JPS64408B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for the stereoregular polymerization of olefins, more particularly propylene, butene-1,3-methylbutene-1, pentene-1,
This invention relates to a polymerization method using a polymerization catalyst suitable for stereoregularly polymerizing one type of olefin selected from 1,4-methylpentene-1, etc., or for copolymerizing the above olefin with ethylene or other olefins. be. As a stereoregular polymerization catalyst for olefins, the so-called Ziegler-Natsuta catalyst system is known, which consists of a transition metal compound of Groups 1 to 3 of the Periodic Table of the Elements and an organometallic compound of Groups 1 to 3 of the Periodic Table of the Elements. Among them, combinations of titanium halides and organoaluminum compounds such as triethylaluminum or diethylaluminum chloride are used industrially as catalysts for the production of stereoregular polyolefins. In the polymerization of olefins such as propylene, these catalyst systems produce polyolefins with fairly high stereoregular polymer yields, that is, with boiling n-heptane insoluble fractions, but their polymerization activity is not necessarily high. This is not entirely satisfactory and therefore requires a step to remove catalyst residues from the resulting polymer. Further, as highly active olefin polymerization catalysts, many catalyst systems comprising an inorganic or organic magnesium compound and a titanium or vanadium compound, or the above two components and an electron donor have been proposed.
Examples of inorganic magnesium catalysts include:
According to Polymer Letters, Vol. 3, p855-857 (1965), it has been shown that after reacting magnesium chloride and titanium tetrachloride, triethylaluminum and optionally additives are added to polymerize propylene. In this case, it is described that the use of an electron donor such as ethyl acetate as an additive improves the stereoregularity of the resulting polymer. Furthermore, in Japanese Patent Publication No. 39-12105, particles of magnesium chloride, cobalt chloride, etc. are coated with titanium tetrachloride, etc., and then a metal alkyl such as triethylaluminum, diethylaluminum chloride, etc. is combined and polymerized with ethyl acetate, etc. The addition of additives has been shown to increase the insoluble content of the polymer, and metal salts such as magnesium chloride are used after grinding, and solutions of supported metal salts such as titanium tetrachloride have been shown to increase the insoluble content of the polymer. It is stated that the novel catalyst can be prepared by adding the mixture to 100% and shaking the mixture together. Now, as for the organomagnesium catalyst, which is the other trend, in Japanese Patent Publication No. 31968/1987, when mixing an aluminum halide compound, a titanium compound, and an organomagnesium compound, alkanol, alkenol, etc. are used before, during, or after mixing. , alkanolates, alkenolates, carboxylic acids, esters or salts of carboxylic acids, aldehydes or ketones to form alkenes.
A method of polymerizing at 110°C or higher is described. This method has the advantage that the polymerization can be carried out in such a way that the residence time of the polymer solution in the polymerization reaction zone is kept within 10 minutes, especially 5 minutes. The ratio is still not high enough, the polymer yield per solid catalyst component is insufficient, the content of halogen in the polymer is high, which causes corrosion of the manufacturing process equipment and molding machine, and the product physical properties are not satisfactory. isn't it. The present inventors have published Japanese Patent Application Laid-open No. 54-127889, No. 54-
No. 136591, etc., a chlorosilane compound containing a soluble organomagnesium component and an H-Si bond,
It was proposed that an excellent olefin polymerization catalyst could be obtained by bringing a titanium compound and an electron donor into contact and combining the obtained solid component with an organometallic compound component. It was hoped that it would be simplified. In view of the above points, the present inventors have conducted extensive studies on stereoregular polymerization catalysts for olefins, and have found that
