Note: Descriptions are shown in the official language in which they were submitted.
~_~.~~D~;~
HOECHST ~iR~TENGESELLSCHAI~'T HOE 89/F 053 Dr.DA/bs
Description
Process for the preparation of a random propylene
copolymer
The polymerization of olefins, depending on the process
used, gives copolymers with different properties and
different proportions of comonomerss
a) random copolymers with a low proportion of comonomers,
b) polymer blends containing a larger proportion of
incorporated comonomers than the random copolymers and
c) copolymer rubbers containing the comonomers incor-
porated in similar proportions.
As a rule, random copolymers differ from the correspond-
ing homopolymers in having a lower crystallinity and a
lower hardness. It is desirable for the random copolymers
to have as random a chain structure as possible. The
prior art olefin copolymers which are prepared with the
aid of heterogeneous catalysts can only fulfil this
requ:irernent to a very limited extent.
Random terpolymers of CZ/C;~/Cn with n > 3 have been
described and were obtained using heterogeneous catalysts
(cf. EP 263,718). The proportion of C3 is 97 to 86 mol
the proportion of CZ is 0.5 to 6 ~ and the proportion of
Cn (n > 3) is 2 to 13 mol ~C. The material has good heat
sealing properties but is obtained in a two step process
with a suspension polymerization step and a gas phase
polymerization step. In order to obtain the desired anti-
blocking properties, a terpolymer with a high proportion
of the third monomer has to be prepared. However bipoly-
mere are however required since these are easier to
manipulate and have a chemically homogeneous chain
structure.
furthermore, random C2/C~ copolymers are known, prepared
by suspension polymerization ( cf . EP 74,194 ) . In order to
~:~~.~3~E~~
obtain the desired properties, the polymers obtained must
be broken down. Moreover, the proportion of ethylene is
greater than 6 $. This high proportion of C2 is necessary
in order to reduce the chemical inhomogeneity of a
heterogeneous catalyst system, this inhomogeneity tending
to produce a relatively high proportion of crystallizable
sequences in the polymer.
Finally, an ethylene/propylene copolymer with a high
proportion of ethylene and a process for its preparation
has been described (cf. JP 62/121,707). The process is
carried out using ethylenebisindenylzirconium dichloride
at a temperature of less than -10°C and is consequently
unsuitable for industrial production. Apart from that,
the activity of the catalyst is very low. .,
The object was therefore to provide a process for the
preparation of a propylene copolymer, which can be
carried out within an industrially relevant temperature
range with adequate catalyst activity and provides a
copolymer which is suitable for thermoforming and blow
molding.
It was found that this object can be achieved by copoly-
merization of propylene with other olefins in the pre-
sence of certain metallocene catalysts.
The invention accordingly provides a process for the
preparation of a propylene copolymer composed of 99.9 to
80.0 mol ~, relative to the total polymer, of propylene
units and 0.1 to 20.0 mol ~, relative to the total
polymer, of units which are derived from ethylene or from
an olef in with at least 4 carbon atoms of the formula
R15-CH=CH-Rle, where Ri5 and R18 are identical or different
and denote a hydrogen atom or an alkyl radical having 1
to 28 carbon atoms or R15 and RiB with the carbon atoms
