Note: Descriptions are shown in the official language in which they were submitted.
~g
PROOESS FOR PE~EPARING POLYOLl~.FINS
Background of the Invention
The presen~ invention relates to a process or preparing
polyolefins using a novel polymerlzation catalyst.
Heretofore in this technical field9 a catalyst compris~ng
a ~la~nesium hallde a.d a transition metal compound ~uch as a titanium
compound supported thereon has been known from Japanese Patent
Publicatio~l No.1.2105/1964, and a catalyst prepared by the co-pulver:Lzation
of a magnesium halide and titanium tetrachloride has been known from
Belgian Patent No.742,112.
But in the production of polyoleflns it is desirable
that the catalyst activity be as high as posslble, and when viewed
from this standpoint, the process disclosed in Japanese Patent
Publication No.12105/1964 afford~ a still low polymerization acti.vity,
and ln the proces~ diaclosed in Belgian Patent No.742,112, the
polymerization activlty is falrly high, but a further improveme~t
is desired.
In 5erman Patent No.2,137,872, the amount of a magnesium
hallde used 15 substantlally decreased by its pulverization together
20 with titanium tetrachloride and alumina, but a remarkable increase
in activity per solid, which can be regarded as a guideline for
productivity, is not recognized~ and a catalyst of higher activity
is deslred.
In the productlon of polyolefins, moreover, 1t is
desirable from the aspects of productivlty and slurry handling
that the bulk density of the resulting polymer be as hlgh as possible.
From this standpoint, in the process disclosed in Japanese Patent
Publication No.12105/1964~ the bulk denslty of the resultant polymer
is low and the polymerization activlty ls not ~n a satlsfactory
state, and in the process disclosed in Belgian Paten~ No.742,1127 the
bulk density of the resultant polymer i3 low although the polymeri~at~on
actlvity is hlgh, and thus further ~mprovemen~ are deslred.
Summary of the Invention
It 18 the ob~ect of the presen~ invention to provlde
a novel polymerization cataly~t capable of remedying the above-
mentioned drawbacks, exhiblting a high polymeri7ation actlvity9
affording a polymer of high bulk density ln hlgh yield and permitting
an extremely easy execution of a continuous polymerization, as
well as a process for homopolymerlæing or copolymerizing oleflns
using such polymerization catalyst.
The present invention resides in a process for preparing
olefin~ by homopolymerizing or copolymeri~ing olefins in the presence
of a catalyst comprising a solid catalyst component and an organo-
metallic compound, which solid catalyst component compriscs asubstance obtained by the reactlon o~ at least the following
four component~:
(1) a compound represented by the general formula
R ~(~R )nMgX2
~2) a compound represented by the general formula
Me(OR ~ X
(3) a compound represented by the general formula
R4
R6 _~- Si - O ~ R7 and
R5 -
~4) a halo~en-containing titanium compound
~n whlch formulae R , R , R3 ~nd R7 are each a hydrocarbon radlcal
havin~ l to 24 carbon atoms, R4, R5 and R~ are each a hydrocarbon
radlcal havlng 1 to 24 carbon atoms, a~koxy, hydrogen or halogen,
X i~ halogen, Me is an element of Group~ I through VIII in the
3~
Perlodic Table, provided that silicon and titanium are excluded~
z ~8 the valenc~ o Me9 and m, nl p and q are as follo~s:
O ~ m c 2, 0 ~ n C 2, 0 ~ m~n c 2, 0 c p ~ z, 1 ~ q c 30
The catalyst of the present inventlon exhibits an
e~tremely high polymerization activity, and consequently the partial
pressure of monomer is kept law during poly~erization. Furthermore9
t~e bulk density of the resultant polymer is so high that the
productivity can be improved. Besides, the amount of cat`alyst
rP~n~g in the resultant polymer at the end of polymerization
0 iS 80 small that the polyolefin manufacturlng process can dispense
with the catalyst removing step, thus permitting simpllfication
of the polymer treating process, ~Id as a whole polyolefins can
be prepared extremely economically.
~ In the process of the present invention, the amount
of polymer produced per unit polymerization reactor i9 larg~ because
of a high bulk density oE the polymer.
1~e present invention has a further advantage such that
from the ~tandpoint of particle slze of the resultant polymer,
the proportlon of coar~e particles and fine particles below 50
is small despite of a hlgh bulk density, and that consequently
not only it becomes easy to perform a continuou~ polymerization
reaction but also lt becomes easy to handle polymer particles,
for e~ample, ~n centrifugal separation in the polymer treating
process and ln powder transportat~on.
