JPS64970B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides ethylene or ethylene and other α
- It relates to a catalyst used in the polymerization of olefins. More specifically, the present invention relates to a catalyst for ethylene polymerization or ethylene-α-olefin copolymerization comprising a solid component in which a reaction product of chromium trioxide and a nitrogen-containing organic compound is supported on an inorganic oxide, and an organometallic compound. An ethylene polymerization catalyst obtained by supporting a chromium compound such as chromium oxide on an inorganic oxide support such as silica or silica-alumina and firing it is
It is widely known as a so-called Phillips type catalyst. However, when using this catalyst, the activity of the catalyst and the average molecular weight of the polymer greatly depend on the polymerization temperature, and commercially suitable polymers with molecular weights of tens of thousands to hundreds of thousands can be produced with sufficient catalytic activity. In order to achieve this, it was generally necessary to set the polymerization temperature to 100 to 200°C.
When polymerization is carried out in such a temperature range, the resulting polymer is dissolved in the reaction solvent, so
The viscosity of the reaction system increases significantly, resulting in
It was difficult to increase the concentration of the produced polymer above 20%. Therefore, there has been a strong demand for the development of a catalyst that exhibits high activity at a polymerization temperature of 100° C. or lower, at which polymerization becomes so-called slurry polymerization. Furthermore, in recent years, in order to reduce production costs, it has become important to be able to omit the catalyst removal step in the post-polymerization step, and for this purpose, there has been a need to develop catalysts that exhibit even higher activity. In order to improve these drawbacks, a method of supporting chromic acid ester (JP-A-54-110190, JP-A-54
-120290, Japanese Patent Publication No. 120290, Japanese Patent Publication No. 44-20350), method of supporting tin chromate (Japanese Patent Publication No. 52-36960), method of supporting link chromate (Japanese Patent Publication No. 1972-36960),
-21718 Publication), a method of adding an aluminum compound and firing after supporting link chromate (Japanese Unexamined Patent Application Publication No. 1983-21718),
116192), after supporting various chromates,
Method of treatment with phenol compounds
117986), method of supporting a reaction product of silazane and chromic acid, (Japanese Unexamined Patent Publication No. 1983-80187), 3
A method of supporting a reaction product of a chromium carboxylate and an amine and then firing it (Japanese Patent Publication No. 55-34163, Japanese Patent Publication No. 55-34164), a method in which a chromium compound is supported, a fired solid is combined with an organomagnesium compound. Examples include a catalyst (UK Patent No. 2023153). In order to improve the above drawbacks, the present inventors have conducted various studies on the reaction between germanium, tin compounds, and chromic acid compounds. As a result, the present inventors have found that when polymerized in a slurry state at 100°C or less, the molecular weight is tens of thousands to hundreds of thousands. The results showed that the productivity per catalyst was also high, leading to the present invention. That is, the present invention provides: 1 [A] (1) An inorganic oxide carrier (2) General formula R ¹ R ² R ³ R ⁴ Ge [wherein, R ¹ R ² R ³ R ⁴ has the following meaning ( Either a) or (b). (a) When R ¹ , R ² and R ³ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms,
R ⁴ is a hydrogen atom, halogen, -OH, -
OGeR ¹ R ² R ³ (R ¹ , R ² , R ³ are the same as above)
represents. (b) R ¹ , R ² , R ³ , R ⁴ are −OR ^a
(R ^a represents a hydrocarbon group having 1 to 10 carbon atoms) or halogen. (however
Germanium compounds represented by the general formula R ¹ R ² R ³ R 4 Sn (except when R 1 , R 2 , R 3 , and R ⁴ are all halogens)] or germanium compounds represented by the general formula R ¹ R ² R ³ R ⁴ Sn (in the formula,
R ¹ , R ² and R ³ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R ⁴ represents halogen or -OH. ) A solid component supported by a reaction product of a tin compound and a chromic acid compound and activated by firing [B] (1) General formula M〓Mg〓R ⁵ _p R ⁶ _q X _r Y _s (in the formula ,
M is an element selected from Al, B, Be, Zn, Li, α is 0 or a number larger than 0, p,
q, r, s are 0 or larger than 0, p, q are not 0 at the same time, and 0≦(r+
s)/(α+β)≦1.5 and p+q+r+
The relationship is s=mα+2β, where m is the valence of M, R ⁵ and R ⁶ are the same or different groups and represent a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms, and X and Y are the same. or different groups, such as OR ⁷ , OSiR ⁸ R ⁹ R ¹⁰ , NR ¹¹ R ¹² ,
SR ¹³ represents a halogen group, R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen groups or hydrocarbon groups having 1 to 20 carbon atoms, and R ¹³ is 1 to 20 carbon atoms.