bonding them form a ring having 4 to 28 carbon atoms, by
polymerizing 50 to 99.5 ~ by weight, relative to the
total amount of monomers, of propylene and 0.5 to 50 ~ by
- ~ - ~~.~~E~;~
weight, relative to the total amouwt of monomers, of at
least one representative of the group consisting of
ethylene and olefins having at least 4 carbon atoms of
the formula Rls-CH=CH-Rls, where Rlj and Rls have the
meaning given above, at a temperature of 30 °C to x.50 °C at
a pressure of 0.5 to 100 bar in solution, in suspension
or in the gas phase in the presence of a catalyst com-
posed of a metallocene and an aluminoxane, wherein the
metallocene is a compound of the formula I
R'1 ( CRBR~ D m
Z0 R'~ R 7 I
R R R
iCRBR9?n
R6 R6
in which
R1 and RZ are identical or different and denote a hydrogen
atom, a C1-C1o-alkyl group, a Cl-Clo-alkoxy group, a
Cs-Clo-aryl group, a Cs-Clo-aryloxy group, a CZ-Clo-
alkenyl group, a C~-Cao-arylalkyl group, a C~-C4o-
alkylaryl group, a Cs-Cqo-arylalkenyl group or a
halogen atom,
R3, R', RS and Rs are identical or different and denote a
hydrogen atom, a halogen atom, a Cl-Clo-alkyl group, a
radical -NRz -, -SR1°-, -OSiR3°-, -SiR3°- or -PRZ°-
in which
Rz° is a Cl-Cl°-alkyl group, a Cs-Cz°-aryl group or
if the
radical contains Si or P may also be a halogen atom,
or each pair of adjacewt radicals R3, R', R5 or Rs forms a
ring with the carbon atoms linking them,
R' is
Rll Rll Rll Rll Rll
1 1 I I 13 1
M M ,
_ Ml _ , _ 1 _ 1 _ M1 _ CR2 _ . _ O _ Ml _ O _
g12 X12 X12 R12 X12
R4
3 R3
R11 R11
1 t
C - . - O - ~1 -
R12 R12
~~.~D~~~
=BRZ1, =~a1R11, -Ce-, -sn-, -o-, -s-, =so, =gp2, =p~11,
=pRll or =g(o)RW
where
R1', R1z and Rz3 are identical or different and denote a
hydrogen atom, a halogen atom, a Cl-C3o-alkyl group,
a C1-C1o-flaaoroalkyl group, a Ce-C~o-ax~yl group, a
Cs-Clo-fluoroaryl group, a Cl-Clo-alko3ry group, a
C2-Clo-alkenyl group, a C,-C~o°arylal~~cyl group, a Cg
C4o-arylalkenyl group, a C~-C4o-81ky1~iry1 group or R1g
and R12 or Rzl and R13 in each case form a ring with
the atoms bonding them,
X11 is silicon, germanium or tin,
Ro and R9 are identical or different and have the meaning
given for Rzl,
m and n are identical or different and are zero, 1 or 2,
m glue n being zero, 1 or 2,
and the alum.ino~cane is one of the formula (II)
R~4 -Rig Rx4
A1 - O AI ~ A1 r (II)
R14 ''~ p ' . R14
in the instance of the linear type andfor of the formula
(III)
R14
(III)
p~2
in the instance of the cyclic type, R1" in the formulae
( I I ) and ( I I I ) denoting a C1-CB-alkyl group and p denoting
an integer from 2 to 50.
The invention furthermore relates to the copolymer
prepared by the above process and to its use for the
preparation of thermoforming sheets and for the blow-
- 5 ~ ~:~~.C~~D~~
molding of hollow articles.
The catalyst which is to be used for the process accord-
ing to the invention is composed of an aluminoxane and a
metallocene of the formula T.
R~ ccR~Rg~m
R1 R 7
BHP
R~ R5 R
tCRBRg)n
_U
R~ R~
R1 and RZ are identical or different and denote a hydrogen
atom, a C1-Clo°, preferably Cl-C3-alkyl group,
a Cl-Clo- r preferably Cl-C3-alkoxy group,
a Cs-Cso-, Preferably Cs-Cs-aryl ,clroup,
1~ a Cs-Clo-, preferably Cs-Cs-aryloxy group.
a C~-Clo-, preferably Ca-C,~-.alkenyl group,
a C'-C~°-, preferably C~-Cl°-arylalkyl group,
a C,-C4o-, preferably C~-C12-alkylaryl group,
a CB-Cao-, preferably C8-Cxz-arylalke~zyl group,
or a halogen atom, preferably chlorine.