By combining a reaction mixture obtained by adding a specific titanium compound and an electron donor to a reaction mixture obtained by reacting a specific organomagnesium component and a chlorosilane compound containing an H-Si bond, with an organometallic compound. It was discovered that a catalyst suitable for producing excellent polyolefins can be obtained, and the present invention was achieved. That is, the present invention provides a method for polymerizing olefin using a catalyst consisting of a magnesium compound, a titanium compound, an electron donor, and an organoaluminum compound, wherein: [A] (1) (i) (a) General formula M〓Mg〓 _R ¹ _{p R} ² _q
or a number of 0 or more, m is the valence of M, and has the relationship mα+2β=p+q+r+s, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and X and Y are the same or different. Different groups include hydrogen group, OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a halogen, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ represents a hydrogen group or a hydrocarbon group, and R ⁹ represents a hydrocarbon group. Represents a hydrogen group. ), or (a) and
(b) 1 mole of a component (based on magnesium) reacted with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or their derivatives, or alcohols, thioalcohols, amines; (ii) the general formula HaSiCl _b R ¹⁰ _4-(a+b) (In the formula, R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and 0<a
≦2, b is a number greater than 1. ) 0.1 to 10 mol of silicon compound shown at 20 to 150℃
A slurry ^- like reaction mixture obtained by reacting at _a ^temperature of
Represents 20 hydrocarbon groups. ), (3) a slurry-like catalyst component obtained by adding a sulfur-containing or nitrogen-containing heterocyclic carboxylic acid ester, and [B] an organoaluminum compound, the titanium compound of (2) /(3) A method for producing a polyolefin in which a catalyst having a molar ratio of heterocyclic carboxylic acid ester of 0.3 or more is brought into contact with an olefin at a temperature of 100°C or less. The first feature of the present invention is that catalyst synthesis is simple. According to the method of the present invention, a reaction mixture obtained by adding reaction components can be used as is, and a catalyst can be synthesized without undergoing operations such as filtration and drying, thereby reducing waste generation. It has the advantage that there are fewer The second feature of the present invention is that the obtained polymer has good particle properties, especially large particle size. The third feature of the present invention is that the resulting polymer has a good color tone during thermoforming. General formula used in the synthesis of the solid catalyst of the present invention
M〓Mg〓R ¹ _p R ² _q X _r Y _s (where α, β, p, q, r,
s, M, R ¹ , R ² , X, Y have the above meanings)
The organic magnesium component (a) will be explained. Although this compound is shown as a complex compound of organomagnesium, it includes all R ₂ Mg and complexes thereof with other metal compounds. The hydrocarbon group represented by R ¹ to R ⁹ in the above formula is an alkyl group, cycloalkyl group, or allyl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc. are mentioned, especially
Preferably, R ¹ is an alkyl group. Also R ³
or R ⁸ does not prevent it from being a hydrogen atom. As the metal atom M, a metal element belonging to Group 1 or Group 3 of the periodic table can be used, and examples thereof include lithium, sodium, potassium, calcium, beryllium, zinc, barium, boron, aluminum, etc. In particular, lithium, Aluminum, zinc, boron, and beryllium are particularly preferred because they facilitate the formation of hydrocarbon-soluble organomagnesium complexes. Ratio of magnesium to metal atom M β/α
can be set arbitrarily, but is preferably 0 to
Particularly preferred are hydrocarbon soluble organomagnesium complexes in the range 10, especially 0.5 to 10. Relational expression p+q+ of symbols α, β, p, q, r, s
r+s=mα+2β indicates the stoichiometry between the valence and substitution valence of the metal atom, and is in a preferable range of 0≦
(r+s)/(α+β)<1.0 indicates that the sum of X and Y with respect to the sum of metal atoms is greater than or equal to 0 and less than 1.0. A particularly preferred range is 0 to 0.8. These organomagnesium compounds or organomagnesium complexes have the general formula R ¹ MgQ, R ¹ ₂ Mg (R ¹
has the above-mentioned meaning, Q is a halogen), and an organomagnesium compound represented by the general formula MR ² _n
or an organometallic compound represented by MR ² _n-1 H (M, R ² , m have the above-mentioned meanings) in hexane,
The reaction is carried out in an inert hydrocarbon medium such as heptane, cyclohexane, benzene, toluene, etc. between room temperature and 150°C, and if necessary, this is further treated with alcohol, water, siloxane, amine, imine, etc.
