SOLID CATALYST FOR OLEFIN POLYMERIZATION AND PROCESSES FOR ITS PRODUCTION

CATALYSEUR SOLIDE DE LA POLYMERISATION D'OLEFINES ET PROCEDES D'OBTENTION

English Abstract

ABSTRACT OF THE DISCLOSURE
This invention is a catalyst for polymerization
of olefins, comprising a compound of a transition metal
of Group IVB of the periodic table, an aluminoxane and a
particulate organic or inorganic compound carrier.
This catalyst shows very high activity in the
polymerization and copolymerization of olefins and gives
polymers having a high bulk density, a uniform particle
size, a low content of fine particles and a narrow mole-
cular weight distribution and in the case of copolymers,
a narrow composition distribution as well.

Claims

42 67566-1106

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for forming a solid catalyst for olefin
polymerization from an aluminoxane, a compound of a transition
metal of group IVB of the Periodic Table and a particulate organic
or inorganic compound carrier, which comprises: at least a step
comprising contacting a solution of the aluminoxane in a first
solvent with a second solvent in which the aluminoxane is
insoluble or sparingly soluble, in the presence of the particulate
organic or inorganic compound carrier, to deposit the aluminoxane
on the particulate organic or inorganic compound carrier.



2. The process of claim 1, wherein the process comprises:
(1) contacting a suspension of the particulate organic or
inorganic compound carrier dispersed in a solution of the
aluminoxane in the first solvent with the second solvent in which
the aluminoxane is insoluble or sparingly soluble, to form an
aluminoxane supported on the particulate organic or inorganic
compound carrier, and
(2) contacting the aluminoxane supported on the particulate
organic or inorganic compound carrier with a solution of the
compound of a transition metal of Group IVB of the Periodic Table
in a third solvent.


43 67566-1106
3. The process of claim 1, wherein the process comprises:
(1) dispersing the particulate organic or inorganic compound
carrier in a solution of the aluminoxane and the compound of a
transition metal of Group IVB of the Periodic Table in the first
solvent to prepare a suspension, and
(2) contacting the suspension with the second solvent in
which the aluminoxane is insoluble or sparingly soluble.



4. The process of claim 1, wherein the process comprises:
(1) contacting a suspension of the particulate organic or
inorganic compound carrier dispersed in the second solvent in
which the aluminoxane is insoluble or sparingly soluble with a
solution of the aluminoxane in the first solvent to form an
aluminoxane supported on the particulate organic or inorganic
compound carrier, and
(2) contacting the aluminoxane supported on the particulate
organic or inorganic compound carrier with a solution of the
compound of a transition metal Group IVB of the Periodic Table in
a third solvent.



5. The process of claim 1, wherein the process comprises,
(1) preparing a suspension of the particulate organic or
inorganic compound carrier in the second solvent in which the
aluminoxane is insoluble or sparingly soluble and preparing a
solution of the aluminoxane and the compound of a transition metal
of Group IVB of the Periodic Table in the first solvent, and
(2) contacting the suspension and the solution.

44 67566-1106
6. The process of claim 1, 2, 3, 4 or 5, wherein the
catalyst contains 0.5 to 500 milligram-atoms of the transition
metal of the compound of a transition metal of Group IVB of the
Periodic Table and 5 to 50,000 milligram-atoms of aluminum of the
aluminoxane per 100 grams of the particulate organic or inorganic
compound carrier, has an atomic ratio of aluminum atoms of the
aluminoxane to transition metal atoms of the compound of a
transition metal of Group IVB of the Periodic Table in the range
of from 1 to 1,000, and has an average particle diameter of 5 to
200 micrometers.



7. The process of claim 2 wherein step (1) further
comprises evaporating the first solvent to promote precipitation
of the aluminoxane.



8. The process of claim 2, wherein the aluminoxane solution
contains 0.1 to 50 liters of the first solvent per gram-atom of
aluminum in the aluminoxane.



9. The process of claim 8, wherein the second solvent is
used in an amount of 10 to 10,000 parts by weight per 100 parts by
weight of said aluminoxane solution.



10. The process of claim 8, wherein the particulate organic
or inorganic carrier compound is present in the aluminoxane
solution in an amount of 1 to 500 grams per liter of the
aluminoxane solution.


67566-1106
11. The process of claim 8, wherein the transition metal of
Group IVB of the Periodic Table is used in an amount of 0.0005 to
1 gram-atom per gram-atom of aluminum in said aluminoxane.



12. The process of claim 11, wherein the third solvent is
present in an amount of 1 to 500 liters per gram-atom of the
transition metal of the compound of a transition metal of Group
IVB of the Periodic Table.



13. The process of claim 3, wherein step (2) further
comprises evaporating the first solvent to promote precipitation
of the aluminoxane or the compound of a transition metal of Group
IVB of the Periodic Table.



14. The process of claim 3, wherein the second solvent is
used in an amount of 10 to 10,000 parts by weight per 100 parts by
weight of the solution of the aluminoxane and the compound of a
transition metal of Group IVB of the Periodic Table.



15. The process of claim 3, wherein the solution of the
aluminoxane and the compound of a transition metal of Group IVB of
the Periodic Table contains 0.1 to 50 liters of the first solvent
per gram-atom of aluminum in the aluminoxane.




16. The process of claim 15, wherein the compound of the
transition metal of Group IVB of the Periodic Table is present in
an amount of 0.0005 to 1 gram-atom transition metal per gram-atom
of aluminum in the aluminoxane.


46 67566-1106
17. The process of claim 16, wherein the particulate organic
or inorganic compound carrier is present in an amount of 1 to 500
grams per liter of the solution of the aluminoxane and the
compound of a transition metal of Group IVB of the Periodic Table.



18. The process of claim 4, wherein step (1) further
comprises evaporating the first solvent to promote precipitation
of the aluminoxane.



19. The process of claim 4, wherein the suspension of the
particulate organic or inorganic compound carrier in the second
solvent contains 1 to 500 grams of the particulate organic or
inorganic compound carrier per liter of the second solvent.



20. The process of claim 4, wherein the aluminoxane solution
is used in an amount of 1 to 1,000 parts by weight per 100 parts
by weight of the suspension.



21. The process of claim 4, wherein the aluminoxane solution
contains 0.5 to 50 liters of the first solvent per gram-atom of
aluminum in the aluminoxane.




22. The process of claim 4, wherein the compound of a
transition metal of Group IVB of the Periodic Table is used in an
amount of 0.0005 to 1 gram-atom transition metal per gram-atom of
aluminum in the aluminoxane supported on the particulate organic
or inorganic compound carrier.


47 67566-1106
23. The process of claim 5, wherein step (2) further
comprises evaporating the first solvent to promote precipitation
of the aluminoxane or the compound of a transition metal of Group
IVB of the Periodic Table.



24. The process of claim 5, wherein the suspension of the
particulate organic or inorganic compound carrier in the second
solvent contains 1 to 500 grams of the particulate organic or
inorganic compound carrier per liter of the second solvent.



25. The process of claim 5, wherein the solution of the
aluminoxane and the compound of a transition metal of Group IVB of
the Periodic Table in the first solvent contains 0.1 to 50 liters
of the first solvent per gram-atom of aluminum in the aluminoxane
and 0.0005 to 1 gram-atom of the transition metal in the compound
of a transition metal of Group IVB of the Periodic Table per gram-
atom of aluminum in the aluminoxane.



26. The process of claim 5, wherein 1 to 1000 parts by
weight of the solution of the aluminoxane and the compound of a
transition metal of Group IVB of the Periodic Table in the first
solvent is contacted with 100 parts by weight of the suspension of
the particulate organic or inorganic compound carrier in the
second solvent.


- 48 - 67566-1106

27. A solid catalyst for olefin polymerization,
characterized in that:
(A) it comprises
(A1) a compound of a transition metal
of Group IVB of the periodic table as
a catalyst component,
(A2) an aluminoxane as a catalyst
component, and
(A3) a particulate organic or in-
organic compound carrier,
(B) it contains 0.5 to 500 milligram-atoms of
the transition metal atom and 5 to 50,000 milligram-atoms
of aluminum atoms per 100 g of the particulate carrier
(A3),
(C) the atomic ratio of aluminum atoms (Al) to
the transition metal atoms (M), Al/M, is in the range of
from 1 to 1,000, and
(D) it has an average particles diameter of 5 to
200 micrometers.
28. The catalyst set forth in claim 27 in which the
transition metal of Group IVB of the periodic table is
selected from the group consisting of zirconium, titanium
and hafnium.
29. The catalyst set forth in claim 28 in which the
compound of a transition metal of Group IVB of the periodic
table is a compound of the following formula (I)

R1kR2?R3mR4nZr ...... (I)

in which R1 represents a cyaloalkadienyl group,
R2, R3 and R4, independently from each other,
represent a cycloalkadienyl group, an aryl
group, an alkyl group, a cycloalkyl group, an
aralkyl group, a halogen atom, a hydrogen atom,
ORa, SRb, NR2c or PR2d where Ra, Rb, Rc and Rd,

67566-1106
- 49 -
independently from each other, represent a hydrocarbon
group such as an alkyl, cycloalkyl, aryl or aralkyl
group, or a silyl group, and two Rc and Rd may be linked
to form a ring, k is 1, 2, 3 or 4, ?, M and n are 0, 1, 2
or 3, k+?+m+n=4, and when R2 is a cycloalkadienyl group,
R1 and R2 may be bonded through a lower alkylene group.
30. The catalyst set forth in claim 29 in which the
aluminoxane is selected from compounds represented by the
following formula (II)
Image ... (II)

wherein R is a hydrocarbon group and m is a
number of at least 2, and
compounds represented by the following formula (III)


Image ... (III)

wherein R and m are as defined above.
31. The catalyst set forth in claim 29 in which the
atomic ratio of the transition metal atom to the aluminum
atom is from 0.05 to 0.002.
32. The catalyst set forth in claim 29 which has an
average particle diameter in the range of 10 to 100
micrometers.

