Thermoplastic elastomer carbon monoxide/olefin copolymers

Details Thermoplastic elastomer carbon monoxide/olefin copolymers Thermoplastic elastomer carbon monoxide/olefin copolymers

1999-05-12

2001-06-26

Acquah, Samuel A. (Department: 1711)

Stock material or miscellaneous articles

Coated or structually defined flake, particle, cell, strand,...

Rod, strand, filament or fiber

C528S392000, C502S152000, C502S154000, C502S162000, C502S168000, C502S170000

Reexamination Certificate

active

06251518

ABSTRACT:

The present invention relates to linear, thermoplastic, elastomeric copolymers of carbon monoxide and at least one olefinic C
7
- to C
20
-monomer, which have an average molecular weight M
w
greater than 15,000 g/mol and a T
g
-value of less than −20° C.
The present invention furthermore relates to linear, thermoplastic, elastomeric copolymers of carbon monoxide, at least one olefinic C
2
- to C
4
-monomer and at least one olefinic C
6
- to C
20
-monomer, which have an average molecular weight M
w
greater than 40,000 g/mol and a T
g
-value of less than 20° C.
The present invention also relates to processes for the preparation of such copolymers, the use of the copolymers for the production of fibers, films, moldings and coatings and to fibers, films, moldings and coatings obtainable from the copolymers.
Carbon monoxide/ethylene copolymers and carbon monoxide/ethylene/propylene terpolymers have very recently attracted interest as engineering plastics for the production of articles having a relatively high melting point, for example gearwheels. As a rule, carbon monoxide copolymers with ethylene as comonomer are very hard and brittle and have poor impact strength or none at all, so that they are unsuitable for many applications in which these properties are desirable.
U.S. Pat. No. 5,352,767 describes alternating, elastomeric copolymers of carbon monoxide and &agr;-olefins, which are prepared with the aid of a catalyst system which contains cationic metal complexes of group VIIIB of the Periodic Table of Elements and activators based on primary and secondary alcohols.
However, the carbon monoxide/propylene, carbon monoxide
-butene or carbon monoxide
-hexene copolymers described in said U.S. patent do not have thermoplastic elastomeric properties even at average molecular weights M
w
of up to 50,000 and are therefore unsuitable for applications as engineering materials.
According to German Patent Application 196 10 358.4, it is known that the elastomer properties of said copolymers improve with increasing molecular weight. These copolymers are industrially usable in general only at average molecular weights M
w
in the region of 80,000 g/mol or higher. However, it would be desirable to be able to realize wide industrial use even in the case of lower molecular weights without, for example, having to accept disadvantages with regard to the processability.
It is an object of the present invention to provide copolymers of carbon monoxide and olefinic monomers, which copolymers have said disadvantages only to a minor degree if at all and can be prepared economically on an industrial scale.
We have found that this object is achieved by linear, thermoplastic, elastomeric copolymers of carbon monoxide and at least one olefinic C
7
- to C
20
-monomer, which have an average molecular weight M
w
greater than 15,000 g/mol and a T
g
-value of less than −20° C.
We have also found linear, thermoplastic, elastomeric copolymers of carbon monoxide, at least one olefinic C
2
- to C
4
-monomer and at least one olefinic C
6
- to C
20
-monomer, which have an average molecular weight M
w
greater than 40,000 g/mol and a T
g
-value of less than 20° C.
We have also found processes for the preparation of linear, thermoplastic, elastomeric copolymers of carbon monoxide and olefinic monomers and the use of the copolymers for the production of fibers, films, moldings and coatings and the fibers, films, moldings and coatings obtainable thereby.
The novel copolymers are composed of units which are based on the monomers carbon monoxide and one or more olefinically unsaturated compounds, ethylene, propylene, 1-butene, 1-pentene and 1-hexene being excluded in binary copolymers.
