ethyl coumarate, methyl coumarate, ethyl,
5-Hydroxy-4-ethoxycarponylcoumarin, 4
Examples include ethoxycarbonyl inkmarin, ethyl 3-methylfuran-2-carboxylate, isodehydroacetic acid, and methyl, ethyl, propyl, butyl furan-2-carboxylate, methyl, ethyl, and propyl furan-3-carboxylate. , butyl, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, methyl tetrahydrofuran-2-carboxylate, methyl coumarate, methyl coumarate, ethyl and the like give preferable results. The oxygen-containing or sulfur-containing heterocyclic carboxylic acid ester added to the organometallic compound may be the same or different from the oxygen-containing or sulfur-containing heterocyclic carboxylic acid ester used in the synthesis of the solid catalyst component. As for the addition method, the two components may be mixed in advance prior to polymerization, or they may be added separately into the polymerization system. Particularly preferably, a metal compound previously reacted with an oxygen-containing or sulfur-containing heterocyclic carboxylic acid ester and an organometallic compound are separately added to the polymerization system. The ratio of both components to be combined is in the range of 0 mol to 10 mol, particularly preferably 0 mol to 1 mol, of the oxygen-containing or sulfur-containing polycyclic carboxylic acid ester per mol of the organometallic compound. The catalyst comprising the solid catalyst component of the present invention and a component obtained by adding an oxygen-containing or sulfur-containing heterocyclic carboxylic acid ester to an organometallic compound may be added to the polymerization system under polymerization conditions, or
They may be roughly combined in advance prior to polymerization. The ratio of each component to be sutured is in the range of 1 mmol to 3000 mmol of the component consisting of the organometallic compound and the oxygen-containing or sulfur-containing heterocyclic carboxylic acid ester to the solid catalyst component 1, based on the organometallic compound. is preferable. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins. In particular, the present invention provides propylene, butene-1, bentene-1
, 4-methylbentene-1, 3-methylbutene-1 and similar olefins alone in a stereoregular manner. It is also suitable for copolymerizing the olefin with ethylene or other olefins, and for efficiently polymerizing ethylene. Furthermore, in order to adjust the molecular weight of the polymer, it is also possible to add hydrogen, halogenated hydrocarbons, or organometallic compounds that tend to undergo chain transfer. As the polymerization method, ordinary suspension polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization are possible. Suspension polymerization involves reacting the catalyst with a polymerization solvent, e.g., aliphatic hydrocarbons such as hexane and hebutane, aromatic hydrocarbons such as benzene, toluene, and xylene, and cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane. olefin such as propylene under an inert atmosphere.
It can be press-fitted into a 20k9' substrate and polymerization can be carried out at a temperature of room temperature to 150 oo. In the bulk polymerization, olefins can be polymerized under conditions where the catalyst is a liquid olefin such as propylene, and a liquid olefin is used as a polymerization solvent. For example, in the case of propylene, the polymerization can be carried out in liquid propylene under a pressure of 10 to 45 k9/h, at a temperature of 90° C. without room temperature. On the other hand, gas phase polymerization is performed under conditions where the olefin such as propylene is a gas.
Mixing is carried out in the absence of a solvent at a pressure of 1 to 50 k9/cm and at a temperature of room temperature to 120 qo using a fluidized bed, moving bed, or concentrated speculum to ensure good contact between the olefin such as propylene and the catalyst. It is possible to carry out the polymerization through the following means. The present invention will be explained below using examples. In addition, the n-heptane extraction residue used in the examples means the residue obtained by extracting the polymer with boiling n-heptane for 6 hours. Example 1 (i) Synthesis of hydrocarbon-soluble organomagnesium armor 138.0 g of di-butylmagnesium and 19.0 g of triethylaluminum were placed in a flask purged with nitrogen. The reaction was carried out for 2 hours at 8,000° C. while keeping the lamp lit, to obtain an organomagnesium body solution. As a result of analyzing this rust body, the composition was AIMg6. . (C2
Day 5) 2.9 (n-C4 ratio), 2. , and the organometallic concentration was 1.25 mol/sleeve. (ii) Synthesis of magnesium-containing solid materials by reaction with chlorosilane compounds Into a well degassed and dry flask with a volume of 2 l mol of trichlorosilane (HSiC13)/1. While preparing the enemy hol and keeping it at 6 0,
500 mmol of the above organomagnesium solution was added dropwise over 1 hour, and the mixture was further reacted at 65° C. for 1 hour. The white solid produced was separated from the furnace and washed with n-hexane.
