JPH0242365B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a method for polymerizing olefins using a novel catalyst, and more specifically, a method for polymerizing olefins using a novel catalyst, and more specifically, a method for polymerizing olefins using a novel catalyst. The present invention relates to a method for polymerizing olefins using the catalyst used. As a polymerization catalyst for olefins, a so-called Ziegler catalyst system consisting of a transition metal compound of Groups A to A of the Periodic Table of the Elements and an organometallic compound of Groups A to A of the Periodic Table of the Elements is known. Catalyst systems consisting of inorganic magnesium compounds and titanium or vanadium compounds or additionally electron donors, such as polymers, can be used as catalysts.
Letters Vol. 3, p. 855, Japanese Patent Publication No. 39-12105, etc., have proposed many catalyst systems comprising an organomagnesium compound and a titanium or vanadium compound, or further an electron donor. In the case of organomagnesium catalysts, for example,
In Publication No. 31968, when mixing an aluminum halide compound, a titanium compound, and an organomagnesium compound, alkanol, alkenol, alkanolate,
by adding an alkenolate, a carboxylic acid, an ester or salt of a carboxylic acid, an aldehyde or a ketone,
A method for polymerizing alkenes at 110°C or higher is described. Furthermore, Tokuko Sho No. 50-32270, Tokuko Sho
53-46799, JP 50-95382, JP 55-58207, JP 57-205407,
A proposal has also been made in Japanese Unexamined Patent Publication No. 57-205409. In addition, Special Publication No. 43046, Publication No. 56-43046, Special Publication No. 57-43046,
Publication No. 9567, Patent Application No. 14940, Patent Application No. 1982-
No. 64006, Patent Application No. 1983-67303, Patent Application No. 1983-68834
In this issue, organomagnesium components and H-Si
-We are proposing an olefin polymerization catalyst using a solid material containing active organomagnesium obtained by reacting chlorosilane containing a Cl bond. Although these catalyst systems show excellent performance, they are still not satisfactory. The present inventors have discovered that the organomagnesium component H—Si—
As a result of intensive investigation into a polymerization method using a catalyst system comprising a Cl bond-containing chlorosilane, an electron donor compound, a transition metal compound, and an organometallic compound, an excellent method for polymerizing olefins was discovered. That is, the present invention provides the following formula: [A](1)(i) (a) General formula M〓Mg〓R ¹ _p R ² _q XrYs (wherein, M
are Al, Zn, B, Be, Li atoms, R ¹ and R ² are the same or different C ₁ to C ₁₀ hydrocarbon groups,
X, Y are the same or different OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a halogen group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸
is a hydrogen atom or a _C1 - _C10 hydrocarbon group, ^R9 is a _C1 - _C10 hydrocarbon group,
α≧0, β>0, p, q, r, s≧0, m
is the valence of M, p+q+r+s=mα+
2β, 0≦(r+s)/(α+β)≦1. ), or a component reacted with (a) and (b) an electron donor selected from ethers, thioethyls, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. 1 mol, (ii) General formula HaSiClbR ¹⁰ _4-(a+b) (where a, b are numbers larger than 0, a+b≦4, 0<a≦
2. ^R10 represents a hydrocarbon group having 1 to 20 carbon atoms) 0.01 to 100 mol of a H--Si bond-containing chlorosilane compound is added to (i) an inorganic carrier in the presence or absence of an inorganic carrier selected from the following. Oxide (ii) Inorganic carbonate, silicate, sulfate (iii) Inorganic hydroxide (iv) Double salt, solid solution or mixture of (i) to (iii), C contained in the solid obtained by reaction -Mg
For 1 mole of bond, (2) the solid obtained by reacting 0.05 to 20 moles of a compound selected from the following: (i) aldehyde (ii) silanol (iii) hydrogen siloxane (3) titanium compound, vanadium compound, 1 selected from zirconium compounds, hafnium compounds, and mixtures or reactants thereof
A solid catalyst component obtained by reacting more than one component, or (4) a titanium tetrahalide compound, a halide of aluminum, a halide of silicon,
Solid catalyst component [B] obtained by treatment with a component selected from tin halides This is an olefin polymerization method in which a catalyst consisting of [A] and [B], which is an organometallic compound component, is brought into contact with olefin. The first feature of the present invention is that especially titanium