~ a still further advantage of the present invention,
polyoleflns prepared by using the cataly3t of the present lnvention
have a h1~h bulk density as prevlo~sly noted, and those having
a desired melt index are obtainable wi~h a l~wer hydrogen concentration
than in the conventional processes, thus permitting the total
pressure to be set at a relatively small value during polymerization,
and consequently a gre~t improvement is attainable in point of
economy and productlvity.
Additionallq~ in the polymeri~ation of ole~ins using
the catalyst of the present invention 7 the olefln absorbing rate
S does not decrease Sd much with the lapse of time, and therefore
the polymerization can be conducted for a long ti~e in a smaller
amount of the catalyst.
Furthermore9 polymers obtained by using the catalyst
of the present invention have an extremely narrow molecular weight
distributlon and their hex~ne extraction is small, thus reflecting
a minlmi~ed by-production of low grade polymers. Therefore, for
example, in the fllm grade, lt is possible to obtain products
of good quality superior in ant~-blocking and other properties.
~ The present invent:Lon provides a novel cat`alyst system
having many such rharacteristic features and capable of remedying
the above-mentloned drawbacks of the prlor art. It is quite
surprising that those ~eature~ should be attainable easily by
using the catalyst of the present inven~:ion.
Descrlption of the Preferred Embodiments
A~ compounds of the formula Rlm(OR2)nMg~ m n used
ln the presen~ in~ention, there essentially may be any co~pounds
of the same formula provided Rl and R2 are each a hydrocarbon
radical having 1 to 24 carbon atoms, but particularly preferred
are those wherein Rl and R2 are each an alkyl group. Examples
of such compounds include dlethylmagnesi~m, diisopropylmagnesium,
di-n-butylmagnesium, di-sec-butylmagnesium, methylmagnesium chloride,
ethylmagnesium chloride, ethylmagnesium bromide, ethylmagneslum
iodlde, n-propyl~agnesium chloride, n-butylmagnesium chloride9
n-butylmagnesium bromlde, sec-buty~magnesl~mm chloride, phenylmagnesium
3~3~
chloride, decylmagneslum chloride, metho-xymagnesium chlorlde,
etho~ymagneslum ~hlorlde~ isopropoxymagnesium chloride, n-
butoxymagnesium chlorlde, n-octoxymagnesium chloride, methylmagneslum
methox~de, ethylmagnesium methoxide9 n-butylmagnesium ethoxide,
sec-butylmagnesium ethoxide, and decylmagnesium ethoxide. Complex
with a trlalkylaluminum is also employable, e.g. a c~mp~ex of
di-n-butylmagnesium and triethylaluminum~
As compounds of the general formula Me~OR3~ X~ used
in the present invention, mention may be made of various compounds
such as NaOR, Mg(oR3)2, Mg(oR3)X, CaCOR3?2, Zn~OR3~2, ZnCOR3)X,
Cd(OR )2~ Al~OR )3, Al(OR )2X, B(OR )3, B(OR )2X, GaCOR )3, GetoR )
SntoR )4~ P(oR3)3, Cr(OR3)2, Mn(OR3)2, FeCO~ )2~ Fe~OR3)3, Co(OR ~2~
and Ni(oR3)2, in whlch formulae R3 may essentially be any hydrocarhon
radical having 1 to 24 carbon atom~, but alkyl and aryl groups are
particularly preEerred. Preferred examples of such compounds
include Na0C2H5, Na0C4Hg~ Mg(OC~3)2~ g( 2 5 2 3 5 2
Ca(OC2H5)2, Zn(0C2Hs)2, ~n(OC2H5)51~ Al(0~13)3, Al(OC2H5)3, Al(OC2H5)Cl~
Al~OC3~l7)3l Al(OC4~19)3, Al(OC5l~s)3, B(OC2H5)3, BCC2H5)2Cl~ P(OC2H5)
P(0C6H5)3, and Fe(0C4Hg~. Especially preferred :Ln the present
invention are compolmds represented by the general formulae Mg(oR3) X2 s
Al~OR )pX3 p and B(OR )pX3 p, wherein alkyl of Cl to C4 and phenyl
are especially preferred as R .
R4
I~ compounds cf the general formula R -~- Si - O ~ R
R
used in the present invention, R4, R and R6 each may essentially
be any of hydrocarbon radicals having 1 to 24 carbon atoms, alkoxy,
hydrogen and halogen, but alkyl, aryl, alkoxy and halogen are
preferred, and R may essentially be any of hydrocarbon radlcals
havlng 1 to 24 carbon atoms, but alkyl and aryl groups are preferred.
