PROCEDE EN PHASE GAZEUSE POUR LA COPOLYMERISATION DU MONOXYDE DE CARBONE ET DE COMPOSES INSATURES ETHYLENIQUES

GAS PHASE PROCESS FOR THE CO-POLYMERIZATION OF CARBON MONOXIDE AND ETHYLENICALLY UNSATURATED COMPOUNDS

Abrégé anglais

A gas phase process for the preparation of co-
polymers comprising reacting carbon monoxide and an
ethylenically unsaturated compound in the presence of a
catalyst system based on
(a) a source of cations of a metal of Group VIII of the
Periodic Table;
(b) a source of anions which comprise a plurality of
boron atoms or a source of organic boron containing
anions or an aluminoxane; and
(c) a source of ligands.

Revendications

- 24 -
The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A gas phase process for the preparation of co-
polymers comprising reacting carbon monoxide and an
ethylenically unsaturated compound in the presence of a
catalyst system based on
(a) a source of cations of a metal of Group VIII of the
Periodic Table;
(b) a source of anions which comprise a plurality of
boron atoms or a source of organic boron containing
anions or an aluminoxane; and
(c) a source of ligands.
2. A process as claimed in claim 1, characterized in
that the catalyst system is based, as regards (b), on a
boron containing anion selected from anions which contain
a plurality of boron atoms and, such as a carborate
anion, for example an anion of the formula B11CH12-, and
anions of the general formula BZ4- wherein each Z
independently represents a substituted or unsubstituted
hydrocarbyl group, such as an anion selected from
tetraphenylborate, tetrakis(perfluorophenyl)borate and
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anions, or
it is based on a borane of the general formula BZ13
wherein each Z1 independently represents a substituted or
unsubstituted hydrocarbyl group, such as triphenylborane,
tris(perfluorophenyl)borane and tris[3,5-bis(trifluoro-
methyl)phenyl]borane, or an aluminoxane, such as an
aluminoxane containing on average 3 - 5 aluminium atoms
per molecule.
3. A process as claimed in claim 1 or 2, characterized
in that the catalyst system is based, as regards (a), on
a salt of palladium and a carboxylic acid, such as
palladium (II) acetate, and, as regards (c), on a

- 25 -
bidentate ligand of the general formula
R1R2M1-R-M2R3R4 (I)
wherein M1 and M2 represent phosphorus atoms, each of R1,
R2, R3 and R4 independently represents a non-substituted
or polar substituted aryl group and R represents a
bivalent bridging group containing 2 to 4 carbon atoms in
the bridge.
4. A process as claimed in claim 3, characterized in
that in the bidentate ligand of formula (I), each of R1,
R2, R3 and R4 represents an ortho-alkoxyphenyl group and
R represents a trimethylene group.
5. A process as claimed in any of claims 2-4,
characterized in that the catalyst system is based on, as
regards (b), 1.0 to 50 equivalents, preferably 1.0 - 10
equivalents, of boron containing anions or a quantity of
an aluminoxane which contains 100 - 2,000 gram atom
aluminium and, as regards (c), 0.5 to 8 moles of
bidentate ligand, all quantities being defined per gram
atom of Group VIII metal.
6. A process as claimed in any of claims 1-5,
characterized in that the catalyst system is based on a
noble Group VIII metal and, as an additional catalyst
component, on a source of cations of one or more metals
selected from the group consisting of cobalt, nickel,
manganese, lead, zinc, magnesium, iron (II), copper (II),
lanthanum and neodymium, in particular selected from the
group consisting of cobalt, nickel and manganese.
7. A process as claimed in claim 6, characterized in
that the metal(s) selected from the group consisting of
cobalt, nickel, manganese, lead, zinc, magnesium, iron
(II), copper (II), lanthanum and neodymium are present in
a quantity of 1.0 to 10 gram atom per gram atom of Group
VIII metal.
8. A process as claimed in any of claims 1-7,
characterized in that the Group VIII metal of the

- 26 -
catalyst system is covalently bonded with a single
hydrocarbyl or acyl group.
9. A process as claimed in any of claims 1-8,
characterized in that the catalyst system additionally
comprises a promoter, such as benzoquinone,
naphthoquinone or anthraquinone, in a quantity of 1 to 50
mole per gram atom of Group VIII metal.
10. A process as claimed in any of claims 1-9,
characterized in
that the catalyst system is supported on a carrier, such
as a co-polymer of carbon monoxide with one or more
ethylenically unsaturated compounds.
11. A process as claimed in any of claims 1-10,
characterized in that as ethylenically unsaturated
compound ethene or a mixture of ethene with propene or
ethene with 1-butene is used, the reaction is carried out
at a temperature in the range of 30 to 150°C and at a
pressure in the range of 20 to 100 bar.
12. A catalyst system based on
(a) a source of cations of a metal of Group VIII of the
Periodic Table;
(b) a source of anions which comprise a plurality of
boron atoms or a source of organic boron containing
anions or an aluminoxane;
(c) a source of ligands; and
(d) a solid carrier material.
13. A catalyst composition comprising
(a) a cation of a metal of Group VIII of the Periodic
Table;
(b) a boron containing anion selected from anions which
contain a plurality of boron atoms and anions of the
general formula BZ4- wherein each Z independently
represents a substituted or unsubstituted hydrocarbyl
group, or a borane of the general formula BZ13 wherein
each Z1 independently represents a substituted or