The catalytic efficiency per gram is high. In the case of Example 1, 1670Kg-PE/g-Ti and 33400g-
PE/g-solid catalyst component is obtained. The second feature of the present invention is that the obtained polymer particles have a large bulk density. In the case of suspension polymerization (in the case of Example 1-(4)), 0.48 g/cm ³ was obtained. The third feature of the present invention is that the copolymerization effect during olefin copolymerization is good. The fourth feature of the present invention is that the olefin polymer or olefin copolymer has a good hue. The organomagnesium component used in this application has the general formula M〓Mg〓R ¹ _p R ² _q XrYs (where M is
Al, Zn, B, Be, Li atoms, R ¹ and R ² are the same or different C ₁ to ₁₀ hydrocarbon groups, X and Y are the same or different OR ³ , OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represent a halogen group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
^R8 is hydrogen or _{a C1-10 hydrocarbon} group, ^R9
is a _C1-10 hydrocarbon group, α≧0, β>0,
p, q, r, s≧0, m is the valence of M, p+q+
r+s=mα+2β, 0≦(r+s)/(α+β)≦
There is a relationship of 1. ) can be used. 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, a cycloalkyl group, or an aryl group, such as methyl, ethyl,
propyl, butyl, amyl, hexyl, decyl,
Examples include cyclohexyl, phenyl groups, etc., especially
Preferably, R ¹ is an alkyl group. Also,
There is no preclude that R ³ to R ⁸ are hydrogen atoms. As the gold element M, metal elements belonging to Group 1 or Group 3 of the periodic table can be used, such as sodium, potassium, calcium, beryllium,
Examples include zinc, barium, boron, aluminum, lithium, etc., especially aluminum, zinc,
Boron, beryllium, and lithium 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 of the metal atom and the substituent, and is in a preferable range of 0≦
(r+s)/(α+β)≦1.0 indicates that the ratio of the sum of X and Y to the sum of metal atoms is 0 or more and less than 1.0. A particularly preferred range is 0 to 0.8. These organomagnesium compounds or organomagnesium complexes have the general formula RMgQ, R ₂ Mg (R
has the above-mentioned meaning, and Q is a halogen), and an organomagnesium compound represented by the general formula MR _n
or an organometallic compound represented by MR _n-1 H (M, R, 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, organomagnesium compounds or organomagnesium complexes include MgX ₂ ,
RMgX and MR _n , MR _n-1 H, or RMgX,
MgR ₂ and R _o MX _no , or RMgX, MgR ₂ and Y _o
MX _no (where M, R, X, Y are as described above, including the case where X, Y are halogen, n
is a number from 0 to m). In general, 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 has 4 or more carbon atoms
6 is a secondary or tertiary alkyl group. Preferably R ¹ and R ² both have 4 carbon atoms.
-6, and at least one of them is a secondary or tertiary alkyl group. () R ¹ and R ² are alkyl groups with different numbers of carbon atoms, preferably R ⁴ 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, R ¹ ,
Both 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 and 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 () the number of carbon atoms is 2
Examples of the alkyl group of or 3 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, octyl group, etc.
Butyl group and hexyl group are particularly preferred. Examples of the hydrocarbon group having 6 or more carbon atoms in () include hexyl group, octyl group, decyl group, phenyl group, etc., and alkyl groups are preferable, with hexyl group being particularly preferable. It is important that the organomagnesium compound used in the present invention is soluble in the 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-mentioned organomagnesium compound is used as a hydrocarbon solution, but it can be used without any problem even if a trace amount of a complexing agent such as ether, ester, or amine is contained or remains in the solution. It is also possible to use an organomagnesium halide as the organomagnesium component. 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. The electron donor (b) to be reacted with the hydrocarbon-soluble organomagnesium component (a) 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,
Examples include hydrocarbon groups such as octyl, dodecyl, cyclohexyl, phenyl, and benzyl. Also for the thioether RSR', R and R' are aliphatic, aromatic and alicyclic hydrocarbons, for example, hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl, etc. Can be mentioned. For the ketone RCOR', R and R' are aliphatic, aromatic and cycloaliphatic hydrocarbon groups, e.g.