Synthesized by reacting with mercaptans or dithio compounds. Furthermore, the organomagnesium compound or organomagnesium complex may contain MgX ₂ ,
R ¹ MgX and MR ² _n , MR ² _n-1 H, or R ¹ MgX,
MgR ¹ ₂ and R ² _o MX _no , or R ¹ MgX, MgR ₂ and _Yo
By reaction with MX _no (where M, R ¹ , R ² , X, and Y are as described above, including the case where X and Y are halogens, and n is a number from 0 to m) Can be synthesized. Generally, organomagnesium compounds are insoluble in inert hydrocarbon media, and organomagnesium complexes where α>0 are soluble. Further, even when α=0, certain organomagnesium compounds, such as sec-Bu ₂ Mg, are soluble in hydrocarbon media, and such compounds also give favorable results when used in the present invention. I will explain about it. In the general formula Mg〓R ¹ _p R ² _q X _r Y _s , R ¹ and R ² are assumed to be one of the following three groups (), (), and (). () At least one of R ¹ and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ^{1 and R 2 are 4 to 6 carbon atoms, and at least one of R 1} and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms. One of both is a secondary or tertiary alkyl group. () R ¹ and R ² are alkyl groups with different numbers of carbon atoms, preferably R ¹ is an alkyl group with 2 or 3 carbon atoms, and R ² is an alkyl group with 4 or more carbon atoms. thing. () At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, preferably
Both R ¹ and R ² are alkyl groups having 6 or more carbon atoms. These groups will be specifically shown below. Examples of secondary or tertiary alkyl groups having 4 to 6 carbon atoms in parentheses include sec-C ₄ H ₉ , tert-C ₄ H ₉ ,

【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

[Formula] etc. are used, preferably a secondary alkyl group, sec-C ₄ H ₉
is particularly preferred. Next, in (), examples of the alkyl group having 2 or 3 carbon atoms include ethyl group and propyl group, with ethyl group being particularly preferred, and examples of the alkyl group having 4 or more carbon atoms include butyl group, amyl group, hexyl group, Examples include octyl group, and butyl group and hexyl group are particularly preferred. In (), hydrocarbon groups having 6 or more carbon atoms include hexyl group,
Examples include octyl group, decyl group, phenyl group, etc., with alkyl groups being preferred, and hexyl groups being particularly preferred. It is important that the organomagnesium compound used in the present invention is soluble in a hydrocarbon medium. Increasing the number of carbon atoms in an alkyl group makes it easier to dissolve in a hydrocarbon medium, but this tends to increase the viscosity of the solution, and it is not preferable to use an alkyl group with an unnecessarily long chain from the viewpoint of handling. The above organomagnesium compound is used as a hydrocarbon solution, but it can be used even if a trace amount of a complexing agent such as ether, ester, or amine is contained or remains in the solution. In the general formula, α=0, β=1, q=0, r=
The organomagnesium halide No. 1 will be explained. This compound is a so-called Grignard compound and is generally synthesized by reacting magnesium with an organic halide in an ether solution, but the reaction can also be carried out in a hydrocarbon medium in the absence of ether. known and both can be used. Examples of these include, for example, methylmagnesium chloride, methylmagnesium bromide,
Methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide,
Ethylmagnesium iodide, n- or
iso-propylmagnesium chloride, n- or iso-propylmagnesium bromide, n- or iso-propylmagnesium iodide,
n-butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, iso-, sec- or tert-butylmagnesium chloride, iso-, sec- or
tert-butylmagnesium bromide, iso-, sec
- or compounds such as tert-butylmagnesium iodide, n-amylmagnesium chloride, n-amylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, octylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, and ethers thereof Complexes can be mentioned. Examples of these ether compounds include various ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diallyl ether, tetrahydrofuran, dioxane, and anisole. Next, the reaction between (a) the organomagnesium component and (b) the electron donating compound will be explained. (a) As the organomagnesium component, each of the above components can be used, but it is preferable to react with (b) an electron donating compound in the liquid phase, and an organomagnesium soluble in a hydrocarbon or ether solvent. Ingredients give favorable results. (a) The electron donating compound (b) to be reacted with the organomagnesium component is as follows. Ether represented by the general formula ROR' (where R
and R' is an aliphatic, aromatic or cycloaliphatic hydrocarbon group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl, cyclohexyl, phenyl, benzyl, etc.), general A thioether of the formula RSR′, where
R and R' are aliphatic, aromatic or cycloaliphatic hydrocarbons, for example methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl, etc.), ketones of the general formula RCOR' ( In the formula, R
and R' is an aliphatic, aromatic or alicyclic hydrocarbon group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl, etc., with dimethyl ketone, diethyl ketone, etc. being particularly preferred) , aliphatic, aromatic and cycloaliphatic aldehydes, hydrocarbon carboxylic acids or derivatives thereof, more specifically hydrocarbon carboxylic acids, hydrocarbon carboxylic acid anhydrides, hydrocarbon carboxylic esters, hydrocarbon carboxylic acids These are carboxylic acid halides and hydrocarbon-based carboxylic acid amides. These will be described in more detail below. Examples of the hydrocarbon carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, acrylic acid, benzoic acid, toluic acid, and terephthalic acid. Examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, and the like. Hydrocarbon carboxylic acid esters include methyl and ethyl formate, methyl acetate, ethyl, propyl, methyl propionate, ethyl, propyl,
Butyl, ethyl butyrate, ethyl valerate, ethyl caproate, ethyl n-heptanoate, dibutyl oxalate, ethyl succinate, ethyl malonate, dibutyl maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate , ethyl, propyl, butyl, methyl toluate, ethyl, propyl, butyl, amyl, methyl and ethyl p-ethylbenzoate, methyl anisate, ethyl, propyl and butyl, methyl, ethyl p-ethoxybenzoate. As hydrocarbon carboxylic acid halides,
Acid chlorides are preferred, and include acetyl chloride, propionyl chloride, butyryl chloride, succinyl chloride, benzoyl chloride, and tolyl chloride. Examples of the hydrocarbon 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.
