Note: Descriptions are shown in the official language in which they were submitted.
,6~3
OLEFIN POLY21F,RIZING CATALYST
Background of the Invention
The present invention relates to a novel catalyst for
the polymerization of olefins.
Heretofore, in the technical field of this sort there
have been known various catalysts comprising lnorganic magnesium
solids as carriers such as magnesium halides, magnesium oxide and
magnesium hydroxide, and transition metal compounds supported
thereon such as titanium compounds and vanadium compounds. However,
if olefins are polymerized using these known catalysts, the bulk
density of the resulting polymer is generally low, the average
particle size is relatively small and the particle size distribution
is generally wide, allowing a particulate portion to occupy a
iairly large portion, thus causing a serious drawback in the aspects
of productivity and handling. Moreover, when molding the resulting
polymer, there arise problems such as the generation of dust and
the decrease of efficiency in the molding operation. Therefore,
it has been a keen desire to increase the bulk density and to
decrease a fine particulate portion. Furthermore, for the application
to a processing method wherein a pelletizing step is omitted and
a powdered polymer is directly fed to a processing machine, a
demand for which has recently been increasing, it is considered
that further improvements are necessary.
It is an ob;ect of the present invention to remedy
the above-mentioned drawbacks.
It is another ob~ect of the present invention to provide
a novel polymerization catalyst which can afford olefin polymers
having a hlgh bulk density, a large average particle size, a narrow
particle size distribution and a remarkably small proportion of
~.
-- 1 _
~.~'72~3
a fine particulate portion.
Other ob~ects and advantages of the present invention
will become apparent from the following description.
Summary of the Invention
The aforesaid objects of the present invention can be
attained by using an olefin polymerizing catalyst which comprises
a solid catalyst component and an organometallic compo-md, said
solid catalyst component comprising a substance obtained by contacting
and reacting the following compounds with one another:
(1) a silicon oxide and/or an aluminum oxide,
(2) a magnesium halide,
(3) a compound represented by the general formula
Me(OR)nXz n wherein Me is an element belonging to
I-IV Groups in the Periodic Table, z is the valence
of the element Me, n is O ~ n ~ z, X is a halogen
atom and R is a hydrocarbon radical having 1 to 24
carbon atoms,
(4) a titanium compound and/or a vanadium compound, and
(5) a compound represented by the general formula
R"nSi(OR')mX4_m_n wherein R' and R" are each a
hydrocarbon radical having 1 to 24 carbon atoms,
X is a halogen atom, n is O S n ~ 4 and m is
O ~ m ~ 4, with the limitation that O C m + n ~ 4,
and/or a polysiloxane.
Detailed Description of the Invention
The silicon oxide used in the present invention is
silica or a double oxide of silicon and at least one other metal
of Groups I-VIII in the Periodic Table.
~1'7~i23
The aluminum oxide used in the present invention is
alumina or a double oxide of aluminum and at least one other metal
of Groups I-VIII in the Periodic Table.
As the double oxide of silicon or aluminum and at least
one other metal of Groups I-VIII in the Periodic Table there may
be used various natural and synthetic double oxides, typical of which
are A123 Mg- A1203 Ca- A1203 siO2, A1203 MgO CaO, A1203-MgO-SiO2,
A1203 CU. A123 Fe23- A1203-NiO, and SiO2-MgO. These formulae
are not molecular formulae, representing only compositions. The
structure and components ratio of the double oxides whlch may be
used in the present invention are not specially limited. As a
matter of course, the silicon oxide and/or aluminum oxide used in
the invention may adsorb a small amount of moisture and may contain
small amounts of impurities.
As the magnesium halide used in the present invention
there may be employed substantially anhydrous ones, for example,
magnesium fluoride, magnesium chloride, magnesium bromide and magnesium
iodide with magnesium chloride being particularly preferred.
In the present invention, these magnesium halides may
have been treated with an electron donor such as an alcohol, an
ester, a ketone, a carboxyllc acid, an ether, an amine or a phosphine.
As the compound used in the invention represented by
; the general formula Me(OR)nXz_n wherein Me is an element belonging
to Groups I-IV in the Periodic Table such as Na, Mg, Ca, Zn, Cd,
B or Al, z is the valence of the element Me, n is O ' n ~ z, X
is a halogen atom and R, wh~ch may be alike or different, represents
a hydrocarbon radical having 1 to 20 carbon atoms such as an alkyl,
aryl or aralkyl group, there may be employed various compounds,
; for example, those represented by the following formulae: NaOR,
30 Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR32, Cd(OR)2, B(OR)3, Al(OR)3,
7 ~ ~
Al(OR)2X, Al(OR)X2. More particularly, the following compounds
are preferred: Mg(OC2Hs)2, Mg(OC2~ls)Cl, Al(OCH3)3, Al(OC2Hs)3,
Al(On-C3H7)3, ~l(Oi-C3H7)3, Al(On-C4Hg)3, Al(Osec-C4~1g)3,
Al(Ot-C4H9)3~ Al(OCH3)2Cl, Al(OC2H5)2Cl~ Al(OC2Hs)C12, Al(Oi-C3H7)2Cl,
Al(Oi-C3H7)Cl2-
Examples of the titanium compound and/or vanadium compound
used in the invention include halides, alkoxyhalides, alkoxides
and halogenated oxides of titanium and/or vanadium. Preferred
titanium compounds are tetravalent and trivalent titanium compounds,
lC and preferred tetravalent titanium compounds are those represented
by the general formula Ti(OR)nX4_n wherein R is an alkyl, aryl
or aralkyl group having 1 to 20 carbon atoms, X i5 a halogen atom
and n is 0 ~ n < 4, examples of which are titanium tetrachlolide,
titanium tetrabromide, titanium tetraiodide, monomethoxytrichloro-
titanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium,tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichloro-
titanium, triethoxymonochlorotitanium, tetraethoxytitanium,
monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium,
triisopropoxymonochlorotitanium, tetraisopropoxvtitanium,
monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxy-
trichlorotitanium, monophenoxytrichlorotitanium~ diphenoxydichloro-
titanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium.
