Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Le A 33 769- Foreign Countries SCJ/klu/vosNT
-1-
A process for copolvmerizing polar and non-polar monomers
The invention provides a process for copolymerising polar and non-polar
monomers,
a catalyst system suitable for this containing one or more transition metal
compounds
from groups 5-10 of the Periodic System, one or more radical-producers and
option-
ally one or more co-catalysts, the polymers obtainable therefrom and use of
the
polymers which can be prepared by the process to produce molded articles of
all
types.
The copolymerisation of polar and non-polar monomers by radical polymerisation
under high pressure is a known process. By way of example, the preparation of
eth-
ylene/acrylate copolymers may be mentioned (M. Buback et al., Macromol. Chem.
Phys. 1997, 198, 3627) which proceeds at pressures between 1500 and 2500 bar
be-
tween 130 and 225°C. Furthermore, ethylene/vinyl acetate copolymers are
typically
prepared at 2380 bar and 280°C. This high pressure of generally 500 to
3000 bar in-
wolves not only technical problems but also economic problems. The manufacture
of
ethylene/vinyl acetate/C0 terpolymers also proceeds in a similar manner.
Further-
more, the following may be mentioned here as examples: US 3 264 275, US 3 509
115, US 3 948 850, US 4 217 431, US 4 260 722 and US 4 267 090. Solution
polymerizations of ethylene and vinyl acetate are described, for example, in
EP-A-
374 666, EP-A-341 499 and EP-A-307 755. Further references may be found in M.
Busch et al., Macromol. Theory Simul. 1998, 7, 435.
According to the prior art, therefore, only acrylates or their salts, vinyl
esters and
carbon monoxide are suitable for use as monomers for the manufacture of
ethylene
copolymers. These are used in high pressure processes or else emulsion
polyrneri-
sations with radical initiation.
Ethylene/acrylonitrile copolymers have hitherto only been accessible by
subsequent
hydrogenation of butadiene/acrylonitrile copolymers as described, for example,
in
DE-A-33 29 974.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-2-
The alternating radical copolymerization of acrylic derivatives and ethene at
low
pressure is known and is described, for example, in DE-A-19 49 370 and in DE-A-
44
04 320. The disadvantage of the process described is that copolymerization
takes
place only in the presence of equimolar, with respect to the polar monomers,
amounts
of acids or complexing agents and leads only to alternating products and that
the re-
moval of these complexing agents after completion of polymerization is
achieved
only by costly means.
WO-A-96/23010 discloses that acrylic ester derivatives or methyl vinyl ketone
can
be successfully copolymerized using diazadienepalladium complexes. The disad-
vantages of this process are that polar monomers are incorporated to only a
small
extent, that the molecular weight of the copolymers obtained is comparatively
low
even with low rates of incorporation and that comparatively high amounts of
catalyst
have to be used to prepare the copolymers, which is a problem from an economic
point of view.
EP-A-558 143 describes a catalyst based on nickel which can be used to
copolymer-
ize ethylene and methyl methacrylate. The disadvantage of this process,
however, is
that again only insufficient amounts of the polar comonomer are incorporated.
WO-A-98/27124 describes a process for polymerizing non-polar monomers (eth-
ylene) using bisiminopyridyl cobalt or iron complexes of the general formula
(I) and
co-catalysts, and also the support of this type of catalyst systems in the
liquid phase
or in a fluidised bed process. WO-A-98/30612 describes a process for
polymerizing
non-polar monomers (propylene) using the catalysts disclosed in WO-A-98/27124.
WO-A-99/02472 describes bisiminopyridyl complexes of iron and a process for
the
oligomerisation and polymerization of ethylene.
WO-A-99/12981 describes a catalyst system consisting of bisiminopyridyl com-
plexes of iron, cobalt, ruthenium or manganese for the homopolymerisation and
co-
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-3-
polymerization of ethylene and a-olefins and claims the use of ethene,
propene, bu-
tene, hexene, methyl methacrylate, methyl acrylate, butyl acrylate,
acrylonitrile, vinyl
acetate and styrene. The disadvantage of the process described is that
organoalu-
minium compounds have to be used to activate the bisiminopyridyl complexes and
these, as is understood by any person skilled in the art, can react with the
claimed
polar monomers and thus are then no longer available for activating the
catalyst.
G.J.P. Pritovsek et al., Chem. Commun. 1998, 849 describes bisirninopyridyl
com-
plexes of iron and cobalt of the general formula (I) and also their use as
polymeriza-
tion catalysts for non-polar monomers.
R3 R~
R~ -N
Re ~ ~ ~X
(I)
B.L. Small. M. Brookhart, A.M.A. Bennett, J. Am. Chem. Soc. 1998, 120, 4049
and
B.L. Small, M. Brookhart, J. Am. Chem. Soc. 1998, 120, 7143 also describe bis-
iminopyridyl complexes of iron and cobalt of the general formula (I) and their
use as
polymerization catalysts. Bisiminopyridyl complexes of iron and cobalt of the
gen-
eral formula (I) and their use as polymerization catalysts for propylene are
also de-
scribed in C. Pellecchia, M. Mazzeo, D. Pappalardo, Macromol. Rapid. Commun.,
19, 651-55 (1998) and B.L. Small, M. Brookhart, Macromolecules 1999, 32, 2120-
30
( 1999).
It is a common feature of all the documents that the polymerisations described
there
are purely coordinative polymerisations and copolymerization with polar
molecules
does not take place.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-4-
There is therefore the object of providing a process for the copolymerization
of polar
and non-polar monomers and a catalyst system suitable for this purpose.
Furthermore, there is the object of avoiding the disadvantages of the
copolymeriza-
tion processes described in the prior art.