After drying, 42.5 kg of white solid material (A-1) was obtained.
As a result of analyzing this solid material, it was found that M chicks per night. 16
mmol, CII9.20 mmol, Sil. 70mm
ol, contains 0.58 mmol of alkyl group, and B
．． E. T. The specific surface area measured by the method was 269 mm. Plate Synthesis of Solid Catalyst In a nitrogen-substituted container, 600 mo of n-hexane and 15.0 mo of ethyl thiophene-2-carboxylate were added.
Add 20 tbsp of the above solids to the l) and mix with 8 oz.
The reaction was carried out at 0qo for 1 hour to obtain a solid (B-1). This solid 189 was weighed and reacted with 300% titanium tetrachloride in a pressure-resistant container purged with nitrogen, and reacted for 2 hours in a 13000-meter tank.
-1) was obtained. As a result of analyzing this solid catalyst, the Ti content was 2.2% by weight. The solid catalyst 80-9 synthesized by propylene slurry polymerization (iii) in G, 2.4 mmol of triethylaluminum, and 0.8 mmol of thiophene-2-carbo)/ethyl acid were mixed with 0.8 mmol of hexane that had been thoroughly degassed and dehydrated. Both were placed in an autoclave with a capacity of 1.5 cm that had been vacuum dried and replaced with nitrogen, and the internal temperature was maintained at 6,000. Propylene was pressurized to a pressure of 5.0 k9/m and the total pressure was 4.8 k9/m2. (maintain the enemy's gauge pressure)
Polymerization was carried out for 2 hours, and the polymerized hexane-insoluble polymer 170
After that, 6.2 ml of polymerized hexane soluble material was obtained. Catalyst efficiency is 9660 pp/tertitanium component/hour/
propylene pressure and n of polymerized hexane-insoluble polymer
- Hebutane extraction residue was 95.7%. The particle properties were good, with a high density of 0.37 m/m, and a ratio of 35 to 150 mesh particles of 90.5%. Example 2 (i) Synthesis of hydrocarbon-soluble organomagnesium body 138.0 g of di-n-butylmagnesium and 19.0 g of triethylaluminum were placed in a flask purged with n-heptane and nitrogen. The reaction was carried out at 80 qo for 2 hours under lighting to obtain an organomagnesium body solution. As a result of analyzing this body, the composition was found to be AIM Kurashin (C2 day 5
)2.9(n-C4 is),2. , and the organometallic concentration was 1.20 mol/sleeve. (ii) Synthesis of a magnesium-containing solid material by reaction with a chlorosilane compound In a well degassed and dry flask with a volume of 2 l mol' of dichloromethylsilane (HSiCQC12), a solution in n-heptane 1. 500 mmol of the above organomagnesium solution was added dropwise over 1 hour while maintaining the temperature at 660° C., and the reaction was further carried out under concentration at 650° C. for 1 hour. The white solid produced was filtered, purified with n-hexane, and dried to yield 42.6 g of white solid material (A-2). As a result of analyzing this solid substance, it was found that Mg9.1 per solid substance per evening
8 m. I, CI19,20 machines. I, m of Si1,70. I,
Contains 0.60 mol of alkyl group, B. E.
The specific surface area measured by the T method was 261st/day. (i
ii) Synthesis of solid catalyst In the nitrogen-substituted container, add n
- Hexane 600 (and ethyl thiophene-2-carboxylate 15.0 mmol) was added with 20 mmol of the above solid, added dropwise at 80 qo over 1 hour, and further heated at 65 oz for 1 hour. Azusa reacted. The produced white solid was separated by furnace, washed with n-hexane, and dried to obtain a white solid substance (B-2). This solid (18%) was weighed out in a pressure-resistant container purged with nitrogen (300% titanium tetrachloride) and reacted for 2 hours at 13,000% titanium tetrachloride. C-2) was obtained. Next, this solid (C-2) 4.0 mm and 25 steel balls with a diameter of 10 mm were transferred into a steel mill with a diameter of 95 mm and a length of 100 mm. The solid catalyst (S-2) was obtained by pulverizing it for 5 hours using a vibrator at a vibration speed of min or more. As a result of analyzing this solid catalyst, the Ti content was 2.2% by weight. Skin: 50 m9 of solid catalyst (S-2) synthesized with propylene slurry polymerization side, 2.4 mmol of triethylaluminum, and thiophene-2-
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 0.8 mmol of ethyl carboxylate to obtain 151 polymerized hexane-free polymers and 5.1 polymerized hexane solubles.