Examples of trivalent titanium compounds include titanium
trihalides obtained by reducing titanium tetrahalides such as
titanium tetrachloride and titanium tetrabromide with hydrogen,
aluminum, titanium or an organometallic compound oL a metal of
Groups I-III in the Per:Lodic Table, as well as trivalent titanium
compounds obtained by reducing tetravalent alkoxytitanium halides
of the general formula Ti(OR~mX4_m with an organometallic compound
of a metal of Groups I-III in the Periodic Table, in which formula
7~ 3
R is an alkyl, aryl or aralkyl group having 1 to 20 carbon atoms,
X is a halogen atom and m is 0 < m ~ 4. Examples of the vanadium
compound are tetravalent vanadium compounds such as vanadium
tetrachloride, 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.
To make the present invention more effective, both the
titanium compound and the vanadium compound are often used together,
and in this case the V/Ti mole ratio is preferably in the range
of 2/1 to 0.01/1.
As the compound used in the present invention represented
by the general formula R"nSi(OR')mX~,_m~n wherein R' and R" are each
a hydrocarbon radical such as an alkyl, aryl or aralkyl group having
1 to 24 carbon atoms, X is a halogen atom, n is 0 ~ n ~ 4, m is
0 ~ m c 4, and n and m are in the relation of 0 C n + m c 4, there
may be employed, for example, monomethyltrimethoxysilane,
monomethyltriethoxysilane, monomethyltri.-n-butoxysilane,
: 20 monomethyltri-sec-butoxysilane, monomethyltriisopropoxysilane,
monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyl-
tristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxy-
silane, trimethylmonomethoxysilane, trimethylmonoethoxysilane,
trimethylmonoisopropoxysilane, trimethylmonophenoxysilane,
monomethyldimethoxymonochlorosilane, monomethyldiethoxymonochloro-
silane, monomethylmonoethoxydichlorosilane, monomethyldiethoxy-
monochlorosilane, monomethyldiethoxymonobromosilane,
monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochloro-
silane, monoethyltrimethoxysilane, monoethyltriethoxysilane,
-- 5
fl L7~3
monoethyltriisopropoxysilane, monoethyltriphenoxysilane,diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane,
triethylmonomethoxysilane, triethylmonoethoxysilane, triethyl-
monophenoxysilane, monoethyldimethoxymonochlorosilane,
monoethyldiethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane,
monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane,
mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, mono-
phenyltriethoxysilane, diphenyldiethoxysilane, diphenylmonoethoxy-
monochlorosilane, monomethoxytrichlorosilane, monoethoxytrichloro-
silane, monoisopropoxytrichlorosilane, mono-n-butoxytrichlorosilane,
monopentoxytrichlorosilane, monooctoxytrichlorosilane,
monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono-p-
methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxy-
dichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane,
dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymono-
chlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochloro-
silane, tri-sec-butoxymonochlorosilane, tetraethoxysilane, and
tetraisopropoxysilane.
Chainlike or cyclic polysiloxanes resulting from
0 condensation of the above compounds, having recurring units represented
y
by ( Si - O -~- wherein Y and Z each represents R", (OR') or
z
halogen, are also employable in the present invention.
The compounds represented by the general formula
Si(OR')mX4_m are particularly preferred in the present invention.
The sequence and method for contactLng and reacting
the components (1~ through (5) in the present invention are not
specially limited, but preferably, first the components (1), (2),
(3) and (4) are reacted and then the component (5) is reacted with
the resulting product, or the component (4) is reacted with the
7~6~
reaction product of the components (13, (2), (3) and (5).
In the former method, that is, in case the component
(5~ is reacted with the reaction product of the components (1), (2),
(3) and (4), the sequence and method of the reaction among the
components (1), (2), (3) and (4) are not specially limited. For
example, the reaction may be carried out in such a manner that
the components ~1) and ~2) are contacted with each other, then the
component (3) Cor the component (4)) is contacted with the resulting
product and thereafter the remaining one component is brought
into contact. Preferably, the components (2) and (3) are reacted
in advance and the reaction product thereby obtained is used as
the components (2) and (3). More particularly, the silicon oxide
and/or aluminum oxide (1), the reaction product (hereinafter referred
to as the component (2-3)) of the magnesium halide (2) with the
co~pound (3) of the general formula Me(OR)nXz_n wherein Me is an
element belonging to Groups I-IV in the Periodic Table, z is the
valence of the element Me, n is 0 ~ n c ~, X is a halogen atom and
R is a hydrocarbon radical having 1 to 20 carbon atoms, and the titanium
compound and/or vanadium compound (4), are contacted and reacted
with one another.
