Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~.~l &~
TITLE OF THE Ir`~TENTION
Process for producing ~-olefin polymers
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for producing
~-olerin polymers. More particularly it relates to a
process for producing ~-olefin polymers which are highly
crystalline and have a good particulate form,
wlth a good yield, by the use of a novel catalyst
which is suitable for a-~lefin polymerization,
particularly gas phase polymerization ~nd further, combina-
tions of gas phase polymeri2ation with slurry polymexization
or bulk polymerization, as modifications of gas phase
polymerization.
2. Description of the Prior Art
It has been well known that ~-olefins are polymerized
in the presence of the so-called Ziegler-Natta catalysts
comprising a compound of transition metals of groups IV to
VI of the Periodic Table and an organome~allic compound of
metals of groups I to III of the Table and including those
modified by adding an electxon donor, etc. Further, for
producing highly crystalline polymers of propylene, butene-1,
etc., titanium trichloride has been most widely used for
the above compound of transition met ls as a component of
the catalysts. Th~ titanium trichloride is ~lassified into
~h
.,
... , . :
~ ~&5~3~
the following three kinds according to its preparation:
(1) a product obtained by reducing TiCQ4 with hydrogen,
followed by milling in a ball mill for activati.on (which
is called titanium trichloride (HA));
~2) a product obtained by reducing TiCQ4 with metallic
aluminum~ followed by milling in a ball mill for activation,
i.e. a compound expressed by the general ormula TiCQ3 1/3_
AQCQ3 (the so-called titanium trichloride (AA)); and
~3) a product obtained by reducing TiCQ4 with an organo
aluminum compound, followed by heat treatment.
However, these kinds of titanlum trichloride are not
fully satisfactory, and various improvements have been
considered and attempted. As one of such improved processes,
a process has been proposed ~herein TiC~ is reduced with
an organoaluminum compound to obtain a titanium trichloride
which is then treated with an electron donor and TiCQ4
whereby the activity of the resulting catalyst is enhanced
and also the amount of amorphous polymer formed is reduced
te.g. Japanese patent application laid-open No.Sho 47-34~78/1972).
However~ such a process has a drawback that the catalyst is
deficlent in the heat stability.
Further another process has been proposed wherein
TiCQ4 and an organoaluminum compound arP respectively and
separately mixed and reacted with a definite amount of a
complex-forming agent ~including electron donors~ in advance,
-- 2 --
,
~R .,
,, , ,,, ., ., , . , , , ,,, . , , . ,,, , ., , . , , ,, ., . , ., . , . , , ,,,, , , ., . , . .. , ., , . ,,, ..
_, .. . . ..
~ '3~
to obtain two separate reaction liquids which are then
mixed and reacted together to prepare a solld catalyst
component (Japanese patent application laid-open
No.Sho 53-9296/1978). Such a process also has the same
drawbac~ as in the above Japanese patent application
laid open No.Sho 47-34478/1972 that the catalyst iS
deficient in the heat stability.
Still further, there have been proposed a process
wherein a uniform liquid material consisting of an
srganoaluminum compound and an ether is added to TiCQ4
or this addition order is reversed to prepare a liquid
material containing titanium trichloride (Japanese patent
application laid-open No.Sho 52-115797/1977), and a process
wherein the above liquid material is heated to a temperature
of 150C or lower to deposit a finely particulate titanium
trichloride. However, such pxocesses also have the same
drawback as above that the catalyst is deficient in the
heat stability.
On the other hand, as to the phase of a-olefins in
which they are polymerized in the presence of the Ziegler-
Natta catalysts, slurry polymerization which is carried
out in a solvent such as n-hexane (e. gJ Japanese patent
publication No~Sho 32-1059~tl9571, bulk polymerization
which is carried out in a liquefied monomer such as li~uefied
I propylene 5e.g. Japanese patent publication Nos.Sho 36-6686jl961
'.
and Sho 38-14041/1963), and gas phase polymerlzation which
is carried out in a gaseous monomer such as gaseous
propylene le.g. Japanese patent pu~licatior. Nos~Sho 39-
14812/1964 and Sho 42-17487/1967) have been well known.
Furt.her a process of carrying out bulk polymerization
followed by gas phase polymerization has a1SQ been known
(e.g. Japanese patent publication No.Sho 49-14862/1974 and
Japanese patent application laid-open No.Sho $1-135987/1976).
Among these processes, g~s phase polymerization is advan
tageous in ~hat recovery and re~se of solvent used for
polymerization as in the case of slurry polymerization
are unnecessary; recovery and reuse of liquefied monomer
used for polymerization as in the case of bulk polymerization
are um~ecessary; the recovery cost of solvent or monomer
is small; e~uipments for producing ~-olefins are simplified;
etc. On the other hand, gas phase polymeri~ation is
disadvantageous in that since the monomer inside ~he reaction
vessel is present in gas phase, the monomer concentration is
lower than those in the case of slurry polymerization process
or bulX polymerization process to make the reaction rate
lower; hence, in order to increase the polymer yield per
unit weight of catalyst, it is necessary to prolong the
retention time or there~or to enlarge the reaction vessel,
or in order to enhance the catalyst activity, it is necessary
to use a modified trial~ylaluminum whereby the stereoregularity
!l
~&5~
of polymer is reduced. Further according to gas phase
polymerizat}on, uneve~ ~olymer particles are liable to
form due to wleven c~talyst particles. This is lilable
to cause agglomeration of polymer particles~ clog~ing at
the polymer discharge port of the polymerizat~`on vessel
or on the transportation line or clogging due to fi~e
particles accompanying unreacted u-olefin from the polymerization
vessel to thereby make difficult a long term stabilized,
oontinuous operation and make the quality dispersion greater.
The present inventors have previously invented as a
polymerization process which does not ha~e the above-described
drawbacks even in the case of gas phase polyme ization, a
process ~or producing ~-olefin polymers wherein a reaction
product o an organoaluminum compound with an electron-
donor is reacted with TiCQ4 to obtain a solid, which is
r~acted with an electron donor and an electron acceptor
to obtain a solid product, which is combined with an
organoaluminum compound to obtain a catalyst, in the presence
of which a-olefins are polymerized (co ~ ding Cana~an patent application
369,855, filed Feb. 2/81, now patent 1,151,142, issued AugO 2/83, whi-ch
will here~after be referred to as "previous invention A"~.
This previous invention A has been characterized in
that a long term stabilized gas phase polymerization can
be operated; the catalyst has a high storing st-~bility and
heat stability during poly~erization; the polymer yield in
~ , .
the gas phase polymerization amounts to 5,000 to 6,000 g/g
(solid product3; and the amount of amorphous polymer formed
is reduced. However, the storing stab~lity of the catalyst
at high temperatures above 35C has been insufficient, and
also the heat stability of the catalyst has been required
to be higher~
The present inventors have made further studies for
improving the catalyst, and as a result, have found ~hat if
the above-mentioned solid obtained by reacting a reaction
product of an organoa1.~minum compound with an electron
donor, with TiCQ4, is subjected to polymerization treatment
with an ~-olefin, and the thus-treated solid is reacted with
an electron donor and an electron acceptor, then it is
possible to further improve the storing stability and heat
stability of the catalyst. Thus the present invetntors havei,;
attained a first aspect of the present lnvention.
Further, as a process which does not have the above-mentioned
: drawbacks even in the case of gas phase polymerization,
the present inventors have previously invented a process
for producing ~-olefins wherein a reaction product of an
organoaluminum compound with an electron donor is reacted
\
with TiC~4 to obtain a solid material, which is then reacted
with an electron donor and an electron acceptor to obtain
a solid product, whicn is then combined with an organo
al~minum compound and a reaction product (C-) of an ~-olefln
and an organoal~num compound wi~ an elec~on donor, to obtain a pre- -
ac~vat~d catalyst, and ~-olefins are pol~iz~ ~ the presence of the
preactivated ca~lyst (co ~ d~g ~adian patent application 370,888,
filed Feb. 13J81, now patent 1,142,698, issued March 8/83; this applica-
tion will her ~ after be referred to as "previous ~vention B"~.
The above pre~ious invention B of the present i~.ventors
has been characterized in that no polymer lump is formed
in the gas phase polymerization; a long term stabilized
operation is possible even in the case of gas phase
polymerization; the polymer yield in the gas phase
polymerization amounts to 7,000 to 12,00Q g/g (solid
productl and the amount of amorphous polymer formed is
reduced; without increase in the a~ount. of atactic pol~mer,
lt is possible to control the stereoregularity of polymer
and it ls also possible to control the toughness, particularly
the bending modulus, of polymer, and the storage stability
5~
and the heat stability of catalyst are superior, On the
other hand, such pr~blems have been raised that when the
catalyst is stored at a high temperature of 35C or higher,
reduction in the catalyst activity is observecl; a long term
storage of the mixture catalyst obtained by adding an
organoaluminum compound and a reaction product tG) of an ~-olefin,
an organoaluminum compound and an electron donor, to the solid
product raises a problem; and in the case of a high temperature
polymerization at 90C or higher, the resulting polymer
has a.n inferi~r form and the percentage of amorphous polymer
~ormed increases,
The present inventors have continued further studies
for improvement, and as a result have found that if a solid product
: subjected to polymerizat:ion treatment with an ~ olefin .
at either one of the steps for preparing the solidl'product
i5 used in place of the solid product tIII3 used in the
previous invention A or B, then i-t is possible for further improve
the storing stability and the heat stability of the catalystO
Thus a .first or second aspect of ~he present invention has been
attained,
The object of the present invention having
the first and second aspects is to provide
a process for producing ~-olefin polymers wherein a catalyst
having a furthe:r improved storage stability and heat
stability is used~ whereby even when gas phase polymerization,
slurry polymerization or bulk polymerizat:ion is c~rried out
at a further higher temperature than those in the previous
inventions A and B, the resulting polymer has
a uniform particle size; the catalyst activity is higher;
the percentage of amorphous polymer formed is lower;
particularly the advantages of gas phase polymerization
can be fully exhibited; and in addition, the stereoregularity
of poly~er can be easily co~trolled in the second aspect.
SUI~MARY OF THE INVENTION
The present invention resides briefly in
a process for producing ~-olefin polymers which cQmprises
- polymerizing an ~-olefin in the presence of a preacti~ated
catalyst obtained by
reacting a reaction product II) of an organoaluminum
compound ~Al) with an electron donor (Bl), with TiC~4 ~C)
to obtain a solid product (II;;
further reacting this solid product ~II) with an
electron donor (B2) and an electron acceptor ~E) to obtain
a solid product (III),
during or/and after the reaction step for obtaining
the solid product (II) or/and during or/and after the
reaction step for obtaining the solid product (III),
subjecting the solid prcduct (II) or (III) to a
polymerization treatment with an ~-olefin; and
.
_ g
combining the resulting final solid product with an
organoaluminum compound (A2) or an organoallIminum
compound IA2) and a reaction prcduc~_ (G)
of an organoal-~inum compour.d (A3) with an electron donor --
(B3) to obtain a preactivated catalyst; and preferably,
in this combination,
further subjecting a part or the total of said
preactivated catalyst to a polymerization treatment with
an ~-olefin in the presence of said final solid product
and said organoaluminum compound (~2) to obtain another
preactivated catalyst.
The "polymerization treatment" referred to herein
means that a small amount of an ~-olefin is contacted with
catalyst components (i.e. solid product ~II), solid product
(III) or final soiid product), under polymeri7able conditions
of the ~-olefin to polymerize the ~-olefin, and this
polymerization treatment brings about a state where the catalyst
components are coated with polymer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preparation of the catalyst used in the present
invention will be ~irst described below.
_ The above-mentioned final solid product is prepared
as lollows:
First, an organoaluminum compound is reacted with an
electron donor to obtain a reaction product (I~, which is
then reacted with TiCQ~ to obtain a solid product (II),
which is further reacted with an electron donor and an
--10 --
., i !
electron acceptox to obtain a solid product (III), and at
either one or both of the steps for obtaining the solid
product (II) or (III~, either one or more of the solid product
(II~ during its formation, the solid product (II) formed or
the solid product (III) are subjected to a polymerization
treatment with an ~-olefin to obtain a final solid product.
The reaction of an organoaluminum compound (Al) with
an electron donor (Bl) is carried out in solve.nt (D) at a
temperature of -20C to 2~0C, preferably -10C to 100C,
for a time of ~0 second~s to 5 hours. The addition order
of (A~ B13 and ~D) has no particular limitation, and
suitable proportions of their amounts used are 0~1 to 8
mols, preferably 1 to 4 mols, of the electron donor and
0.5 to SQ, preferably 0.5 to 2Q, of the solvent, each based
on one mol of the organoaluminum compc`undO The solvent is
preferred to be aliphatic hydrocarbons. Thus a reaction
product (I) is obtained. This reaction product (I) can be
subjected to the succeeding reaction without separating it
i.e. in a liquid state where the reaction has ~een completed
(this liquid state will hereinafter be referred to as
reaction liquid (I)).
.....
The method o~ subjecting the solid product (IIj or (III)
to a polymeri~ation treatment with an ~-olefin, during or/and
after the reaction step for obtaining the solid product (II)
or/and during or/and after the reaction step for obtaining
the solid product (III), includes
(1) a method wherein an a-olefin is added at an optional
tlme during the reaction of the reaction liquid (I) with
"
8~;~fG8
TiCQ4 (C) -to subject the solid product (II) to poly~erization treat-
~e.nt, during its for.mation;
(2) a Ire-thod wherein af-ter completion of the reac-tion of the reaction
l.iquid (I) wi-th TiCQ4, an ~-olefin is added to subject the solid
product (II) to polymerization treat~ent;
(3) a method wherein a solid product (II) obtained after filtering
off or decantation and then washin~ or the solid pr3duct ~II) subjected
to polymerization -treatment, obtained according to the above method (1~
or (2), is ccmbined wi-th an organoaluminum compound, f~ ed ~y adding
an a-olefin to subject the combina-tion to polymeriza~ion t~eatm~n~;
(4) a method wherein during the step where the solid product (II) or
the solid product (II~ subjected to polyrrerization ~reatm~n~, ob-taine~
in the above method (1) or (2), is reac-ted with an electron donor and
an electron accep-tor -to obtain a solid product ~ , an ~-olefin is
added to carry out polymerization treatment; and
: (5) a m~e-thod wherein a solid produc-t (III) obtained after filtering
off or decan ation and then washing is combined with an orga~oaluminum
compound, follcwed by adding an ~-olefin to subject the combination
to polymeriza-tion treatment.