Exa~ples of such compounds include monomethylt~imethoxysllane,
monomethyltriethoxyRilane, monomethyltri--n-butoxysllane,
monomet~yltri-sec-butoxysilane, monomethyltriisopropoxysilaIIe~
monomethyltrlpentoxysllane, monomethyltrloctoxysilane,
5 monomethyltristearoxysllalle, monometllyltriphenoxysilane, dimethyl-
dimethoxysilane, dimethyldiethoxysilane, dimethyldii~opropoxysilane 9
dimethyldiphenoxysilane, trimethylmonomethoxysllane, trimethyl-
monoethoxysilane, trimethylmonoisopropoxysilaner trimeth~lmono~
phenoxysilane, monomethyldimethoxymonochlorosilane,
10 monomethyldiethoxymonochlorosilane, monomethylmonoethoxydichloros~lane,
monomethyldiethoxymonochlorosilane, monomethyldiethoxymonobromosllane,
monoethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane9
monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltri-
, isopropoxy~sllane, monoethyltriphenoxycilane, diethyldimetho~y~ilane,
dlethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethox;y-
silane, triethylmonoethoxysilane, trlethyl~lonophenoxysilane,
monoethyldimethnxymonochlorosi.lane9 monoethyldiethoxymonochlorosilane,
monoethyldiphenoxymonochlorosllane, monoisopropyltrlmethoxysilane,
mono-n-butyltrimethoxysilane, mono-n-butyltrlethoxysllane, mono-
sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldi-
ethoxy3ilane~ diphenylmonoethoxymonochlorosilane, monomethoxytri-
chlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane,
mono-n-butoxytrichlorosilane, monopentoxytrichlorosilane,
monooctoxytrichlorosllane, monostearoxytrichlorosilane,
monophenoxytrlchlorosilane, mono-p-methylphenoxytrlchlorosilane,
dlmethoxydichlorosilane, dlethoxydlchloroqilane~ diisopropoxydi-
chlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane,
trimethoxymonochlorosilane; triethoxymonochlorosllane~
trii~opropoxymonochlorosilane~ tri-n-butoxymonochlorosilane, tri-
sec-butoxymonochlorosilané~ tetraethoxysilan~, tetrsisopropoxysilané,
and chain-like or cyclic polysiloxanes havlng a repeatlng unlt
represented by the formula -~- Si - O t --- obta~ned by condensation
of the a~ove compounds.
As halogen-containing titanium compounds used in the
present invention, there may be mentioned halides and alkoxyhalidPs
of titanium. A~ tltanium compounds are preferred tetravàlent
and trivalent titanium compounds. Preferred e-xamples of tetravalent
tltanium compounds are those represe~ted by the general formula
Ti(OR)rX4 wherein R i8 an alkyl, aryl or aralkyl group havlng
; 10 1 ~o 24 carbon ato~s, X is a halogen atom and r i9 0 ~ r C 4,
such a6 tltanium tetrachloride~ titanium tetrabromide, titanium
tetraiodide, monomethoxytrichlorotitanium, dilDethoxydi~hlorotitanium,
trimethoxymonochlorotitanium, monoethoxytrichlorotitanium,
dietho~ydichlorotitanium, triethoxymonochlorotitaniu~, monoiso-
propoxytrichlorotitani~m7 diisopropoxydichlorotitanium, tril~o-
propoxymonochlorotitanium; monobutoxytrichlorotitani~m,
di~utoxydichlorotltanium, monopentoxytrichlorotitanium, monophenoxy-
trichlorotitanium, diphenoxydichlorotitanium, and triphenoxymono-
chlorotitanium. As trivalent titanium compounds there may be
mentioned titanium trihalides obtained by reducing tltanium
tetrahalldes such a~ tltanium tetrachloride and tltanium tetrabromide
with hydrogen, aluminum, titanium or an organometallic compound
of a Group I-III metal ln the Periodic Table, as well as trivalent
titanium compounds obtained by reducing tetravalent alkoxytitanlum
halide~ of the general formula Ti(OR) X~_ with an organometallic
compound of a Group I III metal in the ~erlodlc Table in whlch
formula R l~ an alkyl~ aryl or aralkyl group having 1 to 24 carbon
atom~9 X iB a halogen atom and ~ i~ O ~ ~ C 4. Tetravalent titanium
compound~ are mo~t preferred ln the present inventicn
In the pre~ent lnvention, the method for obtaining
the solid cataly~ componen~ by reacting tl) a compound o the
general formula R m~OR )nX2_m_n~ C2~ a compound of the general
for~ula Me(OR )pX p, C3~ a compound of the general formula
R -~- Si - O ~ R and (4) a halogen-containing titanlum compo~md,
i9 not specially limited. The component~ ~l)-C4) may be ~eacted
under heating at a temperature in the range of 20 to 400C, preferably
50 to 300~C9 for a period of time usually in the range of 5 m~nutes
to 20 hours, in the presence or absence of an inert solvent, or may
be reacted by a co-pulverization treatment, or by suitably co~bining
these methods. The order of reaction of the components C1~-(4
, i8 not specially limited9 either. The four components may be
reacted at a time, or three of them may be reacted followed by
reaction of the remaining one component, or t~o of them may b~
reacted followed by reactlon of on~ of the rP~n~ng two componenta
and then reaction of the r~ n~ng one component.
