JPS62100505A - Production of polyolefin - Google Patents

Abstract

PURPOSE:The polymerization of an olefin is carried out in the presence of a catalyst which has been prepared by adding an organometallic intramolecular complex, an organoaluminum compound and an electron donor to the components of polymerization catalyst to produce polyolefin which has good moldability, because it has a broad molecular weight distribution. CONSTITUTION:The polymerization of an olefin is conducted in the presence of a catalyst which has been prepared by adding, to a polymerization catalyst components, titanium trihalide and diethylaluminum chloride, (A) an organometallic intramolecular complex such as (3-ethoxypropyl)-i-butylaluminum hydride, (B) an organoaluminum compound of the formula (R<1>, R<2> are H, hydrocarbon residue of 1-12 carbon atoms; Y is group bearing at least one of heteroatoms which do not directly bond to Al; 0<=k, l, m<=2, k+l=3-m) such as bis(3-diethylaminopropyl) ether and (C) an electron donor such as methanol or ethyl acetate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing polyolefins by polymerizing olefins using a novel catalyst system, and particularly to a method for producing polyolefins having a wide molecular weight distribution and excellent formation properties.

(Prior Art and its Problems) Conventionally, polyolefins have been produced from transition golds of groups Vb to V+b of the periodic table, metallologides of metals, and organometallic compounds of groups 1 to m of the periodic table. It is known that it is suitable to polymerize olefins using a catalyst consisting of:

It is also known that the use of a catalyst component in which a transition metal compound is supported on carriers 1 and 4 improves the catalytic activity per transition metal compound.

However, when olefins are polymerized using these catalyst systems, the resulting polyolefins generally have a narrow molecular weight distribution, and are often difficult to use for film molding, extrusion molding, hollow molding, etc.

(Means for Solving the Problems) The present inventors have focused on the fact that such difficulties can be overcome by providing polyolefins with high stereoregularity and a wide molecular weight distribution, and have conducted various studies. As a result, they discovered a new catalyst component system, completed and proposed the present invention. That is, the present invention provides a catalyst component for olefin polymerization containing (A) an organometallic intramolecular coordination compound (B) general formula % formula % (wherein R and R in formula 1 are each a hydrogen atom or a carbon number of 1 to 1). 12 hydrocarbon residues, Y is a group having one or more pete p atoms that are not directly bonded to the aluminum atom, and 0<k≦2,0≦t≦2.0<m≦2゜k + t = 3 - A method for producing a polyolefin or in, which comprises polymerizing an organoaluminum compound represented by (m) and (C) a 1-child donor compound in the presence of a catalyst. It is.

In the present invention, the catalyst component for the polymerization of 5-olefins is mainly composed of the above-mentioned transition metal compounds of groups 1Vb to 1b of the periodic table and organometallic compounds of groups 1-1 of the periodic table. It is a catalyst for

Catalyst components for the polymerization of such olefins are generally titanium compounds and compounds with the general formula Rn AZ
An organoaluminum compound represented by an alkyl group of 1 to 20, X is a halogen atom or a hydrogen atom, and n≦3 is preferably used.

As the above-mentioned titanium compound, titanium-containing catalyst components that are generally suitably used include, for example, Tic
TiBr,,TiI,.

4+ CH0TiCt8. C,H,0TiCt8゜CHOT
I C1s, C2H5T I C1s.

C, H, TrCt3. (C2H,O), TiC72゜(
C8H70), Tict2. (C,H,)2TiC4
2゜(C2H,0)8TICt, (C,H,),Ti
.

(C,,H50)4Ti, (C,H,O),TI.

Tetravalent titanium compounds such as (CHB oc 2 H4o) 4 T I; TiC78, TiBr, , T
II.

CH8jlct,,CH30TiCt,,C,H,0T
iCt2°C, H80TrC12, C6H, T:C12
゜(C2H50)2Tict, (C8H70)2TjB
r.

(C2H50) B T l , (C4Ho O) a
Trivalent titanium compounds such as T1; Tict2. Tie
r.

'r l I y, etc., and divalent titanium halides.

Two or more kinds of the above titanium compounds may be used as a titanium-containing catalyst component.

In addition, among titanium compounds, titanium halides such as titanium mihalide are particularly preferred. Those obtained by reduction with compounds, such as δ type, α
Titanium trihalides of type and gamma type are particularly preferred.

Furthermore, it is effective to treat the titanium compound described in "-" with an electron-donating compound in order to enhance the polymerization activity and the stereoregularity of the polymer. Examples of such electron-donating compounds include alcohols (general formula RO1()
, Neil (R-0-R'), Ester (RCOO
R”).

aldehyde (RCHO), fat re (RCOOH).

Ketone (RCOR'), nitrile (RCN).

Amine (RnNH3-n) (n; 0, 1, 2.3).

Incyanate (RNCO), 7zo compound (R-N=N
-R''), phosphine (RnPHa-n) (n=Q,
! , 2.3), Phos7phyto (P(OR)8).

Phosphinite (RP(OR')2), thioether (
RnSR'), 1,000-alcohol (R8H), etc. (However, in the above general formula, R and R' are respectively the same or different hydrogen atoms; an alkyl group.

