Note: Descriptions are shown in the official language in which they were submitted.
l~iS~7
This invention relates to a process which can afford highly
stereoregular polymers or copolymers in high yields when applied to the
polymerization or copolymerizaLion of ~-olefins, especially those having
at least 3 carbon atoms.
Many prior suggestions have been known for the preparation
of highly stereoregular polymers or copolymers by using a solid complex
titanium component at least containing magnesium, titanium and halogen,
preferably treated with an electron donor, as a titanium catalyst component
which constitutes a catalyst for the polymerization or copolymerization of
~-olefins containing at least 3 carbon atoms (for example, German Laid-Open
Patent Publication Nos. 2,153,520, 2,230,672 and 2,553,104).
These prior suggestions teach combinations of specific catalyst-
forming components, and combinations of catalyst-forming procedures and the
catalyst-forming components as essential conditions. As is well known, the
characteristics of catalysts containing a solid complex titanium component
of this type vary greatly according to differences in the combination of
the above catalyst-forming components, the combinations of the catalyst-
forming procedures, and the combinations of these conditions. When catalyst- ;
forming components and/or catalyst-forming procedures which are essential
in a given combination of conditions are used in a different combination of
conditions, it is quite impossible to anticipate whether similar results
will be obtainable. Frequently, the result is a catalyst having quite
poor properties.
The aforesaid solid complex titanium component at least containing
magnesium, titanium and halogen is no exception. If in the polymerization
or copolymerization of ~-olefins containing at least 3 carbon atoms in the
presence of hydrogen using a catalyst composed of the aforesaid titanium
component and an organometallic compound of a metal of Groups I to IV of
the periodic table, a catalyst composed of a titanium trichloride component
obtained by reducing titanium tetrachloride with metallic aluminum, hydro-
'X - 1 -
S'~`7
gen, or an organoaluminum compound is used together with a donor known to
have an effect of inhibiting the formation of an amorphous polymer, the
effect varies unanticipatably according to the donor used.
The present inventors have made efforts for many years in order
to provide a process which can produce highly stereoregular polymers in
high yields while advantageously overcoming the trouble of forming an amor-
phous polymer in the presence of a catalyst composed of ~a) a solid complex
titanium component at least containing magnesium, titanium and halogen, and
(b) an organometallic compound of a metal of groups I to III of the periodic
table.
It has now been found that an organic acid anhydride, preferably
a carboxylic acid anhydride including an aromatic carboxylic acid anhydride,
used together with ~a) and (b) can afford a catalyst which can overcome the
above trouble and has high activity and superior reproducibility of its
properties.
Accordingly, it is an object of this invention to provide an im-
proved process for preparing highly stereoregular olefin polymers in high
yields by overcoming the trouble of forming an amorphous polymer.
The present invention provides a process for preparing olefin
polymers or copolymers which comprises polymerizing or copolymerizing olefins
in the presence of a catalyst comprising (a) a solid complex titanium com-
ponent at least containing magnesium, titanium and halogen and an electron
donor, (b) an organometallic compound of a metal of Groups I to III of the
Mendelejeff's periodic table, and ~c) an organic carboxylic acid anhydride.
The present invention also provides a catalyst composition for
polymerization or copolymerization of olefins, said composition comprising
(a) a solid complex titanium component at least containing magnesium, tita-
nium and halogen obtained by reacting a magnesium compound with an electron
donor, and then reacting the reaction mixture with a titanium compound by
suspending the mixture in a liquid tetravalent titanium compound with or
without using an inert solvent, (b) an organometallic compound of a metal
X - 2 -
S~7
of Groups I to III of the Mendelejeff's periodic table, and ~c) an organic
carboxylic anhydride.
The solid complex titanium component (a) is a solid complex which
has a halogen/titanium molar ratio of more than about 4, and does not
substantially permit the liberation of a titanium compound by washing with
hexane at room temperature. The chemical structure of this solid complex
is not known, but presumably, the magnesium atom and the titanium atom are
bonded firmly by, for example, having the halogen in common. The solid
complex may, depending upon the method of preparation, contain other metal
atoms such as aluminum, silicon, tin, boron, germanium, calcium and zinc,
electron donors, or organic groups ascribable thereto. It may further con-
tain an organic or inorganic inert diluent, suchas LiCl, CaC03, BaC12, NaC03,
2 2 3 2 4' 2 3' Si2' Ti2' NaB407, Ca3(P04)2, CaS04, Al (S0 )
CaC12, ZnC12, polyethylene, polypropylene, and polystyrene. Preferably,
the solid complex is the one treated with an electron donor. In preferred
examples of the solid complex titanium component (a), the halogen/titanium
molar ratio is above about 4, preferably at least about 5, more preferably
at least about 8, and the magnesium/titanium molar ratio is at least about
3, preferably about 5 to about 50, and the electron donor/titanium molar
ratio of about 0.2 to about 6, preferably about 0.4 to about 3, more prefe-
rably about 0.8 to about 2. Furthermore, the specific surface area of the
solid is at least 3 m2/g, preferably at least about 40 m2/g, and more pre-
ferably at least about 100 m2/g. It is also desirable that the X-ray spec-
trum of the solid complex ~a) should show amorphous character irrespective
of the starting magnesium compound, or it is in a more amorphous state than
ordinary commercially available grades of magnesium dihalide.