Inert solvents which may be u~ed in the above reaction
are not specially limited. ~sually, there may be used hydroca~bon
compounds and/or derivatives thereoE not inactivating Ziegler type
cataly~ts. E~amples of ~uch solvents include various ~atura~ed
allphatic hydrocarbons, aromat~c hydrocarbons and allcycllc hydrocarbons
such a~ propane, butane, pentane, hexane, heptane~ octane, benzene,
toluenej xylene and cyclohexane, as well a8 alcohols, ethers and
e~ters such as ethanol, diethyl ether~ tetrahydrofuran, ethyl
acetate and ethyl be~zoa~e.
The appara~us to be u~ed for the co-pulverization
is not spec~ally limlted, but u~ually there ia employed a ball
mill, a vibration mill, a rod mill~ or an impact mill. Condition~
S
33~
such as pulverization temperature and pulverlæation tlme can be
determined easil~ by those skilled ln the art according to the
pulverizatlon method adopted. Generally, the pulverization temperature
ranges from 0 to 200C, preferably 20 to 100C, and the pulverization
time fro~ 0.5 to 50 hours, prefera~ly l to 30 hours. Of course;
the co-pulverizing cperation should be performed in an lnert gas
atmosphere, and the moisture should be kept to a m~n~m~
Partlcularly preferred in the present invention is`
the method wherein the components ~ 4~ are reacted in solution,
or the method wherein the components ~1)-C3) are reacted ln solution
and the reaction product is co-pulverized and reacted with the component
~4).
As to the ratio of the components Cl) and C2) to be
' used, both too small and too large amounts of the compound of
the general formula MeCOR ~ Xz_ptend to lower the polymerization
activity. l~e range of 1/0.001 to 1/20, preEerably 1/0.01 to
ltl and most preferably l/O.OS to 1/0.5, in terms o Mg/Me mole
ratio, ls desirable for preparing a high activity catalyst.
The ratio of the componellts ~1) and (3) to be used
ls such that the amount of component (3) i3 in the range of 0.i
to 300 g., preferably 0.5 to 200 g., per 100 g. of component (1).
The amount of the halogen containing titanium compound
i8. most preferably adjusted so that the amount of titanium contained
ln the solid catalyst component is in the range of 0.5 to 20%
by weight. The range of 1 to 10% by weight is especially desirable
for obtaining a well-balanced activity per titanium
and that per solid.
In the preparation of the solid catalyst component,
it is also preferable to use as component (5) a member or members
selected from the group consisting of organic halides, halogenating
agents, phosphoric esters, electron donor~ and polycyclic aromatic
compounds, in addition to the components (l)-C4). ~le react-lon
me~hod in the case of u6ing the component ~5~ is not specially
limited. Preferably employed is the method whereln the components
(1)-(5~ are reacted ~n 901ution~ or the method wherein the components
(1), ~2) 3 (3~ and ~5) are reacted in solution and the reac~ion
product ~e co-pulveri~ed with the component C4~.
In the ca~e of using the component C5~, its àmount
range3 from 0.01 to 5 ~ole3~ preferabiy 0.~5 to 2 moles, per mole
of the component Cl~.
Organic hallde~ which may be used as component ~5)
are saturated or unsaturated aliphatic hydrocarbons and aromatlc
hydrocarbons which are partially substituted by halogen. The
, halogen may be any of fluor~ne, chlorine, bromine and iodi~e.