Description

- 131~37

SPECIFICATION
SOLID CATALYST FOR OLEFIN POLYMERIZATION AND
PROCESSES FOR ITS PRODUC~ION
T~C~NOLQGICAL FI~LD

This invention relates to a solid catalyst for
polymerization of olefins, and processes for its production.
More specifically, it relates to a solid catalyst for
polymerization of olefins comprising a particulate carrier,
a compound of a transition metal of Group IVB of the
10 periodic table and an aluminoxane as catalyst components,
and processes for its production.
BACRGRO~ND TECENOLGGY
For production of an alpha-olefin polymer,
especially an ethylene homopolymer or an ethylene/alpha-
15 olefin copolymer, a method has heretofore been known topolymerize ethylene or copolymerizing ethylene with an
alpha-olefin in the presence of a titanium-containing
catalyst comprising a titanium compound and an organo-
aluminum compound or a vanadium-containing catalyst
20 comprising a vanadium compound and an organoaluminum
compound.
Catalyst comprising zirconium compounds and
aluminoxanes have recently been proposed as a new Ziegler-
type olefin polymerization catalyst.
Japanese Laid-Open Patent Publication No.
19309/1983 describes a process for polymerizing ethylene
and at least one C3-C12 alpha-olefin in the presence of a
catalyst composed of a transition metal-containng compound
represented by the following formula

(cyclopentadienyl)2MeR~al

in which R is cyclopentadienyl, Cl-C6 alkyl, or
halogen, Me is a transition metal and Hal is
halogen,5 and a linear aluminoxane represented by tha following

~31~537

formula

A12OR4(AlSR) )n

in which R is methyl or ethyl, and n is a
number of 4 to 20, or
5 a cyclic aluminoxane represented by the following formula

L-A1 ( R ) _O ~

in which R and n are as defined above,
at a temperature of -50 C to 200 C.
Japanese Laid-Open Patent Publication No.
95292/1984 describes an invention relating to a process
for producing a linear alu~inoxane represented by the
following formula
R




R \ t R
Al-O-(Al-O)n-Al
R / R

in which n is 2 to 40, and R is Cl-C6,and a
cyclic aluminoxane represented by the following
formula

r
~ Al- ~
in which n and R are as defined.
This patent publication discloses a specific example in
which methylaluminoxane, for example, produced by the
process of this patent publication is mixed with a bis-
~cyclopentadienyl) compound of titanium or zirconium, and
an olefin is polymerized in the presence of the mixture.

1314537

Japanese Laid-Open Patent Publication No.
350Q5/1985 discoses a process for producing an olefin
polymerizat.ion catalyst, which comprises reacting an
aluminoxane represented by the following formula

Rl Rl
Al O-(Al-O)n-Al
R / I ~ R
Rl

in which R is Cl-C10 alkyl, and R is Rl or is
bonded to represent -O-.
with a magnesium compound, chlorinating the reaction
product, and treating the chlorinated product with a
compound of Ti, V, Zr or Cr. This patent publication
describes that the above catalyst is especially suitable
for copolymerization of a mixture of ethylene with a
C3-C12 alpha-olefin.
Japanese Laid-Open Patent Publication No.
35006/1985 discloses a combination of (a) a mono-, di- or
tri-cyclopentadienyl compound of two or more different
transition metals or its derivative and (b) an alumoxane
~aluminoxane) as a catalyst system for production of a
reactor blended polymer.
Japanese Laid-Open Patent Publication No.
35007/1985 describes a process for polymerizing ethylene
alone or together with an alpha-olefin having at least 3
carbon atoms is polymerized in the presence of a catalyst
system comprising a metallocene and a cyclic aluminoxane
represented by the foll~wing formula

~ Al-O ~
R

131~537

in which R is an alkyl group having 1 to 5
carbon atoms, and n is an integer of 1 to about
20,
or a linear alumoxane represented by the following formula

R~Al-O~----AlR

in which R and n are as defined above.
Japanese Laid-Open Patent Publi~tion No. 35008/-
1985 discloses that by using a catalyst system containing
at least two metallocenes and an alumoxane, polyethylene
10 or an ethylene~C3-C10 alpha-olefin copolymer having a
broad molecular weight distribution is produced.
The catalysts formed from transision metal
compounds and aluminoxanes as proposed in these prior ar~
references have much higher polymerization activity than
15 catalyst systems formed from transition metal compounds
and organoaluminum com~ounds known heretofore. But these
catalyst systems are soluble in the reaction systems, and
the resulting pol~mer has a low bulk density. It is
20 difficult to obtain polymers having excellent powder
characteristics.
On the other hand, the above-cited Japanese
Laid-Open Patent Publications Nos. 53006/lg85, 35007/1985
and 35008/1985 propose methods in which catalysts formed
25 fr~m a solid catalyst component deposited on a porous
inorganic oxide carrier such as silica, silica-alumina or
alumina and an aluminoxane are used. Japanese Laid-Open
Patent Publications Nos. 31404/1986, 108610/1986 and
30 106808/1985 pxopose methods in which a solid catalyst
component deposited on a similar porous inorganic oxide
carrier is used~ In many of the methods described in
these prior art references, the polymerization activity
is reduced, or the the resulting polymers have insuffici-


131~7

-- 5ent powder characteristics such as low bulk density as a
result of using the deposited solid components.
~ISCLOS~E OF THE INVENTION
It is an object of this invention is to provide
a catalyst for for olefin polymerization.
Another object of this invention is to provide
a catalyst for olefin polymerization comprising a compound
of a transition metal of Group IVB of the periodic table
and an aluminoxane as catalyst components.
Still another object of this invention is to
provide a solid catalyst for olefin polymerization which
can give an olefin polymer having a high bulk density and
excellent powder characteristics and has high polymeriza-
tion activity.
A further object of this invention is to provide
processes for producing the catalyst of the invention.
Other objects of the invention along with its
advantages will become apparent from the following descrip-
tion.
According to this invention, these objects and
advantages of the invention are achieved by a solid
catalyst for olefin polymerization, characterized in that
(A) it comprises
(Al) a compound of a transition metal
of Group IVB of the periodic tab]e as
a catalyst component,
tA2) an aluminoxane as a catalyst
component, and
(A3) a particulate organic or in-
organic compound carrier,
(B) it contains 0.5 to 500 milligram-atoms of
the transition metal atoms and 5 to 50,000 milligram-
atoms of aluminum atoms per 100 g of the particulate
carrier tA3),
(C) the atomic ratio of aluminum atoms (Al) to
the transition metal atoms (M), Al/M, is in the range of

1314537

from 1 to 1,000, and
(D) it has an average particle diameter of 5 to
200 micrometers.
The transition metal of Group IVB of the periodic
table in the catalyst component (Al) is, for example,
selected from titanium, zirconium and hafnium. Preferab-
ly, it is titanium or zirconium, and zirconium is especial-
ly preferred.
The compound of the transition metal of Group
IVB in the catalyst component (Al) may be, for example, a
zirconium compound having a group containing a conjugated
~electron as a ligand.
Examples of the zirconium compound having a
group containing a conjugated electron as a ligand
which is used preferably are compounds of the following
formula (I)

RlkR~ ~3mR4nZr ...... (I)

in which Rl represents a cyaloalkadienyl group,
R2, R3 and R4 represent a cycloalkadienyl
group, an aryl group, an alkyl group, a cycloalkyl
group, an aralkyl group, a halogen atom, a
hydrogen atom, ORa, SRb, NR2C or PR2d where Ra,
Rb, Rc and Rd represent a hydrocarbon group
such as an alkyl, cycloalkyl, aryl or aralkyl
group, or a silyl group, and two Rc and Rd may
~e linked to form a ring, k>l, k~+m+n=4, and
when R2 is a cycloalkadienyl group, Rl and R2
may be bonded through a lower alkylene gxoup.
Examples of the cycloalkadienyl group are
cyclopentadienyl, methylcyclopentadienyl, ethylcyclopenta-
dienyl, pentamethylcyclopentadienyl, dimethylcyclopenta-
dienyl, indenyl and tetrahydroindenyl groups. Examples
of the alkyl group are methyl~ ethyl, propyl, isopropyl,
butyl, hexyl, octyl, 2-ethylhexyl, decyl and oleyl groups.