Represents 20 hydrocarbon groups. ), and (2) 0.1 to 1 mole of carbinol having 1 to 20 carbon atoms, or silanol or siloxane per mole of the trialkylaluminum compound.
Catalyst 2 for polymerization of ethylene or copolymerization of ethylene and α-olefin consisting of [A] and [B], which is a component consisting of an organoaluminum component in which 0.1 to 2 moles of the inorganic oxide support is silica or Catalyst 3 for polymerization of ethylene or copolymerization of ethylene and α-olefin according to the above item 1, which is silica-alumina. % by weight of chromium atoms supported in component [A]
Catalyst 4 for polymerization of ethylene or copolymerization of ethylene and α-olefin according to Items 1 and 2 above, wherein the organomagnesium component is α>0 and β/α
≧0.2 Catalyst 5 for polymerization of ethylene or copolymerization of ethylene and α-olefin according to Items 1 to 3 above, wherein the organomagnesium component is α>0 and β/α
≧0.5 Catalyst 6 for polymerization of ethylene or copolymerization of ethylene and α-olefin according to Items 1 to 4 above In the organomagnesium component, X and Y are
Catalyst ⁷ for polymerization of ethylene or copolymerization of ethylene and α-olefin according to items 1 to 5 above, which is OR 7 or OSiR ⁸ R ⁹ R ¹⁰ 0≦(r+
s)/(α+β)≦1, the first to sixth
Polymerization of ethylene or ethylene and α-
Olefin copolymerization catalyst 8 In the organomagnesium component, 0≦(r+
s)/(α+β)≦0.8, the first to seventh
Polymerization of ethylene or ethylene and α-
Olefin copolymerization catalyst 9 In the hydrocarbon-soluble organomagnesium component represented by the general formula M〓Mg〓R ⁵ _p R ⁶ _q X _r Y _s ,
OSiR ⁸ R ⁹ R ¹⁰ (R ⁸ , R ⁹ , R ¹⁰ are hydrogen groups or hydrocarbons having 1 to 20 carbon atoms). Copolymerization catalyst 10 In the hydrocarbon-soluble organomagnesium component represented by the general formula M〓Mg〓R ⁵ _p R ⁶ _q X _r Y _s ,
10. The group OSiR ⁸ R ⁹ R ¹⁰ , wherein R ⁸ is a hydrogen group or R ⁸ , R ⁹ and R ¹⁰ are hydrocarbon groups having 1 to 7 carbon atoms. Olefin polymerization catalyst 11 In the hydrocarbon-soluble organomagnesium component represented by the general formula M〓Mg〓R ⁵ _p R ⁶ _q X _r Y _s ,
is a group OSiR ⁸ R ⁹ R ¹⁰ , where R ⁸ is a hydrogen group and R ⁹ R ¹⁰ is a hydrocarbon group selected from methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, and tolyl. Catalyst 12 for polymerization of ethylene or copolymerization of ethylene and α-olefin according to items 1 to 10 above, wherein the organoaluminum component [B] is a component obtained by reacting a trialkylaluminum compound with silanol or siloxane. Catalyst for polymerization of ethylene or copolymerization of ethylene and α-olefin according to any one of Items 1 to 11 above, Items 1 to 12 above, wherein the silicon group contained in component [B] is a compound having an Si-H bond. Catalyst 14 for the polymerization of ethylene or the copolymerization of ethylene and α-olefin described above The silicon group contained in the [B] component is 0.1 to 2 mol per 1 gram atom of the metal in the organometallic compound of the [B] component. Catalyst 15 for the polymerization of ethylene or the copolymerization of ethylene and α-olefin according to items 1 to 13 above, wherein the [A] component is brought into contact with a small amount of the [B] component in advance and used as the [A] component. The present invention provides a catalyst for polymerizing ethylene or