Examples include methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, phenyl and the like, with dimethyl ketone, diethyl ethone and the like being particularly preferred. Regarding aldehydes, aliphatic, aromatic and cycloaliphatic aldehydes are also used. Examples of carboxylic acids or derivatives thereof include carboxylic acids, carboxylic anhydrides, carboxylic esters,
Carboxylic acid halides and carboxylic acid amides are used. Examples of carboxylic acids include formic acid, acetic acid,
Examples include 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. Carboxylic acid esters include methyl and ethyl formate, methyl acetate, ethyl, propyl, methyl propionate, ethyl, propyl, butyl, ethyl butyrate, ethyl valerate, ethyl caproate, n
- Ethyl 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, ethyl, propyl and butyl anisate, methyl, ethyl p-ethoxybenzoate. The carboxylic acid halide is preferably a chloride oxide, and examples thereof include acetyl chloride, propionyl chloride, butyryl chloride, succinyl chloride, benzoyl 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.
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. For reactions of hydrocarbon-soluble organomagnesium components with electron donors, the reaction is carried out in an inert reaction medium,
For example, the reaction can be carried out in an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a mixed solvent thereof. Regarding the reaction order, the method of adding the electron donor to the organomagnesium component (), the method of adding the organomagnesium component to the electron donor (), and the method of adding both at the same time () can be used. can. The reaction ratio between the hydrocarbon-soluble organomagnesium component and the electron donor is 1 mol or less, preferably 0.05 to 0.8 mol, of the electron donor per 1 mol of the organomagnesium component. Next, the general formula HaSiCl _b R ¹⁰ _4-(a+b) (where a, b,
The Si—H bond-containing chlorosilane compound represented by (R ¹⁰ has the above-mentioned meaning) 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 values of a and b are a, 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 ₂ n-C ₃ H ₇ ,
HSiCl ₂ i―C ₃ H ₇ , HSiCl ₂ n―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 (i-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 (i-
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. As is clear from the Examples and Comparative Examples described below,
Favorable results are not obtained when using silicon compounds that do not contain Si--H bonds. The reaction between the organomagnesium component (i) and the chlorosilane compound (ii) will be explained below. The reaction between an organomagnesium compound or an organomagnesium complex and 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 from 20 to 150°C, but from the viewpoint of reaction progress, it 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 usually 0.01 to 100 mol of chlorosilane per mol of organomagnesium component, preferably 0.1 to 10 mol of chlorosilane per mol of organomagnesium component, particularly preferably 0.1 to 10 mol of chlorosilane. ranges from 0.2 to 5 moles. Regarding the reaction method, there is a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted (method ○a),
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 ○ B), or a method in which the organomagnesium component is charged in advance and the chlorosilane component is added (method There is method ○c), but the latter two are preferred, and method ○b gives particularly preferable results. The reaction of components (i) and (ii) can also be carried out in the presence of an inorganic carrier. As the inorganic carrier, the following can be used. (i) Inorganic oxides (ii) Inorganic carbonates, silicates, sulfates (iii) Inorganic hydroxides (iv) Double salts, solid solutions, or mixtures of (i) to (iii) Specific examples of inorganic carriers include: , silica, silica alumina, hydrated alumina, magnesia, thoria, titania, zirconia, calcium phosphate, barium sulfate, calcium sulfate, magnesium silicate, magnesium calcium, aluminum silicate [(Mg・Ca)O・Al ₂ O ₃・5SiO ₂・nH ₂ O], potassium silicate/aluminum [K ₂ O・Al ₂ O ₃・
6SiO ₂ ], mica [K ₂ O・3Al ₂ O ₃ ―6SiO ₂・
2H ₂ O], magnesium iron silicate [(Mg,
Fe) ₂ SiO ₄ ], aluminum silicate (Al ₂ O ₃・SiO ₂ ),
Examples include calcium carbonate, but silica or silica/alumina is particularly preferred.
The specific surface area of the inorganic carrier is preferably 20 m ² /g or more, particularly preferably 90 m ² /g or more. Next, the compound (2) to be reacted with the solid will be explained. Regarding aldehydes, aliphatic, cycloaliphatic and aromatic aldehydes are used, including acetaldehyde, propionaldehyde, butyraldehyde,
Valeraldehyde, hexaldehyde, octaldehyde, ateardehyde, benzaldehyde, etc. can be used. Silanol includes trimethylsilanol,
In addition to triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, etc., chlorosilane hydrolyzate, polysilanol, etc. may be mentioned. As hydrogen siloxane, methylhydrosiloxane

[Formula] Ethyl hydrosiloxane

[Formula] Propyl Hydro siloxane

[Formula] Butyl hydrosiloxane

[Formula] Phenyl Hydro siloxane

Examples include [Formula]. Next, the amount of component (2) used is the amount of C contained in component (1).