Thus, the invention provides a process for copolymerizing polar and non-polar
monomers, characterized in that at least one polar and at least one non-polar
mono-
mer are polymerized in the presence of one or more transition metal compounds
from
groups 5-10 of the Periodic System according to the TUPAC 1985, one or more
radi-
cal-producers and optionally one or more co-catalysts.
Polar monomers, in the context of the invention, are understood to be
radically
polymerizable monomers with more or less highly pronounced partial charge
distri-
bution within the molecule. Examples of these are chloroprene, styrene,
acrylonitrile,
vinyl chloride, acrylic acid, acrylates, cyanacrylates, methacrylic acid,
methacrylates,
acrylamide, methacrylonitrile, vinyl acetate, propene oxide, ethene oxide,
vinyl car-
bazole, vinylpyrrolidone, vinyl esters, and compounds built up from these
parent
molecules. Acrylonitrile, acrylates, methacrylates and styrene are preferred.
Non-polar monomers, in the context of the invention, are understood to be
monomers
which are polymerizable by coordinative polymerization, without any particular
charge separation within the molecule. Examples of these are olefins, in
particular
ethylene, propylene, butenes, pentenes, hexenes, heptenes, octenes and their
higher
homologues, diolefins, in particular butadiene, isoprene, pentadienes,
hexadienes,
heptadienes, .octadienes, methyloctadienes, ethylidene norbornene, vinyl
norbornene,
norbornadienes, cyclooctadienes and their higher homologues and trienes.
Obviously the list of suitable polar and non-polar monomers could be extended,
but a
longer list would certainly not contribute further to understanding the
invention.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-S-
Suitable transition metal compounds, in the context of the invention, are
compounds
which correspond to the general formula (II),
MLa~ (II)~
wherein M is a metal from groups 5-10 of the Periodic System according to the
IUPAC 1985, preferably a metal selected from the group comprising vanadium,
chromium, manganese, iron, cobalt, nickel, ruthenium, rhodium and palladium,
wherein L is a 2-, 3- or 4-dentate chelating ligand, preferably a 3-dentate
chelating
ligand,
wherein Q is a mono-anionic or non-ionic ligand,
wherein a and b are each integers with b > 1, preferably b > 2 and a is
calculated
from the (total number of receptor coordination sites on M - b) / the number
of donor
coordination sites on the ligand.
Examples of 2-dentate chelating ligands are diamines such as, for example,
ethylene
diamine, propylene diamine and butylene diamine, diimines, dipyridyls,
dioximes,
dioximates, 1,3-diketones such as, for example, acetylacetonate and hexafluoro-
acetylacetonate, carboxylates, diquinones, semiquinones, bisoxazolines, bisthi-
azolines, 1,10-phenanthroline, 1,8-naphthyridine, pyridyl-2-alkylamines,
pyridyl-2-
dialkylamines, pyridyl-2-arylamines, pyridyl-2-diarylamines, 2-pyridylimines,
pyri-
dine-2-nitriles, dinitriles such as, for example, 1,2-benzodinitrile, 1,8-
naphthodini-
trile, sulfur diimines, dipyrazolyl borates, dipyrazolyl alkanes, dipyrazolyl
ketones,
aliphatic and aromatic diphosphines, phosphorimines or phosphorylides.
Preferred 2-dentate chelating ligands are ethylene diamine, propylene diamine,
bi-
pyridyl, diimines, 2-pyridylamines, 2-pyridylimines, ethylene diphosphine, 1,3-
di-
phosphinopropane and phosphorylide ligands.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-6-
Examples of 3-dentate chelating ligands are terpyridine, triamines, 2,6-
diamino-
pyridyls, 2,6-bisiminopyridyls, 2,6-biscyclopentadienylpyridines, bis-(2,6-
hydra-
zonyl)-pyridines, trispyrazolyl borates, trispyrazolyl alkanes, trispyrazolyl
ketones or
triphosphines.
Preferred 3-dentate chelating ligands are triamines, trispyrazolyl borates,
2,6-diami-
nopyridyls, triphosphines and bisiminopyridyl ligands of the general formula
(III)
R3
(III)
wherein
Rl, R2, R3, R4, R5, R6 and R' are chosen, independently, from hydrogen,
optionally
substituted C1-Clo-alkyl groups, optionally substituted C6-Cla-aryl groups or
are part of a ring system.
Particularly preferably, R' and R2, independently, represent an optionally
substituted
aryl group and
R3, R4, R5, R6 and R' are chosen, independently, from hydrogen, optionally
substi-
tuted C~-Coo-alkyl groups, optionally substituted C6-C~4-aryl groups or are
part of a ring system.
Examples of 4-dentate chelating ligands are tetraamines, tetrapyridines,
tetraphos-
phines, salen, bis-(pyridylimino)-isoindolines and porphyrins.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
_7_
Preferred 4-dentate chelating ligands are trialkyltetraamines,
triaryltetraamines, tetra-
phosphines and salen.
In general, a list of different 2-, 3- or 4-dentate ligands may be found, for
example, in
G. Wilkinson, R.D. Gillard and J.A. McCleverty (eds), Comprehensive
Coordination
Chemistry - The synthesis, reaction, properties & applications of coordination
com-
pounds, Volume 2: Ligands, Pergamon Press, New York, 1 st edition 1987, p. 30-
56.
Examples of mono-ionic and non-ionic ligands Q are halide, hydride, C1-Clo-
alkyl or
-alkenyl, C6-Clo-cycloalkyl, C6-C14-aryl, alkylaryl with a C1-C~o-grouping in
the
alkyl group and a C6-C14-grouping in the alkyl group, -OR8, OR8R9, -
NRl°Rly
-NRIORaRi2, -N(SiRI°RuRl2)z, -N(SiRI°RI1RI2)3~ -PRi°Rll,
PRl°RuRiz, CO, tetra-
hydrofuran, pyridine, acetonitrile, wherein the Q's may be identical or
different,
wherein one or more of the two Q groupings may also be bridged and wherein R8
to
R12 may be chosen from H, Cl-Clo-alkyl, C3-Clo-cycloalkyl, C6-C14-aryl,
alkylaryl or
arylalkyl and may be identical or different.