Examples of such organic halides include methylene
chloride, chloroform9 carbon tetrachloride, b~omochloromethane,
dichlorodifluoromethane, l-bromo-2-chloroethane, chloroethane,
1,2-dibromo-l,l-dichloroethane, l,l-dlchloroethane, 1,2-
dlchloroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane,
hexachloroethane, pentachloroethane, 1,1,1,2-tetrachloroethane,
1,192,2-tetrachloroethane7 l,l,l-trichloroethane, 1,1,2-
trichloroethane, l-chloropropane, 2-chloropropane, 1,2-dichloropropane,
1,3-dichloropropane~ 2,2-dichlo~opropane, 1,1,1,2,2,3,3-
heptachloropropane, 191,2,2~3,3-hexachloropropane, octachloropropane~
1~1,2-trichloropropane, ~-chlorobutane, 2-chlorobutane, 1 chloro-2-
methylpropane~ 2-chloro-2-methylpropane, 1,2-dichlorobutane,
1,3-d~chlorobutane, 194-dichlorobutane, 2,2-dic~lorobutane,
1 chloropentane, l-chlorohe~ane, l-chloroheptane, l-chlorooctane,
l-~hlorononane~ l-chlorodecane, Ylnyl chloride, l,l-dichloroethylene9
1,2-dichloroethylene, tetrachloroethylene, 3-chloro-1-propene,
1~
~33~
1,3-dichloroprope~e, chloroprenej oleyl chlorlde, chlorobenzene9
chloronaphthalenej benzyl chloride, benzylldene chloride,
chloroethylbenzene, styrene dichlorlde, and ~-chlorocumeneO
Examples of halogenating agents which may be used
as component ~5? include non-metal halides such as sulfur chloride,
PC13, PC15 and SiC14, and non-metal oxyhalides such as POC13,
Cl:)C12, NOC12, SOC12 and S02C12.
Examples of electron donors ~7hich may be use~ as
component ~5) include alcohols, ethera, ketones, aldehydes, organic
aclds, org~nlc acld esters~ acld halides, acid amides, amines
and nitriles.
As alcohols, there may be used, for example, alcohols
havlin~ 1 to 18 carbon atoms such as ~ethyl alcohol, ethyl alcohol,
~ n-propyl alcohol, lsopropyl alcohol, allyl alcohol, n-butyl alcohol,
isob~tyl alcohol, sec~butyl alcohol, t-butyl alcohol, n-amyl alcohol,
n-hexyl alcohol, cyclohexyl alcohol, decyl alcohol, lauryl alcohol,
myristyl alcohol, cetyl alcohol, ~tearyl alcohol, oleyl alcohol,
benzyl alcohol, naphthyl alcohol, phenol, and cresol.
As ethersl there may be used, Eor example, ethers having
2 to 20 carbon atoms auch as dimethyl ether, diethyl ether, dibutyl
ether, isoamyl ether~ an-lsole9 phenetole, diphenyl ether, phenylallyl
ether3 and benzofuran.
AB ketones3 there may be used, for example, those
- having 3 to 18 carbon atoms such as acetonea methyl ethyl ketone,
methyl lsobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone~
and diphenyl ketone.
As aldehyde$, there may be used, for example, those
having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde,
octylaldehyde, benzaldehyde, and naphthaldehyde.
As organ~c acids~ there may be used, for exan!ple~ tho~e
having 1 to 2ll carbon atoms such as formic, acetic, propionic,
butyric, valer~c, pivalic? caproic, caprylic, stearic, oxalic,
ma]onic, succlnic, adiplc, methacrylic, benzoic, toluic, anlslc,
oleic, l~noleic and linolenic acids.
As organlc acid esters, there may be used, for example,
those having 2 to 30 carbon atoms such as methyl formate, methyl
acetate, ethyl acetate, propyl acetate, octyl acetate, ethyl propionate,
methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate,
ethyl benzoate, propyl benzoate, octyl benzoate, phenyl benzoate,
10 benzyl ben~oate, butyl p-ethoxybenzoate, methyl ~ toluylate,
ethyl p-toluylate, ethyl p-ethylbenzoate, methyl
salicylate, phenyl salicylate, methyl naphthoate, ethyl
naphthoate, and ethyl anisate.
As acid halldes, there may be used, Eor exarnple, those
15 havin~ 2 to 15 carbon atoms such as acetyl chloride, ben70yl chloride,
toluoyl chloride; and anisoyl chloride.
As acid amides, there may be used, for examyle, acetamide,
benzamide and toluamide.
As amines; there may be used, for example, methylamine,
ethylamine, diethylamine~ tributylamine, piperidine, tribenzylamine,
aniline, pyridincl plcoline, and tetramethylenedlamine.
As nitriles, there may be used, for e~ample, acetonitrlle,
~enzonitrile and tolunitrile.
Phosphoric esters which may be used as component C5)
OR
are those represented by the generaI formula P - OR whereln R,
o OR
which may be alike or different, is a hydrocarbon radical having
1 to 24 carbon atom~. Examples of such compounds include triethyl
phosphate, tri-n-butyl pho~phate9 triphenyl phosphate, tribenzyl
- 12
~33~
phosphate, trioctyl phosphate9 tricresyl phos2hate, tritolyl phospha~e,
trlxylyl phosphatej ~nd diphenyl~ylenyl phosphate.
E~amples of polycrcl~c aromatic compoundx which mc~y
be used as component (5) lnclude naphthaleney phenanthrene, triphenylene,
S chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene,
tetraphene, 1,2,3,4-dibenzanthracene, pentaphene, 394-benzopentaphene,
tetracene, 1,2-ben~otetracene, hexaphene, heptaphene, diphenyl,
fluorene, biphenylene, perylene, coronene, bisantene, ovàlene,
pyrene, perinaphthene, and halo~en- and alkyl-substituted derivative~
i 10 thereof.