In the case of the polymeriza-tion treatment with an
~-olefin according to the above rrethod (1) or ~2), an ~-olefin i5
passed under the a-tm.ospheric pressure, or added so as to give a
pressure of 10 kg/cm or lower, at a reaction temperakure of 30 ~o
90C for 5 minutes to 10 hours. As -to the amount of ~.-olefin added,
it is preferred to use 10 to 5,000 g of ~-olefin per 100 g of ~he
solid product (II) to be formed or formed or the solid prcduct (III) to
be formed or formed and polymerize 0.05 to 100 g thereof. ~fter
completion of -the polymerization trea-tment with ~-oleEin, unreacted
- 12 -
rrab/
olefin is purged and the resulting material is used for the
succeeding step, in the suspension state in so:Lvent, as
it is, or in the form of solid matter obtained after drying
the suspension. --
In the case where the polymerization treatment with
an ~-clefin is applied to the solid product (II) or the
olid product (III~ obtained after filtering off or decanta-
tion and then washing, or the solid product (II) subjected
to polymerization treatment, obtained accordi~g to the above
method (1) or (2), it is preferred to add 10 to 2,000 mQ
of a solv~nt and S to 500 g of an organoaluminum compound
to 100 g of the solid product (II~ or the solid prod~ct (III),
and add 10 to 5,000 g of an ~-olefin under 0 to 10 kg/cm2G
at a xeaction temperature of 0 to 90C for .5 minutes to
10 hours to polymerize 0.05 to 100 g of the olefin. The Ii
solvent is preferably aliphatic hydrocarbons, and the
organoaluminum compound may be either the same as or different
from that used for the reaction liquid (I). After the poly-
merization treatment with an ~-olefin, unreacted ~-olefin
is purged and the resulting material is filtered off or
decanted and then washed with a solvent. Thereafter it is
used at the succeeding step, in a state where it is suspended
in a solvent or in the form of solid matter obtained aft~r
drying the suspensionO
The reaction of the reaction product (I~ with TiCQ4 (c) is
- 13 -
, . . .
! ~
carried out at 0 to 200C, preferably 10 to 90C, for
5 minutes to 10 hours. Although solvent is preferably not
used, aliphatic or aromatic hydrocarbons may be used.
Mixing o-~ tI), (C) and solvent may be carried c,ut iIl any
order, and it is preferred to complete mixing of the
total amount within 5 hours. Even during the mixing, the
reaction is carried out, and aftex mixing of the total
amount, it is pre~erred to further continue the reaction
within 5 hours. As to the respective amounts used for
the reactiont the ~olvent is ~sed in an amount of 0 to 3,000 mQ
per mol of TiCQ4, and the reaction product (I) is used in a
ratio of the number o~ A~ atoms in (I~ to the number of Ti
atoms in TiCQ4 IAQ/Ti)~ of O.OS to 10, pre~erably 0.06 to
0.3. It is also possible to add an ~olefin at an optional
time during the reacti~n of ~I) with (C~ to carry out thei'
polymerization treatment. A~ter completion of the reaction,
a solid product (II) obtained by filtering off or decanting
a li~uid portion, followed by repeating washing with a
solvent, or a solid product (II) subjected to polymeri2ation
treatment with an ~-olefin, may be used at the succeeding
step in a state where the product (II) is suspended in a
solvent, or in the form of solid matter obtained after
drying the suspension. The former solid product tII) or
the solid product (II) subjected to polymerization treatment
may be further combined with an organoaluminum compound,
14.
followed by adding an ~-ole~in to the resulting com~ination
to carry out polymerization treatment. After the polymer-
ization treatment with an ~-olefin, the resulting material
is subjected to filtering off or decantation and then
washing, and used a-t the succeeding step in a state where
it is suspended in a solvent or in the form of solid matter
obtained af er drying the suspension.
The former solid product (II) or the solid product ~II)
subjected to polymerization treatment is then reacted with
an electron donor IB2) and an electron acceptor (E). Although
this reaction can be carried out without any solvent, use
o~ aliphatic hydrocarbons affords preferable results.
. Further, in this step, an a-olefin may be added to carry out
pol~merization treatment. The respective amounts used are
. 10 to 1,000 g, preferably 50 to 200 g, of (B~), 10 to 1,000 g,
preerably 20 to 50Q g~ of (E), 0 to 3,000 mQ, preferably
100 to 1,000 mQt of the solvent, and 0 to 5,000 g~of an
a-olefin, each based on 100 g of the solid product (II~ or
. . _ . .
t~e solid produc~ ~II) subjected to polymerization treatmentO
._ ., . _ .. . . . . . . . _ .. ___ _ _ .
These four or five substances are preferably mixed at -10C to
40C for 30 seconds to 60 minutes and reacted at 40 to 200C, pre-
ferably 50 to 100C for 30 seconds to 5 hours. The mixing orderof the solid product (II~, (B2~, (EJ, the solvent and the a-olefln .
has no particular limitation. (B~) and (E) may be reacted with
one another ln advance of mixing them with the.former solid
product (II~ or the-solid product (II) subjected to poly-
merization treatment, and in this case, (B2~ is reacted
with (E~ at 10 to 100C for 30 minutes to 2 hours, followed
- 15 -
',t l!
, ~
~s~
by cooling down to 40C ox lower for use~ After completion
of the reaction of the solid product iII~ or the solid
product (II) subjected to polymerization treatment, (~21 and (E),
a llquid portion is separated and removed by filter.ing off
or decantation, followed by repeating washing with a solvent
te obtain a solid product (III). This solid product (III)
may be further combined with an organoaluminum compound,
follo~ed by adding an ~-olefin to carry out polymerization
treatment. After the polymerization treatment with an
~-olefin, the resulting material is subjected to filtering
off or decantation, followed by washing to obtain a final
solid product. This final solid product is used at the
succeeding step in a state where it is suspended in a solvent,
or in the foxm of solid matter obtained after drying the
suspension. Yn the case where the solid product ~iIII) is not
sub~ected to the polymerization treatment with an ~-olefin,
tl~e solid product (III) corresponds to the inal solid
product~ In this case, polymerization treatme~t must have been
carried out at least at the step of the solid pro~uct (II).
The final solid produc~ thus obtained is then combined
with an organoaluminum compound (A2) or
an organoaluminum compound (A2) and a reaction product
.. ..
tG) of an organoaluminum compound (A3) with an electron
donor (B3), or preferably an ~-olefin is further added to
the resulting combination, to obtain a preactivated catalyst.
By adequately selecting the reaction product ~G) at the time
o~ the combination, it: is possible to control the stereoregularity
of the resulting polymer. This preactivation will be
describzd later in det:ail.
- 16 -
The organoaluminum compounds employed in the present
invention are expressed by the general formula AQ~nR'nX3_
wherein ~ and R' each represent a hydrocarbon group such as
al~cy:l group, aryl group, alkaryl group, cycloalkyl group, etc. ^-
~r alkoxy group; ~ represents a halosen such as ~luorine, chlorine,
or iodine; and n and n' each represent an optional
number of O ~ n+n' _ 3, and as concrete examples,
trialkylaluminums such as trimethylaluminum, triethylaluminum,
tri~n-propylaluminum, tri-n~butylalumi~um, tri-i-butylaluminum,
tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methyl-
pentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, etc.,
dialkylaluminum monohalides such as diethylaluminum monochloride,
di-n-propylaluminum monochloride, di-i-butylaluminum monochloride,
d~ethylaluminum monofluoride, diethylaluminum,monobromide,
diethylaluminum mo~oiodide, etc.; alkylaluminum hydrides such
as diethylaluminum hydride; an~ alkylaluminum halides s1~ch as
methyl2iumi.num sesquichloride, ethylaluminum sesauichloride,
.... - 17 ~
'' , :
!, 1/
,, , . , _ _ _ _,,,,,,,,, ~,,,, ,,,,, " _, _, _,, ,,,,,, , , _,, _,__,,,__ .,, _,,__ _ _, " ., . , .. _ ,, , _ _ _ _,,, _ ___~ _,,, .,, , ... .
,,, _ . , , _ .. ,,. ,, .. __ , ..
~.~&~5~
ethylaluminum dichloride, i-butylaluminum dichlorlde, etc.
are mentioned. Besides, alko~yalkylaluminums such as mc!)no-
- etho~cydiethylaluminum, diethoxymonoethylaluminum, etc.
may be also employed. These organoaluminums may be employed
in admixture of two or more ~inds. The organoaluminum compound
(Al~ for obtaining the solid product (I3, the organoaluminum
compound (A2) to be combined with the final solid product and
~A3) for obtaining the reaction product (G) may be the same
~s or differen~ from one another.
As for the electron donors employed in the present
inventlon, various kinds are illustrated below, but it is
preferable that electron donors composed mainly of ethers
be employed ~s ~Bl) and ~B2), and other electron donors
be ~inployed togeth~r wlth ethers.
As for the electron donors employed, organic compounds oon~aining
at least one atom of oxygen, nitrogen, sulfur and phosphorus,
such as ethers, aleohols, esters, aldehydes, fatty acids~
aromatic acids, ketones, nitriles, amines, amides, urea,
thiourea, isocyanates, a~o compounds,
. ..
, ,
phosphines, phosphites, phosphinites, H2S, thioethers,
thioalcohols, etc. are mentioned. As for concrete
examples, ethers such as diethyl ether, di-n-propyl e-ther,
di-n-butyl ether, diisoamyl ether, di-n-~entYl ether, di-
n-hexyl e-ther, di-i-hexyl ether, di-n-octyl ether, di-i-
oc-tyl ether, di-n-dodecyl ether, diphenyl ether, ethylene
glycol monomethyl e-ther, diethylene glycol dimet~yl ether,
tetrahydro.Luran; alcohols such as methanol, ethanol,
propanol, butanol, pen-tanol, hexanol, ~ctanali phenols
such as phenol, cresol, xylenol, e-thylphenol t na~hthoate
esters such as methyl methacrylate, ethyl aceta~e, butyl
formate, amyl acetate, vinyl lacta,e, vinyl acetate~ ethyl
benzoate, propyl benzoate, butyl benzoate~ oc-~yl benzoa-te,
2~ethylhexyl benzoate, methyl -toluylate, e-thyl toluylate,
2-ethylhexyl -toluylate, methyl anisate, ethyl anisate,
propyl anisate~ ethyl cinnamate, methyl nap~tnoate, e-thyl
naphthoate, propyl naphthoate, butyl naphthoate, 2-ethyl-
hexyl naphthoate, ethyl phenylacetater aldehydes such as
acetaldehyde, benzaldehyde; fatty acids such ~s formic
acid, ace-tic acid, propionic aci~d, lactic acid, oxalic
acid, succinic acid, acrylic acid, male.~c acid; aromatic
acids such as benzoic acid; ketones such as-me~hyl ethyl
ketone, methyl isobutyl ketone, benzophenone; nitriles
such as acetonitrlle; amines such as methylamine, diethyl-
amine, tributylamine, -triethanolamine, ~N~N-dimethylamino~
ethanol, pyridine, quinoline, u-picoline, 2,4,6-trimethyl-
pyridine, N,N,N',N'-tetramethylhexaethylenediamine~ ~niline,
dimethyl-aniline; amides such as
~, - 19 -
ma~/
formamide, hexan1~t1ly~ osL-horic acid ~riamide, N,N,N' ,N' ,N"
pentamethyl ~ dime~hylaminoethyl phosphoric alcid triamide,
octamethylpyrophosphoroamide; ureas such as N,N,N',N'-
tetramethylurea; isocyanates such as phenylisocyanate,
toluylisocyanat~; azo compounds such as azobenzene; phosphines
5uch as ethylphosphine, triethylphosphine, tri-n butylphosphine,
tri-n-octylphosphine, triphenylphosphine, triphenylphosphlne
oxide; phosphites such as dimethylphosphite, di-n-octylph-
osphite, ~riethylphosphite, tri-n-butylphosphite,
~0 triphenylphosphi~e; phosphinites such as ethyldiethylphosphinite,
ethyldibutylphosphinite, phenyldiphenylphosphinite; thioethers
such as diethyl thioether, diphenyl thioether, methyl phenyl
thioether, ethylene sul~ide, propylene sulfide; and thioalcohols
such as ethyl thioalcohol, n-propyl ~hioalcohol, thiophenol, -
are mentioned. These electron''donors may ~e employed in
admixture. The electron donor (Bl) for obtaining the reaction
produc (I), (B2~ to be reacted with the solid product (II) or
the solid product (II~ subjected to polymerization trea~ment
and IB3) for obtaining the reaction product ~G) may be the same
as or di~ferent ~rom one another.
The electron acceptoss (E) employed in the present invention
are represented by halides o~ elements o III Group to VI Group
o~ 'che Periodic Table. As concre~e examples, anhydrous
AQC~3, organoaluminum compounds~expressed by the general formula
AQRnX3 (0<n~2),~SiCQ4~ SnCQ2, SnCQ4, TiCQ4, ZrCQ4, PCQ , PCQ
VC~4, SbCQ5, etcO are mentioned~ They may be employed in
admix~ure. TiCQ4 is most preferable.
As or the solvent 9 the following ones are employed~
As aliphatic hydxocarbons, n-pentane, n-he~ane, n-heptane,
n-octane, i~octane, etc. are mentioned. Further, in place
of the aliphatic hydrocarbons or tog~ther therewith,
halogenated hydrocarbons such as carbon tetrachloride;
chloroform, dichloroethylene, trichloroethylene~ tetra-
chloroethylene, etc~ may be also employed. As for aromatic
compounds, aromatic hydrocaxbons such as naphthalene, and as
their derivatives, alkyl substitutes such as mesitylene,
durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene,
1-phenylnaphthalene, etc., and halides such as monochloro-
benzene, chlorotoluene, chloroxylene, dichlorobenzene,
bromobenzene, etc. are mentioned.
As for a-olefins employed for the polymerization
treatment, i~
straight chain monoolefins such as ethylene~ propylene,
butene-l pentene-l, hexene-l, heptene-l, etc.,branched
chain monoolefins such as 4-me~hyl-pentene-1, 2-methyl-
pentene-1,3-methyl-butene-1, etc. are mentioned. Styren
may also be used. These ~ ole~ins may be same as or
di~erent from those used for preliminary aotivation or
those used for regular polymerization, and may be employed
in admixture.
- 21 -
Next, a method of combining the final solid product,
an organoaluminum compound (A2) and the reaction product ~G)
of an organoaluminum compound (A3) wirh an electron donor
(B3) to prepare the cacalyst, in the second aspect of the
present invention, and a preferable method of further carrying
out preactivation with an ~-olefin to prepare the catalyst,
in the first and second aspects of the present invention,
will be described below in detail.