As to the sequence of the contact, the above contacting
operation may be performed in such a manner that the component
(1) and the component (2-3) are contacted with each other and then
the component (4) is contacted with the resulting product, or first
the components (l) and (4~ are contacted with each other and then
the component (2-3) is contacted with the resulting product, or
first the component (2-3) and the component (4) are contacted with
each other and then the component (1) is contacted with the resulting
product. Preferably, the components (1) and (2-3) are contacted with
each other and then the component (4) is contacted with the resulting
7~ 3
product.
The contacting method is not specially limited, that is,
known methods can be adopted. In the case of contacting the components
(1~ and (2-3) with each other, or in the case of contacting the
component (2-3) with the contacted product of the components (1)
and (4), or in the case of contacting the componant (1) with the
contacted product of the components (2-3) and (4), there may be
applied a co-pulverization treatment at a temperature of 0 to 200C
for a per~od of time ranging from 0.5 to 50 hours, or there may
be performed mixing and heating at 50 to 300C for 1 minute to
48 hours in an organic solvent such as an inert hydrocarbon, an
alcohol, an ether, a ketone or an ester followed by removal of
the solvent. Furthermore, in the case of contacting the components
(1) and (4) with each other, or in the case of contacting the
; 15 component (4) with the contacted product of the components (1)
and (2-3), or in the case of contacting ~he components (2-3) and
~4) with each other, there may be performed a co-pulverization
treatment at a temperature of 0 to 200C for a period of time
ranglng from 0.5 to 50 hours, or there may be performed mixing
~ 20 and heating at 50 to 300C for 5 minutes to 10 hours in the presence
; or absence of an inert solvent .ollowed by removal of unreacted
titanium compound and/or vanadium compound by washing with an inert
solvent.
~he method of reaction between the magnesium halide
and the compound of the general formula Me(OR)nXz_n is not specially
limited~ Both may be reacted by mixing and heating for 5 minutes
to 10 hours at a temperature in the range of 20 to 400C, preferably
50 to 300C, in an organic solvent such as an inert hydrocarbon,
an alcohol, an ether, a ketone or an ester. Alternatively, both
may be reacted by a co-pulverization treatment.
The application of a co-pulverization treatment is
particularly preferred in the present invention. The apparatus
to be used for the co-pulverization treatment is not specially
limited, but there usually is employed a ball mill, a vibration
mill, a rod mill or an impact mill. Conditions for the co-
pulverization treatment such as the co-pulverization temperature
and time can be decided easily by those skilled in the art according
to which co-pulverization system is adopted. Generally, the
co-pulverization temperature is in the range of 0 to 200~,
preferably 20 to 100C, and the co-pulverization time is in the
range of 0.5 to 50 hours, preferably 1 to 30 hours. It goes without
saying that the operation should be carried out in an inert gas
atmosphere and that the moisture should be avoided as Ear as possible.
The reaction ratio of the magnesium halide to the
compound of the general formula Me(OR)n~z_n is in the range of
1 : 0.01 to l : 10, preferably 1 : 0.1 to l : 5, in terms of
Mg : Me (mol ratio).
The amount of the component (2-3) to be used in the
invention is in the range of 0.01 to 5 grams, preferably 0.1 to
2 grams, per gram of the component (1). As to the amount of the
component (4), it is desirable to ad~ust so that the titanium
and/or vanadium content of the resulting solid component is in
the range of 0.5 to 20% by weight, with the range of 1 to 10~
by weight being particularly preferred in order to attain a well-
balanced activity per titanium and/or vanadium and that per solid.
The most preferable sequence and method of contactingthe components (l), (2-3) and (4) in the present invention are as
follows.
First, the component (2-3) which is the reaction product
of the magnesium hallde and the compound of the general formula
g
~'7~
Me(OR)nXz n and the component (1) are reacted with each other
at 0-300C, preferably 10-200C and most preferably 20-100C,
for 1 minute to 48 hours, preferably 2 minutes to 10 hoursJ in
a solvent which dissolves the component (2-3~. Examples of the
solvent includes alcohols, ethers, ketones and amines. Preferred
examples of such solvent are methanol, ethanol, isopropanol, butanol,
pentanol, hexanol, octanol, benzyl alcohol, methylcellosolve,
ethylcellosolve, methyl formate, ethyl formate, methyl acetate,
ethyl acetate, butyl ace~ate, vinyl acetate, methyl acrylate,
methyl methacrylate, octyl butyrate, ethyl laurate, octyl laurate,
methyl benzoate, ethyl benzoate, octyl para-hydroxyben~oate, dibutyl
phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate,
diethyl maleate, dimethyl ether, diethyl ether, diisopropyl ether,
dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, anisole,
acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl
ketone, dihexyl ketone, acetophenone, diphenyl ketone, cyclohexanone,
diethyl amine, triethyl amine, tetramethylene diamine, aniline,
N,N-dimethyl aniline and pyridine. Ethanol, tetrahydroEuran and
ethyl acetate are more preferable. In this case, the components
(1) and (2-3) are contacted with each other in such a ratio as
0.01 to 5 grams, preferably 0.1 to 2 grans, of the component (2-3)
per gram of the component (1). After the reaction, the solvent
is removed to obtain the reaction product of the components (1)
and (2-3).