1 3 1 4 3 3 7

Phenyl and tolyl groups may be cited as the aryl group,
and benzyl and neophile groups may be cited as the aralkyl
group. Examples of the cycloalkyl group include cyclo-
pentyl, cyclohexyl, cyclooctyl, norbornyl, bicyclononyl
and alkyl-substituted derivatives of these groups.
Unsaturated aliphatic groups such as a vinyl, allyl,
propenyl, isopropenyl or l-butenyl ~roup may also be
cited as examples. Examples of the halogen atom are
fluorine, bromine and chlorine. Examples of the silyl
group are trimethylsilyl, triethylsilyl, phenyldimethyl-
silyl and triphenylsilyl groups.
Examples of the zirconium compound include
bis(cyclopentadienyl)zirconium monochloride
monohydride~
bis(cyclopentadienyl)zirconium monobromide
monohydride,
~ bis(cyclopentadienyl)methylzirconium hydride,
bis(cyclopentadienyl)ethylzirconium hydride,
bis(cyclopentadienyl)cyclohexylzirconium
hydride,
bis(cyclopentadienyl)phenylzirconium hydride,
bis(cyclopentadienyl)benzylzirconium hydride,
bi~;(cyclopentadienyl)neopentylzirconium
hydride,
bis(methylcyclopentadienyl)zirconium mono-
chloride monohydride,
bis(indenyl)zirconium monochloride monohydride,
bis(cyclopentadienyl~zirconium dichloride,
bis(cyclopentadienyl)zirconium dibromide,
bis(cyclopentadienyl)methylzirconium mono-
chloride,
bis(cyclopentadienyl)ethylzirconium mono-
chloride,
bis(cyclopentadienyl)cyclohexylzirconium mono-
chloride,
bis(cyclopentadienyl)phenylzirconium mono-


5 3 7


chloride,bis(cyclopentad.ienyl)benzylzirconium mono-
chloride,
bis(methylcyclopentadienyl)zirconium di-
chloride,bis(indenyl)zirconium dichloride,
bis(indenyl)zirconium dibromide,
bis(cyclopentadienyl)diphenyl zirconium,
bistcyclopentadienyl)dibenzyl zirconium,
bis(cyclopentadienyl)methoxyzirconium chloride,
bis(cyclopentadienyl)ethoxyzirconium chloride,
bis(cyclopentadienyl~butoxyzirconium chloride,
bis(cyclopentadienyl)2-ethylhexoxyzirconium
chloride~
bis(cyclopentadienyl)methylzirconium ethoxide,
bis(cyclopentadienyl)methylzirconium butoxide,
bis(cyclopentadienyl)ethylzirconium ethoxide,
bis(cyclopentadienyl)phenylzirconium ethoxide,
bis(cyclopentadienyl)benzylzirconium ethoxide,
bis(methylcyclopentadienyl)ethoxyzirconium
chloride,
bisindenylethoxyzirco~ium chloride,
bis(cyclopentadienyl)ethoxyzirconium,
bis(cyclopentadienyl)butoxyzirconium,
bis(cyclopentadienyl)2-ethylhexoxyzirconium,
bis(cyclopentadienyl)phenoxyzirconium mono-
chloride,
bis(cyclopentadienyl)cyclohexoxyzirconium
chloride,
bis(cyclopentadienyl)phenylmethoxyzirconium
chloride,
bis(cyclopentadienyl)methylzirconium phenyl
methoxide,
bis(cyclopentadiphenyl)trimethylsiloxyzirconium
chloride,
bis(cyclopentadienyl)triphenylsiloxyzirconium

1 314~37

chloride,
bis(cyclopentadienyl)thiophenylzirconium
chloride,
bis(cyclopentadienyl)neoethylzirconium
chloride,
bis(cyclopentadienyl)bis(dimethylamide)-
zirconium,
bis(cyclopentadienyl)diethylamidezirconium
chloride r
ethylenebis(indenyl)ethoxyzirconium chloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
ethoxyzirconium chloride,
ethylenebis(indenyl)dimethylzirconium,
ethylenebis(indenyl)diethylzirconium,
ethylenebis(indenyl)diphenylzirconium,
ethylenebis(indenyl)dibenzylzirconium,
ethylenebis(indenyl)methylzirconium mono-
bromide,
ethylenebis(indenyl)ethylzirconium mono-
0 chloride,
ethylenebis(indenyl)benzylzirconium mono-
chloride,
ethylenebis(indenyl)methylzirconium mono-
chloride,
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(indenyl)zirconium dibromide,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
dimethylzirconium,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
methylzirconium monochloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
zirconium dichloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
zirconium dibromide,
ethylenebis(4-methyl-1-indenyl)zirconium

3 7
- 10 -
dichloride,
ethylenebis~5-methyl-1-indenyl)zirconium di-
chloride,
ethylenebis(6-methyl-1-indenyl)zirconium di-
chloride,ethylenebis(7-methyl-1-indenyl)zirconium di-
chloride,
ethylenebis(5-methoxy-1-indenyl)zirconium
dichloride,
ethylenebis(2,3-dimethyl-1-indenyl)zirconium
dichloride,
ethylenebis(4,7-dimethyl-1-indenyl)zirconium
dichloride,
ethylenebis(4,7-dimethoxy-1-indenyl)zirconium
5 dichloride,
etbylenebis(indenyl)zirconium dimethoxide,
ethylenebis(indenyl)zirconium diethoxide,
ethylenebis(indenyl)methoxyzirconium chloride,
ethylenebis(indenyl)ethoxyzirconium chloride,
ethylenebis(indenyl)methylzirconium ethoxide,
ethylenebis(4,5,fi,7-tetrahydro-1-indenyl~-
zirconium dimethoxide,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
zirconium diethoxide,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
methoxyzirconium chloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
ethoxyzirconium chloride, and
ethylenebis(4,5,6~7-tetrahydro-1-indenyl.)-
methylzirconium ethoxide.
Examples of the titanium compound include
bis(cyclopentadienyl)titanium monochloride
monohydride,
bis(cyclopentadienyl)methyltitani~n hydride,
bis(cyclopentadienyl3phenyltitanium chloride,

13~37

-- 11 --
bis(cyclopentadienyl)benzyltianium chloride,
bis(cyclopentadienyl)titanium chloride,
bis(cyclopentadienyljtibenzyl titanium,
bis(cyclopentadienyl~ethoxytitanium chloride,
bis(cyclopentadienyl)butoxytitanium chloride,
bis(cyclopentadienyl)methyltitanium ethoxide,
bis(cyclopentadienyl)phenoxytitanium chloride,
bis(cyclopentadienyl)trimethylsiloxytitanium
chloride,
bis(cyclopentadienyl)thiophenyltitanium
chloride,
bis(cyclopentadienyl)bis(dimethylamide)-
titanium,
bis(cyclopentadienyl)ethoxytitanium,
ethylenebis(ind~nyl)titanium dichloride, and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-
titanium dichloride.
The following compounds may be cited as ex~mples
of the hafnium compound.
bis(Cyclopentadienyl)hafnium monochloride
monohydride,
bis(cyclopentadienyl)ethylhafnium hydride,
bis(cyclopentadienyl)phenylhafnium chloride,
bis~cyclopentadienyl)hafnium dichloride,
bis(cyclopentadienyl)benzyl hafnium,
bis(cyclopentadienyl)ethoxyhafnium chloride,
bis(cyclopentadienyl)butoxyhafnium chloride,
bis(cyclopentadienyl)methylhafnium ethoxide,
bis(cyclopen~adienyl)phenoxyhafnium chloride,
bis(cyclopentadienyl)thiophenylhafnium
chloride,
bis(cyclopentadienyl)bis(diethylamide)hafnium,
ethylenebis~indenyl)hafnium dichloride, and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-5 hafnium chloride.
The catalyst component (A2) is an aluminoxane.

1314 ~ 3 7

12 -
Examples of the aluminoxane used as the cataly~
st component tA2) are organoaluminum compounds of the
following formulae (II) and (III).


R .. (II)


~ O-Al ~ ..................... ~III)
R

In the aluminoxanes above, R is a hydrocarbon
group such as a methyl, ethyl, n-propyl, isopropyl,
n-butyl or isobutyl group, preferably a methyl, ethyl or
isobutyl group. The methyl group is especially preferred.
m is an integer of at least 2, preferably at least 5~
The aluminoxane may be produced, for e~ample,
by the following method.
(1) A trialkyl aluminum is added to a suspension
in a hydrocarbon medium of a compound containing water of
adsorption or a salt containing water of crystallization,
such as magnesium chloride hydrate, copper sulfate hyd-
rate, aluminum sulfate hydrate, nickel sulfate hydrate
and cerous chloride hydrate, and reacted with the above
compound .
(2) A trialkyl aluminum is directly reacted
with water in a medium such as benzene, toluene, ethyl
ether or tetrahydrofuran.
Of these methods, method (1) is prefera~ly
employed. The aluminoxane may contain a small amount of
an organometallic component.
The particulate carrier (A3) may be organic or
inorganic.