The solid complex titanium component (a) can be formed by various
means, and most commonly, a magnesium compound and a titanium compound are
contacted while at least one of them contains halogen, and if desired, the
product is treated with an electron donor. Various suggestions have been
known for the preparation of such component ~a), and can be used in this
inven1:ion. Some of such suggestions are disclosed in German Laid-Open
Patent Publications Nos. 2,230,672, 2,504,036, 2,553,104 and 2,605,922 and
Japanese Laid-Open Patent Publications Nos. 28189/76, 127185/76, 136625/76
and 87486/77.
Typical methods disclosed in these documents involve the reaction
of at least a magnesium compound (or metallic magnesium), an electron donor
and a titanium compound.
Examples of the electron donor are oxygen-containing electron
donors such as water, alcohols, phenols, ketonesJ aldehydes, carboxylic
acids, esters, ethers and acid amides, and nitrogen~containing electron
donors such as ammonia, amines, nitriles and isocyanates.
Specific examples of such electron donors include alcohols contain-
ing 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol,
hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl
alcohol, cumyl alcohol, and isopropyl benzyl alcohol; phenols containing
6 to 15 carbon atoms which may contain a lower alkyl group, such as phenol,
cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenyl, and naphthol;
ketones containing 3 to 15 carbon atoms such as acetone, methyl ethyl ketone,
methyl isobutyl ketone, acetophenone and benzophenone; aldehydes containing
2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde,
benzaldehyde, tolualdehyde and naphthoaldehyde; organic acid esters con-
taining 2 to 18 carbon atoms such as methyl formate, methyl acetate, ethyl
acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate,
ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate,
ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl
cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate,
butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl
benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate,
methyl anisate, ethyl anisate, ethyl ethoxybenzoate, y-butyrolactone,
~-valerolactone, coumarine, phthalide and ethylene carbonate; acid halides
containing 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride,
- 4 -
toluic acid chloride, and anisic acid chloride; ethers containing 2 to 20
carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl
ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acid amides
such as acetamide, benzamide and toluamide; amines such as methylamine,
ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine,
aniline, pyridine, picoline and tetramethylethylene diamine; nitriles such
as acetonitrile, benzonitrile and tolunitrile; and compounds of aluminum,
silicon, tin etc. which contain the aforesaid functional groups in the
molecule. These electron donors can be used as a mixture of two or more.
Suitable magnesium compounds used for the formation of the solid
complex titanium compound (a) are those containing halogen and/or organic
groups. Specific examples of such magnesium compounds include magnesium
dihalides, magnesium alkoxyhalides, magnesium aryloxyhalides, magnesium
hydroxyhalides, magnesium dialkoxides, magnesium diaryloxides, magnesium
alkoxyaryloxides, magnesium acryloxyhalides, magnesium alkylhalides,
magnesium arylhalides, magnesium dialkyl compounds, magnesium diaryl com-
pounds, and magnesium alkylalkoxides. They may be present in the form of
adducts with the aforesaid electron donors. Or they may be double compounds
containing other metals such as aluminum, tin, silicon, germanium, zinc or
boron. For example, they may be double compounds of halides, alkyl com-
pounds, alkoxyhalides, aryloxyhalides, alkoxides and aryloxides of metals
such as aluminum, and the above-exemplified magnesium compounds. Or they
may be double compounds in which phosphorus or boron is bonded to magnesium
metal through oxygen. These magnesium compounds may be a mixture of two
or more. Usually, the above-exemplified compounds can be expressed by
simple chemical formulae, but sometimes, according to the method of prepara-
tion of the magnesium compounds, they ~annot be expressed by simple formu-
lae. They are usually regarded as mixtures of the aforesaid compounds.
For example, compounds obtained by a method which comprises reacting magne-
sium metal with an alcohol or phenol in the presence of a halosilane, phos-
phorus oxychloride, or thionyl chloride, and a method which comprises pyro-
~ 5 ~
lyzing Grignard reagents, or decomposing them with compounds having a hydro-
xyl group, a carbonyl group, an ester linkage, an ether linkage, or the like
are considered to be mixtures of various compounds according to the amounts
of the reagents or the degree of reaction. These compounds can of course
be used in this invention.