- 27 -
unsubstituted hydrocarbyl group, or an aluminoxane; and
(c) a ligand selected from
(1) bidentate ligands of the general formula
R1R2M1-R-M2R3R4 (I)
wherein M1 and M2 independently represent a phosphorus,
arsenic or antimony atom, each of R1, R2, R3 and R4
independently represents a non-substituted or polar
substituted hydrocarbyl group and R represents a divalent
bridging group containing 1 to 5 carbon atoms in the
bridge,
(2) bidentate ligands of the general formula
<IMG> (II)
wherein X1 and X2 independently represent organic
bridging groups each containing 3 or 4 atoms in the
bridge at least 2 of which are carbon atoms,
(3) bidentate ligands of the general formula
R5S-Q-SR6 (III)
wherein R5 and R6 independently represent a non-
substituted or polar substituted hydrocarbyl group and Q
represents a bivalent bridging group containing 2 to 4
carbon atoms in the bridge, and
(4) monodentate ligands of the general formula
R7R8R9M3 (IV)
wherein M3 represents a phosphorus, arsenic or antimony
atom, R7, R8 and R9 independently represent a non-
substituted or polar substituted hydrocarbyl group,
with the provisos that if the catalyst composition is
based on palladium as a Group VIII metal and a bidentate
ligand of the general formula (II) as catalyst component
(c), catalyst component (b) is other than a tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate anion, and if the
catalyst composition is based on a bidentate ligand of
the general formula (I) as catalyst component (c),

- 28 -
catalyst component (b) is other than an alkyl aluminoxane
of which the alkyl groups have 2 - 6 carbon atoms and
carry .beta.-hydrogen atoms.

Description

215~239
-- 1 --
TS 0047
GAS PHASE PROCESS FOR THE CO-POLYMERIZATION OF CARBON
MONOXIDE AND ETHYLENICALLY UNSATURATED COMPOUNDS
The invention relates to a gas phase process for the
co-polymerization of carbon monoxide and ethylenically
unsaturated compounds.
The preparation of co-polymers of carbon monoxide and
ethylenically unsaturated compounds, in which co-polymers
the units originating from carbon monoxide alternate or
substantially alternate with the units originating from
the ethylenically unsaturated compounds, has been
described in numerous patent publications, most of which
deal with the preparation of the co-polymers in a liquid
phase process.
These co-polymers can also be prepared by a gas phase
process. In such a process the monomers are contacted
with a catalyst composition based upon
(a) a compound of a metal of Group VIII of the Periodic
Table;
(b) an anion; and
(c) a bidentate ligand
in the substantial absence of a liquid diluent, i.e. such
that the gas phase forms the continuous phase.
Examples of such gas phase processes are known from
EP-A-248483. An example of a suitable anion is the para-
toluenesulphonate anion. The corresponding acid, in the
exemplified case para-toluenesulphonic acid, is a
suitable source of the anion.
The present Applicant has devoted a considerable
amount of research towards improving the performance of
the catalyst composition, for example by varying the type
and the source of the anion used as catalyst component
b). EP-A-508502 discloses that high activity catalysts

21~8239
for the gas phase process can be obtained by
incorporating therein certain types of Lewis acids as
component b). In EP-A-501576 the use of Lewis
acid/Bronsted acid mixtures is recommended for that
purpose.
The present invention provides improved catalysts for
the gas phase process which comprise, as anions, anions
containing a plurality of boron atoms, such as carborate
anions, or organic boron containing anions, such as
hydrocarbylborate anions. These anions are non- or
weakly co-ordinating with the Group VIII metal and they
are bulky. It is surprising that these anions give an
improvement in catalyst activity in the gas phase process
and an improvement in the molecular weight of the co-
polymer obtained, as they fail to give improvements in
liquid phase polymerizations carried out under otherwise
similar conditions. It is also remarkable that neutral
organic boranes, such as trihydrocarbylboranes can act as
suitable source of anions. Aluminoxanes, when used as a
source of anions, provide also catalyst compositions with
attractive activity in the gas phase process.
Published Netherlands patent application 9001229
suggests the use of carborate anions as a catalyst
component in the Group VIII metal catalyzed alternating
co-polymerization of carbon monoxide with olefins.
However, this document does not give any further details
as regards the conditions of the use of the carborate
anions and the benefits thereof. The document is
concerned with liquid phase slurry polymerizations and it
is entirely silent as regards gas phase processes.
Brookhart et al. (J. Am. Chem. Soc. 114 (1992) p. 5894
and 116 (1994) p. 3641) have used the tetrakis[3,5-bis-
(trifluoromethyl)phenyl]borate anion in combination with
certain palladium/nitrogen bidentate complexes in the
liquid phase synthesis of stereoregular co-polymers of

21582~9
carbon monoxide with styrene related olefins. EP-A-
590942 discloses the use of certain aluminoxanes in Group
VIII metal catalyzed liquid phase slurry polymerizations
of carbon monoxide with ethene. The present favourable
results are not deducible from any of these documents and
are indeed surprising.
A study of the use of boron hydrocarbyl compounds as
catalyst component in liquid phase copolymerizations of
carbon monoxide with ethylenically unsaturated compounds
is the subject matter of the earlier filed non-
prepublished patent application EP-A-619335.
Accordingly, the present invention relates to a gas
phase process for the preparation of co-polymers
comprising reacting carbon monoxide and an ethylenically
unsaturated compound in the presence of a catalyst system
based on
(a) a source of cations of a metal of Group VIII of the
Periodic Table;
(b) a source of anions which comprise a plurality of
boron atoms or a source of organic boron containing
anions or an aluminoxane; and
(c) a source of ligands.
The invention also relates to a catalyst composition
comprislng
(a) a cation of a metal of Group VIII of the Periodic
Table;
(b) a boron containing anion selected from anions which
contain a plurality of boron atoms and anions of the
general formula BZ4- wherein each Z independently
represents a substituted or unsubstituted hydrocarbyl
group, or a borane of the general formula BZ13 wherein
each zl independently represents a substituted or
unsubstituted hydrocarbyl group, or an aluminoxane; and
(c) a ligand selected from
(1) bidentate ligands of the general formula