A halogen is understood, by a person skilled in the art, to be fluorine,
chlorine, bro-
mine or iodine, preferably chlorine and bromine.
C1-Clo-alkyl groups are understood to be all linear or branched alkyl groups
with 1 to
10 carbon atoms which are known to a person skilled in the art, such as
methyl,
ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neo-
pentyl and
hexyl, heptyl, octyl, nonyl and decyl which, for their part, may also be
substituted.
Suitable substituents here are halogen, vitro, hydroxyl or also a C1-CIO-
alkyl, and
C6-C14-cycloalkyl or aryl group, such as benzoyl, trimethylphenyl,
ethylphenyl, chlo-
romethyl, chloroethyl and nitromethyl.
C6-C14-cycloalkyl groups are understood to be all mononuclear or polynuclear
cyclo-
alkyl groups with 6 to 14 carbon atoms which are known to a person skilled in
the
art, such as cyclohexyl, cycloheptyl, cyclooctyl and cyclononyl or also partly
or fully
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
_g_
hydrogenated fluorenyl which, for their part, may also be substituted.
Suitable sub-
stituents here are halogen, vitro, C~-Coo-alkoxy or also C~-Coo-alkyl and
C6-C12-cycloalkyl or aryl groups such as methylcyclohexyl, chlorocyclohexyl
and
nitrocyclohexyl.
C6-C14-aryl groups are understood to be all mononuclear or polynuclear aryl
groups
with 6 to 14 carbon atoms which are known to a person skilled in the art, such
as
phenyl, napthyl, fluorenyl which, for their part, may also be substituted.
Suitable
substituents here are halogen, vitro, C1-Clo-alkoxy or also Cl-Clo-alkyl and
C6-C14-cycloalkyl or -aryl groups such as bromophenyl, chlorophenyl, toluyl
and
nitrophenyl.
Q is preferably chosen from halide, in particular chloride and bromide,
hydride,
methyl, ethyl, butyl, tetrahydrofuran, CO and pyridine.
A particularly preferred transition metal compound is represented by the
general
formula (IV)
R3 R~
-N
~Q
N -~- n
wherein
M is chosen from iron, cobalt, nickel or palladium,
Q is a mono-anionic or non-ionic ligand, in particular chlorine, methyl, ethyl
or
hydride,
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-9-
R1 and R2, independently, represent an optionally substituted aryl group, in
particular
a dialkylphenyl,
R3 and R4 are chosen, independently, from hydrogen, an optionally substituted
C1-
Clo-alkyl group, an optionally substituted C6-Ct4-aryl group or are part of a
ring system,
n is 1,2 or 3, in particular 2.
The transition metal compound is preferably selected so that the transition
metal
compound, optionally in the presence of a co-catalyst, can reversibly form a
complex
with the radically growing polymer chain and non-polar monomers, in particular
ole-
fins, can be inserted into the bond formed between transition metal and
polymer
chain. Without wishing to be firmly committed to this, the applicant's
hypothesis is
that this insertion takes place via the so-called monometallic mechanism
according to
Arlman and Coissee in: Journal of Catalysis 1964, 3, 99 et seq. or the
bimetallic
mechanism according to Patat and Sinn in: Angewandte Chemie 1958, 70, 496.
Suitable radical-producers are all radical-producers known to a person skilled
in the
art which initiate the radical polymerization of polar monomers and
simultaneously
do not react in a detrimental fashion with the transition metal compound.
Depending on the monomer combination used, the most suitable radical-producer
can
be chosen from the many radical-producers available by means of a few
preliminary
trials. To list all of these would not contribute anything further to the
understanding
of the invention. A review of radical-producers which are suitable in
principle can be
found in G. Allen, J.C. Bevington (eds), Comprehensive Polymer Science,
Pergamon
Press, 1989, 123 et seq., to which express reference is made at this point.
Nevertheless, the following examples of suitable radical-producers may be
explicitly
mentioned: peroxides such as potassium or sodium peroxodisulfate, dibenzoyl
per-
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-10-
oxide, dicumyl peroxide, tert.-butylcumyl peroxide, cumyl hydroperoxide, tert.-
butyl
hydroperoxide, di-tert.-butyl peroxide, diisobutyryl peroxide, dilauryl
peroxide, dide-
canoyl peroxide, diisopropyl peroxydicarbonate, dibutyl peroxydicarbonate,
tert.-butyl peroxyisopropylcarbonate, tert.-butyl peroxypivalate, tert.-amyl
peroxy-
pivalate, tert.-butyl peroxyisononate, tert.-butyl peroxydiethylacetate or
tert.-butyl
peroxyacetate and diazo compounds such as 2,2'-azo-bis-(isobutyronitrile),
2,2'-azo-
bis-(2-valeronitrile), 1,1'-azo-bis-(1-cyclohexanenitrile) or 4,4'-azo-bis-(4-
cyanova-
leric acid), or mixtures of these.
The choice of suitable radical-producer depends on the reaction medium and
poly-
merization temperature. To summarize, it may once again be stressed that the
radical-
producer is chosen so that it initiates radical polymerization of the polar
monomer
under the given conditions (temperature, pressure, type of monomer, any
solvent
present, etc.) and at the same time does not react in a detrimental fashion
with the
transition metal compound or the active transition metal species formed
therefrom.
For this reason molecular oxygen, for example, is not generally suitable as a
radical-
producer.
In the case of strongly coordinating ligands Q, such as halogen or hydride or
even
alkylene, it may be necessary to use a co-catalyst in order to replace ligands
Q in the
transition metal compound with so-called non-coordinating or weakly
coordinating
ligands. Express reference is made at this point to W. Beck et al., Chemical
Reviews
1988, 88, 1405 and S. Strauss, Chemical reviews 1993, 93, 927.