copolymerizing ethylene and α-olefin as described in Items 1 to 14 above. The features of the present invention are that the molecular weight can be adjusted in polymerization in a slurry state at 100°C or less, and as shown in Example 1, the polymer productivity per chromium atom is sufficiently high, and the catalyst removal step can be omitted. is possible. A further feature of the present invention is that the resulting polymer has a high bulk density. The present invention will be explained below. There are two cases (a) and (b) for the compound of the general formula R ¹ R ² R ³ R ⁴ Ge used in the present invention. In the case of (a), R ¹ , R ² and R ³ represent a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is a hydrogen atom, halogen, -
OH, −OGeR ¹ R ² R ³ . In the case of (b), R ¹ , R ² , R ³ and R ⁴ represent -OR ^a (R ^a represents a hydrocarbon group having 1 to 10 carbon atoms) or halogen. However, the case where R ¹ , R ² , R ³ , and R ⁴ are all halogens is excluded. A germanium compound in which R ¹ R ² R ³ R ⁴ Ge is (a) will be explained. In the formula, R ¹ , R ² and R ³ represent a hydrocarbon group having 1 to 10 carbon atoms. Specific examples include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl, and aromatic hydrocarbon groups such as phenyl and tolyl, but aromatic hydrocarbon groups are preferred. . ^R4
represents a hydrogen atom, halogen, -OH, -OGeR ¹ R ² R ³ . The halogen atom represents Cl, Br, and I, with Br being particularly preferred. Further, when R ⁴ is -OH, it is unstable when R ¹ R ² R ³ is an aliphatic hydrocarbon, and it is preferable that R ¹ R ² R ³ is an aromatic compound. Specifically, the compounds include trimethylgermane, trimethylchlorogermane, trimethylbromogermane, trimethyliodogermane, bis-trimethylgermoxane,
Triethylgermane, triethyl chlorogermane, triethyl bromogermane, triethyl iodogermane, bis-triethylgermoxane, tripropylgermane, tripropyl chlorogermane, tripropyl bromgermane, tripropyl iodogermane, bis-tripropylgermoxane, tributyl germane, tributylchlorogermane, tributylbromogermane, tributyl iodogermane, bis-tributylgermoxane,
Trihexylgermane, trihexyl chlorogermane, trihexylbromogermane, trihexyliodogermane, bis-trihexylgermoxane, trioctylgermane, trioctylchlorogermane, trioctylbromogermane, trioctyliodogermane, bis-trioctyl germoxane, tridecylgermane, tridecylchromegermane, tridecylbromogermane, tridecyliodogermane, bis-tridecylgermoxane, triphenylgermane, triphenylchlorogermane, triphenylbromogermane, triphenyliodogermane, Examples include triphenylgermanol, bis-triphenylgermoxane, tritolyl germane, tritolyl chlorogermane, tritolyl brogermane, tritolyl iodogermane, tritolyl germanol, bis-tritolyl germane, and the like. Next, a germanium compound in which R ¹ R ² R ³ R ⁴ Ge is (b) will be explained. -OR ^a 's R ^a has 1 carbon number
Represents ~10 hydrocarbon groups. Specifically, R ^a includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl,
Examples include decyl, henyl, tolyl, cyclohexyl and the like. The halogen is preferably Cl, and the amount of halogen is 0 to 3 substitutions, preferably 0 to 2 substitutions, particularly preferably 0 to 1 substitutions. Therefore, particularly preferred compounds are represented by the general formulas (R ^a O) ₃ GeCl and (R ^a O) ₄ Ge. The compound represented by the general formula R ¹ R ² R ³ R ⁴ Sn will be explained. R ¹ R ² R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ represents halogen or -OH.
