JPS59120602A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a high-bulk density polymer in high yields at a high productivity, by effecting continuous polymerization or copolymerization in the presence of a novel high-polymerization activity catalyst system comprising specified components. CONSTITUTION:The desired polyolefin is obtained by polymerizing or copolymerizing an olefin by using a catalyst system obtained by combining (A) a solid substance obtained by reacting a magnesium halide with a titanium compound and a vanadium compound, with (B) a compound of formula I (wherein R<1> and R<2> are each a 1-24C hydrocarbyl group and 0<=m<=3), (C) a compound of formula II (wherein R<3> and R<4> are each a 1-24C hydrocarybl group and 1<=n<=2), and (D) an organometallic compound so as to satisfy the following conditions 0.1<=Si in (B)/Ti and V in (A) (molar ratio) <=100; 0.01<=Al in (C)/Si in (B) (molar ratio) <=10; and 0.1<=metal in (D)/Ti and V in (A) (molar ratio) <=100.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins using a novel polymerization catalyst.

Conventionally, in this type of technical field, the
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known from Publication No. 05, and furthermore, a catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known.
A co-pulverized catalyst with magnesium genide and titanium tetrachloride is known.

However, in the production of polyolefins, it is desirable that the catalyst activity be as high as possible, and from this point of view, the polymerization activity is still low in the method described in Japanese Patent Publication No. 89-12105, and the polymerization activity is still low in the method described in Belgian Patent No. 742112. Although it has become quite high, improvement is still desired.

In addition, in German Patent No. 2187872, the amount of magnesium halide used is substantially reduced by co-pulverizing all of magnesium halide, titanium tetrachloride, and alumina. No significant increase in per unit activity was observed, and a catalyst with even higher activity is desired.

Furthermore, in the production of polyolefins, it is desirable that the bulk density of the resulting polymer be as high as possible from the standpoint of productivity and slurry stress. From this point of view, the method described in Japanese Patent Publication No. 89-12105 has a low bulk density and unsatisfactory polymerization activity, while the method described in Belgian Patent No. 742112 has a high polymerization activity. However, there is a drawback that the bulk density of the produced polymer is low, and improvement is desired.

The present invention aims to improve all of the above-mentioned drawbacks, to provide a novel polymerization catalyst that can obtain polymers with high polymerization activity and bulk in high yield, and to carry out continuous polymerization very easily, as well as a new polymerization catalyst that can be used to It provides a full range of olefin polymerization or copolymerization methods, and because the polymerization activity is extremely high, the monomer partial pressure during polymerization is low, and the resulting polymer has a high bulk density, so productivity can be improved.
The residual weight of the catalyst in the resulting polymer after completion of the reed polymerization is extremely small, and therefore the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer processing process and making it possible to produce polyolefins extremely economically as a whole. can.

In the method of the present invention, since the 1'+f degree of the obtained polymer is large, the amount of polymer produced per unit reactor is large.

Further, the advantage of the present invention is that although the bulk of the produced polymer is small from the viewpoint of particle size, there are few coarse particles and fine particles of 50μ or less, so continuous combination reaction is facilitated. In addition, handling of polymer particles such as centrifugation and powder cross-feeding in polymer processing steps is facilitated.

Another advantage of the present invention is that, as mentioned above, the polyolefin obtained using the catalyst of the present invention has a large bulk and a high concentration of hydrogen compared to the conventional method in order to obtain a polymer with a desired melt index. Therefore, the total pressure during polymerization can be made relatively small.
It can also be mentioned that it has a large effect on economic efficiency and productivity.

In addition, when olefins are polymerized using the catalyst of the present invention, an advantage is that the olefin absorption rate decreases little with time, so polymerization can be carried out for a long time with a small amount of catalyst.

Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution, and is characterized by extremely low by-products of low polymers, such as a small amount of hexane extraction. Therefore, it is possible to obtain a product of good quality, such as film grade, which has excellent anti-blocking properties.

The catalyst of the present invention provides a novel catalyst system that has many of these features and improves the drawbacks of the prior M1 techniques, and these points can be easily overcome by using the catalyst of the present invention. It must be said that what can be achieved is something to be admired.