In this case, coordination complex compounds may be used as co-catalysts,
these
being chosen from the group comprising strong, neutral Lewis acids, ionic com-
pounds with Lewis acid cations or Broenstedt acid cations and non-coordinating
ani-
ons.
Strong, neutral Lewis acids which can form stable salts of coordination
complexes
with Q are preferably compounds of the general formula V in which
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-11-
MZXIXzX3 (V)
M2 represents an element from group 3 of the periodic table of elements (IUPAC
S 1985), preferably B, A1 or Ga, in particular B,
Xl, X2 and X3 represent H, a C1-Cta-alkyl, C6-C14-cycloalkyl, C6-C14-aryl
group or
an alkylaryl, arylalkyl, halogenoalkyl, halogenoaryl, halogenoalkylaryl or
halogenoarylalkyl group, each containing C1-Clo-alkyl, C6-C14-cycloalkyl and
C6-C,4-aryl groups and/or fluorine, chlorine, bromine or iodine, in particular
halogenoaryl compounds, preferably perfluoro-substituted.
In the context of the invention, however, compounds of the general formula (V)
in
which Xl, X2 and X3 are identical and preferably represent tris-
(pentafluorophenyl)
1 S borane are particularly preferably used. These compounds and processes for
prepar-
ing them are known per se and are described, inter alia, in WO-A-93/03067.
Compounds of the general formula VI are suitable as ionic compounds with Lewis
or
Broenstedt acid cations and non-coordinating anions,
[L]d+[(Mz)'T'+AlA2 ... A"]d' (VI)
wherein
L represents a Lewis acid cation in accordance with the Lewis acid/base
theory,
preferably carbonium, oxonium and/or sulfonium cations and also cationic
transition metal complexes, in particular a triphenylmethyl cation, silver ca-
tion or ferrocenyl cation, or L represents a Broenstedt acid cation in accor-
dance with the Broenstedt acid/base theory, preferably trialkylammonium, di-
alkylarylammonium and/or alkyldiarylammonium, in particular N,N-dimeth-
ylanilinium,
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-12-
M2 represents an element from group 3 of the periodic table of the elements
(IUPAC 1985), in particular B, Al or Ga, preferably B,
A' to A° represent singly negatively charged groups such as hydride, a
C~-C2g-alkyl,
C3-C,a-cycloalkyl, C6-C14-aryl group or an alkylaryl, arylalkyl,
halogenoalkyl, halogenoaryl, halogenoalkylaryl or halogenoarylalkyl group,
each containing a C1-C28-alkyl, C~-C14-cycloalkyl and C6-Ci4-aryl groups, or
a halogen, alkoxide, aryl oxide or organometalloid group, and A1 to A" are
identical or different,
d is an integer from 1 to 6 and d = n-m,
n is an integer from 2 to 8 and
m is an integer from 1 to 6.
Preferred anions [(MZ)~A~Az ... A"]d- in the general formula VI are those in
which
A1 to An are identical, spatially voluminous, aromatic hydrocarbon groups and
M2 is
boron or aluminium, in particular tetraphenyl borate, tetrakis-(3,5-bis-
(trifluo-
romethyl)phenyl) borate and tetrakis-(pentafluorophenyl) borate.
Obviously, mixtures of different compounds of the general formulae (II),
(III), (N),
(V) and (VI) and mixtures of different radical-producers and different co-
catalysts
may also be used.
The radical-producers) are generally used at (total) concentrations in the
range
0.01 mol.% to 5 mol.%, with respect to the total concentration of polar
monomer(s),
preferably in the range 0.01 - 1 mol.%. The most appropriate concentration can
easily
be determined in a few preliminary trials.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-13-
The transition metal compounds) are used in the range 0.005 to 10 mol.%, with
re-
spect to the total concentration of radical-producer(s), preferably in the
range 0.01 to
0.1 mol.%. The most appropriate concentration can easily be determined in a
few
preliminary trials.
The amount of co-catalyst(s) used depends on the number of ligands Q to be re-
moved from the transition metal compound. Theoretically, one to 1.2 co-
catalyst
molecules are used per strongly coordinating ligand Q to be removed. This
means
that, in general, an amount in the range 0.01 to 20 mol.%, with respect to the
total
concentration of radical-producer(s), preferably in the range 0.01 - 0.5
mol.%, is
used.
It may be advantageous to apply the catalyst system according to the invention
to a
support. In this case, bonding should preferably take place via the ligand L
so that the
components in the catalyst system do not react or interact in a detrimental
fashion
with the support.
Particulate organic or inorganic solids, the pore volumes in which are between
0.1
and 15 ml/g, preferably between 0.25 and 5 ml/g, the specific surface areas of
which
are greater than 1, preferably 10 to 1000 m2/g (BET), the particle sizes of
which are
between 10 and 2500 mm, preferably between 50 and 1000 mm, and the surface
areas of which can be modified in an appropriate manner are preferably used as
sup-
port materials.
The specific surface area is determined in a conventional manner using
Brunauer,
Emmet and Teller's method, J. Anorg. Chem. Soc. 1938, 60, 309, the pore volume
is
determined by McDaniels's centrifuge method, J. Colloid Interface Sci. 1980,
78, 31
and the particle size is determined by Cornillaut's method, Appl. Opt. 1972,
11, 265.
The following may be mentioned as suitable inorganic solids without, however,
in-
tending to restrict the present invention: silica gels, precipitated silicas,
clays, alumi-
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
- 14-
nosilicates, talcum, zeolites, carbon blacks, inorganic oxides such as, for
example,
silicon dioxide, aluminium oxide, magnesium oxide, titanium dioxide, inorganic
chlorides such as, for example, magnesium chloride, sodium chloride, lithium
chlo-
ride, calcium chloride, zinc chloride or calcium carbonate. The inorganic
solids men-
tinned which satisfy the specification mentioned above and are therefore
particularly
suitable for use as support materials are described in more detail, for
example, in
Ullmann's Enzyclopaedie der technischen Chemie, vol. 21, p. 439 et seq.