Secondary, tertiary or aromatic alcohols such as sec-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol, sec-amyl alcohol, tert-amyl alcohol, sec-hexyl alcohol, phenol, o, m, p-cresol, etc. is preferred. Examples of thioalcohols include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan,
Examples include hexyl mercaptan and phenyl mercaptan, but secondary, tertiary or aromatic thioalcohols are preferred. Examples of amines include aliphatic, alicyclic and aromatic amines, secondary to tertiary amines,
For example, trialkylamines, triphenylamines, pyridine, etc. give favorable results. Next, for the reaction of (a) the organomagnesium component and (b) the electron donor compound, the reaction is carried out in an inert reaction medium, e.g., an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, etc. The reaction can be carried out in a hydrocarbon, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, an ether solvent, or a mixed solvent thereof. Regarding the reaction order, it is possible to use the method of adding the electron donating compound to the organomagnesium component (), the method of adding the organomagnesium component to the electron donating compound (), or the method of adding both at the same time (). can. Regarding the reaction ratio of the organomagnesium component and the electron donating compound, per 1 mole of the organomagnesium component, the electron donating compound is 1 mole or less, preferably
0.01 to 0.8 mol, particularly preferably 0.05 to 0.5
It is a mole. Next, (ii) general formula HaSiCl _b R ¹⁰ _4-(a+b) (wherein a,
b, R ¹⁰ has the above meaning)
The bond-containing chlorosilane compound will be explained. The hydrocarbon group represented by R ¹⁰ 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, decyl, Examples include cyclohexyl, phenyl group, etc.
Preferred are alkyl groups having 1 to 10 carbon atoms, and lower alkyl groups such as methyl, ethyl, and propyl are particularly preferred. The value of b is b>0, a+b≦4, 0
<a≦2, and preferably 0.5≦a≦1.5. These compounds include HSiCl ₃ ,
HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl _2o ―C ₃ H ₇ ,
HSiCl ₂ iso―C ₃ H ₇ , HSiCl _2o ―C ₄ H ₉ ,
HSiCl ₂ C ₆ H ₅ , HSiCl ₂ (4-Cl-C ₆ H ₄ ),
HSiCl ₂ CH=CH ₂ , HSiCl ₂ CH ₂ C ₆ H ₅ , HSiCl ₂ (1
-C ₁₀ H ₇ ), HSiCl ₂ CH ₂ CH=CH ₂ , H ₂ SiClCH ₃ ,
H ₂ SiClC ₂ H ₅ , HSiCl(CH ₃ ) ₂ , HSiClCH ₃ (iso-
C ₃ H ₇ ), HSiClCH ₃ (C ₆ H ₅ ), HSiCl (C ₂ H ₅ ) ₂ ,
HSiCl(C ₆ H ₅ ) ₂ , etc., and chlorosilane compounds consisting of mixtures of these compounds and compounds selected from these compounds are used, including trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, and ethyldichlorosilane. Chlorosilane and the like are preferred, and trichlorosilane and monomethyldichlorosilane are particularly preferred. The reaction between the organomagnesium component (i) and the chlorosilane compound (ii) will be explained below. The reaction of an organomagnesium compound or an organomagnesium complex with a 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, cyclohexane, methylcyclohexane, etc. The reaction can be carried out in an alicyclic hydrocarbon, an ether medium such as ether or tetrahydrofuran, or a mixed medium thereof. In terms of catalyst performance, aliphatic hydrocarbon media are preferred. The reaction temperature can be carried out at 20-150℃,
In view of the progress of the reaction, the reaction is preferably carried out at a temperature above the boiling point of chlorosilane or above 40°C. There is no particular restriction on the reaction ratio of the two components, but it is preferably in the range of 0.1 to 10 mol, particularly preferably 0.2 to 5 mol, of the chlorosilane component per 1 mol (based on magnesium) of the organomagnesium component. Regarding the reaction method, two types of components are simultaneously introduced into the reaction zone and reacted (method I○);
Alternatively, a method in which the chlorosilane component is charged in advance into the reaction zone and then the organomagnesium component is introduced into the reaction zone and reacted (method RO○), or a method in which the organomagnesium component is charged in advance and the chlorosilane component is added (method Method C○), but the latter two are preferable, and Method B○ gives particularly preferable results. In the present invention, the reaction mixture obtained by reacting the organomagnesium component and the chlorosilane compound is not subjected to any operations such as filtering or washing.