Various methods for producing the magnesium compounds exemplified
hereinabove are known, and products of any of these methods can be used in
this invention. Also, prior to use, the magnesium compound may be treated,
for example, by a method which comprises dissolving it singly or together
with another metal compound in ether or ace~one, and then evaporating the
solvent or putting the solution into an inert solvent thereby to separate
the solid. A method can also be employed which involves pre-pulverizing
mechanically at least one magnesium compound with or without another metal
compound.
Preferred among these magnesium compounds are magnesium dihalides,
aryloxyhalides and aryloxides, and double compounds of these with aluminum,
silicon, etc. More specifically, they are MgC12, MgBr2, MgI2, MgF2, MgCl-
~OC6H5), Mg~OC6115)2, MgCl~OC6H4-2-CH3), Mg~OC6H4-2-CH3)2, ~MgC12)X~Al(OR)n
C13 ~ y, and ~MgC12)x~Si(OR)mCl4 ~ y. In these formulae, R is a hydrocarbon
group such as an alkyl or aryl group, m or n R groups are the same or dif-
ferent, O_ n _3, O-m _4, and x and y are positive numbers. MgC12 and its
complexes or double compounds are especially preferred.
Suitable titanium compounds used for the formation of the solid
complex titanium compound (a) are tetravalent titanium compounds of the
formula Ti~OR)gX4 g wherein R is a hydrocarbon group, preferably an alkyl
group containing 1 to 6 carbon atoms, X is a halogen atom, and 0_g _4.
Examples of the titanium compounds are titanium tetrahalides such as TiC14,
TiBr4 or TiI4; alkoxytitanium trihalides such as Ti~OCH3)C13, Ti(OC2H5)C13,
Ti(0 n-C4Hg) C13, Ti(OC2H5)Br3, and Ti(O iso-C4Hg)Br3; alkoxytitanium
dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, T ( 4 9 2 2
Ti(OC2H5)2Br2; trialkoxytitanium monohalides such as Ti~OCH3)3Cl, Ti~OC2H5)3
-- 6 --
X
~.5~7
Cl, ri(O n-C4Hg)3CI and Ti~OC2H5)3 Br; and tetraalkoxytitanium such as
Ti(OCH3)4, Ti (OCH3)4, Ti(OC2H5)4, and Ti(O n-C4Hg)4. Of these, the tita-
nium tetrahalides are preferred, and especially preferred is titanium tetra-
chloride.
Preferably, the solid complex titanium compound (a) is pre-treated
with an electron donor. Examples of the electron donor are esters, ethers,
ketones, tertiary amines, acid halides, and acid anhydrides, which do not
contain active hydrogen. Organic acid esters and ethers are especially
preferred, and most preferred are aromatic carboxylic acid esters and alkyl-
containing ethers, Typical examples of suitable aromatic carboxylic acid
esters include lower alkyl esters such as lower alkyl esters of benzoic
acid, and lower alkyl esters of alkoxy benzoic acid. The term "lower"
means the possession of 1 to 4 carbon atoms. Those having 1 or 2 carbon
atoms are especially preferred. Suitable alkyl-containing ethers are those
containing 4 to 20 carbon atoms such as diisoamyl ether and dibutyl ether.
There are various examples of reacting the magnesium compound (or
metallic magnesium), the electron donor and the titanium compound, and ty-
pical ones are described below.
~I~ Method involving reacting the magnesium compound with the electron
donor and then reacting the reaction mixture with the titanium compound:-
~I-a) Method ~I~ with the copulverization of the magnesium com-
pound and the electron donor:-
The electron donor added at the time of copulverization needs
not to be in the free state, and may be present in the form of an adduct
with the magnesium compound. At the time of copulverization~ additional
ingredients, which may be included in the complex titanium component (a),
for example, the aforesaid organic or inorganic inert diluent, a halogena-
ting agent such as a halogen compound of silicon, a silicon compound such
as polysiloxane, and a compound of aluminum, germanium or tin, or a part of
the titanium compound may be present together. Or the electron donor may ~~`
be present in the form of an adduct (complex compound) with such a compound.
. . : .
The amount of the electron donor used is preferably about 0.005 to about
10 moles, more preferably about 0.01 to about 1 mole, per mole of the mag-
nesium compound.
The copulverization may be carried out by using ordinary devices
such as a rotary ball mill, a vibratory ball mill, and an impact mill. If
the rotary ball mill is used, and 100 stainless steel ~SUS 32) balls having
a diameter of 15 mm are accomodated in a ball mill cylinder having an inner
capacity of 800 ml and an inside diameter of 100 mm and made of stainless
steel ~SUS 32) and 20 to 40 g of the materials to be treated are put into
it, it is advisable to perform the pulverization for at least 24 hours,
preferably at least 48 hours at a rotating speed of 125 rpm. The tempera-
ture of the pulverization treatment is usually room temperature to about
100C.