2158239
R1R2M1-R-M2R3R4 (I)
wherein M1 and M2 independently represent a phosphorus,
arsenic or antimony atom, each of R1, R2, R3 and R4
independently represents a non-substituted or polar
substituted hydrocarbyl group and R represents a divalent
bridging group containing 1 to 5 carbon atoms in the
bridge,
(2) bidentate ligands of the general formula
xl x2
/ \ / \ (II)
N = C - C = N
wherein xl and x2 independently represent organic
bridging groups each containing 3 or 4 atoms in the
bridge at least 2 of which are carbon atoms,
(3) bidentate ligands of the general formula
R5S-Q-SR6 (III)
wherein R5 and R6 independently represent a non-
substituted or polar substituted hydrocarbyl group and Q
represents a bivalent bridging group containing 2 to 4
carbon atoms in the bridge, and
(4) monodentate ligands of the general formula
R7R8R9M3 (IV)
wherein M3 represents a phosphorus, arsenic or antimony
atom, R7, R8 and R9 independently represent a non-
substituted or polar substituted hydrocarbyl group.
Unsupported catalyst compositions which are based on
palladium, a bidentate ligand of the general formula (II)
and a tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
anion, as employed by Brookhart et al., and unsupported
catalyst compositions which are based on a Group VIII
metal, a bidentate ligand of the general formula (I) and
an alkyl aluminoxane, the alkyl groups having 2 - 6
carbon atoms and carrying ~-hydrogen atoms, as employed
in EP-A-590942, are excluded from patent protection.
In the present specification and claims the term

2158239
"metals of Group VIII of the Periodic Table" encompasses
the noble metals ruthenium, rhodium, palladium, osmium,
iridium and platinum, and the iron group metals iron,
cobalt and nickel.
The catalyst systems, suitable for use in the process
of the invention, are based, as regards (a), on a source
of cations of the said metal(s).
Suitable sources of cations of metals of Group VIII
include salts of mineral acids, such as salts of
sulphuric acid, nitric acid and phosphoric acid, and
salts of sulphonic acids, such as methanesulphonic acid
and para-toluenesulphonic acid.
Preferred sources are salts of carboxylic acids, such
as acetic acid, propionic acid and trifluoroacetic acid.
If desired, as cation source use may be made of the
metals in their elemental form, or in a zero-valent state
thereof, e.g. in complex form, such as complexes wherein
the Group VIII metal is covalently bonded to one or two
hydrocarbyl groups. These covalently bonded hydrocarbyl
groups may be aliphatic or aromatic and contain typically
up to 12 carbon atoms. Preferred covalently bonded
hydrocarbyl groups are aliphatic groups, in particular n-
alkyl groups, such as methyl and n-butyl groups.
Catalyst systems based on a noble Group VIII metal
are preferred, those based on palladium being most
preferred. A preferred source of these cations is
palladium (II) acetate.
According to this invention the catalyst compositions
may be based, as regards (b), on anions which contain a
plurality of boron atoms. The number of boron atoms is
typically from 4 to 20, more typically from 8 to 16.
These anions may be unsubstituted or substituted, for
example halogenated. Di-negatively charged polyhedral
borates can be used, such as anions of the formulae
B1oH1o2- and B12H122-, and their halogenated analogues.

21582~9
It is however preferred to use a carborate anion, for
example 1,2-dicarbaundecaborate and 7,8-dicarbaundeca-
borate, in particular an anion of the formula B11CH12-.
Such carborates are known and can be prepared by methods
such as that of K. Shelly et al. (J. Am. Chem. Soc. 107
(1985) 5955).
According to this invention the catalyst compositions
may also be based, as regards (b), on organic boron
containing anions. Very suitable anions of this class
are anions of the general formula BZ4- wherein each Z
independently represents a substituted or unsubstituted
hydrocarbyl group, such as an aliphatic group or an
aromatic group, such groups typically having up to 12
carbon atoms. Preferred groups Z are aryl groups which
may or may not be substituted. Preferred substituents
are electron withdrawing groups or atoms, such as halogen
atoms, trihalomethyl groups and nitro groups. In
particular the groups Z are phenyl groups, more in
particular perfluorophenyl or 3,5-bis(trifluoromethyl)-
phenyl groups. The four groups Z are typically
identical. Preferred anions of the general formula BZ4-
are tetraphenylborate, tetrakis(perfluorophenyl)borate
and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
anions. Examples of suitable aliphatic groups Z are
methyl, n-butyl and isobutyl groups.
Other organic boron containing anions which can be
used in the catalyst system are
tetra(hydrocarbyloxy)borates of the general formula
O O
A B- A
\ / \ /
O O
in which the bivalent groups A are independently selected
from alkylene groups typically having from 2 to 6 carbon