The halogen atom represents Cl, Br, I,
Cl and Br are preferred. Specifically, the compounds are trimethylchlortin, trimethylbromtin, trimethyliodotin, trimethyltin hydroxide, triethylchlortin, triethylbromtin, triethyliodotin, triethyltin hydroxide, tripropylchlortin, tripropylbrom Tin, tripropyl iodotin, tripropyltin hydroxide, tributylchlortin, tributylbromtin, tributyliodotin, tributyltin hydroxide, trihexylchlortin, trihexylbromtin, trihexyliodotin, trihexyltin hydroxide, trioctylchlortin,
trioctylbromtin, trioctyl iodotin, trioctyltin hydroxide, tridecylchlortin, tridecylbromtin, tridecyl iodotin, tridecyltin hydroxide,
Examples include triphenylchlortin, triphenylbromtin, triphenyliodotin, triphenyltin hydroxide, tritolylchlortin, tritolylbromtin, tritolyl iodotin, tritolyltin hydroxide, and the like. As the chromic acid compound used in the present invention,
Examples include chromium trioxide, chromic acid, silver chromate, potassium chromate, sodium chromate, magnesium chromate, calcium chromate, and the like. In the case (a) of the general formula R ¹ R ² R ³ R ⁴ Ge, the reaction between a germanium compound and a chromic acid compound is a reaction between a trialkylbromogermane or a triarylbromogermane and silver chromate, and a bis-trialkylbromogermane reaction with a silver chromate. Examples include reaction of germoxane or bis-triarylgermoxane with chromic acid, reaction of triarylgermanol with chromium trioxide, and reaction of trialkylgermane or triarylgermane with chromic acid. Specific examples of reaction solvents include methylene chloride, chloroform, carbon tetrachloride,
Examples include benzene, toluene, pentane, hexane, heptane, and cyclohexane. In R ¹ R ² R ³ R ⁴ Ge, the molar ratio of germanium compound to chromium compound in case (a) is preferably 1:0.1 to 1:10. If there are fewer chromium compounds than this,
The amount of reactants decreases; if the amount is greater than this, the amount of unreacted chromium compounds will only increase. The reaction temperature is 10°C to 100°C, preferably 20°C
~80°C, reaction time is several minutes to 20 hours, preferably
The duration is 10 minutes to 5 hours. The compounds produced by these reactions are described in known literature (Z.Chem. 20 , 31 ('80)).
According to the structural formula

It is presumed to be germanium chromate represented by the formula: Furthermore, in the reaction of a germanium compound and a chromic acid compound in case (b) of R ¹ R ² R ³ R ⁴ Ge, chromium trioxide is particularly preferred as the chromic acid compound. Specifically, the reaction solvent is methylene chloride,
Examples include chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane. The molar ratio of germanium compound and chromium trioxide is preferably 1:0.1 to 1:10. When the amount of chromium compound is less than this, the amount of reactants decreases, and when it is more than this, the amount of unreacted chromium compound increases. The reaction temperature is
The reaction time is 10°C to 100°C, preferably 20°C to 80°C, and the reaction time is several tens of minutes to 50 hours, preferably 30 minutes to 30 hours. Among the products produced by these reactions are

It is presumed that something with the structure of [Formula] exists, but it is not certain. The reaction between a tin compound represented by the general formula R ¹ R ² R ³ R ⁴ Sn and a chromic acid compound is a reaction between a trialkyl tin halide or a triaryl tin halide and silver chromate, a reaction between a trialkyl tin hydroxide or a chromic acid compound. Examples include the reaction between triaryltin hydroxide and chromium trioxide. The reaction solvent used is the same as that used for the reaction of R ¹ R ² R ³ R ⁴ Ge with the chromic acid compound. The molar ratio, reaction temperature, and reaction time are also equivalent to the case (a) of R ¹ R ² R ^{3 RA} Ge and the reaction of chromic acid compound. The compounds produced by these reactions are described in known literature (Z.Chem. 20 , 31
('80)), the structural formula

It is presumed to be tin chromate represented by the following formula. As the inorganic oxide carrier used in the present invention,
Silica, alumina, silica-alumina, thoria,
Zirconia etc. can be used, but silica,
Silica-alumina is particularly preferred. The carrier is preferably dried before supporting the reaction product of the R ¹ R ² R ³ R ⁴ Ge or R ¹ R ² R ³ R ⁴ Sn compound and the chromic acid compound. Drying of the carrier is generally carried out in the presence of an inert gas substantially free of moisture, such as oxygen, nitrogen, helium, air, etc., but it can also be carried out under reduced pressure. Drying temperature is 100℃ or higher, preferably