The copulverized product can also be reacted with the titanium
compound by copulverizing means. However, it is preferred to suspend the
copulverized product in at least about 0.05 mole, preferably about 0.1 to
about 50 moles, per mole of the magnesium compound, of a liquid titanium
compound with or without using an inert solvent. The reaction temperature
is from room temperature to about 200C, and the reaction time is from 5
minutes to about 5 houTs. The reaction can of course be performed under
conditions outside these specified ranges. After the reaction, the reaction
mixture is hot-filtered at a high temperature of, say, about 60 to 150C
to isolate the product which is then well washed with an inert solvent
before use in polymerization.
~I-b) Method ~I) without the copulverization of the magnesium
compound and the electron donor:-
Usually, the magnesium compound is reacted with the electron donor
in an inert solvent, or the magnesium compound is dissolved or suspended in
the liquid electron donor for reaction. It is possible to employ an embodi-
ment in which magnesium metal is used as a starting material, and reacted
with the electron donor while forming a magnesium compound.
- 8 -
~5~
The amount of the electron donor used is preferably about 0.01 to
about 10 moles, more preferably about 0.05 to about 6 moles, per mole of
the magnesium compound. The reaction proceeds sufficiently at a reaction
temperature of from room temperature to about 200C for 5 minutes to about
5 hours. After the reaction, the reaction mixture was filtered or evapora-
ted, and washed with an inert solvent to isolate the product. The reaction
of the reaction product with the titanium compound can be performed in the
same way as described in (I-a).
(I-c) Method which comprises reacting the reaction product bet-
ween the magnesium compound and the electron donor with a compound selected
from organoaluminum compounds, silicon compounds and tin compounds, and
then reacting the resulting product further with the titanium compound:-
This method is a special embodiment of the method (I-b~. General-
ly, complexes obtained by the method (I-a) have superior properties, but
some of complexes obtained by the method (I-b) have inferior properties to
those obtained by method (I-a). The properties of such complexes can be
very effectively improved by the performance of method (I-c) in which the
organoaluminum compound, silicon compound or tin compound is reacted prior
to the reaction with the titanium compound.
Examples of the organoaluminum compounds that can be used in this
method are trialkyl aluminums, dialkyl aluminum hydrides, dialkyl aluminum
halides, alkyl aluminum sesquihalides, alkyl aluminum dihalides, dialkyl
aluminum alkoxides or phenoxides, alkyl aluminum alkoxy halides or pheno-
xyhalides, and mixtures of these. Of these, the dialkyl aluminum halides,
alkyl aluminum sesquihalides, alkyl aluminum dihalides, and mixtures of these
are preferred. Specific examples of these include triethyl aluminum, trii- ;
sobutyl aluminum, diethyl aluminum hydride, dibutyl aluminum hydride,
diethyl aluminum chloride, diisobutyl aluminum bromide, ethyl aluminum ses-
quichloride, diethyl aluminum ethoxide, ethyl aluminum ethoxy chloride,
ethyl aluminum dichloride, and butyl aluminum dichloride.
The silicon or tin compounds, for example silicon or tin halogen
X - g _
~ . . . : : .
compounds or organic compounds, are compounds containing at least one halo-
gen or hydrocarbon group directly bonded to silicon or tin, and may further
contain hydrogen, an alkoxy group, a phenoxy group, or the like. Specific
examples include, silicon tetrahalides, tetraalkyl silicons, silicon alkyl
halides, silicon alkylhydrides, tin tetrahalides, tin dihalides, tin alkyl-
halides, and tin hydride halides. Of these, silicon tetrachloride and tin
tetrachloride are preferred.
The reaction between the magnesium compound and the electron
donor can be performed by the method (I-b). The reaction of the resulting
reaction product between the magnesium compound and the electron donor with
the organoaluminum compound, silicon compound or tin compound may be carried
out in an inert solvent. Such a compound is used in an amount of preferably
about 0.1 to about 20 moles, more preferably about 0.5 to about 10 moles,
per mole of the magnesium compound. The reaction is carried out preferably
at a temperature of from room temperature to about 100C for 5 minutes to
5 hours. After the reaction, the reaction mixture is preferably well washed
with an inert solvent, and then reacted with the titanium compound. The
reaction of this reaction product with the titanium compound can be perfor-
med in accordance with the method described in (I-a).
~ ~ Method which comprises simultaneously reacting the magnesium com-
pound, the electron donor and the titanium compound.
