Patent GB-384655-A (GB)
Title: Polymerisation products of non-benzenoid acetylene polymers, and compositions containing the same
IPC: C08F38/00
Filed: 1931-05-27
Abstract: Oily, gelatinous, or resinous products are obtained by polymerizing non-benzenoid acetylene polymers, particularly monovinylacetylene, divinylacetylene, and the acetylene tetramer, C8H8, the preparation of all of which is described in Specification 384,654.  The polymerization may be effected by the action of heat and (or) of a gas containing oxygen, such as air. Examples 1-5 describe polymerization processes effected at temperatures ranging from 85 to 100 DEG  C.  The polymerization products so <PICT:0384655/IV/1> obtained tend to absorb oxygen with the formation of explosive compounds, but this tendency can be reduced by effecting the polymerization in a non-oxidizing atmosphere and (or) in the presence of an antioxidant, or by incorporating an antioxidant in the polymerization products.  Suitable antioxidants are the known antioxidants for rubber, particularly phenols and amines; specified antioxidants are phenol, o-, m-, and p-cresol, eugenol, thymol, b -naphthol, guaiacol, hydroquinone, pyrogallol, resorcinol, dihydroxynaphthalenes, catechol, the ethyl- and propyl-amines, dibutylamine, amylamine, isoamylamine, allylamine, diethyland dimethyl-aniline, aniline, o- and p-toluidine, a -naphthylamine, phenyl-a -naphthylamine, m-toluylenediamine, p-aminophenol, dimolecular ethylidene-aniline, and acetaldehydeaniline acid condensation product.  Examples 6-10 describe polymerization processes conducted in a non-oxidizing atmosphere and (or) in the presence of one of the antioxidants specified above.  The liquid polymerization products have the properties of drying oils and are useful as constituents of coating compositions.  Examples 11-16 describe polymerization processes conducted as described generally above and yielding liquid products, the polymerization being accelerated in example 12 by means of cobalt linoleate.  Examples of coating compositions including the liquid products are given as follows: (17) a polymerization product of divinylacetylene and acetylene tetramer, used directly or after dilution with xylene; (18) as in example 17, with addition of oleic acid; (19) a polymerization product of divinylacetylene containing unchanged hydrocarbon with addition of oleic acid; (20) as in example 17, with addition of dibutyl phthalate and zinc oxide; (21) as in example 17, with addition of China wood oil and a solution of ester gum in xylene; (22) as in example 17, with addition of a solution of metastyrene in xylene; (23) as in example 22, but with butyl acetate instead of xylene; (24) as in example 17, with addition of a little eugenol. Acetone is also mentioned as a suitable solvent.  The coating compositions may also include natural drying oils, natural or synthetic resins, rubber softeners, and driers.  They may be applied to sheet metal.  The liquid polymerization products may also be used in the production of moulding compositions, by mixing them with a filler and a small amount of an anti-oxidant. Specified fillers are asbestos, clay, mica, silica cement, magnesia, cotton, wood pulp, wood flour, pyrites, asbestos, carbon black, and gypsum.  Examples 25 and 26 describe moulding compositions comprising the liquid polymerization products in admixture with wood flour and a little phenyl-a -naphthylamine, moulding being effected at a temperature up to 160 DEG  C., preferably at 140-160 DEG  C., at a pressure of 2000-6500 lb. per sq. inch.  Apparatus for preparing the liquid polymerization products comprises a tank 1 from which the hydrocarbon passes through an expansion chamber 2 to a heated coil 3, which may have a single heating jacket, as shown, or two or more jackets heated to successively increasing temperatures in the direction of flow of the hydrocarbon.  The lower end of the coil 3 communicates through a control valve 17 with a vessel 4 surrounded by a heating jacket and connected to a receiver 5 and a condensing coil 6, the latter communicating through cooled receivers 7 with the tank 1.  In operation the hydrocarbon, preferably mixed with a solvent of higher boiling point such as toluene, xylene, ethylbenzene, or solvent naphtha, is fed continuously to the coil 3, which may be heated to 85-87 DEG  C., and suction is applied at the outlets 13, 15 of the receivers 5, 7.  The mixture leaving the coil 3 passes to the vessel 4, which may be heated to 85-100 DEG  C.  Unchanged hydrocarbon and part of the added solvent is vaporized in the vessel 4 and the residue, comprising liquid polymerization products and remaining solvent, is withdrawn continuously or at intervals into the receiver 5.  The vapours from the vessel 4 are condensed in the condenser 6 and returned through one of the receivers 7 to the tank 1.  Vapours evolved from the coil 3 are returned to the system by a reflux condenser 8.  