The present invention will be explained in detail below. That is, the present invention also provides [1] a solid substance obtained by reacting at least the following two components (() magnesium halide and (ill titanium compound and/-!1' or vanadium compound, cu) general formula R LSi (OR2) ke77, (here RI and in2 indicate the residual hydrocarbons having 1 to 24 carbon atoms,
OID general formula R'n Al(OR') sn
(Here, R3 and R4 represent the remaining hydrocarbons of carbons e1 to 24, and ■≦n≦2), and q■ an organometallic compound; 1 < fIIJ] in S・I, in )T, and /1 engineering, Mor ratio <100. 0.01〈”” Medium (7-)” IJD Medium (7) S i
Molar ratio < 10, machining ratio 0.1 (metal in mouth 41). 7., and □, the condition of tomolar ratio <, 1000 k Y4 plus catalyst system gives olefin *1
The present invention relates to a method for producing a polyolefin having a t4'Y characteristic by polymerization or copolymerization.

The magnesium halides used in the present invention are substantially anhydrous, such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide. Magnesium chloride is particularly preferred.

Examples of the titanium compound and the vanadium compound used in the present invention include titanium and/or vanadium 7''-0 genated ml, alkoxy-benzened compounds, alkoxides, halogenated oxides, and the like.

For the titanium compound and I~, a tetravalent titanium compound and an octavalent titanium compound are suitable, and a tetravalent titanium compound or specifically a compound with the general formula Ti ((]R), X, -r (where R represents an alkyl group, an aryl group, or an aralkyl group having 1 to 24 carbon atoms, X represents a halogen atom, and r is 0≦r≦4. Titanium tetrachloride, titanium tetrabromide, , titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, jetoxydichlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, triethoxymonochlorotitanium, te)-laethoxytitanium, monoisoprobogiso Trichlorotitanium, diynepropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetrainpropoxytitanium, quinobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenokiditrichlorotitanium, diphenoxydichlorotitanium, triethoxymonochlorotitanium Titanium, tetraphenoxy titanium, etc. can be mentioned. As trivalent titanium compounds, titanium tetrachloride, titanium tetrabromide, etc., titanium gold hydride,
Examples include titanium halides obtained by reduction with aluminum, titanium, or organometallic compounds of metals from groups 1 to m of the periodic table.

Furthermore, the general formula Ti (OR)s:&-s (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, and X represents a halogen atom; S represents 0(4(4)
Examples include trivalent titanium compounds obtained by reducing halogenated alkoxy titanium of 4 (illi) with an organometallic compound of a metal of Group 1 to vanadium chloride,
Tetravalent vanadium compounds such as vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium, pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and tributoxyvanadyl, vanadium trichloride, Examples include octavalent vanadium compounds such as vanadium triethoxide.

In the present invention, tetravalent titanium compounds are most preferred.

In order to make the present invention even more effective, titanium compounds and nadium compounds are often used in combination.

In this case, the V/Ti molar ratio is preferably in the range of 2/1 to 0.01/1.

In the present invention, (1) magnesium chloride;
(n) There is no particular restriction on the method for obtaining the catalyst component [1] of the present invention by carrying out a total reaction with a titanium compound and/or a vanadium compound. Preferably 50-80
A method of reacting by contacting under heating at 0° C. for usually 5 minutes to 20 hours, or a method of reacting by co-pulverization can be used. In the present invention, a method of reacting by co-pulverization is particularly preferred.

The inert solvent used is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane,
Hexa/, heptane, octane, benzene, toluene,
Various aliphatic saturated hydrocarbons such as xylene and cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and alcohols, ethers, and esters such as ethanol, diethyl ether, tetrahydro7rane, ethyl acetate, and ethyl benzoate. etc. can be given.

The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, 4-mill mills, etc. are usually used, and conditions such as grinding temperature and grinding time can be easily determined by commercial operators depending on the grinding method. It is something that can be done. Generally, the grinding temperature is 0°C to 200°C, preferably 1 and 2.
The time for heating the powder in a basket at 0°C to 100°C is θ', 5 to 50 hours, preferably 1 to 86 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. □ The reaction ratio between the magnesium halide and the titanium compound and/or vanadium compound is 0.5 to 2% of the titanium and/or vanadium contained in the catalyst component [l].
It is most preferable to adjust it so that it is within the order of 0%, and has a well-balanced activity per titanium and/or vanadium, per solid. A range of 1 to 10 is particularly desirable in order to obtain a host property of 1 to 10.

