JPS6010527B2 - Catalyst for polyolefin production - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly active catalyst for the stereoregular polymerization of olefin. In particular, this competition focuses on propylene, butene-1, and bentene-1.
Suitable for stereoregularly polymerizing olefins such as 4-methylbentene-1 and 3-methylbutene-1, and polymerizing the above olefins with ethylene or other olefins. A stereoregular polymer can be obtained by contacting an olefin with a Ziegler-Natsuta catalyst system consisting of a transition metal compound and an organometallic compound of Groups 1 to M of the Periodic Table of the Elements, in particular titanium halides and triethylaluminum. or organic aluminum compounds such as diethylaluminum chloride, are used industrially as catalysts for the production of stereoregular polyolefins. When olefins such as propylene are polymerized using this catalyst, boiling hebutyl Although the proportion of insoluble polymers, that is, stereoregular polymers, is quite high, the polymerization activity is not satisfactory, and a step is required to remove the catalyst residue from the resulting polymer.In recent years, high activity polymers for ethylene polymerization have been developed. A number of catalyst systems have been proposed that consist of reaction products of inorganic or organomagnesium compounds, titanium or vanadium compounds, and organoaluminum compounds.These catalyst systems have shown remarkable activity in the polymerization of propylene. However, the proportion of stereoregular polymers in the total polymer is low, and it is very difficult to apply it to the industry for producing stereoregular polymers of olefins such as propylene. Showa 47
-9342, Japanese Patent Publication No. 43-1305) As improvements to these, Japanese Patent Publication No. 52-39431, Japanese Patent Publication No. 52-361
53 and Samurai Seki Sho 48-16988 have been proposed. These methods use a solid catalyst component obtained by co-pulverizing a key compound of a titanium halide compound and an electron donor and anhydrous magnesium halide, and an addition reaction product of aluminum trialkyl and an electron donor. This is a catalyst system. However, even with these methods, the proportion of stereoregular polymer in the biopolymer is still not sufficiently high, the polymer yield per solid catalyst component is insufficient, and the catalyst residue during polymerization, especially 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.
As a result of intensive studies aimed at improving these points, the present inventors found that an organomagnesium component soluble in an inert hydrocarbon medium, or combination thereof with ether, thioether, ketone,
An alkyl group-containing solid magnesium compound is produced by reacting a component obtained by reacting an electron donor selected from aldehydes, carboxylic acids or their derivatives, alcohols, thioalcohols, and amiso with a chlorosilane compound containing Si-Nihongyo. Then, this solid is reacted and/or pulverized with a titanium compound, a sulfur-containing or oxygen-containing double ring carboxylic acid ester, or is further treated with a tetravalent titanium compound, and a nitrogen-containing double ring carboxylic acid ester. and the catalyst obtained in combination with an organoaluminium compound,
We have discovered that it has extremely excellent performance as an olefin polymerization catalyst and have arrived at the present invention. That is, the first invention is [A], {11, (i), '
a) The general formula MQMgBR also has an R content (in the formula ~M is an atom selected from aluminum, zinc, boron, or beryllium, R1, R2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, Q≧0 8>0, p・q>0, m is the valence of M, and the relationship is p+q=mQ+28. , ketones, aldehydes, carboxylic acids or their derivatives, alcohols, thioalcohols, and amines, and a compound with the general formula HasiC1bR
4-(a + b) (where a, b are numbers larger than 0, a
+bmi4, R represents a hydrocarbon group having 1 to 20 carbon atoms. ) a solid obtained by reacting with a Si-bond-containing chlorosilane compound represented by (1) a titanium compound containing at least one halogen atom, {3} a sulfur- or oxygen-containing heterocyclic carboxylic acid ester; (2) A solid catalyst obtained by reacting and/or pulverizing '3', and [B] a component consisting of an organometallic compound and a nitrogen-containing polycyclic carboxylic acid ester, which consists of [A] and [B]. This is a catalyst for producing polyolefins. The second invention is [A] “(1), (l)”

[a) - Crotch type MQMgPR also has R cost (in the formula, M is aluminum, zinc,
Atoms selected from boron or beryllium, R1, R2
are the same or different hydrocarbon groups having 1 to 20 carbon atoms, Q
≧0, 8>0, p, q>0, m is the valence of M, p+q=
The relationship is mQ+28. ), or [a] and [b'] are reacted with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. Ingredients and general formula HasiC1bR4
-(a+b) (in the formula, a and b are numbers greater than 0, and a
R represents a hydrocarbon group having 1 to 20 carbon atoms.
), a solid obtained by reacting with a Si-daily-containing chlorosilane compound represented by [2-a titanium compound containing at least one halogen atom, a sulfur-containing or oxygen-containing polycyclic carboxylic acid stenole, above '1] , ■, '3} is further reacted and/or pulverized.
}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 nitrogen-containing heterocyclic carboxylic acid ester; This is a catalyst for producing polyolefin consisting of [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 was 330,000 pp/tertitanium component/hour and 7,600 pp/ter solid catalyst. It's more than an hour. The second feature of the present invention is
In addition to having high activity as described above, high stereoregularity can also be obtained. The value of the present invention is 94.9%.
When an organic carboxylic acid ester such as a benzoic acid ester is coarsely combined with an organometallic compound, the stereoregularity is generally improved, but the polymerization activity is significantly reduced. On the other hand, in the present invention, when an appropriate amount of nitrogen-containing double ring carboxylic acid ester is used in combination with an organometallic compound, improvement in stereoregularity and maintenance or increase of polymerization activity are observed. It exhibits excellent effects different from acid esters. The third feature of the present invention is that when hydrogen is used as a molecular weight regulator during polymer production,
The advantage is that only a small amount of hydrogen is needed. 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 polymer has a good particle size and a high density. Large polymer particles can be produced. Each raw material component and reaction conditions used in the preparation of the catalyst of the present invention will be explained. 01 General formula MQMgPR also has R cost (Q, B, p, q in the formula
, M, R1, and R2 have the above-mentioned meanings).This organomagnesium component is shown as a tsuba compound of organomagnesium, but it is contained in the so-called Grignard compound of RMgX. 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 thereof include a phenyl group, and it is particularly preferable that RI is an alkyl group. M is aluminum, zinc,
Boron or beryllium atoms are preferred because they facilitate the formation of a hydrocarbon-soluble organomagnesium armor body. When used as a catalyst component in the present invention, an organomagnesium lead body or compound that is soluble in an inert hydrocarbon solvent is preferred. When the above formula Q>0, the ratio 3/Q of magnesium to metal atom M is 0.0 for this organomagnesium fin body.