(representing a hydrocarbon residue such as a 7lyl group) can be used.

As specific examples of these electron-donating compounds, the following compounds are preferably used.

Alcohols include methanol and ethanol.

Propanol, butanol, pentanol.

hexanol, octatool, phenol.

Xylenol, ethylphenol, benzyl alcohol, phenethyl alcohol, and the ethers include diethyl ether, di-n-phyl ether, di-n-butyl ether, di(isoacyl)ether, di-n-pentyl needle, di- n-hexyl ether,
di-n-octyl ether, diisooctyl ether,
Ethylene glyfur monomethyl ether, tetrahydrofuran 7 methyl, diphenyl ether ester, organic acid esters include ethyl acetate, stutyl formate, 7 mil lactate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid. Ethylhexyl, methyl triylate, ethyl triylate, 2-ethylhexyl triylate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate.

Propyl naphthoate, butyl naphthoate, naphthoic acid 2
- Ethylhexyl, ethyl phenylacetate, etc. Aldehydes include acetaldehyde and benzaldehyde, and fatty acids include formic acid, acetic acid, and propionic acid.

These include butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, and benzoic acid. Ketones include methyl ethyl ketone,
Examples include methyl isobutyl ketone and benzophenone.

Examples of nitriles include acetonitrile, and examples of amines include methylamine, diethylamine, tributyl7mine, 9triethanolamine, pyridine, aniline, and dimethyl7niline. Examples of incyanates include phenyl incyanate, toluyl incyanate, -to, etc., and examples of ab compounds include 7-nobenzene. Ethylphosphine is the phosphine.

Triethylphosphine, )! Examples of phosphites include dimethyl phosphite, diro-octyl phosphite, and tri-n-butyl phosphite, and phosphinites include ethyldityl diethyl phosphite. , ethyl dibutyl phosphinite, phenyl diphenyl phosphinite, etc.

Examples of 1,000-onythyl include diethylthioether, diphenylthioether, methylphenylthioether, ethyln sulfide, propylene sulfide, etc., and examples of thioalcohol include ethylthioalcohol, n-propylthioalcohol, etc.

Next, the catalyst component used in the present invention has the general formula RA7X8-
n (wherein R is a furkyl group having 1 to 20 carbon atoms,
is a halogen atom or a hydrogen atom; 1 (represents n≦3)
The organoaluminum compound represented by is not particularly limited to those known as aluminum-containing catalyst components for olefin polymerization, and the following compounds are examples of compounds that are generally preferably used. Namely, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-
n-Butylaluminum chloride.

Di-isobutylaluminum chloride, di-n-hexylaluminum chloride, di(2-ethylhexyl)
Aluminum chloride.

Di-n-dodecylaluminum chloride, methylisobutylaluminum chloride, ethylimbutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum r7A-t=skikplide, diethylaluminum bromide, diethylaluminium iodide and mixtures thereof with E, t ktctl, 7 and 1.8 Bu AZ Ct o. A fulkylalkinium halide compound with an average composition of 2.4? can be mentioned. Also trimethylaluminum.

Triethylaluminum, )! J-n-7'q
Hill aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-
Trialkylaluminium compounds such as octylaluminum, tri-n-dodecylaluminum, tri-n-dodecylaluminum, and mixtures thereof can also be used.

Furthermore, compounds such as diethylaluminum hydride, diisobutylaluminum hydride, dioctylaluminum hydride, di-n-butylaluminum hydride, and alkylaluminum hydrides such as compounds with average compositions such as Et□, s A t Hx, s. can also be used.

Among the above compounds, particularly preferred examples are diethyl heptaluminium couraidol aluminum, diisobutyl aluminum hydride,
Et2. , AtCt, etc.

In the catalyst composition used for olefin polymerization, the titanium atom of the titanium-containing catalyst component and the A. The molar ratio of 2 to atoms can be selected from a wide range of 1:1 to 1:200, but it is preferably used in a range of 2:1 to 1:100.

In the present invention, the following (A) organometallic intramolecular coordination compound, (B) an organoaluminum compound represented by the general formula Rj RL AIYm, and (C) an electron donor are added to the known catalyst components for olefin polymerization as described above. By using these compounds in combination, it is possible to obtain the desired polyolefin with an extremely wide molecular weight distribution. That is, (A) an organometallic intramolecular coordination compound or (B) the general formula R kR
IAIYm organoaluminum compound was added alone, (
C) Also by use with the m-child compound,
Polyolefins with a wide molecular weight distribution can be obtained.

Therefore, in the present invention, (A) an organometallic intramolecular coordination compound and (B) an organoaluminum compound having the general formula R kR tAtYm are used in combination with (C) an electron-donating compound as a catalyst component for olefin polymerization. This makes it possible to obtain a polyolefin with a broader molecular weight distribution than when (A) or (B) is used alone in combination with (C).

The organometallic intramolecular coordination compound (A) used in the present invention is not particularly limited, but is represented by the general formula (I) (M=metal atom, Y=ligand atom or group.

Compounds represented by n≧1) are most preferably used.

The metal atom of these compounds is At.

T.I., V., Li, B. Mg, Co, Ni, Fe, Cr.