In the present invention, in addition to the (t)no-rogenated magnesium compound and (11) titanium compound and/or vanadium compound, other components, i.e., the compound α) of the general formula ygcOR)pXz-p (where Me is periodic table] group ~
■Indicates group elements. However, Ti and V are excluded. R represents a hydrocarbon compound having 1 to 24 carbon atoms and a halogen atom as the bride of X. 1 represents the valence of Mε, and n is 0<p≦2), organic halogen compounds, halogenating agents, phosphoric esters, electron donors, and polycyclic aromatic compounds. It is also preferably employed to prepare catalyst component CI] using one or more types of compounds.

The amount of the above ingredient (if used) is Component (1)'
Component (α) per mole of magnesium chloride
is 0.01 to 5 mol J, preferably 0.05 to 2 mol.

Examples of compounds represented by the general formula Me(ON)pXz-a used at this time include NaOR, Ai
g(0R)t, M'y(OR)X, Ca(OR)t
, ZnC0Il)t, Zn((]It)X.

Cd(OR)t,Aj? (OR)s, AI! (OE)t
X, B(OR)s, B(OR)xX, Ga(OR)s,
Ge(OJR')4.5TL(OR)4, PCOR)s
, Ct”(OE)t, MnC0R)t, Fe(OR)t
, F's (OR)s, Co(ORh, N1(011)
Examples include various compounds such as Na, OC, H, Na,
OCdi G, Mg(OCRs)t, Ma (tl to 0
M) t, M Q (OCs1b) 2, Ca (OCtl
ls ) 2, Zn(OCzlis)t-Z n (0
C7Hs) Cl! , A 14 (OC11s)
s, AI! (OCJb)s, A6 (0CtHs)t
C1l, AI! (0Csl17)s, All (0
CJo)s, Al (0CJIs)s-B (OC!H
s) s, B (QCJi5 )2 Ci! .

, P (OCtlI,) s, P (Q CJs )
Compounds such as s, F e (0CdIo ) sYK can be mentioned.

In the present invention, in particular, the general formula M Q (OR) p
N2- p, Ai (OR), X, -a and 11 (O
R) p Compounds coated with Xs-p are preferred. As 17, an alkyl group having 1 to 4 carbon atoms and a phenyl group are particularly preferred.

The organic halogen compound used at this time is a compound in which a portion of a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, etc. is directly replaced with a halogen, and includes mono-substituted compounds, di-substituted compounds, and rt-substituted compounds, etc. be. Also, halogen is fluorine,
Any of chlorine, bromine and iodine may be used.

Specific examples of these organic halogen compounds include methylene chloride, chloroform, carbon tetrachloride, bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 112-cyfuromo-1,1
-Jiku o.

xy, 1, 1-dichloroethane, ], 2-dichloroethane, 1,2-dichloro-1,1,2,2-tetrachloroethane, hexachloroethane, pentachloroethane, 111.1.2-tetrachloroethane, 1, 1, 2.
2-tetrachloroethane, 1,1.1-trichloroethane, 1.1゜2-trichloroethane, 1-chloropropane, 2-chloropropane, ■, 2-dichloropropane,
1. B-8'lolopropane, 2,2-dichloropropane, 1.1.1,2゜2.3,8-heptachloropropane, 1,'i, 2.2.3゜3-hexachloropropane, octachloropropane Han, L.

1.2-) dichloropropane, 1-chlorobutane, 2-
Chlorobutane, 1-chloro-2-methylpropane, 2-
Chloro-2-methylpropane, 1,2-dichlorobutane, 1°8-dichlorobutane, 1,4-dichlorobutane,
2.2-Dichlorobutane, 1-chloropentane, 1-chlorohexane, 1-chlorohebutane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, vinyl chloride, 1.1-dichlorothylene, 1.2- Dichloroethylene, tetrachlorethylene, a-chloro-1-propene, 1,8-dichloropropene, chloroprene, 1st/
Examples include yl chloride, chlorobenzene, chloronaphthalene, benzyl chloride, benzyritine chloride, chloroethylbenzene, styrene dichloride, and α-chlorocumene.