I got 7 nights. The catalytic efficiency is 13,700 multi-pp' tertitanium component time propylene pressure and the n of the polymerized hexane-insoluble polymer.
-Heptane extraction residue was 95.0%. Example 3
2.0 tons of the solid catalyst (S-2) synthesized in Example 2 and 30 tons of titanium tetrachloride were placed in a pressure-resistant container purged with nitrogen, and after reacting for 2 hours at 130 degrees Celsius under Hinazusa, the solid portion was removed. A solid catalyst (S-3) was obtained by heating, washing, and drying. As a result of analyzing this solid catalyst, the Ti content was 2. It was round weight %. The above solid catalyst (S-3) 30-9, triethylaluminum 2.4 mmol and thiophene-2
- Example 1 using 0.8 mmol of ethyl carboxylate
Slurry polymerization of propylene was carried out in the same manner as above to obtain 145 polymerized hexane-insoluble polymers and 4 polymerized hexane-soluble polymers.
．． I got 4 nights. The catalyst efficiency was 21,000 pp/tertitanium component/hour, propylene pressure, and n of the polymerized hexane-free polymer.
-Heptane extraction residue was 96.4%. Example 4 350 ml of liquefied propylene was introduced into the autoclave which had been thoroughly purged with nitrogen and dried under vacuum, and the internal temperature was brought to 60 ml.
Solid catalyst (S-3) 1 synthesized in Example 3 while maintaining qo
0M, 1.8 mol of triethylaluminum and 0.6 mol of ethyl thiophene-2-carboxylate were added to an autoclave, and polymerization was carried out at 60° C. for 2 hours under a Takazusa to obtain Polymer 152. The catalytic efficiency is 330,000 pp' for the titanium component and n-heph for this polymer. Tan extraction residue is 94.6
%Met. Reference Example 1 A solid catalyst was synthesized in the same manner as in Example 1, except that commercially available anhydrous magnesium chloride was used instead of the magnesium-containing solid on the side. As a result of analyzing this solid catalyst, the Ti content was 0.81% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 9:9 of this solid catalyst, 2.4 mol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate. 2.1 polymerized hexane solubles were obtained. The total residue of the polymerized hexane-insoluble polymer extracted with n-heptane was 77.2%, and the catalyst efficiency was 962 pp' Ti component/hour. Reference Example 2 In the synthesis of the magnesium-containing solid substance in Example 1-(ii), everything was carried out in the same manner as in Example 1-(ii), except that methyltrichlorosilane (CH3SIC13) was used instead of trichlorosilane (HSiC13). As a result of synthesizing a magnesium-containing solid substance, 2.06 g of a white solid was obtained. Compared to Example 1-(ii), the yield of solid material is approximately 1
'20. Example 5 5.0 mmol of the magnesium-containing solid synthesized in the same manner as in Example 1 (ii) and 40 mmol of methyl thiophene-2-carboxylate were reacted in the same manner as in Example 1 (lii). 4.5 hours of the obtained solid and 0.382 hours of titanium trichloride (AA grade, manufactured by Toyo Stoffer Co., Ltd.) were ground in a vibrating ball mill under a nitrogen atmosphere for 5 hours. This solid (C-5)4.
After reacting for 3 hours and 60 degrees of titanium tetrachloride in a 130-degree oven under Takaazusa for 2 hours, the solid portion was filtered, washed with rice bran, and dried to obtain a solid catalyst (S-5). This solid catalyst (S-5)
As a result of analysis, the Ti content was 2.2% by weight.
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 9 of 50 of the above solid catalyst (S-5), 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl thiophene-2-carboxylate, and the results shown in Table 1 were obtained. Obtained.
