Patent GB-389108-A (GB)
Title: Reduction compounds of non-benzenoid acetylene polymers and methods of preparing thesame
IPC: C07C5/02
Filed: 1931-05-30
Abstract: Nonbenzenoid acetylene polymers, particularly mono- and di-vinylacetylene (cf. Specification 384,654), or the polymerization products of those polymers (cf. Specification 384,655), are converted into less unsaturated products by treatment with hydrogen in the presence of a hydrogenation catalyst; the complete conversion of divinylacetylene into hexane is excluded.  Hydrogenation may be effected in the vapour or liquid phase at 15-150 DEG  C. and 2-10 atm. pressure in the presence or absence of an inert gas or vapour, e.g. nitrogen, carbon dioxide, dry steam, or ethyl alcohol vapour, or of a solvent; specified solvents are acetic acid; acetone, methyl, ethyl, propyl, isopropyl, butyl or isobutyl alcohol; methyl, ethyl, propyl or butyl acetate; methyl, ethyl or butyl butyrate; mixtures of water with methyl or ethyl alcohol, acetone, or acetic acid; benzene; toluene; xylene; tetra- and deca-hydronaphthalene; cyclohexane; methylcyclohexane; cyclohexanol; pentane; hexane; heptane and octane. Specified catalysts are platinum (including reduced platinum black); palladium (including palladium black or colloidal palladium); osmium; nickel; cobalt; copper; nickel or kieselguhr, alumina or silica; nickel and chromium; and nickel and copper.  In the examples, (1) the hydrocarbon C8H8, described in Specification 384,654, is hydrogenated in decahydronaphthalene in the presence of platinum oxide, yielding octane; (2) a mixture of hydrogen and monovinylacetylene is passed over a nickel catalyst at 80-150 DEG  C., yielding a mixture of butane, butylene, butadiene, and ethylacetylene; (3) an oily polymerization product of divinylacetylene is hydrogenated in benzene in the presence of platinum oxide; (4) a resinous polymerization product of divinylacetylene is hydrogenated as in example 3; (5) divinylacetylene is hydrogenated in acetone in the presence of nickel supported on kieselguhr, giving a product containing hexatriene -- 1 : 3 : 5, hexadienes, ethylvinylacetylene, and diethylacetylene; (6) a mixture of acetylene polymers is hydrogenated as in example 5; (7) an oily polymerization product of divinylacetylene is hydrogenated in benzene in the presence of platinum oxide, giving a product useful as a coating composition.  Unsaturated mixtures of hydrogenation products obtained as described above can be polymerized to give products generally useful as constituents of coating compositions. Such mixtures may be polymerized alone or in admixture with unreduced acetylene polymers or other polymerizable substances such as isoprene, dimethylbutadiene, Chinawood oil, styrene, furylethylene, mixtures of phthalic anhydride and polyhydric alcohols, and phenol-formaldehyde condensation mixtures. Polymerization may be effected in the presence or absence of a catalyst and a solvent; specified catalysts are lithium, sodium, potassium, calcium, barium and other alkali or alkaline earth metals or their alloys, such as the eutectic of sodium and potassium; chlorides of aluminium zinc and calcium; stannous and stannic chloride; antimony tri- and penta-chloride; arsenic tri- and penta-chloride; sulphur monochloride; titanium tetrachloride; boron fluoride; sodium, potassium, or barium peroxide; benzoyl peroxide; percarbonates and perborates, such as those of sodium or potassium; acetic, maleic or phthalic anhydride; sulphuric, chlorsulphonic and formic acids; the solvent may be any of those specified above, or solvent naphtha. Oxygenated products are formed when polymerization is effected in an atmosphere containing oxygen.  The following examples are given: (8) hydrogenated crude divinylacetylene is boiled under reflux in an atmosphere of nitrogen, yielding a viscous oil which can be mixed with solvent naphtha to produce a coating composition; (9) a distillation fraction of hydrogenated crude divinylacetylene is heated in a closed bomb, giving a product similar to that of example 8; (10) hydrogenated crude divinylacetylene is heated in benzene solution in the presence of benzoyl peroxide; (11) the fraction taken in example 9 is mixed with divinylacetylene, and the mixture polymerized as in example 8; (12) the fraction taken in example 9 is heated in nitrogen after addition of benzoyl peroxide or sodium perborate or percarbonate, giving an insoluble resin; (13) a polymerization product of crude divinylacetylene is hydrogenated as described above and the product is heated to effect further polymerization; the product resembles that of example 8, and can be further polymerized to a resin; (14) the product of example 9 is mixed with xylene and titanium oxide to form an enamel; (15) hydrogenated crude divinylacetylene is heated after addition of benzoyl peroxide, and the product is mixed with xylene and aluminium powder to produce a paint; (16) hydrogenated crude divinylacetylene is added to concentrated sulphuric acid in the cold, giving