The amount is 0.05 to 20 mol, preferably 0.1 to 10 mol, particularly preferably 0.2 to 8 mol, per mol of -Mg bond. The reaction between solid substance (1) obtained by reacting an organomagnesium component and a chlorosilane compound and component (2) will be explained. The reaction is carried out in the presence or absence of an inert medium. As the inert medium, any of the aforementioned aliphatic, aromatic or alicyclic hydrocarbons may be used. There are no particular restrictions on the temperature during the reaction, but
It is preferably carried out at room temperature to 200°C. solid(1)
Regarding the method of reacting component (2) with component (2), there is a method of adding component (2) to solid material (1) in a suspended state (fluid state) (), a method of adding solid material to component (2), method of adding both (), method of adding both at the same time ()
etc., but methods () and () are preferred. Incidentally, after reacting component (2), it is also possible to treat with an acid such as dialkyl aluminum halide. Furthermore, even after reacting solid substance (1) with component (2),
Although the content of hydrocarbon groups contained in the solid substance is slightly reduced, it is important that the content still remains constant. The titanium compound, vanadium compound, zirconium compound, and hafnium compound to be reacted with the solid substance reacted with component (2) will be explained. Halides, oxyhalides, alkoxyhalides, alkoxides of titanium, vanadium, zirconium, hafnium and mixtures thereof are used. As a titanium compound, the general formula Ti (OR ¹¹ )
A titanium compound represented by sX _4-s is used.
In the formula, s is a number satisfying 0≦s≦4, and the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ includes methyl,
Ethyl, n- and iso-propyl, n-, iso- and tert-butyl, n-, iso-, sec- and
tert-amyl, neo-pentyl, hexyl, 2-
Ethylhexyl, heptyl, octyl, decyl,
Aliphatic hydrocarbon groups such as undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, allyl, alicyclic hydrocarbon groups such as cyclohexyl, 2-methylcyclohexyl, cyclopentyl, aromatic carbonization such as phenyl, cresyl, xylyl, naphthyl, etc. Examples include hydrogen groups, but aliphatic hydrocarbon groups are preferred. It is possible to use a mixture of two or more of the titanium compounds selected from the above. Examples of the halogen represented by X include chlorine, bromine, and iodine, with chlorine being preferred. Vanadium compounds include VCl ₄ , VOCl ₃ ,
VOCl ₂ (On-C ₄ H ₉ ), VOCl (On-C ₄ H ₉ ) ₂ , VO
(On-C ₄ H ₉ ) ₃ , VCl ₃ (OC ₂ H ₅ ), etc. are used.
VCl ₄ and VOCl ₃ are preferred. Examples of zirconium compounds include ZrCl ₄ , Zr(On
―C ₄ H ₉ ) ₄ , Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr
(OiPr) ₄ , Zr(OnPr) ₄ , ZrO(CH ₃ COO) ₂ and the like are used. Hafnium compounds include HfCl ₄ , Hf
(OnBu) ₄ , Hf(OPr) ₄ , etc. are used. For the reaction between a solid substance and a titanium compound, an inert reaction medium is used, or the titanium compound itself is used as the reaction medium. Examples of the inert reaction medium include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. preferable. The reaction temperature is not particularly limited, but it is preferably carried out in the range of room temperature to 150°C. A mixture or reactant of a titanium compound, a vanadium compound, a zirconium compound, and a hafnium compound will be explained. Regarding the mixture, two or more types of compounds may be mixed in advance, or two or more types of compounds may be mixed in the presence of a solid substance. The mixture is
Although it is preferable to carry out dilution in an inert solvent such as a hydrocarbon solvent, it is also possible to use two or more components themselves as a medium. Regarding the reactants, two or more compounds are reacted in advance and used, but the reaction can be carried out in the presence or absence of an inert hydrocarbon solvent.
