Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
12~;8~
P~OCE5S FO~ PREPARING POLYOLEFINS
B~CKG~OUND OF Tll~ INV~NTION
The present lnventlon relates to a process
for preparing polyolefins us'lng a novel polymerization
cata1yst.
Heretoforej in this technical field there has
been known from Japanese Patent Publication No.12105/1964
a catalyst whlch compr~ses a magnesium hal~de and a transi
tlon metal compound such as a tl-tanium compound supported
1~ thereon, and also known from Belgian Patent No.742,112
a catalyst ob~ained by co-pulverizing a magne8iu~ halide
and tltanium tetrachloride.
However, when viewed from the standpoint that
as high a catalytlc activity as possible is desired in
the production of,polyolefins, the process disclosed
in the Japanese Patent Pu~lication 12105/1964 is still
' unsatisfactory ln po~nt of polymerization activi-ty, and
the process of the Belgiam Patent. 742,112 gives a fairly
lmproved polymerizat~on activity, bu-t s-till leaves room
for lmprovement.
I'n West German Patent No.2137872, the amount
o a magnes~um halide used is substantially decreased
by the co-puIverizat~on of the,magnesium halide with
titanium tetrachlor~de'and alumina. But a remarkable
lncrease ln act.ivl~y per sol~d which can be regarded
as the guidetine for productivity is not recognized,
thus leading to a des~re for catalyst of, higher activity.
:~L2~
In the preparation of polyolefins, moreover,
it is desirable from the aspects of produc-tivity and
slurry handling -that the bulk density oE the resultan-t
polymer be as hlgh as posslble. When viewed from this
standpoint, the process disclosed in the foregoing
Japanese patent publication 12105/1964 affords polymers
low in bulk densi-ty and is not satisfactory in point
of polymerization activity, and the process of the Belgian
patent 742,112 also disadvantageous in that the bulk
density of the resuItant polymer is low, although it
affords a high polymerization activity. Thus, in both
processes, a further improvemen-t is desired.
SUMMARY OF THE INVENTION
It is an object of the present invention to
remedy the above-mentioned drawbacks of the prior art.
It is another object of the present invention
to provide a process for preparing a novel polymerization
catalyst which exhibits a high polymerization activity,
which is capable of affording a polymer of high bulk
density in high yield and which permits an extremely
easy execution of a continuous polymerization, as well
as a process ~or homo~ or copolymerizing olefins in the
presence of the said polymerization catalyst.
The present invention is concerned with a
process for preparlng a polyolefin, characterized by
polymerizing at least one olefin in the presence of a
catalyst, which catalyst comprises either the following
combination ~1) or (2~:
840~
(1) ~I~ a solid substance obtained by the reaction
of
(i) a magnesium halide,
(ii) a compound represented by the general
formula Me(OR~nXz n wherein Me is an element
of Groups I through VIII of the Periodic
T~ble, provided silicon, titanium and vanadium
are excluded, R is a hydrocarbon radical
having 1 to 24 carbon atoms, X is a halogen
atom, z is the valence of Me and n is
O ~ n ~ z,
(iii) a compound represen$ed by the general
mSi(oR )nX4_m_n wherein R' and R"
are each a hydrocarbon radical having 1 to
24 carbon atoms, X is a halogen atom, m and
n are O ~ m ~ 4 and O C n c 4, provided
O ~ m ~ n ~ 4, and
(iv) a titanium compound and/or a vanadium
compound;
II a compound represented by the genera1 formula
Rl . .
R3-~ S ~ O~qR wherein Rl, R2 and R3 are each
R
a hydrocarbon radical having 1 to 24 carbon atoms,
alkoxy, hydrogen or halogen, R4 is a hydrocarbon
radical having~l to.24 carbon atoms and q is
1 c q ~.30 and
~8~
tIII~ an organometallic compound.
~2~ [I~ a solld substance obtained by -the reac-tion of
(i) a magnesium hal.ide,
(li) a compound represented by the yeneral Eormula
Me(OR)nXz n wherein Me is an element of Groups
I through VIII of the Periodic Table, provided
silicon, titanium and vanadium are excluded,
R is a hydrocarbon radical having 1 to 24 carbon
. atoms, X is a halogen atom, z is the valence of
10. Me and n is 0.< n c z,
liii) a compound represented ky the general ~ormula
R'mSi~oR")nX4_m_n wherein R' and R" are each a
hydrocarbon radical having 1 to 24 carbon atoms,
X is a halogen atom, m and n are O ~ m C 4 and
0 < n ~ 4, provided O < m + n c 4, and
(iv) a titanium compound and/or a vanadium
compound; and
rII] a product obtained by the reaction of
(v) a compound represented by the general ormula
Rl
R3 ~ Si - O ~qR4 wherein Rl, R2 and R3 are
R2
each a hydrocarbon radical having 1 to 24 carbon
atoms, alkoxy, hydrogen or halogen, R4 is a
hydrocarbon radlcal having 1 to 24 carbon atoms
and q i.s 1-~ q -~ 30~.and
Ivi) an organometallic compound.