Component [A] can be obtained by adding a titanium compound and a heterocyclic carboxylic acid ester. Next, (2) a titanium compound represented by the general formula Ti(OR ¹¹ ) ₄ (wherein R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms) will be described. The hydrocarbon group represented by R ¹¹ 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, heptyl, Octyl, nonyl, decyl, cetyl, stearyl, 2-ethylhexyl, cyclopentyl,
Examples include cyclohexyl, phenyl, cresyl, naphthyl, and the like. Specific examples of these compounds include Ti
(OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti
(Oiso―C ₃ H ₇ ) ₄ , Ti (On―C ₄ H ₉ ) ₄ , Ti (Osec―
C ₄ H ₉ ) ₄ , Ti (Oiso-C ₄ H ₉ ) ₄ , Ti (Otert-C ₄ H ₉ ) ₄ ,
Ti(On―C ₅ H ₁₁ ) ₄ , Ti(Otert―C ₅ H ₁₁ ) ₄ , Ti(On
―C ₆ H ₁₃ ) ₄ , Ti(On―C ₇ H ₁₅ ) ₄ , Ti(On―
C ₈ H ₁₇ ) ₄ , Ti (Oiso-C ₅ H ₁₁ ) ₄ , Ti (On-C ₉ H ₁₉ ) ₄ ,
Ti(On-C ₁₀ H ₂₁ ) ₄ , Ti(On-C ₁₆ H ₃₃ ) ₄ , Ti(On-
C ₁₈ H ₃₇ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ [Titanium 2etyl
hexoide], Ti(OC ₆ H ₁₁ ) ₄ , Ti(OC ₆ H ₅ ) ₄ , Ti
Examples include (OC ₆ H ₄ CH ₃ ) ₄ and Ti(OC ₁₀ H ₇ ) ₄ , and titanium compounds consisting of these compounds and mixtures selected from these compounds are used. Examples of the sulfur-containing heterocyclic carboxylic acid esters in (3) include thiophene carboxylic esters, thianaphthenes carboxylic esters, isothianaphthene carboxylic esters, benzothiophene carboxylic esters, phenoxathiine carboxylic esters, and benzothiane carboxylic esters. Examples include esters, thiaxanthenes carboxylic acid esters, thioindoxyls carboxylic acid esters, etc. More specifically, methyl, ethyl, propyl, butyl and amyl thiophene-2-carboxylate, thiophene-3-carboxylic acid Methyl, ethyl, propyl, butyl and amyl, methyl thiophene-2,3-dicarboxylate, ethyl, methyl thiophene-2,4-dicarboxylate, ethyl, methyl thiophene-2,5-dicarboxylate, ethyl, 2-thienylacetic acid Methyl, ethyl, propyl, butyl, methyl 2-thienyl acrylate, ethyl, methyl 2-thienylpyruvate, ethyl,
thianaphthene-2-carboxylic acid methyl, ethyl,
thianaphthene-3-carboxylic acid methyl, ethyl,
methyl thianaphthene-2,3-dicarboxylate, ethyl, methyl 3-oxy-2-thianaphthenecarboxylate, ethyl, methyl 2-thianaphthenylate,
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 phenoxathiin-2-carboxylate, ethyl, phenoxathiin-3
- Methyl carboxylate, ethyl etc. More preferred are methyl, ethyl, propyl and butyl thiophene-2-carboxylate,
Thiophene-3-carboxylic acid methyl, ethyl, 2
-methyl thienyl acetate, ethyl, methyl 2-thienyl acrylate, ethyl, methyl thianaphthene-2-carboxylate, ethyl, and the like. Examples of nitrogen-containing heterocyclic carboxylic esters include pyrrole carboxylic esters, indoles carboxylic esters, carbazole carboxylic esters, oxazole carboxylic esters, thiazole carboxylic esters, imidazoles carboxylic esters, and pyrazole carboxylic esters. Ester, pyridine carboxylic acid ester, phenanthridine carboxylic acid ester, anthrazoline carboxylic acid ester, phenanthroline carboxylic acid ester, naphthyridine carboxylic acid ester, oxazine carboxylic acid ester, thiazine carboxylic acid ester, pyridazine carboxylic acid ester Examples include acid esters, pyrimidine carboxylic esters, pyrazines carboxylic esters, and preferred ones include methyl, ethyl, propyl, and butyl pyrrole-2-carboxylate, methyl, ethyl, propyl, and pyrrole-3-carboxylate. Butyl, methyl pyridine-2-carboxylate,