It is carried out at a temperature range of 200°C to 1000°C for several minutes to several tens of hours, preferably 30 minutes to 20 hours. Particular preference is given to drying under fluidized conditions of the solid with a sufficient amount of inert gas. As a method for supporting the reaction product of ^{R 1} R ² R ³ R ⁴ Ge or R 1 R ² R ³ R ⁴ Sn compound and chromic acid compound on a carrier, after reacting the inorganic oxide carrier with the above reaction solution, , inert hydrocarbons are removed by distillation or filtration. The temperature during the reaction is preferably 0°C to 100°C, and the time is preferably 10 minutes to 10 hours. The amount of chromium supported is expressed as weight percent of chromium atoms relative to the carrier, and is not particularly limited, but preferably ranges from 0.01 to 5%. Firing activation is generally carried out in the presence of oxygen, but it can also be carried out in the presence of an inert gas or under reduced pressure. Preferably, air substantially free of moisture is used. Firing temperature is over 200℃,
It is preferably carried out at a temperature range of 300°C to 900°C for several minutes to several tens of hours. During firing, it is recommended to blow in sufficient dry air and activate firing under a fluidized state. The [B] component used in combination with the solid catalyst component will be explained. The organic magnesium component has the general formula M〓Mg〓R ⁵ _p R ⁶ _q
X _r Y _s (where M represents an element selected from Al, B, Be, Zn, Li, α is 0 or a number greater than 0, p, q, r, s are 0 or greater than 0) It is a large number, p and q are not 0 at the same time, but p+q+r+s
= mα + 2β, where m is the valence of M, R ⁵ ,
R ⁶ is the same or different hydrocarbon group having 1 to 20 carbon atoms, X and Y are the same or different groups,
OR ⁷ , OSiR ⁸ R ⁹ R ¹⁰ , NR ¹¹ R ¹² , SR ¹³ represents a group selected from halogen, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ and R ¹² represent a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ represents a hydrocarbon group having 1 to 20 carbon atoms. ) is a hydrocarbon-soluble organic magnesium component. In the above formula, the hydrocarbon group represented by R ⁵ to R ¹³ is an alkyl group, a cycloalkyl group, or an aryl group, such as methyl, ethyl, propylbutyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc. mentioned, especially R ⁵ ,
Alkyl groups are preferred. Furthermore, R ⁷ to R ¹² may be a hydrogen group, and R ⁷ is preferably a hydrogen group. When α>0, aluminum, boron, zinc, beryllium, and lithium are preferable as M because they facilitate the formation of hydrocarbon-soluble organomagnesium complexes. The ratio of magnesium to metal atom M (β/α) is not particularly limited, but is preferably 0.2 or more, particularly 0.5.
Hydrocarbon-soluble organomagnesium complexes within the above range are preferred. Relational expression p+q+ of symbols α, β, p, q, r, s
r+s=mα+2β indicates stoichiometry in the organomagnesium component, and 0≦(r+s)/(α+β)≦
It is 1.5. The preferred range is 0≦(r+s)/
(α+β)≦1.0 means that X and Y
It shows that the sum is 0 or more and less than 1.0, and the more preferable range is 0 to 0.8. These organomagnesium complex compounds have the general formula
Organomagnesium compounds represented by R ^{5 MgX} , ^{R 5} _{2 Mg} (R ⁵ is ^the above _- mentioned meaning, meaning)
It is synthesized by reacting an organometallic compound represented by the formula in an inert hydrocarbon solvent such as hexane, heptane, cyclohexane, benzene, toluene, etc. at room temperature to 150°C. Furthermore, MgX ₂ and MR ⁶ _n , MR ⁶ _n-1 H,
or R ⁵ MgX, MgR ⁵ ₂ and R ⁶ _o MX _no (where M,
R ⁵ and R ⁶ have the above-mentioned meanings, and n is a number from 0 to m). Next, when α=0 and r=0, that is, the general formula,
The hydrocarbon-soluble organomagnesium compound represented by MgR ⁵ _p R ⁶ _q will be explained. (a) When at least one of R ⁵ and R ⁶ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms (b) When R ⁵ and R ⁶ are alkyl groups with different numbers of carbon atoms Case (c) When at least one of R ⁵ and R ⁶ is a hydrocarbon group having 6 or more carbon atoms. Among these, preferably R ⁵ and R ⁶ are in any of the following three cases. (a′) R ⁵ and R ⁶ both have 4 to 6 carbon atoms,
When at least one of them is a secondary or tertiary alkyl group (b') When ^R5 is an alkyl group with 2 to 3 carbon atoms and ^R6 is an alkyl group with 4 or more carbon atoms (c') When R ⁵ and R ⁶ are both alkyl groups having 6 or more carbon atoms, these groups will be specifically shown below. In (a) and (a'), secondary to tertiary alkyl groups having 4 to 6 carbon atoms include sec-C ₄ H ₉ , tert-