~2~
The catalyst of the present invention exhihits
a very high polymerization activity, resulting in a
decreased partial pressure of monomer during polymeriza-
tion~ afEords a polymer having a high bulk ~ensity, thus
permitting improvement of produc-tivity, remains in -the
resultant polymer after polymerization in an extremely
small quantity~to the extent that the polyolefin manufac-
turing process can dispense with the catalyst removing
steps, resulting in a more simplified step for polymer
treatment, and thus permits an extremely econQmical
production of polyolefins as a whole.
According to the process of the present
invention, the amount of polymer produced per unit
polymerization reaction vessel is large because of a
high buIk density of the poly~er.
Further, when viewed fxom the standpoint of
particle size of the resulting polymer, the proportion
of coarse particle~ and fine particles below 501u is
low despite o a high bulk density of the polymer, thus
20: permitting an sasy execution of a continuous polymeriza-
tion reaction and an easy handling of polymer particles,
for example, in centrifugal separation in the polymer
treating step or in transportation of the powdered
polymer.
As a `further advantage of the present invention,
mention may be made of an outstanding effect on economy
and on productivity. More particuIarly, polyolefins
prepared by using the catalyst of the present invention
have a high bulk density as previously noted, and lesshydrogen concentration is required -than in -the prior art
process Eor obtalnlng a polymer having a desired me:lt
lndex, thus resulting in -that -the total pressure can
be maintained at a relatively small level throughout the
polymerizatlon.
More,over, in the polymerization of olefin using
the catalyst of the present invention, the decrease of the
olefin absorbing rate is not accelerated with the lapse of
time, so the polymerization can be continued for a long
time in a small quantity of the catalyst.
Additionally, polymers prepared by using the
catalyst of the present invention are extremely narrow in
molecular weight distribution and their hexane extraction
15' ,is very small, that is, the by-production of low polymers
is mi,nimized. Consequently, it is possible to obtain
products of good quality, for example, a product superior
in anti-blocking property in film grade.
Thus, the catalyst o the present invention is
a novel catàlyst whlch has many such characteristic
features and which has remedied the above-mentioned
drawbacks of the prior art. And it is quite surprising
that the ~oregoing features can easily be attained by
using the catalyst of the present invention.
DESCRIPTION OP'PREFERRED'EM~ODIMENTS
As the magnesium ha'ide used in the present
invention there is'used a substantially anhydrous one~
8~
examples of which include'magnesium fluoride, magnesium
chloride, maynesium bromide and magneslum iodide, with
magnesium chloride being par-ticularly preferred.
As examples of the compound represented by the
general formula Me(OR)nXz n used in the presen-t invention
wherein Me, z, n and R are as previously defined, men-tion
may be made of such various compounds as ~aOR, Mg(OR)2,
Mg(OR)X, Ca(OR)2, Zn(OR)2,, Zn(OR)X, Cd(OR)2, Al(OR)3,
Al(OR)2X, BIOR)3, B(OR)2X, Ga(OR)3, Ge(OR~4, Sn(OR)4,
P~OR)3, Cr(OR)2, Mn(OR)2, Fe(OK)2, Fe~OR)3, Co(OR)2 and
Ni~OR)2, and as more preferable concrete examples there
may be mentioned 'such compounds as NaOC2H5, NaOC4Hg,
3 2 g 2 5)2' Mg50C3H532~ Ca(OC2H5)2' ~n~oC H )
Zn(OC H5)Cl, Al(OCH3)3, Al(OC2H5)3, 2 5 2
Al(OC3H7)3, Al(OC4Hg)4, Al(OC6H5)3, B(OC~H5)3, B~OC2H5)2Cl,
( 2H5)3, P(OC6H5)3 and Fe(OC4Hg)3.
Compounds representedby the general formulae
Mg(R)nX2~n' A150R)nX3-n and B(OR)nX3_n are partiCularly
preferred'in the present invention. And as the substitu-
ent R, alkyl groups having 1 to 4 carbon atoms and phenylgroup are especially preferred.
