Patent GB-1105713-A (GB)
Title: Copolymers of bicyclobutanes
IPC: C08G61/06
Filed: 1966-07-26
Abstract: A copolymer comprises (1) from 1 to 90 mole per cent of structural units derived from at least one bicyclo [1, 1, 0]-butane of the formula <FORM:1105713/C3/1> where R1 and R2 are hydrogen, halogen, hydroxyloweralkyl, hydroxyphenyl, loweralkoxyloweralkyl, loweralkoxyphenyl, haloloweralky, halophenyl, -COOH, -COOR, -COSR, -COOM, -CONH2, -CONHR, -CONR2, -SO2R, -CHO, -COR, -OCOR, -OR, -NO2, -CN, or R where M is one equivalent of a metal cation of an element having an atomic number of 3, 4, 11, to 13, 19 to 32, 37 to 51, 55 to 84 and 87 to 103, and R is a hydrocarbyl group of up to 18 carbon atoms free of aliphatic carbon-to-carbon unsaturation, and R3, R4, R5 and R6 are each hydroxy, amino, -NR2 or R1; and (2) the remainder being structural units derived from at least one unsaturated compound which undergoes addition homopolymerization in the presence of a free-radical forming initiator and has the formula <FORM:1105713/C3/2> where R7 has the same definition as R1, R8 is hydrogen, halogen, cyano, vinyl or lower alkyl, R9 is hydrogen, halogen or -COOR where R has the same definition is in (1) and R10 is hydrogen or halogen.  By "lower" alkyl or alkoxy is meant one having not more than 6 carbon atoms.  In Examples are used: as component (1): 3-methylbicyclo [1. 1. 0] butane-carbonitrile, 1-cyanobicyclo [1, 1, 0] butane, 1,3 - bis(methyoxcarbony) - bicyclo [1, 1, 0] butane, 1-methoxycarbonyl bicyclo [1. 1. 0] butane and a long list of other monomers is given; as component (2): acrylonitrile, styrene, vinyl acetate, methyl methacrylate; as initiators: benzoyl peroxide, a ,a 1-azodiisobutyronitrile, n-butyl lithium, 1,11-azodicyclohexanecarbonitrile, sodium cyanide potassium persulphate and sodium bisulphate, azobisisobutyronitrile; and as solvents: acetonitrile, dimethyl formamide, tetrayhydrofuran, hexane, water with sodium sulphate and an anionic dispersing agent, toluene, water with polymethacrylic acid and dipotassium phosphate.ALSO:Substituted bicyclo [1.1.0]-butanes are prepared by a variety of methods.  In Example 8A 1-cyanobicyclo [1.1.0] butane a solution of 3-chlorocyclobutanecarbonitrile in THF to a solution of potassium t-butoxide in THF.  A number of 1-substituted bicyclo [1.1.0] butanes are prepared by irradiating the corresponding 2-substituted butadiene with ultra-violet light, the substituents being phenyl, p-hydroxyphenyl, p-chlorophenyl, chloro, methoxy and acetoxy. The 1-ethylthiocarbonyl derivative is prepared by ester interchange of the 1-methoxycarbonyl derivative with ethyl mercaptan. The 3-chloro-1-methoxycarbonyl derivative is prepared by treatment of 3-methoxycarbonylcyclobutanone with PCl5 and dechlorinating the resulting 3,3-dichloro - 1 - methoxycarbonylcyclobutane with potassium t-butoxide in ether. The 1-acetoxy derivative is prepared by peracid oxidation of the 1-acetyl derivative.  The 1-nitro derivative is prepared by treating 1-chloro-3-bromocyclobutane with silver nitrite and dehydrochlorinating the resulting 1-chloro-3-nitro-cyclobutane with potassium t-butoxide in ether.  The 1-p-tolylsulphonyl derivative is prepared by treating 1-chloro-3-bromocyclobutane with sodium p-tolylsulphinate and dehydrochlorinating the resulting 1-chloro-3-p-tolylsulphonylcyclobutane with potassium t-butoxide in ether.  The 1-(N-ethylcarbamoyl) and 1-(N,N-dimethylcarbamoyl) derivatives are prepared by reacting the 1-methoxycarbonyl derivative with ethylamine and dimethylamine respectively.  The 1-formyl derivative is prepared by treating 3-chlorocyclobutanecarbonitrile with lithium tributoxy aluminium hydride and dehydrochlorinating the resulting 1 - formyl - 3 - chlorocyclobutane with potassium t-butoxide in ether.  The 1-(b -hydroxyethyl) derivative is prepared by reacting 4-hydroxy but-l-yne with two equivalents of diazomethane in the presence of U.V. light or a copper catalyst.  The 1-(b -chloroethyl) derivative is similarly prepared from 4-chlorobut-l-yne. The 2,4-dicyano, 2,4-dichloro and 2,4-diacetyl derivatives are prepared by treating acetylene with two equivalents of diazoacetonitrile, chlorodiazomethane and diazoacetone respectively.  The 1,2,3,4-tetracyano derivative is prepared by treating dicyanoacetylene with two equivalents of diazoacetonitrile. The 2,4-bis-(methylsulphonyl), 2,4-dinitro, 2,4-bis-(diethylamino), 2,4-bis-(n-butoxy), 2,4 - bis - (hydroxy), 2,4 - dibromo- and 2,4-diiodo derivatives are prepared by treating the 2,4-dichloro derivative with sodium methylsulphinate, silver nitrite, diethylamine, potassium n-butoxide, potassium hydroxide, lithium bromide and lithium iodide respectively. The 1-acetyl derivative is prepared by treating 3 - chloro - 1 - cyanocyclobutane with methylmagnesium bromide and reacting the resulting 1 - acetyl - 3 - chlorocyclobutane with sodium hydride in N-methylpyrrolidone.  Sodium bicyclo-[1.1.0] butane - 1 - carboxylate is prepared by hydrolysis of 1-methoxycarbonyl bicyclo [1.1.0] butane with sodium hydroxide.