1314~3~

- 13 -
Examples of the organic compound carrier
include polyolefins such as polyethylene, polypropylene,
poly-l-butene and poly-methyl-l-pentene, polyolefins
obtained by copolymerizing the monomers used as starting
materials for these compounds, polyesters, polyamides,
poly~inyl chloride, polymethyl methacrylate, polymethyl
acrylate, polystyrene, natural polymers, and various
monomeric compounds.
The molecular weights of these carriers may be
any at which the compounds can exist as solid substances.
For example, polyethylenes having a weight average mole-
cular weight of about 1,000 to 10,000,000 may be used.
In the present invention, the organic compounds
used as the carrier not only act as a catalyst support
but also may sometimes affect the properties of the
resulting polymer. For example, by using polyethylene
having a weight average molecular weight of about
2,000,000, an increase in the melt tension of the result-
ing polyethylene can be expected. On the other hand, by
using polyethylene having a weight average molecular
weight of about 50,000 ~s a carrier, an increase in the
transparency of the resulting ethylene copolymer film can
be expected.
Porous oxides are preferred as the inorganic
compound carrier. Specific examples include SiO2, A12O3,
MgO, ~rO2, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, and
mixtures of these, such as SiO2-MgO, SiO2-A12O3,
2 2' 2 V2O5, SiO2-Cr2O3 and SiO2-TiO2-MgO
Carriers containing at least one component selected from
the group consisting of SiO2 and A12O3 as a main
component are preferred.
The inorganic oxides may contain small amounts
of carbonates, nitrates, sulfates and oxides such as
Na CO3, K2CO3, CaCO3, MgCO3~ ~a2S4' A12(S 4 3' 4
3/ g( 3)2' Al(NO3)3, Na2o, K2O and Li2o.
The porous inorganic carriers differ in pro-


1 3 1 ~ ~ 3 7

perties depending upon their types and the method ofproduction. Carriers preferably used in this invention
have a specific surface area of 50 to 1000 m2/g, pre-
ferably 100 to 700 m2/g, and a pore volume of 0.3 to 2.5
cm /g. These carriers are obtained by calcination usual-
ly at 150 to 1000 C, preferably 200 to 800 C.
The carriers preferably used in this invention
vary in characteristics depending upon their types and
the method of production, and have a particle diameter of
5 to 200 micrometers, preferably 10 to 150 micrometers,
preferably 20 to 100 micrometers.
The solid catalyst for olefin polymerization in
accordance with this invention is characterized in that
it is formed from the particulate organic or inorganic
compound carrier, the compound of a transition metal of
Group IVB of the periodic table and the aluminoxane
described above; it contains 0.5 to 500 milligram-atoms,
as the transition metal atoms, of the transition metal
compound and 5 to 50,000 milligram-atoms, as the aluminum
atoms, of the aluminoxane; the atomic ratio of the alu-
minum (A) to the transition metal (M), A1/M, is in the
range of from 1 to 1,000; and that it has an average
particle diameter of 5 to 200 micrometers.
The solid catalyst of this inventîon for olefin
polymerization usually contains 0.5 to 500 milligram-
atoms, preferably 1 to 200 milligram-atoms, more prefer-
ably 3 to 50 milligram-atoms, as the transition metal
atoms, of the transition metal compound per 100 g of the
particulate orgnic or inorganic compound carrier from the
standpoint of activity per unit weight of the catalyst
and per unit weight of the transition metal compound.
The solid catalyst of this invention for olefin
polymerization usually contains 5 to 50,000 milligram-
atoms, preferably 50 to 10,000 milligram-atoms, more
preferably 100 to 4,000 milligram-atoms, as aluminum
atoms, of the aluminoxane per 100 g of the particulate

13145~7

- 15 -
carrier frGm the sta~dpoint of polymerization activity
and economoy.
In the solid catalyst of this invention for
olefin polymerization, the atomic ratio of aluminum to
the transition metal (Al/M) is usually from 1 to 1,000,
preferably from 6 to 600, more preferably from 15 to 300,
from the standpoint of polymerization activity per unit
weight of the catalyst and per unit weight of Al atoms.
The average particle diameter of the solid
catalyst of this invention for olefin polymerization is
usually within the range of 5 to 200 micrometers, pre-
fPrably 10 to 150 micrometers, more preferably 20 to 100
micrometers. If the average particle diameter of the
solid catalyst is within the above range, the polymers
obtained by polymerization such as vapor-phase polymeri-
zation or slurry polymerization using the solid catalyst
contain only a small amount of fine powdery polymer
particles formed, and have a high bulk density and an
e~cellent powder shape. Furthermore, coarse polymer
particles are not formed in the resulting polymers, and
troubles such as clogging of a polymer particle discharge
opening do not occur.
The solid catalyst of the invention for olefin
polymerization may be produced by a process for forming a
catalyst for olefin polymerization from an aluminoxane, a
compound of a transition metal of Group IVB of the periodic
table and a particulate organic or inorganic compound
carrier, which comprises ai: least a step of contacting a
solution of the aluminoxane and a solvent in which the
aluminoxane is insoluble or sparingly soluble in the
presence of the particulare carrier to deposit the alumino-
xane on the particulate carrier.
More specifically, the following processes may
be shown.
Firstly, the solid catalyst o~ this invention
for olefin polymerization can be produced by

131~537

- 16 -
~ 1) contacting a suspension o~ the particulate
organic or inorganic compound carrier dispersed in a
solution of the aluminoxane with a solvent in which the
aluminoxane is insoluble or sparingly soluble, to form an
aluminoxane-suported particulate carrier, and
(2) contacting the aluminoxane-supported parti-
culate carrier with a solution of the compound of a
transition metal of Group IVB of the periodic table~
The solvent for the aluminoxane may be, for
example, an aromatic hydrocarbon such as benzene, toluene,
ethylbenzene, propylbenzene, butylbenzene, xylene and
chlorobenzene.
Examples of the solvent in which the alumino-
xane i5 insoluble or sparingly soluble are linear or
branched aliphatic hydrocarbons such as pentane, hexane,
decane, dodecane, kerosene and cyclohexane and alicyclic
hydrocarbons such as cyclohexane, norbornene and ethylcyclo-
hexanone.
Preferably, the solvent in which the aluminoxane
is insoluble or sparingl~ soluble preferably has a higher
boiling point than the solvent used to obtain the alumin-
oxane solution.
Examples of the solvent for the group IVB
transition metal compound include aromatic hydrocarbons
such as benzene, toluene, ethylbenzene~ propylbenzene,
butylbenzene and xylene and halogen-containing hydro-
carbons such as chlorobenzene and dichloroethane.
An aliphatic or alicyclic hydrocarbon such as
pentane, hexane, decane, dodecanea, kerosene or cyclo-
hexane may be cited as examples of a solvent in which theGroup IVB transition metal compound is insoluble or
sparingly soluble.
The above process can be carried out, for
example, by adding the solvent in which the aluminoxane
is insoluble or sparingly soluble to a suspension com-
posed of a solution of the aluminoxane and the particu-


~31 ~37

- 17 -
late inorganic compound carrier or adding a suspension of
the aluminoxane solution and the carrier to the solvent
in which the aluminoxane is insoluble or sparingly solu-
ble to precipitate the aluminoxane, optionally evaporat-
ing the solvent used to foxm the aluminoxane solutionfrom the mixed suspension to promote precipitation of the
aluminoxane and obtain an aluminoxane-deposited particu-
late carrier, and then contacting a suspension composed
of the aluminoxane-deposited carrier and the solvent in
which the aluminoxane is insoluble or sparingly soluble
with a solution of the Group IVB transition metal com-
pound to deposit the transition metal compound as a
catalyst eomponent further on the aluminoxane-deposited
carrier and thus prepar~ a solid catalyst for olefin
polymerization
In the step of contacting the solvent in which
the aluminoxane is insoluble or sparingly soluble with
the suspension composed of the aluminoxane solution and
the particulate carrier, the solvent in which the alumin-
oxane is insoluble sparingly soluble is used in an amountof usually 10 to 10,000 parts by weight, preferably 100
to 1,000 parts by weight, per 100 parts by weight of the
aluminoxane solution. The temperature at the time of
contacting is usually -100 to 300 C, preferably -50 to
100 C, more preferably -30 to 50 C. The contacting is
carried out usually with stirring.
The aluminoxane solution is formed from at
least the aluminoxane and the solvent used to dissolve
it. The aluminoxane solution may be obtained by, for
example, simply mixing the two compounds, or by mixing
them with heating. The amount of the solvent in the
aluminoxane solution is~ for example, 0.1 to 50 liters,
preferably 0.2 to 10 liters, more preferably 0.3 to 2
liters, per gram of the aluminum in the aluminoxane.
The amount of the particulate carrier in the
suspension obtained by dispersing it in the aluminoxane