To exemplify.the compound represented by, the
general formula R'mSi(oR")nX4 m n used in the present
invention wherein R', R", m and n are as previously
defined~ mention may be made of the ollowing:
monomethyltrimethoxysil~ne, ~onomethyltriethoxysilane,
monomethyltri-n-~utoxysilane, monomethyltri-sec-
butoxysilane, monomethyltriisopropoxysllane, monomethyl-
tripentoxysilane, monomethyltrioctoxysilane,
~L2¢;il8~
monomethyltristearoxysilane/ monomethyltriphenoxysilarle,
dimethyldime-thoxysilane, dime-thyldie-thoxysilane/ dimethyl-
diisopropoxysilane/ dimethyldiphenoxysilane/ trime-thylmono-
ethoxysilane, trimethylmonoethoxysilane, trimethylmonoiso-
propoxysilane, trimethylmonophenoxysilane, monomethyldi-
methoxymonochlorosilane, monomethyldietho~ymonochlorosilane,
monomethylmonoethoxydichlorosilane, monomethyldiethoxymono-
chlorosilane, monomethyldiethoxymonobromosilane, monomethyl-
diphenoxymonochlorosilane, aimethylmonoethoxymonochloro-
silane, monoethyltrimethoxysilane/ monoethyltriethoxysilanemonoethyltriisopropoxysilane, monoethyltriphenoxysilane/
diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-
phenoxysilane, triethylmonomethoxysilane, triethylmono-
ethoxysilane, triethylmonophenoxysilane, monoethyldimethoxy-
monochlorosilane, monoethyldiethoxymonochlorosilane,monoethyldiphenoxymonochlorosilane, monoisopropyltri-
methoxysilane, mono-n-butyltrimethoxysilane, mono-n-
butyltriethoxysilane, mono-sec-butyltriethoxysilane,
monophenyltriethoxysilane, diphenyldiethoxysilane,
~0 diphenylmonoethoxymonochlorosilane, monomethoxytrichloro-
silane, monoethoxytrichlorosilane, monoisopropoxytrichloro-
silane, mono-n-butox~trichlorosilane, monopentoxytrichloro-
silane, monooctoxytrichlorosilane, monos-tearoxytrichloro-
silane r monophenoxytrichlorosilane, mono p-
methylphenoxytrichlorosilane, di~ethoxydichlorosllane,diethoxydichlorosilane,~diisopr~poxydichlorosilane,
triethoxymonochlorosilane, triisopropoxymonochlorosilane,
tri-n-butoxymonochloxosilane, tri-sec-butoxymonochloro-
silane, tetraethoxysilane and tetraisopropbxysilane.
:~Z~8~
As examples of the titanium compound and/or
vanadium compound used in the present i.nvention, -there may
be mentioned halides, alkoxyhalides, alkoxides and
halogenated oxides of titanium and/or vanadium.
Suitable examples of titanium compounds are tetravalent
and trivalent titanium compounds. As tetravalent ti-tanium
compounds are preferred those represented by the general
formula Ti(OR)pX4 p wherein R is an alkyl, aryl or aralkyl
group having 1 to 24 carbon atoms~ X is a halogen atom and
p i.s 0 ~ p ~ 4, such as, ~or example, titanium tetrachloride,
titanium tetrabromide, titanium tetraiodide, monomethoxy-
trichlorotitanium, dimethoxydichlorotitanium, trimethoxy
monochlorotitanium, tetramethoxytitanium, monoethoxytri-
chlorotitanium, diethoxydichlorotitanium~ triethoxymono~
chlorotitanium, tetraethoxytitanium, monoisopropoxytri-
ch~orotitanium, diisopropoxydichlorotitanium, triisopropoxy-
monochlorotitanium~ tetraisopropoxytitanium r
monobutoxytrichlorotitanium, dibutoxydichlorotitaniurn,
monopentoxytrichlorotitanium, monophenoxytrichlorotitanium,
diphenoxydichlorotitanium, triphenoxymonochloro-titanium
and tetraphenoxytitaniu~. To illustrate trivalent
titanium compounds, mention may be made of titanium
trihalides obtained by reducing titanium tetrahalides
such as titanium tetrachloride and titanium tetrabromide
with hydrogen, aluminum, titanium-or an organometallic
compound of a metal ~f Gro.ups I through III in the
Periodic Table, as well as trivalent titanium compounds
obtained by reducing tetravalent alkoxytitanium halides
g
8400
of the general formula ~i(OR)rX4 r with an organometallic
compound of a metal of Groups I through III in -the Periodic
Table, in which formula R is an alkyl, aryl or aralkyl
group having 1 to 24 caxbon atoms and r is 0 < r ~ 4.
~s examples of vanadium compounds, there are mentioned
tetravalent vanadium compounds such as vanadium tetra-
chloride~ vanadium tetrabromide, vanadium tetraiodide
and tetraethoxyvanadium; pentavalent vanadium compounds
such as vanadium oxytrichloride, ethoxydichlorovanadyl,
triethoxyvanadyl and tributoxyvanadyl; and trivalent
vanadium compounds such as vanadium trichloride and
vanadium triethoxide.
Tetravalent titanium compounds are most preEerred
in the present invention.
In order to ma~e the present lnvention more
effective, both thè titanium compound and the vanadium
compound are often used in combination~ In this case,
it is preferable that the V/Ti molar ratio be in the
range of 2/1 to 0.01/1.