Sn, Mn, Mo, Pt, In, Rh,
Hg, Ru.

It can be selected from the elements Pd and W. Preferred metal atoms are At, Ti, V, Li, Mg, and B.

Co , Ni , particularly preferably At. It is.

These compounds are also listed in Kagaku Kogyo, November 1982 issue, page 6.
9. Chemistry domain 33', (9).

767, (1979) U.S. Patent No. 3,313,791, Chemical Reviews
) 7 944, 28 7 (1979).

It is a compound known from the literature such as .

Among the organic/organometallic intramolecular coordination compounds used in the present invention, particularly preferred compounds are organometallic intramolecular coordination compounds of aluminum.
A large number of compounds corresponding to 1) and (If) can be used. Among the organoaluminum intramolecular coordination compounds corresponding to the general formula (1), compounds represented by the following general formulas (1) and (IV) are preferable.

C(R)8Q (In the general formulas (1) and (IY), R in the formula is an alkyl group having 1 to 12 carbon atoms, R is an alkyl group having 1 to 12 carbon atoms and a hydrogen atom, and R is a carbon number 1 to 2 alkyl groups and hydrogen atoms y1 is -o+, -8- and -NR, a is 1
2, Q is selected from ) Specific examples of the compound represented by the above general formula (1) include (3-ethoxypropyl)isobutylaluminum hydride, (3-ethoxypropyl)ethylaluminum hydride, , (3-methoxybutyl)methylaluminum hydride, (3-propoxyinbutyl)pentylaluminum hydride, (4-methoxybutyl)ethylaluminum hydride.

(3-Octoxyisobutyl)propylaluminum hydride, (4-ethoxybutyl)inbutylaluminum hydride, (3-ethylmercaptopropyl)hexylaluminum hydride, (3-octylmercaptopropyl)propylaluminum hydride, (4-ethylmercaptopropyl) isobutyl aluminum hydride,
(3-diethylaminopropyl)isobutylaluminum hydride.

(4-Dioctylaminobutyl)propylaluminum hydride, (3-methoxypropyl)diethylaluminum, (3-ethoxypropyl)')ethylaluminum, (3-ethoxypropyl)diisobutylaluminum.

(3-phenoxypropyl)diisobutylaluminum, (3-inptoxypudipyl)dimethylaluminum, (4-ethoxybutyl)diethylaluminum, (4
-inoctoxybutyl)di-n-octylaluminum, (3-diethylaminopropyl)diethylaluminum, (3-diethylaminopropyl)diynebutylaluminum, (3-N-ethyl-N-isopropylaminopropyl)diisobutylaluminum, ( 4-diethylaminopropyl) diethylaluminium.

(4-diisooctyl7!butyl)diynestylaluminum hydride, (3-ethylmerca7')propyl)diethylaluminum.

(3-n-butylmercapdobu-vyl)dibrubyl aluminum, (4-n-butylmercaptomethyl)di-n
Examples include compounds such as -hexylaluminum. Specific examples of the compound of general formula (IV) include (2-(2-furyl)propyl)hexylaluminum hydride, (2-(2-chenyl)ethyl)
Methylaluminum hydride, (3-(1-piperidyl)propyl)isobutylaluminum hydride, (2-
(1-Methyl-2-piperidyl)ethyl)hebutylaluminum hydride, (2-(5-ethyl-2-pyridyl)ethyl)propylaluminum hydride, (2-(2
-quinolyl)ethyl)inpropyl aluminum hydride.

(2-(:2-furyl)ethyl)diethylaluminum, (2-(2-furyl)propyl)di-n-hexylaluminum, (3-(2-chenyl)propyl)diethylaluminum, (2-(4- methyl-2-chenyl)
ethyl)diisobutylaluminum, (3-(1-hiberidyl)propyl)di-n-hexylaluminum, (
2-(2-pyridyl)ethyl)diiso7silaluminum, (2-(5-ethyl-2-bil))yl)ethyl))
Isobutylaluminum, (3-(2-pyridyl)propyl)diisobutylaluminum, (2-(2-quinolyl)ethyl)dimethylaluminum, (2-(2-quinolyl)ethyl)-t, lysooctylanotominium An example is an r-substance such as 2 or the like.

Among the organoaluminum intramolecular coordination compounds corresponding to the general formula (■), the compound represented by the following general formula (V) is particularly suitable.

(R is a furkyl group or an alkoxy group having carbon a1 to a12, B' is an alkyl group having carbon a1 to a8, or an alkoxy group 1m represents an integer of 1 to 3) As a specific example of the adduct of (V) above: is ethylaluminum 7cetylacenate.

Dimxyl 1luminium, acetylacetonate, diimp p-boxyaluminum ether) 7cetoacetate, 22inoclx7luminium ethyl 7cetoacetate, impropoxyaluminum bis(ethyl 7cetoacetate), jetoxyl aluminum 7cetyl Acetonate, aluminum tris(zuzar acetoacetate), methoxyaluminum bis(phthyl 7cetoacetate), dimethylaluminum ethyl acetate, diisobutoxyaluminum 7cetylacetonate.