~ ~ 21à8239
atoms, ortho-phenylene or ortho-biphenylene groups or
groups of the general formula -~-CO- wherein ~ represents
an ortho-phenylene group. The groups A may be
substituted, e.g. with alkyl groups having suitably up to
6 carbon atoms or with halogen atoms. Such anions are
known from EP-A-314309 and EP-A-391579. Preferred anions
of this kind are those based on unsubstituted ortho-
phenylene groups A and in particular those which can be
considered to be derived from salicylic acid or 5-
chloro-, 5-methyl-, 4-methyl- or 5-bromosalicylic acid.
The boron containing anions of this invention may be
introduced in the catalyst composition in the form of a
salt, such as a metal salt or a dialkyloxonium salt.
Preferred metal salts are salts of cobalt, nickel and
silver. Preferred dialkyloxonium salts are
diethyloxonium salts. Very good results can be obtained
with, for example, Co[B11CH12]2, Ni[B11CH12]2 and
Ag[B11CH12]. If the anions are introduced in the form of
an alkali(ne earth) metal, which metal is also present in
the polymerization process, it is eligible to have in the
polymerization process an ether present as an additional
catalyst component, such as linear or cyclic polyalkylene
polyethers, for example tetraethylene glycol or a crown
ether.
The boron containing anions may suitably be
introduced in the catalyst composition by reacting a
neutral complex compound of the Group VIII metal, such as
a dialkyl compound, with a salt of the boron containing
anion and a cation capable of abstracting an anion from
the Group VIII complex compound to form an anionic Group
VIII complex, rendering itself neutral. An illustrative
example is:
L2Pd(CH3)2 + 2 Cat+ + 2 B(C6Fs)4~ ~ [L2Pd2+][B(C6Fs)4~]2
+ CH3-Cat, or

215~2 39
L2Pd(CH3)2 + Cat+ + B(C6Fs)4- ~ [L2PdcH3+][B(c6F5)4-]
+ CH3-Cat,
wherein [Cat+] is for example diphenylmethylammonium
(C6Hs)2CH3NH+), so that [CH3-Cat] becomes methane and
diphenylmethylamine, and L is a complexing site (dentate
group) of a ligand. In this context reference can be
made to the chemistry of the Group IV metals titanium,
zirconium and hafnium where this type of reactions are
known to the skilled person.
It is also possible to generate boron containing
anions in situ, e.g. during the polymerization, by
introducing in the catalyst composition a borane of the
general formula BZ13 wherein each zl independently
represents a substituted or unsubstituted hydrocarbyl
group, such as an aliphatic group or an aromatic group,
such groups typically having up to 12 carbon atoms.
Preferred groups zl are aryl groups which may or may not
be substituted. Preferred substituents are electron
withdrawing groups or atoms, such as halogen atoms,
trihalomethyl groups and nitro groups. In particular the
groups zl are phenyl groups, more in particular
perfluorophenyl or 3,5-bis(trifluoromethyl)phenyl groups.
The three groups zl are typically identical. Preferred
compounds of the general formula BZ13 are
triphenylborane, tris(perfluorophenyl)borane and
tris[3,5-bis(trifluoromethyl)phenyl]borane. Examples of
suitable aliphatic groups zl are methyl and n-butyl
groups.
The type of boron containing anion which is formed
when a borane of the general formula BZ13 is employed as
a catalyst component will depend on reaction conditions
selected, such as the nature of other catalyst
components. Three examples may be given for
illustration:

` 21S8239
(1) When the Group VIII metal, e.g. palladium, is present
as a complex compound containing covalently bonded
hydrocarbyl groups, such as methyl groups, boron
containing anions may, for example, be formed as follows:
L2Pd(CH3)+ + BZ13 ~ [L2Pd2+][BZ13(CH3)-], or
L2Pd(CH3)2 + BZ13 ~ [L2Pd(CH3)+][BZ13(CH3)-], or
L2Pd(CH3)2 + 2 BZ13 ~ [L2Pd2+][BZ13(CH3)-]2,
wherein L denotes a complexing site (dentate group) of a
ligand and BZ13(CH3)- is a boron containing anion.
(2) When the Group VIII metal is present as a complex
compound containing covalently bonded hydrocarbyl groups,
e.g. as described under (1), and in addition there is
present a compound of the general formula YXH in which X
denotes oxygen or sulphur and of which the meaning of Y
is explained below, such as methanol, boron containing
anions may be formed via a neutral borane complex
BZ13(YXH)q wherein q is 1, 2 or 3, in particular 1, for
example as follows:
BZ13 + CH30H ~ [BZ13(CH30H)] and
L2Pd(CH3)+ + [BZ13(CH30H)] ~ [L2Pd2+][BZ13(0CH3)-] + CH4,
or
BZ13 + 2 CH30H ~ [BZ13(CH30H)2] and
L2Pd(CH3)+ + [BZ13(CH30H)2] ~ [L2Pd2+][BZ13(OCH3)-] + CH4
+ CH30H,
wherein BZ13(0CH3)- is a boron containing anion.
Compounds YXH may suitably be water (X is oxygen and Y is
hydrogen) or an alcohol, a silanol, an oxime or a
mercaptan in which cases typical structures of YXH may be
set out as follows. In the case YOH is an alcohol Y
typically denotes an optionally substituted aliphatic or
aromatic hydrocarbyl group which may or may not be
substituted and which contains typically up to 12 carbon
atoms, in particular up to 6 carbon atoms. Suitable
alcohols YOH are for example 2-methoxyethanol, 4-t-butyl-
cyclohexanol, isopropanol, benzyl alcohol, perfluoro-