(silica gels),
vol. 23, p. 311 et seq. (clays), vol. 14, p. 633 et seq. (carbon blacks) and
vol. 24, p.
575 et seq. (zeolites).
Powdered polymer materials, preferably in the form of a free-flowing powder,
with
the properties mentioned above, are suitable as organic solids. The following
ex-
amples may be mentioned, without intending to restrict the present invention:
polyolefins such as, for example, polyethene, polypropene, polystyrene,
polystyrene-
co-divinylbenzene, polybutadiene, polyethers such as, for example,
polyethylene
oxide, polyoxytetramethylene or polysulfides such as, for example, poly-p-
phenylene
sulfide. Particularly suitable materials are polypropylene, polystyrene or
polystyrene-
co-divinylbenzene. The organic solids mentioned, which comply with the
specifica-
tion mentioned above and are therefore particularly suitable for use as
support mate-
rials are described in more detail, for example, in Ullmann's Enzyclopaedie
der tech-
nischen Chemie, vol. 19, p. 195 et seq. (polypropylene) and vol. 19, p. 265 et
seq.
(polystyrene).
The supported catalyst system may be prepared over a wide temperature range.
The
process is usually performed at temperatures of -80 to +200°C,
preferably -20 to
150°C, in particular 20 to 100°C.
The invention also provides a composition consisting of one or more transition
met-
als from groups 5-10 of the Periodic System according to IUPAC 1985, one or
more
radical-producers and optionally one or more co-catalysts and its use as a
catalyst
system in a process for co-polymerization of polar and non-polar monomers.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-15-
Polymerization is preferably performed by placing the monomers in contact with
the
composition according to the invention dissolved in suitable solvents, in the
gaseous
or liquid phase, finely distributed or suspended in a liquid diluent.
Other gases or finely distributed liquids may be mixed with the gaseous,
liquid or
sprayed monomers, these being used for either diluting, spraying or
dissipating heat.
Liquids or liquefied gases which are known to a person skilled in the art and
do not
have a detrimental effect on polymerization or the catalyst system, in
particular satu-
rated hydrocarbons such as pentane, hexane, cyclohexane, petrol and petroleum
ether, are suitable as diluents or solvents.
Polymerization may be performed at pressures of 0.01 bar to 1000 bar,
preferably 0.1
to S00 bar, in particular 1 to 100 bar, quite specifically 1 to 10 bar. In
general,
1 S polymerization is performed at temperatures of -20 to 250°C,
preferably 0 to 200°C,
in particular 20 to 160°C. As a trivial point, the temperature has to
be matched to the
radical-producer being used, since the radical-producer also has to decompose
at this
temperature.
Since the transition metal compound is generally sensitive to oxygen and
water, it is
advantageous to exclude oxygen and water.
The sequence of mixing the individual constituents in the composition may be
any
order at all. As a rule, the final composition is placed in contact with the
monomer
mixture and then the temperature is increased to above the decomposition
tempera-
tore of the radical-producer.
The invention also provides use of the polymers obtainable in accordance with
the
invention for preparing molded items of any type, in particular films, sheets,
hoses,
sections, sheathing, extradites and injection molded articles. At the
molecular level,
said polymers are statistical copolymers and not AB-block copolymers. Another
pre-
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-16-
ferred use is use as a starting material for adhesives and additives, in
particular oil
additives. The composition may be varied over a wide range, depending on the
con-
ditions used, the catalytically active composition and the monomer composition
and
concentration. The molar fraction of polar monomers incorporated to non-polar
monomers incorporated is generally in the range 0.05 - 0.95.
Polymers prepared according to the invention contain homopolymers of the
individ-
ual monomers as impurities. For specific applications, it may be advantageous
to
remove these using appropriate methods, such as fractional precipitation or
extraction
processes.
The following examples are intended to explain the present invention in more
detail
without, however, restricting this to the examples.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-17-
Examples
All reactions were performed with the exclusion of air and moisture, if
required, and
using the variable high vacuum technique. The solvents used were dry,
saturated with
purified argon and stored under an argon atmosphere.
2,2'-azo-bis-(isobutyronitrile), AIBN, is commercially available (Merck KgaA,
Ger-
many) and was used without further purification. The potassium perfluorophenyl
borate, K[B(C6F5)4], used was prepared from the corresponding lithium compound
using S. Cohen and A. Massey's method, Adv. Fluor. Chem. 6, 83-285 (1970),
Na[B(C6H5)4] was purchased from Merck KgaA, Germany and used without further
purification.
The polymerization reactions were performed in a 1 1 Buechi glass autoclave at
60°C
and the amounts of ethene were determined using a mass flow-meter. The
polymers
were isolated by precipitating in ethanol, purified by washing with ethanol
and dried
under vacuum.
The concentration of ethene in the polymers was determined using NMR spectros-
copy in d6-dimethylsulfoxide, the glass transition temperature Tg was
determined by
DSC and the weight average of the molecular weight MW and polydispersity Mw/Mn
were determined using GPC against a polystyrene standard in dimethylacetamide.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-18-
Synthesis of the complexes
2,6-dibenzoylpyridine-bis-(2,6-dimethylphenylimino)-cobalt dichloride
(complex A)
Example la:
Synthesis of 2,6-dibenzoylpyridine
In a 500 ml round-bottomed flask with a reflux condenser, 32.4 g (243 mmol) of
an-
hydrous aluminium trichloride are added to 20.0 g (98 mmol) of pyridine-2,6-
dicar-
boxylic acid chloride in 250 ml of dry benzene under an Ar atmosphere. The
mixture
is stirred under reflux for 4 h, then cooled, stirred overnight at room
temperature and
then again stirred under reflux for 6 h. After cooling, the mixture is
carefully poured
into 500 ml of ice water. The organic phase is separated and the aqueous phase
is
washed twice, using 100 ml of diethyl ether each time. The combined organic
phases
1 S are washed twice, using 100 ml of water each time, and then dried over
sodium sul-
fate. The solvents are removed on a rotary evaporator and the product is
recrystal-
lised from diethyl ether. Yield: 16.80 g.