~I~ Method which comprises reacting the reaction product between the
titanium compound and the electron donor with the magnesium compound.
The reactions in the methods CI~ and ~I~ are preferably perfor-
med by copulverization. The pulverization conditions and the proportions
of the raw materials are the same as set forth under method CI~. In these
methods, however, it is not preferred to use a large quantity of the tita-
nium compound. The amount of the titanium compound is preferably about 0.01
to about 1 mole per mole of the magnesium compound.
The above methods are typical methods, and many modifications are
possible as shown below.
- 1 0
J ~L15L.~
(1) Method CI~ in which the electron donor is caused to be present
when reacting the titanium compound.
(2) ~ method in which the organic or inorganic inert diluent and
the silicon, aluminum, germanium or tin compound are caused to be present
during the reaction; a method in which these compounds are caused to act
before the reaction; a method in which these compounds are caused to act
between the reactions; a method in which these compounds are caused to act
after the reaction. A typical example of methods is the method (I-c).
These reagents can be used at desired points in the above methods.
For example,
(2-a) Method in which a halogenating agent sucl- as SiC14 is
caused to act on the compound obtained by methods CI~ CI~ and ~
(3) Method in which the titanium compound is caused to act two
or more times:-
(3-a) The method in which the titanium compound and the electron
donor are reacted with the reaction product obtained by any of the methods
CI~ to ~
13-b) The method in which the titanium compound, the organoalu-
minum compound and the electron donor are reacted with the reaction product
of any one of these methods CI~ to ~
A number of other modifications can be made by changing the order
of addition of reaction agents, or by carrying out a plurality of reactions,
or by using additional reaction agents. In any of such methods, it is
desirable that the halogen, titanium and magnesium in the complex (a), the
proportion of the electron donor, the surface area of the complex (a) and
the X-ray spectrum of the catalyst be within the above ranges or in the
above-mentioned conditions.
In the present invention, polymerization or copolymerization is
carried out in the presence of a catalyst composed of the solid complex
titanium component (a) at least containing magnesium, titanium and halogen
and preferably being treated with an electron donor, (b) an organometallic
X - 11 -
,
.
:, . .
compound of a metal of Groups I to III of the periodic table, and ~c) an
organic acid anhydride.
The organometallic compound (b) has a hydrocarbon group directly
bonded to the metal, and includes, for example, alkyl aluminum compounds,
alkyl aluminum alkoxides, alkyl aluminum hydrides, alkyl aluminum halides,
dialkyl zincs, and dialkyl magnesiums. Preferred among them are the organo-
aluminum compounds. Specific examples of the organoaluminum compounds are
trialkyl or trialkenyl aluminums such as Al~C2H5)3, Al~CH3)3, Al~C3H7)3,
Al~C4Hg)3 and Al~C12H25)3; alkyl aluminum compounds having such a structure
that many aluminum atoms are connected through oxygen or nitrogen atoms,
2 5 2 ~ 2H5)2, (C4Hg)2AlOAl(C4H9)2, and (C2H )2AlNAl(C H ) ;
C6H5
dialkyl aluminum hydrides such as (C2H5)2AlH or (C4Hg)2AlH; dialkyl aluminum
halides such as (C2H5)2AlCl, (C2H5)2AlI or (C4Hg)2AlCl; and dialkyl aluminum
alkoxides or phenoxides such as (C2H5)2Al(OC2H5) and (C2H5)2Al(OC6H5). Of
these, the trialkyl aluminums are most preferred.
Examples of the organic acid anhydride (c) include aliphatic mono-
carboxylic acid anhydrides containing 2 to 18 carbon atoms such as acetic
anhydride, propionic anhydride, n-butyric anhydride, iso-butyric anhydride,
monochloroacetic anhydride, trifluoroacetic anhydride, caproic anhydride,
lauric anhydride and stearic anhydride; aliphatic polycarboxylic acid
anhydrides containing 4 to 22 carbon atoms such as succinic anhydride,
maleic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhy-
dride, methylsuccinic anhydride, dimethylsuccinic anhydride, ethylsuccinic
anhydride, butylsuccinic anhydride, octylsuccinic anhydride, stearylsuccinic
anhydride, and methylglutaric anhydride; alicyclic carboxylic acid anhydri-
des containing 8 to 1~ carbon atoms such as bicyclo ~.2 ~ heptene-2,3-
dicarboxylic anhydride or methylbicyclo ~.2.~ heptene-2,3-dicarboxylic
anhydride; and anhydrides of aromatic carboxylic acids containing 9 to 15
carbon atoms such as acetobenzoic anhydride, acetotoluic anhydride, benzoic
anhydride, toluic anhydride, phthalic anhydride, and trimellitic anhydride.