It is also possible to use a grinding method such as a ball mill. As the pulverization method, well-known mechanical pulverization means such as a rotary ball mill, a vibrating ball mill, and an impact ball mill can be employed. Grinding time is 0.5
~100 hours, preferably 1-30 hours, the grinding temperature is
The temperature is 0 to 200°C, preferably 10 to 150°C. It is also possible to add an organometallic compound during the reaction of the solid substance with the titanium compound, vanadium compound, zirconium compound, or hafnium compound, or before or after the reaction. As the organometallic compound to be present when the solid substance and the titanium compound are reacted, an organoaluminum compound or an organomagnesium compound can be used. The organoaluminum compound has the general formula AlR ⁰ _t Z _3-t (wherein R ⁰ is a hydrocarbon group having 1 to 10 carbon atoms, and Z is selected from halogen, hydrocarbyloxy group, siloxy group, and hydrogen group). (where t represents a number of 1≦t≦3) and a mixture/reactant of an organoaluminum compound selected therefrom can be used. Preferred organoaluminum compounds include triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin
-Butylaluminum, tri-butylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, isoprenylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, di-i-
Propyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, sesqui-i-propyl aluminum chloride, sesqui-n-propyl aluminum chloride, ethyl aluminum dichloride, n-propyl aluminum dichloride , i-propyl aluminum dichloride, butyl aluminum dichloride, diethylaluminum bromide, diethylaluminium iodide, and mixtures thereof. The solid catalyst component thus obtained is so-called
The surface area indicated by BET specific surface area is exceptionally large.
Olefin has great features such as high polymerization activity, excellent particle properties of the resulting polymer, and excellent copolymerizability. It is not clear what mechanism this feature is due to, but it seems that certain organomagnesium components and H
It is thought to be based on the use of an active organomagnesium-containing solid obtained by the reaction of chlorosilane containing -Si-Cl bonds. Although the solid catalyst of the present invention is useful as a catalyst for olefin polymerization as it is, it becomes an even more excellent catalyst when combined with an organometallic compound.
The organometallic compound is preferably a compound of groups 1 to 10 of the periodic table, and particularly a complex containing an organoaluminium compound and an organomagnesium compound. As an organoaluminum compound, the general formula
AlR ¹⁰ _t Z _3-t (wherein, R ¹⁰ 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 2 to 3 ) is used alone or as a mixture. In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by ^R10 includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Specifically, these compounds are, for example,
triethylaluminum, tri-normalpropylaluminum, triisopropylaluminum,
Tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, trihexadecyl aluminum, diethylaluminium hydride, diisobutyl aluminum hydride,
Diethylaluminium ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide, diethylaluminum chloride, diisobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isobrenyl etc., and mixtures thereof are recommended. A highly active catalyst can be obtained by combining these alkyl aluminum compounds with the solid catalyst described above, and trialkyl aluminum and dialkyl aluminum hydride are particularly preferred because they achieve the highest activity. The complex containing organomagnesium is a complex represented by the above-mentioned general formula M〓Mg〓R ¹ _p R ² _q XrYs.
α, β, p, q, r, s, M, R ¹ , R ² , X, Y
As mentioned above, since a hydrocarbon-soluble complex is preferable, β/α is 0.5 to 10.
are preferred, and particularly preferred are complexes in which M is aluminum. The solid catalyst component and the organometallic compound may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. The ratio of the two components to be combined is preferably in the range of 1 to 3000 mmol of the organometallic compound per 1 g of the solid catalyst. Olefins that can be polymerized using the catalysts of the invention are alpha olefins, especially ethylene. Furthermore, the catalyst of the present invention can also be used for highly stereoregular polymerization of propylene by combining electron donor treatment as described above. It is also possible to use ethylene or propylene for polymerization in the coexistence of monoolefins such as propylene, butene-1, and hexane-1, and dienes such as butadiene and isoprene, and furthermore, for the polymerization of dienes. be. Polymerization methods include normal suspension polymerization, solution polymerization, gas phase polymerization, and high pressure polymerization (approximately 3000 kg/cm ² or less).
is possible. The catalyst is a polymerization solvent such as an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene, or xylene,
Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor, and 1 to 3,000 ethylene or propylene is added under an inert atmosphere.
It is also possible to pressurize the polymer at a rate of Kg/cm ² and proceed with polymerization at a temperature of room temperature to 3000°C. Examples of the present invention are shown below, but the present invention is not limited to these Examples in any way. In addition, MI in the examples represents melt index, and the temperature is 190℃ according to ASTM D-1238.
This was measured under a load of 2.16 kg. FR
means the quotient obtained by dividing the value measured at a temperature of 190°C and a load of 21.6 kg by MI, and is one of the measures of molecular weight distribution. The catalytic efficiency is calculated as follows: 1 g of transition metal component, 1 hour, 1 kg of ethylene (or propylene) pressure It is expressed in g of polymer produced per cm ² . Example 1 (1) Synthesis of organomagnesium component In a flask with a capacity of 2, 50 g of metallic magnesium powder was weighed out under a nitrogen atmosphere, and 20 mmol of butoxyaluminum dichloride and n-octane were added.