_C4H9 , -CH( _{C2H5 ) 2 ,} -C( _C2H5 )( _CH3 ) ₂ , _-CH
( _CH3 )( _C4H9 ) _{, -CH} ( _C2H5 )( _C3H7 ), _-C
(CH ₃ ) ₂ (C ₃ H ₇ ), -C(CH ₃ )(C ₂ H ₅ ) ₂ , etc. are used, preferably a secondary alkyl group, and sec
_{-C4H9 is} particularly preferred. In (b) and (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 (c) and (c'), examples of the hydrocarbon group having 6 or more carbon atoms include hexyl, octyl, decyl, and phenyl groups, and alkyl groups such as hexyl, octyl, and decyl are preferable, and hexyl group is particularly preferable. . Examples of such organomagnesium compounds include (sec- _C4H9 ) _{2Mg ,} (tert- _C4H9 ) _{2Mg ,} n-
C ₄ H ₉ −Mg−C ₂ H ₅ , n−C ₄ H ₉ −Mg・secC ₄ H ₉ ,
n- _C4H9 - _Mg -tert- _C4H9 , n _{- C6H13 -} Mg
−C _{2 H 5 ,} (n−C ₄ H ₉ ) _1.5 (n−C ₈ H ₁₇ ) _0.5 Mg, n−
C ₈ H ₁₇ −Mg−C ₂ H ₅ , (n−C ₆ H ₁₃ ) ₂ Mg, (n−
_Examples include _C8H17 ) _2Mg , (n- _C10H21 ) _{2Mg ,} and the like. As X, OR ⁷ and OSiR ⁸ R ⁹ R ¹⁰ are preferable, and OSiR ⁸ R ⁹ R ¹⁰ is particularly preferable. OR ⁷ or
The amount of OSiR ⁸ R ⁹ R ¹⁰ relative to metal magnesium atoms, ie, γ, is preferably 0.1 to 2, particularly preferably 0.2
~1.5. As the organoaluminum component, a trialkylaluminum compound is reacted with carbinol and/or silanol or siloxane.
Alternatively, components obtained by mixing are used. Examples of trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-i
-Propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, triamylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, isoprenylaluminum, and the like. Mixtures of these can also be used. As carbinol having 1 to 20 carbon atoms, methyl alcohol, ethyl alcohol, n and i-propyl alcohol, n, i and t-butyl alcohol, n, i, sec, t-amyl alcohol,
Examples include phenol and cresol. The reaction ratio of trialkylaluminium and carbinol is 0.1 to 1 mol, preferably 0.15 mol of carbinol to 1 mol of trialkylaluminium.
~0.9 mol, particularly preferably 0.2-0.8 mol.
If it is below the above range, the effect of the present invention cannot be obtained,
Moreover, if it exceeds the above range, the catalytic activity will decrease. Silanol includes trimethylsilanol,
Hydrolyzed products such as triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, and chlorosilane can also be used, and polysilanol can also be used. As the siloxane, methylhydropolysiloxane (

[Formula] n≧1), ethylhide Ropolysiloxane (

[Formula] n≧1), Lopyruhydrosiloxane (

[Formula] n≧1), butylhydrosiloxane (

[Formula] n≧1), phenylhydrosylo Kisan (

[Formula]n≧1), etc. The reaction ratio of trialkylaluminium and silanol or siloxane is 1 mole of trialkylaluminium, silanol or siloxane.
The amount is 0.1 to 2 mol, preferably 0.1 to 1.5 mol, particularly preferably 0.2 to 1.2 mol. The ratio of the organic magnesium component to the organic aluminum component is preferably 0.05 to 50 moles, particularly preferably 0.1 to 10 moles, of the organic Al compound relative to the mole of the organic Mg component. The organomagnesium component and the organoaluminum component may be added to the polymerization system separately from the solid catalyst component, or the organomagnesium component and the organoaluminum component may be mixed in advance and added. It is preferable to bring the solid catalyst component into contact with a small amount of component [B] in advance. The ratio of [A] component and [B] component to be combined is metal in [B] component/Cr in [A] component from 0.01.
3000, preferably a range of 0.1 to 100 is recommended. Next, a method for polymerizing olefin using the catalyst of the present invention will be explained. Olefins which 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 copolymerization of ethylene with monoolefins such as propylene, butene-1, hexene-1, etc., or for polymerization in the coexistence of dienes such as butadiene, isoprene, etc. By carrying out copolymerization using the catalyst of the present invention, it is possible to produce a polymer having a density in the range of 0.91 to 0.97 g/cm ³ . As the polymerization method, usual suspension polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization or solution polymerization, the catalyst is a polymerization solvent such as propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor under an inert atmosphere. By pressurizing ethylene at 1 to 200 kg/cm ² to the bottom, polymerization can be carried out at a temperature of room temperature to 320°C. On the other hand, in gas phase polymerization, ethylene is heated at room temperature or at a pressure of 1 to 50 kg/ ^cm2 .
