Patent GB-993434-A (GB)
Title: Production of block graft polymers from polyformaldehyde and other thermoplastics
Inventor: CRAUBNER HANS
IPC: C08G81/00
Filed: 1962-02-15
Abstract: Block graft polymers are obtained by intensely kneading a high molecular weight polyform-aldehyde with one or more other thermoplastic synthetic resins together with a free radical forming organic catalyst.  The components may be premixed in conventional mixing machines and kneaded at 100 DEG  to 210 DEG  C. in a machine providing shear stresses between 100 and 1.5 x 103 kg./sq. cm. and velocity gradients G between about 10 and 2000 seconds-1.  Specified other resins are polyamides from caprolactam, oenamtholactam, caprylolactam or the lactam of o -amino-lauric acid or from dicarboxylic acids such as adipic, suberic, sebacic or heptadecanedicarboxylic acid and diamines such as hexa-, octa-, deca-, or dodeca-methylene diamines, 1-4-diaminomethylbenzene, 1-4-diaminomethylcyclohexane and 4-41-diamino-dicyclohexylmethane or polyamide esters from dicarboxylic acids such as adipic, succinic, maleic or sebacic acids and aminoalcohols such as ethanolamine, 6-aminohexanol and 6-amino-2ethylhexanol or such dicarboxylic acids and mixtures of diols such as butanediol-1.4, hexanediol-1.6, octanediol-1.8 and decanediol-1.10, and diamines such as hexa-, octa- and deca-methylene diamine and also polyureas, polythioureas, polyurethanes, and polyesters, e.g. polyethylene glycol terephthalate, all of which may be prepared in the conventional way. Others specified are those from mono-and di-olefins, vinyl halides, derivatives of alphabeta unsaturated mono- and di-carboxylic acids, vinyl esters, vinyl ethers, heterocyclic compounds substituted by vinyl groups, vinyl aromatic compounds containing one benzene nucleus, and olefinically unsaturated aliphatic dicarboxylic acids, their amides and esters. Yet further resins specified are polyvinyl alcohols, chlorinated polystyrene, chlorinated polyvinyl chloride, sulphochlorinated polyethylene and polyethylene cross-linked by irradiation. Catalysts specified are cumene hydroperoxide, dicumyl peroxide, t.-butylhydroperoxide, di-t.-butyl peroxide, 2-5-di-t.-butyl-peroxy-2-5-dimethylhexane, dibenzoyl peroxide, lauroyl peroxide, t.-butylperbenzoate, azo-bis-isobutyro-nitrile and azodisulphonates.  These catalysts may be used in the form of their solutions in solvents such as benzene, toluene, xylenes, dioxane, cyclohexane, methanol, dimethylformamide, carbon tetrachloride and water.  Pigments, fillers, dyes and stabilizers may also be present. Examples are given of intensive kneading of mixtures of polyformaldehyde with (1) polyethylene and di-t.-butyl peroxide, (2) polypropylene and (a) cumene hydroperoxide, (b) dicumyl peroxide and (c) di-t.-butyl peroxide, (3) polycaprylolactam and (a), (b) and (c) above, (4) polyethylene, a polyamide from caprylolactam (20 parts) and the salt of 4-41-diaminodicyclohexylmethane and heptadecanedicarboxylic acid (80 parts) and di-t.-butyl peroxide, (5) styrene (74)-acrylonitrile (26) copolymer and di-t.-butyl peroxide, and (6) polypyrrolidone, dicumyl peroxide and hexamethylene diisocyanate.  The block graft polymers may also be mixed with polyformaldehyde or with the above-mentioned synthetic resins.  In examples: (1) the block graft polymer of Example (1) is mixed with (a) 90 parts (to 10 block) and (b) 99 parts (to 1 block) high-pressure polyethylene, (2) (a) 10 parts of a block graft polymer from 10 parts polyformaldehyde and 90 parts polypropylene are mixed with 90 parts polyethylene (high-pressure), (b) as for (a) replacing the 90 polyethylene with 90 polypropylene, (3) (a) 20 parts of a block graft polymer from 5 parts polyformaldehyde and 95 parts polycaprylolactam are mixed with 80 parts polyformaldehyde, (b) 30 parts of the block graft polymer from 25 parts polyformaldehyde and 75 parts polycaprylolactam are used with 70 parts of polyformaldehyde.  Specifications 919,098, 927,968 and French Specification 1,307,186 are referred to.