Note: Descriptions are shown in the official language in which they were submitted.
CA 022324~6 1998-03-17
W O 97/12920 PCT~NL96/00363
-- 1 --
COPOLYMER OF AN OLEFINIC MONOMER AND 1,2-POLYBUTADIENE
The invention relates to a thermoplastic
polyole~in which is a copolymer o~ at least one ole~inic
monomer and ~rom 0.005 to 10 wt.% 1,2-polybutadiene.
One o~ the characterizing parameters o~
polyole~ins is their molecular weight distribution,
expressed as the quotient o~ the weight average molecular
weight, Mw, and the number average molecular weight, Mn.
This parameter has an in~luence on product properties, ~or
instance, tensile strength and impact resistance. An
important parameter which in~luences the processing
behaviour o~ polyole~ins is the Melt Flow Ratio (MFR).
This is usually calculated as the quotient o~ the melt
index (MI) determined according to ASTM D-1238 using a
weight o~ 21.6 kg and the melt index determined using a
weight o~ 2.16 kg. The MFR o~ common polyole~ins is known
to increase with wider molecular weight distributions or,
in other words, with increasing values o~ Mw/Mn. As a
- consequence, in some applications a compromise needs to be
sought when a particular MFR is desired ~or the processing
properties and a particular Mw/Mn ratio ~or the desired
product properties.
From WO-A-93/08221 it is known to produce
thermoplastic polyole~ins with the aid o~ constrained-
geometry catalysts. The disclosed process allows the MFR
to be varied while the width of the molecular weight
distribution remains almost constant. However, the
polyole~ins disclosed in the application mentioned all
appear to possess a molecular weight distribution which is
very near to 2. It is not taught how polyole~ins with
other molecular weight distributions should be produced.
I CA 022324~6 1998-03-17
.,: . . ' '; ' - '
Enclosure 1.1 PCT/NL 96/00363; 8076WO
- Amended page 2 -
However, to enable optimum mat~erial selection ~or
more applications there is a need ~or thermoplastic
polyole~ins with other combinations o~ MFR and molecular
weight distribution than those according to the prior art.
The object o~ the invention is to provide such
polyole~ins.
This object o~ the invention is achieved with a
copolymer o~ ethylene, 0-50 wt.~ o~ a C4-C20 a-ole~in with
respect to the total amount o~ ole~inic monomer present and
~rom 0.005 to 10 wt.~ 1,2-polybutadiene in which the number o~
1,2-vinyl unsaturations per polybutadiene chain is at least 3.
The 1,2-polybutadiene will hereina~ter also be re~erred to as
(co)monomer. The amount o~ 1,2-polybutadiene is re~erred to
the total o~ the copolymer.
From DE-A-2.123.911 it is known to copolymerize
polybutadiene in the production o~ sulphur-crosslinkable
ethylene-propylene-diene rubbers. In that application no
mention is made o~ a possible in~luence o~ the 1,2-
polybutadiene on the a~orementioned important properties o~
polyole~ins and, moreover, no distinction is made between the
types o~ polybutadiene; as 1,4- or 1,2-polybutadiene.
In DE-A-1.151.941 and EP-A-0.253.752 EPR and EPDM
copolymer rubbers are disclosed containing 1,2-polybutadiene.
In these applications no mention is made on the a~orementioned
important properties o~ copolymers containing ethylene, 0-50
wt.~ o~ a C4-C20 a-ole~in and 0.005-10 wt.~ 1,2-polybutadiene.
DE-A-2.917.403 discloses copolymers o~ propylene and
polybutadiene containing ~rom 10 to 20 ~ 1,2-
(vinyl)unsaturations and having a molecular weight o~ ~rom 105
to 106 g/mol. This application does not mention a di~erence
between the types o~ polybutadiene, too. The described
copolymers behave as a thermoplastic with elastomeric
properties.
AMENDED SHEET
, CA 022324~6 1998-03-17
- ~ ....
- ;.'' ' ~-'~
Enclosure 1.2 PCT/NL 96/00363; 8076WO
- Amended page 2a -
The polyole~in o~ the invention, in contrast, has
essentially thermoplastic and no distinct elastomeric
properties. The polyole~in o~ the invention contains at least
one ole~inic monomer. As ole~inic monomer ethylene, optionally
in combination with one or more o~ a C4 - C20 a-ole~in is used.