300 ml was added and the temperature was raised to 100°C. 1 mol of n-butyl chloride, 1 mol of butyl bromide and n-
A solution consisting of 0.7 octane was added dropwise over about 2 hours while stirring, and after the addition was completed, the reaction was continued by stirring for an additional 1 hour. The solid portion was separated by filtration and the filtrate was analyzed. As a result, the Mg concentration was 0.90 mol/, and the Al concentration was 0.020 mol/. 400ml of this filtrate
Weighed the mixture into a flask, added 130 mmol of n-butyl alcohol under stirring at 0°C, and added 30 mmol of n-butyl alcohol.
The reaction was continued with stirring at ℃ for 1 hour. Analysis of this reaction revealed that AlMg ₆ (C ₂ H ₅ ) ₃ (n-
C ₄ H ₉ ) ₁₁ (On-C ₄ H ₉ ) compound concentration is 0.89 mol/
It was hot. (2) Synthesis of a solid substance by reaction with chlorosilane A flask with a capacity of 2 equipped with a dropping funnel and a condenser was thoroughly degassed and dried, and a solution of 1 mol of trichlorosilane (HSiCl ₃ ) in n-heptane was added under a nitrogen atmosphere. 0.65 mol was charged, and while keeping the temperature at 50°C, 0.5 mol of the above organomagnesium complex solution was added dropwise from the dropping funnel over 1 hour.
The reaction was carried out at 50°C for 1 hour with stirring. Washing was performed five times by decanting to obtain a solid material slurry. As a result of separating and drying this solid, 1 g of solid
per, Mg9.18mmolCl19.15mmol, Si1.73m
mol, and contained 0.60 mmol of alkyl groups. (3) Synthesis of solid catalyst A slurry containing 20 g of the above solid was placed in a pressure vessel purged with nitrogen, and 70 mmol of propionaldehyde,
1 with 2 of n-hexane at 80°C under stirring.
After reacting for an hour, the supernatant was removed by decantation, and the mixture was further washed twice with 300 ml of n-hexane. This slurry was kept at 10℃ and titanium tetrachloride 20
mmol (1Mol/hexane solution) and 20mmol (1Mol/hexane solution) of diethylaluminum chloride.
A hexane solution of
Wash twice with ml of n-hexane, then add 300 ml.
of heptane was added. (Titanium contained in 1 g of solid is 2.0% by weight, and the hydrocarbon group is
It was 0.47 mmol. ) (4) Polymerization of ethylene () 5 mg of the solid catalyst component [A] synthesized in (3) and 0.25 mmol of triisobutylaluminum,
Along with 800ml of dehydrated and degassed n-hexane,
The inside was introduced into a 1.5 autoclave whose interior had been dehydrated and degassed, 120 mmol of butene-1 was charged, the internal temperature was kept at 80°C, hydrogen was pressurized at a pressure of 1.6 Kg/cm ² , and then ethylene was introduced and the total pressure was set at 4Kg/ ^cm2 . By replenishing ethylene, the total pressure can be increased.
Polymerization was carried out for 1 hour while maintaining the gauge pressure at 4.0 Kg/cm ² to obtain 167 g of polymer. The catalyst efficiency is
1670Kg-PE/g-Ti, MI was 0.80g/10min. The polymer powder had a bulk density of 0.48 g/cm ³ and more than 85% by weight of 105-149μ powder. (5) Polymerization of ethylene (). 8 mg of the solid catalyst [A] synthesized in (3) and 0.1 mmol of triethylaluminum were combined with 800 ml of dehydrated and degassed cyclohexane, and the inside was degassed.
It was introduced into a dry 1.5 autoclave. Next, after charging 3 mmol of hydrogen and 800 mmol of 1-octene, the autoclave was heated to 180°C.
Ethylene was introduced and polymerization was carried out for 20 minutes while maintaining the total pressure at a gauge pressure of 19 kg/cm ² to obtain 115 g of polymer. Catalyst efficiency 719Kg-PE/g-Ti MI 0.76g/10min FR 30 Density 0.924g/cm ³ (6) Polymerization of ethylene () Polymerization of ethylene in the gas phase using a stainless steel fluidized bed autoclave with a capacity of 50 did. 80℃
In an autoclave adjusted to
Prepared with 50g, ethylene:butene-1:
A gas with a hydrogen molar ratio of 1:0.25:0.02
Polymerization was carried out for 1 hour at a gauge pressure of 10 Kg/cm ² while introducing it into an autoclave at a speed of 15 cm/sec.