R3, R°, R5 and Rs are identical or different and denote a
hydrogen atom, a halogen atom, preferably a fluorine,
chlorine or bromine atom, a Cz-C1°-, preferably C1-C3-alkyl
group, a radical -I~1R2 -, -SRS°-, -OSiR3°-, -SiR3°- or -
PRz -,
where Rl° is a C~-C2°, preferably Cl-C~-alkyl group or
Cs-Coo-. preferably Cs-Ce-aryl group, or in the case of
radicals containing Si or P may also be a halogen atom,
preferably a chlorine atom, or each adjacent pair of
radicals R3, R", RS or Rs forms a ring with the carbon
atoms bonding them. Particular preference is given to
indenyl, fluorenyl and cyclopentadienyl ligands.
R~
R3
_ ~"~~.~~~
R' is
Rll Rll Rll Rll Rll
is s
- M1 - - Ml - M1 - , - Ml - CR2 - , - O - M1 - O -
R12 , X12 X12 g12 gZl2
R11 Rll
- C - s ° O - M1
g12 p~12
=SRll, =A1R11, -GQ-, -Sn-, -O-, -S-, DSO, ~SOa, ~IJR11, NCO,
=FR11 ox ~F ( O) Rlg, ia'here R11, R~ and R13 ~lre identiC:al or
different and denote a hydrogen atom, a halogen atom, a
C~-C3o, preferably C1-C4-alkyl group, in particular a
methyl group, a Cl-Clo-fluoroalkyl graup, preferably a CF3
group, a Ce-Clo-fluoroaryl group, preferably a penta
fluorophenyl group, a Cg-Clo-, preferably C6-Ce-aryl group,
a C1-Clo°. preferably C1-C4-alkoxy group, ~.r~ particular a
methoxy group, a Cz-Clo-, preferably Cz-C4-alkenyl group,
a C~-C4o-, preferably C~-Clo-arylalkyl group, a Ce-Cao-.
preferably C8-Clz-arylalkenyl group or a C~-C4o-, preferably
C~-Clz-alkylaryl group, or R~1 and Rlz or Ri' and Rl3 in each
case together form a ring with the atoms bonding them.
14T1 is silicon, germanium or tin, preferably silicon and
germanium.
R' is preferably =CRllRizr =SiRllRlz, =GeR11R12A -~_~ -S_~
-SO, -PR'1 or =P ~ O ) Rl' .
R8 and Re are identical or different and have the meaning
given for Rli.
m and n are identical or different and denote zero, 1 or
2, preferably zero or 1, where m plus n is aero, 1 or Z,
preferably zero or 1.
The metallocenes described above can be prepared by the
2~ following general reaction scheme:
~ - ~~~.~t~f~J
F32R~ + ButylLi --~~ FiR~L~.
~-(CR8R9)m-R7°(CR8R9)n-X
H2Rb * ButylLi -----.~ HRbLi
HRay ( cRaR~ ) ~,- R~- ( cRgR~ ) n- RAH ~i~
LiRa- (CRBR~)tn'R~- (CR8R9)n-RbLi gIfCl4
(CR8R9)m_Rs (~BR~)m_Ra
t
t o
C1 ~ ~ Rl
R~ Hf ~ RR~ Hf'~ R~L~
t C1 ~ I C1
i t
(cR8R~)n_R~ (cR8R9)~_~~
(CR8R9)~_Ra
1
1
R
R7 Iif
a a R2
i
(CRBR~)n_Rb
R3 R5
(~ = C1, Br, I, O-tosyl, HR° ~ R3 ~ g , HRb = R~ ~ H )
R4 R4 R6 R6
Preferred metallocenes are those of the formula I in
which the radical - ( CR8R8 ) m R'- ( CReR9 ) p denotes -CHx-CHx-,
-Ge(CH3)x-r -Si(CH3)x-, -Si(Cells~x- or -Si(CH3) (CBHS)-.