Then, the component (4), namely, the titanium compound
and/or the vanadium compound, is mixed under heating with the
above reactlon product of the components (1) and (2-3) at a
temperature of 20 to 300C, preferably 50 to 150~C, for 5 minutes
to 10 hours ln the presence or absence of an inert solvent such as
hexane or heptane to have the titanium compound and/or the vanadium
-- 10
23
compound supported on the reaction product of the components (1)
and (2-3). In this case, the amount of the component (4) is adjusted
so that the content of the titanium compound and/or the vanadium
compound in the resulting solid component is in the range of 0.5
to 20%, preferably 1 to 10%, by weight. After the reactlon, unreacted
titanium compound and/or vanadium compound is removed by washing
several times with a solvent inert to ~iegler catalysts, followed
by evaporation under reduced pressure, to obtain a solid powder.
The resultant reaction product (hereinafter referred
to simply as the component [I]) of the components (1), (2-3) and
(4) is then reacted with the component (5) of the general formula
R"nSi(OR)mX4_m_n to obtain the solid catalyst component of the present
invention.
The method of reaction between the component ~I] and
the component (5) is not specially limited. Both components may
be reacted together by the co-pulverization treatment; or in the
presence or absence of an inert ~olvent at a temperature of 20
to 400C, preferably 50 to 300C for 5 minutes to 20 hours.
The components [I] and (5) are reacted together in
20 such a reaction ratio as 0.05 to 50 grams, preferably 0.1 to 30
grams, of the component (S) per 100 grams of the component [I].
In the case of reacting the component (4) with the
reaction product of the components (1), (2), (3) and (5), the
sequence and method of the reaction among the components (1),
(2), (3) and (5) are not specially limited, but preferably the
components (2) and (3), or the components (2) and (5), or the
components (2), (3) and (5), are reacted together in advance.
More concretely, the reaction may be carried out by
contacting the reaction product of the components ~2) and (3)
with the component (1) and then contacting the component (5) with
7f~ 3
the resulting product, or by contacting the reaction product oE
the components (2) and (5) with the component (1) and then contacting
the component (3) with the resulting product, or by contacting the
component (1) with the reaction product of the components (2~,
(3~ and (5).
The contact between the components t2) and (3), between
the components (2) and (5~, or among the components (2), (3) and
(5), may be carried out in an organic solvent such as an inert
hydrocarbon, an alcohol, an ether, a ketone or an ester, but preferably
it is carried out by the co-pulverlzation treatment.
The contacting of the component (1) with the reaction
product of the components (2) and (3), with the reaction product
oE the components (2~ and (5), or with the reaction product of the
components (2), (3) and (5), may be carried out by the co-pulverization
treatment, but preferably it is carried out in an organic solvent
such as an inert hydrocarbon, an alcohol, an ether, a ketone or
an ester at a temperature of 50 to 300C for 1 minute to 48 hours.
In case the component (5) is contacted with the product
resulting from contact of the reaction product of the components
(2) and (3) with the component (1), or in case the component (3)
is contacted with the product resulting from contact of the reaction
product of the components (2) and (5) wlth tha component (1),
reaction may be allowed to take place by the co-pulverization
treatment, or in the presence or absence of an inert solvent.
~s to contact ratio (mol ratio) among the components
(1), (2), (3) and (5), component (1) : component (2) is in the
range of 1 : 0.01 to 1 : 5, preferably 1 : 0.1 to 1 : 2, component
(2) : component (3~ is in the range of 1 : 0.01 to 1 : 10, preferably
1 : 0~1 to 1 : 5, and component (2~ : component (5) is in the
range of 1 : 0.01 to 1 : 10, preferably 1 : 0.1 to 1 : 5.
~ 12
The contacting of the component (4) with the reaction
product of the components (1), (2), (3) and (5) may be carried
out by the co-pulverization treatment, but preferably the component
(4) is mixed with the reaction product of the components ~1), (2),
(3) and (5) in the presence or absence of an inert solvent such as
hexane or heptane and reaction is allowed to take place at a temperature
of 20 to 300C for 5 to 10 hours. The amount of the component (4)
is adjusted so that its content in the resulting solid component is
in the range of 0.5 to 20%, preferably 1 to 10%, by weight.
As the organometallic compound used in the present
invention, there may be employed organometallic compounds of Group
I-IV metals in the Periodic Table known as one component of Ziegler
catalysts, with organoaluminum compounds and organozinc compounds
being particularly preferred, for example, organoaluminum compounds
of the general formulae R3Al, R2AlX, RAlX2, R2AlOR9 RAl(OR)X and
R3A12X3 wherein R is an alkyl or aral group having 1 to 20 carbon
atoms and may be alike or different and X is a halogen atom, and
organozinc compounds of the general formula R2Zn wherein R is an
alkyl group having 1 to 20 carbon atoms and may be alike or different,
such as triethylaluminum, triisopropylaluminum, triisobutylaluminum,
tri-sec~butylaluminum, tri-tert-butylaluminum, trihexylaluminum,
trioctylaluminum, diethylaluminum chloride, diisopropylaluminum
chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures
thereof. The amount of the organometallic compound is not specially
limited, but usually the organometallic compound may be used in
an amount of 0.1 to 1,O00 mols per mol of the titanium compound
and/or the vanadium compound.
It is also preferable in the present invention to
use the organometallic compound component as a mixture or addition
compound of the organometallic compound as enumerated above and
_ 13
~1'7~3
an organic acid ester.
In case the organometallic compound and the organic
acld ester are used as a mixture, the organic acid ester is used
usually in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol,
per mol of the organometallic compound. In case the organometallic
compound and the organic acid ester are used as an addition compound,
; the ratio of the organometallic compound to the organic acid ester
is pre~erably in the range of 2 : 1 to 1 : 2 in terms of molar ratio.
