Functionalized carbon monoxide copolymers

Details Functionalized carbon monoxide copolymers Functionalized carbon monoxide copolymers

1999-12-13

2001-09-04

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...

C528S086000, C528S205000, C502S202000, C502S208000, C502S230000

Reexamination Certificate

active

06284868

ABSTRACT:

The present invention relates to functionalized linear alternating carbon monoxide copolymers of carbon monoxide and at least one 1-alkene (A), wherein compound (A) is an aryl derivative substituted with at least one terminal allyl and/or homoallyl moiety and containing one or more polar groups, with the proviso that 4-allylanisole is excluded.
The invention further relates to functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A) and at least one C
2
-C
10
-1-alkene (B).
In addition, the invention relates to processes for preparing functionalized linear alternating carbon monoxide copolymers of carbon monoxide, 1-alkenes (A) and, if desired, 1-alkenes (B) and to the use of the carbon monoxide copolymers for the preparation of sheets, films, moldings and coatings.
Given that a multiplicity of ways are known for making binary and ternary carbon monoxide copolymers (cf. E. Drent, P. H. M. Budzelaar, Chem. Rev. 1996, 96, 663-681), recent work has been directed to the extension or controlled modification of the property profile of conventional carbon monoxide copolymers by process or product modifications. One possibility is, for example, the incorporation of long-chain &agr;-olefin units in the carbon monoxide copolymer framework giving copolymers having comparatively low glass transition temperatures (T
g
), as shown by Rieger et al. (Macromolecules 1996, 29, 4806).
Sen et al. (Macromolecules 1996, 29, 5852-5858) describe the preparation of chiral, functionalized polyketones of carbon monoxide and various linear &agr;-olefins having a hydroxyl or carboxyl group in &ohgr;-position. Satisfactory yields and molecular weights M
w
, however, have only been obtainable using the chiral dicationic complex [Pd((R,R)—(CH
3
)-DUPHOS)(CH
3
CN)
2
](BF
4
)
2
([(R,R)—(CH
3
)-DUPHOS]=(−)-1,2-bis((2R,5R)-2,5-dimethyl-phospholano)benzene). This complex cannot, however, be prepared in a chemically trivial manner and does not make it possible to obtain functionalized carbon monoxide copolymers in an economical way. Furthermore, the abovementioned chiral complexes give polymer products which have a high degree of order and are thus obtained crystalline in most cases. The associated poor solubility characteristics are disadvantageous with regard to reaction control, work-up and further processing or an industrial scale in particular. The success of the catalyst system described by Sen et al. is attributed to the bulky bidentate chelating ligand which prevents the undesirable blocking of the metal coordination sphere by functional groups. The copolymerization of carbon monoxide with 4-allylanisole yielded, for example, a product mixture comprising an alternating 1,4-copolymer and a copolymer having spiroketal units incorporated in a regular manner.
As disclosed in EP-A 0 463 689, the functional group present in a monomer should not be too close to a terminal double bond, because otherwise little or no copolymerization will be observed. Using known catalyst systems, for example based on palladium(II) acetate, 1,3-bis(diphenylphosphino)propane and copper p-tosylate, however, the preparation of functionalized carbon monoxide copolymers is said to be successful when the functional group is not directly attached to the terminal double bond system and at least one alkylene bridge is interposed. Functionalized carbon monoxide copolymers having molecular weights M
w
>1000, in particular >5000 g/mol, however, are only obtained on using a special bidentate bridging phosphine ligand having only aliphatic substituents on the phosphorus atoms, e.g. 1,3-bis(di-n-butyl-phosphino)propane.
It would therefore be desirable to be able to obtain carbon monoxide copolymers of carbon monoxide and &agr;-olefins having one or more functional units adjacent to the terminal double bond by processes which are unproblematical on an industrial scale and by using easily obtainable catalyst systems.
It is an object of the present invention to provide functionalized carbon monoxide copolymers having high molecular weights using easily obtainable catalyst systems and straightforward processes in good yields.
We have found that this object is achieved by functionalized linear alternating carbon monoxide copolymers of carbon monoxide and at least one 1-alkene (A), wherein compound (A) is an aryl derivative substituted with at least one terminal allyl and/or homoallyl moiety and containing one or more polar groups, with the proviso that 4-allylanisole is excluded.
Furthermore, we have found functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A) and at least one C
2
-C
10
-1-alkene (B).
Furthermore, we have found processes for the preparation of functionalized linear alternating carbon monoxide copolymers and their use for the preparation of sheets, films, moldings and coatings.
Copolymers of the present invention are made up of units which are derived from the monomers carbon monoxide and one or more olefinically unsaturated compounds.
In the binary copolymers of the present invention, the different monomer units are generally present in strictly alternating order. In the ternary and higher copolymer systems, the order of carbon monoxide and olefin components is generally likewise strictly alternating, with the functionalized &agr;-olefins being incorporated into the linear copolymer chain essentially randomly with regard to the possible olefin unit positions.
Suitable &agr;-olefinically unsaturated compounds (A) for the binary and higher copolymers of the invention are in principle aryl derivatives substituted with at least one terminal allyl and/or homoallyl moiety and containing one or more polar groups, except that 4-allylanisole is excluded for binary systems.
Functionalized &agr;-olefins or 1-alkenes (A) used are preferably compounds of the formula (Ia) or (Ib)
where
X is OR
1
, NR
2
R
3
, halo, such as fluoro, chloro, bromo, iodo, nitro or CO
2
R
4
where
R
1
is hydrogen, linear and branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, C
3
-C
10
-cycloalkyl, preferably C
3
-C
6
-cycloalkyl, such as cyclopropyl or cyclohexyl, C
6
-C
14
-aryl, preferably C
6
-C
10
-aryl, especially phenyl, C(O)R
5
or Si(R
6
)
3
where
R
5
is linear and branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, or C
6
-C
14
-aryl, preferably C
6
-C
10
-aryl, especially phenyl,
R
6
is independently of each appearance linear or branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, C
3
-C
10
-cycloalkyl, preferably C
3
-C
6
-cycloalkyl, such as cyclopropyl or cyclohexyl, or C
6
-C
14
-aryl, preferably C
6
-C
10
-aryl, especially phenyl,
R
2
, R
3
are each hydrogen, linear or branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, C
3
-C
10
-cycloalkyl, preferably C
3
-C
6
-cycloalkyl, such as cyclopropyl or cyclohexyl, or C
6
-C
14
-aryl, preferably C
6
-C
10
-aryl, especially phenyl, or are, together with N, a saturated or unsaturated cycle consisting of 2-10 carbon atoms, preferably 4-6 carbon atoms, such as pyrrole, pyrrolidine or pyrrolidinone, or a cycle consisting of 2-10 carbon atoms, preferably 4-6 carbon atoms, and at least one further hetero atom such as nitrogen or oxygen in the cycle, for example morpholine,
R
4
is linear or branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, or C
6
-C
14
-aryl, preferably C
6
-C
10
-aryl, especially phenyl,
Y is a compound of the formula (II)
CH
2
=C(R
7
)(C(R
8
)
2)q)
—  (II),
where
R
7
is hydrogen, linear or branched C
1
-C
10
-alkyl, preferably C
1
-C
6
-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially me

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