The ole~inic monomer can contain 0-50 wt.~ o~ a C4 - C20 a-ole~in
with respect to the total amount o~ ole~inic monomer present
in the polyole~in o~ the
AMENDED SHEE~
CA 022324~6 1998-03-17
W O 97/12920 PCTANL96/00363
-- 3 --
invention.
Pre~erably the a-ole~in combined with ethylene
is a C4 -ClO ~-ole~in. Examples o~ such
a-ole~ins are butene, hexene and octene.
It is known that in particular copolymers o~ ethylene with
one or more a-ole~ins in which dienes are copolymerized as
third monomer exhibit elastomeric properties. Since it
possesses thermoplastic properties, the polyole~in o~ the
invention does not contain any substantial amounts o~
diene-derived units other than those originating ~rom the
1,2-polybutadiene. It is pre~erred ~or at most 1 wt.~
re~erred to the total polymer o~ these other diene-derived
units to be present but most pre~erably they are
completely absent.
15The polyole~in o~ the invention does not contain
substantial amounts o~ monomers other than the ole~inic
monomer and the 1,2-polybutadiene as described be~ore.
The molecular weights, Mw and Mn o~ the
polyole~in are determined by means o~ Size-Exclusion
Chromatography in combination with a viscosity detector,
with the polyethylene calibration samples being used as a
re~erence.
For the purposes o~ the invention, 1,2-
polybutadiene is understood to be a polymer o~ butadiene
in which the number o~ t-CH2-CH-] units is
XC=CH2
greater than the number o~ other butadiene-derived units
such as t-CH2-CH=CH-CH2-] units and units in which there
are no longer any unsaturations.
The length o~ the incorporated polybutadiene
chains, expressed as the number o~ polymerized butadiene
units, should be at least 4. Pre~erably, this length is at
least 10, more pre~erably at least 25.
The number o~ 1,2-vinyl unsaturations per chain is at
~ CA 022324~6 1998-03-17 ~
A ~ 1- rl ~D ~D
- 4 - ~:
. ' ~ : .
least 3, pre~erably at least 6 and more pre~erably at
least 13. I~ the requirements relating to the chain length
and the number o~ vinyl unsaturations remain satis~ied, it
is within the scope of the invention also permissible ~or
the 1,2-polybutadiene to be partially saturated.
Saturation may be e~ected by, ~or instance, hydrogenation
or copolymerization o~ butadiene with ~-ole~ins. The chain
length o~ the polybutadiene pre~erably is not more than
5000~ Greater chain lengths result in deterioration o~ the
normal properties o~ the polyole~in and the polyole~in
begins to exhibit strongly inhomogeneous behaviour.
It has been ~ound that the MFR is relatively
strongly dependent on the amount o~ incorporated 1,2-
polybutadiene in that the MFR increases with increasing
amounts o~ polybutadiene, whereas the Mw/Mn ratio appears
to be relatively less sensitive. However, the ~w/Mn ratio
does tend to increase with increasing 1,2-polybutadiene
content, especially with copolymers incorporating ~
di~erent a-ole~inic monomeric units, so that this content
can be used to control this ratio as well.
- In general, the Mw/Mn ratio o~ the polyole~in o~
the invention is higher than that o~ a ~co)polymer
produced under otherwise equal conditions but not
incorporating any 1,2-polybutadiene. It is pre~erred ~or
this increaso to amount to not more than a ~actor o~ 3.5.
Any higher increases involve the risk o~ gel ~ormation in
the copolymer. On being processed, especially on being
processed into ~ilms, such a copolymer yields products
whose appearance is less attractive. In view o~ the
requirement o~ a limited increase in the Mw/Mn ratio, the
amount o~ 1,2-polybutadiene is pre~erably at most 10 wt.
i~ the chain length o~ the 1,2-polybutadiene is at least
4, more pre~erably this amount is at most 5 wt.~ when the
chain length is 10 or more, most pre~erably this amount is
at most 3 wt.~ when the chain length is 25 or more. The
AMENDED SHEET
. _ _
CA 022324S6 1998-03-17
W O 97/12920 PCTANL96/00363
-- 5 --
e~ect o~ the 1,2-polybutadiene is very readily
appreciable even at an amount o~ 1,2-polybutadiene o~ at
most 5 wt.~ at a chain length o~ 10 or more. Polyole~ins
containing a larger amount o~ 1,2-polybutadiene than 10
may exhibit increased susceptibility to oxidation.