Ethyl, propyl, butyl and amyl, methyl pyridine-3-carboxylate, ethyl, propyl,
Butyl and amyl, methyl pyridine-4-carboxylate, ethyl, propyl, butyl and amyl, methyl pyridine-2,3-dicarboxylate, ethyl, methyl pyridine-2,5-dicarboxylate,
Ethyl, methyl pyridine-2,6-dicarboxylate, ethyl, methyl pyridine-3,5-dicarboxylate, ethyl, methyl quinoline-2-carboxylate, ethyl, ethyl dimethylpyrrolecarboxylate, ethyl N-methylpyrrolecarboxylate, 2-
Ethyl methylpyridinecarboxylate, piperidine
Examples include ethyl 2-carboxylate, ethyl piperidine-4-carboxylate, and ethyl pyrrolidine-2-carboxylate. To explain the reaction of components (1), (2) and (3), a solid component is produced by the reaction of (i) and (ii),
After the reaction of (i) and (ii) is completed, it is preferable to add and react this reactant with component (2) and component (3). The amount of component (2) used is a molar ratio of 3≦Mg/Ti≦500,
Preferably, the reaction is carried out in the range of 10≦Mg/Ti≦100, and it is desirable that the concentration of Ti in the reaction solution is 4 mol/or less. The reaction temperature is not particularly limited, but is preferably carried out within the range of 50 to 150°C in view of the progress of the reaction. The amount of component (3) used is preferably such that the ratio of component (2) to component (3), ie, the molar ratio component (2)/component (3), is 0.3 or more, particularly 0.4 or more. The concentration of the heterocyclic carboxylic acid ester in the reaction solution is preferably 5 mol/or less, and the reaction temperature is carried out in the range of 40 to 160°C. Regarding the method of reacting components (1), (2), and (3),
The heterocyclic carboxylic acid ester (3) can be added before, after, or simultaneously with the addition of the titanium compound (2) to the component (1);
A method of adding before or at the same time as adding (2) is preferred. Examples of the organic aluminum compound [B] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-
n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum,
Trialkylaluminiums such as tri-n-dodecylaluminum, trihexadecylaluminum, and aluminum isoprenyl are mentioned,
(C ₂ H ₅ ) ₂ Al―O―Al(C ₂ H ₅ ) ₂ ,

Organoaluminum compounds having two or more aluminum atoms bonded via O or N atoms such as [Formula], dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum Chloride, di-i-butylaluminum chloride, di-
n-hexylaluminum chloride, di-i-hexylaluminum chloride, di(2-ethylhexyl)aluminum chloride, di-n-dodecylaluminum chloride, methyl-i-butylaluminum chloride, ethyl-i-butylaluminum chloride, methylaluminum sesquichloride , ethylaluminum sesquichloride, i-butylaluminum sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, i-butylaluminum dichloride, diethylaluminum bromide, diethylaluminum chloride, and the like. Components [A] and [B] may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. Further, the ratio of both components to be combined is defined by the molar ratio of Ti and M in the [A] component and Al in the [B] component, and the preferable range is (M+Al)/Ti from 3/1 to 1000. /1. The present invention is a highly active and highly stereoregular polymerization catalyst for olefins. In particular, the present invention provides propylene,
Suitable for stereoregular polymerization of butene-1, pentene-1,4-methylpentene-1,3-methylbutene-1 and similar olefins alone.