1 or more "preferably 0.5 or more, particularly preferably 1 to
It is 10. These organomagnesium mirror compounds have the general formula RIMgX, R Mg (RI has the above meaning,
An organomagnesium compound represented by the formula M (X represents halogen) and an organometallic compound represented by the general formula M (M, R2, m have the meanings described above) were combined in hexane,
It is synthesized by reaction in an inert hydrocarbon solvent such as heptane, cyclohexane, benzene, toluene, etc. at room temperature to i50°C. Furthermore, MgX2, RIMgX and M Kyumine, MR Kyu-, Japan,
or RIMgX “MgRki and RtoMXmm (in the formula,
M, R1, and R2 are as described above, X represents a halogen, and n is a number from 0 to m). In general, organomagnesium compounds are immovable in activated hydrocarbon media, but organomagnesium compounds with Q>0 are soluble, and in the present invention, hydrocarbon-soluble compounds are preferred. gives the desired result. As the organomagnesium component, in the case of o: 0 in the above formula, that is, the M station also has R costs (in the formula, R1, R2, p,
The hydrocarbon-soluble organomagnesium compound represented by (q has the above-mentioned meaning) will be described. In the above formula, R1 and R2 are assumed to be in any of the following three cases. When at least one of R1 and R2 is a secondary to tertiary alkyl group having 4 to 6 carbon atoms. {When o'RI and R2 are alkyl groups having different carbon numbers. (1) When at least one of RI and R2 is a hydrocarbon group having 6 or more carbon atoms. Preferably R1, R
2 is one of the following three cases. (A') When R1 and R2 both have 4 to 6 carbon atoms, and at least one of them is a secondary to tertiary alkyl group. (b') RI is an alkyl group having 2 to 3 carbon atoms, and R2
is an alkyl group having 4 or more carbon atoms. (c') R1
, R2 are both alkyl groups having 6 or more carbon atoms.
These groups will be specifically shown below. {i' and (i'
), examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms include sec-C49, tert-C4, 1CH(C25)2, 1C(C25)(CH3 )
2, -CH (C horse) (C4 day 9), 1CH (C2 day 5)
(C3 day 7), -C (C to) 2 (C3 day 7), 1C (C
H3)(C2day5)2 etc. are used, preferably a secondary alkyl group, and the sec-C4 ratio) is particularly preferred.
In (b'), examples of the alkyl group having 2 to 3 carbon atoms include ethyl and propyl, with ethyl being particularly preferred. Examples of the alkyl group having 4 or more carbon atoms include butyl, amyl, hexyl, octyl and the like, with butyl and hexyl being particularly preferred. In (1) and (c'), examples of the hydrocarbon group having 6 or more carbon atoms include hexyl, octyl, decyl, and phenyl groups, with alkyl groups being preferred, and hexyl groups being particularly preferred. Examples of such organomagnesium compounds include (sec-C4)
2Mg, (grip rt-C4 ratio) 2Mg, n-C4 Yamaichi Mg
-C2 insect, n-C4 day 9-Mg-sec-C4 is n-
C4 day 91 Mg-tert-C4 day 9, n-C side, 3-
Mg-C2 days 5, n-C8 days, 7-Mg-C2 days 5, (
n-C 6 days, 3) 2Mg, (n-C 8 days, 7) 2M
g, (n-C, Niji 2,) 2M ships, etc. The electron donor to be reacted with the hydrocarbon-soluble organomagnesium component will be explained. For ethers of the general formula ROR', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl Examples include hydrocarbon groups such as , cyclohexyl, phenyl, and benzyl. Regarding the thioether RSR', R and R are aliphatic, aromatic, and aliphatic hydrocarbons, such as hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, and phenyl. It will be done. For ketones RCOR', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl, etc., but especially dimethyl ketone. , diethyl ketone and the like are preferred. Regarding aldehydes, aliphatic, aromatic and cycloaliphatic aldehydes are also used. As the carboxylic acid or its derivative, carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid halide, and carboxylic acid amide are used. Carboxylic acids include, for example, formic acid, acetic acid, propionic 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 the carboxylic anhydride include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, and the like. Examples of carboxylic acid esters include methyl and ethyl formate, methyl acetate, ethyl, propyl, methyl propionate, ethyl, propyl, butyl, ethyl butyrate, ethyl claurate,
Ethyl caproate, ethyl n-heptanoate, dibutyl oxalate, ethyl succinate, ethyl malonate, dibutyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl, propyl,
Mention may be made of butyl, methyl toluate, ethyl, propyl, butyl, amyl, methyl and ethyl p-ethylbenzoate, methyl anisate, ethyl, propyl and butyl, methyl and ethyl p-ethylbenzoate. As the carboxylic acid halide, acid chlorides are preferred;
Examples include acetyl chloride, propionyl chloride, butyryl chloride, succinyl chloride, penzoyl chloride, and toluyl chloride. Examples of the carboxylic acid amide include dimethylformamide, dimethylacetamide, dimethylpropionamide, and the like. Examples of alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, phenol, cresol, etc., but sec-propyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, SeC-amyl alcohol, ten-amyl alcohol, SeC-hexyl alcohol, phenol, o,
Secondary, tertiary or aromatic alcohols such as m-p-cresol are preferred. Examples of the thioalcohol include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, phenyl mercaptan, etc., but secondary, tertiary or aromatic thio alcohols are preferred. Examples of the amine include aliphatic, alicyclic and aromatic amines, but secondary to tertiary amines such as trialkylamine, triphenylamine, pyridine and the like give preferable results. For reactions between hydrocarbon-soluble organomagnesium components and electron donors, the reaction may be carried out in an inert reaction medium, such as aliphatic hydrocarbons such as hexane, hebutane, 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 are two methods: adding the electron donor to the organomagnesium component (■), adding the organomagnesium component to the electron donor (■), and adding both at the same time (■).