As a halogenating agent, sulfur chloride, FC13s, PC
l3. s.

5i (of non-metals such as A4), rogens, pocps
, cocbz, NOCI! t, S OC (3t, SO,
Gold can be used, such as non-metallic oxynologenides such as carbon.

Phosphate esters are compounds represented by the general formula ON 1 / (where R represents a hydrocarbon residue having 1 to 24 carbon atoms, which may be the same or different, and specifically: is triethyl phosphate, tri-n-butyl phosphate, triethyl phosphate,
Tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate and the like can be mentioned.

As electron donors, alcohol, ether, keto/,
aldehyde, organic acid, organic acid ester; acid)/ride,
Can be used for acid amides, amines, nitriles, etc.

As alcohol, methyl alcohol, ethyl alcohol, %-propyl alcohol, in-butyl alcohol, prill alcohol, n-butyl alcohol, in-butyl alcohol, %-butyl alcohol, t-'7''
Chill alcohol, n-ami□rual! Sf s-hexyl alcohol, cyclohexyl alcohol, prill alcohol, '5')') /l/7 L=r-L, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, liquid alcohol2. , Nafuchi J1A7. Cor 2. Alcohols having 1 to 18 carbon atoms such as , pheno, , creso, and 2 are mentioned.

Examples of the ether include ethers having 2 to 20 carbon atoms, such as dimethyl ether, diethyl ether, dibutyl ether, isoamyl ether, anisole, phenethole, diphenyl ether, phenyl allyl ether, and be/syfuran.

Ketones include acetone, methyl ethyl ketone, methyl imbutyl ketone, methyl phenyl ketone, ethylphenyl ketone, diphenyl ketone, etc. having 3 to 180 carbon atoms.
By opening the ketone, we can form R, C, and.

Examples of the a''de3d include aldehydes having 2 to 15 carbon atoms such as a''a''de8d, bupi7'aldehyde, octylaldehyde, benzaldehyde, and naphthaldehyde.

Organic acids include J formic acid, acetic acid, bu-ro-acid, i-acid, and ki-acid.
Grass acid, pivalic acid, □Cab7J/acid, caprylic acid mistearic acid, oxalic acid, malonic acid, copacic acid, adipic acid, □methacrylic acid, benzoic acid, toluic acid, anise green,
Oleic acid, linoleic acid, lylunic acid, etc. with 1 or more carbon atoms
24 organic acids can be mentioned.

Examples of organic acid esters include methyl formate, methyl acetate, Shinano acid ester, propyl acetate, octyl acetate, propio/ethyl acetate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, and benzoic acid. Propyl, octyl benzoate, phenyl benzoate, benzyl benzoate, butyl ethoxybenzoate, methyl toluate,
Organic acid esters having 2 to 30 carbon atoms such as ethyl toluate, ethyl ethylbenzoate, methyl salicylate, phenyl salicylate, methyl naphthoate, ethyl naphthoate, and ethyl anisate can be used.

Examples of the acid halide include acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzyl chloride, toluoyl chloride, and aninyl chloride.

Examples of the acid amide include atriamine), tri-soyamide, and toluoylamide amines include methylamine, ninalamine, diethylamine, tributylamine, piperidine, and tri-soylamide.
Amines such as zylamine, annealine, bilin/picoline, and detramethylene diamine can be found1.
Nitriles include acetonitrile, benzo; tolyle,
21. such as tolnitrile. IJ files can be opened.

A polycyclic aromatic compound and [2, specifically nanosilane,
Noenane, triphenylene, chrysene, 3.4
-benzophenanthrene, ], ]2-benzochrysenpinane, anthracene, tetraphene, 1. Z, 3.4-
, >benzanthracene, bentafcone, 3,4-benzopentaphene, detracene, 1,2-benzatracene, hex-/, hebetafen, synenyl, norolene, biphenylene, perileno, :Ironene, byzanthene , pyrene, belinafden, etc., and examples thereof include substituents and alkyl-substituted substituents.

In the present invention, it is also preferred that the catalyst component 11 obtained in Hidden 1 is supported on an oxide of a metal of Groups H to II of the periodic table.

The oxides of groups H to II of the periodic table to be used are those of groups 1 of the periodic table.
Not only the oxides of metals of Groups 1 to 2, but also the double oxides of these metals, and of course mixtures thereof may be used.Specific examples of these metal oxides include M
g O, Ca. O.