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, usual suspension polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization are possible. Suspension polymerization involves using a catalyst in a reactor with a polymerization solvent such as an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane. 1 to 20 kg of olefin such as propylene under an inert atmosphere.
cm ² can be press-fitted and polymerization can be carried out at a temperature of 100°C or less. In the bulk polymerization, 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, 100℃
Polymerization can be carried out in liquid propylene at the following temperatures: On the other hand, gas phase polymerization involves contacting an olefin such as propylene with a catalyst in the absence of a solvent at a pressure of 1 to 50 kg/cm ² and at a temperature below 100°C, under conditions where the olefin such as propylene is a gas. Polymerization can be carried out using means such as a fluidized bed, a moving bed, or mixing using a stirrer so that the polymerization can be carried out in a good manner. The present invention will be explained below using examples. In addition,
The boiling n-heptane extraction residue used in the examples means the residue obtained by extracting the polymer with boiling n-heptane for 6 hours, and the melting index (MFI) is:
According to ASTM D-1238, temperature 230℃, load
Measured under the condition of 2.16Kg. Yes,
The symbols in Table 1 are Et=C ₂ H ₅ , Pr=C ₃ H ₇ , Br=
_C4H9 , _{Am = C5H11} . Example 1 (1) Synthesis of hydrocarbon-soluble organomagnesium complex 69.5 g of di-n-butylmagnesium chloride and 9.73 g of triethylaluminum were mixed with n-heptane.
The mixture was placed in a nitrogen-purged flask with 500 ml, and reacted at 80°C for 2 hours with stirring to obtain an organomagnesium complex solution. As a result of analyzing this solution, the organic metal concentration was 1.25 mmol/, and the composition was
AlMg _6.0 (C ₂ H ₅ ) _3.0 (n-C ₄ H ₉ ) _12.0 . (2) Synthesis of component [A] A sufficiently dried flask with a capacity of 1 was charged with 500 mmol of a solution of 1 mol of trichlorosilane (HSiCl ₃ ) in n-heptane, and 500 mmol of the above organomagnesium complex solution was added to the system at 65°C for 1 hour. The reaction was continued at 65°C for an additional hour with stirring. Next, at 60℃, 25 mmol of ethyl thiophene-2-carboxylate (n-hexane solution: 0.5 mol/)
was added and reacted for 1 hour, then Ti
12.8 mmol of (OnC ₄ H ₉ ) ₄ was added and reacted at 70°C for 1 hour. (3) Polymerization of propylene 0.040mg atom of Ti was taken from the component [A] synthesized in (2), and 0.20mmol of triethylaluminum and 0.8mole of hexane were added to a sufficiently dried volume of 1.5
Place it in an autoclave and keep the internal temperature at 60℃.
Pressurize propylene to a pressure of 5.0Kg/cm ² and reduce the total pressure.
Polymerization was carried out for 2 hours while maintaining the gauge pressure at 4.8 kg/cm ² to obtain 160 g of hexane-insoluble polymer and 13.6 g of hexane-soluble material. Catalyst efficiency is 83500g-pp/g
-Ti, the n-heptane extraction residue of the hexane-insoluble polymer was 92.7%, and the average particle size was 60 mesh. (4) Polymerization in liquefied propylene The catalyst slurry [A] synthesized in (2) was changed to Ti.
0.040mg atomically weighed triethylaluminum
After charging 0.2 mmol and 10 mmol of hydrogen into an autoclave and introducing liquefied propylene 2, the temperature was lowered to 65
Polymerization was carried out for 2 hours with stirring while maintaining the temperature at °C to obtain 502 g of polypropylene powder. This powder n-
The heptane extraction residue was 93.9%. Examples 2 to 15 In the synthesis of the catalyst of Example 1, the compounds and components shown in Table 1 were used to synthesize the catalyst.
Polymerization of propylene was carried out in the same manner as above, and the results shown in Table 1 were obtained.