■) can be used. The reaction ratio between the hydrocarbon-soluble organomagnesium component and the electron donor is 1 mol or less, preferably 0.05 mol to 0.8 mol, of the electron donor per 1 mol of the organomagnesium component. Next, the general formula ratio SIC1bR4-(a + b) (in the formula, a
, b (R is the meaning described above). The hydrocarbon group represented by R in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, An aromatic hydrocarbon group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc., preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, Lower alkyl groups such as bropyl are particularly preferred.The values of a and b are a, b>0, a+bmi4
and preferably 0<ami2. These compounds include HSiC13, HSiC12CH3, HSi
C12C 2 days 3, HSIC12n-C 3 days 7, HSiC
12i-C3 day 7, HSiC12n-C4 day 8, HSj
C12C 6 days 5, HSiC12 (41 CI-C 6 days 4)
, HSiC12CH=CH2, HSIC12CH2C6
is HSiC12(1-C,oH7), HSi
C12CH2CH = CH2, ratio SICIC ratio
, SICIC2 day 5, HSiC1 (C melon) 2, HSi
CICH3 (i-C3 day 7), HSiCICH3 (C6
4), HSiC1 (C2 day 5) 2, HSiC1 (C6 day 5) 2, etc. Chlorosilane compounds consisting of mixtures of these compounds and compounds selected from these compounds are used, trichlorosilane, monomethyl Dichlorosilane, dimethylchlorosilane, ethyldichlorosilane 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 explained below. It can be carried out in a hydrocarbon, an aromatic hydrocarbon such as benzene, toluene, or xylene, an octocyclic hydrocarbon such as cyclohexane or methylcyclohexane, an ether medium such as ether or tetrahydrofuran, or a mixed medium thereof. From the viewpoint of catalytic performance, an aliphatic hydrocarbon medium is preferable.The reaction temperature is not particularly limited, but from the viewpoint of reaction progress, it is preferably carried out at a temperature of 4 to 4 or higher.The reaction ratio of the two components is also not particularly limited. , preferably per mole of organomagnesium component,
Chlorsilane component o. The range is from 1 mol to 100 mol, particularly preferably from 0.1 mol to 10 mol. Regarding the reaction method, there is a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted (method ①), or the chlorosilane component is charged into the reaction zone in advance, and then the organomagnesium complex component is introduced into the reaction zone while the organic magnesium complex component is introduced into the reaction zone. A method of reacting (Method @), or a method of preparing an organomagnesium rust component in advance and adding a chlorosilane component (Method Q)
However, the latter two are preferred, and method @ gives particularly favorable results. When the organomagnesium compound is indispensable, it is also possible to use a chlorosilane compound as a reaction agent in a heterogeneous 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 m above) obtained by the above reaction may vary depending on the type of starting materials and reaction conditions, but from the composition analysis value, the stiffness of solid substance 1 is approximately 0.1 to 2. .5 mmol M
It is presumed to be a halogenated magnesium compound containing an alkyl group having a g-C bond. This solid substance has an extremely large specific surface area, and B
．． E. T. When measured by the method, it shows a high value of 100 to 300 makunota. Compared to conventional magnesium halide solids, the solid materials of the present invention have a very high surface area;
Another major feature is that it is an active magnesium-containing solid containing an alkyl group with reducing power. Next, a tetravalent titanium compound containing at least one halogen atom■
I will explain about it. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride,
A single or a mixture of titanium halides and alkoxy halides, such as propoxytitanium trichloride, poxytitanium trichloride, diptoxytitanium dichloride, and triptoxytitanium monochloride, can be used. Preferred compounds are those containing three or more halogens, and titanium tetrachloride is particularly preferred. Next, trivalent titanium halide (2) will be explained. Examples of trivalent titanium halides include titanium trichloride,
Examples include titanium tribromide and titanium triiodide, but a solution containing these as one component may also be used. Oka solutions include 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 ports 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). [A] The sulfur-containing heterocyclic carboxylic acid esters in the legs include thiophene carboxylic esters, chanapthenes carboxylic esters, isothianaphthene carboxylic esters, benzothiophene carboxylic esters, and phenoxathine carboxylic esters. , benzothianes carboxylates, thiaxanthenes carboxylates, thioindoxyls carboxylates, etc. More specifically, methyl thiophene-2-carboxylate, ethyl, propyl, butyl and amyl, methyl thiophene-3-carboxylate. , ethyl, propyl,
Butyl and amyl, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl, methyl 2-chenylacetate, ethyl, propyl, butyl, 2 -Methyl chenylacrylate, ethyl, methyl 2-chenylpyruvate, ethyl, methyl thianaphthene-2-carboxylate "Ethyl, thianaphthene-3
-methyl carboxylate, ethyl, thianaphthene-2,3
- methyl dicarboxylate, ethyl, methyl 3-oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenyl acetate, ethyl, methyl 3-thianaphthenyl acetate, ethyl, methyl benzothiophene-2-carboxylate,
Ethyl, methyl benzothiophene-3-carboxylate, ethyl, methyl benzothiophene-4-carboxylate, ethyl, methyl phenoxathiin-1-carboxylate, ethyl, methyl phenoxathiiso-2-carboxylate, ethyl,
Examples include methyl and ethyl phenoxathin-3-carboxylate. More preferred are methyl, ethyl, propyl and butyl thiophene-2-carboxylate, methyl thiophene-3-carboxylate, ethyl, methyl 2-thienyl acetate, ethyl, methyl 2-thienyl acrylate, ethyl, and thianaphthene-2. -Methyl carboxylate, ethyl etc. Next, the oxygen-containing heterocyclic carboxylic acid ester will be explained. Examples of oxygen-containing heterocyclic carboxylic acid esters include L-furan carboxylic esters, dihydrofuran carboxylic esters, penzofuran carboxylic esters, coumaran carboxylic esters, pyran carboxylic esters, pyrone carboxylic esters, and coumarin carboxylic esters. Examples include acid esters, inkmarin carboxylic acid esters, etc. 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, furan- Methyl 3,4-dicarboxylate, methyl 4,5-dihydrofuran-2-carboxylate, ethyl, methyl tetrahydrofuran-2-carboxylate, methyl coumarate ~ (benzofuran-2
-methyl coumaran-2-carboxylate, methyl coumarate, ethyl, methyl comanate, ethyl, 5-hydroxy-4-ethoxycarbonyl coumarinto 4-ethoxycarbonyl. Examples include inkmarin, ethyl 3-methylfuran-2-carboxylate, isodehydroacetic acid, and methyl furan-2-carboxylate, ethyl, propyl, butyl, methyl furan-3-carboxylate,
Ethyl, propyl, butyl, methyl 4,5-dihydrofuran-2-carboxylate, ethyl "tetrahydrofuran-
Methyl 2-carboxylate, methyl coumarate, methyl coumarate, ethyl etc. give preferable results. The reaction between the solid substance '11, the titanium compound {2), and the sulfur- or oxygen-containing heterocyclic carboxylic acid ester {3} results in a reaction between the titanium compound [2] or the sulfur- or oxygen-containing enocyclic carboxylic acid ester [3]. } Any method can be adopted, such as a method [1] in which the reaction with the pulverization reaction is carried out in a liquid phase or a gas phase, a method [2] in which the reaction in a liquid phase or a gas phase and a pulverization reaction are roughly combined. Regarding method [1], a method (■) of simultaneously reacting solid substance '1}, titanium compound (2), and sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester [3}, or solid substance {1) and titanium compound A method in which {2} is first reacted and then a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester '3' is reacted (■), or a solid substance {1' and a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester '3' are reacted. There is a method (■) in which '3} is first reacted and then titanium compound 2} is reacted. Any method is possible, but the latter two methods are preferred, and method (2) is particularly preferred.