Particular preference is given to the use of the follow-
ing metallocene compoundsa
ethylenebisindenylhafnium dichloride (= 1) and
bisindenyldimethylsilylhafnium dichloride (_
- ~~~.C~~~~
The cocatalyst is an aluminoxane of the formula II
gl.~ ~ R14 ~ g14
X11 - O - Al - O - 1~1 ( zT )
R1~ ~ ~ R1~
P
in the instance of the linear type and/or of the formula
(IZa)
g14
~~ - o - (xaI)
P~2
in the instance of the cyclic type. In these formulae, gla
denotes a Cl-C6-alkyl group, greferably methyl, ethyl or
isobutyl, in particular methyl, and p denotes an integer
from 2 to 50, preferably 5 to 40. However, the exact
structure of the aluminoxane is not known.
The aluminoxane can be prepared by various methods.
One possibility is the careful addition of water to a
dilute solution of a trialkylaluminum by adding the
solution of the trialkylaluminum, preferably trimethyl-
aluminum, and the water each in small portions to a
previously introduced relatively large amount of an inert
solvent and at each stage waiting until gas evolution has
ended.
In another process, a slurry of finely powdered copper
sulfate pentahydrate is prepared in toluene and admixed
in a glass flask, under inert gas at about -20°C, with
an amount of trialkylaluminum such that for every 4 gram
_ g
atoms of A1 there is available about 1 mole of CuS~a.5H20.
After slow hydrolysis with alkane elimination the reac-
tion mixture is left for 24 to 48 hours at room temper-
ature, which may require cooling so that the temperature
does not exceed 30°C. the aluminoxane dissolved in
toluene is then separated from the copper sulfate by
filtration and the solution is concentrated in vacuo. It
is assumed that during this preparation the low molecular
weight aluminoxanes condense with elimination of tri-
alkylaluminum to form higher oligomers.
Furthermore, aluminoxanes are obtained if trialkyl-
aluminum, preferably trimethylaluminum, dissolved in an
inert aliphatic or aromatic solvent, preferably heptane
or toluene, is brought into reaction at a temperature of
-20 to 100°C with aluminum salts containing water of
crystallization, preferably aluminum sulfate. In this
process, the ratio by volume between the solvent and the
alkylaluminum used is isl to 50x1, preferably 5:1, and
the reaction tame, which can be monitored from the.
elimination of the elkane, is 1 to 200 hours, preferably
10 to 40 hours.
Particular preference is given to aluminum salts contain-
ing a high proportion of water of crystallization.
Hydrated aluminum sulfate is especially preferred,
particularly the compounds A12 ( SOa ) 3 ~ 16H20 and
Alz ( S04 ) 3 ~ 18H2~3 with the particularly high proportion of
water of crystallization of 16 and 18 moles of HZO/mole
of AL2(.~.~p)3'
Another alternative for the preparation of aluminoxanes
is to dissolve trialkylaluminum, preferably trimethyl-
aluminum, in a suspension medium which has been
previously introduced into the polymerization vessel,
preferably in liquid monomer in heptane or toluene and
then to react the aluminum compound with water.
In addition to the processes which have been described
above for the preparation of aluminoxanes, there are
other usable processes.
Whatever the method of preparation, all solutions of
aluminoxane contain a variable amount of unconverted
trialkylaluminum which is present in the free state or as
an adduct.
The metallocene can be preactivated be:~ore use in the
polymerization reaction with an alum.inoxane of the
formula (TI) and/or (TIT). This significantly increases
ZO the polymerization activity and improves the particle
morphology.
'The preactivat3on of the transition metal compound is
carried out in solution. Here, it is preferable to
dissolve the metallocene in a solution of the aluminoxane
in an inert hydrocarbon. Suitable hydrocarbons afire
aliphatic or aromatic hydrocarbons. Toluene is preferably
used.
The concentration of the aluminoxane in the solution is
in the range of from about 1 ~ by weight up to the
saturation limit, preferably of 5 to 30 ~ by weight,
relative in each case to the total solution. The metal-
locene can be used in the same concentration, but is
preferably used in an amount of 10-4 - 1 mole per mole of
aluminoxane. The preactivation time is 5 minutes to
60 hours, preferably 5 to 60 minutes. Preactivation is
carried out at a temperature of -78°C to 100°C, prefer-
ably 0 to 70°C.