As examples of the compound of the general
R~
formula R3-t-Si - O ~qR4 used in the present invention,
R
mention may be made of the compound of the general formula
R'mSi(OR")nX4 m n which is used in the catalyst component
~I~, as well as chain-li-ke or cyclic polysiloxanes with
~' 1
a recuxring unit represented by -~ Si - O ~- obtained
- 10 R2
~2~ 0~
by condensation of the compounds R'mSi(OR")nX4 m n
The method for ob-taining the component LI~ by
reacting (i) a magnesium halide, (ii) a compound of the
general formula Me(OR)nXz n~ (iii) a compound of the
general formula R'mSi(OR")nX4 m n and (iv) a titanium
compound and/or a vanadium compound, is not specially
limited. For example, these constituents may be contacted
together and thereby reacted under heating at a temperature
ranging from 20 to 400C, preferably 50 to 300C, usually
10: for 5 minutes to 20 hous in the presence or absence of an
inert solvent, or they may be reacted by a co-pulverization
treatment, or may be reacted by a combination of these
methods. The reaction order of the constituents (i) - (iv)
is not specially limited, either.
~s the inert solvent, which is not specially
limited, there may be used hydrocarbon compounds and/or
derivatives thereof which do not inactivate Ziegler type
catalysts. Examples are saturated aliphatic hydrocarbons,
aromatic hydrocarbons and alicyclic hydrocarbons, such as
propane, butane, pentane, hexane, heptane, octanel benzene~
toluene, xylene and cyclohexane, as well as alcohols,
ethers and esters such as ethanol, diethyl ether,tetra-
hydrofuran,~ ethyl acetate and ethyl benzoate.
; In case a co-pulverization treatment is adopted
for the reaction, the apparatus for the co-pulverizat.ion
,_ .
is not specially limited, but usually employed is a ball
mill, a vibration mill, a rod mill or an impact mill.
Conditions such as the pulverizing temperature and time
` -
~2~34(30
can be decided easily by ~hose skilled in -the art according
to how to pulverize. Generally, the pulverizing tempera-ture
ranges from 0 to 200C, preferably 20 to 100C, and
the pulverizing time ranges from'0.5 to 50 hours,
preferably 1 to 30 h'ours. Of course, the co-pulverizing
operation should be preformed in an inert gas atmosphere,
and moisture should be avoided as far as possible.
As to the mixing ra-tio of the magnesium halide
and the compound of the general formula Me(OR)nXz n and
10. a too large amount thereof tend to result in lowering
of the polymerization act~vity~ A desirable range for
the production of a high activity catalyst is from 1/0.001
to 1/2~, preferably 1/0.01.to 1/1 and most preferably
1/0.05 to 1/0.5 in terms of Mg/Me molar ratio.
As to the mixing ratio of the magnesium halide
and the compound of the general formula R'mSi(OR")nX4 m n~
both a too large amount of the compound of the general
m ~OR )nX4_m_n and a too small amount thereof
would not be eEfective. A desirable range is from 1/0.01
to 1/1, preferably l/0~05 to 1/0.5, in terms of Mg/Si molar
ratio.
As to the amount of the titanium compound
and/or vanadium compound, most preferably it is adjusted
so that thè amount of titanium andlox vanad'ium contained
in the catalyst component LI~ is in the range of 0.5
to 20 wt.%. The range of-l to 10 wt.% is especially
desirable for attaining a well-balanced activity per
titanium and/or vanadium and that per solid.
1 ~
~z~v~
As to the amount of the compound represented
~ 1
by the general formula R3-~ Si - O ~qR4 which is used
R2
as the catalyst component ~II] in the present invention,
both too large and too small amounts thereof would not
be effective. Usually, it is used in the -range of 0.1
to 100 moles, preferably 0.3 to 20 moles, per mole of
the titanium compound and/or vanadium compound in the
catalyst component [I~.
It is also preferable in the present invention
that the catalyst component ~I~ thus obtained be supported
on an oxide of a metal of Groups II through IV in the
Periodic Table. As such oxide, there may be used not
only oxides of metals of Groups II through IV in the
same Table but also double oxides thereof; of course,
mixtures thereof are employable. Examples are MgO, CaO,
ZnO BaO, SiO2, SnO2, A12O3, MgO.A12O3, 2 2 3
MgO.SiO2, MgO~CaO.A12O3 and A12O3.CaO, with SiO2, A12O3,
SiO2.Al~O3 and MgO.A12O3 being especially preferred.
The method for supporting the catalys-t component
~I~ on the said metal oxide is not specially limi-ted.
As a preferable example, there may be adop-ted a method
in which the constituents (i),`~ii), (iii~ and (iv) are
allowed to react under heating in an ether compound as
solvent in the presence,of the said metal oxide and then
the liquid phase portion is removed, or a method in which
a product obtained by co-puIverization of the constituents
13
~ 2~
(i3 and (ii) is allowed t~ react` under heating in an e-ther
compound as solvent in the presence of the said metal
oxide, then the liquid phase portion is removed and
thereafter the constituents (iil~ and (iv) are re~ctcd
therewith in an inert solvent under heating.