~he organoaluminum compounds (A2) and (A3) constituting
10. the catalyst used in the present invention are not required to
be the same as (Al) used for forming the reaction liquid (I),
but (A~ A2) and ~A3) may be the same as or diferent from one
another. The most preferable organoaoluminum compounds are
; dialkylaluminum monohalides as (Al) and (A2~ and trialkylaluminums
as (A3). i,!
... . . . . . -- .
The electron donor (B3) employed for preparing th~ .
react~on pxoduct (G~ may be selected from among those in -
_ . _ _ _ . . . _ .... . .
the same range as that described in the reaction
.... . .. . _ . ............ .. ~ . . . .
- for obtaining the final solid product, but.may not be
necessary to be the same compound as that employed for obtaining
the final solid product. The reaction product (G) is
usually obtained by reacting 1 mol o an organoaluminum compound
(A3) with 0.01 ~o S mols of an electron donor in the
presence o~ a solvent such as n-hexane, n-heptane, i~ an amount
of 10 to 5,000 mQ based on 1 g of the organoaluminum compound
~ ~2 ~
. -- .. . . . . ~ . ~ = = .. =, . = ., = ..
(A3) and based on l y of the electron donor, at -30 to lOO~C
.for lO mi~utes to lO hours~ Usua1.,ly, t~P reaction is carr~ed
out by dropw:ise adding the electron donor diluted with the
~olvent to tll~ org~noaluminum compound (A3) diluted with the
solvent.
In the case where the final solid product is combined
with the organoaluminum compound (A2)~and in the second
aspect of the present invention, further the reaction
~ product (G~ to obtain the catalyst, the organoaluminum
compo17nd (A2? is used in an amount of O.l to 500 g, pxeferably
0.5 to 500 g and the reaction product ~G3, in an amount of
0.05 to lO g, each per g of the final solid product, and
they may be combined together in any order to obtain the
catalyst. For example, the order of combination may be
either the one of (A2~, th~ final solid product and ~G) or
the one of (A~ G) and the final solid pxoduct.
A further preferred method of the present invention is
a method of adding an ~-olefin to the catalyst components
to subject a paxt or the whole of the cataLyst components
to polymerization treatment for preactivation. A method
o combining the final solid product, the organoaluminum
compound (A2), the ~-olefin ~F) and in the second aspect of
the present invent~on, further the reaction product (G), for
preactivation will be described below in detail.
The preactivation may be carried out by
subjecting a part or the whole of the cataLyst components
o~ 1 g of the final solid product, 0.1 to 500 g, preferably
- 0.5 to 50 g of an organoalumQnum compound (A~) and in the ,second
aspect of the present invention~ further 0.05 to 10 g
of the reaction product (G), to polymeri7ation treatment
at l east in the presence of the final solid product and the org-
anoaluminum co~pound ~A2), with 0.~1 to 5000 g, preferably 0.05 to
3000 g of an ~-olefin. As for the conditions of the polymerization
treatment, ~t i5 preferable that the temperature be in the
range of 0 to 100Ç, pr~ferably 10 to 70C, the time be
in the rang~ of one minute ~o 20 hours, and the ~ olefin be
polymeri~ed în an amount o~ 0 . 01 to ~, 000 g, pre~erably
! 0~Os 0 200 g per g o ~he final solid product. In the
polymerization treatment, 10 L or less of hydrogen may be
made present~ In the p~eactivation, 50~ or less of a solvent
may be employed. The solvent may be hydrocarbon solvents
such as propane, butane, n~pentane, n-hexane, n-heptane, benzene,
toluene, etc,, and the preactivation may be carried out in a
~o liquid a-olefin such as liquefied propylene, liquefied butene~l,
etc., or in gaseou~ ethylene or propylene.
In advance of the preactivation~ polymer particles
obtained by slurry, bulk or gas phase polymerizatlon
may be made coexis~ent. Such polymer may be the s~e
as or di~erent from ~-olefin polymers as the object of
polymerization. The amount of such polymer capable of being
made coexistent may be in ~he range of 0 to 5,000 g per g o
tha final solid product.
~he 501vent or ~-olein employed in the preactivation may be
removed by distil1ina off under reduced pressure, filtration or
~ ~ 5~ ~
the like me,~ns, midway during the preiiminary activation or
after completion of the activation. Further, for suspending
the solid product in a solvent of 80 Q o~ less per g of
the solid product, the solven. may be added. I
For the preactivatlon, -there are va~ious methods.
As for the main embodiments therefor, the following
are illustrated
~1~ a method wherein final solid product is combined
with organoaluminum compound (A2), and ~-olefin (F~ is added
10 ~ to carry out polymerization treatment, followed, in the second
aspect of the present invention, by further adding reaction
product (G);
(2~ a method wherein final solid product is combined
with (A2) in the presence of ~F) to carry out polymerization
treatment with (F), followed, in the second aspect of the present
invention, by further adding (G);
(3)1l~ a method wherein final solid product is combined
with (A2), and in the second aspect of the present invention,
further (G) is added, followed by polymerization treatment with
(F); and
(4) a method wherein, after the polymerization treatment
of the present invention of the above (3), (G) is further added.
In the above embodiments, (G) is, of course, not added in
the case of the first aspect of the present invention.
With regard to the methods (1) and ~2~ of preactivation,
the foliowing concrete methods are further illustrated:
(1-1) a method whe~ein ~inal solid product is combined
wi~h ~A2) and th2 ~esulting combination is subjected to
polym2ri2ation treatme~t with (F~ in ~apor phas~ or in
'_ ':' 1- -~' ' ` - ' `
liquefied ~-olefin or in a solvent, ~ollowed by removing
unreacted (F) or unreac~ed (F3 and solvent and in the second
,aspect of'the present invention, further adding (G);
51-2) a method wherein (G) is added without removing
unxeac:ted (F) or unreacted (F) and solvent, in ~l-l);
~1-3) a method wherein (G) is added and therea~ter
unreacted ~F) or unreacted (F) and solvent are removed,
in (1-2);
(l-4) a method according to ~ 3) wherein
-olefin polymer ohtained in advance i~ added;
tl~5) a method according to ll~ (l 4) wherein
after preactivation, solvent or unreacted IF) and
~olv nt are removed to obtain a catalyst in the form o~
powder;
~2-l) a method wherPin ~A2~ is combinsd wi~h final
~.sol1d product in the presence of a-olefin dissolved in
- a ~olvent or liquefied a-olein or ~-olefin gas~ to carry
out pol~merization treatment with ~-olefin, followe~ i~ the
second aspect of the present invention, by further adding (G);
~2-2) a method wherein (2-l~ is carried out in ~he
presence of ~-olefin polymer ohtained in advance; and
(2-3) a method wherein af~er preactivation,
un~eacted (~) and solvent are removed under reduced p~essura
to obtain a catalyst in the form of powder.
` - 26 - :
In the methods (1) and ~2~, it is possible that a compo-
nent obtained byl reacting final solid product and (A2) with (F)
i5 not mixed with lG) at the time o~ catalyst prepara~ion, but they
are mixed together just before polymerization. Further, in
the methods ~ (4), it is possible to employ h~drogen
together with (F~. Whether the catalyst i5 prepared in
the form of slurry or in the form of powder affords no
essential dif erenceO
The catalyst obtained by combining the final solid product,
~A~ and in the second aspect of ~he present invention,
further ~G), as described above, or the preactivated catalyst
obtained by further reacting it with an ~-olefin is employed
- for producing ~-olefin polymers.
: . .
The~polymcrization may be carried out either by slurry
pol~merization in a hydrocarbon solvent or by ~ulk polymeri-
zation in li~uefied ~-olefin monomer, but, in the present
invention, since the ca alyst has a high activity, gas phase
polymerization of ~-olefins exhibits a particularly notable
effectiveness, and slurry or bulk polymerlzation followed
by gas phase polymerization as a modification of gas phase
polymerization also exhibits a desirable effectiveness.
The gas phase polymerizatj.on of a-ole~ins may be carried
ou~ not only in the absence of solvent such as n-hexane,
n-heptane, but also in a state where 0 to 500 g o~ solvent
p~xXg o~ ~-olefin polymer is contained. Fuxther it may be
carried out either by continuous polymerization or batc~
polymerization. Fuxthermore, i~ may be carried out in
.. `- 27 -
"
fluidized bed manner, or in fluidized manner by w~y or
agitating~lements, or in stirring mann~-r by way lf vertical
or horizontal type paddle.
As for the me~hod of slurry or bulk polymerization
followed by ~as phase polymexization, of ~-olefins, the
following are illustrated: for example, in the case of
batch polymerization, a method wherein ~-olefin is poly-
merized in a solvent or liquefied -olefin monom~r, ~d
thereafter the solvent or ~-olefin monomer is removed so
that it is contained in an amount of SdO g or less per ~
og pulymer par~icles, followed by polymerizing ~-olefin in
~apor phase, and a method wherein polymerization OL ~-olefin
is continued without removing the solvent or liquefied
~olefin, and moves intc.l gas phase polymerization without
aadin~ any op~ration 5ince the solvent or liquefiPd ~-olefin
is ab50rbed in the resulting polymerO A plural step polymeri-
zation co~sisting o~ a combination of slurry or bulk polymeri-
zatio~ with gas phase polymerization exhib~ts a desirable
~esult particular~y in the case o~ continuous polymerization.
This plural step polymerization may be carried out as follows:
~n the first ~tep, slurry or bulk pol~merization is caxried
out wher~n the polymerization i5 continued so as to give
a ~lurry concentration E(PolYmer tKg))/tpolymer tKg) I olvenk
or liquefied ~-olefin tKy))x 100%~ of 70% ox hlgher, or ~he
poly~eri2ation is carried out until a slurry concentration
~ 28 --
: -
~5~
reaches 30 to 50~/ and thereafter solvent or liqueied
~-olefin is removed so as to give a slurry concentration of
70% or higher; and in the second step, ~-olefin is su~ject~d
to vapor phase polymeriz~tion. Xn this method, the catalyst
is added at the time o slurry or bul~ polymerization of
th~ first step, and in th~ gas phase polymeri~ation succes-
sively carried out/ the catalyst of th~ irs~ step may be suffic-
iently employed as it is, but a fresh catalys may be also added
in the second step. As for the proportion of the we.ight
o pol~mer formed by slurry or bulk polymeriæation and that
of polym~r formed by gas phase polymeri~ation, it is prefer-
able that the propor~ion be in the range of 0.1 to 100 parts
~y w~ig~t of polymer of gas phase polymPrization base~ on
one part of polymer of .slurry or ~ulk polymerization.
. "
, 9
As for the polymerization conditions of ~-ole~ins, any
of slurry polymerization, bulk polymerization and gas phase
polymerization may be carried out at a polymerization
temperatu~e o~' room temperature (20C) to 200C, under
a polymerization pressure of the atmospherio pressure
~0 kg/cm2G) to 50 kgJcm G and usually for 5 minutes to 20
hours. In the polymerization, addition of a s~i~able amount
of hydrogen for adjustmes~t of molecular weight, and the like
means are carried out as in c~nventional manner.
1~ As or the ~-olefins employed in the polymerization
oX the present invention, straigh~ chain monoolefins such
as ethylene, propylene, butene-l, hexen~ oc~ene-l, etc.,
branched chain monoolefins such as ~-methyl-pentene~rl,
~ methyl-pentene-l, 3-methyl butene-1, etc~, diole~ins such
as ~utadiena, isoprene, chloroprene, etc- are 1ne~tioned- Styrene
may also be used. These olefins may be homopolymerized or
copolymerized in combination with each other, for example,
in combination of propylene with ethylene; butene with
ethyl~ne; and propylene with butene-l. In this case, they
24 may be polymerized in admixture of mo~omers or in a plurality
of steps where different ~-ole~ins may be employed in the
first step slurry or hul~ polyme~iza~ion and the ~econd step
gas phase polymeriæation.
- 30
s~
The main effectiveness or ~he present invention consists
¦ in that according to the fiirst and second aspects o:E the
present invention, a highly crystalllne polymer having a good
powder form is obtained with a high polymer yield by the use
o~ the catalyst having an improved storage stability and heat
stability, even in the case of gas phase polymerization where
the monomer concentration is relatively low, and also in that
according to the second aspect of the present invention, high
temperature polymerization is possible and yet it is possible
to readily control the stereoregularity of the resulting
polymer with a small amount of amorphous polymer ormed.
The effectiveness of the present invention ~lill be
further described in moxe detail.
- 31 -
~8~4~i~
The first effectiveness of the present invention
is that storage stability of the final solid product and
-the catalyst has been further impro~ed. For example, even
when the final solid product is allowed to stand at a
high temperature of about 40C ror about 4 mon-ths, no
reduction in the polymerization activity occurs; hence
no particular storing equipment for storing the ~inal
solid product is necessary, and even when the final solid
product is combined with an organoaluminum compound and
in the second aspect of the present invention, further
the reaction product ~G), and ~hereafter the resulting
combina-tion is allowed to stand in a high concentration
of the final solid produc-t of 1.0~ or higher~ at 40C or
higher, for about one week till polymeriza-tion is
initiated, no reduction in the polymer.ization activity
occurs; fine pulverization of catalys-t brought abou~ by
agitation in -the ca-talys-t -tank hardly occurs; and the
form of polymer partieles is not degraded.
The second effectiveness o~ the present inven-tion
is that since the resulting catalyst has a very high
activity, a high polymer yield is obtained, of course, in
the slurry or bulk polymerization; further, even in the
gas phase polymeriza-tion where the monomer concentra-tion
is relatively low, the polymer yield per g of the ~inal
solid product amounts to 6,200 to 9,000 g (pol~mer) in
the case of the first aspect of the present invention,
and 9,000 to 15,000 g (polymer) in the case of -the second
aspect of the present inven-tion.
J - 32 -
mab/
s~
The third effectiveness of the present invention
is that since -the polymer is obtained with a high yield,
even if -the amounts of alcohol, alkylene oxide, steam,
etc. employed for killing the catalyst af-ter ~roduction of
~-olefin polymers or purifying the polymer are Eurther
reduced, polymer is no-t colored and has a yellowness
index (YI) as low as 0 to 2.0; further, evolution of
corrosive gas having a bad effect such as degradation of
physical properties of polymer or rusting of mold at the
-time of molding of polymer does not occur: ~or example,
even in the case where ~olymer is heated at 200C,
evolution of a_idic gas changing the color o_ a testing
paper of Congo Red is not observed.
