JPH0995511A - Method for producing polyolefin - Google Patents

Abstract

(57) Abstract: A method for controlling the molecular weight of a polyolefin in a vapor phase polymerization of a polyolefin using a specific catalyst is provided. SOLUTION: The hydrogen concentration in the reactor is adjusted so that the molar ratio of hydrogen existing in the reaction system to the sum of olefins is in the range of 0.1 × 10 ^-4 to 15 × 10 ^-4. A method for producing a polyolefin, comprising:

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an operation method for polymerizing or copolymerizing olefins in a gas phase.
More specifically, the present invention relates to a method for controlling the molecular weight of a polyolefin by allowing a trace amount of hydrogen to exist in a reactor when polymerizing or copolymerizing olefins in a gas phase using a specific catalyst.

[0002]

2. Description of the Related Art It is already known that a new catalyst composed of a zirconium compound and a modified organoaluminum compound exhibits a very high activity for α-olefin (Japanese Patent Laid-Open No. 58-19309). However, polymers produced using this catalyst system have drawbacks such as a small molecular weight and a narrow molecular weight distribution, and poor polymer particle properties. Further, JP-A-61-296008, JP-A-61-108610 and JP-A-6-
JP-A-3-51407 proposes a metallocene catalyst supported on silica, alumina or the like. However, although the polymer particle shape is improved by using these catalysts, the molecular weight is similarly small and the molecular weight distribution is narrow. On the other hand, a novel catalyst which is completely different from the conventional catalyst system has been proposed (JP-A-5-194639 and JP-A-5-132518). The new catalyst system is highly active, the resulting polymers have high molecular weights, relatively wide molecular weight distributions, and in the case of copolymerization, narrow composition distributions.

[0003]

In the above novel catalyst system, the activity decreases when hydrogen of a concentration of 5 to 30 mol% is added to the reaction system as in the case of using the conventional Ti-based Ziegler catalyst. At the same time, only a polymer having a wax having an extremely low molecular weight could be produced, and it was difficult to control the molecular weight.

[0004]

As a result of intensive studies, the inventors of the present invention have found that when a novel catalyst is used to polymerize or copolymerize olefins in a gas phase, a trace amount of olefins is present in the reaction system. We have found a method to control the molecular weight of polyolefins by the presence of hydrogen. That is, the first aspect of the present invention is a method for polymerizing or copolymerizing olefins in a gas phase in the presence of a catalyst obtained by bringing the following components (1) to (5) into contact with each other in a reactor. Hydrogen concentration of 0.1 × 10 ⁻⁴ to 15 × 10 with respect to 1 mol of the total amount of hydrogen and olefins present in the reaction system.
^{The present} invention relates to a method for producing a polyolefin, which comprises adjusting the molecular weight of the polyolefin by adjusting the molecular weight of the polyolefin to be in the range of ^-4 mol. (1) Compound containing group IVB metal of the periodic table (2) Compound containing group I-III metal of the periodic table (3) Organic cyclic compound having two or more conjugated double bonds (4 ) Modified organoaluminum compound and / or boron compound having Al-O-Al bond (5) Inorganic compound carrier and / or particulate polymer carrier

A second aspect of the present invention is a polyolefin which is characterized in that, in the first aspect of the present invention, it is carried out in the presence of a catalyst obtained by bringing the following components (1) to (5) into contact with each other. The present invention relates to a manufacturing method. (1) General formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq (R ¹ and R ² are hydrocarbon groups, X ¹ is a halogen atom, Me ¹ is Ti, Zr or Hf, and 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦
A compound represented by 4), and (2) the general formula Me ² (OR ³ ) _m R ⁴
_n X ² _3-mn (wherein Me ² is a Group III metal of the periodic table, R ³ ,
R ⁴ is a hydrocarbon group, X ² is a hydrogen atom or a halogen atom,
0 ≦ m ≦ 3, 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 3), (3) an organic cyclic compound having two or more conjugated double bonds, (4) an Al-O-Al bond A modified organoaluminum compound and / or a boron compound,
(5) An inorganic compound carrier and / or a particulate polymer carrier.

Hereinafter, the present invention will be described in more detail. The catalyst component (1) used in the present invention is the periodic table IV.
A compound containing a Group B metal, preferably a compound of the general formula
It is represented by Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq . In the formula, R ¹ and R
² each represents a hydrocarbon group, preferably having 1 to 1 carbon atoms.
24, more preferably 1 to 12 hydrocarbon groups.
Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an alkyl group such as a hexyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, an aryl group such as a tolyl group, a benzyl group, Examples thereof include aralkyl groups such as trityl group. These may have branches. When the component (1) has two or more R ¹ or R ² , those hydrocarbon residues may be the same or different. X ¹ is a halogen atom of fluorine, iodine, chlorine or bromine, and Me ¹ is Zr, Ti or Hf, preferably Zr. p is 0 ≦ p ≦ 4, q is 0
≦ q ≦ 4 and p + q satisfy the conditions of 0 ≦ p + q ≦ 4, and preferably 0 <p + q ≦ 4.