- 12 -
.
l~S~g ~
Of these, the aromatic carboxylic acid anhydrides are preferred.
The aliphatic monocarboxylic acid anhydrides are next preferred although
they tend to give somewhat low polymerization ~ctivity. These acid anhydri-
des can also be used as electron donors in the preparation of the solid com-
plex titanium component (a).
These acid anhydrides may be used as addition reaction products or
substitution reaction products with organometallic compound (b). The pre-
ferred method of using the acid anhydrides is to purge the polymerization
system with an olefin monomer, add the acid anhydride and the organometallic
compound ~b), and then add the titanium catalyst component (complex) (a).
It is possible to contact the acid anhydride with the organometallic compound
outside the pol~merization system, and then feed them into the polymerization
system.
According to the process of this invention, olefins such as ethy-
lene, propylene, l-butene or 4-methyl-1-pentene can be advantageously car-
ried out. The process can especially advantageously be applied to the poly-
merization of ~-olefins containing at least 3 carbon atoms, copolymerization
(random copolymerization, and block copolymerization) of these with each
other, copolymerization of these with not more than 10 mole% of ethylene, ;~
and copolymerization of these with polyunsaturated compounds such as conju-
gated dienes.
The polymerization can be carried out either in the liquid or
vapor phase. When it is performed in the liquid phase~ an inert solvent
such as hexane, heptane or kerosene may be used as a reaction medium, but
the olefin itself may serve as the reaction medium. In the case of the
liquid-phase polymerization, the preferred concentration of the solid complex
titanium component (a) in the polymerization system is about 0.001 to about
5 millimoles, preferably about 0.001 to about 0.5 millimole as titanium atom
per liter of the solvent, and the preferred concentration of the organometal-
lic compound is about 0.1 to about 50 millimoles as metal atom per liter of
the solvent. In the case of the vapor phase polymerization, the solid tita-
X - 13 -
5'~7
nium catalyst component (A) is used in an amount of about 0.001 to about
5 millimoles, preferably about 0.001 to about 1.0 millimole per liter of
polymerization zone, more preferably about 0.01 to about 0.5 millimole per
liter of polymerization zone, calculated as titanium atom. The organo-
metallic compound ~B) is used preferably in an amount of about 0.01 to
about 50 millimoles per liter of polymerization zone calculated as metal
atom.
The ratio of the organometallic component ~b) to the solid complex
titanium component ~a) may be such that the ratio of the metallic atom in
component ~b) to the titanium atom in component (a) is preferably 1/1 to
lO00/1, preferably 1/1 to 200/1. The amount of the acid anhydride component
(c) is preferably about 0.001 to about 1 mole, more preferably about 0.01 to
about 1 mole, per metal atom of the organometallic compound (b).
Polymerization reactions of olefins in the presence of the cata-
lyst of this invention can be performed in the same way as in the polymeri-
zation of olefins with ordinary Ziegler-type catalysts. Specifically, the
reaction is performed in the substantial absence of oxygen and water.
When a suitable inert solvent such as an aliphatic hydrocarbon (e~g.,
hexane, heptane or kerosene) is used, the catalyst and an olefin and option-
ally a diolefin are charged into a reactor, and the polymerization is car-
ried out. The polymerization temperature is usually about 20 to 200C,
preferably about 50 to about 150C. Preferably, the polymerization is car-
ried out at elevated pressures, that is, from normal atmospheric pressure
to about 50 kg/cm2, especially about 2 to about 20 kg/cm2. The molecular
weight of the polymer can be adjusted to some extent by changing the poly-
merization conditions such as the polymerization temperature, and the molar
proportion of the catalyst, but the addition of hydrogen to the polymeri-
zation system is most effective.
The process of this invention can aford highly stereoreg~lar
polymers having a large melt index in high yields.
The following examples illustrate the invention in more detail.
y - 14 -
: :
~L15~7
Exam~L_
Anhydrous magnesium chloride (20 g), 6.0 ml of ethyl benzoate and
3.0 m:L of methyl polysiloxane (viscosity 20 centistokes at 20C) were
charged into a stainless steel (SUS-32) ball mill having an inner capacity
of 800 ml and an inside diameter of 100 mm and containing 2 8 kg of a stain-
less steel (SUS-32) balls having a diameter of 15 mm in an atmosphere of
nitrogen. These materials were contacted with one another for 24 hours at
an impact acceleration of 7G. Ten grams of the resulting solid product was
suspended in 100 ml of titanium tetrachloride, and contacted with stirring
at 80C for 2 hours. The solid was collected by filtration, and sufficient-
ly washed with purified hexane until no free titanium tetrachloride was
detected in the wash liquid. The washed solid was dried to afford a solid
complex titanium component (a) which contained 3.0% by weight of titanium
atom, 58.2% by weight of chlorine atom, 18.0% by weight of magnesium, and
15.5% by weight of ethyl benzoate, and had a specific surface area of 180
m /g.