Aluminum tris (acetyl 7cetonate), O-di-n-butylaluminum diethyl malonate, O-diisobroboxyfluminium diethyl malonate,
Compounds such as O-fluminilamtris(diethylmanate) 1 can be mentioned.

Furthermore, the general formulas (1), (IV), (V
), but are considered to be organoaluminum intramolecular coordination compounds and are suitable for use in the present invention.
Specifically, (2-(dimethylethoxysilyl)ethyl)diisobutylaluminum, (3-(diethylethoxysilyl)7c=biru)dimethylaluminum, (2-(dimethylethoxysilyl)ethyl)ethylaluminum hydride, tris(2-( dimethylethoxysilyl)ethyl)aluminum.

Compounds such as bis-(2-(uethylmethoxysilyl)ethyl)furobylaluminum, (3-<t')methylsiloxy)propyl)diisobutylaluminum, (3-()limethylcypxy)propyl)ethylaluminum hydride, etc. can be mentioned.

Various methods for synthesizing the organometallic intramolecular coordination compound (A) used in the present invention are described in the above-mentioned known literature, and the organometallic intramolecular coordination compound is synthesized by distillation or other operations. The common method is to use it after separating it. However, depending on the synthesis method, by-products or unreacted raw materials obtained along with the main product, the organometallic intramolecular coordination compound, may have a negative impact on polyolefin polymerization! In some cases, the reactant may not be used as is for polyolefin polymerization (
・It is possible. Specific examples include a reaction product obtained by reacting equimolar amounts of N,N diethylallylamine and diisobutylaluminum hydride in an inert hydrocarbon solvent, and an equimolar amount of ace)l in a similar inert hydrocarbon solvent.
Name the reaction product obtained by reacting ethyl acid and triethylaluminum.

The amount of the organometallic intramolecular coordination compound used in the present invention (A) is generally such that the molar ratio of the titanium atom of the titanium compound and the metal atom of the organometallic intramolecular coordination compound is 10=1.
to 1:200, preferably 2
:1 to 1:50.

°Also, other catalyst components (B) used in the present invention, general formula R
kRtA4Ym (in the formula, R9R2 is a water source atom and a hydrocarbon residue, Y is a group having one or more pete p atoms that are not directly bonded to an aluminum atom, 0 m≦2.0
≦to≦2.0≦t≦2. In the organoaluminum compound represented by +t=3-m), the hydrocarbon residue means an alkyl group, a fulkenyl group, an alkynyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and generally In the alkyl group, and as the hetep atom of the substituent Y, O9S
, N, P, Si, Se, As, Hg, etc., but O, S, N, P, and Si atoms are preferred for use in the present invention, and O, N, and 81 atoms are particularly preferred.

Specific examples of organoaluminum compounds represented by the general formula RkR,, AtYm include bis(3-diethylaluminopropyl) ether, bis(3-diisobutylaluminobouyl) ether, (3-(P- ans)propyl)dipropylaluminum, (2-(p-
anth)ethyl)dioctylaluminum, (3-(P
-7 ance) propyl) methylaluminum hydride, 3
-diisobutylaluminopropoxy 7nisole (3-(
3.4-dimethoxyphenyl)propyl)diingtylaluminum. Bis(3-(3.4-dimethoxyphenyl)propyl)ethylaluminum, (3-( 3
．． 4-Meq-dioxyphenyl)propyl)dioctylaluminum. (3-Glycidyloxypropyl)diisobutylaluminum, (3-diethylaluminum/propyl)ethylmalonate.

(3-()ethoxysilyl)propyl)ethylaluminumhydride)', (2-()limethoxysilyl)ethyl)octylaluminum hydride, (3-()limethylsilyl)propyl)diisobutylaluminum, (3
-(triethylsilyl)propyl)dimethylalumium, bis(3-diethylaluminopropyl)dimethylsilane, bis(3-dimethylfluminopropyl)allylmethylsilane.

1,3-bis(2-(diisobutylflumino)ethyl)-1.1,3.3-tetramethyldisiloxane,
Bis(3-diethylaluminium/propyl) sulfide, bis(3-diisobutylaluminopropyl)ethylphosphine, bis(2-diisobutylfluminoethyl)vinylphosphine, bis(3-diethyl methylphosphonate) aluminopropyl), (2-(4-pyridyl)ethyl)
Diisobutylaluminum.

Examples include (2-(4-pyridyl)ethyl)hexylaluminum hydride, (3-diethylaluminopropyl)morpholine, and (B) general formula Rk R,A
The organoaluminum compound represented by 4Yrn, the organoaluminum compound represented by the general formula RnAtX8-n of the catalyst component for olefin polymerization, and (A) the organometallic intramolecular coordination compound are mixed and aged in advance, and then the average It is also possible to use it for polymerization as an organometallic compound with a specific composition.

As an example of this, (3-(3,4-dimethoxyphenyl)7'c-bil)diisobutylfluminicum, diethylaluminum chloride, and (3-(N,N-diethyl7mino)propyl)diisobutylaluminum are ．． 1 5: 0. 1 5: 0. Polymerized E t s. + s n u o. a AZ (4cH
s ) 8 NE t 2 ) a. ,.

can be mentioned.