Specific examples of the compound which can be used as the component (1) include tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium and tetratolyl. Oxyzirconium, tetrabenzyloxyzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetrabutylzirconium, tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetrachlorozirconium, triethoxy Monochloro zirconium, diethoxydichlorodiene Conium, monoethoxytrichlorozirconium, triisopropoxymonochlorozirconium, diisopropoxydichlorozirconium, monoisopropoxytrichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, monobutoxytrichlorozirconium, triphenoxymonochlorozirconium, di Phenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tetrabenzyloxyzirconium, tribenzyloxymonochlorozirconium, dibenzyloxydichlorozirconium, monobenzyloxytric B zirconium, tetrabromo zirconium, etc. tetraiodothyronine zirconium and the like. Further, a compound in which zirconium in the above zirconium compound is replaced with titanium and hafnium can also be used. Among these, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium and tetrabenzylzirconium are preferable. Further, these compounds can be used as a mixture of two or more kinds.

Component (2) is a compound containing any of the metals of Groups I to III of the Periodic Table, preferably of the general formula Me
It is represented by ² (OR ³ ) _m R ⁴ _n X ² _3-mn . In the formula, Me ² represents a Group III metal of the periodic table, and includes boron, aluminum and the like. R ³ and R ⁴ each represent a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, decyl group,
Alkenyl group such as vinyl group and allyl group, phenyl group,
Examples thereof include an aryl group such as a tolyl group and an aralkyl group such as a benzyl group and a trityl group. These may have branches. If component (2) has more than one R ³ or R ⁴ , the hydrocarbon residues can be the same or different. X ² represents a hydrogen atom or a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n ≦ 3, and m + n is 0 ≦ m + n ≦ 3.

Specific examples of compounds usable as the component (2) include trimethylboron, triethylboron, tri-n-propylboron, triisopropylboron, tri-n-butylboron, tri-tert-butylboron and tripentylboron. , Trioctylboron, triphenylboron, tribenzylboron, trimethylaluminum, triethylaluminum, diethylaluminum hydride, diethylaluminum chloride, ethylaluminum dichloride, tripropyloaluminum, dipropylaluminum hydride, dipropylaluminum chloride, propylaluminum dichloride, tri Isopropyl aluminum, diisopropyl aluminum hydride, diisopropyl aluminum chloride, ethyl Aluminum sesquichloride, propyl aluminum sesquichloride, isopropyl aluminum dichloride, tributyl aluminum, dibutyl aluminum chloride, butyl aluminum sesqui chloride, butyl aluminum dichloride, triisobutyl aluminum, diisobutyl aluminum hydride, diisobutyl aluminum chloride, trihexyl aluminum, dihexyl aluminum chloride, hexyl Aluminum dichloride,
Tripentyl aluminum, tridecyl aluminum,
Dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, diisobutyl aluminum methoxide, diisobutyl aluminum ethoxide,
Examples thereof include diisobutylaluminum propoxide and diisobutylaluminum butoxide. Among them, trimethylaluminum, triethylaluminum, diethylaluminum chloride, tripropyroaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tripentylaluminum, diisobutylaluminum hydride and tridecylaluminum are preferable.

As the component (3), an organic cyclic compound having two or more conjugated double bonds is used, and preferably a cyclic carbonized compound having 2 to 4 conjugated double bonds and a total carbon number of 4 to 24. It is a hydrogen compound. Further, the cyclic hydrocarbon compound may be partially substituted with 1 to 6 hydrocarbon residues, and the hydrocarbon residue may contain a silicon atom.
Those having a cyclopentadiene structure in the molecule are particularly desirable.

Therefore, specific examples of the organic cyclic compound usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene,
tert-butylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,2,
4-trimethylcyclopentadiene, 1-ethyl-4,
5-dimethylcyclopentadiene, 2-methyl-5-te
rt-butylcyclopentadiene, pentamethylcyclopentadiene, indene, methylindene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, cycloheptatriene, cyclooctatetraene,
Examples thereof include azulene, methylazulene, fluorene, methylfluorene, cyclopentadienylsilane, cyclopentadienylmethylsilane, cyclopentadienyldimethylsilane, cyclopentadienyltrimethylsilane, indenylsilane and indenyltrimethylsilane.