The polymerization is carried out in a known manner in
solution, suspension or in the gas phase, continuously or
batchwise, in one or more steps at a temperature of 30 to
150°C, preferably 30 to 80°C. Propylene is copolymerixed
with at least one representative of the group consisting
of ethylene and olefins having at least 4 carbon atoms of
the formula R15-~H=CH-Rls. In this formula, ~t15 and Ris are
identical or different and denote a hydrogen atom or an
- 1 ~ - ~'~.C~t~~6~
alkyl radical having 1 to 28 carbon atoms. However, Rls
and R'6 may also form a ring with the carbon atoms bonding
them which contains 4 to 28 carbon atoms. Examples of
olefins of this type are 1-butane, 1-hexane, 4-methyl-1-
pentane, 1-octane, norbornene, norbornadiene, cyclopen-
tene, cyclohexene and cyclaoctene. The amount of
propylene used is 50 to 99.5, preferably ~0 to 99 ~c by
weight, relative to the total amount of monomers, and the
amount of comonomer, there being at least one, is 0.5 to
50, preferably 1 to 40 ~ by weight relative to the total
amount of monomers.
If necessary, hydrogen is added as a molecular weight
regulator. The total pressure in the polymerization
system is 0.5 to 200 bar. Preference is given to polymer-
ization in the industrially particularly relevant pres-
sure range of 5 to 64 bar.
In polymerization, the metallodene compound is used in a
concentration, relative to the transition metal, of 10-'
to 10-', preferably 10-4 to 10-6 moles, of transition metal
per dm3 of solvent or per dm~ of reactor volume. The
aluminoxane is used in a concentration of 10-s to
10-1 moles, preferably 10-4 to 10-2 males per dm3 of solvent
ar per dm3 of reactor volume. However, in principle higher
concentrations can also be used.
If the polymerization is a suspension or solution poly-
merization, an inert solvent customary for the Ziegler
process is used. The polymerization may be carried out
for example in an aliphatic or cycloaliphatic hydro-
carbon; examples of these are butane, pentane, hexane,
heptane, isooctane, cyclohexane, and methylcyelahexane.
naphtha fraction or hydrogenated diesel oil fraction
may also be used. It is also possible to use toluene.
Preference is given to polymerization in liquid monomer.
If inert solvents are used, the monomers are metered. in
in the gaseous or liquid form. If only one monomer is
_ 12 - ~~~.~~~5
used as the suspending medium, the comonomer(s) is/are
metered in in the gaseous or liquid form. Furthermore, it
is possible to carry out the polymerization in a mixture
of different monamers as the suspending medium; a further
monomer can then be metered in liquid or gaseous form. It
is advantageous when using ethylene to charge part of the
ethylene initially and then to meter in the remainder
during the polymerization.
The duration of the polymerization is optional, since the
catalyst system which is to be used according to the
invention has only a slight loss of polymerization
activity over time.
.A feature of the process according to the invention is
that the hafnium compounds used are very heat stable so
that they can also be used with high activity at tempera-
tures up to 90°C. Moreover, the aluminoxanes used as
cocatalysts can be added in lower concentrations than
hitherto. Finally, it has now become possible to prepare
random copolymers at industrially relevant temperatures.
The copolymer (or terpolymer) prepared according to the
invention is a copolymer (terpolymer) composed of 99.9 to
80.0 mol ~, relative to the total polymer, of propylene
units and 0.1 to 20.0 mol ~, relative to the total
polymer, of units which are derived from the above
Z5 comonomers in which the comonomers are incorporated in
blocks with an average sequence length n < 1.25. The
copolymers have a uniform composition i.e. no distribu-
tion of composition is observed> The polydispersity ~,/Mn
is in the range of 2.5 to 5.5 and the molecular weight is
in the range of about 100,000 to 360,000 g/mole. Due to
these molecular properties, the copolymers have, in
addition to low crystallinity, a high transparency, are
not tacky and have an enormous tensile strength.