The amount of the organoaluminum compound (B) represented by the general formula R kR tAtYm used in the present invention is generally the same as the titanium atom of the titanium compound described above and the general formula R kR
The molar ratio of aluminum atoms in the organoaluminum compound represented by IAtYm can be selected in the range of 10:1 to 1:200, preferably in the range of 2:1 to 1=50.

Methods for synthesizing the organoaluminum compound represented by the general formula Rk RA AZYm (B) above include a method using a reaction between a halogenated organoaluminum compound and a Grignard reagent, and a method using the general formula Z-CH=CH, (where z is A group having one or more heteroatoms) and an alkenyl compound represented by the general formula R B + i At H i (wherein R is a hydrocarbon residue having 1 to 12 carbon atoms, generally an alkyl group,
A method using a reaction of an organoaluminum hydride compound represented by 1≦i≦2 is known. Comparing the two synthetic methods, the latter has the advantage that the synthetic operation is simpler and the reaction can be carried out in an inert hydrocarbon solvent. In addition, the organic aluminum hydride compound during the reaction and the general formula Z-CH=CI(.

Depending on the molar ratio of the alkenyl compound represented by , and the type and properties of the products and unreacted substances from the reaction between the two, the reactants may be used as they are for distillation, or they may be diluted to an appropriate concentration with an inert hydrocarbon solvent. It is also possible to use it for polymerization. In addition, after performing the above synthesis reaction in an inert hydrocarbon solvent, if the inert hydrocarbon solution of the obtained reaction product is directly used for polymerization, RkRp; AZYm can be separated by operations such as distillation. In some cases, the same or better effect of broadening the molecular weight distribution can be obtained when used as a compound. Here, the molar ratio of the organoaluminium hydride compound and the alkenyl compound represented by the general formula Z-CH=CII during the reaction may be particularly limited. When the indicated reaction products are used for polymerization without separation, 5:1 to 1:1
The range of 0 is preferably L<, particularly preferably 1-< is 2:1 to 1:
The range is 3.

In the present invention, it is necessary to add and use (C) [a child-toxic compound] as a catalyst component. like this(
C) It is a child-injecting compound known as a component of an olefin polymerization catalyst [D is not particularly limited and can be used, but in general, oxygen, nitrogen,
Organic compounds containing phosphorus or sulfur, such as water, flucols, ethers, and esters.

These include aldehydes, fatty acids, getones, nitriles, amines, incyanates, azo compounds, phosphines, phosphinites, phosphoramides, thioethers, thioalcohols, and acid amides. (C) More specifically, what is preferably used as the one-child donating compound is alcoholic acid such as methanol, ethanol, purpanol, stanol, pentanol, hexanol, octatool,
Phenol, xylenol, ethylphenol, benzyl alcohol, phenethyl alcohol natcal.

Also, examples of ether include diethyl ether, :)-n-
7'robyl ether, :)-n-7'thyl ether, di(isoamyl)ether, di-n-pentyl ether,
In addition to di-n-hexyl ether, di-n-octyl ether, diisooctyl ether, ethylene glycol monoethyl ether, diphenyl ether, tetrahydrofuran, anisole, and 2,3-dihydrofuran, vinyl ethyl ether, allyl ethyl ether, anethole,
These are ethers having a vinyl substituent such as p-methoxystyrene, safrole, phenyl p-7lylphenyl ether, and p-styrylanisole.

Furthermore, esters include ethyl acetate, butyl formate, amyl acetate, butyl oxalate, vinyl acetate, ethyl benzoate, and propyl benzoate.

Octyl benzoate, ethylhexyl benzoate.

Bensyl, methyl toluate, ethyl toluate, 2-ethylhexyl toluyl, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, naphthoate), propyl naphthoate, naphthoate Examples of esters of heterocyclic compounds such as butyl acid and ethyl phenylacetate include ethyl thiophene-2-carboxylate, methyl 2-pyridinecarboxylate, and ethyl biru-2-carboxylate.

N-carboethoxyvirol, methyl 2-chenyl acetate, etc. can be preferably used. Furthermore, as an aldehyde, 7
Examples include cetaldehyde and benzaldehyde. Furthermore, the fatty acids include formic acid, acetic acid, bupionic acid, butanoic acid, and Shiil! , succinic acid, acrylic acid, maleic acid, benzoic acid, etc. Furthermore, the ketones include methyl ethyl ketone, methyl isobutyl ketone, benzophenone, and N-vinylpyridone.

There are 77 chills and 7 setons. Furthermore, nitriles include acetonitrile, and amines include methylamine and diethylamine.

Triethylamine, triethanolamine/pyridine,
4-vinylpyridine, 7-niline.

Examples include N,N-diethylaniline. Furthermore, examples of incyanates include phenyl isocyanate and tolylisocyanate, and examples of azo compounds include azobenzone.

Furthermore, examples of phosphine include ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, and triphenylphosphine, and examples of phosphite include dimethylphosphine.

Examples include di-n-octyl phosphite and tri-n-butyl phosphite. Furthermore, examples of phosphinite include ethyl diethyl phosphinite and ethyl dibutyl phosphinite.