1314~37


- 18 -
solution is, for example, 1 to 500 g, preferably 10 to
200 g, more preferably 20 to 100 g, per liter of the
aluminoxane solution.
The amount of the transition metal compound
used is 0.0005 to 1 gram-atom, preferably 0.001 to 0.1
gram-atom, more preferably 0.002 to 0.04 gram-atom, per
gram of the aluminum in the aluminoxane suspension during
contacting.
The temperature of contacting is usually -50 to
200 C, preferably -20 to 100 C, more preferably -10 to
50 C. The contacting is usually carried out with stir-
ring.
The solution of the transition metal compound
is formed from the transition metal compound and the
solvent used to dissolve the transition metal compoundO
The transition metal compound solution may be obtained,
for example, by simply mixing the two compounds, or by
mixing them with heating. The amount of the solvent in
the transition metal compound solution is, for example, 1
to 500 liters, preferably 2 to 200 liters, more prefer-
ably 3 to 100 liters, per ~ram-atom of the transition
metal compound
Secondly, the catalyst of this invention for
olefin polymerization can be produced by
(1) dispersing the particulate organic or
inorganic compound carrier in a soluticn of the alumin-
oxane and the Group IVB transition metal compound to
prepare a suspension, and
(2) contacting the suspension with a solvent in
which the aluminoxane is insoluble or sparingly soluble.
This process can be carried out, for example,
by adding the solvent in which aluminoxane is insoluble
or sparingly soluble to the suspension containing the
aluminoxane, the Group IVB transition metal compound and
the particulate carrier, or adding the suspension contain-
ing the aluminoxane, the Group IVB transition metal

131~37

compound and the particulate carrier to the solvent in
which the aluminoxane is insoluble or sparingly soluble,
thereby to precipitate the aluminoxane and the transition
metal compound, optionally evaporating the solvent used
to dissolve the aluminoxane from the mixed solution to
promote precipitation of the aluminoxane and/or the
transition metal compound, whereby a solid catalyst for
olefin polymerization composed of the transition metal
compound and the aluminoxane deposited on the particulate
carrier is formed.
In the step of contacting the suspension of the
aluminoxane, the Group IVB transition metal compound and
the particulate carrier with the solvent in which the
aluminoxane is insoluble or sparingly soluble, the solvent
in which the aluminoxane is insoluble or sparingly soluble
is used in an amount of usually 10 to 10,000 parts by
weight, preferably 10 to 1,000 parts by weight, per 100
parts by weight of the solution of the aluminoxane and
the Group IBV transit on metal compound. The contacting
temperature is usually -100 to 300 C, preferably -50 to
100 C, more preferably -30 to 50 C. The contacting is
carried out usually with stirring.
The solution of the aluminoxane and the transi-
tion metal compound is prepared from at least the alumin-
oxane, the transition metal compound and the solvent usedto dissolve the aluminoxane. The solution may be obtained,
for exampler by simply mixing the two compounds, or
heating them with heating. The amount o~ the solvent in
the solution is, for example, 0.1 to 50 liters, prefer-
ably 0.2 to 10 liters, more preferably 0.3 to 2 liters,per gram-atom of the aluminum in the aluminoxane.
The amount of the transition metal compound in
the solution is O.OOOS to 1 gram atom, preferably 0.001
to 0.1 gram atom, more preferably 0.002 to 0.4 gram-atom,
per gram of aluminum in the aluminoxane.
The amount of the carrier in the suspension of

131~37

- 20 -
the particulate inorganic compound carrier in the solu-
tion of the aluminoxane and the transition metal compound
is, for example, 1 to 500 g, preferably 10 to 200 g, more
preferably 20 to 100 g, per liter of the solution.
The temperature at the time o~ contacting is
usually -100 to 300 C, preferably -50 to 100 C, more
preferably -30 to 50 C. The contacting is carried out
usually with stirring.
Thirdly, the solid catalyst of the invention
for olefin polymerization can be produced by
(1) contacting a suspension of the particulate
organic or inorganic compound carrier dispersed in a
solvent in which the aluminoxane is insoluble or sparing-
ly soluble with a solution of the aluminoxane to form an
aluminoxane-supported particulate carrier, and
(2) contacting the aluminoxane-supported parti-
culate carrier with a solution of the Group IVB transi-
tion me~al compound.
This process can be carried out by adding the
solution of the aluminoxa~e to the suspension of the
particulate carrier in the solvent in which the alumin-
oxane is insoluble or sparingly soluble or adding the
suspension of the particulate carrier and the soLvent in
which the aluminoxane is insoluble or sparingly soluble
to the solution of the aluminoxane, to thereby precipi-
tate the aluminoxane, optionally evaporating the solvent
used to dissolve the aluminoxane from the mixed suspen-
sion to promote precipitation of the aluminoxane and/or
the transition metal compound, to obtain an aluminoxane-
deposited particulate organic or inorganc compoundcarrier, and then contacting a suspension composed o~ the
aluminoxane-deposited carrier and the solvent in which
the aluminoxane is insoluble or sparingly soluble with a
solution of the Group IVB transition metal compound,
whereby the transition metal compound as a catalyst
component is deposited on the aluminoxane-deposited

1314537
- 21 -
carrier and to prepare a solid catalyst for olefin poly-
meri~ation.
In the suspension composed of the particulate
carrier and the solvent in which the aluminoxane is
insoluble or sparingly soluble, the amount of the carrier
is usually 1 to 500 g, preferably 10 to 200 g, more
preferably 20 to 100 9, per liter of the solvent. The
contacting of the suspension and the aluminoxane solution
is carried out usually at -100 to 300 C, prefeeably -50
to 100 C, moee preferably -30 to 50 C. The contacting
is carried out usually with stirring. The amount of the
aluminoxane solution at the time of contacting is usually
1 to 1000 parts by weight, preferably 10 to 100 parts by
weight, per 100 parts by weight of the suspension.
The aluminoxane solution used in contacting is
formed at least from the aluminoxane and the ~olvent used
to dissolve the aluminoxane. The solution may be obtain-
ed, for example, by simply mixing the two compounds or by
mixing them with heating. The amount of the solvent in
the solution i8, for example, 0.1 to 50 liters, prefer-
ably 0.2 to 10 liters, more preferably 0.3 to 2 liters~
per gram atom of the aluminum in the aluminoxane.
In contacting the aluminoxane-supported particu-
late carrier with the solution of the Group IVB transi-
tion metal compound, the transition metal compound isused in an amount of 0.005 to 1 g-atom, preferably 0.001
to 0.1 g-atom, more preferably 0.002 to 0.04 g-atom, per
g~a~om of aluminum in the supported carrier.
The contacting temperature is usually -50 to
200C, preferably -20 to 100C, more preferably -10 to
50CO The contacting i5 usually carried out with stir-
ring.
The solution of the transition metal compound is
formed at leas~ from the transition metal compound and
the solvent used to dis~olve it. The solution may be
obtained, for example, ~y simply mixing the two compounds

131~37

- 22 -
or mixing them with heating. The amount of the solvent
in the solution of the transition metal compound is, for
example, 1 to 500 liters, preferably 2 to 200 liters,
preferably 3 to 100 liters, per gram-atom of the transi-
tion metal compound.
Fourthly, the solid catalyst of the invention
for olefin polymerization can be produced by
(1) preparing a suspension of the particulate
organic or inorganic compound carrier in a solvent in
which the aluminoxane is insoluble or sparingly soluble
and a solution of the aluminoxane and the Group IVB
transition metal compound, and
(2) contacting the suspension and the solution.
This process can be carried out, for example,
by adding the solution of the aluminoxane and the Group
I~B transition metal compound to the suspension of the
particulate carrier in the solvent in which the alumin-
oxane is insoluble or sparingly soluble or adding the
suspension of the particulate carrier and the solvent in
which the aluminoxane is insoluble or sparingly soluble
to the aluminoxane solution to precipitate the alumin-
oxane and the transition metal compound, optionally
evaporating the solvent used to dissolve the aluminoxane
and the transition metal compound from the mixed suspen-
sion to promote precipitation of the aluminoxane and/orthe transition metal compound whereby a solid catalyst
for olefin polymerization composed of the transition
metal compound and the aluminoxane deposited on the
particulate carrier is prepared.
In the suspension formed from the particulate
carrier and the solvent in which the aluminoxane is
insoluble or sparingly soluble, the amount of the carrier
is usually 1 to 500 g, preferably 10 to 200 g, more
preferably 20 to 100 g, per liter of the solvent. The
contacting of the suspension with the solution of the