The sequence length of the comonomer blocks in the
copolymers according to the invention are preferably
'~~~.~t'~~ a
13
below 1.25, particularly below 1.2 and especially below
1.1.
The invention is described in more detail in the follow-
ing examples.
The following symbols are useds
V'~ = viscosity number in cma/g
I~" = weight average mole- determined by gel perinea
cular weight Lion chromatography (data
M" = number average mole- in units of g/mole)
cular weight
Mw/Mn = polydispersity
average block length
n~2 = polyethylene
(the block lengths were determined by 13C-INPiR spectro_
soapy)
example 1
A dry 16 dm~ vessel was purged with nitrogen and charged
with 10 dm3 of liquid propylene. Then 35 cm~ of methyl-
aluminoxane solution in toluene (_ :~iAO, corresponding to
50.7 mmols of A1, having an average degree of oligomer-
ization n = 30) were added and the batch was stirred at
30~C for 15 minutes. 12 g of ethylene were then added.
meanwhile, 52.5 mg (= 0.103 mmols) of bisindenylethylene-
hafnium dichloride were dissolved in 16 cm3 of ~IAO (_
23.2 mmols of A1) and preactivated by being left to stand
for 15 minutes.
The solution was then added to the vessel. The polymeriz-
ation system was brought to a temperature of 60°C and the
polymerization begun. During the following 120 minutes,
38 g of ethylene were added in small portions and the
temperature maintained. -
- 14 - ~~.'~1~~5
1.33 kg of random ethylene-propylene copolymer were
obtained. The activity was thus 12.7 kg of PP/g of
metallocene/h or 6.5 PP/mmols of Hf/h.
The following analytical data were determined from the
polymers
V2 - 168 cm~/g, M" = 196000 g/mole, M" = 44550 g/mole,
M,oJl~i~, = 4.4, n~a -- 1.0, 3.5 ~ by weight of incorporated
ethylene, Tm = 126.5°C, eHm = 65 ~lg.
Example 2
The procedure of Example 1 was followed. 23 g of ethylene
were charged. During the polymerization, 68 g of ethylene
were metered in.
The polymerization time was likewise 2 hours. 40.0 mg
(0.078 mmols) of metalloeene compound were used. 1.42 kg
of random ethylene-propylene copolymer were obtained. The.
activity of the metallocene was thus 17.8 kg of PP/g of
metallocene/h or 9.0 kg of PP/mmol of Hf/h.
V~ - 182 cm3/g, 1~, = 207000 g/mole, Ma = 46000 g/mole,
= 4.5, n~2 = 1.0, 6.4 ~ by weight of incorporated
ethylene, Tm = 127 °C, dI~ = 67 3/g.
Example 3
The procedure of Example 1 was followed. 1.5 g of ethyl-
ene were charged. During the polymerization, 4.5 g of
ethylene were metered in.
The polymerization time was likewise 2 hours. 49.0 mg
(0.096 mmols) of metallocene compound were used. Z.43 kg
of random ethylene-propylene copolymer were obtained. The
activity of the metallocene was thus 22.8 kg of PP/g of
metallocene/h or 11.6 %g of PP/mmol of Hf/h.
~~~~.~1~~~
-- 15 _
V2 -- 137 cm3/g, M" = 151000 glmole, 3~ = 30200 glmole,
~"!M" = 5.0, aa~2 = 1.0, 2.4 ~ of incorporated ethylene,
Tm = 126 °C, eHm = 69 J/g.
$xample 4
The procedure of Example 1 was followed, but 13.5 g of
ethylene were charged. During the polymerization, 40 g of
ethylene were metered in.
The polymerization time was likewise 2 hours. 53.4 mg
(0.105 mmolj of metallocene compound were used. 2.53 kg
of random ethylene-propylene copolymer were obtained. The
activity of the metallocene was therefore 23.7 kg of PP/g
of metallocene/h or 12.0 kg of PP/mmol of Hf/h.
