Process for grafting functions onto chlorinated (co)polymers, co

Details Process for grafting functions onto chlorinated (co)polymers, co Process for grafting functions onto chlorinated (co)polymers, co

1991-10-28

1993-11-30

Schofer, Joseph L.

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

525102, 5253307, 5253313, 5253314, 5253315, 525342, 525360, 525374, 525385, 525479, 526291, 526344, 526345, C08F 842, C08F 826, C08F 830, C08F 1406

Patent

active

052666379

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a process for grafting functions onto chlorinated polymers or copolymers, compositions and shaped objects.
The functionalization (or grafting of chemical functions) of thermoplastic polymers during implementation is an advantageous way of giving them new properties such as adhesion, the ability to fix colours in a non-reversible way or improving their compatibility with other polymers. It also allows the addition of photostabilizers or additives of organic or mineral origin such as fillers. Also it notably allows post-cross-linking.
The functionalization route for chlorinated polymers by copolymerization of functionalized monomers has major inconveniences such as the disturbance, of a chemical nature, of the polymerization processes leading to agglomeration processes and modification of particle morphology. This route generally requires the producers to prepare special batches as a function of the comonomer and of its content in the copolymer.
The functionalization route by photochemical route of poly(vinyl chloride) by electron bombardment or by gamma irradiation by subjecting the polymer to these radiations in the presence of a monomer such as, for example, hexyl-2-ethyl acrylate has the inconvenience of causing its degradation by the elimination of hydrogen chloride.
The chemical route by nucleophilic substitution reaction of the chlorine atoms of the chlorinated polymer by sulphurated compounds also has the inconvenience of rendering said copolymer very sensitive to UV radiations which initiate radical-like degradation reactions the initiation phase of which is the radical-like cutting of disulphide bridges which are always present as impurities in these compounds.
The grafting of alkoxysilane functions onto polyethylene or the copolymers of ethylene and an alkyl acrylate followed by their cross-linking by a condensation reaction of the alkoxysilanes in the presence of water is described in the literature, for polyethylene, for example, in the British Patent 1,286,460 or in the U.S. Pat. Nos. 4,291,136 or 4,328,323 for the copolymers of ethylene and an alkyl acrylate.
It is also known that alkoxysilane groups can be grafted onto polyvinyl chloride during implementation operations in the molten state in the presence either of an aminoalkoxysilane (GILBERT Polymer Communications Vol. 31, pages 194-197, 1990), or in the presence of mercaptoalkoxysilane (KELNAR and SCHATZ Preprints 31st Microsymposium sur les Macromolecules PVC Prague, Jul. 18/21, 1988). Once grafted, the polymer is cross-linkable in the presence of water. In the first case the basicity of the aminoalkoxysilane makes the polymer sensitive to degradation and in the second case, the presence of mercaptans makes the polymer sensitive to photochemical ageing.
The hydroxylation of ethylene--vinyl acetate copolymers during the extrusion phase by transesterification of the acetate groups in the presence of an alcohol is described in the literature.
On the other hand, the only route used up until now for the hydroxylation of chlorinated polymers or chlorinated (co)polymers such as for example polyvinyl chloride, is the copolymerization of vinyl chloride and functionalized vinyl monomers containing alcohol functions such as acrylic or methacrylic esters. Another possible route is the hydrolysis of acetate functions of a chlorinated (co)polymer and vinyl acetate but this hydrolysis cannot be carried out during a working operation such as extrusion, calendering, injection or coating.
It would be most useful to be able to functionalize the chlorinated polymers and copolymers and more particularly, in a non-limitative fashion, poly(vinyl chloride) with alkoxysilane functions either at the moment of implementing in the extrusion, calendering, coating or injection process and in the absence of a solvent, or by the dry-blend technique, or in suspension in an organic liquid, advantageously in a hydrocarbon controlling the functionalization rate as a function of the desired application.
It would also be very useful to be abl

REFERENCES:
patent: 3494905 (1970-02-01), Tyran
patent: 4291136 (1981-09-01), Keogh
patent: 4343917 (1982-08-01), Keogh
Chemical Abstracts, vol. 77, No. 14, Oct. 2, 1972, Columbus, Ohio, USA; J. Masoijdek: "Substitution reactions of poly(vinyl chloride)" ref. No. 88846D, see abstract & Chem. Listy 66(5), 458-78, (1972).

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