2 3 9
-- 10 --
hexanol and hexafluoroisopropanol. A preferred alcohol
YOH is methanol. In case YOH is a silanol the group Y
contains a silicium atom attached to the hydroxy group of
YOH. This silicium atom may carry phenyl groups or
linear or branched alkyl groups which typically have up
to 12 carbon atoms, more typically up to 6 carbon atoms,
and which alkyl groups may contain further silicium atoms
or -SiO- groups. Examples of silanols YOH are
(phenyl)(CH3)2SiOH, (t-C4Hg)(CH3)2SiOH and
((CH3)3SiO)3SiOH. In the case YOH denotes an oxime, it
is a condensation product of hydroxylamine with an
aldehyde (in which case it may be a cis or a trans
oxime), not formaldehyde, or a ketone. Such aldehydes
and ketones may be aliphatic or aromatic and contain
typically up to 12 carbon atoms, more typically up to 6
carbon atoms. Very suitable are, for example,
cyclohexanone oxime and acetone oxime. In the case YSH
denotes a mercaptan the group Y is typically specified as
an optionally substituted aliphatic or aromatic
hydrocarbyl group which may be substituted and which
contains typically more than 6 carbon atoms, in view of
an objectionable odour of the mercaptan, and in
particular up to 25 carbon atoms. Suitable mercaptans
YSH are, for example, 4-t-butylcyclohexyl mercaptan,
para-octylbenzyl mercaptan and octadecyl mercaptan.
(3) When there is present a compound of the general
formula YXH, as defined hereinbefore, for example
methanol, and in addition there is present a base, boron
containing anions may be formed via a neutral borane
complex BZ13(YXH)q, as described hereinbefore, for
example as follows:
BZ13 + CH30H ~ [BZ13(CH30H)] and
[BZ13(CH30H)] + base ~ [base-H+] + BZ13(0CH3)-, or
BZ13 + 2 CH30H-~ [BZ13(CH30H)2] and
[BZ13(CH30H)2] + base ~ [base-H+] + BZ13(0CH3)- + CH30H,

~- 21~8239
wherein BZ13(OCH3)- is a boron containing anion.
Suitable bases which are capable of abstracting a proton
from the complex BZ13(YXH)q are tertiary amines or
tertiary phosphines, such as trihydrocarbylamines and -
phosphines of which the hydrocarbyl groups contain
typically up to 12 carbon atoms and which are preferably
aliphatic groups. Preferably these hydrocarbyl groups
are identical. Suitable tertiary amines and phosphines
are for example tr`iethylamine, N,N-dimethylaniline and
tri-n-butylphosphine. Other suitable bases are
carboxylate anions, typically anions of carboxylic acids
having a pKa of more than 2, preferably from 4 - 10 (when
measured in water at 18 C), in particular of acids which
comprise up to 12 carbon atoms and which are aromatic or
aliphatic. The carboxylate anions are typically anions
of fatty acids. Examples of suitable carboxylate anions
are acetate, propionate, pivaloate and para-methyl-
benzoate anions. Other suitable bases may be inorganic,
such as anions of phosphoric acid, for example
dihydrogenphosphate and phosphate anions. The quantity
of the compound YXH and the base which may be used in the
catalyst composition may vary between wide limits.
However, it is preferred that the molar ratio of the
compound YXH and borane BZ13 is from 1:10 to 10:1, in
particular from 1:5 to 5:1, more in particular from 1:2
to 2:1. The quantity of base in equivalents relative to
the quantity of borane BZ13 in moles is in the range of
from 1:10 to 10:1, in particular from 1:5 to 5:1, more in
particular from 1:2 to 2:1.
The amount of the boron containing anions which is
present in the catalyst composition of this invention is
not critical. Typically they are used in an amount of
0.5 to 200, preferably of 1.0 to 50, more preferably 1.0
to 10 equivalents per gram atom of Group VIII metal.

215~239
- 12 -
It is possible to isolate the catalyst composition as
a complex compound which, for example, does not contain a
metal cation introduced together with the boron
containing anion and to use the isolated complex in the
process of this invention. However, when the Group VIII
metal is a noble metal the presence of cations of cobalt,
nickel, manganese, lead, zinc, magnesium, iron (II),
copper (II), lanthanum or neodymium in the gas phase
process may have an advantageous effect on the catalyst
activity which is additional to the effect of the
presence of the boron containing anions. Hence, it is
advantageous to apply in the invented process a catalyst
composition which is based on, as an additional
component, a source of cations selected from cobalt,
nickel, manganese, lead, zinc, magnesium, iron (II),
copper (II~, lanthanum or neodymium, preferably selected
from cobalt, nickel, manganese, lead, zinc, magnesium and
iron (II), and most preferably selected from cobalt,
nickel and manganese. Said metal cations are preferably
present in a quantity of 1.0 to 50 gram atom, in
particular 1.0 to 10 gram atom per gram atom of Group
VIII metal.
As regards (b) the catalyst compositions may comprise
an aluminoxane. Aluminoxanes, or alumoxanes, are well
known in the art. They are typically prepared by
controlled hydrolysis of aluminium alkyls. Preferably
aluminoxanes are used which contain on average 2 - 10, in
particular 3 - 5, aluminium atoms per molecule.
Attractive results in the gas phase polymerization
process can be obtained with methyl aluminoxanes. Other
preferred aluminoxanes are alkyl aluminoxanes, in which
the alkyl groups have 2 - 6 carbon atoms and carry ~-
hydrogen atoms, in particular t-butyl groups. In
particular the latter are known from M.R. Mason et al.
(J. Am. Chem. Soc. 115 (1993) 4971).