1H NMR (in acetone-d~/TMS): d = 8.32-8.26 (m, 3H), 8.14-8.06 (m, 4H), 7.7-7.4
(m,
6H).
MS: 287, 259, 230, 182, 105, 77, 51
Example 1b
Synthesis of 2,6-dibenzoylpyridine-bis-(2,6-dimethylphenylimino)-nickel di-
bromide
1.20 g (5.S mmol) of anhydrous nickel dibromide are added to a solution of
1.42 g
(5 mmol) of 2,6-dibenzoylpyridine and 1.2 ml (10 mmol) of 2,6-dimethylaniline
in
50 ml of glacial acetic acid. The mixture is stirred under reflux for 6 h. An
orange-
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-19-
brown powder precipitates and this is filtered hot. The residue is washed
twice, using
50 ml of diethyl ether each time, and dried. Yield: 3.35 g
FT-IR (KBr): n(C=N) = 1579 cm 1, 1610 cm''.
Examule lc
Synthesis of 2,6-dibenzoyl-bis-(2,6-dimethylphenylimino)-pyridine
ml of a 10 % strength aqueous NaCN solution are added to a suspension of 0.71
g
10 (1 mmol) of 2,6-dibenzoylpyridine-bis-(2,6-dimethylphenylimino)-nickel
dibromide
in 10 ml of THF and stirred at RT for 30 min. The organic phase is separated
and
dried over sodium sulfate. After removing the solvent, the bis-irninopyridyl
deriva-
tive remains as a pale yellow powder. Yield: 0.40 g.
1H NMR (in CDC13): d = 8.07 (m, 1H), 7.77 (m, 2H), 7.43-7.36 (m, 6H), 6.93-
6.81
(m, l OH), 2.01 (s, 12H); MS: M+ = 494 g/mol.
Example 1d
Synthesis of 2,6-dibenzoylpyridine-bis-(2,6-dimethylphenylimino)-cobalt di-
chloride
0.07 g (0.5 mmol) of anhydrous cobalt(II) chloride are added to a solution of
0.28 g
(0.5 mmol) of 2,6-dibenzoyl-bis-(2,6-dimethylphenylimino)-pyridine in 20 ml of
dry
THF, at room temperature, and the mixture is stirred at room temperature for
48
hours. Then the solution is evaporated down to one half the volume and 100 ml
of
hexane is added thereto. The bisiminopyridylcobalt complex precipitates as a
pale
brown powder and is dried under vacuum after filtration. Yield: 0.15 g.
FT-IR (KBr): n(C=N) 1571 cm'1.
CA 02377249 2001-12-21
_.__ _.______ -_
Le A 33 769- Foreign Countries
-20-
2,6-dibenzoylpyridine-bis-(2,b-diisopropylphenylimino)-cobalt dichloride
(complex B)
Examule 2a
Synthesis of 2,6-dibenzoyl-bis-(2,6-diisopropylphenylimino)-pyridine
A solution of 0.4 ml (3.5 mmol) of titanium tetrachloride in 20 ml of toluene
is added
dropwise to a solution of 3.6 ml (19 mmol) of 2,6-diisopropylaniline and 0.91
g
(3.2 mmol) of 2,6-dibenzoylpyridine, which had been prepared in the same way
as
described in the example for preparing complex A, in 50 ml of toluene at
0°C. After
completion of the addition procedure, the mixture is stirred at room
temperature for
90 min and then under reflux for 12 h. After cooling to room temperature, the
orange
suspension is filtered and the residue is washed three times, using 30 ml of
toluene
each time. The solvent is distilled off and 100 ml of hexane are added to
complete
precipitation of the hydrochloride. The mixture is filtered again and the
residue is
washed free of solvent. Then the residue is recrystallised from methanol. At -
18°C,
2,6-dibenzoyl-bis-(2,6-diisopropylphenylimino)-pyridine crystallizes out as a
pale
yellow solid. Yield: 0.92 g.
1H NMR (in CDC13): d = 8.05-6.83 (m, 19H), 2.87 (m, 4H), 1.10-0.89 (dd, 24H).
Example 2b
Synthesis of 2,6-dibenzoylpyridine-bis-(2,6-diisopropylphenylimino)-cobalt(In
dichloride
0.07 g (0.5 mmol) of anhydrous cobalt(II) chloride are added, at room
temperature, to
a solution of 0.30 g (0.5 mmol) of 2,6-dibenzoyl-bis-(2,6-
diisopropylphenylimino)-
pyridine in 30 ml of dry THF and the mixture is stirred at room temperature
for 12 h.
Then the solution is evaporated down to half the volume and 100 ml of hexane
is
added thereto. The bisiminopyridylcobalt complex precipitates out as a golden
yel-
low precipitate and is dried under vacuum after filtration. Yield: 0.26 g.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-21 -
FT-IR (KBr): n(C=N) 1572 cm 1.
Polymerization trials
Example 3
Radical polymerization of acrylonitrile (comparison trial)
ml (150 mmol) of acrylonitrile in 200 ml of toluene are initially introduced
into a
10 1000 ml glass autoclave. After adding 230 mg (1.4 mrnol) of AIBN, the
mixture is
heated to 65°C and stirred for 4 h at this temperature. Yield: 1.98 g.