A compound in which any of the above compounds is bound via a silicon atom or an alkylene group can also be used as the component (3) of the present invention. Specific examples are dicyclopentadienylsilane, dicyclopentadienylmonomethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiphenylsilane, bis (3-methylcyclopentadienyl) silane, and bis. (3-Methylcyclopentadienyl) dimethylsilane, bis (1,3-dimethylcyclopentadienyl) silane, bis (1,3-dimethylcyclopentadienyl) dimethylsilane, diindenylsilane, diindenyldimethyl Silane, diindenyldiphenylsilane,
Bis (3-methylindenyl) silane, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3-bisindenylpropane,
1,3-Bis (4,5,6,7-tetrahydroindenyl) propane, 2,2-bisindenylpropane, isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropyl Examples thereof include cyclopentadienyl-1-fluorene.

Among them, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, tert-butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, indene, methylindene, 4,7-dimethylindene. ,
Diindenyldimethylsilane and bisindenylethane are preferred.

As the component (4), a modified organoaluminum compound having an Al--O--Al bond and / or a boron compound is used. The modified organoaluminum compound has preferably 1 to 100, particularly preferably 1 to 50 Al-O-Al bonds in the molecule. The modified organoaluminum compound can be produced by a known method and is not particularly limited, but it is generally produced by reacting organoaluminum with water. This reaction is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or The use of aromatic hydrocarbons is preferred.

The organoaluminum compound used to prepare the modified organoaluminum compound has the general formula R ¹ _n Al (OR ² ) _m
It is represented by X _3-mn . In the formula, R is a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group, X is a hydrogen atom or a halogen atom, and n is 1 ≦ n ≦. Indicates an integer in the range of 3. Although any of the compounds represented by the above formula can be used, trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, etc., but a methyl group is particularly preferable. The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is 0.25 / 1.
˜1.5 / 1, particularly preferably 0.5 / 1 to 1.2 / 1. The reaction temperature is generally -70 to 150 ° C, preferably -20 to 100 ° C. Reaction time is usually 5
It is selected from the range of minutes to 50 hours, preferably 10 minutes to 20 hours. As the water used in the reaction, in addition to ordinary water, water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can be used.

As the boron compound as the component (4), a compound having at least one boron-carbon bond is preferably used, and examples thereof include borate and borane compounds. As the borate, the general formula [L ¹ ] ⁺ [BR ⁵ R ⁶ R
⁷ R ^{8] -} a compound represented by are preferred. In the formula, L ¹ is a compound capable of becoming a cation, and a Bronsted acid such as ammonium, anilium, phosphonium, or carbocation, methyl cation, ethyl cation, propyl cation, butyl cation, tropinium cation,
Examples thereof include benzyl cation and trityl cation. R ⁵ is an aromatic or substituted aromatic hydrocarbon group containing ⁵ to 20, preferably 6 to 16 carbon atoms, and the substituent is preferably an alkyl group or a halogen atom. R ^6, R ^7, R ⁸ is 5 to 20, preferably 6 to 16
An aromatic or substituted aromatic hydrocarbon group containing 1 carbon atom, a hydride group, a halide group, a hydrocarbyl group, the substituent is preferably an alkyl group or a halogen atom, and R ⁶ , R ⁷ , and R ⁸ are It may be the same as or different from R ⁵ .

Specific examples of borate include tributylammonium tetra (o-fluorophenyl) borate, tributylammonium tetra (p-fluorophenyl) borate, tributylammonium tetra (m-).
Fluorophenyl) borate, tributylammonium tetra (3,5-difluorophenyl) borate, tributylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (o-fluorophenyl) borate, dimethylanilinium tetra (p
-Fluorophenyl) borate, dimethylanilinium tetra (m-fluorophenyl) borate, dimethylanilinium tetra (3,5-difluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trityl tetra (o-fluorophenyl) ) Borate, trityl tetra (p-fluorophenyl) borate, trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tropinium tetra (o- Fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m-fluorophenyl) borate, tropinium tetra (3,5
-Difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate and the like. Among these, tributylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate and tropinium tetra (pentafluorophenyl) borate are preferable.

The borane compound is represented by the general formula BR ⁹ R ¹⁰
The compound represented by R ¹¹ is preferred. In the formula, R ⁹ is the same as R ^{5 in} the general formula of the borate compound, and R ¹⁰ is R ⁶ and R ¹¹
Are the same as R ⁷ . R ¹⁰ and R ¹¹ may be the same as or different from R ⁹ . Specific examples of the borane compound include tri (o-fluorophenyl) borane, tri (p-fluorophenyl) borane, tri (m-fluorophenyl) borane, tri (3,5-difluorophenyl) borane, tri (penta). Fluorophenyl) borane and the like. Among these, tri (pentafluorophenyl) borane is preferable.

As the component (5), an inorganic carrier and / or
Alternatively, a particulate polymer carrier is used. The inorganic carrier may have any shape such as powder, granules, flakes, foil or fibrous shape as long as it retains its original shape at the stage of preparing the catalyst of the present invention.
In any case, the maximum length is usually 5 to 200 μm, and preferably 10 to 100 μm. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g and a pore volume of 0.05 to ³ cm ³ .