The organic acid ester is an ester of a saturated or
unsaturated mono- or dibasic organic carboxylic acid having 1 to
24 carbon atoms with an alcohol having 1 to 30 carbon atoms.
Examples of such organic acid ester are methyl formate, ethyl acetate,
amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate,
ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate,
isopropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl
benzoate, cyclohexyl benzoate, phenyl benzoate, benzolc acid-4-tolyl,
methyl salicylate, ethyl salicylate, methyl p-hydroxybenzoate, ethyl
p-hydroxybenzoate, phenyl salicylate, cyclohexyl p-hydroxybenzoate,
benzyl salicylate, ethyl Orresorcinate, methyl anisate, ethyl anisate,
phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl
p-ethoxybenzoate, methyl p-toluylate, ethyl p-toluylate, phenyl
p-toluylate, ethyl o-toluylate, ethyl m-toluylate, methyl
p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate,
benzyl benzoate, methyl naphthoate, and ethyl naphthoate. Particularly
preferred are alkyl esters, especially methyl and ethyl esters,
of benzoic acid, o or p-toluic acid and p-anisic acid.
The olefin polymerization using the catalyst of the
invention may be carried out in the form of a slurry polymerization,
a solution polymerization or a vapor phase polymerization~ Particularly,
the catalyst of the present invention is suitable for the vapor phase
_ 14
polymerization. The polymerization reaction is carried out in
the same manner as in the conventional olefin polymerization reaction
using a Ziegler type catalyst; that is, the reaction i8 performed
in a substantially oxygen- and water-free condition and in the
S presence or absence of an inert hydrocarbon. Conditions for the
olefin polymerization involve temperatures ranging from 20 to
120C, preferably from 50 to 100C, and pressures ranging from
atmospheric pressure to 70 kg/cm2, preferably from 2 to 60 k&/cm2.
Ad~ustment of the molecular weight can be made to a certain extent
by changing polymerization condition.s such as the polymerization
temperature and the catalyst mol ratio, but the addition of hydrogen
into the polymerization system is more effective for this purpose.
Of course, two or more stage polymeriæation reactions having different
polymerization conditions such as different hydrogen concentrations
and different polymerization temperatures can be performed without
any trouble by using the catalyst of the present invention.
The present lnvention is applicable to the polymerization
of all olefins that are polymerizable with Ziegler catalysts, preferably
a~olefins having 2 to 12 carbon atoms. For example, the present
invention is suitable for the homopolymerization of such ~-olefins
as ethylene, propylene, l-butene, hexene-l and 4-methylpentene-1,
the copolymerization of ethylene and propylene, ethylene and l-butene,
ethylene and hexene-l, propylene and l-butene, and the copolymerization
of ethylene with two or more other ~-oleflns.
Copolymerization with dienes for the modification of
polyolefins is also preferable. Examples of diene compounds used
in this copolymerization are butadiene, 1,4-hexadiene, ethylidene
norbornene and dicyclopentadiene.
By using the catalyst of the present invention there is
obtained in high activity a polyolefin having a large average particle
_ ]5
~ ~.'7~2~Z3
size, a narrow particle size distribution and a decreased proportion
of fine particles, and the bulk density of the polyolefin ls high,
which is very advantageous to the polymerizing operation. The
polyolefin thus obtained can be sub~ected to molding not only as
pellets but also directly as powder while causing little trouble
in the molding operation. Thus, polyolefins can be prepared very
advantageously.
The polymer obtained by using the catalyst of the present
invention is further characteristic in that the molecular weight
distribution is very narrow and that the smaller the hexane extraction,
the smaller the by-production of low grade polymer. Therefore,
if the polyolefin having a narrow molecular weight distribution
obtained by using the catalyst of the present invention is used
for the formation of a film, the resulting film will have many
merits~ for example, high strength, high transparency, and superior
anti blocking and heat-sealing properties.
Th0 present invention provides a novel catalyst system
which exhibits many such characteristic features and which overcomes
the foregoing drawbacks associated with the prior art. It is quite
surprising that the above-mentioned advantages can be attained
easily by using the catalyst of the present invention.
The following examples are illustrative of the present
invention and are not intended to limit the invention in any manner.
:
Example 1
` 25 (a) Preparation of a Solid Catalyst Component
10 g. of a commercially available anhydrous magnesium
chloride and 4.2 g. of aluminum triethoxide 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 diameter, and ball milling
- 16
.
;23
was made for 16 hours at room temperature under a nitrogen atmosphere
to obtain a reaction product. Then, a three-necked flask equipped
wlth a stirrer and a reflux condenser was purged with nitrogen,
into which were charged 5 g. of the above reaction product and
5 g. of SiO2 (Fuji-Davison, #952~ 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 120C
under reduced pressure to remove tetrahydrofuran. Then, after
adding 50 cc. of hexane and subsequent s tirring, 1.1 ml. of titanium
tetrachloride was added and reaction was allowed to proceed for
2 hours under reflux of hexane to obtain a solid powder (A~ which
contained 40 mg. of titanium per gram thereof.
The solid powder (A) was added into 50 ml. of hexane,
then 1 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.
(b) Vapor Phase Polymerization
A stainless steel autoclave was used as a vapor phase
polymerization apparatus, and a loop was formed by a blower, a flow
control device and a dry cyclone. The temperature of the autoclave
was adjusted by passing a warm water through a jacket.