AS examples of the or~anometallic compound
' used in the present invention, there may be mer~tioned
organometallic c'ompourids of metals of Groups I through
IV in the Periodic Table which are known as a Ziegler
catalyst component. Especial~y preferred are organoaluminum
compounds and organozinc compounds. Concrete examples
are organoaluminum compounds of the general formulae R3Al,
R2AlX, RAlX2, R2AlOR, RAl(oR)x and R3A12X3 wherein Rs,
which may be alike or different, are each an alkyl or
aryl group having 1 to 20 carbon atoms and X is a halogen
atom, and organozinc compounds of the general formula
R2Zn wherein Rs, which may be alike or different, are
each an alkyl grouF having 1 to 20 carbon atoms, such
as triethylaluminum, triisopropylaluminum, triisobutyl
20: aluminum, tri~sec-bu~ylaluminum, tri-tert~butylaluminum,
t~ihexylaluminum, trloctyla'luminùm, diethylaluminum
chloride, diisopropyla'luminùm chloride, ethylaluminum
ses~uichloride, diethylæinc, and mixtures thereof.
Together with these organome~allic compounds there may
be used-organic carboxylic'acid'esters such as, for
example, ethyl benzoate,_..eth~l o- or p-toluylate and
ethyl.p-anisate. ~ ""
The amount of the organometallic compound used
is not specially limited, but usually ranges from 0.1
_ 14
34~
to 1,000 moles per mole o~ the titanium compound and/or
vanadium compound.
In the present lnvention, moreover, the compound
1 1
of the genera]. formula R3-~ Si - O ~qR4 may be reac-ted
R
wi~h the above-exemplified organometallic compound and
the product thereby ob~ained may be used. In this case,
the reaction ratio is in the range of 1 : 500'to 1 : 1,
preferably 1 : lOO'.to 1 : 2, in terms of the compound
of,the said general formula : the organometallic compound
(molar ratio).
The product obtained by the reaction of the
compound of the general formuIa R3-~ Si - O t-qR4 wi-th
R2
the organometallic compound is .used in an amount ranging
preferably fxom 0.1 : 1 to 100:: 1 and more preferably
0.3': 1 to 20.: 1 in terms of Sl : ~i and/or V ~molar
ratio) with respect to the titanium compound and/or
vanadium compound in the catalyst component ~
The olefIn polymerization using the catalyst
of the present inventlon may be performed in the form
of,s'lurry polymerization, solution poiymerization or
vapor phase polymerization, with the vapor phase polymeri ~
atlon and s'lurry polymerization being particularly suitable.
The polymerization reaction is carried 'out in the same
way as in the conventional olefin polymerization reaction
_ 15
841~0
using a Ziegler type cata~yst. That is, the reac-tion
is performed in a substantially oxygen- and water-free
conditlon and in khe presence or absence of an iner-t
hydrocarbon. olefin polymerlzlng condltions lnvolve
tempera-tures ranging from 2~ to 120C, preferably 50
to 100C, and pressures ranging from atmospheric pressure
to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment
of the molecular weight can be done to some extent by
changing polymerization conditions such as the polymeriza-
tion temperature and the catalyst molar ratio, but the
addition of hydrogen into the polymerization system is
more effective for this purpose. Of course, using the
catalyst of the present invention there can be performed,
without any trouble, two- or more-stage polymerization
reactions involving different polymerization conditions
such as different hydroge~ concentrations and different
polymerization temperatures.
The process of the present invention is applic-
able to the po~ymerization of all olefins that are polymer-
izable with a Ziegler catalyst. Particularly, ~-olefins
f C2 to C12 are preferred. For example, the process
of the invention is suitabie for the homopolymerization
of such ~-olefins as ethylene, propylene, butene-l,
hexene-l r 4-methylpentene-1 and octene-l, the copolymeriza-
tion of ethylene and propylene, ethylene and butene-l,
ethylene and hexene-l, e-thylene and 4-methylpentene-1,
ethylene and octene-l, and propylene and bu-tene-l, as
well as the copolymerization of ethylene and two or more
other ~-olefins.
- 16
1~84~
Copolymerization with dienes for the modific-
ation of polyolefins is also preferable, for example,
w~th bu~adiene, 1,4-hexadierle, ethylidene norbornene
and dlcyclopentadiene.
The Eollowing examples serve -to illustrate
the invention ln more detail, but shouId not be construed
as limiting the invention thereto.
Example 1
(a) Preparation of Solid Catalyst Component [I]
10 g. of a commercially available anhydrous
magnesium chloride, 2~3 g. of aluminum triethoxide,
3.2 g. of tetraethoxysilane and 2.5 g. o titanium
tetrachloride were placed in a stainless steel pot
having a content volume o 400.ml. and containing 25
stainless steel balls each 1/2 inch in diameter, and
ball-milled for 16 hours at room temperature in a nitrogen
atmosphere to obtain a sQlid catalyst component [I]
containing 35 mg. o titanium per gram thereo.
~b) Polymerization
20. As a vapor phase polymerization apparatus there
was used a stainless steel autoclave, and a loop was
formed by using a blower, a flow control device and a
dry cyjclone. The temperature of the autoclave was
adjusted by passing warm water through its jacket.