13:14~37
- 23 -
aluminoxane and the Group IVB transition metal compound
is carried out usually at a temperature of -100 to 300
C, preferably 50 to 100 C, more preferably -3~ to 50
C. The contacting is usually carried out with stirring.
The amount of the solution of the aluminoxane and the
transition metal compound at the time of contacting is
usually 1 to 1,000 parts by weight, preferably 10 to 100
parts by weight, per 100 parts by weight of the suspen-
sion.
The solution of ~he aluminoxane and the transi-
tion metal compounds used in the contacting is formed
from at least the aluminoxane, the transition metal
compound and the solvent used to dissolve the alumin-
oxane. The solution may be obtained, for example, by
simply mixing the two compounds, or by mixing them with
heating. The amount of the solvent in the solution is,
for example, 0.1 to 50 liters, preferably 0.2 to 10
liters, more preferably 0.3 to 2 liters, per gram of the
aluminum in the aluminoxane.
The amount of the transition metal compound in
the solution is 0.0005 to 1 gram-atom, preferably 0.001
to 0.1 gram-atom, more preferably 0.002 to 0~4 gram-
atom, per gram-atom of the aluminum.
The contacting is usually carried out at a
temperature of -50 to 200 C, preferably -20 to 100 C,
more preferably -10 to 50 C. The contacting is carried
out usually with stirring.
The catalyst of this invention is effective for
production of olefin polymers, particularly an ethylene
polymer or a copolymer of ethylene with an alpha-olefin.
Examples of olefins that can be polymerized by using the
catalyst of this invention include alpha-olefins having 2
to 20 carbon atoms such as ethylene, propylene, l-butene,
l-hexene, 4-methyl-1-pentene, l-octene, l-decene, 1-
dodecene, l-tetradecene, l-hexadecene, l-octadecene and
l-eicocene. The catalyst is especially suitable for

~ 131~37
- 24 -
polymerization of ethylene or copolymerization of
ethylene with an alpha-olefin having 3 to 10 carbon
atoms.
In a polymerization process using the catalyst
5 of this invention, olefins are usually polymerized in the
vapor phase or in slurry. In the slurry polymerization,
an inert hydrocarbon may be used as a solvent, or the
olefin itself may serve as a solvent.
Examples of the hydrocarbon medium include
10 aliphatic hydrocarbons such as butane, isobutane, pen-
tane, hexane r octane, decane, dodecane, hexadecene and
octadecane, alicyclic hydrocarbons such as cyclopentane,
methylcyclopentane, cyclohexane and cyclooctane, and
petroleum fractions such as kerosene and light oil.
In carrying out the slurry polymerization
method using the catalyst of this invention, polymeri-
zation temperatures of -50 to 120 C, preferably 0 to 100
C, are usually employed D
The vapor-phase polymerization using the cata-
20 lyst of this invention is carried out normally at poly-
merization temperatures of 0 to 120 C, preferably 20 to
100 C.
In using the catalyst of this invention in the
slurry polymerization method or the vapor-phase poly-
25 merization method, the proportion of the transition metal
compound is, for example, 10 8 to 10-7 gram-atom~liter,
preferably 10 7 to 10 3 gram-atom/liter, as the concen-
tration of the transition metal atom in the polymeriza-
tion reaction system.
In the above polymerization reaction, an alumin-
oxane or an organoaluminum compound represented by the
general formula
RpRqAlX3 p q
in which Rh represents a hydrocarbon group

1314537
- 25 -
having 1 to 10 carbon atoms, preferably an
alkyl group having 1 to 6 carbon atoms, an
alkenyl group, a cycloalkyl group or an aryl
group, Rk represents an alkoxy group having 1
to 6 carbon atoms or an aryloxy group, X is a
halogen atom, and 3~p>0, and 2~q~0,
may be used. The addition of an organoaluminum compound
having a branched group such as triisobutyl aluminum or
isoprenyl aluminum is particularly effective for increas-0 ing polymerization activity.
The polymerization is carried out usually under
normal atmospheric pressure to 100 kg/cm2, preferably 2
to 50 kg~cm2, batchwise, semi-continuously or continu-
ously. It is possible to carry out the polymerization in5 two or more stages having different reaction conditions.
Preferably, in the process of this invention,
the olefin is preliminarily polymerized in the presence
of the solid catalyst prior to the main polymerization of
the olefin. The preliminary polymerization is carried
out, for example, by polymerizing 1 to 1000 g, preferably
S to 500 g, more preferably 10 to 200 g, of the alpha-
olefin per gram-atom of the Group IVB transition metal
compound (Al) in the solid catalyst. Examples of the
olefin used in the preliminary polymerization include
ethylene and alpha-olefins having 3 to 20 carbon atoms
such as propylene, l-butene, 4-methyl-1-pentene, 1-
hexene, l-octene, l-decene, l-dodecene and l-tetradecene.
~thylene or both ethylene and a small amount of the
alpha-olefin, are preferred.
The preliminary polymerization temperature is
-20 to 70 C, preferably -10 to 60 C, more preferably 0
to ~0 C.
The above prelimianry polymerization may be
carried out batchwise or continuously under atmospheric
pressure or elevated pressures. The preliminary poly-
merization may be carried out in the presence of a mole-


~31~37
- 26 -
cular weight controlling agent such as hydrogen. The
amount of the molecular weight controlling agent, how-
ever, should preferably be limited to an amount in which
at least a prepolymer having an intrinsic viscosity [~],
measured in decalin at 135 C, of at least 0.2 dl/g,
preferably 0.5 to 20 dl/g, can be produced.
The preliminary polymerization is carried out
in the absence of a solvent or in an inert hydrocarbon
medium. In view of operability, it is preferred to carry
out the prelimianry polymerization in an inert hydrocarbon
medium. Examples of the inert hydrocarbon medium used in
the preliminary polymerization may be the same as those
exemplified above as the solvent in which the aluminoxane
is insoluble ro sparingly soluble.
The concentration of the solid catalyst in the
preliminary polymerization reaction system in the prelimi-
nary polymerization is, for example, 10-6 to 1 qram-
atom/liter, preferably 10 4 to 10 2 gram-atom/liter, as
the concentration of the transition metal atom in the
~olid cataly5t
Synthesis of Aluminoxane
A 400 ml glass flask equipped with a stirrer
and thoroughly purged with nitrogen was charged with 37 g
of A12lSO4)3.14H2O and 125 ml of toluene. The flask was
cooled to 0 C, and then 125 ml of toluene containing 50
ml of trimethylaluminum was added dropwise over 1 hour.
The mixture was then heated to 40 C over 3 hours, and
the reaction was continued at this temperature for 48
houirs. After the reaction, the reaction mixture was
subjected to solid-liquid separation by filtration.
Low-boiling substances were removed from the separated
li~uid by using an evaporator. Toluene was added to the
remaining solid and the desired aluminoxane was recovered
as a toluene solution.
~he molecular weight of the aluminoxane, deter-
mined from freezing point depression in benzene, was

~3~4~37

- 27 -
1879, and therefore its degree of polymerization was 15
EXAMPLE 1
Preparation_of a solid catalyst
A 300 ml pressure-reducible reactor equipped
with a stirrer was charged with 67 ml of a toluene solu~
tion containing the methylalumioxane synthesized as above
in an amount corresponding to 100 millimoles of Al atomks
and 2 g of silica (Davison Co., #952) obtained by calci-
nation at 500 C for 12 hours, and at room temperature,
100 ml. of purified n-decane was added over about 0.5
hour with stirring to precipitate the methylaluminoxane.
Then, while the inside of the reactor was reduced in
pressure to 4 torr by using a vacuum pump, the inside of
the reactor was heated to 35 C over about 3 hours to
remove toluene from the xeactor and further precipitate
the methylaluminoxane. The reaction mixture was filtered
through a filter to remove the liquid portion. The solid
portion was then suspended in n-decane, and 5 ml of a
toluene solution containing 0.2 millimole of bis~cyclopenta-
dienyl)zirconium dichloride was added. After mixing atroom temperature for about l hour, the liquid portion was
removed by using a filter to prepare a solid catalyst for
olefin polymerization.
The amount of Zr contained in the solid catalyst
was 7 millimoles per lO0 g of silica used as a carrier,
and the amount of A1 contained in the solid catalyst was
2.4 moles per 100 g of silica used AS a caxrier. The
catalyst had an average particle diameter, determined by
microscopiec observation, of about 40 micrometers.
Preliminary polymerization
A 400 ml reactor equipped with a stirrer was
charged with lO0 ml of purified n-decane and 0.1 milli-
mole, as Zr, of the solid catalyst under a nitrogen
atmosphere. Then, ethylene was fed into the reactor at a
rate of 4 Nl/hour for one hour, and during this time, the
temperature was maintained at 20 C. After the feeding
inside of the ractor was purged with nitrogen and then