a thermoplastic polymerization product; a portion of the starting material reacts with the acid, forming esters containing sulphur; alcohols and glycols are formed from these esters by treatment with water, and hexenyl alcohol may thus be isolated; (17) the product of example 7 is mixed with xylene and Chinawood oil to form a coating composition; (18) the fraction taken in example 9 is mixed with styrene, and the mixture is heated in an atmosphere of nitrogen after addition of benzoyl peroxide, giving a product useful as a coating composition; (19) the product of example 9 is mixed with solvent naphtha, powdered silica, and ground asbestine to form a paint; (20) the product of example 9 is mixed with solvent naphtha and a little eugenol or other antioxidant to form a coating composition; (21) the product of example 8 is mixed with toluene, xylene, or solvent naphtha and heated to effect further polymerization, giving a solution useful as a lacquer.  The coating compositions described above may also include rubber softeners such as oleic acid; synthetic resins such as metastyrene; solvents such as acetone or butyl acetate; small amounts of amines; driers, such as soluble compounds of lead, cobalt, and manganese; drying oils; natural gums; and pigments or fillers as required.ALSO:Nonbenzenoid acetylene polymers, particularly mono- and divinylacetylene (cf. Specification 384,654), or the polymerization products of those polymers (cf. Specification 384,655), are converted into less unsaturated products by treatment with hydrogen in the presence of a hydrogenation catalyst; the complete conversion of divinylacetylene into hexane is excluded. Hydrogenation may be effected in the vapour or liquid phase at 15-150 DEG  C. and 2-10 atm. pressure in the presence or absence of an inert gas or vapour, e.g. nitrogen, carbon dioxide, dry steam, or ethyl alcohol vapour, or of a solvent; specified solvents are acetic acid; acetone; methyl, ethyl, propyl, isopropyl, butyl or isobutyl alcohol; methyl, ethyl, propyl or butyl acetate; methyl, ethyl or butyl butyrate; mixtures of water with methyl or ethyl alcohol, acetone, or acetic acid; benzene; toluene; xylene; tetra- and decahydronaphthalene; cyclohexane; methylcyclohexane; cyclohexanol; pentane; hexane; heptane and octane.  Specified catalysts are platinum (including reduced platinum black); palladium (including palladium black or colloidal palladium); osmium; nickel; cobalt; copper; nickel on kieselguhr, alumina or silica; nickel and chromium; and nickel and copper.  In the examples, (1) the hydrocarbon C8H8, described in Specification 384,654, is hydrogenated in decahydronaphthalene in the presence of platinum oxide, yielding octane; (2) a mixture of hydrogen and monovinylacetylene is passed over a nickel catalyst at 80-150 DEG  C., yielding a mixture of butane, butylene, butadiene, and ethylacetylene; (3) an oily polymerization product of divinylacetylene is hydrogenated in benzene in the presence of platinum oxide; (4) a resinous polymerization product of divinylacetylene is hydrogenated as in example (3); (5) divinylacetylene is hydrogenated in acetone in the presence of nickel supported on kieselguhr, giving a product containing hexatriene-1 : 3 : 5, hexadienes, ethylvinylacetylene, and diethylacetylene; (6) a mixture of acetylene polymers is hydrogenated as in example (5); (7) an oily polymerization product of divinyl-acetylene is hydrogenated in benzene in the presence of platinum oxide, giving a product useful as a coating composition. Unsaturated mixtures of hydrogenation products obtained as described above can be polymerized to give products generally useful as constituents of coating compositions. Such mixtures may be polymerized alone or in admixture with unreduced acetylene polymers or other polymerizable substances such as isoprene, dimethylbutadiene, Chinawood oil, styrene, furylethylene mixtures of phthalic anhydride and polyhydric alcohols and phenol-formaldehyde condensation mixtures.  The following examples of coating compositions are given: (8) hydrogenated crude divinylacetylene is boiled under reflux in an atmosphere of nitrogen, yielding a viscous oil which can be mixed with solvent naphtha to produce a coating composition; (9) a distillation fraction of hydrogenated crude divinylacetylene is heated in a closed bomb, giving a product similar to that of example (8); (13) a polymerization product of crude divinylacetylene is hydrogenated as described above and the product is heated to effect further polymerization; the product resembles that of example (8); (14) the product of example (9) is mixed with xylene and titanium oxide to form an enamel; (15) hydrogenated crude divinylacetylene is heated after addition of benzoyl peroxide, and the product is mixed with xylene and aluminium powder to produce a paint; (17) the product of example (7) is mixed with xylene and Chinawood oil to form a coating composition; (18) the fraction taken in example (9) is mixed with styrene, and the mixture is heated i