ZnO,BaO,,SiO□,,St+02,At,0
3, MgO-At,,03.

SiOz-Atz, U3, MaO-, 5 ioz
, MgO-CaO-Atz03, AkOg
・CaO can be used as an example, but Si
Oz , , A li 03 .

−'; i (J2 At2 03 , M g O
-A tz 03 is preferred.

The method of supporting the catalyst component [I] on the oxide of a metal of group 11 to group II of the periodic table is not particularly limited. 1) If there is any peace of mind, it is preferable to add the component (α), react under heating, and then remove the liquid phase.

1 used in the present invention - General formula R'mS i (
OR2) Examples of the compound represented by 4-971 include monomethyltrimethoxysilane, monomethyltriethoxysilane, monomenaltrimethoxysilane, monomethylcitrinylcarbonsilane, monomethyltriisobutyboxysilane, monomethyltripentoxysilane,
Monomethyltrioctoxysilane, monomethyltristearogycinlan, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane phenoxysilane, trimethyltazume 1-xysilane,
Trimethylmonoethoxysilane, trimethylthinoisobroboxosilane, trimethylmonofuconoquine 7ran,
Monomethyltrimethoxysilane, monomethyltriethoxysilane, monoethyltriisobrobogycinlane, monomethyltriphenoxysilane, diethyljethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, trimethylmonoethoxysilane, triethyl heptanoyl-disilane!・Ethyl monophenoxysolane, monoisopropyltrimethogine silane, mono-1-butyltrimethoxysilane, 1,000-η-butylene triethoxysilane, mono-butyltriethoxysilane, monophenyltriethoxysilane, dino-1. Nealshedoxinlan, Tetraetogycinlan, Detrine broboxinlan, etc. can be mentioned.

In the present invention, the general formula R'mS t (OR2)4
．． The use of the compound represented by − or □ is such that no effect can be expected if it is added in too much or too little amount, and usually the catalyst component C
0.1 to 100 mol, preferably 0.1 to 100 mol, preferably 0.1 to 100 mol, per mol of the titanium compound and/or vanadium compound in I).
It ranges from 3 to 20 moles.

General formula R3, At(OR4) used in the present invention
3-.

Compounds represented by include dimethylaluminum monoethoxide, dimethylaluminum monopropoxide, dimethylaluminum 7-n-butoxide, dimethylaluminum monobutoxide, diethylaluminum monoethoxide, diethylaluminium monomethoxide, diethylaluminum monoethoxide. , ethylaluminum monoisobroboxide, diethylaluminium mono-n-butoxide, diethylaluminum mono-butoxide, diethylaluminum monoethoxide, diethylaluminum monooctoxide, diethylaluminum mono-n-butoxide, diisobunalaluminum monoethoxide, methylaluminum Dimethoxide, methylaluminum jetoxide, ethylaluminum jetoxide, ethylaluminum jetoxide, ethylaluminum diimpropoxide, ethylaluminum di-n-
Specific examples include butoxide, ethylaluminum diphenoxide, isobutylaluminum jetoxide, isobutylaluminum jetoxide, and the like.

In the present invention, if the amount of the compound represented by the general formula R3nAt(OR')3-n is too large or too small, the addition effect cannot be expected, and the catalyst component [S(
The amount is in the range of 0.01 to 10 mol, preferably 0.05 to 2 mol, per 1 mol □ of the compound.

As the organometallic compound used in the present invention, organometallic compounds of Groups 1 to 1 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R3A L'p R2A AX, RA
tX2k J:0: Rs AA2Xa Teab Sah
organoaluminum compound (where R has 1 to 20 carbon atoms)
an alkyl group or an aryl group, It is an organic zinc compound represented by triethylaluminum, triimpropylaluminum, triimbutylaluminum, tri(8)-butylaluminum, tri(8)-butylaluminum, tri(8)-butylaluminum, tri(8)-butylaluminum, tri(8)-butylaluminum, to! J
Specific examples include tert-7'' methylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. Organic carboxylic acid esters such as ethyl benzoate, ethyl toluate, and ethyl anisate can also be used together with the organometallic compound.The amount of the organometallic compound used is 0 relative to the titanium compound and/or vanadium compound. .1~100
It can be used 100 times more.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization, and it can be particularly suitably used for slurry polymerization and gas phase polymerization.