A 2-liter autoclave was purged with propylene, and then 750 ml of
hexane which had been fully deprived of oxygen and moisture, 4.5 millimoles
of triethyl aluminum, 1.5 millimoles of phthalic anhydride, and 0.03 milli-
mole, calculated as titanium atom, of the component (a) were charged into
the autoclave. The autoclave was sealed, and then, 250 ml of hydrogen was
charged, and the temperature was raised. When the temperature of the poly-
~erization system rose to 60C, propylene was introduced into the autoclave
and its polymerization was started at a total pressure of 8 kg/cm2. The
polymerization was performed at 60C for 6 hours. Then, the introduction
of propylene was stopped, and the contents of the autoclave were cooled to
room temperature. The resulting solid was collected by filtration, and
dried to afford 335.7 g of polypropylene as a white powder. The polymer
had a boiling n-hepcane extraction residue of 94.9%, an apparent density
of 0.31 g/mlJ and a melt index of 2.7. Concentrating the liquid layer
afforded 13.4 g of a solvent-soluble polymer.
.XI
- 15 -
- ' ' .
Example 2
Commercially available anhydrous magnesium chloride (9.5 g; 0.1
mole) was suspended in 0.3 liter of kerosene, and at room temperature,
23.3 ml ~0.4 mole) of ethanol and 14.3 ml (0.1 mole) of ethyl benzoate
were added. The mixture was stirred for 1 hour. Then, 24.2 ml (0.2 mole)
of diethyl aluminum chloride was added dropwise at room temperature, and
stirred for 1 hour. The solid portion of the reaction product was collect-
ed, washed fully with kerosene, and suspended in 0.3 liter of kerosene
con~aining 30 ml of titanium tetrachloride. The reaction was performed
at 80C for 2 hours. After the reaction, the supernatant liquid was removed
by decantation. The solid portion was fully washed with fresh kerosene to
afford a solid complex titanium component (a) which contained 3.5% by
weight of titanium atom, 59.3% by weight of chlorine atom, 19.3% by weight
of magnesium atom, and 14.7% by weight of ethyl benzoate, and had a speci-
fic surface area of 175 m2/g.
Propylene was polymerized in the same way as in Example 1 except
that 0.05 millimole, as titanium atom, of the component (a) was used. Poly-
propylene was obtained in an amount of 327.4 g as a white powder. The
polymer has a boiling n-heptane extraction residue of 95.0% by weight, an
apparent density of 0.32 g/ml and a melt index of 3.6.
Concentrating the liquid layer afforded 11.7 g of a solvent-
soluble polymer.
Examples 3 to 8
Propylene was polymerized in the same way as in Example 1 except
that each of the acid anhydrides shown in Table 1 was used instead of the
phthalic anhydride. The results are shown in Table 1.
Xl - 16 -
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Example 9
Commercially available Mg(OCH3~2 (8.6 g; 0.1 mole) was suspended
in 0.3 liter of kerosene, and 10.6 ml (0.1 mole) of o-cresol was added. The
reacl;ion was performed for 1 hour at 80C. At the same temperature, 7.2 ml
(0.05 mole) of ethyl benzoate was added, and the reaction was further car-
ried out for 1 hour. The reaction mixture was cooled to 60C, and 2.9 ml
(0.025 mole) of SiC14 was added dropwise over the course of 30 minutes,
and the reaction was performed at 60C for 1 hour. After cooling, the
solid portion of the product was collected. It was fully washed with kero-
sene, and suspended in 300 ml of titanium tetrachloride and reacted at
130C for 2 hours. After the reaction, the supernatant liquid was removed
by decantation. The solid portion was fully washed with fresh kerosene to
afford a solid complex titanium component (a) which contained 4.1% by
weight of titanium atom, 54% by weight of chlorine atom, 16.7% by weight
of magnesium atom, and 11.3% by weight of ethyl benzoate.
Propylene was polymerized in the same way as in Example 1. There
was obtained 296.2 g of polypropylene as a white powder. The polymer had
a boiling n-heptane extraction residue of 95.1%, an apparent density of
0.30 g/ml and a melt index of 3.6.
Concentrating the liquid layer afforded 12.0 g of a solvent-
soluble polymer.
Example 10
Ball milling was performed in the same way as in Example 1 except
that 6.5 ml of isoamyl ether were used instead of ethyl benzoate. The
pulverized product was contacted with titanium tetrachloride in the same
way as in Example 1 to afford a component (a) which contained 2.1% by
weight of titanium atom and 69% by weight of chlorine atom.