As the inorganic carrier of the present invention, a carbon material,
Metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used. Suitable metal oxides that can be used for the inorganic carrier include I to VII of the periodic table.
Examples thereof include single oxides or complex oxides of Group I metals, such as SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ ,
ZrO ₂ , Fe ₂ O ₃ , SiO ₂ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · C
aO, Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , A
l ₂ O ₃ · CuO, Al ₂ O ₃ · Fe ₂ O ₃ , Al ₂ O ₃ · NiO, SiO
₂ · MgO and the like. It should be noted that the above formula expressed as an oxide does not represent a molecular formula but represents only the composition. Specific examples of metal chlorides include MgCl ₂ and CaC.
l _{2 and the} like are particularly preferable, and examples of the metal carbonate include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but metal oxides, silica, alumina and the like are particularly preferably used.

On the other hand, as the particle polymer carrier, either a thermoplastic resin or a thermosetting resin may be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. Can be made and its particle size is 5 to 2
It is preferably 000 μm. Specifically, various polyolefins (preferably having 2 carbon atoms) represented by particulate ethylene polymers, ethylene / α-olefin copolymers, propylene polymers or copolymers, poly-1-butene, etc.
~ 12), polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate,
In addition to polystyrene and polynorbornene, various natural polymers and mixtures thereof can be used as the polymer carrier.

These inorganic carrier and / or particulate polymer carrier may be used as they are for catalyst preparation, or may be used for catalyst preparation after being pretreated with an organic aluminum compound. Furthermore, regarding the inorganic carrier,
Component (5) after contacting with active hydrogen-containing compounds such as alcohols and aldehydes, electron-donating compounds such as esters and ethers, alkoxide group-containing compounds such as tetraalkoxysilicates, trialkoxyaluminums, transition metal tetraalkoxides, etc. The method used as is also preferably used.

The olefin polymerization catalyst used in the present invention is obtained by bringing the components (1) to (5) into contact with each other. The order of contacting these is not particularly limited, but preferably they can be prepared by any of the following methods. A. A method in which the components (1) to (3) are simultaneously contacted, then the component (4) is contacted, and then the component (5) is contacted. B. A method in which components (1) to (3) are contacted at the same time, while components (4) and (5) are contacted, and finally all are contacted. C. A method of contacting components (1) and (2), then component (3), then component (4), and finally component (5). D. A method of contacting the components (1) and (3), then the component (2), then the component (4), and finally the component (5). E. FIG. A method wherein components (1) and (2) are contacted, then component (3) is contacted, while components (4) and (5) are contacted and finally all are contacted. F. A method wherein components (1) and (3) are contacted, then component (2) is contacted, while components (4) and (5) are contacted and finally all are contacted. G. A method wherein components (2) and (3) are contacted, then component (1) is contacted, while components (4) and (5) are contacted and finally all are contacted. H. A method of contacting the components (1) and (5), then the component (2), then the component (3), and finally the component (4). I. A method of contacting the components (1) and (5), then the component (3), then the component (2), and finally the component (4).

The method of contacting these components is not particularly limited, but usually, in an inert atmosphere of nitrogen or argon, aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane,
A method of contacting each component in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon such as dodecane or cyclohexane is adopted. Contact is usually -100 ℃
To 200 ° C, preferably 0 ° C to 180 ° C, for 10 minutes to 50 hours, preferably 30 minutes to 30 hours.

The blending ratio of the components (1) to (5) of the present invention is usually 0.
It is 1 to 100 mol, preferably 1 to 50 mol, and the component (3) is usually 0.1 to 100 mol, preferably 1 to 50 mol.
It is a molar ratio. Further, with respect to 1 mol of the component (1),
Component (4) is 1 to 1 as an aluminum or boron atom.
The ratio is 10,000 mol, preferably 10 to 1,000 mol. In addition, for 1 g of the component (5), the component (1)
Transition metal component of 0.0001-5 mmol, preferably 0.001
001-0.5 mmol, more preferably 0.01-0.0 mmol.
Used in the range of 1 mmol.

When each component is contacted in an inert hydrocarbon solvent, the hydrocarbon solvent is removed once,
It may be contacted with the next component, or may be directly contacted with the next component without removing the hydrocarbon solvent. Further, after the contact of all the components in the inert hydrocarbon solvent is completed, the produced catalyst can be directly subjected to the polymerization together with the solvent, and once taken out as a solid catalyst by a means such as precipitation and drying, it is used for the polymerization. You can also The solid catalyst obtained by the above method may be directly supplied to the polymerization reactor, or may be pretreated with olefins and then supplied to the polymerization reactor.