The fourth effectiveness of the present invention
is that the percentage of amorphous polymer formed a-t the
time of produc-tion of ~-olefin polymers, is reduced, and
also such effectiveness is grea-t particularly at the time
of production of copolymer. For example, in the pro~uction
of propylene polymer, the amount of isotactic polypropylene
as n-hexane-insoluble (20C). reaches 98 to 99.8% in terms
of iso-tactic index, and that of atac-tic polypropylene as
n-hexane-soluble is only 0.2 to 2% in terms of atac-tic
index. Thus, even when atactic polymer is not remov~d~
disadvantages such as degrada-tion of physical properties
of polymer such as rigidity, heat stability, etc. are
overcome, whereby removing s-tep of atactic polymer can be
omitted, resulting in simplification of production process
of polymer.
- - 33 -
mab/
~s~
The fifth effectiveness of the present invention is that
pol~mer part~cles having a good form are obtained and also
the av~rage particle slze is small, that is, 90 to 99% of
polymer is in a proportion of 32 mesh pass to 60 mesh on. Il~
The form of particles is close to sphere; the amounts of .-
large particles and fine particles are reduced; and
the particle size distiribution i5 narrow. Further, the bulk
density (BD) of polymer is in the ~ange of 0.45 to 0.52 and
a small area of storage tank per unit weight of polymer may
be sufficient; he~ce it is possible to make compact the plant
~or producing polymer: neither clogging trouble brought by
cohe~ion of polymer particles nor transporting ~rouble
bxo~ght about by fin par~icles occurs; hence particularly
in the gas phase polymerization, it is possible to
carry out a long term stabilized, continuous operation, since
the amount of fine particles entrained in the unreacted
a-olefin gas discharged from the polymerization vessel is
reduced.
. ~4 -
. :-
! ! i
~5~
The fi.rst effecti~ene~s specific of the second
aspect of the present,l invention is that the
high heat-stability of the catalyst has enabled
the pol~merization of ~-olefins to be effected at high 1
temperatures. Heretofore, polymerization at high
temperatures:above 90C often has degraded the powder I -
form and also has increased the percentage of amorphous
polyme.r formed, whereas according to the present invention,
. even when polymerization is carried out above 90C, the
resulting polymer has a uniform powder form and a low
percentage of amorphous polymer formed. Due to the fact
that such a high temperature polymerization is possible,
a large difference between the polymerization temperature
and the temperature of cooling water could have been
afforded to increase the capacity of heat removal and also
the production capacity per a polymerization vessel.
. .
- 35 -
The second effectiveness specific of the second.
aspect of the present invention is that
itliS poss~le to control the sterèoregularity of
polymer without increasing the amount of atactic ~l~lyme.r
as n-hexane-soluble. Fox example, in the case of poly~ ~
propylene, it is possible to ~ptionally control the
., I ..
stereo1egularity of homopolymer in the range of 0~88 to ~.96
in terms of absorbancy ratio of those at 995 cm 1 to those
at 974 cm 1, measured by infrared absorption method ~which
ratio will be hereinafter express~d by IR-T), and also
th~ stereoregularity of capolymer in the range of 0.83 to
0~5, without increase in the amount of atactic polymer.
~eretorore, when the stereoregularity of homopolymer has
been reduced, or when copolymers have been produced, for
lmproving the physical properties o~ molded product of polymer
such as rigidity, impact strength,-~eat seal temperature, e~.c.,
thQ àmo~nt of atactic polymer h~s increased~ Whereas
according to the present invention, it has become possible
to omit the removing step of atactic polymer and yet
optiona~ly controL the stereoregulari~y of polymer depending
~n the appli~ation ields of polymer, in the production of
-polymer.
. ~ 36 ~
:, .
(1~ Pr~para~ion of final solid product
. ~ .
n~Hexane (60 mQ)~ daethylaluminum monochloride (D~AC~
~OOOS mol) and diisoamyl ether ~0.12 mol) wer!~ mixed toget~her
at 25C for on~ minute and then reacted at the same temper-
ature for 5 minutes, to obtain a reaction ~'iquid (I) ~molar
~atio of diisoamyl ether/DEAC:2.4). TiCQ4 (0.4 mol) was
introduced into a reactor pu ~ed with nitrogen gas and heated
to 35C, and thereto was dropwise added the total amount of
the above~mentioned reaction liquid tI) for 180 minutes,
~ollowed by maintainil~g the resulting material at ~he same
t,emperature for 60 minutes, elevating the temperature to 80C,
carrying out further reaction for one hour to form a solid
product ~II), cooling down to 50C, adding propylene (2.85 g)
and carryin~ out polymerization treatment at 50C for 2 hoursO
A~ter the treatment, the liquid was heated to 70C and the
supernatant was removed~ followed by 4 times repeating a
procedure of addlng 400 mQ of n-hexane and removing the
supernatant by decantation to obtain a solid product (II)
subjected to the polymerization treatment ~2004 g i.e.
solid product (II) (19.0 g) plus polymer (1.4 g)). The
total amount of this III) was suspended in 25 mQ of n-hexane,
. - 37 -
,
11
and to the resulting suspensicn were added diisoamyl ether (16 g)
and TIC~ (35 q) at 20C for about one minute, followed by
reastion at 70~C for one hour. A~ter com~letion of th~
reaction, t-he resulting material was cooled down ~o room
temperature (20C~ and the supernatant w~s removed by
I decantation, followed by 5 times repeati~g a procedure of
~dding 400 mQ of n-hexane, stirring for 10 minutes, still
~tanding ana removing the supernatant, and drying llnder reduced
pressure, to obtain a solid product (III). .
~2) ~ f preactLvated~ catal~st
A 2 ~ apacity stainless steel reactor equipped with
slant blades was purged by nitrogen gas, and into this
x~actor were added n-hexane ~20 mQ), diethylaluminum
monochloride (414 mg) and the solid product IIII) (28 mg)
at room temperature. Reaction was then carried out at 40C
under a partial pressure of propylene of 2 ky/cm2G for
lO minutes (reacted propylene per g of solid product tIII):
16.3 g), followed by removing unreac~ed propy-lene and-
n-hexane under reduced pressure to obtain a preactivated catalyst.
- 38 -
,, ., , . . . ~ ,.. ... . . ... . . .. .
(3) ~
il I
Int:o the reactor con~aining the catalyst after completion
o~ ~he preactivation was introduced 3,0~ mQ of hyd~ogen,
and gas phase polymeriza~ion was carried out under a partial
,1 pressure of propylene of 25 Kg/cm Grla~ a polymerization
tempexature o 7;0C for 2 hours. After completion of the
reaction~ S g of methanol wa~ introduced and killing rPaction was
carried out at 70C for 30 minutes, followed by cooling down
to room temperature ~20C) and drying the resulting polymer,
to o~tain 18~-.8 g of polymer-The polymer yield per g of solid
product (I-I~ .Was 6,528 g, the isotactic index (n-hPxane-
insoluble at 20C ~ , 99.8, BD o polymer, 0.50, and the
polymer particles had a form close to sphere, 98 ~ thereof
having sizes between 32 meshes and 60 meshes, and 150 meshes~p
being 0.2~o No coloration of polymer was observed and yellowness
ndex was 2Ø
Example 2
The solid product (III) obtained in Example l was preserved
at 40C for 4 months, and propylene polymerization was then
carried out as in the steps (2) and (3) of Example 1.
Compara~ive e~r~Le 1
The solid product (II) obtained in Example l was preserved
at 40C for 4 months as in Example 2, and propylene polymeri-
zation was then carried out.
~ 39 -
, _, .. , . ,, .,,, , ., .,,, .. , ,, , ., ,, . . . , . , . .. , _ .. . .. . .. . . . .
~1~5~
Comparative example 2
The solid product (II) subjected to polymerization
treatment, obtained in Example l~lwas preserved at 40C for
4 months as in Example 2, and propylene polymerization was
then carried out. ---
Comparative example 3
Propylene pol~merization was carried out as in Example 1
except that the solid product (III) was obtained by reacting
diisoamyl ether with TiCQ4, without subjecting the solid
pxoduct (II) to polymerization treatment.
~.~
A preactivated catalyst was obtained as in the steps
(1) and (2) of Example 1, and n-hexane (1,500 mQ) and
hydrogen ~200 mQ) were introduced, îollowed by slurry
polymerization under a propylene partial pressure of
10 kg/cm G at 70C for 4 hours. After completion of the
polymerization, n-hexane was removed by steam stripping to
obtain a polymer~
Example 4
Propylene slurry polymexization was caxried out as in
Example 3 except that polymerization was carried out at 82C
in place of 70C. The particle form, bulk density and
isotactic index of the polymer were almost unchanged from
those in Example 3.
-4~ -
Comparative exa~le 4
The solid product (II) was reacted wi-th diisoamyl
ether and TiCQ4 as in Exampleil, but ~-ithout subjecting
the solid product (II) to polymerization treatment, to
obtain a solid product (III), an~ propylene polymerization
was carried out at 82C as i~l Example 4~ The resulting
polymer swelled in n-hexane.
Comparative exampl 5
Using the solid product (II~ obtained in Example 1,
propylene polymerization was carried out at 82C as in
Example 4. The resulting polymer swelled in n-hexane.
Comparative example 6
Using the solid product (II) subjected to polymeri-
zation treatment, obtained in Example 1, propylene
polymerization was carried out at 82C as in Example 4.
The resultin~ polymer swelled in n-hexane.
The results of the above Examples and Comparative
examples are shown in Table 1.
41 -
jll
Table 1
~_ _ . ..i ,.... I ,,
No. of Polymer Isotac- BD of Propor- 150 MFR **
Exa~le yield tic EX~ er tion of meshes
~.~1 (g) ! j~dex 32 topass
Comp~rative per g I 60 (%)
example of 11 ~ meshes
solid sizes
p~du~ (%)
_ (III ? , _ ~ _
Ex. 1 6,528 99.8 0.50 98 0.2 4.1 2.5
Ex. 2 6,200 99.0 0.50 96 0.4 3.8 3.0
Ccmpar. ex. 1 1,000 98.0 0.45 60 2. 4 3 . 8 18.0
CQmpar. ex. 2 1,100 9~.2 0.44 65 1.8 3.6 17.5
Cbmpar. ex. 3 4,100 98.5 0.49 92.0 1.0 4.3 800
Ex. 3 ~,800 99.0 0.50 96.0 0.6 4.2 2.0
Ex. ~ 7,200 98.0 0.49 96.0 0.8 4.1 1.8
C~?ar. ex. 4 _ _ _ _- _ _ _
C~r~ar.ex. 5 _ ~ _ _ . _ _
C~par. ex. 6 _ _ _ _ _ _ _
__ , _. . _ _ _
* Melt flow ra~e taccording to ASTM D-1238 (L)3
** Yello ~ ess index (according to JIS K7103)
Symbol (- ~ in the Table means "unmeasurable" .
-42 -
n-Heptane (40 mQ), diethylaluminum monochloride
(0.05 molj, diisoamyl ethex (0.09 mol) and di-n-butyl
e~her (0.05 mol) were reacted at 18C for 30 minutes to
obtain a reactio~ lliauid, ~hic~ was dropwise added to
TiCQ4 (0.275 mol) at 43C over 300 minutes, followed by
reacting the mixture at the same temperature as the above,
for 1.5 hour, raisinglthe temperature to 65C, further
reacting the mixture for one hour, removing the supernatant
and 6 times repeating a procedure of adding n-hexane ~200 m~)
and removins th~ supernatant by decantation to obtain a
solid product (II) ~18 g), which was then suspended in
n-hexane ~S00 m~), followed by adding diethylaluminum monochloride
12 g) and adding propylene (1 g~ at 60C for 1 hour for reaction
to obtain a solid product ~ subjected to polymerizaLi3n
treatment (amount of propylene reacted: 0.3 g). After the
reaction, the supernatant was removed, followed ~y twice " ~
xepeating a procedure of adding n-hexane ~300 mQ~ and removing
the supernatant by decantation. The solid product (II) subjected
20. to polymerlzation treatment (18.3 g) was then
suspended in n-hexane (40 m~), followed by adding ~iCQ~
(18 q) and n-butyl ether (18 g~ and reactin~ the mixture
at 60C for 3 hours. After the reaction, the supernatant
was removed by decantation, followed by three times repeating
a procedure o~ adding n-hexane (20~ mQ~, stirring for
5 minutes, allowing the mixture to stand and removing ~he
supernatant, and then drying the rasulting matexial u~der
reduced pressure to obtain a solid product (III). Using
this product, propylene polymerization was carried out as
in the steps (2) and (3) o~ Example 1.
_ 43 -
Example 6
n-Octane ~80 mQ), diisoproFylaluminum monochloride
(0~05 mol) andjldi-n-oetyl ~ther (0.11 mol) wexe reacted !~,
at 35C for 4 hours to obtain a reaction liquid, which
was dropwise added to TiCQ4 (0.25 mol) at 31C over 120
minutes, rollowe~ y reactilg the mixture at 40C for -.
30 minutes, raising the temperature to 85C, further
reacting the mixture for 30 minutes, adding propylene
~20 g) at the same temperature as the above~ reacting
the mixture for 30 minutes, removlng the li~uid by filtering
off, twice repeating a proceduxe of adding n-octane
(300 mQ), stirring the mixture for 5 minutes and iltering
off, to obtain a solid product (II~ 5ubjected to polymerization
treatmeht (solid product (II~: 17.5 g)~amount of propylene
reacted: 0.1 g). To this solid product subjected to po~ymQri-
zation treatment were added n-octane (40 mQl, diisoamyl
e~her (22 g) and TiCQ4 (14 g), followea ~y reacting the
mixture at 85C for 30 minutes, filtering of, 4 times
repeating a procedure of adding n-pentane (100 m~ tirring
for 10 minutes and filtering o~f, and dr~ing to obtain a solid
product (III).. Propylene polymeriza~ion was t~en carried out
.. ..
as in the steps (2) and ~3) of Example 1.
- 44 - ;
1~ .
Exam~le 7
A solid product (l~) was prepared as in Example l
except tha~ di-n-kutylaluminum monochloride (0.04 mol) was
used in ~lace of diethylaluminum monochloride (0.05 mol~
to obtain-a reaction liquld (I) which was dropwise added
to TiCQ4 at.,45C. Using the solid product (III), propylene
polymerization was carried out.
.. . .