m) The case where tetravalent and trivalent are used together will be described. In the case of (1), a method of pulverizing the solid obtained by simultaneously reacting the solid substance [1}, the tetravalent titanium compound (2-1), and the sulfur- or oxygen-containing heterocyclic carboxylic acid ester ( Synthesis method (■), or a solid obtained by first reacting the above solid substance '1' with a tetravalent titanium compound (2-1), and then reacting a sulfur-containing or oxygen-containing double Qin ring carboxylic acid ester {31]. A method of pulverization (synthesis method ■), or the above solid substance '1) is first reacted with a sulfur-containing or oxygen-containing polycyclic carboxylic acid ester, and then a tetravalent titanium compound (2-1) is reacted. There is a method (synthesis method ■) in which the obtained solid is pulverized. Although either method is possible, the latter two methods are preferred, and especially synthesis method (2) gives more preferable results. In the case of (b), the above solid substance {1- and trivalent titanium compound (2-2
) and sulfur- or oxygen-containing double ring carboxylic acid ester {3
Although various methods are possible for synthesizing the solid component from the three components, the following three methods give particularly preferable results. That is, the method of co-pulverizing the three components (synthesis method ■) involves bringing the solid substance '1' into contact with the sulfur-containing or oxygen-containing carboxylic acid ester '31, and then adding the trivalent titanium compound (2-2). Mechanical crushing method (synthesis method■)
, or a solid substance {1} and a trivalent titanium compound (2-
2) is brought into contact with mechanical crushing, and then treated with a sulfur-containing or oxygen-containing double ring carboxylic acid ester lake (synthesis method ①). In the case of (m), the above solid substance '1}, the tetravalent titanium compound (2-1), the trivalent titanium compound (2-2), and the sulfur- or oxygen-containing double Qin ring carboxylic acid ester '3} (synthesis method ■), the solid obtained by reacting the solid substance {1} with the tetravalent titanium compound (2-1) is pulverized into sulfur- or oxygen-containing double Qin ring carboxylic acid ester [in 3 pieces Treated with trivalent titanium compound (2-2)
(synthesis method ■), the solid obtained by reacting solid substance '11 with a sulfur-containing or oxygen-containing polycyclic carboxylic acid ester [3-] is crushed with a tetravalent titanium compound (2-1).
) and pulverized together with trivalent titanium compound (2-2) (synthesis method ■), the solid obtained by reacting solid substance '1' with tetravalent titanium compound (2-1), A method of adding and pulverizing a trivalent titanium compound (2-2) and a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester (3)
Examples include synthesis method (2), but synthesis method (2) is preferred. 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 [41] containing at least one halogen atom. An even further increase in certain catalyst efficiency is achieved. First, the method of further treating the solid catalyst synthesized by method [1] with the above-mentioned tetravalent titanium halide '4} includes method [1)-■, method [1]-■, method [ 1
There is a method in which the solid catalyst synthesized by method [2] is treated with a tetravalent titanium halide (4). Next, the solid catalyst synthesized by method [2] is further treated with a tetravalent titanium halide (4). For the method of processing, see [2]-(1), [2]-(0) and [2]-(
Each case of m) will be explained. In the case of [2]-(1), synthesis method [2]-(1) 1■, [
It is possible to treat the solid catalyst synthesized by 2]-(1)-1 or [2]-1 with tetravalent titanium halide '41, but the latter two methods is more preferable. In the case of [2]-(0), the synthesis method [2]-(0)-■, [
2]-(mouth)-■, [2]-(m)-■ or [2]-
It is possible to further treat the solid catalyst synthesized by (b)-(ii) with a tetravalent titanium halide [4}. [2] In the case of -(m), solid substance '1), tetravalent titanium compound (2-1), trivalent titanium compound (2-2)
, and a method in which sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester '3' is simultaneously pulverized and then treated with a tetravalent titanium halide (synthesis method ■), (1} and (2-1) are reacted. The solid obtained is treated with (3', (2-2)
The solid obtained by reacting {11 and [3} with (2-1) is treated with (2-2). ) and then further treated with a tetravalent titanium halide (synthesis method ■), the solid obtained by reacting '1' and (2-1) with (2-2) and [3} The method includes adding and pulverizing the material, followed by treatment with a tetravalent titanium halide (synthesis method ①), and methods ①, ②, and ① are preferred. Next, the various reactions and pulverization operations described above will be specifically explained. A solid substance obtained by reacting an organomagnesium component and a chlorosilane compound, or a reaction product of this solid substance and a sulfur-containing or oxygen-containing polycyclic carboxylic acid ester,
The reaction with a titanium compound will be explained. 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 aliphatic hydrocarbons such as hexane, heptane, etc. , aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, among which aliphatic hydrocarbons are preferred.There are particular restrictions on the temperature during the reaction and the concentration of the titanium compound. No, but preferably 80
The reaction is carried out at a temperature of 0.00 or higher and the titanium compound concentration is 2 molar liters or higher, or using the undiluted titanium compound itself as a reaction medium.The reaction molar ratio is a sufficient excess amount relative to the magnesium component in the solid substance. (ii) A solid substance obtained by reacting an organomagnesium component with a chlorosilane compound, or a reaction product of this solid substance with a titanium compound, a sulfur-containing or oxygen-containing complex, etc. The reaction with ring carboxylic acid esters will be explained. The reaction is carried out using an inert reaction medium. As the inert reaction medium, any of the above-mentioned aliphatic, aromatic, and alicyclic hydrocarbons can be used. Good. The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 100°C. When reacting a solid substance with a sulfur- or oxygen-containing polycyclic carboxylic acid ester, the reaction ratio of the two components is not particularly limited, but preferably the sulfur-containing or oxygen-containing enocyclic carboxylic acid ester is 0.001 to 50 moles, particularly preferably 0.001 mole to 1 mole of the alkyl group contained in the organic magnesium-containing solid component. A range of 0.005 to 10 moles is recommended.When reacting a reaction product of a solid substance and a titanium compound with a sulfur-containing or oxygen-containing heterocyclic carboxyl ester, the reaction ratio of the two components is The amount of sulfur-containing or oxygen-containing double ring carboxylic acid ester is 0.01 per mole of titanium atoms in the solid component.