Example 6 Slurry polymerization of propylene was carried out in exactly the same machine as in Example 1, using 9 of 100 of the solid (C-5) synthesized in Example 5 as a solid catalyst (Ti content 1.7% by weight), and the results are shown in Table 1. I got the result. Example 7 In the same manner as in Example 1, a magnesium-containing solid was first reacted with butyl thiophene-2-carboxylate, and then reacted with titanium tetrachloride, and the resulting solid 3.95% and titanium trichloride (Toyo Stoffer Co., Ltd.) were reacted. (AA grade) manufactured by A.D. Co., Ltd. was milled for 5 hours using a vibrating pole mill. After reacting 3.2 hours of this solid (C-7) with 80 minutes of titanium tetrachloride in a 13000-meter machine, the solid portion was heated in a furnace, washed with liquid, and dried to form a solid catalyst (S-7). ) was obtained. As a result of analyzing this solid catalyst, the Ti content was 4.1% by weight. The above solid catalyst (S-7) 30 female, triethylaluminum 2.4 mmol and thiophene-2
- Example 1 using 0.8 mol of ethyl carboxylate
Slurry polymerization of propylene was carried out in the same manner as above, and the results shown in Table 1 were obtained. Example 8 Propylene slurry polymerization was carried out in exactly the same manner as in Example 1 using 9 of 50 of the solid (C-7) synthesized in Example 7 as a collective catalyst (Ti content: 3.9% by weight). Table 1 After obtaining the results shown in Table 1, Example 9, 15 minutes of the solid (A-1) synthesized in Example 1 was placed in a pressure-resistant container purged with nitrogen, along with 250 degrees of titanium tetrachloride.
After reacting for 2 hours at a pressure of 13,000 yen, the solid portion was filtered, washed, and dried to obtain a solid (B-9). This solid (B-9) was dissolved in a solution of 200 g of n-hexane and 3.0 g of ethyl thiophene-3-carboxylate.
The mixture was placed in a container purged with nitrogen, and the reaction was carried out at 80 qo for 1 hour while keeping the atmosphere clean, to obtain a solid catalyst (S-9). As a result of analyzing this solid catalyst, the Ti content was 2.5% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 9 of 80 of the above solid catalyst (S-9), 2.4 mol of triethylaluminum, and 0.8 mmol of ethyl thiophene-3-carboxylate.
I got the result. Example 10 The solid (B-9) of Example 9 was synthesized in the same manner*, and 2.0 parts of this solid and 0.31 parts of butyl thiophene-2-carboxylate were added to the steel vibrator used in Example 2. The mixture was ground using a mill for 5 hours to obtain a group catalyst (S-10). As a result of analyzing this solid catalyst, the Ti content was 2.8% by weight. Slurry monopolymerization of propylene was carried out in the same manner as in Example 1 using this solid catalyst 50:9, 2.4 mol of triethylaluminum, and 0.8 mol of butyl thiophene-2-carboxylate, and the results are shown in Table 2. Obtained. Example 11 The solid catalyst (S-10) obtained in Example 10 was treated with titanium tetrachloride in the same manner as in Example 3, and the solid catalyst (S-11
) (Ti content: 2.9% by weight) was obtained. This solid catalyst 30:9, triethylaluminum 2.4
mol of, and butyl thiophene-2-carboxylate 0
．． Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 8 mol of propylene, and the results shown in Table 2 were obtained. Table 2 Examples 12 to 17 In the synthesis of the solid catalyst of Example 1, the solid catalyst (
B-12 to B-17) were synthesized, 3.09 of each solid and 2.4 mmol of titanium tetrachloride were added, ground for 5 hours in the steel mill used in Example 2, and further treated with titanium tetrachloride. A solid catalyst was synthesized. This solid catalyst 30:9, triethylaluminum 2.4
mmol and ethyl thiophene-2-carboxylate 0.
Slurry polymerization of propylene was carried out in the same machine as in Example 1 using 8 mol of propylene, and the results shown in Table 3 were obtained. Table 3 Examples 18 to 23 The same procedure as in Example 1 was carried out using 9 of 30 of the solid catalyst (S-3) synthesized in Example 3, 2.4 mmol of triethylaluminum, and 0.8 mol of the compound shown in Table 4. Slurry polymerization of propylene was carried out, and the results shown in Table 4 were obtained. Example 24 In the synthesis of the solid catalyst of Example 3, 0.00% of diethyl ketone was added as the hydrocarbon-soluble magnesium component per 1 mole of the organomagnesium component synthesized in Example 1-(i).