ExamPle 8
Example 1 was repeated except that diisoamyl ether
(22 g), TiC~4 (20 g) and silico~ tetrachloride (18 g) were
added to the solid product (II) subjected to polymerization
treatment to obtain a solid product (III). Using this
product, propylene polymerization was carried out.
.. . . . . . .. . . .
~ .
~ 45 -
s~
Exam~le 9
Example 1 was repeated except that di-n-pentyl ether
(28 g) and arhydrous aluminum trichloride (5 g) were added
to n-hleptane (lOO~mQ), followed by reacting the mixtul~e
on heating at 80C for 2 hours tc obtain a solution to which
a solid pr.oduct (II3 subjected to polymerization treatment --
(20.4 g~, as in Example 1, was added, followed by reacting
the mixture at 80C for 2 hours to obtain a-solid product
(III)o Using this product, propylene polymerization was
. carried outD
Example lo
Example 5 was repeated except that TiCQ4 (~5 g),
diisoamyl ether ~12.0 g) and di-n-butyl ether (6 g).were added
to the solid product (II) subjected to polymerization
treatment ~18.3 g) r to obtain a solid product (III). Uslng
this product, propylene polymeri2ation was caL~ ed out.
Triisobutylaluminum l0.03 mol) was reacted with
di-n-dodecyl ether (0.07 mol) in n-hexane (100 mQ) at 20C
for 40 minutes to obtain a reaction liquid, which was then
dropwise added to TiCQ4 ~0.18 mol~ at 20C over 2 hours,
followed by adding propylene (4 g), reacting the mixture
~ 4~ ~
... .
~5~
at 30C for 30 minutes and further at 50C ox 60 minutes,
removing the liquid portion by filtering off and was~ing
wlith n-hexan,_ to obtain a solid product (II~ sublected to
polymerization treatment (23.8 g) (amount of propylene
reacted: 0.8 ~). To this product were added n-heptane --
(5~ mQ), di-n-butyl ether (21 g) and TiCQ4 (40 g), followed
by reacting the mixture at 50C for 140 minutes, filtering
off, washing with n hexane and drying to obtain a solid
produet (III~. Using this product, propylene polymerl-
zation was carried out as in Example 1.
Example 12
~riethylal~minum (0.07 mol) was reacted with diisoamyl
ether ~0.18 mol) in n-hexane (45 mQ) at 40C or 4 hours
to obtain a reaction liquid, which was then dropwise added
to TiC~4 ~0.84 mol) at 32C for 4 hours,~llowed by maint-
aining the temperature at 35C for one hour, adding propylene
(10 ~), raising the temperature up to 78C, reacting the
mixture at this temperature for 2 hours, filtering of,
washing with n-hexane and drying to obtain a solid product
~II) subjected to polymerization treatment (24 g3 t~mount
o~ propylene reacted: 1.0 g). This product was added to
a reaction liquid obtained by reacting n-hexane (4Q m~
diisoamyl ether (27 g) and TiC~4 t20 g) at 35C for 30 minutes,
folIo~ed by reacting the mixture at 75C for one hour,
filtering off, washing with n-hexane and drying to obtain
- 47 -
,
. . .
a solid product (III). Using this product~ propylene
polymerization was carried out as in Example 1.
Exam~le 13
A solid product (III) was obtained as in Example 1
except that butene-l (6 g) was used in place of propylene
I ~2085 g) to obtain a solid product (II) subjected to
polymerization treatment (20.9 g)~amou.nt o~ butene-l
reacted: 0.9 g). Using the solid product (III] propylene
polymerization was carried out as in Example 1.
Example 1~
~ solid product (III) was obtained as in Example 13
e~cept that ethylene ~4.0 g) was used in place of butene 1
(6 g) to obtain a solid product (II) subjected to polymeri-
zation traatment (20.6 g)~c~ount of ethylene reacted: 006 g).
Using the solid product IIII), propyl~ne polymerization was
carried out.
In the same reactor as in the s~ep ~2) of Example 1
were placed and mixed n pentane (4 mQ), diethylaluminum
monochloride ~160 mg), the solid product (III) ~28 mg)
obtained in Example 1 and polypropylene powder (5 g), followed
by removing n-pentane under reduced pressure, carrying out
gas phase reaction while fluidizing the catalyst obtained
above, with propylene gas under a partial pressure of
propylene of 0.8 kg/cm2G at 30C for 20 minutes, and then
,, .
1, .
~l ~ 54~?~
removing unreacted propylene ~o obtain a preactivated
I ~a~alyst (amount of propylene reacted, per g of the solid product
l.6 g). Using this catalyst~ gas phase poly~erl-
zation was carried ou.t as in the step ~3~ of Example l.
~k .
Di n-butylaluminum monochloride (120 mg) and the solid product
(III) (28 mg) obtained in Example l.l were placed in propylene
(30 g) at 20C, followed by reacting the mixture under 9.~ kg/cm2G
for lO minutes and removing unreacted propylene to obtain
a preactivated catalyst in the ~orm of powder ~amount of
propylene reacted per g of the solid product (III~ 9 1. 1 g~,
Using this catalyst, gas phase polymerization of propylene
was carried out as in the step (3) of Example l.
Exam~e l7
Example 1 was repeated exc~r~3'_ that in the preactivation
of the step (2) of Example l, ethylene was used in place of
propylene and ethylene was reacted under a partial pressure
of ethylene o~ 1 kg/cm2G at 35C for lO minutes (amount of
ethylene reacted per g of the solid product (III).: 2.4 g).
Example 18
-
Example l was repeated except that in the preactivation
of Example l, butene-l was used in place of propylene and
butene-l was reacted under a partial pressure of butene of
0.5 kg/cm G at 35C for lO minutes (amount of butene l
reacted per g of the solid product (III~o 0.3 g).
49 -
.
Exam~le 19
Example 1 was repeated except that diisopropvlaluminum
I monochloride (~80 mg) was used in placè of diethylaluminummonochloride ~420 mg) in the step (2) of Example 1.
Example 20 --
Preactivation was carried out as in the step (2) of
E~ample 1 excep! that triethylaluminum 1320 mg) was used
in place of diethylaluminum monochloride (420 mg), and
polymer was obtained as in the step (3) of Example 1 except
that ethylene was polymerized under a hydrogen pressure of
12 kg/cm2G and an ethylene partial pressure of 12 kg/cm2G~
at 85Co
Example,,21
After a preactivated catalyst was prepared as in the
steps (1) and 12) of Example~ , nydrogen (300 m~) and then
propylene t600 g) were introduced, followed by bulk poly
meri~ation under a partial pressure of propylene of 31 kg/cm G
at 70C for one hour. After completion of the reaction,
unreacted propylene was purged and post-treatment was
2U carried out as in Example 1 to obtain a polymer.
The results of the above Examples 5 to 21 are shown in
Table 2.
-- 50 --
Table 2
_ _ Isotac~ ~D!of Pr~por-¦150 _ **
Example yield tic i:~olymer tion of meshes MFR YI
and (g) index 32 to pass
Compara~ive per g 60 (~)
ex~ple of meshes
soli~ sizes
product (%)
_ _ (III) _
Ex. 5 6~400 9906 0.50 98.2 0.3 4.2 20g
EX. 6 6,200 99.3 0.50 98.0 0.4 ~.1 2.8
~. 7 6,300 99.0 0.48 95.0 0.2 4.8 2~5
EX. 8 6,400 98.0 0.48 98.0 0.3 4.1 ~.8
Ex. ~ 6,200 98.0 0.46 98.0 0.~ 4.9 2.8
Ex~ 10 6,800 99.6 0.50 98.0 0.3 3.8 2.0
Ex. 11 6,200 98.0 0.43 95.0 0.5 3.2 2.8
E~ 6,300 ~ 1~ 0.50 94.0 0.4 3.8 2.5
Ex. 13 6,500 99.0 0.50 96.0 0.2 3.8 ~.5
Ex. 14 6,200 99.0 0.50 95.0 0.3 3 2 2.8
Ex. 15 6,520 99.0 0.50 96.0 0.2 3.4 2.5
Ex. 16 6,400 99.0 0.49 94.0 0.2 3.8 2.6
EX. 17 6,200 98~5 0.46 92.0 0.6 3.4 2.9
Ex. 18 6,~50 99.0 0.50 96.0 0.5 ~.3 2.6
Ex. 19 6,200 98.5 0.48 92.0 0.6 ~.2 2.9
Ex. 20 6,900 j _ 0.46 92.0 0.4 ~.1 240
Ex. 21 6,400 99 0 0.50 98.0 0.2 4.3 ~.2
~ 51 -
."
~5~
Example 22
A preactivated catalyst in the form of powder was
prepared in a reactor as in the steps (1) and (2) of Example
1, followed by introducing hydrogen (300 mQ) and propylene
(200 g) and then carrying ou~i bulk polymerization under
.
a partial pressure of propylene of 26 kg/cm2G at 60C for
30 minutes (amount o~ propylene polymerized: 35 g).
Thereafter, the resultin~ slurry containing unreacted
propylene was flushed into a fluidized bed of 20 cm in
!~) diameter and 20Q in volwme, equipped with agitating elements,
while fluidizing polymer with propylene gas circula-ting
at a flow rate of 5 cm/sec. to carry out gas phase polymeri-
zation at a reaction temperature or 70C under a partial
~xessure of propylen~ of 21 k~/cm G for 2 hours. Post-
treatment was then carried out as in Example 1 to obtain
a polymer. ~.
Example 23
Bulk polymerization was carried out under a partial __
pressure o propylene of 26 kg/cm2G at 60C or 30 minutes
~o as in Example 21, followed by transferring unreacted
liquefied propylene into a separate feed tank connected to
the reactor, rai5ing the temperature o~ the reactor to 72C
and carrying out gas phase polymerization for 2 hours while
feeding propylene from the feed tank so as to give a
polymerization pressure of 26 kg~cm G. Thereafter the same
treatment was carried out as in Ex~mple ~ to obtain a polymer~
~g
Bulk polymerization was carried out under 26 kg/cm2G, at
60C for 30 mir.utes as in Example 21. The polymerization
tempera~ure was then raised up to 70C to give a polymeri-
- 52 -
zation pressure of 31 kg/cm G. When the polymerization
was continued as it was, the pressure lowered down to
26 kg/cm G in 40 minutes. IlTlus the ~ul'~t polymerization
moved continuously to gas phase polymerization. Gas phase
poly~erizaticn was further carried out while feeding
propylene for 60 minutes so as to keep the pressure at
26 k~/cm2G. Post-treatment was carried out as in Ex~nple
1 to obtain a polymer.
Example 25
n-Hexane ~1,000 mQ), diethylaluminum monochloride
(320 mg) and the soILd prQduct 71I~)(18 mg) obtained in
.. . ....... . . . . . . . . .
Example 5 were introduced, and propylene was reacted under
a propylene partial pressure of 1.2 kg/cm~G at 20C for
10 minutes to clrry out preactivation (amount of propylene
reacted per g of the solid product (III3: 0.6 g). Unreacted
propylene was purged and hydrogen (1~0 mQ) was introduced,
~ollowed by slurry polymerization under a propylene partial
pressure of 10 kg/cm G at 70C for 2.5 hours. n-Hexane was
then removed by steam stripping to obtain a polymer.
Example 26
n-Pentane (80 m~), diethylaluminum monochloride (2B0 mg)
and the solid product tIII) ~25 mg) were introduced. Propylene
was then reacted at 15C while its partial pressure was raised
i.e. b~ raising its pressure up to 5 kg/cm2G in 5 minutes
(1 kg/cm G/min.), to carr~ out preactivation (amount of
- 53 -
PrOpylene reacted per g of the solid product (III) 3. 2 g) .
Unreacted propylene wasjpurged and hydrogen (200 mQ) was
introduced, followed ~y slurry polymerization under a
propylene partial pressure of 10 kg/cm2G at 70C for
60 minutes (amount of propylene polymerized: 63 ~). The
resulting slurry containing the solvent was introduced
into a fluidized bed equipped with agitating elements,
followed by propylene gas phase polymerization as in
Ex~mple 22.
~
n-Hexane (1,000 m~), diethylaluminum monochloride
(320 mg) and the solid product (III) obtained in Example
5 (30 mg) were introduced, and without preactivation~;
hydrogen,~20 m9~) was introduced, followed by slurry
polymerization under a propylene partial pressure of
10 kg/cm G at 70C for 2.5 hours. n-Hexane was then removed
by steam stripping to obtain a polymer~
. _ _ _ _ . , ... .. .. . _ . . . _ , .. .
Example ~8
Propylene was su~jected to slurry polymerization uslng
the non-preactivated catalyst as in Example 2i, followed
by purging unreacted propylene and hydrogen and distilling
off n-hexane under reduced pressure till n-hexane was
contained in the polymer in an ~mount of 30%~ This sol~ent-
contalning polymer was introduced into the fluidized bed
.. ..
5~
equipped with agitating elements used in Example 2~ and
hydrogen ~450 m~) was introduced to carry out gas phase
polymerization under a partial pressure of propylene of
21 kg/cm G at 70C for 2 hours as in Example 22. Post-
treatment was then calrried out as in Example l to obtain
a polymer. I'
Example 2g --
Propylene-ethylene block copolymerization was carried
out as in Example 28 except that the slurry polymerization
of the first step was carried out with propylene, and as
the gas phase polymerization of the second step, ethylene
polymexization was carried out under a partial pressure of
hydrogen of 8 kg/cm G and a partia~ pressure of ethylene of
12 kg/cm2G at 70C ~or 2 nours.
Example 30
Example 22 was repeated except tnat an ~-olofin mixture
of pr ~,ylene ~200 g) with ethylene (20 g3 was used in placing ~;I;
of using propylene (200 g) to obtain a polymex (propylene
ethylone copolymer).
Example 3~
Example 3~ was repeated except that butene-l (30 g) was
used in place of using ethylene ~20 g), to obtain a polymer
(propylene-butene-l copolymer).
. _ . . . . .