In the present invention, in the presence of the above catalyst,
The olefins can be homopolymerized or copolymerized. The olefins referred to in the present invention include α-olefins, cyclic olefins, dienes, trienes and styrenes. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specific examples include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like. It is illustrated. α
-For olefins, the catalyst component of the present invention can be used for homopolymerization, and it is also possible to copolymerize two or more kinds of α-olefins. For the copolymerization of α-olefins, ethylene and propylene, ethylene and 1-
Like butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, ethylene and 3 to 1 carbon atoms
When 2, 2, preferably 3 to 8 α-olefin is copolymerized, propylene and 1-butene, propylene and 4-methyl-1-pentene, propylene and 4-methyl-1-butene, propylene and 1-hexene, A case where propylene is copolymerized with α-olefin having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, such as propylene and 1-octene, is included.

The cyclic olefin has 3 to 2 carbon atoms.
4, preferably 3 to 18 can be used in the present invention, for example, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, cyclotetradecene, cyclooctadecene, dicyclopentadiene. , Norbornene, 5-methyl-2-norbornene, 5
-Ethyl-2-norbornene, 5,6-dimethyl-2-
Norbornene, ethylidene norbornene and the like are included. When a cyclic olefin is used in the present invention, it is usually copolymerized with the above-mentioned α-olefin.

As the dienes and trienes, polyenes having 4 to 26 carbon atoms, preferably 4 to 20 carbon atoms are used. Specifically, butadiene, 1,3-pentadiene,
1,4-pentadiene, 1,3-hexadiene, 1,4-
Hexadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene, 2- Methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene, 2,3
Examples include dimethyl butadiene, ethylidene norbornene, dicyclopentadiene, isoprene, 1,3,7-octatriene, and 1,5,9-decatriene. When the chain diene or triene is used in the present invention, it is usually copolymerized with the above-mentioned α-olefin.

Styrenes include styrene and styrene derivatives, and examples of the styrene derivative include tert-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-.
Examples thereof include dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene.

In the present invention, the reactor used for polymerizing or copolymerizing an olefin in a gas phase includes a fluidized bed system and a stirred bed system which are operated substantially in a gas-solid system, and includes a stirrer. It may be either with or without. The catalyst used in the present invention is
It may be fed directly into the polymerization reactor or it may be entrained in a carrier gas such as nitrogen. As polymerization conditions, the temperature is usually 20 to 200 ° C., preferably 40 to 150 ° C., and the pressure is atmospheric pressure to 7 MPa · G, preferably 0.2 to 6 MPa ·
G. During steady operation, the raw material olefins and the above catalyst are constantly introduced into the polymerization system, while the produced polymer particles are extracted. Further, an inert gas such as nitrogen may be supplied into the reactor as a diluent for the polymerization gas.

The hydrogen concentration for controlling the molecular weight is usually 0.1 × 10 ^-4 to 15 × 10 ^-4 mol, preferably 0.1 ×, relative to 1 mol of the total olefins present in the reaction system.
It is important to adjust it to be in the range of 10 ⁻⁴ to 10 × 10 ⁻⁴ . By allowing a trace amount of hydrogen to be present in the reaction system, the MFR of the obtained polyolefin is 0.001-200 g / 10 minutes, preferably 0.01-100.
It is possible to adjust in the range of g / 10 minutes.

The method for adjusting the hydrogen concentration in the reaction system is not particularly limited as long as the hydrogen concentration in the reaction system is within the range specified above. For example, the MFR can be adjusted by changing the hydrogen concentration in the reaction system by appropriately adopting a method of feeding a small amount of hydrogen into the reaction system. In addition, since the adjustment of the minute amount of hydrogen concentration is performed as described above, it is possible to adjust the MFR by changing the hydrogen concentration by a method of appropriately venting the gas in the reaction system to the outside of the system. Further, since it can be controlled by a slight amount of hydrogen, there are cases where hydrogen gas contained as an impurity in the raw material gas can be used. After completion of the reaction, a polyolefin can be obtained according to a conventional method.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION In the operation of a polyolefin gas phase polymerization reactor using a catalyst obtained by contacting five specific components, the molar ratio of hydrogen existing in the reaction system to the total amount of olefins is 0. to be in the range of ^{.1 × 10- 4 ~15 × 10 -4} , it is possible to adjust the molecular weight of the polyolefin by adjusting the hydrogen concentration in the reactor.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. <Physical property measurement method> Physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. Melt Flow Rate (MFR): According to ASTM D1238-57T Density: According to ASTM D1505-68