Examples of phosphoramide include phenyldiphenylphosphinite and hexamethylphosphoric triamide. Furthermore, thioethers include diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide, etc., and thioflucols include ethylthioalcohol, n-propylthioflucol, and the like. Furthermore, examples of the acid 7amide include formamide, 7ceto7mide, acryl7mide, dimethylform7ξmide, benzoylamide, phthadiyl7mide, and the like.

Two or more kinds of the above-mentioned electron-donating compounds (C) may be selected and used. (C) The amount of the electron-donating compound used is generally 0.000000000000 yen per titanium atom of the titanium-containing catalyst component. G O can be used in a range of 1 mol to 100 mol, but preferably in a range of 0.01 mol to 5 mol.

The catalyst system of the present invention includes (A) as a catalyst component for olefin polymerization.
Organometallic intramolecular coordination compound, (B) general formula RkRtAt
A catalyst system in which an organometallic compound of an element selected from zinc, lithium, magnesium, and boron is added together with the organoaluminum compound represented by Ym and the electron-donating compound (C) is often more preferably used.

The organometallic compound of the element selected from zinc, lithium, magnesium, and boron is not particularly limited, but the following compounds and metals may generally be used. for example,
Examples of zinc organometallic compounds include dialkylzinc, furkylzinc halide, alkylzinc alkoxide, etc.
Specifically, compounds such as diethylzinc, dimethylzinc, ethylzinc chloride, ethylzinc 7'R mite, ethylzinc ethoxide, methylzinc impp-box, and ethylzinc n-butoxide can be suitably used. In addition, organic compounds of magnesium include difurkylmagnesium, furkylmagnesium halide, and furkylmagnesium furkoxide, and specifically, di-n-butylmagnesium, ethylmagnesium chloride, di-n-octylmagnesium, and inbutylmagnesium. magnesium chloride,
Compounds such as n-butylmagnesium fluoride and n-propylmagnesium ethoxide can be suitably used.

Furthermore, a specific compound of lithium is n-butyllithium, and an organic compound of boron is triethylboron. Among the compounds listed above, particularly preferred compounds are organometallic compounds of zinc.

The amount of the organometallic compound of an element selected from zinc, magnesium, lithium, and boron can generally range from 0.001 mol to 100 mol based on the titanium atom of the titanium-containing catalyst component, but 0.001 mol to 100 mol can be used. 01 mole to 2
It is preferable to use it in a range of 0 mol.

(C) Electron-donating compound, zinc, and lithium.

The use of an organometallic compound of an element selected from magnesium and boron together with the above catalyst component is also an effective method for further broadening the molecular weight distribution of polyolefins.

At this time, the amount of the organometallic compound selected from zinc, lithium, magnesium, and boron and the electron-donating compound (C) relative to the ethane atom of the titanium-containing catalyst component is the same as when each is added alone to the catalyst system of the present invention. It can be used in the same range. Further, (C) the electron-donating compound and the organometallic compound of an element selected from zinc, lidarium, magnesium, and boron are prepared in advance by the general formula RAt.
It may be used for polymerization after mixing with the organic aluminum compound represented by B) It may be used for polymerization after being mixed with an organoaluminum compound represented by the general formula RkRA AtYm.

Further, the catalyst components of the present invention may be prepared by mixing them in advance in the presence or absence of a catalyst, or these catalyst components may be added directly to the polymerization tank. In the latter case, the catalyst components may be added in any order without any restriction.

The olefin used in the present invention is not particularly limited, and any olefin that can be polymerized with the above catalyst can be used, but in general, olefins having 2 to 1 carbon atoms such as ethylene, propylene, butene, and pentene are used.
00 olefin is preferably used. Further, as defined above, it is also possible to use a mixture of olefins or olefins and other copolymerizable polymers. The copolymerizable monomer is not particularly limited, and monomers known to be copolymerizable with olefins may be used.

Furthermore, during the polymerization of olefins, known molecular weight regulators such as hydrogen/% IJ-genated hydrocarbons and the like can be used to control the molecular weight of the resulting polyolefin.

The olefin polymerization method in the present invention is not particularly limited, and any known polymerization or copolymerization method can be used as is. For example, ordinary slurry polymerization, bulk polymerization in a liquid monomer, and gas phase polymerization can be suitably employed. In addition, in slurry polymerization, hexane, heptane, benzene, toluene,
Inert hydrocarbons such as cyclohexane are used as solvents. Further, as the polymerization method, either a batch method or a continuous method is possible, and the polymerization can also be carried out in two or more stages with different reaction conditions. Furthermore, if necessary, (A) an organometallic intramolecular coordination compound in the presence of a titanium-containing catalyst component and an organoaluminum compound represented by the general formula RnAtX8-n.

(B) an organoaluminum compound represented by the general formula ⑋ Ri AZYm; (C) a child-toxic compound and zinc;
In the presence of an organometallic compound selected from lithium, magnesium and boron, 0.0.
2,! i' ~ 50 g of sour reflex, preferably 0.
It is also a preferred embodiment to use a slurry obtained by prepolymerizing 5 g to 209 olefins using an inert hydrocarbon as a solvent as the titanium compound.