Into the autoc-l-ave.adjusted to 80~C were fed
the above solid;c.atalyst component tI~, monomethyltri-
ethoxysilane and triethylaluminum at rates o~ 50 mg/hr r
_ 17
o
0.2 mmol/hr and 5 mmol/hr; respectively, and further
fed were butene-l, e-thylene and hydrogen gases while
adjusting the butene-l/ehtylene ratio (molar ratlo) ln
the vapor phase ln the autoclave -to 0.28 and the ilydro~erl
concentration to 17~ of the total pressure, and polymeriza-
tion was carrled out while maintaining the total pressure
at 10 kg/cm .G by circulating the intra-system yases
by means of the blower, to afford an ethylene copolymer
having a bulk density of 0.35, a melt index (MI) of 1.0
and a density of 0.. 9217. Catalyst activity was 294,000~.
copolymer/g.Ti.
After a continuous operation for 10 hours,
the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto.
F.R. value (F.R. = MIlo/MI2 16) represented
in terms of the ratio of a melt index (MIlQ) of the
copolymer determined at a load of 10 kg. to a melt index
(MI2 16) thereof determined at a load of 2.16 kg. both
~0. at 190C according to the method of ASTM-D1238-73 was
6.7 and thus the molecular welght distribution was
extremely narrow.
When a film formed from this copolymer was
extracted in boillng hexane for lO hours, its hexane
2S extraction was 0.5 wt % and thus was very small.
Comparative Example 1
A continuous vapor phase polymerlzation of
- 18
~2C184~3~
ethylene and butene-l was carried out in the same way
as in Example 1 excep-t that the monome-thyl-triethoxysilane
was not added, to afford an ethylene copolymer having
a bulk density of 0.30, a denslty oE 0.9210 and a melt
index of 1.3. Catalytic activity was 310,OOOg.copolymer/g.
Ti.
The F.~R. value of this copolymer was 7.3, and
when a film formed from the copolymer was extracted in
boiling hexane for lO hours, its hexane extractior- was
1.6 wt.%.
Example 2
10 ml. of ethanol, 20 g. o an anhydrous
magnesium chloride and 4.6 g. of triethoxyboron were
charged into a three-necked 300 ml. flask equipped with
a magnetic induction stirxer and allowed to react for
3 hours under reflux. Thereafter, 150 ml. of n-hexane
was added to allow precipitation to take place. Then,
after standing, the supernatant liquid was removed,
followed by vacuum drying at 200C to obtain a white
dry powder.
11 g. of the above white powder, 3~0 g. of
dietho~cydiethylsilane and 2.4 g. of titanium tetrachloride
were placed in a stainless steel pot having a content
volume of 400 ml. and containing 25 stainless steel balls
each 1/2 inch in diamete~, and ball milled for 16 hours
at room temperature in a nitrogen atmosphere, to give
a solid catalyst component ~I~ containing 39 mg. of
titanium per gram thereof~
_ 19
:12~8~0
A continuous vapor phase polymerization of
ethylene and butene-l was carried 'out in -the same way
as in Example 1 excep-t that -the above solid catalyst
componen~ CI~ was E~d at a rate oE 5() nlg/llr, to aEEc)r~
an ethylene copolymer having a bulk density of 0.33,
a density of 0.9220 and a melt index of 1.2. Catalytic
activity was'340,000g.copolymer/g.Ti and thus very high.
After the continuous operation for lO'hours,
the autoclave' was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto.
The F.R. value of this copolymer 6.9, and when
a film formed from the copolymer was extracted in boiling
hexane for lO hours, its hexane extraction was 0 8 wt.%
and thus very small.
Example 3
10 g. of an anhydrous magnesium chloride,
3~1 g. of diethoxymagnesium and 2.9 g. of titan'ium
tetrachloridè were placed in the ball mill pot described
in Example 1, and ball-milled for 5 hours at room
temperature in a nitrogen atmosphere, then'3.8 g. of
. .
methyltriethoxysilane was added, followed by 'further
ball milling for ]2 hours, to give a solid catalyst
component ~I 3 containing '37 mg. of titanium per gram
thereof. ~
A con~in~ous vapor phase polymerization of
ethylene and butene-l was carried 'out in the same way
as in Example 1 eY.cept that the solid catalyst component
_ 20: ~
- ~2~840~
~I~ just prepared above was fed at a rate of 50 mg/hr
and a mixture obtained by reacting -triethylaluminum and
tetraethoxysilane at a ratio of 1 mole triethylaluminum
and 0.1 mole tetraethoxysilane at 85C for 2 hours was
fed at a rate of 5 mmol/hr as aluminum, to afford an
ethylene copolymer having a buIk'density of 0.34, a density
of 0.9215'and a melt index of 0.95. Cataly-tic activity
was 258,OOOg.copolymer/g.Ti and thus very high.