A solid catalyst was synthesized in the same manner as in Example 3, except for using a hexane-soluble complex organomagnesium component that was reacted at a ratio of 5 mol (both in a hexane solution of 0.9 hol, room temperature, 30 minutes). . This solid catalyst (Ti content: 2.0% by weight), 2.4 mmol of triethylaluminum and thiophene-
Slurry polymerization of propylene was performed in the same manner as in Example 1 using 0.8 mmol of ethyl 2-carboxylate, and the results shown in Table 4 were obtained. Example 25 In the synthesis of the solid catalyst of Example 24, a solid catalyst (Ti content 2.% by weight) was prepared in the same manner as in Example 24, except that sec-butanol was used instead of diethyl ketone.
was synthesized, propylene slurry polymerization was carried out in the same manner as in Example 24, and the results shown in Table 4 were obtained. Table 4 Examples 26 to 27 The solid catalyst (S-3) synthesized in Example 3 was prepared as in Example 1 using 0.8 mmol of ethyl thiophene-2-carboxylate and the organometallic components shown in Table 5. Slurry polymerization of propylene was carried out in the same manner, and the results shown in Table 5 were obtained. Table 5 Example 28 Polymerization of butene-1 was carried out in Example 1 using 200 pieces of the solid catalyst (S-3) synthesized in Example 3, 4.6 mmol of triethylaluminum, and 1.2 mol of ethyl thiophene-2-carboxylate. White polymer 5
I got 0 nights. Example 29 200 pieces of the solid catalyst (S-3) synthesized in Example 3, 4.6 mmol of triethylaluminum, and thiophene
Polymerization of 4-methylbentene-1 was carried out according to Example 1 using 1.2 mmol of ethyl 2-carboxylate,
A white polymer 46 was obtained. Example 30 Solid catalyst (S-3) 3 synthesized in Example 3
0-9, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl thiophene-2-carboxylate were used, and propylene was used as a propylene-ethylene mixed gas containing 2 mol% of ethylene. Polymerization was carried out using the following methods to obtain white polymer 1439. Example 31 Solid catalyst 60-9 synthesized in Example 3, 1.0 mmol of tri-isobutylaluminum, and 0.1 mmol of ethyl thiophene-2-carboxylate were dried under vacuum with 0.8 mmol of dehydrated and degassed n-hexane. Replaced 1
．． 5 Place it in the autoclave and keep the internal temperature at 80℃.
Hydrogen was pressurized to 1.6k9' and then ethylene was added to bring the total pressure to 4.0k9/carp.

Claims (1)

[Claims] 1 [A] (1) (i), (a) General formula MαMgβ
R^1_pR^2_q (where M is an element selected from aluminum, zinc, boron or beryllium, R^1,
R^2 is the same or different hydrocarbon group having 1 to 20 carbon atoms, α≧0, β>0, p, q>0, m is the valence of M, p
+q=mα+2β), or selected from (a) and (b) ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. The component reacted with the electron donor and (ii) the general formula HaSiCl_bR_4_-_(_a_
+_b_) (In the formula, a and b are numbers larger than 0, and a+b
≦4, R represents a hydrocarbon group having 1 to 20 carbon atoms); (2) a titanium compound containing at least one halogen atom; 3) Sulfur-containing heterocyclic carboxylic acid ester A solid catalyst obtained by reacting and/or pulverizing the above (1), (2), and (3), [B] an organometallic compound, and a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester A catalyst for producing polyolefin, which is a component consisting of an acid ester, and is composed of [A] and [B]. 2. The catalyst for producing polyolefin according to claim 1, wherein the ratio β/α is 1 to 10. 3 [A] In the hydrocarbon-soluble organomagnesium compound of (a), α=0 and R^1 and R^2 are any of the following three cases, as described in claim 1 catalyst for the production of polyolefins. (a) Both R^1 and R^2 have 4 to 6 carbon atoms,
At least one of them is a secondary or tertiary alkyl group. (b) R^1 is an alkyl group having 2 to 3 carbon atoms, and R^2 is an alkyl group having 4 or more carbon atoms. (c) R^1 is R
Both ^2 are alkyl groups having 6 or more carbon atoms. 4. The catalyst for producing polyolefin according to any one of claims 1 to 3, wherein the value of a is 0<a<2. 5 [A] Claims 1 to 4, wherein the titanium compound in (2) is a compound containing three or more halogens.
2. Catalyst for producing polyolefin according to any one of the above. 6. The catalyst for producing polyolefin according to any one of claims 1 to 5, wherein the titanium compound in [A] (2) is titanium tetrachloride and/or titanium trichloride. 7 [A] (3) sulfur-containing heterocyclic carboxylic acid ester is added in an amount of 0.00% per mole of alkyl group in the solid [A] (1).
The catalyst for producing polyolefin according to any one of claims 1 to 6, which is reacted at a ratio of 0.001 to 50 moles. 8 [A] The sulfur-containing heterocyclic carboxylic acid ester (3) is added to 0 per 1 gram atom of titanium in the solid [A].