A range of mol to 100 mol, particularly preferably 0.1 mol to 10 mol is recommended. (iii) Above (i}~(li
) A method for pulverizing the solid produced by the reaction in the presence or absence of a reaction reagent will be described. Grinding methods include rotary ball mill, vibrating ball mill,
Known mechanical grinding means such as impact ball mills can be employed. The grinding time is 0.5 to 10 hours, preferably 1 to 3 hours, and the grinding temperature is 0 to 200 qo, preferably 10 to 15 hours.
It is 020. A case where the solid component obtained by (i) to (ili) is treated with a tetravalent titanium halide will be described. 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 hexane, aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. is preferable. Regarding the concentration of titanium compound, ahol/
A concentration higher than that is preferred, and it is particularly preferred to react using the titanium compound itself as a reaction medium. Although there is no particular restriction on the temperature of the reaction, it is preferable to carry out the reaction at a temperature of 80 qo or higher. The composition and structure of the solid catalyst component obtained by the above (i) or skin reaction will vary depending on the type of starting materials and reaction conditions, but from the compositional analysis values, approximately 1 to 1% by weight of the solid catalyst is present in the solid catalyst. It was found that it is a solid catalyst containing titanium and having a surface area of 50 to 300.Next, the organometallic compound used as the component [B] is a compound from the first to blood group of the periodic table, especially an organic Aluminum compounds are preferred.As the organoaluminum compounds, general formula NR-Z3
-t (wherein R10 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a group selected from hydrogen, halogen, alkoxy, allyloxy, and siloxy group, and t is a number from 2 to 3)
The compounds represented by are used alone or as a mixture. In the above formula, RI. The hydrocarbon group having 1 to 20 carbon atoms represented by includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specific examples of these compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and 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.
Examples of nitrogen-containing heterocyclic carboxylic acid esters added to the organometallic compound include pyrrole carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, and imidazole carboxylic esters. , pyrazole carboxylate ester, pyridine carboxylate ester, phenanthridine carboxylate ester, anthrazoline carboxylate ester, phenanthroline carboxylate ester, naphthyridine carboxylate ester, oxazine carboxylate ester, thiazine carboxylate ester , pyridazine carboxylic acid esters, pyrimidine carboxylic esters, and pyrazine carboxylic esters, but preferred ones include methyl, ethyl, propyl, and butyl pyrrole-2-carboxylate, methyl pyrrole-3-carboxylate, and ethyl pyrrole-3-carboxylate. , propyl and butyl, N-carboethoxypyrrole, N-carbomethoxypyrrole, pyridine-2
- Methyl, ethyl, propyl, butyl and amyl carboxylates, methyl pyridine-3-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-4-carboxylate, ethyl, propyl, butyl and amyl, pyridine-2,3-dicarboxylate Methyl, ethyl, pyridine-2,5-dicarboxylate, ethyl, pyridine
Methyl, ethyl, pyridine-3, 2,6-dicarbosoate
Methyl 5-dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl piperidine-4-carboxylate, ethyl piperidine-2-carboxylate, pyrrolidine-
Examples include ethyl 2-carboxylate. The nitrogen-containing double ring carboxylic acid ester used together with the organometallic compound may be used alone or in a mixture of two or more, and may include ordinary ethers,
Electron donors such as esters and amines may also be used together. The organometallic compound and the nitrogen-containing heterocyclic carboxylic acid ester may be added by mixing the two components prior to polymerization, or by adding them separately into the polymerization system. The ratio of both components to be sutured is 1 mol or less, particularly preferably 0.9 mol or less, of the nitrogen-containing polycyclic carboxylic acid ester per 1 mol of the organometallic compound. Further, the ratio of each component to be finely mixed is preferably in the range of 1 to 3000 mmol based on the organometallic compound and the component consisting of the organometallic compound and the nitrogen-containing double ring carboxyl ester to the solid catalyst component 1. . The nitrogen-containing square ring carboxylic acid ester to be added to the organometallic compound may be mixed in advance prior to polymerization, or may be added separately into the polymerization system. Particularly preferably, a metal compound reacted with a nitrogen-containing heterocyclic carboxylic acid ester and an organometallic compound are separately added to the polymerization system. The ratio of the two components to be mixed is in the range of 0 mol to 10 mol, particularly preferably 0 mol to 1 mol, of the nitrogen-containing heterocyclic carboxylic acid ester per 1 mol of the organometallic compound. The catalyst consisting of the solid catalyst component of the present invention and a component with or without adding a nitrogen-containing heterocyclic carboxylic acid ester to an organometallic compound may be added to the polymerization system under polymerization conditions, or may be added in advance to the polymerization system prior to polymerization. May be combined. The ratio of each component to be combined is 1 mmol to 3,000 mmol of the component consisting of the organometallic compound and the nitrogen-containing heterocyclic carboxyl ester to the solid catalyst component 1, based on the organometallic compound.
Preferably, the amount is in the millimolar range. 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 stereoregularly. It is also suitable for copolymerizing the olefin with ethylene or other arefins, 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. Possible polymerization methods include ordinary suspension polymerization, bulk polymerization in liquid monomers, and gas phase polymerization. , aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane.
Polymerization can be carried out at temperatures ranging from room temperature to 15,000 degrees Celsius. In bulk polymerization, t-olefins can be polymerized under conditions where the olefin such as propylene is a catalyst and a liquid olefin is used as a polymerization solvent. For example, in the case of propylene, room temperature
The polymerization can be carried out in liquid propylene at a temperature of qo and under a pressure of 10 to 45 k9/kg. On the other hand, gas phase polymerization is carried out under conditions in which the olefin such as propylene is a gas, at a pressure of 1 to 50 kg/ground in the absence of a solvent, from room temperature to 1 kg.