Furthermore, it has been ~ound that the presence
o~ partially saturated 1,2-polybutadiene brings about an
increase in the Mw/Mn ratio in that the Mw/Mn ratio
increases as the number o~ double bonds in the
polybutadiene decreases. In addition, in this case as well
the MFR increases with increasing amounts o~ partially
saturated 1,2-polybutadiene.
~ he polyole~ins o~ the invention possess good
processability and melt strength and are suited to
application in a wider range o~ products, both thin-walled
objects, ~or instance ~ilms, and thick-walled objects.
The invention also relates to a process ~or the
manu~acture o~ a thermoplastic polyole~in by contacting
ethylene and optionally one or more C4 - C20
a-ole~ins with a cyclopentadienyl-containing transition
metal complex as catalyst under conditions whereby the
monomers polymerize in the presence o~ the catalyst.
It is generally known to produce polyole~ins
with the aid o~ catalysts containing non-cyclopentadiene-
derived ligands, such as Phillips and Ziegler catalysts.The molecular weight distribution, Mw/Mn, and the Melt
Flow Ratio o~ polyole~ins so produced appear to be
interdependent. Given a certain value o~ the Mw/Mn ratio,
the MFR is virtually ~ixed so that when a polymer with a
particular desired Mw/Mn ratio is to ~e produced, there is
no more scope ~or selecting a particular MFR.
From WO-A-93/08221 it is known to produce
polymers o~ ethylene and copolymers thereo~ with ~-ole~ins
under the in~luence o~ a cyclopentadienyl-containing
transition metal compound as catalyst. The process
CA 022324~6 1998-03-17
WO 97/12920 PCT~L~6/0036
- 6 - .
disclosed in that application yields polyole~ins with an
Mw/Mn ratio of~ 1. 86--2.32 and with values o~ 5.6--16~or a
quantity equivalent to the MFR. It is not taught how
polyole~ins having other molecular weight distributions
can be produced.
Thus, there is a need ~or a process ~or
producing thermoplastic polyole~ins having other
combinations o~ Mw/Mn ratio and MFR than the known
polyole~ins.
This need is met by the invention in that
polymerization takes place in the presence o~ 1,2-
polybutadiene.
It has been ~ound that the MFR and the Mw/Mn
ratio can be controlled by the amount and type o~ 1,2-
polybutadiene present in the polymerization medium. The
manner in which this amount in~luences the properties
mentioned is indicated in the discussion o~ the
polyole~ins in the ~oregoing.
The amount o~ copolymerized 1,2-polybutadiene is
20 at most 10 wt.~, pre~erably at most 5 wt.95, more
pre~erably at most 3 wt.~ too much 1,2-polybutadiene
is copolymerized, this is at the expense o~ the
thermoplastic properties o~ the polyole~in obtained. It is
surprising that a clearly measurable e~ect on the polymer
structure and end-product properties obtained is observed
even when very small amounts o~ 1,2-polybutadiene are
added as comonomer and/or termonomer. The permissible
amounts depend on the chain length o~ the 1,2-
polybutadiene as indicated in the above description o~ the
polyole~ins o~ the invention.
The amount o~ 1,2-polybu'adiene that must be
present in the reaction mixture in order ~or polyole~in
having the desired amount o~ copolymerized 1,2-
polybutadiene to be obtained depends on, inter alia, the
activity o~ the catalyst used and can easily be determined
CA 022324~6 1998-03-17
WO 97/12920 PCTANL96/00363-- 7 -- .
experimentally. The e~ect o~ ~or instance the 1,2-
polybutadiene content on ~or instance the MFR will be
apparent ~rom the ~oregoing and ~rom the examples. Those
skilled in the art can determine this relationship ~rom a
- 5 ~ew experiments under the reaction conditions chosen and
subsequently determine the right amount and/or the right
molecular weight ~or a copolymer having the desired
properties.