Example 32
A polymer was obtained as in Example 1 except that
ethylene polymerization was carried out under a hydrogen
pressure of 12 kg/cm2G and an ethylene partial pressure
of 12 kg/cm2G at 85C, by the use of the preactivated
catalyst, in place of carrying out propylene polymerization,
using hydrogen (300 mQ), under a propylene partial
pressure of 25 kg/cm G at 70C~
~ 55 -
~1~5~
Example 3~
The solid product (III) (300 mg) obtained in Example 1
and diethylaluminum monochloride (3,000 mg) were suspended
in n-hexane (200jm~), followed by reaction under a partial
pressuxe o pr~pylene of 1.3 kg/cm~G at 20C for 10 minutes,
purging unreacted propylene, preserving the resulting material
with stirring at 30C for one week, introducing the resulting
catalyst slurry containing the solid product (III) (25 m
into a polymerization vessel and then carrying out slurry
polymerization and succeeding gas phase polymerization as
in Example 26
Comparative examples 7, ~ ~n~_~
Using each of the following solid products in place of
the.solid product (III~ obtained in Example 1, the respective
resulting catalyst slurries were preserved a-~ ~0C for one
tl~r.,~ek as in Ex~mple 33:
- Comparative example 7: the solid product (II) obtained
in Example 1~
Comparative example 8: the solid product (II~ subjected
to polymeriza~ion treatment,
obta~ned in Example 1.
comparatlve example .. 9: the solid product (III) obtained
in Comparative example 3.
The results of the above Examples 22 to 33 and Comparative .
examples 7 to 9 are shown in the following Table 3
- 56 -
Table 3
~. of I Polymer Isotac- BD of Propor- 150 _ **
Example I yield t~cpolymer tion of meshes MFR YI
and l~, (g) index 32 to pass
Cbmparative per g 60 (~)
example of meshes _.
solid sizes
P(I~II ~UCt: ( % ) .
. _ -._.
E~. 22 7,200 99.2 0.49 95.0 0.3 2.6 2.0
EX. 23 7,400 99.0 0.49 96.0 0.2 2.9 1.5
Ex. 24 7~100 99.2 0.50 96.0 0.3 3.~ 2.2
Ex. 2s 6,700 99.4 o.so 94.0 0.3 3.8 2.
EX. 26 7,100 99.0 0.49 96.0 0.2 3.8 200
Ex. 27 6,200 gg.o 0.45 gl~o 0.2 3.4 3~0
EX. 28 7,400 98.5 0.45 go.o 0.2 3.6 1.5
Ex~ 29 7,500 98.0 ~.45 go.o 0.2 3.4 1.5
x. 30 70600 98.0 0.46 91.4 0.2 3.2 i !i.4
Ex. 31 7,500 98.0 0.46 92.0 0.2 3.8 1.8
Ex. 32 6,600 _ 0.45 go.o 0.3 ~.1 ~.4
Ex. 33 6,200 98.s 0.46 go.o o.g 2.9 3.0
CQmpar. ex. 7 600 98.5 0.~5 go.o 4.8 2.9 >20
CGmpar. ex. 8 700 98 ~ 5 o .45 92.0 4.2 2.9 >20
Ccmpar. ex. 9 4,200 98.5 o 4s 93.0 2.2 2.9 4.o
.
~s~
Example 34
(1) Preparatlon of solid product (III)
l~ solid product (III) (a final solid product) was
obtained in the same manner as in the step (1) of Example 1.
~2
A 2 Q capacity stainless steel reactor equipped with
slant blades was purged by nitrogen gas, and into thi~
reactor were added n-hexane (20 mQ~, diethylaluminum
mono hlori~e ~414 mg) and the final solid product ~2 mg)
at room temperature. Reaction was then carried out at 40C
under a partial pressure of propylene of 2 kg/cm2G for
10 mlnutes (reacted propylene per g of inal solid product:
16,3 g), followed by purging unreacted prop~lene and then
adding a reaction product (G) obtained by reactin~ triethyl-
aluminum (23 mg) with methyl p-toluylate (30.3 mg) in n~
hexane (20 mQ) at 25C for 30 minutes, to obtain a pr~activated
catalyst.
58 -
~3) ~
IjInto the reaator containing the catalyst after completionO~ ~h~ preactivation was introduced 150 m~ of hydrogen,
and gas phase polymerization wa~ carried out under a partial
press1~re of propylene o~ 22 Kg/cm G, at a polymeri~ation
~emperature o ~0C for 2 hours. After completion of the
re~ction, 3 g of methanol was introduced and ~illir.,g reac~ion wa~
rarried out ~ 70~C for 30 minutes, followecl by cooling down
~o room tempera~ure ~20C~ and drying the resulting polymerr
to obtain 286 g of polymer. The polymer yield per g of final
solid product ~s 13,000 g, ~he isotactic index (n-hexane-
in~oluhle at 200C (~)), 99.2, BD of polymer, 0. 50, and ~he
polymer particles had a form elose to sphere, 99.0~ thereof
having siæes between 32 meshes and 60 meshPs, ar;~'150 meshes-paS5
being 0.1% or less. No lump was observed.
No coloration of polymer was observed and yellowness index
~YI~ was 0.5. Further, in order to observe tha extent of
corxo~ivenes~ o~ polymer brought about by ~he ex~en~ o~ heat
- 8tability o~ ca~alyst a~r killing, polymer was heated o
a d~finito tempe~aturè and whether acidic gas is easily or
dif~lcul~ly evolved was o;~s~rved ~hrough ~he preseDce or
abscnc~ of color change o~ Congo ~ed (according to ~IS ~-6~23~.
As a re~ul~, no color chan~e was observed.
. -- ,
The polymer was annealed at 135C for 120 minutes according
to J.P. Luongo's method (Journal of Applied polymer Science, 3,
302 ~1960)) to give an IR-~ of 0.94.
I
_ ~9 _
~5~
~ E~__35
!T~e steps (1) and (2) of Example ~ were repeated to
ob~!~in a preactivated catalyst~ n-Hexane (1,500 mQ) and
hydrogen (200 mQ) were then introduced and slurry
polymerization was carried out under a partial pressure
of propylene of 10 kg/cm2G at 70C for 4 hours. After
completion of the polymerization, n-hexane was removed by
steam stripping to obtain a polymer.
~xample 36
Example ~ was repeated except that propylene slurry poly~
merization was carried out at 92C in place of 70C. The par~icle
orm, bulk density and isotactic index of the resulting polymer
were almost unchanged from those OL Example 35
Comparative example ~
Propylene polymerization was carried out as in Example
36 except that the reaction product (G) was not used. The
resulting polymer swelled in n-hexane.
ComParative example_ll
Diisoamyl ether and TiCQ4 were reacted with the solid
product (II) as in Example ~ but without subjecting the
solid product (II) to polymerization treatment with propylene,
to obtain a final solid product, followed by propylene
polymerization as in Example 36, but at 92C. The BD and
isotactic index of the resulting polymer both loweredO
~ 60 -
Rropylene polymerization was carrled out using the
11 solid prod~ct (II) obtained in Example 34, in the same
manner as in Example ~, but at 92C. The reslllting
polymer swelled in n-hexane.
Com~arative example 13
Propylene polymerization was carried out using the
solid product (II) subjected to polymerization treatment,
obtained i~ Example 34, in the same manner as in Example 36
but at 9~C. The resulting polymer swelled in n-hexane.
The final solid product obtained in Example ~ was
preserved at 40C for 4 months. Propylene polymerization
was carried out as in the steps (2) and (3~ of Example 34,
Com~arative example 14 ~l
The solid product (II) obtained in Example34 was
preserved at 40C for 4 hours as in Example 37. Propylene
polymerization was then carried out.
Com~arative example 15
The solid product (II) subjected to polymerization treatment,
obtained in Example 34, was preserved at 40C for 4 months as in
Example 37. Propylene polymerization was then carried out.
Comearative example 16
Propylene polymerization was carried out as in Example 3i
except ~hat the solid product (II), without being subjected
61 ~
to pclymerization ~reatment, was reacted with diisoamyl
ether and TiCQ4 to obtain a final solid product.
I' Compl~rative exam~le ~7
Polymerizatlon was carried out without adding the
reaction product (G) in Example 37.
Example 38
A preactivated catalyst was prepared as in Example 35
except that methyl p-toluylate ~15 mg) was used in the
preparation of the reaction product (G). Using this catalyst,
propylene polymerization was carried out.
A preactivated catalyst was prepared as in Example 35
except that methyl p-toluylate (7.5 mg) was used in the
preparation of the reaction product (G). Using this catalyst,
propylene polymerization was carried o~!
A preactivated catalyst was prepared as in Example 35
except that methyl p-toluylate (4.7 mg) was used in the
preparation of the reaction product (G). Using this catalyst,
2~ propylene polymerization was carried out.
EY.ample 41
A preactivated catalyst was prepared as in Example 35
except that methyl p-toluylate (60 mg) was used in the
preparation of the reaction product (G). Using this catalyst,
propylene polymerization was carried out.
621
Co~ arative example la
A preactivated catalyst was prepared as in Example 35
! except that triethylaluminum (23 mg) was used in place o~
the reaction product (G), in the prepara~ion of the catalyst.
Vsing the catalyst, propylene polymerization was carried out.
The amount of atactic polymer increased notably.
Com~arative examplesl~ and 20
A preactivated catalyst was prepared as in Example 35
except that methyl p-toluylate (30.3 g)(Compaxative example
19) or (7.5 mg)(Comparative example 20) was used in place
of the reaction product (G). Using the catalyst,propylene
polymerization was carried out. The value o~ IR-I was
unchanged. I
~ ;l 1
A preactivated catalyst was prepared as in Example 34
except that triisobutylaluminum (50 mg) and ethyl benzoate
(38 mg) were used in the preparation of the reaction
product (G). Using the catalyst, propylene polymeri~ation
was carried ou~.
Example 43
A preactivated catalyst was prepared as in Example 34
except that tri-n-butylaluminum (40 mg) and ethyl p-anisate
(55 mg) were usPd in the preparation of the reaction product
(G). Using the catalyst, propylene polymerization was carried out.
Example _ 4
-
n-Heptane (40 mQ), die~hylaluminum monochloride
~ 63 -
5~
(0.05 mol~, diisoamyl ether (0.09 mol) and di-n-butyl
ether (0.05 mol) were reacted at 18~C for 30 minutes to
o~tain a reaction liquid, which was dropwise added to
TiCQ~ (0~275 mol) at 40C O~Jer 300 minutes, followed by
reacting the mixture at the sa~ne temperature as the abo~e,
for 1.5 hour, raising the temperature to 65C, further
reacting the mixture for one hour, removing the supernatant
and 6 times repeating a procedure of adding n-hexane (200 mQ)
and removing the supernatant by decantation to obtain a
solid product (II) (18 g), which was then suspended in
n-hexane (500 mQ), followed by adding diethylaluminum monochloride
(~ g) and adding propylene (1 g) at 60C for 1 hour for reaction
to obtain a solid product (II3 subjected to polymeri~ation
treatment (amount of propylene reacted: 0.3 g~. After ~he
reaction, the supernatant was r~moved, followed by twice
repeating a procedure of adding n-hexane ~300 mQ) and removing
the supernatant by decantation~ The solid product (II) subjected
to polymerization treatment (18.3 g) was then
suspended in n~hexane (40 mQ), followed ~y adding TiCQ~
~0 (18 g) and n-butyl ether (18 g) and reacting the mixture
at 60C for 3 hours. After the xeaction, the supernatant
was removed by decantation, followed by three times repeating
a procedure of adding n-hexane ~200 mQ), stirring for
5 minutes, aliowing the mixture to stand and removing the
supernatant, and then drying the resulting material under
reduced pressure to obtain a final solid product~ Using
this product, propylene poly~erization was carriPd out ~s
in the 3teps (2) and (3) o~ Example 34,
64
n-Octane (30 mQ), diisopropylaluminum monochloride
(o~0s mol) a~d di-n-octyl ether (0.11 mol) wex~ reacted
at 35C for 4 hours to obtain a reaction liquid, which
was dropwise added to TiCQ4 (0.25 mol~ at 31C over 120
minutes, followed by reacting the mixture at 40C for
30 minutes, raising the temperature to 85C, further
reacting the mixture for 30 minutes, adding propylene
(20 g) at the same temperature as the above, reacting
the mixture for 30 minutes, removing the liquid by filtering
off, twice repeating a procedure oE adding n-octane
~300 mQ~, stirring the mixture for 5 minutes and filtering
off, to obtain a solid product (II) subjected to polymerization
treatmeAt tsolid product (II): 17.5 g)(amount of propylene
reacted: 0~1 g~. To this solld product subjected to polymeri-
zation txeatment were added n-octane (40 mQ1, diisoamyl
ether ~22 g) and TiC~4 (14 g), followed by reacting the
mixture at 85C for 30 minutes, filtering off, 4 times
repeating a procedure of adding n-pentane (100 mQ), ~tirring
for 10 minutes and filtering off, and drying to obtain a solid
product (III). This product.~17 g) was then suspended in n-pentane
(100 m~j, followed by adding diethylaluminum monochloride
(2.4 g)~ adding propylene (3 g) and reacting the mixture
at 45~C for 2 hours (amount of propylene reacted: 0.6 g).
After the reaction, filtering off, washing an~ drying were
carried out to obtain a final solid p~oduct, from whih
a preactiva~ed catalyst was prepared as in Example 34.
Using this catalyst, propylene polymeriza~ion was carried
out.
Example 46
A final sol id product was prepared as in Example 45
except that di-n-butylaluminum monochloride (0.04 mol) was
usQd in place of diisopropylaluminum monochloride (0.05 mol)
to obtain a xeaction liquid (I~ which was dropwise added
to TiCQ4 at 45C. Using the final solid product, propylene
polymerization was carried out.
Example 47
n-Hexane ~60 mQ), diethylaluminum monochloride (DEAC)
(0.05 mol) and diisoamyl ether (0.12 mol) were mixed at
25C for one minute and the mixture was then reacted at
the same temperature as the abov~ for 5 minutes to obtain
a reaction liquid (I) (the molar ratio of diisoamyl ether
to DEACo 2.4). TiC~4 (0.5 mol~ was placed in a reactor
purged wi~h nitrogen ga~ and heated to 35C, ~ollowed by
dropwise adding to the mixture the total amo.unt of the
above reaction liquid ~I) over 120 minutes, maintaining
the temperature at the sams t~mperature as the above for
30 minutes, raising the temperature to 75C, further
reacting for one hour, cooling down to room temperature,
remsvi~g the supernatant and 4 ~imes repea~ing a procedure
j 66
1~854G~O
of adding n-hexane (400 mQ) and removing the supernatant
by decantat.ion to obtain a solid product (II) (19 g).
The total amount of this tII) was suspended in n-hexane
(300 mQ~, followed by adding diisoamyl ether (16 g) and
TiCQ4 (35 g) at room temperature ~20C) over about one
minute and reacting the mixture at 65C for one hour.