Propylene was polymerized in the same way as in Example 1. There
was obtained 325.3 g of polypropylene as a white powder which had a boiling
n-heptane extraction residue of 93.3%, an apparent density of 0.35 g/ml,
and a melt index of 4Ø
~r - 18 -
5~ 7
Concentrating the liquid layer afforded 9.9 g of a solvent-
soluble polymer.
Example 11
A reactor equipped with a reflux condenser was charged with 200
ml of Grignard reagent ~ethyl ether solution, 2 moles/liter), and 0.4 mole
of p-cresol was added dropwise at room temperature. After the reaction,
the ethyl ether was removed by distillation. The resulting white powder
was suspended in 200 ml of purified kerosene. Ethyl benzoate ~0.1 mole)
was added to the suspension, and the reaction was performed at 80C for 2
hours. After the reaction, the reaction mixture was cooled to room tempera-
ture. The resulting solid was collected by filtration, washed with puri-
fied hexane, and dried at reduced pressure.
The reaction product was suspended in 300 ml of titanium ~etrachlo-
ride, and with stirring, reacted at 80~C for 2 hours. After the reaction,
the product was hot-filtered, and sufficiently washed with purified hexane.
Drying under reduced pressure afforded a solid complex titanium component
(a) which contained 3.3% by weight of titanium atom, 56% by weight of chlo-
rine atom, 18.7% by weight of magnesium atom, 8.7% by weight of ethyl ben-
zoate, and has a specific surface area of 170 m2/g.
Propylene was polymerized in the same way as in Example 1. There
was obtained 264.2 g polypropylene as a white powder. The polymer had a
boiling n-heptane extraction residue of 93.7%, an apparent density of 0.32
g/ml, and a melt index of 3.2.
Concentrating the liquid layer afforded 9.7 g of a solvent-
soluble polymer.
Example 12
Anhydrous magnesium chloride (20 g) and 1.2 ml of titanium tetra-
chloride were placed in a stainless steel (SUS-32) ball mill cylinder having
an inner capacity of 800 ml and an inside diameter of 100 mm and having
accomodated therein 100 stainless steel (SUS-32) balls having a diameter of
15 mm, and contacted with each other for 30 hours at a speed of 125 rpm.
X - 19 -
~ ~5~7
Ten grams of the solid powder obtained was suspended in 100 ml of kerosene
and at 60C, 15 ml of ethyl p-toluate was added dropwise over the course
of 30 minutes. The reaction was performed at 70C for 1 hour. The pro-
duct was collected by filtration, washed with hexane, dried. Ten grams
of the resulting solid product was suspended in 100 ml of titanium tetra-
chloride, and reacted at 100C for 2 hours. The product was filtered,
sufficiently washed with hexane, and dried. The resulting solid complex
titanium component (a) contained 2.0% by weight of titanium atom and 56.0%
by weight of chlorine atom.
Propylene was polymerized in the same way as in Example 1. There
was obtained 265.4 g of polypropylene as a white powder. The polymer had
a boiling n-heptane extraction residue of 93.7%, an apparent density of
0.32 g/ml and a melt index of 6.2.
Concentrating the liquid layer afforded 10.3 g of a solvent-
soluble polymer.
Example 13
Ten grams of the solid complex titanium com~ound (a) obtained
in the same way as in Example 1 was suspended in 200 ml of purified kero-
sene, and 6.3 millimoles of titanium tetrachloride was added at room
temperature. The reaction was performed for 1 hour. Further, 6.3 milli-
moles of ethyl benzoate was added, and the reaction was performed for 1
hour. The reaction product was filtered, washed with hexane, and dried
to afford a solid complex titanium component (a) which contained 3.5% by
weight of titanium atom.
Propylene was polymerized in the same way as in Example 1.
There was obtained 276.2 g of polypropylene as a white powder. The poly-
mer had a boiling n-heptane extraction residue of 93.7~, an apparent den-
sity of 0.34 g/ml and a melt index of 4.8.
Concentrating the liquid layer afforded 10.2 g of a solvent-
soluble polymer.
~ - 20 -
~5~7
Examples 14 to 18
Solid complex titanium components ~a) were prepared in the same
way as in Example 1 except that ethyl benzoate was changed to electron
donors as shown in Table 2, and propylene was polymerized. The results are
shown in Table 2.
- 21 -
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- 22 -
5~
Examples 19 to 23
Solid titanium complexes were prepared in the same way as in
Example 2 except that the alcohol, ester and organoaluminum compound (or
tin or silicon compound) were changed as shown in Table 3, and propylene
was polymerized in the same way as in Example 1. The results are shown
in Table 3.
- 23 -
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~ - 25 -