The 1,2-polybutadiene appears to be incorporated
in a highly e~icient manner. This is surprising because
the vinyl-unsaturated side groups may be regarded as y-
substituted ole~ins, which have an alkyl group substituent
on the 3-site. Such substituents are known to strongly
suppress the reactivity o~ an ole~in in catalytic
polyole~in processes due to what is known as steric
hindering around the ole~inic bond. Such a y-substituted
ole~in is there~ore not an obvious choice as comonomer ~or
e~ecting a high degree o~ incorporation o~ the 1,2-
polybutadiene with a high degree o~ conversion in a
catalyzed polyole~in process.
Furthermore, incorporation o~ only a minor amount o~ 1,2-
polybutadiene appears to have a signi~icant e~ect on the
MFR. Minor here means: in an amoun~ at which the
detectable number o~ unsaturations in the polyole~in o~
the invention is in the same range as the number o~
unsaturations o~ an otherwise similar thermoplastic
polyole~in in which no 1,2-polybutadiene is copolymerized.
A ~urther advantage o~ the process o~ the
invention is the ~ollowing. In W0-A-93/08221 the variation
in the MFR is e~ected by suitably choosing the amount o~
catalyst. This entails that the reaction conditions must
be adapted also. The process o~ the invention, in
contrast, can be practised with a constant amount o~
catalyst and otherwise equal conditions because the amount
o~ 1,2-polybutadiene in the reaction mixture is in
CA 022324~6 1998-03-17
W O 97/12920 PCTANL96/00363
- 8 -
principle the determining parameter.
For the de~initions o~ the copolymers to which
the process o~ the invention relates and ~or the
requirements ~or the 1,2-polybutadiene to be
copolymerized, see the ~oregoing.
The polymerization is e~ected by contacting
ethylene and optionally one or more C4-C20 ~-ole~ins with
a cyclopentadienyl-containing transition metal complex as
catalyst.
This metal complex contains a transition metal
pre~erably ~rom group 3 or 4 o~ the Periodic System o~
Elements in the new IUPAC version as shown in the cover o~
Handbook o~ Chemistry and Physics, 70th Edition CRC Press,
1989-1990. If the valency o~ the metal is 3', the complex
can be represented as RlMXlX2 or RlR2MXl. I~ the valency o~
the metal is 4+ the complex can be represented as
RlR2MXlX2 or RlMXlX2X3
In the ~ormulae given, Rl is a substituted or
unsubstituted cyclopentadienyl ligand, ~or instance
indenyl, ~luorenyl, methyl-cyclopentadienyl,
pentamethylcyclopentadienyl or a heteroatom-containing
derivative o~ the cyclopentadienyl ligand. In the group
last mentioned, the heteroatom may be an element ~rom
group 15 or 16 o~ the Periodic System o~ Elements, ~or
instance N, P, As, O or S. The heteroatom may ~orm part o~
the cyclopentadienyl ring or may be located outside
thereo~. R2 may be a Cp derivative as de~ined ~or Rl but
may also be a substituent containing an element ~rom group
15 or 16 o~ the Periodic System, ~or instance N, P, As, 0
or S, which element is linked to the metal via a covalent
or coordinate bond. Rl and R2 may be linked to one another
by an -Si(R)2 group, where R represents an aliphatic or
aromatic group, by an aliphatic or aromatic group or by a
group which contains an element ~rom group 15 or 16 o~ the
Periodic System.
CA 022324~6 1998-03-17
W O 97/12920 PCT~NL96/00363
_ g _ .
I~ R2 is neutral and is not a cyclopentadiene-
derived compound and, also, is linked to Rl in one o~ the
a~orementioned manners, this combination o~ Rl and R2 is
considered a heteroatom-containing derivative o~ the
- 5 cyclopentadienyl ligand as meant in the description o~ Rl.
Xl, x2 and X3 may or may not be the same and are
chosen ~rom the group o~:
- halogens
- aliphatic or aromatic substituents
- substituents which contain an element ~rom group 15 or
16 o~ the Periodic System such as oR3, NR3 and the like,
where R3 may be an aliphatic or aromatic substituent which
may optionally contain silicon.