2158239
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The quantity of aluminoxanes which can be used may
vary between wide limits. They are preferably used in a
quantity which contains per gram atom of Group VIII metal
10 - 4,000 gram atom aluminium, more preferably 100 -
2,000 gram atom aluminium.
As regards (c), the catalyst system of the invented
process is based on a source of ligands. It would appear
that the presence of two complexing sites in one ligand
molecule significantly contributes to the formation of
stable catalysts. It is thus preferred to use a ligand
containing at least two dentate groups which can complex
with the Group VIII metal. Although less preferred, it
is also possible to employ a monodentate ligand, i.e. a
compound which contains a single dentate group which can
complex with the Group VIII metal. Suitably a bidentate
ligand is used which contains two phosphorus-, nitrogen-
or sulphur containing dentate groups. It is also
possible to use a bidentate mixed ligand such as 1-
diphenylphosphino-3-ethylthiopropane.
A preferred group of bidentate ligands can be
indicated by the general formula
R1R2M1-R-M2R3R4 (I)
In this formula M1 and M2 independently represent a
phosphorus, arsenic or antimony atom, R1, R2, R3 and R4
independently represent a non-substituted or polar
substituted hydrocarbyl group, in particular of up to 10
carbon atoms, and R represents a divalent organic
bridging group containing 1 to 5 atoms in the bridge.
In the ligands of formula (I) M1 and M2 preferably
represent phosphorus atoms. R1, R2, R3 and R4 may
independently represent optionally polar substituted
alkyl, aryl, alkaryl, aralkyl or cycloalkyl groups.
Preferably at least one of R1, R2, R3 and R4 represents
an aromatic group, in particular an aromatic group
substituted by polar groups.

21~82~9
- 14 -
Suitable polar groups include halogen atoms, such as
fluorine and chlorine, alkoxy groups such as methoxy and
ethoxy groups and alkylamino groups such as methylamino-,
dimethylamino- and diethylamino groups. Alkoxy groups
and alkylamino groups contain in particular up to 5
carbon atoms in each of their alkyl groups.
If one or more of R1, R2, R3 and R4 represents a
substituted aryl group, preference is given to a phenyl
group substituted at one or both ortho positions with
respect to M1 or M2, with an alkoxy group, preferably a
methoxy group.
In the ligands of formula (I), R preferably
represents a divalent organic bridging group containing
from 2 to 4 bridging atoms, at least two of which are
carbon atoms.
Examples of suitable groups R are: -CH2-CH2-CH2-,
-cH2-si(cH3)2-cH2-/ -cH2-c(cH3)2-cH2-/ and
-CH2-CH2-CH2-CH2-. Preferably R is a trimethylene group.
Other suitable bidentate ligands are nitrogen
containing compounds of the general formula
xl x2
/ \ / \ (II)
N = C - C = N
wherein X1 and x2 independently represent organic
bridging groups each containing 3 or 4 atoms in the
bridge at least 2 of which are carbon atoms. There may
be an additional bridging group connecting the bridging
groups xl and X2. Examples of such compounds are 2,2'-
bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-di-
methoxy-2,2'-bipyridine, 1,10-phenanthroline, 4,7-
diphenyl-1,10-phenanthroline and 4,7-dimethyl-1,10-
phenanthroline. Preferred compounds are 2,2'-bipyridine
and 1,10-phenanthroline.
Again other suitable bidentate ligands are sulphur
containing compounds of the general formula

21~8239
-
- 15 -
R5S-Q-SR6 (III)
wherein R5 and R6 independently represent a non-
substituted or polar substituted hydrocarbyl group and Q
represents a bivalent bridging group containing 2 to 4
carbon atoms in the bridge. The groups R5 and R6 are
preferably alkyl groups, each having in particular up to
10 carbon atoms. Very suitable bis thio compounds are
1,2-bis(ethylthio)ethane and 1,2-bis(propylthio)ethene.
It is preferred to use as a monodentate ligand a
compound of the general formula
R7R8R9M3 (IV)
wherein M3 represents a phosphorus, arsenic or antimony
atom, each of R7, R8 and R9 independently represents a
non-substituted or polar substituted hydrocarbyl group,
such as n-alkyl groups and aryl groups, in particular
phenyl groups. Eligible substituents are alkoxy groups,
in particular having up to 5 carbon atoms, such as
methoxy and ethoxy groups. Preferred monodentate ligands
are tris(o-tolyl)phosphine, tris(o-
methoxyphenyl)phosphine, trinaphthylphosphine and tris(n-
butyl)phosphine.
The amount of bidentate ligand supplied may vary
considerably, but is usually dependent on the amount of
metal of Group VIII, present in the catalyst system.
Preferred amounts of bidentate ligands are in the range
of 0.5 to 8, preferably in the range of 0.5 to 2 moles
per gram atom of metal of Group VIII, unless the
bidentate ligand is a nitrogen bidentate ligand, in which
case the bidentate ligand is preferably present in an
amount of from 0.5 - 200 and in particular 1 - 50 moles
per gram atom of metal of Group VIII. The monodentate
ligands are preferably present in an amount of from 0.5 -
50 and in particular 1 - 25 moles per gram atom of metal
of Group VIII.
The stability of the catalyst system may be increased