<Preparation of Catalyst> The catalysts used in Examples and Comparative Examples were prepared as described in (1) to (5) below. (1) Preparation of catalyst A 300 ml with electromagnetic induction stirrer under nitrogen atmosphere
60 ml of purified toluene was placed in an eggplant-shaped flask, and then 0.65 g of tetrapropoxyzirconium and 1.32 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, then kept at 0 ° C and 1.84 g of triethylaluminum.
Was added dropwise over 30 minutes, and after completion of the addition, the temperature was raised to room temperature 24
Stir for hours. Next, in this solution, a toluene solution of methylaluminoxane (concentration: 1.3 mmol / ml, manufactured by Witco) 15
After adding 0 ml and reacting at room temperature for 1 hour, the mixture was allowed to stand at room temperature for one day. This solution is called a solution. Next, in a 500 ml three-necked flask equipped with a stirrer under a nitrogen atmosphere, silica (grade # 952, surface area 300 m ² / g;
(Manufactured by K.K.) was added, the whole amount of the solution a was added, and the mixture was stirred at room temperature for 2 hours. Then, nitrogen blowing was performed to remove the solvent to obtain a solid catalyst A. (2) Preparation of catalyst B In the catalyst preparation (1), 1.16 g of 1,2,4-trimethylcyclopentadiene was used instead of cyclopentadiene.
A solid catalyst B was obtained in the same manner except that was used. (3) Preparation of catalyst C Solid catalyst C was obtained in the same manner as in catalyst preparation (1) except that 1.85 g of indene was used instead of cyclopentadiene. (4) Preparation of catalyst D In the catalyst preparation (1), 0.77 g of tetrabutoxyzirconium instead of tetrapropoxyzirconium
Was used in the same manner as above, except that 3.17 g of triisobutylaluminum was used instead of triethylaluminum to obtain a solid catalyst D.

<Polymerization apparatus> Polymerization in the examples was carried out using a continuous gas phase fluidized bed polymerization apparatus shown in FIG. Ethylene or butene-1 was supplied from the raw material supply line 8 and the catalyst was supplied from the catalyst feed line 1 to copolymerize ethylene using 1-butene as a comonomer. The inner diameter of the fluidized bed of the fluidized bed reactor 4 is 25 cm,
A dispersion plate 3 is installed at the bottom of the reactor. The polymer was extracted from the polymer extraction line 2 while adjusting the extraction amount so that the volume of the portion forming the fluidized bed of the polymer was kept at 0.05 m ³ . During steady operation, the internal pressure was adjusted to 1.9 MPa · G and the temperature was 75 ° C. The reaction gas leaving the reactor 4 is pressurized by a circulating gas blower 6, cooled by a circulating gas cooler 7, and circulated in the reactor through a gas circulation line 5. Due to this flow of the reaction gas, the polymer in the reactor is fluidized and the heat of polymerization is taken out of the reactor. The flow rate of the circulating reaction gas was adjusted so that the superficial velocity in the fluidized bed portion in the reactor was 0.45 m / s.

Example 1 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst A, and the catalyst was supplied to the reactor at a rate of 1.15 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.5 kg per hour. Nitrogen concentration in the reaction gas is 30 mol%
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so that The molar ratio of 1-butene to ethylene in the reaction gas was 0.085. In addition, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1
The amount of hydrogen gas supplied was adjusted so that the molar ratio of the hydrogen gas to the butene) was 1.2 × 10 ⁻⁴ . As a result of the above polymerization operation, the bulk density was 0.50 g / cm ³ , the average particle size was 650 μm, and M
A copolymer having an FR of 3.0 g / 10 min and a density of 0.9164 g / cm ³ was obtained, and the catalytic efficiency was 2.2 kg per 1 g of the catalyst. Table 1 shows the results.

Example 2 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst A, and was supplied to the reactor at a rate of 1.22 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.6 kg per hour. The supply amount of nitrogen and the amount of the reaction gas discharged outside the reaction system were adjusted so that the nitrogen concentration in the reaction gas was 30 mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.070. Also, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1-
The supply amount of hydrogen gas was adjusted so that the ratio with the sum of butene) was 2.2 × 10 ⁻⁴ in molar ratio. As a result of the above polymerization operation, the bulk density is 0.49 g / cm ³ , the average particle size is 690 μm, and the MF is
A copolymer having an R of 6.1 g / 10 min and a density of 0.9212 g / cm ³ was obtained, and the catalyst efficiency was 2.1 kg per 1 g of the catalyst. Table 1 shows the results.

Example 3 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst A, and the catalyst was supplied to the reactor at a rate of 1.25 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.5 kg per hour. The supply amount of nitrogen and the amount of the reaction gas discharged outside the reaction system were adjusted so that the nitrogen concentration in the reaction gas was 30 mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.067. Also, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1-
The supply amount of hydrogen gas was adjusted so that the molar ratio with (the sum of butene) was 3.5 × 10 ⁻⁴ . As a result of the above polymerization operation, the bulk density was 0.49 g / cm ³ , the average particle size was 680 μm, and the MF was MF.
A copolymer having an R of 15.6 g / 10 min and a density of 0.9230 g / cm ³ was obtained, and the catalytic efficiency was 2.0 kg per 1 g of the catalyst. Table 1 shows the results.