The solid catalyst component thus obtained may be
; supyorted on oxides of Group II-IV metals in the Periodic Table,
and this mode oE use i~ al~o adoptable preferably. In this case,
not only oxides of Group II-IV metals in the Periodic Table each
1 15 alone, but also double oxides of the~e metals, as well as mixt~res
thereoE, are employable. Exatnples of such metal oxlde~ :Lnclude
MgO CaO ZnO, ~aO, SiO2, SnO2, A1203, MgO ~1203, 2 2 3
MgO-SiO2, MgO-CaO-A1203, and A1203 CaO, with S102, A1203,
SiO2-Al~03 and MgO-A1203 belng particularly preferred.
The method for supporting the solld catcalyst component
on the oxide of a Group II-IV metal in the Periodlc Table is not
specially limited. As a preferable e~ample~ there may be adopted
method wherein the components ~1~, C2)l (3) and also the component
(5~ ~ required, are reac~ed using an ether compound as a solvent
~n the presence of the metal oxlde, then the liquid phase portion
ls removed by washing, dry up or other suitable means and thereater
the component (4) is added and reacted together wi~h a hydrocarbon
such as he~ane to obtain a supported solid catalys~ component.
As organometalllc compound used in the pre~ent inventlon,
there may be mentloned organometallic compounds of Group I-IV metals
_ 13
33~
in the Perlodic Table which are known as a component of Ziegler
type catalysts, with organoalumlnum compounds and organozinc
compounds being particularly preferred. E~amples of such compou~ds
include organoaluminum compounds of the general formulae R3Al,
R2AlX, RAlX2~ R2~10R, RAl~OR?X and R3Al~X3 whereln R, which may
be allke or,different~ is an alkyl, aryl or aralkyl group having
1 to 24 carbon atoms and X is a halogen atom, and organozinc compounds
o~ the general formula R2 & wherein R, which may be alike or
different, is an alkyl group having 1 to 24 carbon atoms, such
as triethylaluminum, triisopropylaluminum, triisobutylaluminum,
tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum,
trioctylaluminum, diethylaluminum chloride, diisopropylaluminum
chloride, ethylaluminum sesquichlorlde, d:Lethylzlnc, and mixtures
~ thereof. Together with these organometalllc compounds there may
be used organocarboxylic acid ester~ such as ethyl benæoate, ethyl
o- or p-toluylate and ethyl p-anisate. The amount of the organometallic
compound to be u3ed ls not specially limited. Usually, it may
range from 0.1 to 1,000 moles per mole of the titanium compound.
The olefin polymerization using the catalys~ of the
present invention may be carried out in the form of slurry polymerization,
solution polymeriæation or vapor phase polymerizatlon, wl~h vapor
phase polymerizatlon bein8 partlcularly suitable. The polymerl~ation
r~act~on is performed in the same way as in the conventional olefin
polymerl~ation reactlon using a Ziegler type catalyst; that is,
the reactlon ls conducted in a substantlally oxygen- and water-free
condition and in the presence OT absence of an inert hydrocarbon.
Olefin polymerizing condltions involve temperatures in the range
of 20 to 12GC, preferably 50 to 100C , and pressures ranging
30 from atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kgjcm .
_ 14
~33~
/
Ad~ustment of the molecular ~eight can be made to some extent
by changin~ polymeriza~ion condltions ~uc~ as the polymerization
temperature and the catalyst mole ratio, but the addition of hydrogen
into the polymerization system is more effective for thls purpo~e.
Of course~ uslng the catalyst of the present lnvent~on, there
can be performedg without any trouble, ~wo or more multi-~tage
polymerization reactions involvlng different polymerizatlon conditions
8UC~ as different hydrogen concentrations and different polymerization
temperatures.
The process of the present lnvention is applicable ts
the polymerlzation of all olefins that can be polymer~zed wl~h a
Ziegler type catalyst~ wlth ~-olæfins having 2 to 12 carbon atoms
being particularly preferred. For example~ it iB suitable to
the hom~polymeri~ation oE ~-olefin~ such as ethylene, propylene,
butene-l, hexene-l, 4-methylpentene-l and octene-l, the copolymer-lza-
tion of ethylene and propylene, ethylene and butene-l, ethylene
and hexena 1, ethylene and 4-methylpen~ene-1, ethylene and octene-l,
and propylene and butene-l, and the copolymerization of ethylene
and other two or more a-olefi~s.