The polymerization reaction is carried out in the same manner as a typical olefin polymerization reaction using a Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are a temperature of 20°C to 120°C, preferably 50°C.
The temperature is from normal pressure to 100°C, and the pressure is from normal pressure to 70 Ky.
/crd, preferably 2 Kf/-1 or 60 Kf
/cJ. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by completely adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, hydrogen concentration,
A two-step or more multi-step polymerization reaction with different polymerization conditions such as polymerization temperature can also be carried out without any problems.

The method of the present invention can be applied to the polymerization of all meleninoins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, phthene-1, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene tofurobyrene, ethylene tophthene-1,
Suitable for copolymerization of ethylene and hexene-1, ethylene and 4-methylbenzone-1, ethylene and octene-1, propylene and butene-1, and copolymerization of ethylene and two or more other α-olefins. Ru.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of compounds that can be used at this time include butadiene, :I-7,1,4
-Hecadiene, ethylidenenorbornene, dicyclopentadiene, etc. can be added.

Examples will be described below, but these are for illustrative purposes in carrying out the present invention, and the present invention is not limited to kneading.

Example L (a) Production of solid catalyst component [l] Two stainless steel balls each having a diameter of 7 inches were prepared.
5 pieces / ζContents f't 400 ml stainless steel bottle with commercially available anhydrous magnesium chloride 10y1
Add 2.32 kg of aluminum triethogide and 2.52 kg of titanium tetrachloride and conduct ball milling for 16 hours at room temperature under a nitrogen atmosphere. After voluminous milling, the obtained solid catalyst component [:D1y] contained 41~ titanium.

(b>Polymerization A 2-ton stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 1.000 vrlfH of hexanoyl was added, 1 mmol of triethylaluminum, 0J of diethyljetoxysilane) 5 mmol, diethyl aluminum monoethoxide o, o i mmol. and ``Solid catalyst component CI]], Omy was added and the temperature was raised to 90℃ while stirring [secondary 3, the system was 2Ky/-・G with the vapor pressure of hexylene.
However, hydrogen was added until the total pressure reached 4.8~/crl-G, and then ethylene was added until the total pressure reached 10 Kr/-・G.
The pressure of the autoclave was increased to 1. Polymerization was carried out for 1 hour at a temperature of 1 to maintain OKy/dG. After the polymerization was completed, the polymer slurry was transferred to a beaker, the hexanoyl was completely removed under reduced pressure, and the melt index was 1.
1. 175f of white polyethylene with a bulk density of 0.38 was obtained. Catalytic activity is 82.10 (H'polyethylene/2Ti
-hr-Cd pressure, 8.870? It was polyethylene/1 solid/hr-CJ+pressure.

In addition, the F, R, value (F'', R9 value of the obtained polyethylene is a scale representing the breadth of the molecular weight distribution and is calculated by the following formula.
On 2.16! ? Melt index under load The method for measuring the melt index was ASTM 1288. ) was 7.5, and the molecular weight distribution was extremely narrow compared to Comparative Example 1.

Comparative Example Ethylene polymerization was carried out in the same manner as in Example 1 except that diethylaluminum monoethoxide was not added. White polyethylene 140 with bulk density g0.8B and melt index 1.0? I got it.

Catalytic activity is 65,7009 polyxfV/1Ti-hr
・cJI4.2.7002 polyethylene/2 solid ・h
The pressure was 2114 r'C''.

Also, the l? of the obtained polyethylene? , R, value was 8.0.

Example 2 The same procedure as in Example 1 except that 0.05 mmol of monoethyltriethoxysilane and 0.02 mmol of diethylaluminum monoethoxide were used in place of diethyljethoxysilane in Example 1. Polymerization of ethylene was carried out using

White polyethylene 1639 with a melt index of 0.9 and a bulk density of 0.41 was obtained. Catalytic activity is 76,50
0? Poly: r-f-Vn/yT i ・hrC2
H4 pressure, 3,130 f polyethylene/y solid/hr-
The pressure was C2H4.

Moreover, the F and R values of the obtained polyethylene were 7.4, and the molecular weight distribution was extremely narrow compared to Comparative Example 2.