As catalyst a cyclopentadienyl-containing
transition metal complex with the ~ormula R4MXlX2 is
pre~erably used, where M is a transition metal ~rom Group
4 o~ the Periodic System, not having the highest valency,
pre~erably Ti3+, where Xl and x2 have the same meaning as
in the ~oregoing and where R4 is equal to
[Cp'-Y-Z(R5) n ] -
where Cp'is a cyclopentadienyl derivative substituted with
aliphatic or aromatic groups or with groups containing a
heteroatom, Y is an aliphatic or aromatic group or a group
containing silicon or a heteroatom, Z is an element ~rom
group 15 or 16 o~ the Periodic System, pre~erably N or P,
Rs is an aliphatic, aromatic or silicon-containing group
and n is equal to the valency o~ Z minus 1.
As a rule, the metal complex is employed as
catalyst in conjunction with an activator. As activator
use may be made o~ substances known to be suitable ~or the
purpose, ~or instance methylaluminoxane (MAO) or possibly
(per)~luorinated boron compounds, ~or instance tris-
penta~luorophenylborane and tetrakispenta~luoro-
CA 022324~6 1998-03-17
WO 97/12920 PCTANL96/00363
- 10 -
phenylborate compounds. In addition, organometal compounds
with a metal ~rom group 1, 2, 12 or 13, pre~erably
aluminium-alkyl compounds or magnesium-alkyl compounds,
may be applied in the catalyst system, ~or instance
trimethylaluminium, triethylaluminium,
triisobutylaluminium, trioctylaluminium,
diethylaluminiumethoxide, diethylmagnesium,
dibutylmagnesium, ethyl-butylmagnesium and butyl-
octylmagnesium. The activity o~ the catalyst system can be
increased ~urther by adding these main-group-metal/alkyl
compounds.
The ole~inic monomers are contacted with the
catalyst under conditions at which the monomers polymerize
in the presence o~ the catalyst. The polymerization o~
ole~ins with the aid o~ metal catalysts, ~or instance
classical Ziegler-Natta or Phillips catalysts and the
conditions to be chosen ~orm a technique known per se
which may also be employed ~or the polymerization o~
ole~ins with the aid o~ catalysts as prescribed ~or the
process o~ the invention.
The polymerization reaction may ~or instance be
e~ected in the gas phase, in suspension or in solution,
either (semi)continuously or batchwise. Furthermore, it is
also possible to apply a plurality o~ reactors arranged in
parallel, in series or in a combination thereo~.
Pre~erably, a solution process is used, since this process
is eminently suitable ~or the production o~ very low-
crystalline polymers which at least to some extent are
soluble in hydrocarbons.
As dispersant or solvent ~or the polymerization
reaction any liquid that does not have an adverse e~ect
on the activity o~ the catalyst system may be used.
Saturated, linear or branched aliphatic hydrocarbons, ~or
instance butanes, pentanes, heptanes, pentamethylheptane
or petroleum ~ractions, ~or instance light or regular
CA 022324~6 1998-03-17
W O 97/12920 PCTANL96/00363
- 11 -
gasoline, naphtha, kerosene or gas oil or mixtures o~ the
a~orementioned substances may be used there~or.
Aromatic hydrocarbons, ~or instance benzene and toluene,
are suitable but are not pre~erred ~or reasons o~ cost and
5 sa~ety. For plant-scale polymerization, the aliphatic
hydrocarbons or mixtures thereo~ supplied by the
petrochemical industry are pre~erably used as dispersant
or solvent a~ter drying and puri~ication.
The polymer obtained by the process o~ the
10 invention can be worked up by methods known per se. In
general, the catalyst is deactivated in a manner known per
se at some point in this working-up phase o~ the polymer.
The polymerization may be e~ected at
atmospheric pressure but also at increased pressure. I~
15 the polymerization is e~ected at increased pressure, the
polymer yield per unit time can be increased still
~urther. It is pre~erred ~or the polymerization to take
place at pressures between 0.1 and 60 MPa, particularly
between 1 and 30 MPa. Higher pressures o~ 100 MPa and
20 above may be used when the polymerization takes place in
so-called autoclaves.