【table】

[Table] Example 16 Component [A] synthesized in Example 1 (titanium
0.04mg atom) and triethylaluminum 0.2mmol
Butene-1 was polymerized using
Obtained 35g. Example 17 Component [A] synthesized in Example 1 (titanium
0.04mg atom) and triethylaluminum 0.2mmol
Polymerization of 4-methylpentene-1 was carried out using the following method to obtain 31 g of a white polymer. Example 18 Component synthesized in Example 1 (0.04mg titanium)
Polymerization was carried out in the same manner as in Example 1, except that propylene was replaced with propylene containing 2 mol% of ethylene, using 0.2 mmol of triethylaluminum, and 165 g of a white polymer was obtained. Example 19 Component [A] synthesized in Example 1 (titanium
0.04mg atom) and triethylaluminum 0.2mmol
The procedure was repeated in the same manner as in Example 1 except that propylene was replaced with propylene containing 2 mol % of butene-1, and 131 g of a white polymer was obtained. Example 20 Component [A] synthesized in Example 1 (titanium
0.03mg atom) and triisobutylaluminum
Put 0.2 mmol of purified hexane and 0.8 of purified hexane into a 1.5 capacity autoclave purged with dry nitrogen.
Maintaining the internal temperature at 80℃, pressurizing hydrogen to 1.6Kg/ ^cm2 ,
Next, ethylene was replenished and polymerization was carried out for 1 hour while maintaining the total pressure at 4.0 Kg/cm ² to obtain 106 g of a white polymer.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a catalyst in the present invention.

Claims (1)

[Claims] 1. A method for polymerizing olefin using a catalyst consisting of a magnesium compound, a titanium compound, an electron donor, and an organoaluminum compound, wherein [A] (1) (i) (a) General formula M〓Mg _〓R ¹ _{p R} ² _q
s is 0 or a number of 0 or more, m is the valence of M, and has the relationship mα+2β=p+q+r+s, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X, Y are the same or different groups, such as a hydrogen group, OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represent halogens, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ represent hydrogen groups or hydrocarbon groups, and R ⁹ represents carbonized Represents a hydrogen group. ), or (a) and (b) react with an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. (ii) General formula HaSiCl _b R ¹⁰ _4-(a+b) (where R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and 0< a≦
2, b is a number greater than 1. ) to a slurry-like reaction mixture obtained by reacting 0.1 to ¹⁰ _mol of silicon compound represented ^by ~
Represents 20 hydrocarbon groups. ), (3) a slurry-like catalyst component obtained by adding a sulfur-containing or nitrogen-containing heterocyclic carboxylic acid ester, and [B] an organoaluminum compound, the titanium compound of (2) A method for producing a polyolefin, which comprises contacting an olefin with a catalyst having a molar ratio of heterocyclic carboxylic acid ester of /(3) of 0.3 or more at 100°C or less. 2 (1) - In the organomagnesium component of (i), M
The method for producing a polyolefin according to claim 1, wherein is lithium, beryllium, boron, aluminum or zinc. 3 In the organomagnesium component of (1)-(i), α
>0 and β/α is 0.5 to 10, the method for producing a polyolefin according to claim 1 or 2. 4 (1) - In the organomagnesium component of (i), 0
≦(r+s)/(α+β)<1 The method for producing a polyolefin according to any one of claims 1 to 3. 5 (1) - In the organomagnesium component of (i), α
The method for producing a polyolefin according to claim 1, wherein: =0. 6 In the organomagnesium component of (1)-(i), α
The method for producing a polyolefin according to claim 1, wherein R 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, and at least one is a secondary or tertiary alkyl group. (b) R ¹ is a noalkyl group having 2 to 3 carbon atoms, and R ² is an alkyl group having 4 or more carbon atoms. (c) R ¹ and R ² are both alkyl groups having 6 or more carbon atoms. 7 The halogenated silicon compound of (1)-(ii) has the general formula
Silicon represented by HaSiCl _b R ¹⁰ _4-(a+b) (wherein R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, 0.5≦a≦1.5, and b is a number larger than 1) A method for producing a polyolefin according to any one of claims 1 to 6, which is a compound. 8 The heterocyclic carboxylic acid ester in (3) is a thiophene carboxylic ester, a pyridine carboxylic ester, a pyrrole carboxylic ester, a furan carboxylic ester, and is an ester of a lower alcohol (having 1 to 5 carbon atoms). A method for producing a polyolefin according to any one of claims 1 to 7. 9. The method for producing a polyolefin according to any one of claims 1 to 8, wherein the organoaluminum compound [B] is trialkylaluminum or dialkylaluminum hydride.