Multilayer, fluorine-containing polymeric material

Coating processes – Interior of hollow article coating – Coating by vapor – gas – mist – or smoke

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4272481, 4272554, 428409, 428421, 428422, 5253261, 5253264, B05D 722

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active

058827285

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a polymeric material consisting of at least two layers and comprising at least one fluorine-containing layer, and at least one non-fluorine-containing layer, wherein the fluorine-containing layer is from 0.01 to 100 .mu.m thick, contains from 0.1 to 0.76 g of fluorine/g of the fluorine-containing layer and has from 561 .mu.g to 50 mg of fluorine/cm.sup.2.
The fluorination of different articles for producing a fluorine-containing layer on these articles is known. The fluorine-containing layer of these moldings and films has in many cases a certain barrier action against the penetration of volatile substances.
For example, in order to prevent the permeation of fuels through plastic tank walls, the plastic fuel tanks are fluorinated.
DE-C 36 40 975, DE-C 26 44 508, DE-C 35 23 137, DE-C 42 12 969, DE-A 36 40 975, DE-B 19 05 094, DE-C 24 01 948 and U.S. Pat. No. 2,811,468 describe the fluorination of polymeric moldings, films and other articles.
However, the processes used for this purpose and the barrier action of the fluorinated layers are unsatisfactory.
DE-B 19 05 094 describes storage containers for fuel whose container wall has from 0.01 to 30 .mu.g of fluorine/cm.sup.2 of wall.
U.S. Pat. No. 2,811,468 cited above describes a fluorinated polyethylene film whose fluorine content is so high that it is virtually impermeable to atmospheric gases, but whose fluorine content does not exceed 3.5% by weight.
However, the barrier action of the fluorinated articles, described in the literature cited at the outset, against organic chemical compounds is unsatisfactory.
On the basis of the present state of knowledge, it may be assumed that the chemical structure of the surface layer obtained by fluorination plays a decisive role in determining the permeability of this layer or in other words its barrier action against relatively small molecules. On the other hand, it is not possible to predict or even to plan the methods by means of which precisely the adequate or optimum quality of the barrier layer can be obtained.
It is an object of the present invention to remedy the deficiencies described; in particular, it is intended to reduce the permeability of the fluorine-containing polymeric materials to relatively small molecules.
We have found that this object is achieved by the polymeric materials defined at the outset. We have also found a process for the preparation of the novel polymeric materials, the use of the novel polymeric materials as permeation barrier, the use of the novel materials for the production of films, fibers and moldings and the fibers, films and moldings comprising the novel polymeric materials.
The novel multilayer fluorine-containing polymeric materials are obtained by the novel process, by the fluorination of polymers.
Polymers suitable for this purpose are in general those which are not completely degraded in the reaction with the fluorinating agent under the novel conditions. For the purposes of the present invention, not completely degraded means that the polymer is not destroyed by the fluorination process, for example by decomposition into useless fragments.
Suitable polymers generally have carbon-hydrogen bonds, some or all of which can be replaced by carbon-fluorine bonds during the fluorination process.
Examples of suitable polymers of this type are all plastics which can be processed by thermoplastic methods, for example polyesters, polyethers, polyetherketones, polyamides, polystyrenes and polyolefins.
Polyolefins, for example homopolymers of propylene, copolymers of propylene with C.sub.2 -C.sub.4 -.alpha.-olefins, homopolymers of ethylene, copolymers of ethylene with C.sub.3 -C.sub.8 -.alpha.-olefins or .alpha.,.beta.-unsaturated carboxylic acids or derivatives thereof, are particularly suitable. Ethylene polymers having a density of from 0.890 to 0.968 g/cm.sup.3, in particular HDPE having a density of from 0.940 to 0.962 g/cm.sup.3, are preferably used.
Such polyolefins are prepared by the known polymerization methods. These are, for example, the l

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