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by incorporating a promoter therein. Suitably, an organic
oxidant promoter is used, such as a quinone. Preferred
promoters are selected from the group consisting of
benzoquinone, naphthoquinone and anthraquinone. The
amount of promoter is advantageously in the range of 1-
50, preferably in the range of 1 to 10 mole per gram atom
of metal of Group VIII. The catalyst activity can also
be maintained at a high level by feeding ~further)
organic oxidant during the polymerization, at a constant
or varying rate or intermittently.
Preferably in the process of the invention use is
made of a catalyst system, supported on a solid carrier,
usually in order to facilitate the introduction of the
catalyst system into the reactor. The invention also
relates to these supported catalysts compositions.
Suitable carrier materials may be inorganic, such as
silica, alumina or charcoal, or organic such as cellulose
or dextrose. Furthermore a polymer material may be used
as carrier, such as polyethene, polypropene or a co-
polymer such as a co-polymer of carbon monoxide with an
ethylenically unsaturated compound, for example linear
alternating co-polymers of carbon monoxide with ethene or
carbon monoxide with ethene and propene or butene-1.
When as regards (b) an aluminoxane is used it may be
attractive to employ commercially available supported
aluminoxane, for example methyl aluminoxane on silica.
The quantity of catalyst composition relative to the
quantity of carrier may vary between wide limits.
Preferred supported catalysts contain from 0.0002 -
0.001 gram atom of metal of Group VIII per kg of carrier
material, in particular 0.00005 - 0.005 gram atom of
metal of Group VIII per kg of carrier material, more in
particular 0.00001 - 0.010 gram atom of metal of Group
VIII per kg of carrier material.

`~ 21a8239
Conveniently the carrier is impregnated with a
solution of the catalyst system in a suitable solvent or
liquid diluent. It will be appreciated that the amount
of solvent or liquid diluent used is relatively small, so
that any excess thereof can easily be removed before or
during the initial stage of the co-polymerization
process. On the other hand it has been observed, that the
presence of a minor amount of liquid during the process
has a delaying effect on the deactivation rate of the
catalyst system, the quantity of liquid being so small
that the gas phase is the continuous phase during the
polymerization. The quantity of liquid is in particular
selected such that it is 20 - 80 % by weight, more in
particular 40 - 60 % by weight, of the quantity which is
sufficient to saturate the gas phase under the conditions
of the polymerization. Polar solvents are preferred,
such as lower alcohols, for example methanol and ethanol,
ethers such as diethylether or the dimethylether of
diethylene glycol (diglyme) and ketones such as acetone
and methylethylketone. An apolar solvent, such as
toluene, may also be used or the co-polymerization may
advantageously be carried out in the absence of a
solvent, in particular, when the catalyst composition
comprises a Group VIII metal which is covalently bonded
with a single hydrocarbyl or acyl group, such as in
[L2PdCH3+][B(C6Fs)4~] or [L2PdCOCH3+][B(C6Fs)4 ], in
which L represents a dentate group.
The amount of catalyst used in the process of the
invention may vary between wide limits. Recommended
amounts are in the range of 10-8 to 10-2, calculated as
gram atoms of metal of Group VIII, per mole of
ethylenically unsaturated compound to be co-polymerized
with carbon monoxide. Preferred amounts are in the range
of 10-7 to 10-3 on the same basis.

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Ethylenically unsaturated compounds suitably to be
used as monomers in the co-polymerization process of the
invention, include compounds consisting exclusively of
carbon and hydrogen and compounds which in addition
comprise hetero atoms, such as unsaturated esters.
Unsaturated hydrocarbons are preferred. Examples of
suitable monomers are lower a-olefins, i.e. olefins
containing from 2 to 6 carbon atoms, such as ethene,
propene and butene-1, cyclic olefins such as
cyclopentene, aromatic compounds, such as styrene and
alpha-methylstyrene and vinyl esters, such as vinyl
acetate and vinyl propionate. Preference is given to
ethene and mixtures of ethene with another a-olefin, such
as propene or butene-1.
Generally, the molar ratio between on the one hand
carbon monoxide and on the other hand the ethylenically
unsaturated compound(s), is selected in the range of 1:5
to 5:1. Preferably the molar ratio is in the range of
1.5:1 to 1:1.5, substantially equimolar ratios being
preferred most.
The co-polymerization process is usually carried out
at a temperature between 20 and 200 C, preferably at a
temperature in the range of 30 to 150 C. The reaction
is conveniently performed at a pressure between 2 and 200
bar, pressures in the range of 20 to 100 bar being
preferred.
The co-polymers obtained according to the invention
are suitable as thermoplastics for fibres, films or
sheets, or for injection moulding, compression moulding
and blowing applications. They may be used for
applications in the car industry, for the manufacture of
packaging materials for food and drinks and for various
uses in the domestic sphere.
The invention will be illustrated by the following
examples.

-- ` 21S~239
-- 19 --
Example 1
Gas phase co-polymerization of carbon monoxide and
ethene.
A catalyst solution was prepared as follows: 57.4 mg
(0.11 mmole) of 1,3-bis[bis(ortho-methoxy-
phenyl)phosphino]propane was dissolved in 2.5 ml of
tetrahydrofuran. After complete dissolution, the solution
was added to 22.0 mg ~0.10 mmole) of palladium (II)
acetate. Subsequently 17.5 ml of methanol was added and
the mixture was stirred during 1 hour, to form a clear
light brown solution. Subsequently 84.5 mg (0.25 mmole)
of purchased cobalt carborate (Co[B11CH12]2) and 33.4 mg
(0.22 mmole) of naphthoquinone (33.4 mg) was dissolved.
Of this solution 2.0 ml was taken and diluted with 2.0 ml
of methanol.
Of the resulting 4.0 ml of diluted catalyst solution
1 ml was charged to a 0.5 l autoclave, together with 8
gram of a dried, previously prepared terpolymer of carbon
monoxide, ethene and propene. The autoclave was equipped
with a fixed stirring device and an automatic pressure
relief.
Subsequently, the reactor was closed and pressurized
at 50 bar with nitrogen. The pressure was released and
the autoclave was purged twice with carbon monoxide, (6
bar), after which it was pressurized with carbon monoxide
(24 bar) and ethene (24 bar).
The contents of the reactor were heated to 90 C.
The supply of carbon monoxide/ethene feed (molar ratio
1:1) was started to maintain the pressure at 50 bar
absolute.
A solution of 111.3 mg of naphthoquinone in 100 ml of
methanol was added at a rate of 2.0 ml/mg palladium and
per hour, starting 0.5 hour after the beginning of the
reaction (defined as the moment that the temperature of
the reaction mixture reached 60 C).