672 g of powder with a bulk density of 0.44 g/cm ² was obtained. Catalyst efficiency 1040g-PE/g-Ti MI 1.05g/10min Density 0.923g/cm ³ (7) Polymerization of ethylene () The solid catalyst synthesized in (3) was placed in an autoclave-type continuous polymerization reactor equipped with a stirrer. 0.05mmol
and 8 mmol of triethylaluminum were dispersed in 250 ml of n-hexane, injected into an autoclave with a stirrer using a high-pressure pump, maintained under the conditions in Table 1, and supplemented with ethylene containing 0.2 mol% hydrogen. Polymerization was carried out and the results shown in Table 1 were obtained.

[Table] Example 2 300 ml of heptane solution of methyldichlorosilane (1 mol/) and n-heptane under nitrogen atmosphere
200ml was placed in a flask and the temperature was raised to 50°C. Next, the organic magnesium component, AlMg ₁₀ (C ₂ H ₅ ) ₅ (n-C ₈ H ₁₇ ) ₇ (OC ₄ H ₉ ) ₁₁ 250m
mol of heptane solution was added dropwise at 50° C. over 1 hour, and the reaction was continued with stirring for another 1 hour. After washing the reactant slurry twice by decantation, the slurry containing 2 g of the above solid was mixed with 3 mmol of triphenylsilanol and 100 ml of n-hexane.
After reacting at 80℃ for 1 hour with stirring, the supernatant was removed by decanting, and 100ml of n-
Washed twice with hexane. This slurry was kept at 50°C, and 5 mmol of diethyl aluminum chloride and 100 ml of n-hexane were added.
was added under stirring, and the mixture was reacted at 60°C for 1 hour. Remove the supernatant by decantation, and add 100 ml of n-hexane to
Washed twice. Next, 5 mmol of diethylaluminum chloride, 5 mmol of titanium tetrachloride, and 100 ml of n-hexane were added and reacted at 50°C for 1 hour, followed by washing twice with 100 ml of n-hexane to obtain solid catalyst component [A]. Using this solid catalyst component [A], Example 1-
Slurry polymerization of ethylene was carried out in the same manner as in (4), and the following results were obtained. Catalyst efficiency 1215g-PE/g-Ti MI 1.0g/10min Bulk density 0.45g/cm ³ Ratio of 105 to 149μ 88% or more Examples 3 to 11 The solid catalyst of Example 1 was synthesized using the components shown in Table 2. The solid catalyst component thus obtained was converted into transition metal atoms, and 0.002 mmol and 0.25 mmol of triethylaluminum were dehydrated and degassed.
1.5 whose interior was dehydrated and degassed with 800ml of hexane
Introduce into autoclave and liquefy butene - 150ml
was introduced, the internal temperature was maintained at 80℃, and hydrogen was introduced at 1.6Kg/cm ²
Then, ethylene was introduced to give a total pressure of 4 Kg/cm ² . Polymerization was carried out for 1 hour while maintaining the total pressure at a gauge pressure of 4 kg/cm ² by replenishing ethylene, and the results shown in Table 2 were obtained.

【table】

[Table] Examples 12 to 17 Organic Mg component Li _0.06 Mg (C ₂ H ₅ ) _0.5 (n-C ₄ H ₉ ) _0.5
On-C ₄ H ₉ ) ₁₀ 500ml and methyldichlorosilane 250m
A solid material was synthesized using a mixture of mol and trichlorosilane, and 250 mmol of propionaldehyde and 50 mmol of propionaldehyde diethyl acetal were used instead of propionaldehyde.
A solid catalyst was synthesized in the same manner as in Example 1 except that the following was used. Using 0.20 mmol of this solid as Ti, 2 mmol of triethylaluminum, and 800 ml of n-hexane, 5 g of ethylene was prepolymerized at 40℃, and the solid catalyst component equivalent to 0.002 mmol of titanium atoms was sampled and autoclaved for 1.5 minutes. was introduced with 800 ml of isobutane, the comonomers shown in Table 3 were further introduced, and the temperature was raised to 80°C. 9.5 hydrogen
Pressurize at a pressure of Kg/cm ² and introduce ethylene to 11.5
The pressure was set to Kg/cm ² and polymerization was carried out for 1 hour to obtain the results shown in Table 3.