There also may be conduc~ed copolymerlzation wit~
dienes for the purpose of modification of polyolefins. Example~
of diene compounds which may be used in t~s copolymerization
lnclude butadiene, 1,4-hexadiene, ethylidene norbornene and
dicyclopentadiene.
Worklng examples of the present invent~on are given
below to further illu9 trate the invention 9 but it 18 to be understood
that the lnvention is not llmited thereto.
_ 15
~a33~
Example 1
(a) Preparation of a Solid Catalyst Component
Into a three-~ecked 500 ml. fiask equipped with a
stirrer were charged 200 ~1. of ~thanol, 20 g. of ethoxymagnesium
chloride CMg/Cl mole ratlo - 0.81~ obtained by treating magnesium
diethoxide,wi~l HCl, 15 g. of alumilium tri-sec-butoxide and 20 g.
of tetraethoxysllane, and reaction was allowed to take place for
3 hours under reflux of ethanol~ Therea~ter, the ethanol was
dried off, then 200 ml of hexane and 5 ml. of titanium tetrachlorlde
were added and reacted for 2 hours under reflux of hexane. Thereaf~er,
the supernatant liqù~d was removed to obtain a sol~d catalyst component,
which was washed with hexane three times. The solid catalyst
component proved to contain 25 mg. of tltanium per gram thereof.
, ~b) Polymerization
A stainles~ ~teel autoclave was used as a vapor phase
polymeri2ation apparatus, and a loop wa~ formed by means of a
blower, a 1OW controller and a dry cyclone. The temperature of
the autoclave wa~ ad~usted ky passing a warm water through a ~acket.
Into the autoclave ad~usted to 8QGC were fed the solid
catalyst component prepared above and triethylaluminum at thè
rates of 50 mg/hr and 5 mmol/hr~ respectlvely9 and ethylene, butene-l
and hydrogen gases were introduced while ad~usting tD give a
butene-l/ethylene ~ole ratio of 0.27 in the vapor phase within
the autoclave and a ~Iydrogen concentration of 15% of the total
pressure. Polymerlzatlon was carried out while recycling the
intra-system ga~es by the blower to maintain the total pressure
at 10 k~/cm G. m e ethylene copolymer thus prepared had a bulk
denslty of 0.289 a melt lndex (MI) of 1.2 and a density of 0.9203.
The catalys~ actiYlty wa~ 254,000g.copolymer/g.Ti.
After a continuous ope~ation for 10 hours, the autoclave
1~
~3;~
wa~ opened and its interlor was checked. As a re~ult, the inner
wall o the autoclave and the ~tirrer prov~dr to be clean with
no polymer adheslon thereto~
l~/MI2.16) represented in terms
of the ratio of a melt index M¢10 of the copolymer determined at
a load of 10 kgo to a melt index MI2 16 thereof determined at a
load of 2.16 kg. both at 190C accordlng to the method defined by
AsTM-Dl238-65T was Y.2 and thus the molecular welght distribution
of the copolymer was very narro~.
A film was formed from the copolymer and extracted in boiling
hexane for 10 hour~; as n result, it~ hexane extraction was 1.3
wt~% and thus very small.
Comparative Example 1
A solid catalyst component was prepared in the same
way as ~n Example 1 except that tetraethoxysilane was not added~
It contained 21 mg. of titanium per gram thereof.
A continuous vapor pha~e polymerization of ethylene and
butene-l was carrled out tn the same manner as ln Example 1 except
that the solid cataly~t component ~ust prepared above was fed at
the rate of 50 ~g/hr. The ethylene copolymer thus prepared had
a bulk density of 0.25, a density of 0.9213 and a melt index of
1.2. The catalyst activity was 186,000g.copolymer/g.Tl.
The ~.R. value of the copolymer was 8.2. A film waR
formed from the copoly~er and extracted in boiling hexane for 10
hours; as a resul~, its hexane extraction proved to be 4.2 wt.%.
Example 2
(a) Preparation of a Solid Cataly~t Component
A solid cat~lyst component was prepared in the same
_ 17
qJ~DqldloJ b
way as in Example 1 except that 15 gO oE boron triethoxlde was used
in place of 15 g. of aluminum trl-sec-butoxide. It contained 27
mg. of titanium per gram thereof.
(b) Polymerizatlon
A rontinuous vapor phase polymerization of ethylene
and butene-l was carried out in the same way as in Example 1 except
that the 301id cataiys~ component prepared above was fed at the
rate of 50 mg/hr. The ethylene copolymer thus prepared had a bulk
density of 0.27, a density of 0.9195 and a melt index of 1.1.
The catalyst actlvity was 223,0QOg.copolymer/g.Ti and thus very
high.