Under the temperature condition of 20q0, it is possible to carry out the polymerization through means such as mixing in a fluidized bed, moving bed, or condenser so that the olefin such as propylene and the catalyst can come into good contact with each other. 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 Synthesis of hydrocarbon-soluble organomagnesium body
- Put 138.0 parts of butylmagnesium and 19.0 parts of triethylaluminum together with 1 part of n-hebutane into a nitrogen-substituted flask, and react at 80 q○ for 2 hours while doing so, to form an organomagnesium complex solution. Obtained. As a result of analysis of this rust body, the composition was AIM node-6 (C2 day 5) 2-9 (n-C4 day 9) 12-1, and the organic metal concentration was 1.25 hol/so. (ii) Synthesis of a magnesium-containing solid material by reaction with a chlorosilane compound Into a well degassed and dried volume 2 flask was added 1 mol of trichlorosilane (HSiC13)/1 mol of its n-heptane solution. While preparing the enemy hol and keeping it at 65qo,
500 hmol of the above organomagnesium complex solution was added dropwise over 1 hour, and the mixture was further reacted at 6500 for 1 hour under Nada Azusa. The produced white solid was heated in an oven for 8U, washed with n-hexane, and dried to obtain 42.5 hours of a white solid substance (A-1). As a result of analyzing this solid substance, it was found that the solid substance had a mass of M. 1
Value mol, CI, 19.2 hmol, Sjl. 7 enemies
mol, contains 0.58 hmol of alkyl group,
B. E. T. The specific surface area measured by the method was 269 force/unit. (1ll) Synthesis of solid catalyst In a nitrogen-substituted container, 600 g of n-hexane and 15 g of ethyl furan-2-carboxylate were added. Add 20 minutes of the above solid with Hmol and heat to 80o while passing.
The mixture was reacted for 1 hour at 1500 ms to obtain a solid (B-1). Weighed out 18 kg of this solid together with 300 kg of titanium tetrachloride in a pressure-resistant container purged with nitrogen, and reacted it for 2 hours at 130 Qo of titanium tetrachloride. 1) was obtained. As a result of analyzing this solid catalyst, it was found that Ti
The content is 2. It was round weight %. (80 m9 of the solid catalyst synthesized on the propylene slurry polymerization side of i, 2.4 mmol of triethylaluminum, and 0.8 hmol of ethyl pyrrole-2-carboxylate were thoroughly degassed and dehydrated, and then the hexane
．． 8 At the same time, the inside was vacuum-dried and replaced with nitrogen, placed in an autoclave with a capacity of 1.5 kg, the internal temperature kept at 6000, and propylene pressurized to a pressure of 5.0 k9/kg, and the total pressure reduced to 4.8 k9/kg. Polymerization was carried out for 2 hours while maintaining the gauge pressure at 1,000 ml, and 174 ml of polymerized hexane-insoluble polymer and 6.3 ml of polymerized hexane-soluble material were obtained. Catalyst efficiency is 9460 terpp/tertitanium component/time/
The pressure was propylene, and the n-heptane extraction residue of the polymerized hexane-insoluble polymer was 96.2%. The particle characteristics were good, with a high density of 0.375 mesh/ground and a ratio of 35 to 150 mesh particles of 90.8%. Example 2 Synthesis of hydrocarbon-soluble organomagnesium rust
138.0 ml of -butylmagnesium and 19.0 ml of triethylaluminum were placed in a nitrogen-substituted flask with 1 part of n-hebutane, and reacted at 8000 for 2 hours with stirring to obtain an organomagnesium key solution. Ta. As a result of analyzing this key body, the composition was NMg6. . (C2 day 5) 2.9 (n-C4 &), 2. , and the organometallic concentration was 1.2 hmol/cell. (ii} Synthesis of a magnesium-containing solid material by reaction with a chlorosilane compound In a well degassed, dry flask with a volume of 2 mmol dichloromethylsilane (HSiCH3CI2)
/The n-heptane solution1. Prepare enemy hol, 690
While maintaining the above organomagnesium solution for 50 hours
mol was added dropwise over 1 hour, and the mixture was further reacted at 6500 for 1 hour. The white solid produced was separated by furnace and refined with n-hexane.
After drying, 42.6 g of white solid material (A-2) was obtained.
As a result of analyzing this solid substance, it was found that M chicks per night. 18 hmol, CII9.2 hmol, Si
l. B.7 hmol, alkyl group 0.6 hmol. E. T. The specific surface area measured by the method is 261
It was evening. (iii) Synthesis of solid catalyst In a nitrogen-substituted container, 600 g of n-hexane and 15 g of methyl thiophene-2-carboxylate were added. India hmol
At the same time, add the above solid 202 and heat to 80o while holding the light.
The mixture was added dropwise at 660° C. over 1 hour, and the mixture was reacted under concentrated conditions at 660° C. for 1 hour. The produced white solid was separated by furnace, purified with n-hexane, and dried to obtain a white solid substance (B-2). This solid was weighed out in a pressure-resistant container purged with nitrogen along with 300 ml of titanium tetrachloride, and reacted for 2 hours at 130 pm under Takaazusa. 2) was obtained. Next, this solid (C-2) 4.0 mm was transferred together with 25 steel balls with a diameter of 10 mm into a steel mill with a diameter of 95 mm and a length of 100 mm. A solid catalyst (S-2) was obtained by pulverizing it using a vibrator for 5 hours. As a result of analyzing this solid catalyst, the Ti content was 2.a% by weight.Synthesized on the propylene slurry polymerization side of ○ Slurry polymerization of propylene was carried out in the same manner as in Example 1 using solid catalyst (S-2) 50:9, 2.4 mmol of triethylaluminum, and 0.8 hmol of ethyl pyrrole-2-carboxylate, and 156 mmol of polymerized hexane-insoluble polymer was obtained. , a polymerized hexane-soluble material of 5.2 mm was obtained.The catalyst efficiency was 14,200 mm-pp/tertitanium component, time, propylene pressure, and n of the polymerized hexane-insoluble polymer.
-Heptane extraction residue was 95.8%. Example 3
2.0 g of the solid catalyst (S-2) synthesized in Example 2 and 30 g of titanium tetrachloride were placed in a pressure-resistant container purged with nitrogen, and after reacting for 2 hours at 13,000 yen under Takaazusa, the solid portion was filtered through a furnace. , refined and dried to obtain a solid catalyst (S-3). As a result of analyzing this solid catalyst, the Ti content was 2. It was $% by weight. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the above solid catalyst (S-3), 2.4 mmol of triethylaluminum, and 0.8 hmol of ethyl pyrrole-2-carboxylate. , polymerized hexane solubles 3.9
I got the evening. The catalytic efficiency is 21,200 pp/tertitanium component/time/propylene pressure, and the n of the polymerized hexane-insoluble polymer is
- Hebutane extraction residue was 96.8%. 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 kept at 600 ml. The solid catalyst (S-3) synthesized in Example 3 was
W9, 1.8 hmol of triethylaluminum and 0.8 hmol of ethyl pyrrole-2-carboxylate were added to an autoclave, and polymerization was carried out at 60° C. for 2 hours under pressure to obtain Polymer 152. Catalyst efficiency is 330,000 terpp/tertitanium component.
time and propylene pressure, and the n-hebutane extraction residue of this polymer was 94.9%. 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 in place of the magnesium-containing solid (il). As a result of analyzing this solid catalyst, the Ti content was 0.81% by weight. Using this solid catalyst 100:9, 2.4 mol of triethylaluminum, and 0.8 hmol of ethyl pyrrole-2-carboxylate, propylene slurry polymerization was carried out in the same manner as in Example 1, and 10.4 mol of hexane-insoluble polymer was polymerized. 2.6 volumes of hexane soluble material were obtained.