VZ = 154 cm3/g, 1~,, = 168000 glmole, Tai" = 303500 g/mole,
~,/M=, = 5.8, n~z = 1.0, 2.1 ~ by weight of incorporated
ethylene, Tm = 126.8°C, eH,~ = 70 J/g.
8xample 5
The procedure of Example 1 was followed, but 30.5 g of
ethylene were charged. During the polymerization, 92 g of
ethylene were metered in.
The polymerization time was likewise 2 hours. 56.5 mg
(0.111 mmolj of metallocene compound were used. 1.45 kg
of random ethylene-propylene copolymer were obtained. The
activity of the metallocene was thus 15.5 kg of PP/g of
metallocene/h or 7.9 kg of PP/mmol of Hf/h.
VZ - 190 cm3/g, 1~ = 217000 g/mole, I~ = 41750 g/mole,
1~,/Ma = 5.2, n~2 = 1.0, 8.4 ~ of incorporated ethylene,
Tm = 127°C, eHm = 6i J/g.
Hxample 6
The procedure of Example 1 was followed. 13 g of ethylene
- 16 -
were charged and then 120 g of 1-butane. During the
polymerization, 40 g of ethylene were metered in.
The polymerization tame was likewise 2 houxs. 64.5 mg
(0.127 mmol) of metallocene compound were used.
2.05 kg of random ethylene-propylene-butane terpolymer
were obtained. The activity of the meta:llocene was thus
15.9 kg of PP/g of metallocene/h or ~.1 kg of PP/mmol of
Hf/h.
VZ = 160 cm3/g, 1~ = 1790~~ g/mole, Pi=, = 400~0 g/mole,
Mw,/Mn = 4.5, nCZ = 1.0, 2.6 ~ of incorporated ethylene,
T~ = 126 .5 °C, eH~ = 65 J/g.
Example 7
The procedure of Example ~. was followed: 35 g of ethylene
were charged and then 70 g of 1-butane. During i:he
polymerization, 105 g of ethylene were metered in.
The polymerization time was likewise 2 hours. 64.5 mg
(0.127 mmol) of metallocene compound were used. 2.70 kg
of random ethylene-propylene-butane terpolymer were
obtained. The activity of the metallocene was thus
21.0 kg of PP/g of metallocene/h or 10.6 kg of PP/ma~ol
of Hf/h.
'~Z - 130 cm3/g, Mo, = 142000 g/mole, Mn = 26320 g/mol,
M~/1~ = 5.4, n~2 = 1.0, 5.2 ~ of incorporated ethylene,
Tm = 126 °C, n~ = 67 J/g.
Example 8
The procedure of Example 1 was followed, but 50°C was
selected as the polymerization temperature. 30 g of
ethylene were charged. During the polymerization, 95 g of
ethylene were metered in.
_ 17 -
The polymerisation time was likewise 2 hours. 55.7 mg
{0.110 mmol) of metallocene compound were used. 2.15 kg
of random ethylene/propylene copolymer were obtained. The
activity of the metallocene was thus 19.3 kg of PP/g of
metallocene/h or 9.8 kg of PP/mmol of Hf/h.
vz = 1.34 cm3/g, P~,, = 115000 g/mole, M" = 20900 g/mole,
Ma,/~, = 5.5, n~2 = 1.0, 5.7 ~ of incorporated ethylene,
Tm = 127°C, dH,a = 69 J/g.
Bxample 9
The procedure of Example 1 was followed, but 70°C was
selected as the polymerization temperature. 11 g .of
ethylene were charged. During the polymerization, 35 g of
ethylene were metered in.
The polymerization tune was likewise 2 hours. 45.5 mg
{0.089 mmol) of metallocene compound were used. 1.74 kg
of random ethylene/propylene copolymer were obtained. The
activity of the metallocene was thus 19.1 kg of PP/g of
metallocene/h or 9.7 kg of PP/mrnol of Hf/h.
vZ - 158 cm3/g, M~ = 158000 glmole, Mn = 32400 g/mole,
t~"/F~, = 4 .9, nCZ = 1. 0, 2 . ~ ~ by weight of incorporated
ethylene, Tm = 128°C, nF~ = 68.5 J/g.