Into the autoclave held at 80C were charged the above
solid catalyst component and triethylaluminum at rates of 250 mg/hr
and 50 mmol/hr, respectively, and butene-l, ethylene and hydrogen
were fed while ad~usting so that the butene-llethylene ratio (mol
ratio) in the vapor phase within the autoclave was 0.27 and the
hydrogen concentration was 17% of the total pressure, and polymeriz-
ation was made while recycling the intrasystem gases by the blower.
The resulting ethylene copolymer was a powder having an average
particle size of 750JU not containing particles below 150/u and
17
~.~'7;~3
having a bulk density of 0.42, a melt index (MI) of 1.0 and a density
of 0.9208. The catalyst activity was 100,000 g. copolymer/g.Ti.
F-R- value (F.R. G MI2 16/MIlo) represented in terms of
the ratio of a melt index ~MI) of the copolymer of 2.16 determined
at a load of 2.16 kg. to a melt index (MI) thereof of 10 at a load
of 10 k8. both at 190C according to the method of ASTM-D1238-65T
was 7.2 and thus the molecular weight distribution was very narrow.
A film was formed from this copolymer and it was extracted
in boiling hexane for 10 hours; as a result, the extraction proved
to be 0.8 wt.% and thus the amount of the extract was very small.
Comparative Example 1
The following vapor phase polymerization was carried out
using the apparatus described in Example 1.
The autoclave held at 80C was charged with the solid
powder (A) obtained in Example 1 and triethylaluminum at rates of
250 mg/hr and 50 mmol/hr, respectively, and butene-l~ ethylene and
hydrogen gsses were fed therein while adjusting so that the butene-l/
ethylene ratio (mol ratio) in the vapor phase within the autoclave
was 0.25 and the hydrogen concentration was 15~ of the total pressure,
and polymerization was carried out at a total pressure of 10 kg/cm2
while recycling the intrasystem gases by the blower. The resulting
ethylene copolymer was a powder having an average particle size of
700~u not containing particles below 150~u and having a bulk density
of 0.41, a melt index (MI~ of 1.2 and a density of 0.9210. The
; 25 catalyst activity was 112,000 g.copolymer/g.Ti.
; The F.R. value of this copolymar was 7.6 and thus the
molecular weight distribution was wider than that in Example 1.
A film was formed from this copolymer and it was extracted
in boiling hexane for 10 hours; as a result, the hexane extraction
- 18
11~7~ 3
proved to be 1.1 wt.%.
Example 2
(a) Preparation of a Solid Catalyst Component
10 g. of an anhydrous magnesium chloride and 4.2 g.
of tetraethoxysilane were placed in the ball milling pot described
in Example 1, and ball milled for 16 hours at room temperature under
a nitrogen atmosphere to obtain a reaction product. Then, 5 g.
of the reaction product and 5 g. of SiO2 which had been calcined
at 600C were placed in the three-necked flask described in Example
- 10 1, thereafter 100 ml. of tetrahydrofuran was added and reaction
was a:Llowed to take place at 60C for 2 hours, followed by drying
at 120C under reduced pressure to remove tetrahydrofuran. Then,
after adding 50 cc. of h~xane and subsequent. stirring, 1.1 ml. of
titanium tetrachloride was added and reaction was allowed to proceed
for 2 hours under reflux of hexane to obtain a solid powder (B)
which contained 40 mg. of titanium per gram of the solid powder (B).
The solid powder (B) was added into 50 ml. of hexane,
then 1 ml. of tetraethoxysilane was added and reaction was allowed
to take pIace for 2 hours under reflux of hexane to obtain a solid
catalyst component.
~:
(b) Vapor Phase Polymerization
~ he following vapor phase polymeri~ation was carried
out using the apparatus described in Example 1.
; ~ The autoclave held at 80C was charged with the above
2S solid catalyst component and triethylaluminum at rates of 250 mg/hr
and 50 mmol/hr, respecclvely, and butene~l, ethylene and hydrogen
gases were fed therein while adjusting so that the butene-l/ethylene
ratio (mol ratio) in the vapor phase within the autoclave was 0.28
and the hydrogen concentration was 17% of the total pressure, and
19
~7~
polymerization was carried out while recycling the intrasystem
gases by the blower. The resulting ethylene copolymer was a powder
having an average particle size of 750~ not containing particles
below 150~ and havlng a bulk density of 0.38, a melt index (MI)
of l.l and a density of 0.9250. The catalyst activity was 100,000 g.
copolymer/g.Ti.
The F.R. value of the copolymer was 7.2. When a film
was formed from this copolymer and it was extracted in boiling
hexane for lO hours, the hexane extraction was found to be 0.8 wt.%.
Comparative Example 2
The following vapor phase polymerization was carried
out using the apparatus described in Example 1.
The autoclave held at 80C was charged with the solid
powder (B) obtained in Example 2 and triethylaluminum at rates
15 of 250 mg/hr and 50 mmol/hr, respectively, and butene-l, ethylene
and hydrogen gases were fed therein while ad~usting so that the
butene-l/ethylene ratio (mol ratio) in the vapor phase within the
autoclave was 0.28 and thP hydrogen concentration was 15% of the
total pressure, and polymerization was carried out at a total pressure
of lO kg/cm2 while recycling the intrasystem gases by the blower.
The resulting ethylene copolymer was a powder having an average
particle size of 750/u not containing particles below 150~u and
having a bulk density of 0.38, a melt index (MI) of 1.0 and a
density of 0.9180. The catalyst activity was 120,000g.copolymer/g.Ti.