The n-heptane extraction residue of polymerized hexane non-falling polymer is 7
4.1%, catalyst efficiency was 1280 terpp/poly-titanium component/hour, propylene pressure. Reference Example 2 In the synthesis of the magnesium-containing solid material of Example 1-(ii), all the procedures were carried out in Example 1-(ii), except that methyltrichlorosilane (C ratio SIC13) was used instead of trichlorosilane (HSiC〆3). ) A magnesium-containing solid substance was synthesized in the same manner as in Example 1, and as a result, 2.06 g of a white solid was obtained. When compared to Example 1-[ii), the yield of solid material was approximately 1'20. Example 5 5.02 kg of the magnesium-containing solid synthesized in the same manner as in Example 1 (ii) and 4 moles of ethyl furan-2-carboxylate were reacted in the same manner as in Example 1 (lii). The obtained solid 4.5 mm and titanium trichloride (AA grade manufactured by Toyo Stoffer Co., Ltd.) 0.38 mm were ground in a vibrating ball mill under a nitrogen atmosphere for 5 hours. This solid (C-5) 43
After reacting with 60 mallets of titanium tetrachloride for 2 hours under 130 mils of water, the solid portion was washed in a furnace, washed with rice bran, and dried.
A solid catalyst (S-5) was obtained. As a result of analyzing this solid catalyst (S-5), the Ti content was 2.2% by weight. 3 of 50 of the above solid catalyst (S-5), 2.4 mmol of triethylaluminum, and 0 of N-carboethoxypyrrole
．． Slurry polymerization of propylene was carried out in the same manner as in Example 1 using 8 hmol, and the results shown in Table 1 were obtained. Example 6 Slurry polymerization of propylene was carried out in exactly the same manner as in Example 5 using 9 of 100 of the solid (C-5) synthesized in Example 5 as a solid catalyst (Ti content 1.6% by weight). The results shown in Table 1 were obtained. Example 7 Analogously to Example 1, a magnesium-containing solid was first reacted with butyl furan-2-carboxylate and then reacted with titanium tetrachloride to give 3.95 g of the resulting solid and titanium trichloride ( AA grade (manufactured by Toyo Stofuer Co., Ltd.) 0.16 mm was ground in a vibrating ball mill for 5 hours. This solid (C-7) 3.2 mm and 60 mm of titanium tetrachloride were
After reacting for 2 hours under a fly pestle at 130 oo, the solid portion was filtered, washed and dried to obtain a solid catalyst (S-7).
As a result of analyzing this solid catalyst, the Ti content was 4. % by weight. 9 of the above solid catalyst (S-7) 30, 2.4 mmol of triethylaluminum, and 0 of N-triboethoxypyrrole. ahmol. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using "The results shown in Table 1 were obtained.
8 Using 9 of the solid (C-7) 50 synthesized in Example 7 as a solid catalyst (Ti content 3.5% by weight), slurry polymerization of propylene was carried out in exactly the same machine as in Example 1. I got the result. Table 1 Example 9 15 kg of the solid (A-1) synthesized in Example 1 was placed in a pressure-resistant container purged with nitrogen, along with 250 m titanium tetrachloride.
After reacting for 2 hours under 130 qo water, the solid portion was filtered, washed with rice bran, and dried to obtain a solid (B-9). This solid (B-9) was mixed with 200 g of n-hexane and 3 g of ethyl thiophene-3-carboxylate. 2 I replaced it with nitrogen along with the skin mol 2 I searched the container and prayed 8
The reaction was carried out at 0°C for 1 hour to obtain a solid catalyst (S-9). As a result of analyzing this solid catalyst, the Ti content was 2.4% by weight.
Met. Slurry polymerization of propylene was carried out in the same manner as in Example 1 using the solid catalyst (S-9) 80-9, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl pyridine-3-carboxylate, and the results shown in Table 2 were obtained. Obtained. Example 10 The solid (B-9) of Example 9 was synthesized in the same manner, and 2.0% of this solid and 0.31% of butyl furan-2-carboxylate were synthesized.
The solid catalyst was ground for 5 hours using the steel vibration mill used in Example 2 to obtain a solid catalyst (S-10). 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 this solid catalyst 50:9, 2.4 mmol of triethylaluminum, and 0.8 hmol of butyl pyridine-4-carboxylate, and the results shown in Table 2 were 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.% by weight) was obtained. This solid catalyst 30 female, triethyl aluminum 2.4 m
mol, and butyl pyridine-4-carboxylate 0.8
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using hmol, 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 compounds shown in Table 3 were used as the hydrocarbon-soluble organomagnesium component and the chlorosilane compound, and ethyl coumarate was used instead of ethyl furan-2-carboxylate. Otherwise, solids (B-12 to B-17) were synthesized in the same manner as in Example 1, and 3.0 mmol of each solid and 2.4 mmol of titanium tetrachloride were added.
It was pulverized for 5 hours in the steel mill used in Example 2, and further treated with titanium tetrachloride to synthesize a collective catalyst. p of this solid catalyst 30, triethylaluminum 2.4
mmol and methyl pyridine-3-carboxylate 0.8
Slurry polymerization of propylene was carried out in the same manner as in Example 1 using hmol, and the results shown in Table 3 were obtained. Table 3 Reference Example 3 and Examples 18 to 20 In the same manner as in Example 1, using 9 of 30 of the solid catalyst (S-3) synthesized in Example 3, 2.4 mmol of triethylaluminum, and the compounds shown in Table 41. Slurry polymerization of propylene was carried out, and the results shown in Table 4 were obtained. Example 21 In the synthesis of the solid catalyst of Example 3, Example 1-(i) was used as the hydrocarbon-soluble magnesium component.
React at a ratio of 0.5 mol of tojethyl ketone to 1 mol of the organomagnesium component synthesized in (both 0.8ho
A solid catalyst was synthesized in the same manner as in Example 3, except that a hexane-soluble composite organomagnesium component prepared in a hexane solution (room temperature; 3 minutes) was used. Slurry polymerization of propylene was carried out in the same machine as in Example 1 using 2.4 mmol of triethylaluminum and 0.8 hmol of N-carbomethoxypyrrole}Table 4 Example 22 In the synthesis of the solid catalyst of Example 21, a solid catalyst (Ti content: 2.3% by weight) was prepared in the same manner as in Example 21 except that sec-butanol was used instead of diethyl ketone.
