Patent GB-964221-A (GB)
Title: Improvements in the production of vinylidene chloride copolymers
IPC: C08J7/052
Filed: 1962-06-07
Abstract: Vinylidene chloride copolymers are prepared by a process which comprises polymerizing 80-97% of vinylidene chloride with 3-20% of a monoolefinic material copolymerizable therewith in the presence of 0.1 to 20% based on the weight of monomers of at least one compound having a nucleus of the following structure: <PICT:0964221/C3/1> Specified compounds are d-limonene,a -pinene, dipentene, dimethyl butenyl phthalic anhydride, a -terpinene, terpinolene and terpineol. Many suitable comonomers are listed including esters of acrylic, methacrylic and chloracrylic acids, nitriles, amides, vinyl esters, vinyl ketones, vinyl and allyl ethers, vinyl aromatic compounds, maleic anhydride, maleic and fumaric esters, halogen substituted olefins and vinyl heterocyclic compounds. The polymerization may be effected in the presence of catalysts, e.g. hydrogen peroxide, persalts, organic peroxides, azines and ketazines, optionally activated with reducing agents and salts of iron, manganese or cobalt; in aqueous media in the presence of emulsifiers, e.g. sodium, ammonium or amine salts of alkylaryl sulphonates, sulphonated fatty alcohols, sulphonated paraffin oils and long chain fatty acids, quaternary ammonium compounds and salts of half amides of dibasic acids. Examples describe the polymerization of vinylidene chloride, methyl acrylate and itaconic acid in aqueous media in the presence of sodium lauryl sulphate using catalyst systems comprising (1 and 5 to 15) ammonium persulphate, sodium metabisulphite and ferrous ammonium sulphate; (2) ammonium persulphate, sodium toluene sulphinate and ferrous ammonium sulphate; (3) hydrogen peroxide and ferrous ammonium sulphate and (4) azo-di-isobutyronitrile; and in the presence of (1 to 6 and 13) d-limonene, (7 and 8) dipentene, (9 and 15) a -pinene and (10 to 12 and 14) dimethyl butenyl phthalic anhydride.  The copolymers may be dissolved in organic solvents, e.g. toluene-tetrahydrofuran mixtures, and coated on flexible substrates, e.g. films of regenerated cellulose, cellulose derivatives, polyesters, polyolefins and polyamides, and paper. Specifications 545,523, 593,947 and 684,105 are referred to.ALSO:Flexible substrates, particularly regenerated cellulose films, may be coated with vinylidene chloride copolymers prepared by copolymerizing 80-97% of vinylidene chloride with 3-20% of a monoolefinic material copolymerizable therewith in the presence of 0,1-20% by weight of the monomers of at least one compound having a nucleus of the following structure:  <FORM:0964221/B1-B2/1> Other substrates specified are cellulose esters and ethers, polyesters, polyolefins, polyamides and paper, and the copolymers may be applied from solutions in organic solvents, e.g. mixtures of toluene and tetrahydrofuran, by dipping, brushing or spraying. Specified compounds are d-limonene, a -pinene, dipentene, dimethyl butenyl phthalic anhydride, a -terpinene, terpinolene and terpineol.  Many suitable comonomers are listed including acrylic and methacrylic acids esters, amides and nitriles, chloracrylic esters, itaconic acid, maleic anhydride, maleic and fumaric esters, vinyl esters, vinyl ketones, vinyl and allyl ethers, vinyl aromatic compounds, halogen substituted olefins and vinyl heterocyclic compounds.  Examples describe the coating of regenerated cellulose film with toluene/tetrahydrofuran solutions of copolymers prepared by copolymerizing vinylidene chloride, methyl acrylate and itaconic acid in the presence of (1 and 5) d-limonene, (14) dimethyl butenyl phthalic anhydride, and (15) a -pinene.  The products may be used as heat sealable packaging materials for food and cigarettes. Specifications 545,523, 593,947 and 684,105 are referred to.