Example 4 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst A, and was supplied to the reactor at a rate of 1.23 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.2 kg per hour. The supply amount of nitrogen and the amount of the reaction gas discharged outside the reaction system were adjusted so that the nitrogen concentration in the reaction gas was 30 mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.072. Also, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1-
The supply amount of hydrogen gas was adjusted so that the ratio with the sum of butene) was kept at 4.4 × 10 ⁻⁴ in molar ratio. As a result of the above polymerization operation, the bulk density was 0.50 g / cm ³ , the average particle size was 660 μm, and the MF was
A copolymer having R23.7 g / 10 minutes and a density of 0.9223 g / cm ³ was obtained, and the catalyst efficiency was 1.8 kg per 1 g of the catalyst. Table 1 shows the results.

Example 5 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. However,
The catalyst used was the catalyst B, and was supplied to the reactor at a rate of 1.04 g per hour. 2.6 kg of copolymer per hour
The fluidized bed volume in the reactor was kept constant by withdrawing from the reactor at a rate of. Nitrogen concentration in reaction gas is 30
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so as to be mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.078. Further, the ratio of hydrogen in the reaction gas to the sum of olefin gases (the sum of ethylene and 1-butene) is 6.0 × 1 in molar ratio.
The hydrogen gas supply rate was adjusted so as to maintain ^0-4 . As a result of the above polymerization operation, the bulk density was 0.50 g / cm ³ , and the average particle size was 710 μm.
m, MFR 0.8 g / 10 min and a density of 0.9194 g / cm ³ were obtained, and the catalytic efficiency was 2.
It was 5 kg. Table 1 shows the results.

Example 6 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst B, and was supplied to the reactor at a rate of 1.02 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.8 kg per hour. The supply amount of nitrogen and the amount of the reaction gas discharged outside the reaction system were adjusted so that the nitrogen concentration in the reaction gas was 30 mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.075. Also, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1-
The supply amount of hydrogen gas was adjusted so that the ratio with the sum of butene) was 10.3 × 10 ⁻⁴ in molar ratio. As a result of the above polymerization operation, the bulk density was 0.48 g / cm ³ , the average particle size was 730 μm, and M
A copolymer having an FR of 19.2 g / 10 min and a density of 0.9212 g / cm ³ was obtained, and the catalyst efficiency was 2.7 kg per 1 g of the catalyst.
Met. Table 1 shows the results.

Example 7 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. However,
As the catalyst, the catalyst C was used, and it was supplied to the reactor at a rate of 1.07 g per hour. 2.4 kg of copolymer per hour
The fluidized bed volume in the reactor was kept constant by withdrawing from the reactor at a rate of. Nitrogen concentration in reaction gas is 30
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so as to be mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.096. In addition, the ratio of the total amount of hydrogen and olefin gas (the sum of ethylene and 1-butene) in the reaction gas is 1.9 × 1 in molar ratio.
The hydrogen gas supply rate was adjusted so as to maintain ^0-4 . As a result of the above polymerization operation, the bulk density was 0.49 g / cm ³ , and the average particle size was 650 μ.
m, an MFR of 2.6 g / 10 min and a density of 0.9181 g / cm ³ were obtained, and the catalytic efficiency was 2.
It was 2 kg. Table 1 shows the results.

Example 8 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. As the catalyst, the catalyst C was used, and the catalyst was supplied to the reactor at a rate of 1.13 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.4 kg per hour. The supply amount of nitrogen and the amount of the reaction gas discharged outside the reaction system were adjusted so that the nitrogen concentration in the reaction gas was 30 mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.085. Also, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1-
The supply amount of hydrogen gas was adjusted so that the molar ratio with (the sum of butene) was 4.8 × 10 ⁻⁴ . As a result of the above polymerization operation, the bulk density is 0.49 g / cm ³ , the average particle size is 630 μm, and the MF is
A copolymer having an R of 20.6 g / 10 minutes and a density of 0.9205 g / cm ³ was obtained, and the catalyst efficiency was 2.1 kg per 1 g of the catalyst. Table 1 shows the results.

Example 9 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. However,
As the catalyst, the catalyst D was used and was supplied to the reactor at a rate of 1.26 g per hour. 3.4 kg of copolymer per hour
The fluidized bed volume in the reactor was kept constant by withdrawing from the reactor at a rate of. Nitrogen concentration in reaction gas is 30
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so as to be mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.090. Further, the ratio of the total amount of hydrogen and olefin gas (the sum of ethylene and 1-butene) in the reaction gas is 1.6 × 1 in terms of molar ratio.
The hydrogen gas supply rate was adjusted so as to maintain ^0-4 . As a result of the above polymerization operation, the bulk density was 0.50 g / cm ³ , and the average particle size was 710 μm.
m, an MFR of 3.1 g / 10 min and a density of 0.9161 g / cm ³ were obtained, and the catalytic efficiency was 2.
It was 6 kg. Table 1 shows the results.