[Table] Examples 18-19 Silica dried at 200°C for 4 hours in a _N2 stream (Fuji Devilin Chemical, 952: specific surface area 300 m ² /g, pore volume
1.65cc/g) 20g and AlMg ₆ Et ₃ n-Bu ₉ (OnBu) ₃ 6
mmol (hexane solution: 100 ml) was weighed into a flask, and while keeping the temperature at 65°C, 8 mmol of trichlorosilane (hexane solution: 100 ml) was added dropwise over 1 hour, and the reaction was further continued at 65°C for 1 hour with stirring. continued. After the reaction was completed, the supernatant liquid was removed by decanting to obtain a solid substance. The solid catalyst component was synthesized in the same manner as in Example 1-(3) except that this solid substance and the compounds shown in Table 4 were used, and ethylene was polymerized in hexane to obtain the results shown in Table 4. Ta.

[Table] Examples 20 to 22 The solid catalyst synthesized in Example 1 was synthesized in the same manner,
The olefins shown in Table 5 were polymerized together with the organometallic compounds shown in Table 5, and the results shown in Table 5 were obtained.

【table】 [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] (1) (i) (a) General formula MαMgβR ¹ _p R ² _q X _r Y _s (wherein,
M is Al, Zn, B, Be, Li atom, R ¹ and R ² are the same or different C ₁ to C ₁₀ hydrocarbon groups,
X, Y are the same or different OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a halogen group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸
is a hydrogen atom or a _C1 - _C10 hydrocarbon group, ^R9 is a _C1 - _C10 hydrocarbon group,
α≧0, β>0, p, q, r, s≧0, m
is the valence of M, p+q+r+s=mα+
2β, 0≦(r+s)/(α+β)≦1. ), or a component reacted with (a) and (b) an electron donor selected from ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols, and amines. 1 mole, (ii) General formula H _a SiCl _b R ¹⁰ _4-(a+b) (where a, b are numbers larger than 0, a+b≦4, 0<a≦
2. ^R10 represents a hydrocarbon group having 1 to 10 carbon atoms) 0.01 to 100 mol of an H--Si bond-containing chlorosilane compound is added to (i) inorganic oxidation in the presence or absence of an inorganic carrier selected from the following. (ii) Inorganic carbonates, silicates, sulfates (iii) Inorganic hydroxides (iv) Double salts, solid solutions, or mixtures of (i) to (iii); C- contained in the reacted solid. Mg
With respect to 1 mole of bond, (2) a solid obtained by reacting 0.05 to 20 moles of a compound selected from the following: (i) aldehyde (ii) silanol (iii) hydrogen siloxane (3) titanium compound, vanadium compound, 1 selected from zirconium compounds, hafnium compounds, and mixtures or reactants thereof
A solid catalyst component obtained by reacting two or more components, or a solid catalyst obtained by further treatment with a component selected from (4) a titanium tetrahalide compound, a halide of aluminum, a halide of silicon, and a halide of tin. Component [B] An olefin polymerization method in which a catalyst consisting of [A] and [B], which is an organometallic compound component, is brought into contact with an olefin. 2. The olefin polymerization method according to claim 1, wherein component (2) is present in an amount of 0.1 to 10 moles per mole of C--Mg bonds in the solid of [A] (1). 3. The olefin polymerization method according to claim 1, wherein component (2) is present in an amount of 0.2 to 8 moles per mole of C--Mg bonds in the solid of [A] (1). 4. Claims ¹ _, ² , or 3 in which M is Al, B, Zn, or Be in the organomagnesium component represented by the general formula M〓Mg〓R 1 p _R 2 q X _r Y _s The olefin polymerization method according to any one of paragraphs. 5 In the organic magnesium component represented by the general formula M〓Mg〓R ¹ _p R ² _q X _r Y _s , α>0, 0.5≦β/α
Claims 1, 2, 3, or 4 where ≦10, 0≦(r+s)/(α+β)≦0.8
The olefin polymerization method according to any one of paragraphs. 6 Claims 1, 2, 3, and 4 in which the reaction between the solid and a component selected from titanium compounds, vanadium compounds, zirconium compounds, and hafnium compounds is carried out in the presence of an organometallic compound.
The olefin polymerization method according to any one of Items 1 and 5. 7. Claim 1, wherein component (3) selected from titanium compounds, vanadium compounds, zirconium compounds, hafnium compounds, or mixtures or reactants thereof is a titanium compound or a component containing a titanium compound. , second term, third term,
The olefin polymerization method according to any one of Item 4, Item 5, and Item 6.