The F.R. value of the copolymer was 8.0 and thus the
molecular weight distribution was wider than that in Example 2.
A film was formed from this copolymer and it was extracted
in boiling hexane for 10 hours; as a result, the hexane extraction
was 2.0 wt.%.
_ 20
~'7~
Example 3
(a) Preparation of a Solid Catalyst Component
10 g. of an anhydrous magnesium chloride and 4.2 g.
of aluminum triethoxide were placed in the ball milling pot described
in Example 1 and the ball milled for 16 hours at room temperature
under a nitrogen atmosphere to obtain a reaction product. 5 g. of
the reaction product and 5 g. of SiO2 which had been calcined at
600C were put into the three-necked flask described in Example 1,
then 100 ml. of ethyl acetate was added, and reaction was allowed
to take place at 60C for 2 hours, followed by drying at 120C
under reduced pressure to remove ethyl acetate. Then, after adding
50 cc. of hexane and subsequent stirring, 1.1 ml. of titanium
tetrachloride was added and reaction was allowed to proceed for 2
hours to obtain a solid powder (C) which contained 40 mg. of titanium
p~r gram thereof.
The solid powder (C) was added into 50 ml. of hexane,
then 0.5 ml. of tetraethoxysilane was added and reaction was allowed
to take place for 3 hours under reflux of hexane to obtain a solid
catalyst component.
(b) Vapor Phase Polymerization
The following vapor phase polymerization was carried
out using the apparatus described in Example 1.
The autoclave held at 80C was charged with the above
solid catalyst component and triethylaluminum at rates of 250
mg/hr and 50 mmol/hr, respectively, and butene-l, ethylene and
hydrogen gases were fed therein while adjusting to give a butene-l/
ethylene ratio (mol ratio) in the vapor phase within the autoclave
of 0.27 and a hydrogen concentration of 17~ of the total pressure,
and polymerization was carried out while recycling the intrasystem
gases by the blower. The resulting ethylene copolymer was a powder
_ 21
6~23
having an average particle size of 6001u not containlng particles
below 150~u and having a bulk density of 0.39, a melt index (ML)
of 1.5 and a density of 0.9200. The catalyst activity was
90JOOOg copolymer/g.Ti.
The F.R. value of the copolymer was 7.5. A film was
formed from this copolymer and it was extracted in boiling hexane
for 10 hours; as a result, the hexane extraction was 0.9 wt.%.
Example 4
(a) Preparation of a Solid Catalyst Component
10 g. of an anhydrous magnesium chloride and 4.1 g.
of triethoxyboron were placed in the ball milling pot described
in Example 1 and ball milled for 16 hours at room temperature under
a nitrogen atmosphere to obtain a reaction product. 5 g. of the
reaction product and 5 g. of SiO2 which had been calcined at 600C
were put into the three-necked flask described in Example 1, then
100 ml. of tetrahydrofuran was added and reaction was allowed to
take place at 60C for 2 hours, followed by drying at 120C under
reduced pressure to remove tetrahydrofuran. Then, after adding 50
cc. of hexane and subsequent stirring, 1.1 ml. of titanium tetra-
chloride was added and reaction was allowed to proceed for 2 hoursunder reflux of hexane to obtain a solid powder (D) which proved
to contain 40 mg. of titanium per gram thereof.
The solid powder (D) was added into 50 ml. of hexane,
then 1 ml. of tetrasilane was added and reaction was allowed to
take place for 2 hours under reflux of hexane to obtain a solid
catalyst component.
(b) Vapor Phase Polymerization
The following vapor phase polymerization was carried
out using the apparatus described in Example 1.
- 22
~ :~'7~3
The above solld catalyst component and trlethylalumlnum
were fed into the autoclave held at 80C at rates of 250 mg/hr
and 50 mmol/hr, respectively, and butene-l, ethylene and hydrogen
gases were introduced while adjusting to give a butene-l/ethylene
ratio (mol ratio~ in the vapor phase within the autoclave of 0.27
and a hydrogen concentration of 17% of the total pressure, and
polymerization was carried out while recycling the intrasystem
gases by the blower. The resulting ethylene copolymer was a powder
having an average particle si~e of 500~u not containing particles
below 44~ and having a bulk density of 0.42, a melt index (MI)
of 1.3 and a density of 0.9205. The catalyst activity was
70,000g.copolymer/g.Ti.
The F.R. value of the copolymer was 7.4. A film was
formed from this copolymer and it was extracted in boiling hexane
for 10 hours; as a result, the hexane extraction was 0.9 wt.%.
Example 5
(a) Preparation of a Solid Catalyst Component
10 g. of an anhydrous magnesium chloride and 4.2 g.
of diethoxymagnesium were placed in the ball milling pot described
in Example 1 and ball milled for 16 hours at room temperature under
a nitrogen atmosphere to obtain a reaction product. 5 g. of the
reaction product and 5 g. of SiO2 which had been calcined at 600C
were put into the three-necked flask described in Example 1, then
lO0 ml. of tetrahydrofuran was added and reaction was allowed to
take place at 60C for 2 hours, followed by drying at 120C under
reduced pressure to remove tetrahydrofuran. Then, after adding
50 cc. of hexane and subsequent stirring, l.l ml. of titanium
tetrachloride was added and reaction was allowed to proceed for
2 hours under reflux of hexane to obtain a solid powder (E~ which
_ 23
7~G~.~
proved to contain 40 mg. of titanium per gram thereof.