After the reaction, the liquid was cooled down to room
temperature (20C), followed by removing the supernatant
by decantation, 5 times repeating a procedure of adding
n-hexane ~400 mQ), stirring for 10 minutes, allowing the
mixture to still stand and removing the supernatant and
drying under reduced pressure to obtain a solid product
(III). A,poxtion (10 g) of this solid product (III) was
suspended in n~hexane (200 mQ), followed by adding
diethylaluminum monochloride (0.7 g), lurther adding
propylene (2 g), reacting tne mixture at 25C for 10
minutes, filtering off when 1 g of propylene reacted,
twice washing with n-hexane (200 mQt and drying under
reduced pressure to obtain a final solid product fxom which
a preactivated catalyst was obtained as in Example 34
Using this cataly~t, propylene polymerization was carried
out.
Example 48
Example ~ was repeated except that diisoamyl ether
(22 g), TiCQ4 ~20 g) and silicon tetrachloride (18 g~ were
- .- 67 -
added to the solld product (II) subjected to polymerization
treatment to obtain a final solid product. Using this
product, propylene polymerization was carried out.
Example ~9
Example ~4 was repeated except that di-n-pentyl ether
(28 g) and anhydrous al~inum trichloride (5 g) were added
to n-heptane ~100 mQ), followed by reacting the mixture
on heating at 80C for 2 hours to ob-tain a solution to which
a ~olid product (II~ su~jected to polymerization treatment
~20.4 g), as in Example 34, was added, followed by reacting
the mixture at 8QC for 2 hours to obtain a final solid
product. ~sing this product, propylene polymerization was
carried out.
Exam~,o
Example 4~w!as repeated except that TiCQ4 (35 g),
diisoamyl ether (12.0 g) and di-n-butyl ether (6 gj were added
to the solid product ~II) subjected to polymerization
treatment (18.3 g), to obtain a final solid product. Using
this product, propylene polymerization was carried out.
Example 51
Triisobutylaluminum (0.03 mol) was reacted with
di-n-dodecyl ether (0.07 mol) in n-hexane (100 mQ~ at 20C
for 40 minutes to obtain a reaction liquid, which was then
dropwise added to TiCQ4 (0.18 mol) at 20C over 2 houxs 5
~ollowed by addLng propylene (4 g)~ reacting the mixture
6~ -
~ ~.8~
at 30C for 30 minutes and further at 50C for 60 minutes,
removing the liquid portion by filtering off and washing
with n-hexane to obtain a soli.d product (II) subjected to
polymerization treatment ~23.8 g) (amount of propylene
reacted: 0.8 g). To this product were added n-heptane
(50 mQ), di~n-butyl ether (21 g) and TiCQ4 ~40 g), followed
by reacting the mixture at 50C for 140 minutes, filtering
off, washing with n-hexane and drying to obtain a final
solid product. Using this product, propylene polymeri-
za~ion was carried out as in Example 34. j!
Ex~E~e 52
Triethylaluminum (0.07 mol) was reacted with diisoamyle,thex l0.18 mol) in n-hexane ~45 mQ) at 40C for 4 hours
to obtain a reaction liquid, which was then dropwise added
to TiCQ4 (0.84 mol~ at 32C for 4 hours, followed by maint-
aining the temperature at 35C for one hour, adding propylene
(10 gt, raising ~he temperature up to 78C, reacting the
mixture at this temperature for 2 hours, filtering off,
washing with n-hexane and drying to obtain a solid product
~ ~II) subjected to polymeri~ation treatment ~24 g) (amount
of propylene reacted: 1.0 g). This product was added to
a reaction liquid obtained by reacting n-hexane (40 m~),
diisoamyl ether t27 g~ and TiCQ4 (20 g) at 35C for 30 minutes,
followed by reacting the mixture at 75C for one hour,
filtering o~f, washing with n-hexane and drying to obtain
69
a inal solid product. Using this product, propylene
polymerization was carried out as in Example 34.
Example 53
A final solîd product was obtained as in Example 34 -~
except that butene-l (6 g) was used in place of propylene
(2. 85 g) to obtain a solid product (II) subjected to
polymexization treatment ~20.9 g)(amount of butene-l
reacted~ 0.9 g). Using the final solid product, propylene
polymerization was carried out as in Example 34.
Example 54
A final solid product was obtained as in Exampie 53
except that ethylene (4.0 g) was used in place of butene-l
(6 g) to obtain a solid product (II~ subjected to polymeri-
zation treatment (20.6 g)(amount of ethylene reacted: 0.6 g).
Using the final solid product, propylene polymeri2ation was
carried out.
In the same reactor as in the step (2) of Example 34
were placed and mixed n pentane ~4 mQ), diethylaluminum
monochloride (160 mg), the final solid product (22 mg)
obtained in Example 34 and po-lypropylene powder lS g), followed
by removing n-pentane under reduced pressure, carrying out
gas phase reaction while fluidizing the catalyst obtained
above, with propylene gas under a partial pressure of
propylene of 0.8 kg/cm2G at 30C for 20 minutes, and then
; 70 -
~ ~L8~
removing unreacted propylene to obtain a preactivated
catalyst (amount of propyl~ne reacted, per g of the final solid
product: 1.8 g). using this catalyst, gas phase polymeri-
zation was carried out as in the step (3) of Example 34 -~
Di n-butylaluminum monochloride (120 mg) and the final solid
product (28 mg) obtained in Example 44 were placed in propylene
(30 g) at 20C, followed by reacting the mixture under 9.8 kg/cm2G
for 10 mlnutes and removing unreacted propylene to obtain
a preactivated catalyst in the form of powder ~amount o
propylene reacted per g of the final solid product: 100 g).
Using this~catalyst, gas phase polymeriz~tion of propylene
, was carried out as in the step (3) of Example 34O
Example ~ was repeated except that in the preactivation
of the step (2) of Example34, ethylene was used in place of
propylene and ethylene was reacted under a partial pressure
of ethylene of 1 kg/cm~G at 35C for 10 minutes ~amount of
ethylene reacted per g of the final solid product: 2.4 g).
2~
Example 34 was repeated except that in the preactivation
of Example 34, butene-l was used in place of propylene and
butene-l was reacted under a partial pressure of butene of
O.5 kg/cm2G at 35C for 10 minutes (amount of butene-l
reacted per g of the final ~olid product: 0.3 g~.
~s~
Example 59
Example ~ was repeated except that diisopropylaluminum
monochloride (380 mg) was used in place of diethylaluminum
monochloride (414 mg) in the step (2) of Example 34.
~0
Preactivation was carried out as in the step ~2) of
Example 34 except that triethylaluminum ~320 mg) was used
in place of die-thylaluminum monochloride (414 mg), and
pol~mer was obtained as in the step (3) of Example ~ excep-t
that ethylene was polymerized under a hydrogen pressure of
12 kg/Gm2G and an ethylene partial pressure o 12 kg/cm2G,
at 85C.
Example 61
i
After a preactivated catalyst was prepared as in the
s~eps (1) and ~2) of ~xample 3~, hydrogen (300 mQ) and then
propylene (600 g~ were introduced, followed by bulk poly-
merization under a partial pressure of propylene of 31 kg/cm2G
~t 70C for one hour. After completion of the reaction,
unreacted propylene was purged and post-treatment was
carried out as ln Example ~ to obtain a polymer.
Example 6~
A preactivated catalyst in the form of powder was
prepared in a reactor as in the steps (1) and (2) of Example
3~ followed by introducing hydrogen (300 m.~) and propylene
(200 g) and then carrying out bulk polymerization under
a partial pressure of propylene of 26 kg/cm G at 60C for
30 minutes ~amount of propylene polymerized: 35 g).
Thereafter, the resulting slurry containing unreacted
propylene was flushed into a fluidized bed of 20 cm i~ -~
diameter and 20Q in volume, equipped with ayitating elements,
while fluidizing polymer with propylene gas circulating
at a flow rate of 5 cm/sec. to carry out gas phase polymeri-
zation at a reaction temperature of 70C under a partial
pressure of propylene o 21 kg/cm G for 2 hours. Post-
treatment was then carried out as in Example ~ to obtain
a polymer.
E~ 3
Bulk polymerization was carried out under a partial
pres~ure of propylene oE 26 kg/cm G at ~O~C for 30 minutes
i;~ i'
as in Examp~e 62, followed by transferring unreacted
liquefied propylene into a separate feed tank connected to
the reactor, raising the temperature of the reactor to 72C
and carrying out gas phase polymerization for 2 hours while
feeding propylene from the feed tank so as to give a
polymerization pressure of 26 kg/cm2G. Thereafter the same
treatment was carried out as in Ex~mple ~ to obtain a polymer.
Example 64
Bulk polymerization was carried out under 26 kg/cm2G, at
60C or 30 minutes as in Example 6~, The polym2ri7ation
temperature was then raised up ~o 70C to give a polymeri~
- 73 -
~L85~
zation pressure of 31 kg/cm G. When the polymeri2ation
was continued as it was, the pressure lowered down to
26 kg/cm~G in 40 minutes. Thus the bulk polymerization
moved continuously to gas phase polymerization. Gas phase
polymerization was further carried out while feeding
propylene for 60 minutes so as to keep the pressure at
26 kg/cm2G. Post-treatment was carried out as in Example
to obtain a polymer.
Exam~le 65
n-Hexane (l,000 mQ), diethylaluminum monochloride
~320 mg) and the final solid prsduct (30 mg) obtained in
the step ~1) o Example ~ were introduced into a reactor,
-~ and without preactivating them, the reaction product (Ç)
used in the step (2) of Example ~ was introduced.
Slurry polymerization was then carried out under a partial
pressure of propylene of 10 kg/cm G at 85C for 3 hour$,
followed by removing n-hexane by steam stripping to obtain
a polymer.
Example 66
Propylene was subjected to slurry polymerization us~ng
the non-preactivated catalyst as in Example 65, followed
by purglng unreacted propylene and hydrogen and distilling
off n-hexane under reduced pressure till n-hexane was
conta1ned in the polymer in an amount of 30~. This solvent-
containing polymer was introduced into the fluidi~ed bed
~ 74
!
g~
equipped with zgitating elements used in Example 29 and
hydrogen (450 mQ) was introduced to carry out gas phase
polymeri~ation under a partial pressure of propylene of
21 kg/cm2G at 70C for 2 hours as in Example 62. Post-
treatment was then carried out as in Example 34 to obtain
a polymer.
Example 67
Propylene-ethylene block copolymerization was carried
out as in Example 66 except that the slurry polymerization
o~ the first step was carried oùt with propylene, and as
the gas phase pol~merization of the second step, ethylene
polymeri~atio~ was carried out under a partial pressure of
hydrogen o~ 8 ky/cm2~ and a partial pressure of ethylene of
12 kg/cm G at 70C for 2 hours.
Example 62 was repeated except that an ~-olefin mixture
of propylene (200 g) with ethylene (~0 g) was used in pla~ing
of usiny propylene (200 g) to obtain a polymer (propylene-
ethylene copolymer).
~xam~le ~69
Example 68 ~as repeated except that butene-l (30 g) was
used in place o using ethylene (20 g), to obtain a polymer
(propylene-butene-l copolymer).
Example 70
The final solid product (300 mg) obtained in Example 34
~5~
and diet~ylaluminum monochloride (3,000 mg) were suspended
in n-hexane (200 m~), followed by reaction under a partial
pressure of propylene of 1.3 kg/cm G at 20C for 10 minutesl,
purging unreacted propylene, preserving the resulting material
with stirring at 40C for one week, introducing the resulting
catalyst slurry containin~ the final solid product (25 mg)
into a polymerization vessel and then carrying out slurry
polymerization and succeeding gas phase polymerization as
in ~xample 66.
Comparative examples!21, 22 and 23
Using each of the following solid products in place of
the fin~l solid product obtained in Example 34, the respective
resulting catalyst slurries were preserved at 40C for one
week as in Example 70:
Comparative example 21: the solid product ~ obtained
in Example 34
Comparative example 22~ the solid product (II) subjected
to polymerization treatment,
obtained in Example 34
Comparative example 23: the final solid product obtained
in Comparat.ive example 11.
The results of the above Ex~nples and Comparative examples
are shown in the following Table:
Il
76
Table 5
~ ~ _ _ __
No. of Polymer Isotac- * ** ~D of Propor- 150 Ccngo
Example yield tic MFR YI polymer tion of meshes ~ed rR-T ¦
and ~g) index 32 to pass ~estl
Ccmparative per g 60 (%~ (time
exa~ple o~ meshes till
final sizes color -
solid (%~ changes)
product
_ _ _ ___ _ _ _ . _
EX. 34 13,00099.2 4.8 0.5 0.50 99.0 <0.1 un- 0.94
changed
Ex. 35 ~ 12,000 9g.0 3.8 0.4 0.50 97.0 <0.1 ,. 0.94
EX. 36 14,000 9~.5 12.0 0.4 0.48 96.0 <0.1 .. 0.93
~cmpar. ~. lo _ _ _ _ _ _ _ _ _
Cbwpar. e~- 11 8,300 95.0 14.0 2.~ 0.40 94.0 ~0.1 ucnhan5ed 0.91
Ccmpar. eX~ 12 _ _ _ _ _ ~ _ _ _
Ccmpar. ex. 13 ~ _ _ _ - _ _ _
Ex. 37 11,000 99.0 4.6 0.8 0.4g 97.0 ~0.1 u~- 0.94
changed
Ccmpar- eX. 14 1,20096.0 3.9 18.00.~5 58.0 4.9 30 sec. 0.93
Compar. ex. 15 1,30096.4 306 15.90.44 60.0 3.8 30 sec. 0.93
Ccmpar. ex. ~ 8,50099.0 3.~ 1.6 0.48 97.5 <0.1 u~- 0,94
changed
Compar. ex. 17 7~20098.4 4.3 2.9 0.48 98.0 <0.1 l~ 0.94
Ex. 38 13,40099.0 4O9 0.4 0.50 98.8 <0.1 ,. 0.93
EX. 39 13,60098.8 5.2 0.4 0.50 98.9 <0.1 l~ 0.91
Ex. 40 13,8009~.6 5.3 0.3 0.50 98.0 <0.1 ll 0.90
Ex. 41 12,90099.0 4.8 0~5 0.50 99.0 ~0.1 .. 0.~6
Cbmpar. ex. 18 6,20088.0 9.6 3.4 0.44 92.0 <0.1 5 min. 0.88
~m?ar. ex. l9 ~ 4,~00 198.o ~ _ ~ I 95.0 ~0.1 ~2 n
_ 77 -
~1
~s~
Table (continued)
. . _ _ _ _ _ . , .