Bzample 10
The procedure of Example 1 was followed, but the catalyst
used was bisindenyldimethylsilylhafnium dichloride. 10 g
of ethylene were charged. During the polymerization, 35 g
of ethylene were metered in. Polymerization Bias carried
out for two hours at 60°C. 53 mg (0.099 mmol) of
metallocene compound were used. 0.88 kg of random
ethylene-propylene copolymer were obtained. The activity
of the metallocene was thus 8.3 kg of PP/g of
metallocene/h or.4.4 kg of PP/mmol of Hf/h.
~~~~.~~D~~~
-ls-
Vz - 2s5 cm3/g, ~ = 336000 g/mole, r~, = 65900 g/m~le,
I~~,/.MI, = 5.1, n~z = 1.0, 4.9 $ of incorporated ethylene,
Tm = 127.5°C, eHm = 62 J/g.
Example 11
The procedure of Example ZO was followed. 1 g of ethylene
was charged. During the polymerization, 5 g of ethylene
were metered in. Polymerization was carried out for two
hours at 60°C. 47.2 mg (0.088 ~aol~ of metallocene
compound were used. 2.4 kg of random ethylene-propylene
copolymer were obtained. The activity of the metallocene
was thus 25.4 kg of PP/g of metallocene/h or 13.6 kg of
PPJmmol of Hf/h.
VZ - 272 cm3lg, I~, = 310000 g/mole, 'N.h = 68000 g/mole,
P~"/1~, = 4.7, n~z = 1.0, 0.2 ~ of incorporated ethylene,
Tm = 12x.5°c, eHm = 65 J/g.
Example z2
The procedure of Example 10 was followed. 7.5 g of
ethylene were charged. During the polymerization, 25 g
of ethylene were metered in. Polymerization was carried
out for two hours at 60°C. 53.3 mg (0.103 mmol) of metal-
locene compound were used. 2.3 kg of random ethylene-
propylene copolymer were obtained. The activity of tine
metallocene was thus 20.8 kg of PP/g of metallocene/h or
11.2 kg of PP/mmol of Hf/h.
VZ = 295 cm3/g, M~, = 349000 g/mole, 3~, = 79000 g/mol~e,
1~/M" _ 4.4, n~z = Z.O, 1.3 ~ s~f incorporated ethylene,
Tm = 128°C, eI~ = 67 J/g.
Example Z3
The procedure of Example ZO was followed. I1 g of ethyl-
ene were charged. During the polymerization, 36 g.of
ethylene were metered in. Polymerization was carried out
a~~~..~~~~~
- 19 -
for two hours at 60°C. 57.8 mg (0.108 mmol) of metal
locane compound were used. 1.7 Jzg of random ethylene
propylene copolymer were obtained. The activity of the
metallocene was thus 14.7 3cg of PP/g of metallocene/h ox
7.8 Dcg of PP/mmol of I3f/h.
VZ -- 277 cm3/g, .M", = 320000 g/mole, I~, = 77600 glmole,
Mo,/Ma = 4.2, n~2 = 1.0, 2.7 ~ of incorporated ethylene,
Tm = 127 °C, ~Ha, = 63 Jlg.
Example 14
The procedure of Example 1 was followed. 37 g of ethylene
were charged. During the polymerization, 112 g of ethyl-
ene were metered in. Polymerization was carried out for
two hours at 60°C. 53.6 mg (0.100 mmol) of metallocene
compound were used. 2.0 kg of random ethylene-propylene
copolymer were obtained. The activity of the metallocene
was thus 18.7 Dcg of PP/g of metallocane/h or 10.0 kg of
PP/mmol of Hf/h.
VZ = 284 cm3/g, Mw = 334000 g/mole, M" = 67000 g/mole,
I~"1M" = 5.0, n~2 = 1.0, 7.4 ~ of incorporated ethylene,
T~ = 126.5°C, eHm = 64.5 J/g.