1314~37

- 28 -
of ethylene, the washed once with purified hexane. The
catalyst was stored as a hexane suspension in a catalyst
bottle.
Polymerization
Sodium chloride (250 g) as a dispersant was
added to a 2-liter autoclave thoroughly purged with
nitrogen, and while the autoclave was heated to 90 C, it
was subjected to pressure-reduction treatment by a vacuum
pump for 2 hours so that the pressure of the inside of
the autoclave reached 50 mmHg or below. The temperature
of the autoclave was then lowered to 75 C. The inside
of the autoclave was purged with ethylene, and 0.007
millimoles, as zirconium atoms, of the solid catalyst
component subjected to the preliminary polymerization was
added. The autoclave was sealed up, and 50 Nml of hydro-
gen was added. The autoclave was pressurized with
ethylene so that its inside pressure reached 8 kg/cm2-G.
The stirring speed was increased to 300 rpm, and the
polymerization was carried out at 80 C for 1 hour.
After the polymerization, all the polymer and
sodium chloride in the autoclave were taken out, and put
in about 1 liter o~ water. By stirring for about 5
minutes, substantially all sodium chloride dissolved in
water, and only the polymer came afloat on the water
surface. The floating polymer was recovered, washed
thoroughly with methanol, and dried overnight at 80 C
under reduced pressure. The amount of the polymer yielded
was 120.8 g. It had an MFR of 2.6 dg/min. and an
apparent bulk density of 0.46 g/ml. The amount of fine
polymer particles having a size of less than 105 micro-
meters was 0.1 % by weight based on the entire polymer
product, and coarse polymer particles having a size of
more than 120 micrometers were not observed. The Mw/Mn
of the polymer measured by GPC was 2.6.
EXAMPLE 2
Preparation of a solid catalvst

13~4~3~

A 300 ml pressure-reducible reactor equipped
with a stirrer was charged with 67 ml of a toluene solu-
tion containing the methylaluminoxane in an amount corres-
ponding to 100 millimoles of Al atoms, 5 ml of a toluene
solution of 0.2 millimole of bis(cyclopentadienyl)-
zirconium dichloride and 2 g of silica (Fuji-Davison Co.,
~952) obtained by calcination as in Example 2, and at
room temperature 100 ml of purified n-decane was added
over about 1 hour with stirring to precipitate particles
composed of the methylaluminoxane and bis(cyclopentadienyl)-
zirconium chloride. Then, while the inside of the reactor
was reduced in pressure to 4 torr by using a vacum pump,
the temperature of the inside of the reactor was increas-
ed to 35 C over about 3 hours to evaporate and remove
toluene from the reactor and precipitate particles com-
posed of methylaluminoxane and bis(cyclopentadienyl)-
zirconiuum chloride. The reaction suspension was trans-
ferred to a filter and the liquid portion was removed.
The solid portion was recovered. The Zr and Al contents
and the average particle diameter of the resulting solid
catalyst are shown in Table 1.
Preliminary polymerization and vapor-phase
polymerization of ethylene were carried out in the same
way as in Example 1. The results are shown in Table 1.
COMPARATIVE EXAMPLE 1
In Example 2, a ,olid catalyst was prepared by
evaporating toluene without using n-decane, i.e. a solvent
in which methylaluminoxane is sparingly soluble, and by
using the solid catalyst, the same preliminary polymeri-
zation and the vapor-phase polymerization of ethylene as
in Example 2 were carried out. Specifically, a 300 ml
pressure-reducible reactor equipped with a stirrer was
charged with 67 ml of a toluene solution containing the
methylaluminoxane in an amount corresponding to 100
millimoles of Al atoms, 5 ml of a ~oluene solution con-
taining 0.2 millimole of bis(cyclopentadienyl)-


131~ ~ 3 7

- 30 -
zirconium dichloride and 2 g of the same silica as used
in Example 2. Thenl while the inside of the reactor was
reduced to 4 torr with stirring, the temperature of the
inside of the reactor was increased to 35 C over about 3
hours to evaporate toluene completely from the reactor
and obtain solid particles composed of methylaluminoxane,
bis(cyclopentadienyl)zirconium chloride and silica parti-
cles. Using the solid particles, preliminary polymeri-
zation and vapor-phase polymerization of ethylene were
carried out by the same operations as in Example 1. The
results are shown in Table 1.
EXAMPLE 3
A solid catalyst was prepared in the same way
as in Example 1 except that 1,2-dichloroethane was used
instead of toluene as the solvent used to dissolve bis-
(cyclopentadienyl)zirconium chloride. Using the solid
catalyst, preliminary polymerization and vapor-phase
polymerization of ethylene were carried out as in Example
1. The results are shown in Table 1.
EXAMPLE 4
A solid catalyst was prepared in the same way
as in Example 1 except that ethylbenzene was used instead
of toluene as the solvent used to dissolve methylalumin-
oxane. Using the solid catalyst, preliminary polymeri-
zation and vapor-phase polymerization of ethylene were
carried out as in Example 1. The results are shown in
Table 1.

- 31 - 131~537



.
aJ ~ ~7
~i ~r ~ ~ ~ ~
o o o o o
~J A ~ _
l ~
:E~ o o o o o
a) ~ o o o o o
O P ~ ~ ~ C~
.rl-~
~1 ~ ~ P t~
O ~ C~ I
0
tD h
~1 ~ ~ C
~ ~
Q~ ~ ~ O tO
Q C~
E~ .
c ~ ~r In ~O
o
~a
~ ~ O ~
.co_
~ O ~ ~d
~ ~i ~ h o~ oti cr~ ~ co
O ~
_ _

. ~ ~
zO aJ
~;
~e ~ o x x x

~31 ~5~7
- 32 -
EXAMPLE 5
Ethylene and l-hexene were copolymerized in the
vapor phase. Specifically, ethylene and l-hexene were
copolymerized in the same way as in Example 1 except that
using the solid catalyst subjected to the preliminary
polymerization described in Example 1, 10 ml of hexene
was added after the addition of the catalyst components,
and the polymerization time was shortened to 20 minutes
from 1 hour. The results are shown in Table 2.
EXAMPLE 6
Slurry polymerization was carried out using the
solid catalyst of Example 1. Specifically, 450 g of
liquefied isobutane was introduced into a 2-liter auto-
clave purged fully with ethylene, and the temperature was
raised to 60 C. The solid catalyst component subjected
to the preliminary polymerization described in Example 1
was added in an amount of 0.008 millimole calculated as
zirconium atoms. Then, 80 ml of 4-methylpentene-1 and 50
Nml of hydrogen were added. Ethylene was then introduced,
and the pressure of the inside of the autoclave was
maintained at 3.5 kg/cm2-G for 1 hour~ During this time,
the temperature was controlled to 70 C. After the lapse
of 1 hour, about 2 ml of methanol was added to th~ autoclave
to stop the polymerization completely, and the pressure
was released. The resulting polymer was recovered, and
dried overnight at 80 C under reduced pressure. The
results are shown in Table 2.
EXAMPLE 7
Preparation of a solid catalyst
A 300 ml. pressure-reducible reactor equipped
with a stirrer was charged with 100 ml of purified n-
decane and 2 g of silica (#952, a product of Davison Co.)
obtained by calcination at 500 C for 12 hours, and while
the resulting suspension was stirred at room temperature,
69 ml of a toluene solution containing the methylalumin-
oxane in an amount corresponding to 100 miillimoles of Al

~ 131~537
- 33 -
atoms was added to the stirred suspension over the course
of about 0.5 hour. The inside of the reactor was then
reduced in pressure to 4 torr by means of a vacuum pump.
By raising the temperarure of the inside of the reactor
to ~5 oC over about 3 hours, toluene was removed from the
reactor. Then, 5 ml of a toluene solution of 0.2 milli-
mole of bis(cyclopentadienyl)zirconium dichloride was
added to the suspension. After mixing a~ room tempera-
ture for about 1 hour, the liquid phase was removed by
using a filter and a solid catalyst for olefin polymeri-
zation was prepared. The results are shown in Table 2.
EXAMPLE 8
A solid catalyst was prepared, and preliminary
polymerization and vapor phase polymerization of ethylene
were carried out, in the same way as in Example 1 except
that in the preparation of the solid catalyst in Example
1, the amount of bistcyclopentadienyl)zirconium chloride
used was changed to 0.33 millimole from 0.2 millimole.
The results are shown in Table 2.
EXAMPLE 9
Ethylene was polymerized in the vapor phase in
the same way as in Example 8 except that in the vapor-
phase polymerizartion of ethylene in Example 8, 1.3
millimoles of triisobutyl aluminum was added immediately
before the addition of the solid catalyst component
subjected to preliliminary polymerization to the auto-
clave. The results are shown in Table 2.