C~mp2r. ex. 20 6,Z00 98.5 1.9 4.1 0.43 ~5.2 <0.1 5mln. 0.93
EX. 42 12,800 g8.9 4.2 0.4 0.50 96.0 <~ un- 0.94
changed
Ex. 43 12,900 99.0 3.6 3.4 0.49 96.5 <0.1 ,. 0.93
Ex. 4~ 13,200 98.8 3.~ 0.4 0.50 94.0 ~0.1 ,. 0.94
Ex. 45 12,200 98.0 4.2 0.6 0.48 92.0 <0.1 0.94
EX. 46 12,000 98.2 3.6 0.7 0.49 92.1 <0.1 ll 0.93
Ex. 47 10,900 98.1 4.6 0.8 0.~ 94.0 <0.1 ll 0.93
EX. 48 12,~00 Ig9.0 4.3 0.6 0.4g 96.0 <0.1 ll 0.9~
Ex. 49 1~000 98.8 4.6 0.7 0.48 92.0 ~0.1 ,. 0.94
E~. 50 13,600 99OO 4.2 Q.3 Q.~0 94.0 <0.1 ll 0.94
Ex. 51 13,200 98.5 4.3 0.4 0.48 92.0 <0.1 ll 0.93
Ex. 52 13,000 98.0 3.6 0.5 0.49 96.0 <0.1 0.93
Ex. 53 12,600 98 ~ 5 4.3 0.5 0.47 92.0 <0.1 ll 0.94
Ex. 54 12,000 98.2 4.1 0.6 0.45 93.0 <0.1 , 0.94
EX. S5 13,200 99.0 4.3 0.4 0.48 92.0 <0.1 ,- 0.94
EX~ 56 13,100 99.1 3.8 0.4 0.49 91.0 <0.1 , 0.94
Ex. 57 12,200 99.0 3.~ 0.7 0.48 92.0 <0.1 .. 0.
Ex. 58 12,~00 98.8 4.1 O.S 0.49 91.~ <0.1 , 0.94
Ex. 59 12,100 98.5 3.6 0.6 0.48 91.0 ~0.1 ~ 0.94
EX. 60 11,800 _ 4.4 0.8 0.46 93.0 <0.1 -
EX. 61 13,000 9~.0 ~3 0.6 0.~9 92.0 <0.1 - 0.~4
Ex. 62 13,20~ 99.2 4.3 0.4 0.48 95.0 <0.1 ~ 0.94
Ex. 63 13,100 99.0 3.9 0.4 0.49 96.0 <0.1 ll 0.94
Ex. 64 13,400 98.8 3.6 0.3 0.50 94.0 <0.1 . 0.94
~j . _ . ~ _ _
- - 78 -
. ~1
1.
l'able (oontinued)
9,400 98.0 3.41.5 0.46 92.0 ~0.1 _ 0.94
1 changed
E~. 66 13,900 98.1 3.00.3 0046 9~.0 ~0.1 , 0.94
EX. 67 13,600 9~.4 3.~0.3 0.47 92~0 ~0.1 ,. ~
E~. 68 13,600 99.0 4.00.3 0.47 92.0 <0.1 ., 0,84
EX. 69 13,200 99.1 3.60.3 0.45 91oO ~O~l ~ 0~90
Ex. 70 12,400 g9.0 4.60.8 0.48 92.0 <0.1 .. 0.93
Compar. ~x. 21 1,400 96.2 3.8 14.0 0.46 62.0 8.9 30 sec. 0.93
Ccmpar. ~Y. 22 1,500 96.4 3.6 13.2 0.47 6~.0 6.2 1 min. 0.93
Compax. eX. 23 8,700 99.0 3.4 2.0 0.48 91.0 ~0.1 un- 0.93
ch~h~ged
. __
* Melt flow rate (according to ASTMD-1238(L~)
** Yellcwness index (accorlitlg to JIS K-7103)
- 79
,. ~
,, - I i
j.
Exam~e 71
A solid product ~III) (15 g) obtained as in E~ample l
except that the solid product (II), without subjecting it
to polymerization treatment with propylene, was reacted
with diisoamyl ether and TiCQ4, was suspended in n-hexane
l500 mQ), and propylene (5 g3 and further diethylaluminum
monochloride (2.4 g) were added. Reaction was then carried
out at 15C for lO hours, followed by filtering off, three
times repeating a procedure of adding ~-hexane (400 m~,
washing and filtering off, and drying under reduced pressure
to obtain a solid product (III) subjected to polymerization
treatment (15.2 g)(polymer: 0.2 g). Using this solid
product subjected to polymerization treatment (30 mg) and
diethylaluminum monochloride (480 mg), propylene polymeri-
zation was carried out as in the step (3) of Example l.
A solid product (III) ~10 g) obtained as in Example l
was suspended in n-heptane (200 mQ). Diethylaluminum
monochloride (3 g) and propylene (8 g) were added, and
reaction was carried out at 20C or 3 hours, followed by
filtering off, washing and drying to obtain a solid product
(III) subjected to polymerization treatment ~10.3 g)
(polymer: 0.3 g). Using this solid product (20 mg) and
diethylaluminum monochloride (420 mg), propylene poly
merization was carried out as in the step ~3) of Example 1.
- 80 -
~1
i
4$~3
n~Hexane (80 mQ), diethylaluminum monochloride
(0.05 mol) and diisoamyl ether (0.13 mol) were mixed
and reacted together at 35C for 30 minutes to obtain
a reaction liquid (I), which was then dropwise added -:~
to TiCQ4 (0O45 mol) at 38C over 4 hours, followed by
keeping the mixture at the same temperature as the above
for 90 minutes, raising the temperature up to 76C,
further reacting it for 1.5 hour to ob-tain a solid product
(ID), which was then filtered off, washed with n-hexane,
filtere~ off and suspended in n~hexane (50 mQ). Diisoamyl
ether (15 g), TiCQ4 (16 g) and propylene (3 g) were added,
followed by reaction at 58C for 2 hours. After completion of the
reaction, filtering off, washing and drying were carried out to
obtain a final solid product. Using this product, propylene
polymerization was carried out as in the steps (2) and ~3)
of Example 1.
EYample 74
A final solid product was obtained as in Example 73
except that in Example 73, ethylal-~inum dichloride (4 g)
was used in place of TiCQ4 (16 g) added for reacting it
with the solid product (II). Propylene polymerization
was then carried out.
Example _
n-Hexane (60 mQ), diethylaluminum monochloride (0.05
i _ 81 -
Il
~5~
mol) and diisoamyl ether (0.12 mol) were mixed and reacted
together at 35C for 30 minutes, and propylene (O.S g) was
dissolved in the resulting reaction liquid, followed by
dropwise adding the liquid to TiC~4 (0.4 mol) at 38C
over 180 minutes, maintaining the mixture at th~ same
temperature for 60 minutes, raising the temperature up to
80C and reacting it further one hour to obtain a solid
product (II) subjected to polymerization treatment, which
was then filtered off at 70C, and washed. The total
amount of this soli.d product was then suspended in n-hexane
(25 mQ~, and diisoamylether (16 g) and TiCQ4 (35 g~ were
added followed by reaction at 70C for one hour. After
the reactlon, filtering off, washing and drying were
carried out to obtain a solid product (III). Propylene
polymerization was then carried out as in the steps 12)
and (3) of F.xample 1.
- 82 -
~1
., I .
~5~
Table 6
. _ _ _ _ _ . _
No. of Example Pol~ner Isotac- BD of Propor- 150
yield tic 1 pol~mer tion of meshes MFR YI
(g) inde~ 32 to pass
per g 60 (~)
o . meshes
solid sizes
product (~)
_ _ _ (III) ~ _ .
71 6,200 99.0 0.50 94 0.2 3.9 3.1
72 6,400 39.2 0.50 92 0.2 4.1 2.8
i~ 73 6~200 ~8.8 0.4~ 9~ 0.6 4.2 3.0
74 6,300 98.8 0.49 93 0.6 4.1 3.0
16,2~0 98.5 0.49 90 0.3 3.9 3.
Example 76
A solid product (III~ (15 g) obtained as in Example 1
except that the solid product (II), without subjecting it to
polymerization treatment with propylene, was reacted with
di-isoamyl ether and TiCQ~, was suspended in n-hexane
(50Q mQ). To the resulting suspention were added propyl-
ene (5 g) and further diethylaluminum monochloride (2.4 g),
and the mixture was reacted at 15C for 10 hours, followed
by filtering off and three ~imes repeating a-procedure
of adding n-hexane (400 m~), washing and filtering off,
and drying under reduced pressure to obtain a sclid
product (III) (a final solid product)(15.2 g)lpol~mer. 0.2 g).
I - 83 -
i
~85~
A propylene polymer was obtained as in Example 1 except
that the above final solid product t30 mg), diethylaluminum
monochloride ~480 mg) a~d a reaction product (G) obtained
by reacting triethylaluminum (23 m~) with methyl p-toluylate
(3.0 mg) in n-hexane (20 mQ) at 25C for 5 hours were
introduced and hydrogen (150 mQ) was added, followed by
gas phase polymerization under a propylene partial pressure
of 22 kg/cm G at a polymerization temperature of 80C for
2 hours.
~
A preactivated catalyst was obtained as in the steps
(2) and (3) of Example 1 except that the final solid product
obtained in Example 76 was used. Propylene polymerization
was then carried out.
Example 78
A solid product tIIII(lO g) obtained as in Example 1
was suspended in n-heptane (200 mQ), and diethylaluminum
monochloride (3 g) and propylene (8 g) were added, followed
by reaction at 20C for 3 hours and then filtering off,
washing and drying to obtain a solid product (III~ subjected
to polymerization treatment (a final solid product)(10.3 g)
(polymer: 0.3 g). Propylene polymerization was then carried
out as in the steps (2) and (3) of Example 1.
Example 79
n-Hexane (80 mQ), diethylaluminum monochloride
- 84 -
~1
(0.05 mol) and diisoamyl ether (0.13 mol) were mixed and
reacted t:ogether at 35C Eor 30 minutes to obtain a reaction
liquid ~I), which ~as dropwise added to TiCQ4 (0.45 mol)
at 38C over 4 hours, followed by keeping the mixture at --
the same temperature for 90 minutes, raising the temperature
up to 76C and urther r~actin~ it for 1.5 hour to obtain
a solid product (II), which was then filtered o~f, washed
and suspended in n-hexane (50 mQ). To the resulting
suspension were added diisoamyl ether ~15 g), TiCQ4 (16 g)
and propylene (3 g), followed by reaction at 68C for
2 hours. After the reaction, filtering off~ washing and
drying were carried out to obtain a final solid product.
Using this product, propylene polymerization was carried
out as in the steps (2) and (3) of Exam~le l.
Example_80
A final solid product was obtained as in Example 79
except that in Example 79, ethylaluminum dichloride (4 g)
was used in place of TiCQ4 (16 g~ added for reacting it
with the solid product (II). Using the final solid product,
propylene polymeri~ation was then carried out.
Example 81
n-Hexane (60 mQ), diethylaluminum monochloride (0~05 mol~
and diisoamyl ether (0.12 mol) were mixed and reacted
together at 35C for 30 minutes, and propylene (0.5 g~
was dissolved in the reaction liquid, followed by dropwise
)I
5~
adding the liquid to TlCQ4 (0.4 mol) 2t 38C over 180
minutes, keeping the mixture at the same temperature for
60 -minutes, 7aising the temperature up to 80C and further
reactin~ it for one hour to obtain a solid product (II)
subjected to polymer.ization treatment, which was then
filtered off and washed at 70C. The total amount of the
product was suspended in n-hexane (25 mQ), and to the
resulting suspension were added diisoamyl ether ~16 g) and
TiCQ4 (35 g) were added! follo~ed by reaction at 70C ~or
one hour~ After the reaction, filtering off, washing and
drying were carriea out to obtain a solid product (III).
Using this product, propylene polymerization was carried
out as in the step ~2) and ~3) or Example 1.
Example 82
Using the solid product [III)~10 g) obtained in
Example 81~ a final solid product subjected to polymeri-
zation treatment was obtained as in Example 78. Using
this product, propylene polymerization was carried out as
in Example 76.
Example 83
A preactivated catalyst was obtained as in the steps
(1) and (2) of Example 1, and butene-l (600 g) was
introduced, followed by polymerization of butene-l at 70C.
Comparative example 24
Using the solid product (III) not subjected to
- 86 -
. .
polymerization treatment, obtained in Example 14, propylene
polymerization was carried out as in Example 3. The BD
of the resulting polymer lowered and its isotactic index
also lowered.
Comparatlve example_25
In Example 78, a final solid product was obtained
without adding propylene (3 g). Propylene polymerization
was then carried out at ~C as in Example 3. The BD of
the resulting polymer lowered and its isotactic index also
lowered.
Comparative exam~le 26
Propylene polymerization was carried out as in Example
3 except that in Example 81, a solid product (III) was
obtained without dissolving propylene ~0.5 g). The BD of
the resulting polymer lowered and it~ isotactic index
also lowered.
I - 87 -
~s~
No, of Polymer Isotac- ~D of ProEx~r- 150 Co~go
EXample yield -tic MFR YI pol~er tion of meshes ~ed rR-T
and (g) index 32 to pass test
Ccmparative per g 60 (%) (time
example of meshes till ._ solid sizes color
_.-- P( I~IdI )uct ( % ) charlgQs )
. _ _ ,
Ex. 76 10,400 9801 4.1 1.00.~9 92.1 <0.1 un~ 0.94
changed
Ex. 77 12,500 99,0 4.8 0.60.50 96.0 <0.1 ll O.g4
EX. 78 1~,800 99.0 4.6 0.50.~0 97.0 <0.1 .. 0.93
EX. 79 12,300 99OO 4.8 0 60.49 94.0 <0.1 ,. ~93
Ex. 80 10,900 98.5 4.3 1.00.48 92.0 <0.1 ll Q.93
Ex. 81 13,000 99.0 4.1 0.60.4g ~4.1 C0.1 17 0.94
E~. 82 10,200 98.0 4.6 1~10.49 92.0 <0.1 ,l 0.94
Ex. 83 9,000 _ _ _ _ _ _ ll _
Ccmpar. ex. 24 7,800 94.0 9.4 3.0O.38 90.0 <0.1 ,. O.90
GQmpar. ~x. ~5 8,000 95.0 8.4 2.80.35 90.0 <0.1 .. 0.90
C~mpar. QX. 26 7,900 95~0 8 6 3.0~ 92 1 <0.1 ~ 0.90
-- ~78 ''-
,, i