The solid powder (E) was added into 50 ml. of hexane,
then 1 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.
(b) Vapor Phase Polymerization
The following vapor phase polymerization was carried
out using the apparatus described in Example 1.
The above solid catalyst component and triethylaluminum
10 were fed into the autoclave held at 80C at rates of 250 mg/hr
and 50 mmol/hr, respectively, and butene-l, ethylene and hydrogen
gases were introduced while adjusting to give a butene-l/ethylene
ratio (mol ratio) in the vapor phase within the autoclave of 0.27
and a hydrogen concentration of 17~ of the total pressure, and
polymerization was carried out while recycling the intrasystem
gases by the blower. The resulting ethylene copolymer was a powder
having an average particle size of 600~ not containing particles
below lOO~u and having a bulk density of 0.40, a melt index (MI)
of 0.5 and a density of 0.9250. The catalyst activity was
lOO,OOOg.copolymer/g.Ti.
The F.R. value of the copolymer was 7.5. A film was
formed from this copolymer and it was extracted in boiling hexane
for 10 hours; as a result, the hexane extraction was 0.4 wt.~.
Example 6
(a) Preparation of a Solid Catalyst Component
10 g. of a commercially available anhydrous magnesium
chloride and 4.2 g. of aluminum triethoxide 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 diameter and balled milled
_ 24
~ 1'72~3
for 16 hours at room temperature under a nitrogen atmosphere to
~ obtain a reaction product. Then, a three-necked flask equipped
; with a stirrer and a reflux condenser was purged with nitro~en,
into which were charged 5 g. of the above reaction product and
5 g. of SiO2 (Fuji-Davison, #952) 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 120C
; under reduced pressure to remove tetrahydrofuran. Then, 50 cc.
of hexane and 2 ml. of tetraethoxysilane were added and reaction
was allowed to take place at 50C for 2 hours, thereafter 1.1 ml.
of titanium tetrachloride was added and reaction was made for 2
hours under reflux of hexane to obtain a solid catalyst component
which proved to contain 38 mg. of titanium per gram thereof.
; (b) Vapor Phase Polymerization
lS A vapor phase polymerization was carried out in the
following manner using the apparatus described in Example 1.
The above solid catalyst component and triethylaluminum
were fed into the autoclave held at 80C at rates of 250 mg/hr
and 50 mmol/hr, respectively, and butene-l, ethylene and hydrogen
gases were introduced while adjusting to give a butene-l/ethylene
ratio (mol ratio) in the vapor phase within the autoclave of 0.28
.
and a hydrogen concentration of 17% of the total pressure, and
polymerization was carried out while recycling the intrasystem
gases by the blower. The resulting ethylene copolymer was a powder
having an average particle size of 730~ not containing particles
below 1501U and having a bulk density of 0.40, a melt index (MI~
of 1.0 and a density of 0.9221. The catalyst activity was
135,000g.copolymer/g.Ti.
The F.R. value of the copolymer was 7.2. A film was
formed from this copolymer and it was extracted in boiling hexane
.
~.~7~3
for 10 hours; as a result, the hexane e~traction was 0.9 wt.%.
Example 7
(a) Preparation of a Solid Catalyst Component
10 g. of a commercially available anhydrous magnesium
chloride, 4.2 g. of aluminum triethoxide and 3 g. of monomethyl-
triethoxysilane were placed in a stainless steel pot having a content
volume of 400 ml. and containing 25 stainless steel balls each 1/2
inch ln diameter and ball milled for 16 hours at room temperature
under a nitrogen atmosphere to obtain a reaction product. Then,
a three-necked flask equipped with a stirrer and a reflux condenser
was purged with nitrogen, into which were charged 5 g. of the above
reaction product and 5 g. of SiO2 (Fuji-Davison, #952~ which had been
calcined at 600C, then lO0 ml. of tetrahydrofuran was added and
; ~ reaction was allowed to take place at 60C for 2 hours, followed
by drying at 120C under reduced pressure to remove tetrahydrofuran.
Then, after adding 50 cc. of hexane and subsequent stirring, 1.1
ml. of titanium tetrachloride was added and reaction was made for
2 hours under reflux of hexane to obtain a solid powder (A) which
proved to contain 40 mg. of titanium per gram thereof.
,~ ~; 20 (b~ Vapor Phase Polymerizatlon
A stainless steel autoclave was used as a vapor phase
~; polymerization apparatus, and a loop was formed by a blower, a
flow control device and a dry cyclone. The temperature of the
autoclave was ad~usted by passing a warm water through a ~acket.
The above solid catalyst component and triethylaluminum
were fed into the autoclave held at 80C at rates of 250 mglhr and
50 mmol/hr, respectively, and butene~l, ethylene and hydrogen gases
were introduced while ad~usting to give a butene-l/ethylene ratio
(mol ratio) in the vapor phase within the autoclave of 0.27 and
_ 26
Z~23
a hydrogen concentration of 17~ of the total pressure, and
polymerization was carried out while recycling the intrasystem gases
by the blowerO The resulting ethylene copolymer was a powder
having an average particle size of 710~ not containing particles
below 150~ and having a bulk density of 0.40, a melt index (MI)
of 0.8 and a density of 0.9210. The catalyst activity was
130,000g.copolymer/g.Ti.
The F.R. value was 7.1. A film was formed from this
copolymer and it was extracted in boiling hexane for 10 hours;
ts a result, the hexsne extraction was 0.8 wt.~.
~ .
! ~:
_ 27
