Patent GB-812902-A (GB)
Title: The production and use of unsaturated cyclic compounds
IPC: C07C2/42
Filed: 1957-08-21
Abstract: In Example I a solution of a cobalt drying agent, in 1,3,5,7-tetramethylanecyclooctane (see Group IV (b)) is flowed out on a glass plate and exposed to the air; the solid film so formed is not softened by toluene after 7 days exposure.  In Example V(a) toluene solution of a copolymer of butadiene and a mixture of 1,2,4- and 1,3,5-trimethylene-cyclohexanes (see Group IV (a)) containing a small amount of a cobalt drying agent is cast on to a phosphatized steel panel and air-dried at room temperature for 1 1/2 hours.  The resulting cross-linked copolymer film is tough and glossy and insoluble in toluene.  Specification 812,901 is referred to.ALSO:1,2,4-Trimethylenecyclohexane can be polymerized at - 80 DEG to 100 DEG  C. under the influence of ionic polymerization catalysts of which there are mentioned aluminium chloride, aluminium bromide, titanium tetrachloride, tin tetrachloride, sulphuric acid, boron trifluoride, titanium tetrachloride/aluminium trialkyl complexes and lithium metal.  The polymers range in consistency from viscous liquids to low-melting resins soluble in benzene, toluene, carbon disulphide and methyl ethyl ketone.  Infra-red analysis indicates the recurring structure <FORM:0812902/IV (a)/1> the unsaturated group of which is available for crosslinking.  The polymers are capable of rapid air-drying to give hard glossy coatings insoluble in solvents and resistant to chemical attack. It can be copolymerized with ethylene, propylene, isobutylene, styrene, alpha-methylstyrene, 1,3-butadiene, isoprene, 2 - chloro - 1,3 - butadiene, vinyl methyl ether and vinyl ethy eether; such copolymers should contain at least 3 per cent by weight of the trimethylenecyclohexane.  Such copolymers are also capable of crosslinking, e.g. by oxidation, to give hard polymers.  In examples: (3) 1,2,4-trimethylenecyclohexane was polymerized in cyclohexane with titanium tetrachloride-aluminium triisobutyl, the mixture warmed up spontaneously.  After 1.5 hours the polymer was recovered by pouring into methanol; it was a white solid melting above 270 DEG  C. and soluble in xylene.  It formed a film from a toluene to solution containing a cobalt drying agent which after 15-20 hours was hard and insoluble in xylene.  (4) A trace of boron trifluoride was added at -60 DEG  C. to a solution of the monomer in petroleum ether which was then allowed to warm up.  A soft solid polymer had separated after 16 hours.  (5) The monomer (7.7 g.) and 1,3-butadiene (50 g.) in cyclohexane were treated with lithium wire in a pressure vessel at 45 DEG  C. with agitation; after one hour the temperature rose suddenly to 115 DEG  C. then fell slowly to 45-50 DEG  C. where it was maintained for 16 hours.  The product was a viscous, rubbery, toluene-soluble copolymer.  On casting as a film from toluene containing a cobalt drying agent a hard film was formed after 1.5 hours insoluble in toluene.  1,3,5,7 - Tetramethylenecyclo - octane is capable of air-drying to insoluble polymers.  In Example (1) it is flowed on to a glass sheet with a cobalt drying agent and exposed to air for 16-18 hours at 18-25 DEG C. when it was nearly dry to the touch and insoluble in toluene although softened by it.  After 7 days it was hard and tack-free and not softened by toluene.  Specification 812,901 is referred to.ALSO:The Specification comprises 1,2,4-trimethylenecyclohexane, 1,3,5-trimethylenecyclohexane and 1,3,5,7-tetramethylenecyclo-octane. These compounds are formed by the polymerization of allene at 70-130 DEG  C. in the presence of a catalyst of formula [(ROm)3P]nNi(CO)4-n where is 0 or 1, n is 1, 2 or 3 and R is a hydrocarbon radical free from aliphatic unsaturation.  Preferred catalysts are those of the formul  (R3P)2Ni(CO)2 or [(RO)3P]2Ni(CO)2, R being of not more than 7 carbon atoms, and particularly the bis-(triaryl phosphite) nickel dicarbonyls; a list of catalytic compounds is given.  The catalyst is used in amounts of 0.001 to 0.5 gram atom of nickel per mol. of allene.  An inert liquid reaction medium preferably containing no active hydrogen atom may be used such as ethyl acetate, methylal, tetramethylene sulphone, tetrahydrofuran, dioxane, benzene or toluene.  Anhydrous conditions must be used and calcium carbide may be added to ensure this.  Atmospheric pressure may be used by bubbling them through a catalyst solution but higher conversions are obtained by using superatmospheric pressures in closed pressure vessels when an additional pressure of 5-200 atmospheres of an unreactive gas such as nitrogen can be used.  Reaction is normally complete in 2-8 hours.  The trimethylenecyclohexanes can be separated from solvents and higher boiling material by fractionation, the mixture contains 75-85 per cent of 1,2,4- the remainder being the 1,3,5-isomer. Hydrogenation gives trimethylcyclohexanes and isomerization trimethylbenzenes (pseudocumene and mesitylene).  In Example (1) allene was heated in a pressure vessel in tetrahydrofuran with calcium carbide and bis-(triphenyl phosphite) nickel dicarbonyl for 5.5 hours at 108-109 DEG  C. during which time the pressure fell from 178 to 20 p.s.i.  A mixture of 1,2,4- and 1,3,5-trimethylene-cyclohexanes, a colourless liquid boiling at 67.5-69 DEG  C. at 60 mm. pressure and n25D 1.4912-1.4919, was obtained by fractionation.  A higher boiling product obtained by polymerizing allene at 105-115 DEG  C. was shown to be 1,3,5,7-tetramethylenecyclo octane, a colourless liquid B.P. 60 DEG C. at 2.5 mm., n25D 1.5091-1.5104.  Example (2) employs bis-(triphenylphosphine) nickel dicarbonyl as catalyst. Specification 812,901 is referred to.