Polymerization can be carried out at a temperature of 120° C. by using means such as a fluidized bed, moving bed, or stirring to achieve good contact between ethylene and the catalyst. The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or using multiple reaction zones.
It may also be carried out by so-called multi-stage polymerization. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in ordinary one-stage polymerization, has a relatively high molecular weight, and is extremely suitable for blow molding and film molding applications. Multi-stage polymerization in which polymerization is carried out under two or more different reaction conditions makes it possible to produce polymers with a wider molecular weight distribution. In order to adjust the molecular weight of the polymer, it is of course possible to use known techniques such as adjusting the polymerization temperature, adding hydrogen to the polymerization system, or adding an organometallic compound that tends to cause chain transfer. Furthermore, it is also possible to perform polymerization by combining methods such as adding a titanate ester to control density and molecular weight. Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way. In addition, the catalytic activity in the examples refers to the monomer pressure.
At 10 kg/cm ² , it represents the amount of polymer produced per gram of chromium in the solid catalyst. Further, MI stands for melt index, which was measured at a temperature of 190° C. and a load of 2.16 kg according to ASTM D-1238. FR is 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 known to those skilled in the art as an index representing the breadth of molecular weight distribution. Example 1 (1) Reaction of germanium compound and chromic acid. 30 ml of CH ₂ Cl ₂ in a 100 ml flask, substituted with N ₂
After adding 5 mmol of hexaphenyl digelmoxane, 5 mmol of chromium trioxide, and 5 mmol of H ₂ O and stirring at room temperature for 2 hours, the aqueous layer was removed to obtain a brown solution. The solution was dried with MgSO ₄ and then filtered. The chromium concentration was 3.4 mg chromium atoms/ml. (2) Supporting and firing chromium compounds. 5 g of silica (manufactured by Fuji Davison, Grade 952) pre-dried at 800°C for 4 hours in a stream of dry nitrogen
into a 100ml flask purged with _N2 ,
_20ml of _CH2Cl2 was added. While stirring at room temperature, 14.6 ml of the liquid synthesized in (1) above was added dropwise. After stirring for 30 minutes, CH ₂ Cl ₂ was distilled off under reduced pressure. Further, this solid was calcined at 800° C. for 4 hours under flowing dry air to obtain a solid component. (3) Synthesis of hydrocarbon-soluble organomagnesium components. 13.6 g of di-n-butylmagnesium and 1.83 g of triethylaluminum were placed in a flask purged with nitrogen along with 100 ml of n-heptane, and reacted at 80° C. for 2 hours to obtain an organomagnesium complex solution. As a result of analyzing this complex, the composition was found to be AlMg _6.0 (C ₂ H ₅ )
_3.0 (n-C ₄ H ₉ ) _11.9 , and the organometallic concentration is
It was 1.18 mol/. (4) Synthesis of organoaluminium components. Triethyl aluminum 22.9g, n-pentane
430 ml and 12.05 g of hydromethylsiloxane tetramer were placed in a pressure-resistant container and reacted at 120°C for 5 hours. The resulting reaction product was weighed and the aluminum concentration and ethane concentration resulting from decomposition were measured, and the composition of the reaction product was found to be Al(C ₂ H ₅ ) ₂ (OSiH・CH ₃・C ₂ H ₅ ). Ta. (5) Polymerization 50 mg of the solid component synthesized in (2), 0.05 mmol of organomagnesium component and 0.15 mmol of organoaluminum component synthesized in (3) [0.20 as organometallic (Mg + Al)]
mmol] and 0.8 mmol of dehydrated, deoxygenated hexane were placed in a 1.5-mm autoclave whose interior was vacuum degassed and replaced with nitrogen. The internal temperature of the autoclave was maintained at 80°C, ethylene was added at 10 kg/cm ² , and hydrogen was added to bring the total pressure to 14 kg/cm ² . By replenishing ethylene, polymerization was carried out for 2 hours while maintaining the total pressure at 14 kg/cm ² to obtain 280 g of polymer. Catalytic activity is 560000g/g・chromium atom, MI is 0.34
g/10 min, FR is 90, bulk density is 0.42 g/cc