As a rule, the different monomer units strictly alternate in the novel binary copolymers. In the case of the ternary and higher copolymer systems, the sequence of carbon monoxide and olefin components is as a rule likewise strictly alternating, the relatively long-chain C
6
- to C
20
-alkene monomers being incorporated essentially randomly in the linear copolymer chain, with regard to the suitable positions for incorporating olefins.
Suitable olefinically unsaturated compounds are in principle all monomers of this class of compounds.
C
7
- to C
20
-alkenes, in particular C
7
- to C
20
-alk-1-enes, for example 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene, are preferably contained in binary carbon monoxide copolymers. C
8
- to C
20
-alk-1-enes are particularly preferably used.
The average molecular weights M
w
of the novel binary carbon monoxide copolymers are usually from 15,000 to 50,000 g/mol, but it is also possible to obtain copolymers having molecular weights of up to 70,000, 100,000 or even 300,000 g/mol.
In the case of average molecular weights M
w
(measured by the gel permeation chromatography (GPC) method at 25° C. using Microstyragel (Waters) as column material and chloroform as solvent against a polystyrene standard) greater than 15,000 g/mol, T
g
-values of less than −20° C. are achieved with the novel binary copolymers. The binary copolymers preferably have T
g
-values of less than −30° C. Depending on the choice of the olefinic comonomer, even T
g
-values in the region of −60° C. are obtained. The melting points of these copolymers are usually from −7 to 45° C. Novel copolymers of carbon monoxide and relatively long-chain olefinic monomers, such as 1-octadecene and 1-eicosene, have two melting points, indicating semicrystalline segments in the region of the nonpolar side chains along the linear copolymer chain. By incorporating
13
CO into binary copolymers with, for example 1-eicosene as an olefin component, it was found that more than 50% of the novel copolymer chains are linked regioselectively head-to-tail.
Suitable olefinic C
6
- to C
20
-monomers for non-binary copolymers, in particular ternary copolymers, of carbon monoxide, an olefinic C
2
- to C
4
-monomer and an olefinic C
6
- to C
20
-monomer are in particular C
6
- to C
20
-alk-1-enes, for example 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicosene. 1-Octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene are preferably used. 1-Octadecene and 1-eicosene are particularly preferred. Preferably used olefinic C
2
- to C
4
-monomers are propylene and buty-1-ene, in particular propylene.
In addition to the abovementioned alkenes, suitable olefinically unsaturated compounds are conjugated or isolated C
6
- to C
20
-dienes, for example 1,4-hexadiene and 1,5-hexadiene.
Carbon monoxide/propylene/C
6
- to C
20
-alk-1-ene terpolymers, such as carbon monoxide/propylene/1-decene, carbon monoxide/propylene/1-dodecene, carbon monoxide/propylene/1-hexadecene-, carbon monoxide/propylene/1-octadecene and carbon monoxide/propylene/1-eicosene terpolymers, are preferred. The content of structural units which is based on propylene in the carbon monoxide/propylene/C
6
- to C
20
-terpolymers is in general from 0.1 to 70, preferably from 5 to 60, in particular from 10 to 50, mol %, based on the terpolymer. Particularly suitable terpolymers having these propylene contents are carbon monoxide/propylene/1-octadecene and carbon monoxide/propylene/1-eicosene terpolymers.
The novel terpolymers have, as a rule, an average molecular weight M
w
greater than 40,000 g/mol and a T
g
-value of less than 20° C., preferably less than −10° C. Terpolymers having an average molecular weight M
w
up to 70,000, 170,000, 300,000 and even 500,000 g/mol are also obtainable.
The novel bindery carbon monoxide copolymers and the carbon monoxide/propylene terpolymers are, for example, readily soluble in tetrahydrofuran, toluene, dichloromethane and chloroform.
The molar ratio of carbon monoxide to the sum of the structural units based on the olefinically unsaturated monomers in the novel binary and higher carbon monoxide copolymers is in general 1:1.
The novel copolymers have thermoplastic elastomeric properties.
The molecular weight distribution M

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