Comparative Example Ethylene polymerization was carried out in the same manner as in Example 2, except that diethylaluminum monoethoxide was not added.

Melt index 1.1. 121 tons of white polyethylene with a bulk density of 0.32 was obtained. Catalytic activity is 56.80
(l polyethylene 7/tTi-hr-CJa pressure,
The pressure was 2,330 f polyethylene/2 solid/hr-Cf4, and the F and R values were 8.1.

Example a In Example 1, diethyljethoxysilane'to 1 mmol was used instead of diethyljethoxysilane, and 0.02 mmol of ethylaluminum diphenoxide was used instead of 4fc diethylaluminum monoethoxide. Polymerization of ethylene was carried out in the same manner as in Example 1.

White polyethylene 1811 having a melt index of 1.3 and a bulk density of 0.39 was obtained. Catalytic activity is 84.90
Of polyethylene / tTi-hr-C2H4
Pressure, 3.480 t polyethylene/V solid・hr・C2
The pressure was H4.

Furthermore, the F and R values of the obtained polyethylene were 7.5, and the molecular weight distribution was extremely narrow compared to Comparative Example 3.

Comparative Example a Ethylene polymerization was carried out in the same manner as in Example 3 except that ethylaluminum diphenooxide was not added.

133 tons of white polyethylene with a melt index of 1.0 and a bulk density of 0.33 was obtained. Catalytic activity is 62.40
OfPolyechv:, r/ IT i-h r-Ca
14 pressure, 2,560 Tapori polyethylene/2 solid/hr
-C2JI4 pressure, and p, R, values were 8°O.

Example 4 (a) Preparation of solid catalyst component C1) Commercially available anhydrous magnesium chloride 10 cm was placed in a stainless steel pot with an internal volume of 400 mJ containing 25 stainless steel balls each having a diameter of 72 inches. and aluminum triethoxide4. ．． Ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. A stirrer and a reflux condenser were attached, and an FC3 flask was purged with nitrogen. The above reaction product 51 and 5f of silica (Fuji Davison, NA952) calcined at 600°C were placed in the 3 flask, and then 100% of tetrahydrone was added. , after reacting at 60°C for 2 hours,
Drying was performed under reduced pressure at 120°C to remove tetrahydrone. Next, 50% of hexane was added and stirred, and then 1.1 ml of titanium tetrachloride was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (A?).
, 01f had a titanium content of 40 kg.

In the above obtained β1 body powder <, A) Gold hexyl 50m
1, and then 1 ml of tetraethogycin run was added thereto, and the mixture was reacted with Hegylin Mb'#F for 2 hours to obtain a solid catalyst component [1].

(b) A 2-ton stainless steel induction stirrer (2 tons) was purged with nitrogen, and 1000 ml of hexane was added, followed by 1 mmol of triethylaluminum, 5 mmol of dimethylsilane (QJ), and 5 mmol of diethyl. Aluminum monoethoxy MO, (11 mmol) and the above solid catalyst component CD 10 were heated at 90°C with stirring.
The system is heated to 6, and the vapor pressure of Kizan is 2 to 7/cd.
-G, but add hydrogen until the total pressure is 4.8KIi/1-GK, then JL butylene total pressure is 1 OKq/
Polymerization was started by filling the autoclave until aA = G, and the autoclave was ladle for 1 hour while maintaining the 1F force of the autoclave at 10 to 9/-.GK. After completion of polymerization, transfer the polymer streak to a beaker, remove the hekah under reduced pressure, and
White polyethylene 602 having an intex of 0.7 and a shaving density of 0.42 was obtained. The catalytic activity is 28.80 (lF polyethylene/'/Ti-h, r・c2H4ff,, i, 1
50 & polyethylene/y16-1 body 'hr'
F- of polyethylene obtained with ivy 1° at C2114 pressure
R, candy was 7.4, and the molecular weight distribution was extremely narrow compared to Comparative Example 4. The obtained polymer particles had poor fluidity, and the average particle size was 730 μtn. .

Comparative Example 4 In Example 4, diezyl aluminum monogot.
-'' Polymerization of Eblen was carried out in the same manner as in Example 4 except that the throat was not added.