After the continuous operation for 10 hours,
the 'autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto.
The F.R. value of this copolymer was 6.7, and
when a film formed from the copolymer was extracted in
boiling hexane for 10 hours, its hexane extraction was
0.4 wt.~ and thus very small.
Example 4
lO'g. of an anhydrous magnesium chloride and
2.1 g. o trie-thoxyphosphorus (P(OEt)3~ were placed in
the ball mill pot described in Example l and ball-milled
for 3 hours at room temperature in a,nitrogen atmosphere,
. .
then 4.5 g. of tetraisopropoxysilane and 3.0 g. of titanium
tetrachloride were added, followed by further ~all milling
for 16 hours, to obtain a solid catalyst component [I~
25' containing 37 mg. of titanium per gram thereof.
A continuous vapor phase polymerization of
- 21
-` ~L2~ 0
ethylene and butene-l was carried out in -the same way
as in Example 1 except that the solid catalys-t component
[I~ just prepared above was fed at a ra-te of 50 mg/hr
and monophenyltriethyoxysilane was fed at a rate of 0.25
mmolJhr in place of the monomethyltriethoxysilane, to
afford an ethylene copolymer having a bulk density of
0.35, a density of 0.9218 and a melt index of 1.1.
Catalytic activity was 270,000g.copolymer/g.Ti and thus
very high.
After the continuous operation for 10 hours,
the autoclave was opened and its interior was checked.
As a resuIt, the inner wall and the stirrer were clean
with no polymer adhered thereto.
The F.R. value of this copolymer was 7.0 r and
15' when a film formed from the copolymer was extracted in
boiling hexane, its hexane extraction was 0.9 wt.% and
thus very small.
Example 5
lO g. of,an anhydrous magnesium chloride, 3.5
2~ g. of diethoxyzinc and'2.8 g. of diisopropoxydichloro-
titanium were placed in the ball mill pot described in
Example 1, and ball-m,illed ~or 16 hours at room
tempe;rature ih a nitrogen atmosphere, then 3.8 g. of
triethoxymonochlorosilane was added, followed by urther
ball milling for 7 hour~ to obtain a solid catalyst
component ~I~ containing 28 mg. of titanium per gram
thereof.
- 22
~z~
A continuous vapor phase polymerization was
carried out in the same way as in Example 1 except that
the solid catalyst component [IJ jus-t prepared above
was fed at a rate of 50 mg/hr and tetraethoxysilane was
fed at a rate of 0.25 mmol/hr in place of the monomethyl-
ethoxysilane, to afford an ethylene copolymer having
a bulk density of 0.39, a density of 0.9224 and a melt
index of 1.2. Catalytic activity was 330,000g.copolymer/g.
Ti and thus very high.
After the continuous operation for 10 hours,
the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto~
The F.R. value of this copolymer was 7.0, and
when a film formed from the copolymer was extracted in
boiling hexane for 10 hours, its hexane extraction was
0.7 wt.% and thus very small.
Example 6
A stainless steel 2 liter autoclave equipped
with an induction stirrer was purged with nitrogen and
charged with l,OOO ml. of hexane, then 1 mmol of
triethylaluminum, 0.1 mmol of tetraethoxysilane and 10 mg.
o the solid catalyst component [I~ obtained in Example 1
were added and the temperature was raised to 85C with
stirring. The pressur~-of the system was adjusted to
2 kg/cm2.G by introducing nitrogen, then hydrogen was
introduced up to a total pressure of 5 kg/cm2.G and then
_ 23
40~
ethylene introduced up to a total pressure of 10 kg/cm2.G
under which condition a polymerization was star-ted, which
was continued for 1 hour while maintaining the internal
pressure of the autoclave at 10 kglcm2.G. Thereafter,
the polymer slurry was transferred into a beaker and
hexane was removed under reduced pressure to yield 116 g.
of a white polyethylene having a melt index of 1.0, a
density of 0.9631 and a bulk density of 0~38. Ca-talytic
activity was 66,300g.polyethylene/g.Ti.hr-C2H4 pressure,
2,320g.polyethylene/g~solid.hr-C2H4 pressure.
The F.R. value of the polyethylene was 7.5
and the molecular weight distribution thereof was very
narrow as compared with that in Comparative Example 2.
Its hexane extraction was 0.2 wt.%.
Comparative Example 2
Polymerization was carried out for 1 hour in
the same way as in Example 6 except that the tetraethoxy-
silane was not added, to yield 134 g. of a white
polyethylene having a melt index of 1.4, a density o~
0.9637 and a bulk density of 0.35. Catalytic activity
was 76,500g.polyethylene/g.Ti.hr C2H4 pressure,
2,680g.polyethylenetg~solid.hr C2H4 pressure.
; The F.R. value of the polyethylene was 8.3
and its hexane extraction was 0.6 wt.~.