13145~7

-- 34 _




_ ,.
JJ ~ ~ ,.
o o
... _
-`
,1 U~
~ ~ ~ ~ d' e
o
,~ ~ C ~ o o o o o
. ... _
l ~
o o o C:7 o
a~ c ,~ ~ o o o o o
O P~ CQ ~ U~
a) ~ ~ ~ O
_~ o ~ U I ~ ~ _1 ,1 _I
Q p~ N ~a ~
E~ _ _
a~ s~
~n_I a)
C) ~ _
~'~ O O O O O
~d ~ IE3 :L
h ~
C~ ~
.
. ~ ~ ~1
.~J ~.a) l¢
~ _
~1 0 Id
t~ ~ ~ U h I` t-- CO
C.) ~ O ~
_
O U~
z a) a1

. ~3 li3 W li3 ~1

1314~37
-- 35 --
EXA~5PLE 1 0
In the method of Example 1, a solid catalyst
was prepared in the same way except that 2 g of poly-
ethylene powder (MIPELON ~, a tradename of a product of
Mitsui Petrochemical Industries, Ltd.) having an average
particle diameter of 35 micrometers was used instead of 2
g of silica in the preparation of the solid catalyst.
The resulting solid catalyst had a Zr content
of 9 millimoles per 100 g of polyethylene used as the
carrier and an Al content of 2.0 moles per 100 g of
polyethylene used as the carrier. The average particle
diameter of the solid catalyst, determined by microscopic
observation, was about 40 micrometers.
Preliminary polymerization and polymerization
were carried out under the same conditions as in the
method of Example 1.
There was obtained 128.2 g of a polymer. It
had an MFR of 1.6 dg/min. and an apparent bulk density of
0.46 g/ml. The amount of a fine powdery polymer having a
size of less than 105 micrometers was 0.1 % by weight
based on the entire polymerization product. On the other
hand, no coarse polymer particles having a particle size
of more than 1120 micrometers were observed. The polymer
had an Mw/Mn of 2.6.
EXAMPLE 11
In the method of Example 2, 2 g of polyethylene
powder (MIPELON ~, a tradename for a product of Mitsui
Petrochemical Industries, Ltd.) having an average particle
diameter of about 35 micrometers was used instead of 2 g
of silica at the time of preparing the solid catalyt
component. The Zr and Al contents and average particle
diameter of the resulting solid catalyst are shown in
Table 3.
Preliminary polymerization and vapor-phase
polymerization of ethylene were carried out by the same
methods as in Example 10, and the results are shown in

1314~37
- 36 -
Table 2.
COMPARATIVE EXAMPLE 2
In Comparative Example 1, ~ g of the same
polyethylene powder as used in Example 11 was used instead
of 2 g of silica, and otherwise, by the same mehod as in
Comparative Example 1, solid particles composed of methyl-
aluminoxane, bis(cyclopentadienyl)zirconium chloride and
polyethylene particles were obtained. By the same opera-
tions as in Example 10, preliminary polymerization and
vapor-phase polymerization of ethylene were carried out.
The results ar~ shown in Table 3.
EXAMPLE 12
A solid catalyst was prepared in the same way
as in Example 10 except that 1,2-dichloroethane was used
instead of toluene as the catalyst used to dissolve
bis(cyclopentadienyl)zirconium chloride. Preliminary
polymerization and vapor-phase polymerization of ethylene
were carried out in the same way as in Example 10. The
results are shown in Table 3.
EXAMPLE 13
A solid catalyst was prepared in the same way
as in Example 10 except that ethylbenzene was used instead
of toluene as the catalyst used to dissolve bis~cyclopenta-
dienyl)zirconium chloride. Preliminary polymerization
and vapor-phase polymerization of ethylene were carried
out in the same way as in Example 10. The results are
shown in Table 3.

3 7




. . ~
a) ~ ~ ~u~
~r~ ~ ~ ~r
~ ~ U
o~ C ~ o o o o o
'¢ Q 'a --
_
'~
O O O O O
~D C~ 3 o o o o o
p O P~ ~c~
_I ~ ~ ~ 00~ ~ 1` ~D
O ~ U I ~ ~
pl N 0 ~
....
J~ a) h
U IJ _ o o ~ J~ O o o
~ ~5 ~ E3 s d'
R ~ ~ nS---- O u~
I
E U ~ 4~5 . Q ~ ~
_ _ ..
C _ O
O ~ ~1
el~
0~,1
U~l 0 ~1
~1 U~ ~1 1^1 -. --------- ,,
r-l O t~
. ~ ~ U
a~ ~ a~
P4~o
_
a
O

zO a)~u 11~ a) a) o
~1~ L/ ~1 ~1 ~1

p x x ~ x ~: ~
w ~ w ~

- 38 - 131~537
EXAMPL~ 14
Ethylene and l-hexene were copolymerized in the
vapor phase. Specifically, using the solid catalyst
subjected to the prelimianry polymerization described in
Example 10, ethylene and l-hexene were copolymerized in
the same way as in Example 10 except that 10 ml of hexene
was added after adding the catalyst components, and the
polymerization time was shortened to 20 minutes from 1
hour. The results are shown in Table 4.
EXAMPLE 15
Slurry polymerization was carried out using the
solid catalyst of Example 10. Specifically, 450 g of
liquefied isobutane was introduced into a 2-liter auto-
clave purged fully with ethylene, and the temperature was
raised to 60 C. The solid catalyst component subjected
to the preliminary polymerization described in Example 10
was added in an amount of 0.008 millimole calculated as
zirconium atoms. Then, 80 ml of 4-me~hylpentene-1 and 50
Nml of hydrogen were added. Ethylene was then introduced,
and the pressure of the insiae of the autoclave was
maintained at 3.5 kg/cm2-G for 1 hour During this time,
the temperature was controlled to 70 C. After the lapse
of 1 hour, about 2 ml of methanol was added to the auto-
clave to stop the polymerization completely, and the
pressure was released. The resulting polymer was re-
covered, and dried overni~ht at 80 C under reduced
pressure. The results are shown in Table 4.
EXAMPLE 16
A solid catalyst was prepared in the same way
as in Example 10 except that 2 g of spherical polystyrene
powder (#200 - #400, a product of Eastman Rodak Co.)
having a particle diameter of about 30 micrometers was
used instead of polyethylene used as the carrier. Pre-
liminary polymerization and then vapor-phase polymeri-
zation of ethylene were carried out in the same way as inExample 10. The results are shown in Table 4.

_ 39 _ 131~337
EXAMPLE 17
Preparation of a solid catalyst
A 300 ml pressure-reducible reactor equipped
with a stirrer was charged with 100 ml of purified n-
decane and 2 g of polyethylene powder (MIPELON ~, atradename for a product of Mitsui Petrochemical Indust-
ries, Ltd.) having an average particle diameter of 35
micrometers, and while the suspension was stirred at room
temperature, 67 ml of a toluene solution containing the
methylaluminoxane in an amount corresponding to 100
millimoles of Al atoms was added to the suspension over
about 0.5 hour. Then, while the inside of the reactor
was reduced in pressure to 4 torr by means of a vacuum
pump, the temperature of the reactor was raised to 35 C
over about 3 hours to remove toluene from the reactor.
Then, 5 ml of a toluene solution containing 0.2 milli-
moles of bis(cyclopentadienyl)zirconium dichloride was
added to the suspension. After mixing at room tempera-
ture for about 1 hour, the liquid phase was removed by
using a filter, and a solid catalyst for olefin poly-
merization was prepared. The results are shown in Table 4.
EXAMPLE 18
A solid catalyst was prepared in the same way
as in Example 10 except that the amount of bis(cyclopenta-
dienyl)zirconium dichloride was changed to 0.33 millimolefrom 002 millimole in the preparation of the solid catalyst
of Example 10. Preliminary polymerization and vapor-
phase polymeri~ation of ethylene were carried out. The
results are shown in Table 4.
EXAMPLE 19
Ethylene was polymerized in the vapor phase in
the same way as in Example 18 except that 1.3 millimoles
of triisobutyl aluminum was added immediately before the
addition of the solid catalyst component subjected to
preliminary polymerization to the autoclave. The results
are sho~n in Table 4.

- 40 _ 1314~37




,
o

~ ~ ~ ~ ~ ~ ~ '*
h ~ ~r ~ ~ ~r ~ ~r
a~a)~ oooooo
f:C .a ~ _
. . _ _____

. ~ ~ O O C~ O O ~
~ 6~P~

Q ~ N 1~ O~ ~
E~ .

o o In o o o
a~ ~ et~ ~ ~ ~ ~r
Id 1
C~

. O ~ ~1 O O
0
U~l O ~-I
~1 U~ _ ..
~1 0
E3 0 ~ a~
C~ ~ O ~ _l ~
_ _ n._. . _
~ ~ ~D 1` CD
O
~z; ~1) a) Q) ~1) ~11 a

_ X ~

~ 3~ ~537

- 41 -
POSSIBILITY OF INDUSTRIAL ~TILIZATION AND ~FFECT
This invention is a solid catalyst for olefin
polymerization having very high polymerization activity
in the homopolymerization and copolymerization of olefins.
This catalyst gives a polymer and a copolymer which have
a high bulk density, a uniform particle size, a low
content of fine powder and a narrow molecular weight
distribution, and in the case of the copolymer, a narrow
composition distribution.