Method for the production of olefin/carbon monoxide copolymers

Details Method for the production of olefin/carbon monoxide copolymers Method for the production of olefin/carbon monoxide copolymers

2002-01-10

2003-12-30

Acquah, Samuel A. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymer of an ethylenically unsaturated reactant with a...

C526S066000

Reexamination Certificate

active

06670443

ABSTRACT:

The present invention relates to a process for preparing linear, alternating carbon monoxide copolymers, in which at least one olefinically unsaturated compound having from two to twenty carbon atoms (component K1) and carbon monoxide are copolymerized.
Linear, alternating copolymers made from carbon monoxide and olefinically unsaturated compounds, for which the abbreviated terms carbon monoxide copolymers or polyketones are also used, are known. High-molecular-weight semicrystalline polyketones with a strictly alternating sequence of the monomers in the main chain, for example, generally have high melting points, good heat resistance, good chemicals resistance, good barrier properties with respect to water and air, and also advantageous mechanical and rheological properties.
Of particular industrial interest are polyketones made from carbon monoxide and two olefins, generally &agr;-olefins, for example carbon monoxide-ethene-propene copolymers, carbon monoxide-ethene-1-butene copolymers, carbon monoxide-ethene-1-hexene copolymers, carbon monoxide-propene-1-butene copolymers and carbon monoxide-propene-1-hexene copolymers.
There are known transition-metal-catalyzed processes for preparing polyketones. For example, EP-A 0 121 965 describes the use of a cis-palladium complex [Pd(Ph
2
P(CH
2
)
3
PPh
2
)](OAc)
2
(Ph=phenyl, Ac=acetyl) chelated with bidentate phosphine ligands. The copolymerization of carbon monoxide may be carried out in suspension, as described in EP-A 0 305 011, or in the gas phase, for example as in EP-A 0 702 045. Frequently used suspension media are low-molecular-weight alcohols, in particular methanol (see also EP-A 0 428 228), and nonpolar or polar aprotic liquids, such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 and EP-A 0 590 942). Another known reaction medium is water (see Jiang and Sen, Macromolecules, 1994, 27, pp. 7215-7216, and Verspui et al., Chem. Commun., 1998, pp. 40-402). Besides the use of water-soluble catalysts in the polyketone preparation processes carried out in an aqueous medium it is also possible to use solubilizers or to use hydroxyl compounds which act as an activator.
Compounds which have proven to have good suitability for said polymerization processes are in particular complexes with bisphosphine chelating ligands, where the radicals on the phosphorus are aryl groups or substituted aryl groups. Accordingly, particularly frequently used chelating ligands are 1,3-bis(diphenylphosphino)propane and 1,3-bis[di(o-methoxyphenyl)phosphino]propane (see also Drent et al., Chem. Rev., 1996, 96, pp. 663-681). In said cases the carbon monoxide copolymerization is usually carried out in the presence of acids.
A common feature of the said processes is that either the entire amount of the starting materials, carbon monoxide and olefins, forms the initial charge prior to the start of the polymerization or individual starting materials or all of the starting materials are metered in continuously during the polymerization.
When the process is conducted continuously, one or more of the starting materials are metered in for the entire duration of the polymerization. This gives copolymers composed predominantly of units built up from carbon monoxide and the fastest-reacting olefin and containing essentially a smaller proportion of units which have been built up from carbon monoxide and slower-reacting olefins. The various carbon monoxide-olefin units have a random distribution in the polymer (Drent et al., Chem. Rev., 1996, 96, pp. 663-681, Rieger et al., Macromol. Chem. Phys. 1997, 198, pp. 1197-1208 and Barsacchi et al., Macromolecules, 1992, 25, pp. 3604-3606).