Example 4
Polymerization of ethene/AN with [(2,6-iPr2Ph)2PhPyr)CoC,z/K[B(C6F5)4]/AIBN
10 ml (150 mmol) of acrylonitrile in 200 ml of toluene are initially
introduced into a
1000 ml glass autoclave. Then 246 mg (1.5 mmol) of AIBN, 1.1 mg (1.5 x 10'2
mmol) of cobalt compound B and 24 mg (3 x 10'2 mmol) of K[B(C6F5)4] are added,
one after the other. The reactor is sealed and ethene is introduced until the
pressure
reaches 4 bar, so that the molar ratio of acrylonitrile to ethene is 2:1. Then
the mix-
tore is heated to 65°C and polymerized for 4 h at this temperature.
Yield: 1.17 g.
Example 5
Polymerization of ethene/AN with [(2,6-iPr2Ph)ZPhPyr]CoCI2/K[B(C6F5)4]/AIBN
S mg (3 x 10'2 mmol) of AIBN and 10 ml (150 mmol) of acrylonitrile in 200 ml
of
toluene are initially introduced and heated to 60°C. Then 22 mg (3 x
10'2 mmol) of
cobalt complex B and 47.4 mg (6 x 10'2 mmol) of K[B(C6F5)4] are added. The
reactor is sealed and ethene is introduced until the pressure reaches 4 bar,
so that the
molar ratio AN:E = 2:1, heated to 65°C and polymerized at this
temperature for 24 h.
Yield: 0.35 g.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-22-
Example 6
Polymerization of ethene/AN with [(2,6-iPr2Ph)2PhPyrJCoCI2/K[B(C6Fs)4]/AIBN
S ml (75 mmol) of acrylonitrile in 200 ml of toluene are initially introduced.
Then
244 mg (1.5 mmol) of AIBN, 11 mg (1.5 x 10'2 mmol) of cobalt complex B and
24 mg (3 x 10'2 mmol) of K[B(C6F5)4J are added, one after the other, at
60°C. The
reactor is sealed and ethene is introduced until the pressure reaches 4 bar,
so that the
molar ratio AN:E = 1:1, heated to 65°C and polymerized at 65°C
for 4 h. Yield:
0.22 g.
Example 7
Polymerization of ethene/AN with [(2,6-Me2Ph)ZPhPyr]CoCI?JK[B(C6F5)4]IAIBN
10 ml (150 mmol) of acrylonitrile in 200 ml of toluene are initially
introduced. Then
246 mg (1.5 mmol) of AIBN, 9.3 mg (1.5 x 10'2 mmol) of cobalt compound A and
24 mg (3 x 10'2 mmol) of K[B(C6F5)4] are added, one after the other, at
60°C. The
reactor is sealed and ethene is introduced until the pressure reaches 4 bar,
so that the
molar ratio AN:E = 2:1, heated to 65°C and polymerized at this
temperature for 4 h.
Yield: 0.84 g.
Example 8
Polymerization of ethene/AN with [(2,6-Me2Ph)2PhPyr]CoCl2/K(B(C6F5)4]/AIBN
5 ml (75 mmol) of acrylonitrile in 200 ml of toluene are initially introduced.
Then
245 mg (1.5 mmol) of AIBN, 9.3 mg (1.5 x 10'2 rnmol) of cobalt complex A and
24 mg (3 x 10'2 mmol) of K[B(C6F5)4] are added, one after the other, at
60°C. The
reactor is sealed and ethene is introduced until the pressure reaches 4 bar,
so that the
molar ratio AN:E = 1:1, heated to 65°C and polymerized at this
temperature for 4 h.
Yield: 0.14 g.
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
- 23 -
Examule 9
Polymerization of ethene/AN with
[(2,6-iPr2Ph)2PhPyr]CoCI2/Na[B(C6H5)4]IAIBN
S 10 ml (150 mmol) of acrylonitrile in 200 ml of toluene are initially
introduced. Then
246 mg (1.5 mmol) of AIBN, 11 mg (1.5 x 10-2 mmol) of cobalt compound B and
11.3 mg (3 x 10'5 mmol) of Na[B(C6H5)4] are added, one after the other, at
60°C. The
reactor is sealed and ethene is introduced until the pressure reaches 4 bar,
so that the
molar ratio AN:E = 2:1, heated to 65°C and polymerized at this
temperature for 4 h.
Yield: 0.95 g
Example 10
Polymerization of ethene/AN with [(2,6-iPrZPh)2PhPyr]CoCI2/K(B(C6F5)4]/AIBN
10 ml (1 SO mmol) of acrylonitrile in 200 ml of toluene are initially
introduced. Then
246 mg (1.5 mmol) of AIBN, 11 mg (1.5 x 10-2 mmol) of cobalt compound B and
24 mg (3 x 102 mmol) of K[B(C6F5)4] are added, one after the other, at
60°C. The
reactor is sealed and ethene is introduced until the pressure reaches 6 bar,
so that the
molar ratio AN:E = 1.5:1, heated to 65°C and polymerized at this
temperature for 4h.
Yield: 1.17 g
Example 11
Polymerization of ethene/styrene with
[(2,6-iPr2Ph)2PhPyr]CoCI2/Na[B(C6H5)4 ]/AIBN
5 ml (43 mmol) of styrene in 200 ml of toluene are initially introduced. Then
142 mg
(0.9 mmol) of AIBN, 6.3 mg (0.9 x 10-2 mmol) of cobalt compound B and 6 mg
(1.8 x 102 mmol) of Na[B(C6H5)4] are added, one after the other. The reactor
is
sealed and ethene is introduced until the pressure reaches 2.6 bar, so that
the molar
ratio styrene:E = 1:1, heated to 65°C and polymerized at this
temperature for 4 h.