The molecular weight o~ the polymer may be
controlled in the usual manner, ~or instance by adding
hydrogen or other chain terminating agents or by adjusting
25 the polymerization conditions.
The 1,2-polybutadiene is pre~erably added as a
solution in a suitable dispersant that has no adverse
e~ect on the polymerization process. In a continuous
process, the 1,2-polybutadiene is pre~erably added to the
30 polymerization reactor on a continuous basis. In a system
employing a plurality o~ reactors it also possible to add
- the 1,2-polybutadiene to only some o~ the reactors
employed. In batch polymerization, the 1,2-polybutadiene
J may be added prior to or during polymerization. The
35 amounts to be used and the molecular weights o~ the 1,2-
CA 022324~6 1998-03-17
W O 97/1~920 PCT~NL96/00363 - 12 -
polybutadiene are described in the ~oregoing.
The invention will be illustrated by the
~ollowing examples without being limited thereto.
The density D23 was determined in accordance
with ASTM Standard D 792-66. The melt index MI was
determined in accordance with ASTM Standard D1238 using a
weight o~ 2.16 kg. The Melt Flow Ratio, MFR, was
determined as the quotient o~ the melt indices determined
to ASTM D1238 using weights o~ 21.6 and 2.16 kg,
respectively. The Mw/Mn ratio was determined with the aid
o~ a Waters M150C Gel Permeation Chromatograph with DRI-
detector as Size Exclusion Chromatograph in combination
with a Viscotek type 502 viscometer as viscosity detector
and using polyethylene calibration samples as re~erence.
ExamPles I-IV
A number o~ polyole~ins o~ the invention were produced as
~ollows.
An autoclave with a capacity o~ 2 litres was
~illed with special boiling point spirit (boiling range
~rom 65 to 70~C) and kept at a temperature o~ 160~C. A
mixture o~ special boiling point spirit (5.5 kg/h) and
ethylene (1.2 kg/h) was continuously added to the
autoclave. Also, in some cases, hydrogen was added in
order to obtain the desired molar mass. The supply to the
autoclave was adjusted so that the autoclave remained
completely ~illed with the reaction medium. A solution o~
a catalyst, a suspension o~ an activator and a solution o~
triethylaluminium was also continuously added to the
autoclave. The ethylene conversion was controlled by means
o~ the amounts o~ catalyst and activator and amounted to
approximately 95~ in each experiment.
Ethylene-dimethylamino-tetramethyl-
cyclopentadienyl-titanium-dimethyl,
Cp (CH2CH2)N(CH3)2Ti(CH3)2, was added as catalyst ~or the
CA 022324~6 1998-03-17
W O 97/12920 PCT~NL96/00363
- 13 -
preparation o~ a copolymer o~ ethylene and 1,2-
polybutadiene. A concentration o~ the catalyst o~ approx.
20 ~mol per litre was needed ~or attaining 95% ethylene
conversion.
Dimethylaniliniumtetrakispenta~luorophenylborate was
applied as activator. A concentration o~ the activator o~
approx. 40 ~mol per litre was needed ~or attaining 95%
ethylene conversion. The concentration o~
triethylaluminium applied in the autoclave amounted to
approx. 40 ~mol per litre. In a seperate vessel a mixture
o~ 1,2-polybutadiene (1,2-polybutadiene) with a Mn o~
approx. 3000 g/mol, containing approx. 50 vinyl groups per
molecule chain ~grade B-- 3000 ~rom Messrs NISSOH IWAI) and
special boiling point spirit was prepared. A certain
amount o~ 1,2-polybutadiene solution was continuously
pumped ~rom this vessel to the autoclave. The desired rate
at which 1,2-polybutadiene was added was adjusted by
suitably choosing the concentration o~ 1,2-polybutadiene
in the solution. Here, 1 g/h o~ 1,2-polybutadiene
corresponded to 0.088 wt.% re~erred to converted ethylene.
The properties o~ the copolymers obtained with various
rates o~ addition o~ 1,2-polybutadiene are shown in Table
1.