If the entire amount of all of the starting materials forms an initial charge prior to the polymerization (batch process) the copolymers obtained have molecules initially built up practically exclusively from units which are formed from carbon monoxide and the fastest-reacting olefin, e.g. generally from the olefin with the smallest number of carbon atoms. Only when the fastest-reacting olefin has been consumed do the macromolecules begin to incorporate significant numbers of units composed of carbon monoxide and other olefins. This means that, for example, two olefins with very different reactivities processes of this type can therefore only give block copolymers whose macromolecules are composed specifically of two different blocks (see, for example, EP-A-429 105).
A common feature of the continuous and the batch processes is that only relatively low incorporation rates of slower-reacting olefins can be achieved. Polyketones obtained in this way therefore have properties which are only slightly better than those of polyketones merely built up from carbon monoxide and a single olefin.
Contrasting with said batch and continuous processes for preparing polyketones, EP-A-619 334 discloses a process which can achieve high incorporation rates of different olefins into a terpolymer. However, this process is complicated and the yields are low. The polymers obtainable are composed of macromolecules again built up from only at most two differing blocks.
It is an object of the present invention, therefore, to provide polyketone preparation processes which, with high catalyst activity and with the associated productivity, ensure high incorporation rates for both fast- and for slow-reacting olefins. A further object was to find polyketones which have high molecular weights and contain, besides carbon monoxide, high proportions of different olefins. The thermal and mechanical performance of these polyketones should be better than that of known carbon monoxide copolymers. In particular the polyketones should have high elasticity.
We have found that this object is achieved by a process for preparing linear, alternating carbon monoxide copolymers, in which at least one olefinically unsaturated compound having from two to twenty carbon atoms (component K1) and carbon monoxide are copolymerized in the presence of
a) metal complexes of the formula (I)
 where:
G is a carbocyclic ring system having 5, 6 or 7 atoms, with or without one or more hetero atoms, —(CR
b
2
)
r
—, —(CR
b
2
)
s
—Si(R
a
)
2
—(CR
b
2
)
t
—, —A—O—B— or —A—Z(R
5
)—B—, where
R
5
is hydrogen, C
1
-C
28
-alkyl, C
3
-C
14
-cycloalkyl, C
6
-C
15
-aryl or alkylaryl having from 1 to 20 carbon atoms in the alkyl radical and from 6 to 15 carbon atoms in the aryl radical, —N(R
b
)
2
or —Si(R
a
)
3
, where said radicals may also have substitution,
A, B are —(CR
b
2
)
r′
—, —(CR
b
2
)
s
—Si(R
a
)
2
—(CR
b
2
)
t
—, —N(R
b
)—, or a constituent having r′—, s—or t— atoms in a ring system, or, together with Z, are a constituent having (r′+1), (s+1) or (t+1) atoms in a heterocycle,
R
a
, independently of one another, are C
1
-C
20
-alkyl, C
3
-C
10
-cycloalkyl, C
6
-C
15
-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl moiety and from 6 to 15 carbon atoms in the aryl moiety, where said radicals may also have substitution,
R
b
is as R
a
, or hydrogen or Si(R
a
)
3
,
r is 1, 2, 3 or 4,
r′ is 1 or 2,
s, t are 0, 1 or 2, where 1≦s+t≦3,
Z is a nonmetallic element from group 15 of the Periodic Table,
M is a metal selected from the class consisting of groups 8 to 12 of the Periodic Table,
E
1
, E
2
are nonmetallic elements from group 15 of the Periodic Table,
R
1
to R
4
are linear or branched C
1
-C
28
-alkyl, C
3
-C
14
-cycloalkyl, C
6
-C
15
-aryl or alkylaryl having from 1 to 28 carbon atoms in the alkyl moiety and from 6 to 15 carbon atoms in the aryl moiety, where said radicals may also have substitution,
L
1
, L
2
are formally charged or neutral ligands,
X are formally mono- or polyvalent anions,
p is 0, 1, 2 or 3,
m, n are 0, 1, 2 or 3,
where p=m×n,
b) if desired, a protonic or Lewis acid, and
c) if desired, a hydroxyl compound,
which comprises metering into the copolymerization, as it proceeds, at least one olefinically unsaturated compound having from two to twenty carbon atoms (component K2, ≠component K1)

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