Yield: 0.19 g
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
-24-
Examine 12
Polymerization of ethene/styrene with
[(2,6-iPr2Ph)2PhPyr]CoCI2/Na[B(C6H5)4]/AIBN
S ml (43 mmol) of styrene in 200 ml of toluene are initially introduced. Then
180 mg
(1.1 mmol) of AIBN, 16 mg (2.2 x 10-2 mmol) of cobalt compound B and 17 mg
(4.9 x 10'2 mmol) of Na[B(C6H5)4] are added, one after the other. The reactor
is
sealed and ethene is introduced until the pressure reaches 5.3 bar, so that
the molar
ratio styrene:E = 1:2, heated to 65°C and polymerized at this
temperature for 4 h.
Yield: 0.20 g
Example 13
Polymerization of ethene/MA with
[(2,6-iPr2Ph)2PhPyr]CoCIzJNa[B(C6H5)4]/AIBN
10 ml (112 mmol) of methyl acrylate in 200 ml of toluene are initially
introduced.
Then 180 mg ( 1.1 mmol) of AIBN, 8 mg ( 1.1 x 10-2 mmol) of cobalt compound B
and 8.6 mg (2.5 x 10-2 mmol) of Na[B(C6H5)4] are added, one after the other.
The
reactor is sealed and ethene is introduced until the pressure reaches 3.4 bar,
so that
the molar ratio MA:E = 2:1, heated to 65°C and polymerized at this
temperature for 4
h. Yield: 4.10 g
Example 14
Polymerization of ethene/MA with
[(2,6-iPr2Ph)2PhPyr]CoCI2/Na[B(C6H5)4]/AIBN
5 ml (56 mmol) of methyl acrylate in 200 ml of toluene are initially
introduced. Then
180 mg (1.1 mmol) of AIBN, 8 mg (1.1 x 10-2 mmol) of cobalt compound B and
8.6 mg (2.5 x 10-2 mmol) of Na[B(C6H5)4] are added, one after the other. The
reactor
is sealed and ethene is introduced until the pressure reaches 3.4 bar, so that
the molar
CA 02377249 2001-12-21
Le A 33 769- Foreign Countries
- 25 -
ratio MA:E = 1:1, heated to 65°C and polymerized at this temperature
for 4 h. Yield:
1.77 g
Example 15
Polymerization of ethene/MA with
[(2,6-iPr2Ph)2PhPyr] CoCI2/Na [B(C6H5)4]/AIBN
5 ml (56 mmol) of methyl acrylate in 200 ml of toluene are initially
introduced. Then
180 mg (1.1 mmol) of AIBN, 8 mg (1.1 x 10'2 mmol) of cobalt compound B and
8.6 mg (2.5 x 10'2 mmol) of Na[B(C6H5)4] are added, one after the other. The
reactor
is sealed and ethene is introduced until the pressure reaches 5.1 bar, so that
the molar
ratio MA:E = 1:1.5, heated to 65°C and polymerized at this temperature
for 4 h.
Yield: 2.01 g
Example 16
Radical polymerization of methyl acrylate (comparison trial)
10 ml ( 112 mmol) of methyl acrylate in 200 ml of toluene are initially
introduced
into a 1000 ml glass autoclave. After adding 180 mg (1.1 mmol) of AIBN, the
mix-
tore is heated to 65°C and stirred at this temperature for 4 h. Yield:
4.72 g.
CA 02377249 2001-12-21
CA 02377249 2001-12-21
O~ h M oo O~ h ~t O O o0 ~nM ~O
O 00 01V1 00 ~O00 00~C V~ "";
,
a
O
U
H
II
o b ~ ~ ~ o ~ b b b ~ b
b N !r".-1.-:.-iN .-~t~ C,'t~!~ C7~ ,::,
4; N
O O O O O O O O
b
'b ~ 'bo ~ N M w b b b Tib
o o ~
, O
t~ M >~O~ N 00N N CI A toI~ i~t
,
o
~ ~ M h N .d b b b O
b
p o p N Oi vDof ~ p (b ibS~ ~
~ 0
~
0
o c~
II ,b
00 h ~nN ~ d'~n l~O~ O O h .-~N
n 0~ .-,M N OO ."~0~ ~ -~ N ~ C~ O C~
,'Y~ .-..--~O O O O O - O O d~-' N d~
~
O
N N O
_ _
h ~'
i i i i i i i i i i -~ ~ ~ ~"._,
1
.
63
O
O
i O
4
~' , ~ , , i , , , M M , , , , -i
V7 , i , , ~ , , , ~ d' , , , , G,
a II N
T
O o U
,''
O O O O O o ~ A
'
V'1V1 V7V1 V N ,!1~!1
.--,~ .-~h 1 h ~ ~ i i i i i i
~
U
C
Q
U N
w V1 V1~ Vl V'1V1 O M ~O ~O~O d'~ b
i h h h h h h .-~'cf'00 V'1V1 00, p
VC
> _t
~ F1
L~ et ~' N d' ~t ~ d' d'd' <t ~td' ~t~t II
Cd
~ b
f"iz
O
yi M
~ h O Y1 V1 Y~V1 Y
o : : ~ o . .., ~ ..
.
o ....~ r .-..... ... . . . . .
.
a
0 0o c~ ~n~n ~n
l
0 0 ~ o 0 o I
Z i i i i i i O i O O O O O i
a
O Y
~
y O O O O O O ,
~ .d b
~
M M M M M M
O O O O O O
r~ i O O O O O i O I t t I I
a
O ~ v7 ~ O~ N .-r~ .-~ ed
v1 n h , -. .. r.,
.-.....-. ...~,O N r . . V
O O O O O O O O O O
y,~ i O O O i i O O O O O O O i
r~,~
>,
Q
1
O O O -~ a
~ , . , . . . , ,
"
V , , , . o o . . , , . . , , ~ i1
,~ , , . ,
a>
' z z
p
y~ M ~ Vi~O h GOO~ O ~ N M ~ ~ ~O
r.r.~ ~ ..r~ .-W-.i