) was synthesized and ``Slurry polymerization of propylene was carried out in Example 21.
The results shown in Table 4 were obtained. Table 4 Examples 23 to 24 Using the same machine as Example 1, using 30% of the solid catalyst (S-3) synthesized in Example 3, 0.8 hmol of ethyl pyrrole-2-carboxylate, and the organometallic components shown in Table 5. Slurry polymerization of propylene was carried out, and the results shown in Table 5 were obtained. Table 5 Example 25 Butene-1
Polymerization was carried out according to Example 1 to obtain a white polymer 54. Example 26 Polymerization of 4-methylbentene-1 was carried out using 200 grams of the solid catalyst (S-3) synthesized in Example 3, 4.6 hmol of triethylaluminum, and 1.2 hmol of N-triboethoxypyrrole. Working according to Example 1, a white polymer 43 was obtained. Example 27 Using the solid catalyst (S-3) 30-9 synthesized in Example 3, 2.4 mmol of triethylaluminum and 0.8 mmol of N-carboethoxypyrrole, propylene containing 2 mol% of ethylene was prepared instead of propylene. Polymerization was carried out in the same manner as in Example 1, except that ethylene mixed gas was used, and a white polymer 140 was obtained. Example 28 9 of the solid catalyst 60 synthesized in Example 3, triisobutylaluminum 1. Melon hmol and 0.1 mmol of N-carboethoxypyrrole were mixed with 0.8 mmol of dehydrated and degassed n-hexane, and the inside was vacuum dried and replaced with nitrogen.
．． 5 Place it in the autoclave and keep the internal temperature at 80℃.
Hydrogen was pressurized to 1.6 kg/kg and then ethylene was added to bring the total pressure to 4.0 kg/kg.

Claims (1)

[Claims] 1 [A] (1) (i) (a) General formula MαMgβR^
1_pR^2_q (where M is an atom 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 (a) and (b) are reacted with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. (ii) general formula HaSiCl_
bR_4_-_(_a_+_b_) (where a, b are 0
The larger number is a+b≦4, and R represents a hydrocarbon group having 1 to 20 carbon atoms. ); (2) a titanium compound containing at least one halogen atom; (3) a sulfur- or oxygen-containing heterocyclic carboxylic acid ester; ), (2)
, a solid catalyst obtained by reacting and/or pulverizing (3), and [B] a component consisting of an organometallic compound and a nitrogen-containing heterocyclic carboxylic acid ester, which are [A] and [B]. Catalyst for use. 2 [A], (1), (i), (a), α>0
The catalyst for producing polyolefin according to claim 1, wherein the ratio β/α is 1 to 10. 3 [A], (1), (i), (a) in the hydrocarbon-soluble organomagnesium components, α = 0, R^1, R
The catalyst for producing polyolefin according to claim 1, wherein ^2 is one of the following three cases. (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. 4 In [A], (1), and (ii), the value of a is 0<a
The catalyst for producing polyolefin according to any one of claims 1 to 3, wherein ≦2. 5. The catalyst for producing polyolefin according to any one of claims 1 to 4, wherein the titanium compound in [A] and (2) is a compound containing three or more halogens. 6. The catalyst for producing polyolefin according to any one of claims 1 to 5, wherein the titanium compound in [A] and (2) is titanium tetrachloride and/or titanium trichloride. 7 React the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester of [A] and (3) in a ratio of 0.001 to 50 moles per mole of the alkyl group in the solid of [A] and (1). A catalyst for producing a polyolefin according to any one of claims 1 to 6. 8 [A], the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester of (3) is reacted with 0.1 to 10 moles per 1 gram of titanium atom in the solid [A], Claim 1 The catalyst for producing polyolefin according to any one of items 6 to 6. 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 a polyolefin according to claim 9, wherein the organoaluminum compound is trialkylaluminum or dialkylaluminum hydride. 11. The catalyst for producing polyolefin according to any one of claims 1 to 10, wherein the nitrogen-containing heterocyclic carboxylic acid ester [B] is a pyrrole carboxylic acid ester or a pyridine carboxylic acid ester. 12 [A] (1) (i) (a) General formula MαMgβR
^1_pR^2_q (where M is aluminum, zinc,
Atom selected from boron or beryllium, R^1,R
^2 is the same or different hydrocarbon group having 1 to 20 carbon atoms, α≧0, β>0p, q>0, m is the valence of M, p+q
=mα+2β. ), or (a) and (b) are reacted with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. (ii) general formula HaSiClb
A Si-H bond-containing chlorosilane compound represented by R_4_-_(_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 obtained by the reaction, (2) a titanium compound containing at least one halogen atom, (3) a sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester, (1), (2),
The solid obtained by reacting and/or pulverizing (3),
Furthermore, (4) a solid catalyst obtained by treatment with a tetravalent titanium compound containing at least one halogen atom;
[B] A catalyst for producing polyolefin consisting of [A] and [B], which is a component consisting of an organometallic compound and a nitrogen-containing heterocyclic carboxylic acid ester. 13 [A], (1), (i), (a), α>
0, and the ratio β/α is 1 to 10.
Catalyst for producing polyolefin as described in . 14 [A], (1), (i), (a) in the hydrocarbon-soluble organomagnesium compounds, α = 0, R^
13. The catalyst for producing polyolefin according to claim 12, wherein 1 and R^2 are in any of the following three cases. (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 [A], (1), (ii), the value of a is 0<
The catalyst for producing polyolefin according to any one of claims 12 to 14, wherein a<2. 16. The catalyst for producing polyolefin according to any one of claims 12 to 15, wherein the titanium compound in [A] and (2) is a compound containing three or more halogens. 17 [A], Claim 12, wherein the titanium compound in (2) is titanium tetrachloride and/or titanium trichloride.
The catalyst for producing polyolefin according to any one of Items 1 to 16. 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] and (4) is titanium tetrachloride. . 19 React the sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester of [A] and (3) 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 claims 12 to 18. 20 [A], (3) sulfur-containing or oxygen-containing heterocyclic carboxylic acid ester is reacted with 0.1 to 10 moles per gram atom of titanium in the solid [A] Claim 12 19. The catalyst for producing polyolefin according to any one of items 1 to 18. 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 polyolefin according to claim 21, wherein the organic aluminum is trialkylaluminum or dialkylaluminum hydride. 23. The catalyst for producing polyolefins according to any one of claims 12 to 22, wherein the nitrogen-containing heterocyclic carboxylic acid ester [B] is a pyrrole carboxylic ester or a pyridine carboxylic ester.