The yield of liquid polymers obtainable while avoiding gelation may be increased by addition of peptizing agents, such as aliphatic amines, or by working in an inert gas, such as nitrogen or carbon dioxide, or with the exclusion of air.ALSO:<PICT:0384655/III/1> Oily products are obtained by polymerizing non-benzenoid acetylene polymers, particularly monovinylacetylene, divinylacetylene, and the acetylene tetramer, C8H8, the preparation of all of which is described in Specification 384,654.  The polymerization may be effected by the action of heat and (or) of a gas containing oxygen, such as air, but the polymerization products so obtained tend to absorb oxygen with the formation of explosive compounds.  This tendency can be reduced by effecting the polymerization in a non-oxidizing atmosphere and (or) in the presence of an anti-oxidant, or by incorporating an anti-oxidant in the polymerization products. Suitable anti-oxidants are the known anti-oxidants for rubber, particularly phenols and amines; specified anti-oxidants are phenol o-, m-, and p-cresol, eugenol, thymol, b -naphthol, guaiacol, hydroquinone, pyrogallol, resorcinol, dihydroxynaphthalenes, catechol, the ethyl- and propyl-amines, dibutylamine, amylamine, isoamylamine, allylamine, diethyl- and dimethylaniline, aniline, o- and p-toluidine, a -naphthylamine, phenyl-a -naphthylamine m-toluylenediamine, p-aminophenol, dimolecular ethylideneaniline, and acetaldehyde-aniline acid condensation product.  The liquid polymerization products have the properties of drying oils and are useful as constituents of coating compositions.  Examples 11 .. 16 describe polymerization processes conducted as described generally above and yielding liquid products; the polymerization being accelerated in example 12 by means of cobalt linoleate.  Examples of coating compositions including the liquid products are given as follows:--(17) a polymerization product of divinylacetylene and acetylene tetramer, used directly or after dilution with xylene; (18) as in example 17, with addition of oleic acid; (19) a polymerization product of divinylacetylene containing unchanged hydrocarbon, with addition of oleic acid; (20) as in example 17, with addition of dibutyl phthalate and zinc oxide; (21) as in example 17, with addition of china wood oil and a solution of ester gum in xylene; (22) as in example 17, with addition of a solution of metastyrene in xylene; (23) as in example 22, but with butyl acetate instead of xylene; (24) as in example 17, with addition of a little eugenol. Acetone is also mentioned as a suitable solvent.  The coating compositions may also include natural drying oils, natural or synthetic resins, rubber softeners, and driers.  They may be applied to sheet metal. Apparatus for preparing the liquid polymerization products comprises a tank 1 from which the hydrocarbon passes through an expansion chamber 2 to a heated coil 3, which may have a single heating jacket, as shown, or two or more jackets heated to successively increasing temperatures in the direction of flow of the hydrocarbon.  The lower end of the coil 3 communicates through a control valve 17 with a vessel 4 surrounded by a heating jacket and connected to a receiver 5 and a condensing coil 6, the latter communicating through cooled receivers 7 with the tank 1.  In operation the hydrocarbon, preferably mixed with a solvent of higher boiling point such as toluene, xylene, ethylbenzene, or solvent naphtha, is fed continuously to the coil 3, which may be heated to 85-87 DEG  C., and suction is applied at the outlets 13, 15 of the receivers 5, 7.  The mixture leaving the coil 3 passes to the vessel 4, which may be heated to 85-100 DEG  C.  Unchanged hydrocarbon and part of the added solvent is vaporized in the vessel 4 and the residue, comprising liquid polymerization products and remaining solvent, is withdrawn continuously or at intervals into the receiver 5.  The vapours from the vessel 4 are condensed in the condenser 6 and returned through one of the receivers 7 to the tank 1.  Vapours evolved from the coil 3 are returned to the system by a reflux condenser 8.  The yield of liquid polymers obtainable while avoiding gelation may be increased by addition of peptizing agents, such as aliphatic amines, or by working in an inert gas, such as nitrogen or carbon dioxide, or with the exclusion of air.ALSO:Oily, gelatinous, or resinous products are obtained by polymerizing non-benzenoid acetylene polymers, particularly monovinyl-acetylene, divinylacetylene, and the acetylene tetramer, C8H8, the preparation of all of which is described in Specification 384,654, [Group IV]. The polymerization may be effected by the action of heat and (or) of a gas containing oxygen, such as air, but the polymerization products so obtained tend to absorb oxygen with the formation of explosive compounds. This tendency can be reduced by effecting the polymerization in a non-oxidizing atmosphere and (or) in the presence of an anti-oxidant, or by incorporating an anti-oxidant in the polymerization products.  Suitable anti-oxidants are the known anti-oxidants for rubber