Example 7
The solid catalyst component tI~ obtained in
_ 24
lZ~
Example 1 was fed at a rate o~ 5a mg/hr and a product
obtained by reacting triethylaluminum and monome-thyl-tri-
ethoxysilane at a composition ratio of 5 : 0.22'(molar
ratio) for 2 hours at room temperature was fed a-t a ra-te
of 5 n~lol/hr as aluminum,' under which condi-tion a
continuous vapor phase polymerization of ethylene and
butene-l was carried out in the same manner as in Example
1 to afford an ethylene copolymer having a bulk density
of 0.34, a density of 0.9214 and a melt index o~ 0.93.
Catalytic activity,was 301,000gOcopolymer/g.Ti and thus
very high.
After the continuous operation for 10 hous,
~ the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto.
The F.R. value of this copolymer was ~.8, and
w~en a film formed from the copolymer was extracted in
boiling hexane for lO hours, its hexane extraction was
0.6 wt.~ and thus very small.
Example 8
10 g. of a commercially available anhydrous
magnesium chloride and 4~2 g. of aluminum triethoxide
were placed in, a stainless steel p~t having a content
volume of 400 ml. and containing 25 stainless steel balls
each 1/2 inch in diameter, and ball-milled for 16 hours
at room tempera'ture in a nitrogen atmosphere to obtain
a reaction product. Then r a three-necked flask equipped
- 25
~-- i2~84~
with a s-tirrer and a reflux condenser was purged wi-th
nitrogen and then charged with 2.5 g. of the above
reaction product and 5 g. of SiO2 (~952, a produc-t of
Fuji-Davison) which had been calcined at 600C, then
100 ml. of tetrahydrofuran was added and reaction was
allowed to take place at 60C for 2 hours, followed by
drying at 12~DC under reduced pressure to remove
tetrahydrofuran. Then, 50.ml~ of hexane was added, and
after stirring, 1.1 ml. of ti.tanium tetrachloride was
added and reaction was allowed to take place for 2 hours
under reflux of hexane to obtain a solid powder ~A)
containing 37 mg. of titaniu~i per gram thereof.
The solid powder ~A) thus obtained was added
into 50 ml. of hexane, then 2 ml.. of tetraethoxysilane
was added and reaction was allowed to take place for
2 hours under reflux of hexane to obtain a solid catalyst
component.
A continuous vapor phase polymerization was
carried out in the same way as in Example 1 except that
the solid catalyst component just prepared above was
fed at a rate of 150 mgjhr and a product obtained by
reacting triethylaluminum and tetraethoxysilane at an
Al/Si molar ratio of 20/1 for 1.5 hours at 85C was fed
at a rate of 5:mmol/hr as aluminum, to afford an ethylene
copolymer having a buIk density of 0.38, a density of
0.9?13 and a melt index o 0.9. Catalytic activity was
543,000g.copolymer./g.Ti and thus.very high.
After the continuous operation for lO.hours,
- 26 ~
~Z~840C3
the autoclave was opened and its interior was checked.
As a result, the inner wall and the s-tirrer were clean
wlth no polymer adhered thereto.
The F.R~ value oE thls copolymer wa8 6.9, alld
when a film formed Erom the copolymer was extracted in
boiling hexane for 10 hours, its hexane extraction was
0.8 wt.~ and thus very small.
Example 9
lO g~ of an anhydrous magnesium chloride and
4.2 g. of diethoxymagnesium were placed in the ball mill
pot described in Example 8, and ball-milled for 16 hours
at room temperature in a nitrogen atmosphere to obtain
a reaction product. Then, 2.5 g, of the reaction product
and 5 g. of SiO2 which had been calcined at 600C were
pu~ in the three-necked flask described in Example 8,
then 100 ml. of ~etrahydrofuran was added and reaction
was allowed to takè place at 60C for 2 hours, followed
by drylng at 120C under re`duced pressure to remove
tetrahydrofuran. Then, 50 ml. of hexane was added, and
after stirring, 1.1 ml. of titanium tetrachloride was
added and reaction was allowed to take place for 2 hours
under re1ux of hexane to obtain a solid powder tB) con-
taining 36 mg. of titanium per gram thereof.
The solid powder tB) thus obtained was added
into 50 ml. of hexane, then 2 ml. oE tetraethoxysilane
was added and reaction was allowed to take place for
2 hours under reflux of hexane to obtain a solid catalyst
component.
_ 27
~z~
A continuous vapor phase polymerization was
carrled out in the same manner as in Example 8 excep-t
that the solid catalyst component just prepared above
was fed at a rate of 150 mg~hr, to aEord an ethylene
copolymer having a bulk density of 0.41, a density of
0.9203 and a melt index of 0.8. Catalytic activity was
497,000g.copolymer/g.Ti and thus very high.
After the continuous operation for 10 haurs,
the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean
with no polymer adhered thereto.
The F.R. value of this copolymer was 6.9, and
when a film formed therefrom was extracted in boiling
hexane for lO hours, its hexane extraction was 1.0 wt.%
and thus very small.
- 28