Example 10 Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. The catalyst used was the catalyst D, and the catalyst was supplied to the reactor at a rate of 1.13 g per hour. The fluidized bed volume in the reactor was kept constant by withdrawing the copolymer from the reactor at a rate of 2.8 kg per hour. Nitrogen concentration in the reaction gas is 30 mol%
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so that The molar ratio of 1-butene to ethylene in the reaction gas was 0.079. In addition, the sum of hydrogen and olefin gas in the reaction gas (ethylene and 1
The amount of hydrogen gas supplied was adjusted so that the molar ratio of the hydrogen gas to butene) was 3.7 × 10 ⁻⁴ . As a result of the above polymerization operation, the bulk density was 0.49 g / cm ³ , the average particle size was 690 μm, and M
A copolymer having an FR of 12.6 g / 10 min and a density of 0.9191 g / cm ³ was obtained, and the catalytic efficiency was 2.5 kg per 1 g of the catalyst.
Met. Table 1 shows the results.

<Comparative Example 1> Copolymerization of ethylene and 1-butene was carried out using the above-mentioned polymerization apparatus and conditions. However,
The catalyst used was the catalyst A, and the catalyst was supplied to the reactor at a rate of 1.51 g per hour. 1.2 kg of copolymer per hour
The fluidized bed volume in the reactor was kept constant by withdrawing from the reactor at a rate of. Nitrogen concentration in reaction gas is 30
The supply amount of nitrogen and the amount of reaction gas discharged to the outside of the reaction system were adjusted so as to be mol%. The molar ratio of 1-butene to ethylene in the reaction gas was 0.105. Further, the ratio of hydrogen in the reaction gas to the sum of olefin gases (sum of ethylene and 1-butene) is 18 × 10 in terms of molar ratio.
^The amount of hydrogen gas supplied was adjusted so as to maintain ^-4 . As a result of the above operation, the bulk density is 0.49 g / cm ³ , the average particle size is 450 μm, and M
A copolymer having an FR of 200 g / 10 min or more and a density of 0.9293 g / cm ³ was obtained, and the catalyst efficiency was 0.1 g per 1 g of the catalyst.
It was 8 kg. Table 1 shows the results.

[0049]

[Table 1]

[0050]

According to the method of the present invention, when the olefins are polymerized or copolymerized in the gas phase using a specific catalyst, the molecular weight of the polyolefin can be controlled by allowing a slight amount of hydrogen to exist in the reactor. It becomes possible to adjust.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a gas phase polymerization reaction device.

[Explanation of symbols] 1 catalyst feed line 2 polymer extraction line 3 dispersion plate 4 fluidized bed reactor 5 gas circulation line 6 circulating gas blower 7 heat exchanger 8 raw material supply line

Claims (2)

[Claims] 1. A method for polymerizing or copolymerizing olefins in a gas phase in the presence of a catalyst obtained by bringing the following components (1) to (5) into contact with each other, wherein the hydrogen concentration in the reactor is Is 0.1 × 10 ⁻⁴ to 15 × 1 with respect to 1 mol of the total amount of olefins present in the reaction system.
A method for producing a polyolefin, which comprises controlling the molecular weight of the polyolefin by adjusting the molecular weight of the polyolefin to be in the range of 0 ^-4 mol, (1) a compound containing a Group IVB metal of the periodic table, (2) a period A compound containing any of Group I to III metals of the table, (3) an organic cyclic compound having two or more conjugated double bonds, (4) a modified organoaluminum compound having an Al-O-Al bond, and / or Boron compound, (5) inorganic compound carrier and / or particulate polymer carrier. 2. The method for producing a polyolefin according to claim 1, which is carried out in the presence of a catalyst obtained by bringing the following components (1) to (5) into contact with each other:
(1) General formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq (R ¹ and R ² are hydrocarbon groups, X ¹ is a halogen atom, Me ¹ is Ti, Zr or Hf, and 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦
A compound represented by 4), and (2) the general formula Me ² (OR ³ ) _m R ⁴
_n X ² _3-mn (wherein Me ² is a Group III metal of the periodic table, R ³ ,
R ⁴ is a hydrocarbon group, X ² is a hydrogen atom or a halogen atom,
0 ≦ m ≦ 3, 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 3), (3) an organic cyclic compound having two or more conjugated double bonds, (4) an Al-O-Al bond A modified organoaluminum compound and / or a boron compound,
(5) An inorganic compound carrier and / or a particulate polymer carrier.