In general, polymerization can be carried out in the range of 0 to 200°C, but it is usually preferable to carry out in the range of room temperature to ioo'c.Also, the polymerization pressure is not particularly limited, but may be at atmospheric pressure or l
, 100 s/'d, preferably I KP/cd ~5
0K? A range of /Gi is preferable.

(Examples) In order to explain the present invention more specifically, Examples will be described below, but the present invention is not limited to these Examples.

In addition, the boiling n-hebutane extraction residue (hereinafter abbreviated as II) used in the examples refers to the insoluble matter obtained when polyolefin is extracted with boiling n-hebutane for 5 hours.

In addition, Fw/Fr is an index of molecular weight distribution, and is the ratio of the weight average molecular weight iFw to the number average molecular wax Fr.
It was measured by gel permeation chromatography) method. The larger the Fw/shar, the broader the molecular weight distribution of the polymer.

(A) Synthesis of organometallic intramolecular coordination compound (A) -
1 Synthesis of (3-(N,N-diethylamino)propyl)diethylaluminum After replacing nitrogen in a 200 m flask, dry hebutane 1
00d Todiethyl aluminum hydride 1001007
W was weighed out, and 100,100 rrL of N,N-diethylallyl 7mine was added dropwise to the flask over 1 hour while stirring.

Next, the reaction mixture was stirred at 85±5° C. for 6 hours and allowed to cool to room temperature.

After the reaction, half of the solution was distilled under reduced pressure to isolate 3-(N,N-diethyl7mino)propyl)diethylaluminum, and further diluted with dry hebutane to give 1 m mot /
A hebutane solution with a concentration of td was prepared. This solution (A-1
), and the remaining half of the undistilled amount is represented by (A'-1).

(A) Synthesis of -2(3-ethoxypropyl)diimptylfluminicum Diisobutylaluminum hydride and allyl ethyl Reacted with ether. Isolated by distillation and then diluted with heptane (3-ethoxypropyl):) isobutylaluminium is represented by (A-2) and the undistilled remainder is represented by (A-2).
A'-2).

(A) -Synthesis of 3-diethylaluminum ethyl 7cetoacetate After replacing the flask with nitrogen, 1QQd of dry hebutane and 10 (1 mmol) of triethylaluminum were weighed out, and ethyl 7cetoacetate was added to the mixture for 1 hour without stirring. Since there was heat generation during this time, cooling was performed with ice water.

Next, this solution was stirred at 65±5° C. for 1 hour to complete the reaction, and then allowed to cool to room temperature.

Since this reaction had a high yield, it was used as it was for polymerization. This solution is designated as (A-3).

(B) Synthesis of an organoaluminum compound represented by the general formula RkRtAIYm An organoaluminium hydride compound and the general formula Z-CH═CH in the same manner as in Example 1 (A)-1.

The reaction of the fulkenyl compound shown was carried out.

The reaction temperature was appropriately selected from 60 to 95°C and the reaction time from 3 to 6 hours.

As in (A)-1 of Example 1, half the amount was isolated by distillation and diluted with heptane, and the remaining solution after reaction was used for polymerization as it was. The synthesis results are shown in the table below.

The following is a white example 1 Polymerization of propylene After replacing nitrogen in a stainless steel autoclave with an internal volume of 2 tons at room temperature, 430 g of liquid propylene was added, and then 1.96 m rnot of diethylaluminum chloride was added while stirring the autoclave. 1 hydrogen
．． After adding the partial pressure of zKy/ad, the temperature was raised to 65°C. After raising the temperature, (A-1) prepared in (A) was added as an organometallic intramolecular coordination compound at a pressure of 0. 30mrno
l, R' kRtAIYm, 0.30 mmol of 1-(B-1), and 0.20 mmol of benzyl benzoate as an electron-donating compound.
m mol was added. After stirring for 5 minutes, δ-type titanium trichloride (Toyo Stoffer Chemical Co., Ltd.!M) was added at 0.19
6 mmol was added to start polymerization. Start of match 120
After a few minutes, stirring was stopped, propylene was purged to complete the polymerization, and the autoclave was replaced with nitrogen. The catalyst was inactivated by adding propylene oxide.

The obtained Bo-11-P pyrene was vacuum-dry-exploded at 40° C. for 12 hours and then weighed to give a weight of 1,551.

TI, which is the n-hebutane extraction residue, was 94.7%.

Titanium compound 1. The yield of polypropylene per g (hereinafter abbreviated as β) was 4430. β is y-bo11pp
6, which represents a pyrene/9-4 tan compound, and Fw7'Fr of polypropylene is 13,5, and the molecular distribution is wide.

Comparative Example 1 Polypyrene was polymerized in the same manner as in Example 1, except that the organometallic intramolecular coordination compound and the organoaluminum compound represented by RkRtAIYm were not added. The results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1, except that no organometallic intramolecular coordination compound was added. (However, general formula R
(0.6 mmol of the organoaluminum compound represented by 1kR''tA4Ym was added) The results are shown in Table 1.

Comparative Example 3 Propylene was polymerized in the same manner as in Example 1, except that the organoaluminum compound represented by the general formula T<kRIAJIYm was not added. (However, 0.6 mmob of the organometallic intramolecular coordination compound was added.) The results are shown in Table 1.