- 2158239
- 20 -
The co-polymerization reaction was stopped by
automatic pressure relief after a reaction period of 5
hours. The product was recovered, dried overnight in a
vacuum oven under a nitrogen purge at 50 C and weighed.
The average polymerization rate was 18.3 kg co-
polymer/(g palladium.hour). The intrinsic viscosity
(Limiting Viscosity Number, LVN) of the co-polymer
obtained was 2.2 dl/g, calculated from determined
viscosity values, measured for different co-polymer
concentrations in m-cresol at 60 C.
Example 2
Example 1 was repeated with the difference that,
instead of cobalt carborate, 0.25 mmole purchased silver
carborate (Ag[BllCH12]) was used.
The average polymerization rate was 14.6 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained was 2.5 dl/g.
Example 3
Example 1 is repeated with the difference that,
instead of cobalt carborate, 0.25 mmole of nickel
carborate (Ni[BllCH12]2 is used.
The result is virtually the same as obtained in
Example 1.
Example 4 (for comparison)
Example 1 is repeated with the difference that,
instead of cobalt carborate, 0.5 mmole of para-
toluenesulphonic acid is used.
The average polymerization rate is between 3 and 4 kg
co-polymer/(g palladium.hour). The LVN of the co-polymer
obtained is approximately 2 dl/g.
Example 5
Example 1 was repeated with the differences (1) that
0.10 mmole of cobalt carborate instead of 0.25 mmole was
used, (2) that 0.10 mmole palladium chloride instead of
palladium acetate was used and (3) that prior to the

2158239
- 21 -
addition of the naphthoquinone the solution is filtered.
The average polymerization rate was 16.9 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained was 2.8 dl/g.
Example 6
Example 1 was repeated with the difference that 0.5
mmole of tris(perfluorophenyl)borane instead of cobalt
carborate was used.
The average polymerization rate was 8.4 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained was 3.0 dl/g.
Example 7 (for comparison)
Liquid phase co-polymerization of carbon monoxide and
ethene.
A catalyst solution was prepared as follows: 57.4 mg
(0.11 mmole) of 1,3-bis[bis(ortho-methoxy-
phenyl)phosphino]propane was dissolved in 2.5 ml of
tetrahydrofuran. After complete dissolution, the
solution was added to 22.0 mg (0.10 mmole) of palladium
(II) acetate. Subsequently 17.5 ml of methanol was added
and the mixture was stirred during 1 hour, to form a
clear light brown solution. Subsequently 84.5 mg
(0.25 mmole) of purchased cobalt carborate (Co[B11CH12]2)
was dissolved in the solution.
Of the resulting catalyst solution 1 ml was charged
to a 0.3 l autoclave, together with 170 ml methanol and
2.7 gram of a dried, previously prepared terpolymer of
carbon monoxide, ethene and propene.
Subsequently, the reactor was closed and pressurized
at 50 bar with nitrogen. The pressure was released and
the autoclave was purged twice with carbon monoxide, (6
bar), after which it was pressurized with carbon monoxide
(25 bar) and ethene (25 bar).
The contents of the reactor were heated to 90 C.
The supply of carbon monoxide/ethene feed (molar ratio

215~239
1:1) was started to maintain the pressure at 50 bar
absolute.
The co-polymerization reaction was stopped by
pressure relief after a reaction period of 5 hours. The
product was recovered, dried overnight in a vacuum oven
under a nitrogen purge at 50 C and weighed.
The average polymerization rate was 6.1 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained was 1.4 dl/g.
Example 8 (for comparison)
Example 7 was repeated with the difference that,
instead of cobalt carborate, 0.5 mmole of trifluoroacetic
acid was used.
The average polymerization rate was 7.1 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained was 1.5 dl/g.
Example 9 (for comparison)
Example 7 is repeated with the difference that,
instead of cobalt carborate, 0.5 mmole of para-toluene-
sulphonic acid is used.
The average polymerization rate is about 6 kg co-
polymer/(g palladium.hour). The LVN of the co-polymer
obtained is about 1.5 dl/g.
Examples 1 - 3, 5 and 6 show that in the gas phase
process an improved average polymerization rate and a
higher LVN of the prepared polymer, reflecting an
improved, higher molecular weight, can be obtained by
using an anion according to this invention, as compared
with a gas phase process in which para-toluenesulphonate
anions are used (Example 4). In Examples 1 - 3 cations
of cobalt, silver and nickel were present as well. In
Example 5 cations of cobalt were removed before the
polymerization was carried out. Example 7 shows that in
the slurry phase polymerizations the carborate anion of
the formula B11CH12- did not give an improvement of the

215~239
polymerization rate and LVN, compared with the use of
para-toluenesulphonate and trifluoroacetate anions
(Examples 8 and 9).
13C-NMR analysis showed that the polymers obtained in
Examples 1 - 9 had linear chains in which the monomer
units originating in carbon monoxide and the monomer
units originating in ethene were arranged in an
alternating order.