．． The catalyst for producing polyolefin according to any one of claims 1 to 6, which is reacted in 1 to 10 moles. 9 The organometallic compound [B] has the general formula AlR^1^0_
nZ_3_-_n (in the formula, R^1^0 is a carbon number of 1 to 20
is a hydrocarbon group, Z represents a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and n is 2 to
The catalyst for producing polyolefin according to any one of claims 1 to 8, which is an organoaluminum compound represented by the number 3). 10. The catalyst for producing polyolefins according to any one of claims 1 to 9, wherein the organometallic compound [B] is trialkylaluminum or dialkylaluminum hydride. 11 The sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester [B] is a thiophene carboxylic acid ester, a furan carboxylic acid ester, or a coumaric acid ester, according to any one of claims 1 to 10. Catalyst for polyolefin production. 12 [A] (1) (i), (a) General formula MαMg
βR^1_pR^2_q (where M is an element selected from aluminum, zinc, boron or beryllium, R^1
, R^2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, α≧0, β>0, p, q>0, m is the valence of M,
hydrocarbon-soluble organomagnesium component represented by p+q=mα+2β), or (a) and (b)
A component obtained by reacting an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, or alcohols, thioalcohols, and amines, and (ii) a compound having the general formula HaSiCl_bR_4_-_(_a
＿+＿b＿)(In the formula, a and b are numbers larger than 0, and a+
b≦4, R represents a hydrocarbon group having 1 to 20 carbon atoms); (2) a titanium compound containing at least one halogen atom; (3) Sulfur-containing heterocyclic carboxylic acid ester, a solid obtained by reacting and/or pulverizing the above (1), (2), and (3), and further (4)
A solid catalyst obtained by treatment with a tetravalent titanium compound containing at least one halogen atom; [B] a component consisting of an organometallic compound and a sulfur- or oxygen-containing heterocyclic carboxylic acid ester; ] and [B] A catalyst for producing polyolefin. 13 Claim 12 in which the ratio β/α is 1 to 10
Catalyst for producing polyolefin as described in . 14 [A] In the hydrocarbon-soluble organomagnesium compound of (a), α=0 and R^1 and R^2 are any of the following three cases, as described in claim 12 catalyst for the production of polyolefins. (a) Both R^1 and R^2 have 4 to 6 carbon atoms,
At least one of them is a secondary or tertiary alkyl group. (b) R^1 is an alkyl group having 2 to 3 carbon atoms, and R^2 is an alkyl group having 4 or more carbon atoms. (c) R^1, R
Both ^2 are alkyl groups having 6 or more carbon atoms. 15 Claim 12 in which the value of a is 0<a<2
The catalyst for producing polyolefin according to any one of items 1 to 14. 16. The catalyst for producing polyolefin according to any one of claims 12 to 15, wherein the titanium compound in [A] (2) is a compound containing three or more halogens. 17. The catalyst for producing polyolefin according to any one of claims 12 to 16, wherein the titanium compound in [A](2) is titanium tetrachloride and/or titanium trichloride. 18. The catalyst for producing polyolefin according to any one of claims 12 to 17, wherein the tetravalent titanium compound containing at least one halogen atom in [A] (4) is titanium tetrachloride. 19 Claims in which the sulfur-containing heterocyclic carboxylic acid ester of [A](3) is reacted at a ratio of 0.001 to 50 moles per mole of the alkyl group contained in the solid of [A](1) The catalyst for producing polyolefin according to any one of Items 12 to 18. 20 [A] (3) The sulfur-containing heterocyclic carboxylic acid ester is added to 0 per 1 gram atom of titanium in the solid [A].
．． The catalyst for producing polyolefin according to any one of claims 12 to 18, which is reacted in 1 to 10 moles. 21 The organometallic compound [B] has the general formula AlR^1^0_nZ_3_-_n (in the formula, R^1^0
is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, halogen,
Claims 12 to 2 are organoaluminum compounds represented by a group selected from alkoxy, allyloxy, and siloxy groups, and n is a number from 2 to 3.
The catalyst for producing polyolefin according to any one of Item 0. 22. The catalyst for producing a polyolefin according to any one of claims 12 to 21, wherein the organometallic compound [B] is trialkylaluminum or dialkylaluminum hydride. 23 The sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester [B] is a thiophene carboxylic acid ester, a furan carboxylic acid ester, or a coumaric acid ester, according to any one of claims 12 to 22. Catalyst for polyolefin production.