Table 1 Example 2 Preparation of prepolymerized catalyst slurry A 1 ton stainless steel autoclave heated to 50°C was replaced with nitrogen and dried with nC? 250 grams ethyl aluminum chloride 8.94 m mol and diethylene glycol dimethyl ether 0.11 m mob,
added.

Next, 11.2 mmot of δ-type titanium trichloride was added and stirred for 10 minutes, and then nitrogen in the autoclaze was replaced with propylene to start polymerization.

Thereafter, propylene was introduced into the autoclave at an average flow rate of 1713+J/mx, and after 1 hour, the introduction of propylene was stopped and the inside of the system was sufficiently replaced with nitrogen.

After collecting the prepolymerized catalyst slurry obtained in the above operation, it was diluted with 15117 n-hebutane.5. ! 1t-T
The concentration was adjusted to iC18/l-heptane.

Polymerization of propylene Propylene was polymerized in the same manner as in Example 1, except that 7 days of the prepolymerized catalyst slurry prepared in (A) above was used instead of δ-titanium trichloride. 160 g of polypropylene was obtained, β was 4570. II is 95.3
%, Fv/Fr was 13.0, and polypropylene with a wide molecular weight distribution was obtained.

Comparative Example 4 Propylene was polymerized in the same manner as in Comparative Example 2, except that the prepolymerized catalyst slurry prepared in Example 2 was used instead of δ-titanium trichloride. 208g of polypropylene was obtained and β was 5940. II is 97.3%,
Fw/Fr was 7.6.

Examples 3 to 14 The organometallic intramolecular coordination compound synthesized in Example 1 (A) and (B) and the organoaluminum compound represented by the general formula RkRlktYm were combined as shown in Table 1. , Bupyrene was polymerized in the same manner as in Example 2. Benzyl benzoate or ethyl P-anthate was used as the electron donating compound. The results are shown in Table 2.

Example is, i6 Propylene was polymerized in the same manner as in Example 9, except that the molar ratio of the organometallic intramolecular coordination compound and the organoaluminum compound represented by general 2 RkRtAtYm to Ti atoms was changed. The results are shown in Table 3.

Example 17 Immediately before adding δ-titanium trichloride, 0.098 m m
Polymerization of propylene was carried out in the same manner as in Example 1, except that diethylzinc ob was added. 121.9 polypropylene was obtained, and β was 3460. II is 92.9%,
The molecular weight distribution is wide with Fw/Fr = 14.1.

Example 18 In the same manner as in Example 1, 3801 m mob- of ethylene and 2.4 m mob- of triethylaluminum were prepared.

Next, add 1. Add so that the partial pressure becomes OKp/cIIl. After raising the temperature to 65°C, 0.30 m of (A-3) prepared in Example 1(A) as an organometallic intramolecular coordination compound
mot, prepared in Example 1(B) as an organoaluminum compound represented by the general formula RkRIAtYm (B-4
) was added at 0.30 mmot. Ethyl benzoate was added as an electron donating compound at 0.20 m mob. After adding the prepolymerized catalyst slurry 7 prepared in Example 2 (A) as a titanium compound and starting the polymerization of ethylene,
The operation was carried out in the same manner as in Example 1.

19211 polyethylene was obtained, β was 5490,
Fw/Fr was 14.4, and polyethylene with a wide molecular weight distribution was obtained.

Example 19 (Copolymerization of propylene and ethylene) Example 1
In the same manner as above, 4001 ml of propylene, 2.0 mmol of diethylaluminum chloride, and 1.0 mmol of hydrogen were added.
It was added to give a partial pressure of 2Ky/di. After raising the temperature to 65°C, ethylene was introduced until the ethylene concentration in the gas phase reached 1.5%. Next, 0.2 m mob of ethyl P-7 phosphate was added as an electron donating compound. After that, propylene and ethylene were copolymerized in the same manner as in Example F.

197 g of propylene-ethylene copolymer was obtained, β
5630.1 was 91.9%, and the ethylene content of the copolymer was 1.78 wt%. Fw/Fr is 1
0.5, and a propylene-ethylene copolymer with a wide molecular weight distribution was obtained.

Comparative Example 5 Copolymerization of propylene and ethylene was carried out in the same manner as in Example 18, except that the organometallic intramolecular coordination compound and the organoaluminum compound represented by the general formula R''kR21AtYm were not added.

230 g of propylene-ethylene copolymer was obtained, β
was 6570. II was 93.1% and the ethylene content of the copolymer was 1.74 wt.%. Fw/Fr of the ethylene-propylene copolymer was 6.0.

Claims (1)

[Claims] (1) For the olefin polymerization catalyst component, (A) Organometallic intramolecular coordination compound (B) General formula R^1_kR^2_lAlYm (However, R^1 and R^2 in the formula are hydrogen atoms or carbon numbers, respectively) 1 to 12 hydrocarbon residues, Y is a group having one or more heteroatoms that are not directly bonded to the aluminum atom, 0<k≦2, 0≦l≦2, 0<m≦2, k+l=3− A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst containing an organoaluminum compound represented by m) and an electron-donating compound (C).