CA 022324~6 1998-03-17
W O 97/12920 PCTANL96/00363
- 14 -
TABLE 1
example addition o~ MI MFR Mw/Mn D23
1,2-
polybutadiene
g/h
I 0 6.1 25.8 2.5 958.9
II 0.25 4.7 27.8 2.5 959.6
III 2.5 4.7 30.2 2.6 959.1
IV 5 4.1 33.0 2.8 959.1
These results indicate that the MFR can be controlled by
means o~ the rate at which 1,2-polybutadiene is added.
Exam~les V-IX
Terpolymerizations o~ ethylene, l-octene and 1,2-
polybutadiene:
Analogously to Examples I-IV, polymerizations
were carried out in which 0.2 kg/hour o~ octene-l was
added to the autoclave as extra monomer.
The properties o~ the copolymers obtained with various
rates o~ addition o~ 1,2-polybutadiene are shown in Table
2. The polymers contained 15 wt.~ octene.
CA 022324~6 l998-03-l7
W O 97/12920 PCT~NL9
- 15 -
TABLE 2
example addition o~ MI MFR Mw/Mn DZ3
1,2-
polybutadiene
g/h
S V 0 4.2 29.1 2.5 914.9
VI 1.0 2. 8 33.4 2. 6 915.4
VII 5 2.4 39.8 3.2 91S.6
VIII 15 0.6 56.7 5.0 916.2
IX 25 0.1 79.4 8. 2 917.7
lQ
The process o~ the invention proves suitable ~or producing
terpolymers also. The MFR shows a distinct increase when
as little as 1 g/h o~ 1,2--polybutadiene, corresponding to
0.088 wt.~ re~erred to the converted ethylene, is added.
ExamPles X-XIII
Analogously to the previous examples,
terpolymers o~ ethylene, 1-octene and 1,2-polybutadiene
were produced using two di~erent 1,2-polybutadiene grades
in order to study the e~ect o~ the molar mass o~ the 1,2-
polybutadiene on the MFR in the terpolymerization o~
ethylene, octene and 1,2-polybutadiene. Use was made o~
grade B-3000 and grade B-2000 already mentioned in
Examples V-IX, ~rom the same supplier, with a Mn o~ 2000
g/mol, containing approx. 33 vinyl unsaturations per
molecule chain. The results are shown in Table 3.
CA 022324S6 1998-03-17 ~~
5 ~Dr~
- 16
TABLE 3
example 1,2- MI MFR Mw/Mn D23 1,2-
polybuta- poly-
diene buta-
diene
grade
g/h
X 0 4.2 29.1 2.4 914.9
XI 2.5 4.1 31.1 2.7 917.0 B-2000
XII 5.0 2.2 38.6 3.0 915.6 B-2000
XIII 2.5 2.3 36.5 2.8 917.0 B-3000
VlI 5.0 2.4 39.8 3.2 915.6 B-3000
ExamPles XIV-XVIII
Polymerizations were carried out analogously to
Examples I-IV exce;~t that diphenylmethylene-~luorenyl-
cyclopentadienyl- -dimethyl {[(C6H5)2CJFluCpZrMe2}
was used as catalyst.
As 1,2-polybutadiene a grade supplied by Messrs Aldrich
with a Mn o~ approx. 1300 g/mol, approx. 99~ unsaturated
and with a vinyl:trans unsaturations o~ 40:30 (designated
grade A) and a grade ~rom the same company with a Mn o~
1800 g/mol, approx. 60~ unsaturations and with the
distribution o~ the unsaturations among the various
possibilities given by vinyl:trans:cis = 45:10:5
(designated grade B) were used. The results are shown in
AMEN~ED SHEE'r
CA 02232456 1998-03-17
W O 97/12920 PCT~L96/~0
- 17 -
Table 4.
TABLE 4
Exam--addition MI MFR Mw/Mn D23 grade
ple oi~ 1,2-
polybuta-
diene
~ m/m
XIV 0 12 n.d. 3.5 956.7
XV 0.30 2.5 52 5.6 951.5 B
XVI 0.60 0.5 98 4.6 949.7 B
XVII 0.09 42 n.d. 3.8 955.8 A
XVIII 0.19 9.6 38 3.8 956.7 A
-
n.d. : not determined