After a continuous operation Eor 10 hours, the autoclave
was opened and i~B interior wa~ checked. As a result, the inner
wall of the autoclave and the stirrer proved to be clean with no
polymer adhesion thereto.
Ihe F.R. value of the copolymer was 7.3. A fllm was
~ormed from the ~opoly~er and extracted ln boiling hexane for 10
hours; a~ a result, lt~ hexane e~tractlon was 1.5 wt.~ and thua
very small.
Example 3
~a~ Preparation of a Solid Catalyst Component
A solid cataly~ component was prepared in the same
way as ln ~xample 1 except that 20 g. of a pentamer of tetraethoxysilane
was used in place of 20 g. of tetraethoxysllane. It contained 21 mg.
of titanium per gram thereof.
~b) ~olymerization
A continuous vapor phase polymerization of ethylene
and butene-l was carrled out in the same manner as in ~xample 1
except that the solid cataly6t component Just prepared above was
- 18
~ed at the rate of 5~ mgihr. The e~hylene copolymer thus prepared
had a bulk denslt~ of 0.34, a densi~y of 0.9200 and a melt index
of 1Ø The catalyst activity was 332,000g.copolymer/g.Ti and
thus ~ery high.
S After a con~inuous operatlon or 10 hours~ the autoclave
was opened and its interior was checked. ~s a result, the inner
wall of the autoclave and the stirrer proved to be clean with
no polymer adhesion thereto.
The T.R. value o~ the copolymer wa~ 7.2. A film was
formed from the copolymer and extracted in boillng hexane for lO
.
hours; as a result, it8 hexane extraction was 1 3 wt.~ and thus
very small.
Example 4
(a) Preparation of a Solid Catalyst Component
Into a three~necked 500 1~ , Elask equipped with a
~tirrer were charged 200 ml. of n-hexane, 20 g. of n~butylmagnesiu~
chlorlde, 15 g. of aluminum triethoxide and 20 g. of trietho~y -,no-
chloro~ilane, and reaction wa~ allowed to take place for 3 hour~
under reflux o hexane. Thereafter, the supernatant liquld wa~
remo~ed and the reaction product was dried up to obtaln a white
solid su~stance.
Then9 10 g. of the solid substance ~ust prepared above
and 1.2 g. of titanlu~ te~rachloride were placed in a ~tainless
steel pot having a content volume of 400 ml~ and containing 25
stainless steel balls each 1/2 inch in diameter, and ball-milled
for 16 hour~ at room temperature ln a nitrogen atmosphere, to
obtain B solld catalyst component which contained 27 mg. of tltanlum
per gram thereof.
(b~ Polymerizat~on
A continuou~ vapor phase polymerizatlon of ethylene
and butene-l was ~arried out in the same way as in Example 1 except
that the solid catalyst component ~ust prepared above was fed
at the rate of 50 mg/hr. The ethylene copolymer thus prepared
had a bulk density of 0.31, a density of 0.9205 and a melt ~ndex
of 1.1. I~e catalyst activity waa 248,000g.copolymer/g.Ti ~nd
thus very hlgh.
After a continuous operation for 10 hours, the autoclave
wa~ opened and its interior wa~ checked. A~ a result, the inner
wall of the autoclave and the stirrer proved to be clean wlth
no polymer adhesion thereto.
The F.R. value of the copolymer was 7.5. A f-llm was
formed from the copolymer and extracted in boiling hexane for
10 hours; as a result, its hexane extraction was 1.4 wt.% and
thus very small.
~xample 5
A stainless steel 2 liter autoclave equipped w~th an
induction stirrer was purged with aitrogen and then charged with
1,000 ml. o~ hexane, then 1 mmol of triethylaluminum and 20 mg.
of the solid powder obtained ~n Example 1 were added and the
temperature was rai~ed to 90C with stirringO The system,
was pressuriæed to 2 kg/cm G due to the vapor pressure of hexane.
Hydrogen was introduced ~mtll the total pressure was 4.8 kg/cm2-G,
then ethylene ~as introduced 80 as to maintaln the total pres~ure
at 10 kgJcm2 G~ and polymerlzatlon was allowed to take place for
1 hour. Thereafter, the polymer alurry was transferred into a
beaker and he~ane removed under reduced pressure to yield 183 g.
of a wh~te polyethylene having a melt index of 1.3 and a bulk
_ 20 ~
3~
denslty of 0.33. The catalyst activity was 709400g.polyethylene/g.
Tl-hr C2HL,~ pressure, 1,760g.polymer/g.solid-hr-C2H,, pressure.
The F.R. value of the polyetl:lylene was 8.2 and ~hus
the molecular we~ght dlstribution was very narrow. It~ he~ane
extraction wa~ 0.15 wt.% and thus very smal1.
21