Polyethylene 48y having a melt index of 0.9 and a bulk density of 0.34 was obtained. Catalytic activity is 23.100f polyethylene/? T i-h, r = C'z 114 pressure, 920y polyethylene/solid・hr ・C2,l
j4 pressure, F, R, 1ifi (or 8.1).

Example Hill (a) Production of solid catalyst component [1] A stainless steel pole with a V2 inch surface diameter is 25: J people and Q. Contents & 400 m! Commercially available anhydrous magnesium chloride 10 F
, Titante I/Line Propo W Cito 2. Of and isopropyruclus Fl, 7? Money box nitrogen perforated air I.
Ball milling was performed at room temperature for 16 hours. Ballmi 1,
The solid catalyst component [, ■] 12 is 25
Contains ~ titanium.

(b) Polymerization: An autoclave equipped with a 2-ton stainless steel induction stirrer was purged with nitrogen, and hexane 1 + OOOml f
Add 1 to 9 mol of triethylaluminum, 0.1 mmol of diphenyldie-11-disilane, 0.05 mol of diethylaluminium monoethyside, and the above solid catalyst component [:l] toq, and heat to 90°C while stirring for 1 to 10 minutes.
The temperature rose to . At the vapor pressure of hexane, the thread is 2Ky/cA-
G to 1. The total pressure of hydrogen is 4-8 K9/cn5
・Put it in until it reaches G, then add ethylene until the total pressure is 1
The pressure was increased to 0Ky/~.GK to start polymerization, and the total pressure was maintained at 101#/~.G to 1-1 for 1 hour. After 1 cup, transfer the car combined slurry to a beaker, remove hexane under reduced pressure, and melt index 1.
．． 1. White poly J-Ren 442 with bulk density 0.38
I got it. Catalytic activity is 33.70 Or polyethylene/?
T1゛・hr-C2114 pressure, 850v polyethylene/y solid・hr-C2Hd(-, F, R
, the value is 7.6 fc.

Comparative Example & Example 5 Ethylene polymerization was carried out in the same manner as in Example 5, except that diethylaluminum uno and ethylene were not added.

Polyethylene 35f having a melt/dex of 0.9 and a bulk density of 0.31 was obtained. Catalytic activity is 26.800?
Polyethylene/lT I・hde・C2H4 pressure, 670v polyethylene/g solid-h, -C2H4 pressure, F, R
, the value was 8.2.

Example G Gas phase polymerization was carried out using the solid catalyst component [I] of Example 1. A stainless steel autoclave was used as the gas phase polymerization apparatus, and a loop was created with a blower 1 flow rate regulator and a dry cyclone. The temperature of the autoclave was regulated by running hot water through the jacket.

In an autoclave adjusted to 80° C., the solid catalyst component (1) of Example 1 was added at 5 Ollv/hr, diethyl jetoxysila/α25/mmol/h, diethylaluminum monoethoxide 0.05 mmol/hr, and triethyl. Aluminum was supplied at a rate of 5 mmol/h, and each gas was supplied while adjusting the hydrogen/ethylene ratio (molar ratio) in the autoclave gas phase to 0.45. Polymerization was carried out by circulating the gas inside to maintain the total pressure at 1016/dG. The polyethylene produced has a bulk density of 0.3B.

Melt index was 0.9.

The catalytic activity was 384.00 (l polyethylene/fTi
The F and R values were 7.6.

Patent applicant: Representative of Nippon Oil Co., Ltd. Patent attorney: Ryoji Kawase, patent attorney
Takehiko Saito

Claims (1)

[Scope of Claims] [l) A solid material obtained by total reaction of at least the following two components (1) magnesium halide and (11) a titanium compound and/or a vanadium compound, having the general formula: ott2), -□ (here R'
, R'' represents a hydrocarbon residue having 1 to 24 carbon atoms, and 0≦m
≦3), B■〇General formula R%A11. (OR') B-B
(CCTER'', R' represents a hydrocarbon residue having 1 to 24 carbon atoms, and 1≦n≦2) and nvr organometallic compound are combined, and each component is 0・1≦7+4 and/or v (% ratio)≦100. ↓bi061≦
avJ inside oi to l] inside. 1. A method for producing polyolefins, characterized in that olefins are completely polymerized or copolymerized using a catalyst system that satisfies the following conditions: