Note: Descriptions are shown in the official language in which they were submitted.
HOECHST AKTIENGESELLSCHAFT HOE 90/F 339 Dr.LO/pe
Description
Bulk polymerization using specific metallocene catalysts
for the preparation of cycloolefin polymers
The invention relates to a process for the preparation of
homopolymers and copolymers of polycyclic olefins in
Which ring opening does not take place.
It is known that polycyclic olefins can be polymerized by
means of various Ziegler catalysts. Depending on the
catalyst, the polymerization proceeds via ring opening
(cf. US 4,178,424) or opening of the double bond (cf.
EP-A 156 464 and EP-A 283 164).
The disadvantage of ring-opening polymerization is that
the polymer obtained contains double bonds which can
result in chain crosslinking and thus considerably limit
the processability of the material by extrusion or
injection molding.
Polymerization of cyclic olefins with opening of the
double bond results in a relatively low polymerization
rate (conversion rate).
A certain increase in the reaction rate has been achieved
by using soluble metallocene compounds such as bis ( cyclo-
pentadienyl)zirconium dichloride (cf. JP 61/221,206).
Catalysts which can be employed for cyclic olefins are
stereorigid, chiral metallocene compounds, such as, for
example, ethylenebis(indenyl)zirconium dichloride (cf.
EP-A 283 164) or dimethylsilylbis(indenyl)zirconium
dichloride (cf. ZA 90/5308),
with the polymerization taking place With
retention of the ring.
2055397
- 2 -
The current state of the art is to carry out the
homopolymerization and copolymerization of cycloolefins
in solution in the presence of soluble metallocene
catalysts, with the solvents employed principally being
hydrocarbons.
Experiments have shown that, under the polymerization
conditions corresponding to the state of the art, in
solution and at relatively low pressures, which are
generally below 10 bar, the space-time yield (reaction
rate) decreases With increasing concentration of the
cycloolefin in the reaction medium, ie. also with in-
creasing incorporation rate of the cycloolefin. Examples
of corresponding cycloolefins are norbornene and tetra-
cyclododecene. The low space-time yield at the same time
as a high cycloolefin incorporation rate makes the
preparation of cycloolefin copolymers having a high
cycloolefin content very complex arid economically un-
favorable.
Due to their high glass transition temperature, cyclo-
olefin copolymers having a high incorporation rate of
cycloolefin have a very high heat distortion temperature.
They are therefore interesting materials which should
advantageously be usable as thermoplastic molding compo-
sitions or in the form of solutions for surface coatings.
However, experiments have shown that such solutions can
only be processed at high temperatures, in particular due
to their tendency to gel.
The object was therefore to find a process for the
preparation of cycloolefin homopolymers and copolymers
which, based on the polymerization via the double bond,
gives, at a high space-time yield, copolymers which have
a high cycloolefin incorporation rate and do not gel in
solution at room temperature.
It has been found that this ob ject can be achieved by
selecting certain reaction conditions and using certain
2Q5539'~
- 3 -
metallocene catalysts. It is important that the polymeri
zation is carried out in the liquid cycloolefin itself or
in extremely concentrated cycloolefin solutions, the
temperature expediently being above room temperature and
the pressure above 1 bar.
The invention thus relates to a process for the
preparation of a cycloolefin polymer or copolymer by
polymerization of from 0.1 to 100% by weight, based on
the total amount of monomers, of at least one monomer of
the formula I, II, III, IV, V or VI
~H ' Rl
HC' -[ CH
( (I).
HC' IH /CH\ RZ
/ CH ~ /. CHZ
HC I CH
C R4 I CH2 (II).
HC ~ I / CH ,~
CH CHZ
/ CH ' / ~ ' R1
HC I CH , CH~
C R4 I R5 C R6 ~ (III).
HC~ ( / CH ~ I ~ CH 'R2
HC/CH.~ H/. CH ~~ CH_CH/Rx
R3~C-R4 ( R5-C"R6 I R~'C'R8 ( (IV).
HC' ~H/CH~'H./~CH' IH/'/~~RZ
205539'7
- 4 -
RS
cx ~H Rl
HC / I \ CH / 'CH
R3 C R4 ~ (V).
HC ~ CH CH
~.. R2
~6
RS
1
HC~ CH '~/~~~~ CH.~~/R
R3 C R4 ~ I R~'C'RB I (VI),
HC' IH/CH' ~ /CH~ ! ~C ~R2
~6
R
in Which R1, RZ, R3, R4, R5, Re, R' and R8 are identical or
different and are a hydrogen atom or a Cl-C8-alkyl radi-
cal, it being'possible for identical radicals in the
different formulae to hare different meanings,
from 0 to 99.9% by weight, based on the total amount of
monomers, of a cycloolefin of the formula v~I
CH ~ CH
(CHZ)n (VII),
in Which n is a number from 2 to 10, and
from 0 to 99.9% by weight, based on the total amount of
monomers, of at least one acyclic 1-olefin of the formula
to vim
Rg R10
'C~C~ (VIII).
R12
Rll
in which R°, R1°, R11 and Rlz are identical or different and
are a hydrogen atom or a Cl-CB-alkyl radical, at
CA 02055397 2002-08-15
29478-1
- 5 -
temperatures of from 20 to 150°C and at a pressure of
from 0.01 to 64 bar, in the presence of a catalyst which
comprises an aluminoxane of the formula IX
R13 R13 R13
~ A1 - O A1 - O Al (IX)
R13~ ~. R13
n
for the linear type and/or of the formula X
R13
I
A1 - (X)
n+2
for the cyclic type, where, in the formulae IX and X, R13 is
a C1-C6-alkyl group, phenyl or benzyl, arid n is an integer.
from 2 to 50, and a met:allacene of the f_ormul_a XI
R16
i R14
R18 M1~ (XI )
~ ~°'' R 15
~' 17
R
in which
M1 is titanium, zirconium, hafnium, vanadium,
niobium or tantalum,
R14 and R15 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C10-alkyl group, a
C1 C10-alkoxy group, a C~-C1p-aryl group, a C'.6-C10-aryloxy
group, a C2-C10-alkenyl group, a C~-C40-aryla.lkyl group, a
C~-C40-alkylaryl group, or a Cg-C40-arylalkenyl group,
R16 and R1~ are a monocyclic or polycyclic
hydrocarbon radical which can form a sandwich structure with
the central atom M1,
20~539'~
- 6 -
R18 is
Rl9 R19 Rl9 R19 R19 19 R19 R19
-M2- . -M2~M2_ , -M2-Cg21_, _C- , _p-M2- , ..~iC- .
R20 R20 R20 R20 R20 ~20 R20 R20
=BR ~=A1R19, -Ge-, -Sn-, -O-, -S-, =SO, =SOz, =NR19,
=CO, =PRl9 or =P ( 0 ) R18 where R18, Rio and RZ' are
identical or different and are a hydrogen atom, a
halogen atom, a C1-C1°-alkyl group, a C1-Clo-fluoro-
alkyl group, a CB-Cl°-fluoroaryl group, a CB-Cl°-aryl
group, a C1-Cl°-alkoxy group, a CZ-C1°-alkenyl group,
a C~-C4o-arylalkyl group, a Ce-C4°-arylalkenyl group
or a C~-C4°-alkylaryl group, or R1s and R2° or R19 and
R21, in each case with the atoms connecting them,
form a ring, and
MZ is silicon, germanium or tin,
which comprises carrying out the polymerization in
the liquid cycloolefin monomer or cycloolefin
monomer mixture or in an at least 95 percent by
volume cycloolefin solution, the substituents R1B and
Rl' in the formula KI being different from one
another.
The polymerization is preferably carried out in the
liquid cycloolefin monomer or cycloolefin monomer mix
ture.
In the process according to the invention, at least one
polycyclic olefin of the formula I, II, III, IV, V or VI,
preferably a cycloolefin of the formula I or ITI, in
which R1, RZ, R3, R~, Rs, Re, R' and R8 are identical or
different and nre a hydrogen atom or a Cl-Ce-alkyl radi-
cal, where identical radicals in the different formulae
may have different meanings, is polymerized.
It is also possible to use a monocyclic olefin of the
formula VII
20~~~9°~
cx = cx
(CH2)n wzI),
in which n is a number from 2 to 10. Another comonomer is
an acyclic 1-olefin of the formula VIII
R9 R10
~C =C / ' (VIII),
R11 ~ R12
in which Rs, Rl°, Rll and R12 are identical or different and
are a hydrogen atom or a C1-Ce-alkyl radical. Ethylene or
propylene is preferred.
In particular, copolymers of polycyclic olefins, prefer-
ably of the formula I or III, with the acyclic olefins
VIII are prepared.
Particularly preferred cycloolefins are norbornene and
tetracyclododecene, it being possible for these to be
substituted by (Cl-CB)-alkyl. They are preferably copoly-
merized with ethylene; ethylene-norbornene copolymers are
particularly important.
The polycyclic olefin (I to VI) is employed in an amount
of from 0.1 to 100% by weight, and the monocyclic olefin
(VII) is employed in an amount of from 0 to 99.9% by
weight, in each case based on the total amount of
monomers.
The concentration of the open-chain olefin arises from
the solubility of the open-chain olefin in the reaction
medium at the given pressure and given temperature.
Polycyclic olefins, monocyclic olefins and open-chain
205~~9'~
- g -
olefins are also taken to mean mixtures of two or more
olefins of the respective type. This means that, besides
polycyclic homopolymers and bicopolymers, it is also
possible to prepare tercopolymers and multicopolymers by
the process according to the invention. Copolymers of the
cycloolefins VII with the acyclic olefins VIII can also
advantageously be obtained by the process described. Of
the cycloolefins VII, cyclopentene, which may be
substituted, is preferred.
The catalyst to be used for the process according to the
invention comprises an aluminoxane and at least one
metallocene (transition-metal component) of the formula
XI
R16
~ R14
~'1~
R M
(XI).
~~~R15
\ X17
In the formula XI, Mi is a metal from the group compris-
ing titanium, zirconium, hafnium, vanadium, niobium and
tantalum, preferably zircanium or hafnium. Zirconium is
particularly preferred.
R1° and Ris are identical or different and are a hydrogen
atom, a C1-Clo-, preferably C1-Ca-alkyl group, a Cl-Clo-,
preferably Ci-C3-alkoxy group, a CB-Clo-, preferably
CB-Ce-aryl group, $ Cs-Clo, preferably Cg-Ce-aryloxy group,
a CZ-Clo-, preferably C2-C4-alkenyl group, a C~-Coo-.
preferably C~-Clo-arylalkyl group, a C~-Coo-, preferably
C~-Cl2-alkylaryl group, a Ce-C4o-, preferably Ce-C12-aryl-
alkenyl group or a halogen atom, preferably chlorine.
R18 and R1' are different and are a monocyclic or poly-
cyclic hydrocarbon radical, which can form a sandwich
structure with the central atom M1. R1° is preferably
fluorenyl and R1' is preferably cyclopentadienyl.
CA 02055397 2002-08-15
29478-1
_ g _
R18 is a single- or multimembered br~_dge which links the
radicals R16 and R17 and is preferably
R19 R19 R19 R19 R19 R19 R19 R19
-M2- ~ ~ 2 ~ 2- ~ 2 21 ~ ~ 2-
-M -M , -M -CR2 - , -C- , -O-M , -C-C- ,
R20 R20 R20 R20 R20 R20 R20 R20
=BR19=AlRl9, -Ge--, -Sn-, -O-, -S-, =SC), =502, =NR19, =CO,
=PR19 or =P(O)R1'~ where R19, R2p and R21 are identical or
different and are a hydrogen atom, a halogen atom, a C1-C10-
alkyl group, a C~-C1p-fluoroalkyl group, a C6-Clp-aryl
group, a Cl-Clp-alkoxy group, a C2-Cep--alkenyl group, a
C7-C4p-arylalkyl group, a Cg-C4p-arylalkenyl group or a
C7-C4p-alkylaryl group, or R19 and R2~~ or R1f and R21, in
each case together with the atoms connecting them, ferm a
ring.
I
R18 is preferably an R19-C-R2p radical and is particularly
preferably CH3-C-CH3 or
I _~ 1 O .
r~2 is silicon, germanium or tin, preferably silicon or
germanium.
The bridged metallocenes can be prepared in accordance
with the known reaction scheme below:
H2R16 + ButylLi -~ HRl6Li
X _ R18 X
H2R17 + ButylLi -~ HRl7Li
HR16 - R18 - R17H + 2-Butyl-Li -
LiRl6 - R18 - Rl7Li + M1C14
R16
// I'C1
18 ~ ~ 1/
R M
(XI)
''~'''~ C 1
R17.
2~~~39'~
- 1U -
or
H2R16 ø ButylLi -~ HRl6Li ,
R19 R20 R17H
C/ a, IiRh R19R20C
R18 b, H2~ ~R16H
2 ButylLi
R17
R19R20C Li2
~R16
M1C14
1
R16
R19 S ~ Cl
,i
' C M1
R20~ ~~ ~Cl
R17
Rl4Li
R16 16
Rlg ~ ~ /R14 R19 ~ ~R14
~C IHl R15L1 'C Ml (XI )
R20~ '; 'wCl ~ R20~ ~ ~ ~R15
R17 R17
The reaction scheme above also applies to the case where
Rse s Rzo and/or Rl" ~ Ris ( c f . Journal of Organometallic
Chem. 288 (1985) 63-67 and EP-A 320 762).
Preferred metallocenes are:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium
dichloride,
isopropylene(9-fluorenyl)cyclopentadienylzirconium
~a~~~97
11 _
dichloride,
methyl(phenyl)methylene(9-fluorenyl)cyclopentadienylzir-
conium dichloride and
diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium
dichloride,
or mixtures thereof.
Particular preference is given to:
diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium
dichloride.
The cocatalyst is an aluminoxane of the formula IX .
R13 R13 R13
\A1- 0 A1 - 0 A1/ ( IX)
R13 / ~R13
n
for the linear type and/or of the formula X
R13
Al - 0 (X)
n+2
for the cyclic type. In these formulae, R13 is a
C1-Ca-alkyl group, preferably methyl, ethyl, isobutyl,
butyl or neopentyl, or phenyl or benzyl. Particular
preference is given to methyl. n is an integer from 2 to
50, preferably from 5 to 40. However, the precise
structure of the aluminoxane is not known.
The aluminoxane can be prepared in vnrious ways (cf.
8. Pasynkiewicz, Polyhedron $ (1990) 429).
In one of the processes, finely powdered copper sulfate
pentahydrate is 8lurried in toluene or a cycloolefin (for
example cyclopentene, norbornene or tetracyclododecene),
and sufficient trialkylaluminum to give about 1 mol of
CA 02055397 2002-08-15
294?8-1
- 12 -
CuSO4.5H2o for every 4 aluminum atoms is added in a glass
flask under an inert gas at about -20°C or just above the
melting point of the cycloolefin. After slow hydrolysis
with elimination of alkane, the reaction mixture is left
at room temperature for from 24 to 48 hours, during which
it may be necessary to cool the mixture so that the
temperature does not exceed 30°C. The aluminoxane,
dissolved in the toluene or cycloolefin, is subsequently
filtered off from the copper sulfate, and the solution is
evaporated in vacuo. It is assumed that the low-molecu-
lar-weight aluminoxanes condense in this preparation
process to form higher oligomers with elimination of
trialkylaluminum.
Aluminoxanes are also obtained when trialkylaluminum,
preferably trimethylaluminum, dissolved in an inert
aliphatic or aromatic solvent, preferably heptane or
toluene, is reacted with aluminum salts, preferably
aluminum sulfate, containing water of crystallization at
a temperature of from -20 to 100°C. The ratio by volume
between the solvent and the alkylaluminum used is from
1:1 to 50:1, preferably 5:1, and the reaction time, which
can be monitored through the elimination of the alkane,
is from 1 to 200 hours, preferably from 10 to 40 hours.
Of the aluminum salts containing water of crystalliza-
tion, those are used, in particular, which have a high
content of water of crystallization. Particular
preference is given to aluminum sulfate hydrate, in
particular the compounds A12(S04)3.1E~H20 and
A12(SO4)3.18H2o, having the particularly high water of
crystallization content ref.. 16 and 18 mol respectively of
H20/mol of Al2(S04)3.
A further variant of the preparation of aluminoxanes is
to dissolve trialkylaluminum, preferably trimethyl-
aluminum, in the liquid monomer in heptane or toluene in
the polymerization reactor, and then to react the alumi-
num compound with water.
205539'
- 13 -
It is also possible for the aluminoxane to be adsorbed
onto a support and then employed as a suspension in
supported form. Several support processes are known. For
example, slightly moist silica gel can act as a support.
In addition to the above-outlined processes for the
preparation of aluminoxanes, there are others which can
be used. Irrespective of the type of preparation, a
varying content of unreacted trialkylaluminum, which is
in free form or as an adduct, is connaon to all the
aluminoxane solutions. This content has an as yet not
precisely explained effect on the catalytic activity,
which varies depending on the metallocene compound
employed.
If preactivation of the transition-metal compound is
necessary, it is carried out in solution. In this case,
the metallocene is preferably dissolved in a solution of
the aluminoxane in a hydrocarbon. Suitable hydrocarbons
are aliphatic yr aromatic hydrocarbons and cycloolefins,
such as, for example, cyclopentene, norbornene or tetra
cyclododecene.
Toluene is preferred.
The preactivation can also be carried out in suspensions
of supported aluminoxane.
The concentration of the aluminoxane in the solution is
in the range from about 1% by weight up to the saturation
limit, preferably from 5 to 30% by weight, in each case
based on the total solution. The metallocene can be
employed in the same concentration, but is preferably
employed in an amount of from 10-"-1 mol per mole of
aluminoxane. The preactivation time is from 0 to 60
minutes. The preactivation temperature is from 0 to 70°C.
If a small amount of solvent is added to the reaction
mixture, the solvent is a customary inert solvent, such
205~39'~
- 14 -
as, for example, an aliphatic or cycloaliphatic hydrocar-
bon, a petroleum ether or hydrogenated diesel oil
fraction, or toluene.
Polymerization by the process according to the invention
offers the advantage of achieving a high space-time yield
(reaction rate) and a high cycloolefin incorporation
rate . It has been found that increasing the concentration
of the open-chain olefin, for example by increasing the
partial pressure of this open-chain olefin, allows the
reaction rate to be significantly increased. If pure
open-chain olefin, for example ethylene, is injected,
pressures of between 0.01 and 64 bar, preferably from 2
to 40 bar and particularly preferably from 4 to 20 bar,
are employed. If an inert gas, for example nitrogen or
argon, is also injected in addition to the open-chain
olefin, the total pressure in the reaction vessel is from
2 to 64 bar, preferably from 5 to 64 bar and particularly
preferably from 6 to 40 bar. The fact that the cyclo-
olefinic component is in undiluted form means that a high
cycloolefin incorporation rate is achieved even at high
pressures. In addition, the reaction rate can also be
increased by increasing the temperature, the upper limit
to the temperature range being set by the thermal stabil-
ity of the catalyst and the lower limit by the melting
point of the cycloolefin at the correspanding pressure.
However, increasing temperature is accompanied by a
simultaneous drop in the solubility of the gaseous olefin
in the reaction medium and results in an increase in the
incorporation rate of the cycloolefin in the copolymer.
In order to obtain constant incorporation rates with
incrensing temperature, the pressure of the open-chain
and gaseous olefin must be increased correspondingly.
Continuous and multistep polymerization processes are
particularly advantageous since they enable efficient use
of the cycloolefin. In continuous processes, the poly-
cyclic olefin, which can arise as a residual monomer
together with the polymer, can also be recovered and
CA 02055397 2002-08-15
29478-1
- 15 -
recycled into the reaction mixture.
Here, the process according to the invention offers the
advantage over polymerization in solution that, due to
the absence of a solvent or an extremely low solvent
concentration, the technical complexity on recovery of
the cycloolefins from the reaction mixture or from a
precipitation bath is much lower.
The metallocene compound i.a used in a con~~~at.rat a c~r-_
based on the transition metal, of from l0-3 to l0-7,
preferably from 10-4 to 10-6, mol of transition metal per
dmWof reactor volume. The al~uminox~ne is used in a con-
centration of from 10-4 to LOwl, preferably from 10-4 to
2.10-2 mol per dm3 of reactor volume, based on the
aluminum content. 1n t~rinciple, hawever, higher con-
centrations are also possible. In order to combine the
polymerization properties of different metallocenes, it
is possible to employ mixtures of a plurality of
metallocenes.
When preparing copolymers, the molar ratios between the
polycyclic olefin and the open-chain olefin (preferably)
employed can be varied within a broad range. Molar ratios
of from 3:1 to 100:1 of cycloolefin to open-chain olefin
are preferably employed. The choice of polymerization
temperature, the concentration of the catalyst component
and the molar ratio employed or the pressure of the
gaseous, open-chain olefin allow the incorporation rate
of comonomer to be controlled virtually as desired.
Preferred incorporation rates are between 20 and 75 mol-~
of the cyclic component and particularly preferred incor-
poration rates are between 35 and 65 mol-~k of the cyclic
component.
The mean molecular weight of the copolymer formed can be
controlled in a known manner by metering in hydrogen,
varying the catalyst concentration or. varying the temper
ature.
2~~5~~'~
- 16 -
The polydispersity 1~,/Mn of the copolymers is extremely
narrow, with values between 2.0 and 3.5. This results in
a property profile of the polymers which makes them
particularly suitable for injection molding.
Surprisingly, it has been found that the bulk process
according to the invention, for the same incorporation
rates and comparable reaction rates, results in higher
molecular weights than does conventional solution poly-
merization.
If the possibilities of varying the molecular weight are
taken into account, the process according to the inven-
tion significantly broadens the accessible molecular
weight range fox the cycloolefin copolymers.
The preferred catalysts according to the invention
result, both in "solution polymerization" and in bulk
polymerization, in significantly higher molecular weights
than do other metallocene catalysts known hitherto.
The process described allows amorphous copolymers to be
pxepared. The copolymers are transparent and hard. They
are soluble, for examplQ, in decahydronaphthalene at
135°C and in toluene at room temperature. The polymers
according to the invention can be processed as ther
moplastics. Both on extrusion and on injection molding,
no significant degradation or decrease in viscosity was
found.
Surprisingly, it has been found that the cycloolefin
copolymers prepared using the process according to the
invention - and the preferred metallocenes according to
the invention - do not gel in solution at room tempera-
ture. They are therefore particularly suitable for
coatings, for the production of cast films and for other
applications in which cycloolefin solutions must be
stored and transported. The flowability of the corres-
ponding solutions also has a positive effect on the
~fl~~~~'~
- 17 -
work-up of the polymer solutions after the polymeriza
tion. For example, the solution can be filtered more
easily; concentration in a thin-film evaporator can be
carried out with lower thermal and mechanical stress of
the polymer solution.
Furthermore, it has been determined from Nl~t spectra that
these cycloolefin copolymers also differ significantly in
their microstructure from those which gel in solution.
This difference could be explained by the fact that the
catalysts according to the invention polymerize strictly
syndiospecifically due to the different R18 and R1' sub-
stituents. according to the current state of knowledge,
it must be assumed that the cycloolefin copolymers
according to the invention contain disyndiotactic cyclo-
olefin sequences which enable structures to be differen-
tiated by NMR.
The materials prepared according to the invention are
particularly suitable for the production of extruded
parts, such as films, tubes, pipes, rods and fibers, and
for the production of injection moldings of any desired
shape and size. An important property of the materials
according to the invention is their transparency. The
optical applications, in particular, of the extruded or
injection-molded parts of these materials thus have
considerable importance. The refractive index, determined
using an Abbe refractometer and mixed light, of the "
reaction products described in the examples below is in
the range from 1.520 to 1.555. Since the refractive index
is very close to that of crown glass (n ~ 1.51), the
products according to the invention can be used in a
variety of ways as a glass substitute, such as, for
example, for lenses, prisms, baseplates and films for
optical data media, for video disks, for compact disks,
as cover and focusing screens for solar cells, as cover
and diffusion screens for high-performance ogtics, and as
optical waveguides in the form of fibers or films.
~0~53~7
- 18 -
The polymers according to the invention can also be
employed for the preparation of polymer alloys. The
alloys can be prepared in the melt or in solution. The
alloys each have a favorable property combination of the
components for certain applications. The following
polymers can be employed for alloys containing the
polymers according to the invention:
polyethylene, polypropylene, (ethylene-propylene) copoly-
mers, polybutylene, poly(4-methyl-1-pentene), polyiso-
prone, polyisobutylene, natural rubber, poly(methyl
methacrylate), further polymethacrylates, polyacrylates,
(acrylate-methacrylate) copolymers, polystyrene,
(styrene-acrylonitrile) copolymers, bisphenol A poly-
carbonate, further polycarbonates, aromatic polyester
carbonates, polyethylene terephthalate, polybutylene
terephthalate, amorphous polyarylates, nylon 6, nylon 66,
further polyamides, polyaramids, polyether ketones,
polyoxymethylene, ,polyoxyethylene, polyurethanes, poly-
sulfones, polyether sulfones and polyvinylidene fluoride.
The glass transition temperatures (Tg) given in the
examples below were determined by DSC (Differential
Scanning Calorimetry) at a heating rate of 20'C/min. The
viacosities given were determined in accordance with
DIN 53 728.
Example 1
A clean and dry 1.5 dm3 polymerization reactor equipped
with stirrer was flushed with nitrogen and then with
ethylene and charged with 560 g of norbornene melt at
70'C. The reactor was then kept at a temperature of 70°C
with stirring, and 6 bar of ethylene (overpreasure) were
injected.
5 cma of a toluene solution of methylaluminoxane (MAO
solution) (10.1% by weight of methylaluminoxane having a
molecular weight of 1300 g/mol, determined
205397
- 19 -
cryoscopically) were then metered into the reactor, and
the mixture was stirred at 70°C for 15 minutes, with the
ethylene pressure being kept at 6 bar by re-metering. In
parallel, 10.2 mg of diphenylmethylene(9-fluorenyl)-
cyclopentadienylzirconium dichloride were dissolved in
5 cm3 of a toluene solution of methylaluminoxane
(concentration and quality see above), and the solution
was preactivated by standing for 15 minutes. The solution
of the complex was then metered into the reactor (in
order to reduce the molecular weight, hydrogen can be
introduced into the reactor via a lock immediately after
the metering-in of the catalyst). The mixture is then
polymerized at 70°C for 0.5 hour with stirring (750 rpm),
during which the ethylene pressure was kept at 6 bar by
re-metering. The reactor contents were then discharged
rapidly into a stirred vessel containing 100 cm3 of
isopropanol. The mixture was introduced dropwise into
2 dm3 of acetone, the mixture was stirred for 10 minutes,
and the suspended polymeric solid was then filtered off.
The polymer filtered off was then introduced into 2 dm3
of a mixture of two parts of 3 normal hydrochloric acid
and one part of ethanol, and this suspension was stirred
for 2 hours. The polymer was then filtered off again,
washed with water until neutral and dried for 15 hours at
80'C and 0.2 bar. 40.4 g of product were obtained. A
viscosity of 112 cma/g and a glass transition temperature
(Tg) of 183'C were measured on the product.
Examples 2 and 3
The polymerizations were carried out analogously to
Example 1, with some conditions, summarized in Table 1,
being changed.
205530'
- 20 -
Table 1
Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg
ample olefin locene of lane (h) (g) (cm3/g) (°C)
(g) metal- pres-
s locene sure
(mg) (bar)
2 Norbor- B 0.5 10 0.5 37 210 161.5
nene
3 DMON 400 A 10.0 6 0.3 31 135 206.9
A = Diphenylmethylene(9-fluorenyl)cyclopentadienyl-
zirconium dichloride
B = Isoprapylene(9-fluorenyl)cyclopentadienylzirconium
dichloride
DMON = Tetracyclododecene
Example 4
A clean and dry 75 dm~ polymerization reactor equipped
with stirrer was flushed with nitrogen and than with
ethylene and charged with 22,000 g of norbornene melt
(Nb). The reactor was then heated to a temperature of
70°C with stirring, and 15 bar of ethylene Were injected.
580 cm3 of a toluene solution of methylaluminoxane (10.1
by weight of methylaluminoxane having a molecular weight
of 1300 g/mol, determined cryoscopically) were then
metered into the reactor, and the mixture was stirred at
70°C for 15 minutes, during wYtich the ethylene pressure
Was kept at 15 bar by re-metering. In parallel, 500 mg of
metallocene A were dissolved in 500 cm3 of a toluene
solution of methylaluminoxane (concentration and guality
see above), and the solution was preactivated by standing
for 15 minutes. The solution of the complex (catalyst
solution) was then metered into the reactor (in order to
reduce the molecular weight, hydrogen can be introduced
into the reactor via a lock immediately after the
_ 21 _ 205539"
metering-in of the catalyst). The mixture was then
polymerized at 70°C for 1.3 hours with stirring (750
rpm), during which the ethylene pressure was kept at
15 bar by re-metering. The reactor contents were then
discharged rapidly into a stirred vessel containing
200 cm3 of isopropanol (as stopper). The mixture was
precipitated in acetone, the precipitate was stirred for
minutes, and the suspended polymeric solid was then
filtered off.
10 The polymer filtered off was then treated with a mixture
of two parts of 3 normal hydrochloric acid and one part
of ethanol, and the mixture was stirred for 2 hours. The
polymer was then filtered off again, washed with water
until neutral and dried for 15 hours at 80°C and 0.2 bar.
5500 g of product were obtained. A viscosity of 163 cm3/g
and a glass transition temperature (Tg) of 144°C were
measured on the product.
_ ~~5j~9'~
p
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- 23 -
205539'7
Comparative Example 13 (solution polymerization)
A clean and dry 1.5 dm3 polymerization reactor equipped
with stirrer was flushed with nitrogen and then with
ethylene and charged with a solution of 411 g of norbor-
none (Nb) and 86 cm3 of toluene. The reactor was then
heated to a temperature of 70°C with stirring and 8 bar
of ethylene were injected.
20 cm3 of a toluene solution of methylaluminoxane (10.1%
by Weight of methylaluminoxane having a molecular Weight
of 1300 g/mol, determined cryoscopically) were then
metered into the reactor, and the mixture was stirred at
70°C for 15 minutes, during which the ethylene pressure
was kept at 8 bar by re-metering. In parallel, 71.8 mg of
dicyclopentadienylzirconium dichloride were dissolved in
10 cma of a toluene solution of methylaluminoxane
(concentration'and quality see above), and the solution
was preactivated by standing for 15 minutes. The Solution
of the complex was then metered into the reactor. The
mixture was then polymerized at 70°C for 2 hours with
stirring ( 750 rpm) , during which the ethylene pressure
was kept at 8 bar by re-metering. The reactor contents
were then discharged rapidly into a stirred vessel
containing 100 cma of iaopropanol. The mixture was intro-
duced dropwise into 2 dm~ of acetone, the mixture was
stirred for 10 minutes, and the suspended polymeric Solid
was then filtered off.
The polymer filtered off was then introduced into 2 dm3
of a mixture of two parts of 3 normal hydrochloric acid
and one part of ethanol, and this suspension was Stirred
for 2 hours. The polymer was then filtered off again,
washed with water until neutral and dried for 15 hours at
80°C and 0.2 bar. 73.5 g of product were obtained. A
viscosity of 17 cma/g and a glass transition temperature
(Tg) of 168.5°C were measured on the product.
- - ~~~~~~~
24
O M M
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U tT N
Cr ~
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to 1 .L1
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r1 1
b ~r~i ~ 4i
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v 3 3 x o ~ >r >,
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o A a
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20~~3~~
- 25 -
Example 17
20% strength by weight toluene solutions of each of the
polymers of Examples 4 and 6 to 9 were prepared in 250 ml
flasks at 70°C. The solutions were clear and free-flow-
ing. The flowability of the solutions was determined by
tilting the flasks. After the solutions had been cooled
to room temperature, the flowability was determined as a
function of time. All the solutions investigated were
still free-flowing after 50 days.
Comparative Example 18
Solutions of various polymers prepared in accordance with
Comparative Examples 5 and 13 to 16 were prepared and
investigated analogously to Example 17. All the solutions
were no longer free-flowing after only 8 hours at room
temperature. All the solutions had gelled, ie. they
remained shape-stable in the tilt experiment.
Example 19
GPC (Gel Permeation Chromatography) measurements were
carried out on various samples. A Millipore Waters Chrom.
type 150-C ALC/GPC chromatograph and a column set
comprising 4 Shodex AT-80 M/S columns were used. The
solvent was o-dichlorobenzen~.
Other measurement parameters werea
Temperature: 135°C
Z5 Flow rate: 0.5 ml/min
Amount of sample: 0.4 ml of sample solution
Concentration of the sample solutions 0.1 g/dl
Calibration: by polyethylene standard
The GPC measurement results are as follows:
- 26 - ~0~~~~~
Sample Weight average 1~, No . average M",/M"
g/mol M"
g/mol
According to 75,600 37,200 2
Comparative
Example 5
According to 391,000 163,000 2.4
Example 7
Example 20
la-C-NMR spectra were recorded for samples from Examples
4 to 7. The samples were dissolved in a mixture of
hexachlorobutadiene and tetrachloroethane-d2 and measured
using a 400 l~iz NMR instrument. The spectra are repro-
duced comparatively in Figure 1. Surprisingly, it can be
seen that the structure of the polymers of Examples 4, 6
and 7 differs~significantly from that of Comparative
Example 5.
In the case of the metallocene C ( rac-dimethylsilylbis ( 1
indenyl)zirconium dichloride) used in Comparative Example
5, the substituents R1° and Rl' are identical.
Examples 21 - 23
The polymerizations were carried out analogously to
Example 1, with some conditions, summarized in Table 4,
being changed.
205397
- 27 _
Table 4
Ex- Cyclo- Metal- Amount Ethy- Time Yield Visc. Tg
ample olefin locene of lene (h) (g) (cm3/g) (°C)
(g) metal- pres-
s locene sure
(mg) (bar)
21 Norbor- E 1 6 1 36 119 178
none
22 Norbor- F 20 6 3 33 125 183
nene
23 Norbor- G 1 1.5 1 22 40 239
nene
E = methyl(phenyl)methylene(9-fluorenyl)cyclopentadienyl
zirconium dichloride
F ~ diphenylmethylene(9-fluorenyl)cyclopentadienylhafnium
dichloride
G ' ieopropylene(1-indenyl)cyclopentadienylzirconium dichloride
Example 24 (polynorbornene)
800 g of norbornene were liquefied with 25 cm3of a 10.1%
strength by weight toluene solution of methylaluminoxane
with warming in a 1.5 dm3 polymerization reactor (see
Example 1).
In parallel, 250 mg of diphenylmethylene(9-fluorenyl)
cyclopentadienylzirconium dichloride were dissolved in
25 cm3 of a 10.1% strength toluene solution of methylalum
inoxane, and the Solution was added to the above melt.
The mixture waS polymerized for 160 hours at 35°C under
argon.
The solution was worked up analogously to Example 1.
After drying, 41 g of a colorless powder were obtained.
A viscosity of 44 cm3/g was measured on the product.
Neither a glass state nor a melting point were detectable
_ 28 _ 20~539'~
up to 380°C using DSC. Softening was observable at about
400°C under a heating-stage microscope.
13C_NI~t spectrum (analogously to Example 20) showed very
broad signals with peak maxima at 31, 40 and 50 ppm.
According to NMR and infra-red spectra, the product
contains no double bonds.
Example 25
10-20% strength toluene solutions of the polymer from
Example 24 Were prepared, and the solution was coated
onto glass plates using a doctor blade. After drying in
vacuo (0.2 bar) at 80°C, transparent, colorless films
having thicknesses between 1 and 100 ~m wexe obtained.