It was hot. Examples 2 to 6 Ethylene polymerization was carried out in the same manner as in Example 1 except that the organic magnesium component and the organic aluminum component were changed as shown in Table 1. The results are shown in Table 1. Example 7 In a 100 ml flask with _N2 substitution, 30 ml of CH ₂ Cl ₂ 5 mmol of trimethylgermane, 5 m of chromium trioxide
After adding 5 mmol of H ₂ O and stirring at room temperature for 2 hours, the aqueous layer was removed to obtain a brown solution. This solution
It was dehydrated with MgSO ₄ and then filtered. The chromium concentration in the solution was 3.7 mg chromium atoms/ml. The solid component was synthesized by carrying this solution onto a carrier and firing in the same manner as in Example 1. Ethylene polymerization was carried out in the same manner as in Example 1 except for using this solid component. The results are shown in Table 1. Example 8 In a 100 ml flask with N ₂ substitution, 30 ml of CH ₂ Cl ₂ ,
After adding 5 mmol of triphenyltin hydroxide and 5 mmol of chromium trioxide and stirring at room temperature for 3 hours, the mixture was filtered to obtain a brown solution. The chromium concentration in this solution was 4.2 mg chromium atoms/ml. The solid component was synthesized by carrying this solution onto a carrier and firing in the same manner as in Example 1. Ethylene polymerization was carried out in the same manner as in Example 1 except that this solid component was used. The results are shown in Table 1. Example 9 30 ml of CCl ₄ 5 mmol of tetra- _n -butoxygermanium and 5 mmol of chromium trioxide were added to a 100 ml flask substituted with N 2 and reacted under reflux for 15 hours, followed by filtration to obtain a black-green-brown solution. The chromium concentration in this solution was 0.32 mg chromium atoms/ml. The solid component was synthesized by carrying this solution onto a carrier and firing in the same manner as in Example 1. Ethylene polymerization was carried out in the same manner as in Example 1 except that this solid component was used. The results are shown in Table 1. Example 10 Ethylene polymerization was carried out in the same manner as in Example 1, except that the solid components of Example 9 were used and the organomagnesium and organoaluminum components shown in Table 1 were used. The results are shown in Table 1.

【table】

[Table] Example 11 A mixed gas of ethylene and butene-1 containing 15 ml% of butene-1 was used instead of ethylene, and isobutane was used as the polymerization solvent instead of hexane, and the mixed gas partial pressure was 10 Kg/1 at 80°C. cm ² , hydrogen partial pressure 1
Polymerization was carried out in the same manner as in Example ¹ except that the total pressure including the solvent vapor pressure was 23 Kg/cm ² . The polymer yield was 220g, the MI was 0.38g/10min, and the density was 0.923.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 [A] (1) Inorganic oxide support (2) General formula R ¹ R ² R ³ R ⁴ Ge [wherein R ¹ , R ² , R ³ ,
The meaning of R ⁴ is either (a) or (b) below. (a) When R ¹ , R ² , and R ³ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom, halogen, -OH, -OGeR ¹ R ² R ³
(R ¹ , R ² , R ³ are the same as above). (b)
R ¹ , R ² , R ³ , R ⁴ are −OR ^a (R ^a has 1 to 1 carbon atoms
Represents 10 hydrocarbon groups. ) or halogen. (However, cases in which R ¹ , R ² , R ³ , and R ⁴ are all halogens are excluded)] or a germanium compound represented by the general formula
R ¹ R ² R ³ R ⁴ _So (wherein R ¹ , R ² and R ³ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R ⁴ represents halogen or -OH. )
[B] (1) General formula M〓Mg〓R ⁵ _p R ⁶ _q X _r Y _s (in the formula, M
is an element selected from Al, B, Be, Zn, Li, α is 0 or a number larger than 0, p, q,
r and s are 0 or a number larger than 0,
p and q are not 0 at the same time, 0≦(r+s)/
(α+β)≦1.5 and p+q+r+s=mα+
2β relationship, m is the valence of M, R ⁵ , R ⁶
are the same or different groups, and represent a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms, and X and Y are the same or different groups, and OR ⁷ ,
OSiR ⁸ R ⁹ R ¹⁰ , NR ¹¹ R ¹² , SR ¹³ represents a halogen group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹²
represents a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ represents a hydrocarbon group having 1 to 20 carbon atoms. ); (2) 0.1 to 1 mole of carbinol having 1 to 20 carbon atoms or 0.1 to 2 silanol or siloxane per mole of the trialkylaluminum compound;
A catalyst for the polymerization of ethylene or the copolymerization of ethylene and α-olefin, which is a component consisting of an organoaluminum component in which moles thereof are reacted, and is composed of [A] and [B].