Patent GB-1089111-A (GB)
Title: High molecular weight polycarbonates
IPC: C08G64/30
Filed: 1964-09-25
Abstract: The invention comprises solid linear polycarbonates of at least 10,000 M.W. having recurring units of formula <FORM:1089111/C3/1> where R1 is a saturated aliphatic chain of at least 3 carbon atoms and having up to 4 substituents. They may also have 5-95% of recurring lactone residues of formula <FORM:1089111/C3/2> where R is H, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, halo, halo-alkyl, alkoxyalkyl, alkoxy, or aryloxy or two R groups together with carbon atoms of the chain represent an aromatic nucleus or a C4- 10 saturated carbocyclic ring, A is O, S or a saturated aliphatic radical, x is 1-15, y is 1-15, z is 0 or 1, x + y + z does not equal 3, the total number of atoms in the linear chain of the unit does not exceed 18 and the total number of substituents does not exceed 4. The polymers may be prepared by heating the corresponding cyclic carbonate, optionally in the presence of a lactone, under a nitrogen atmosphere. Heating may be stopped at 90 DEG  C. when the temperature may rise to 140-150 DEG  C. exothermically.  The product may be made into fibres. In examples cyclic carbonates used are: 4,4-dimethyl-2,6-dioxacyclohexanone, trimethylene carbonate, 4-nitro-4-methyl-2,6 - dioxacyclohexanone, 4 - ethyl - 4 - ethoxymethyl - 2,6 - dioxacyclohexanone, 3-oxo - 8 - thia - 2,4 - dioxaspiro[5.3)nonane, 4,4 - dichloromethyl - 2,6 - dioxacyclohexanone, 4,4 - di(cyanomethyl)-2,6-dioxacyclohexanone, tetra - ethylene glycol carbonate, 3,4,5 - tri-methyl - 2,6 - dioxacyclohexanone, 3 - chloromethyl - 2,6 - dioxacyclohexanone, 3 - phenyl-2,6 - dioxacyclohexanone, 4,4 -diethoxymethyl-2,6 - dioxacyclohexanone, 4,4 - di(acetoxymethyl) - 2,6 - dioxacyclohexanone, 4 - diethylamino - 4 - methyl - 2,6 - dioxacyclohexanone, octadecamethylene carbonate and 4 - nitro - 4-propionyloxymethyl - 2,6 - dioxacyclohexanone. Lactones specified are e -caprolactone, valerolactone, 1,4-dioxan-2-one, propiolactone, a ,a -dimethyl-propiolactone, 2,4-di-methyl-4-methoxymethyl-5-hydroxy-pentanoic acid lactone and 12 - oxa - 15 - hydroxypentadecanoic acid lactone.ALSO:The Specification describes the preparation of cyclic carbonates.  (1) A 4-nitro-4-hydrocarbyloxy - methyl - 2,6 - dioxacyclohexane or 4-nitro - 4 - acyloxymethyl - 2,6 - dioxacyclohexanone may be prepared by reacting nitromethane with (a) formaldehyde, (b) a hydrocarbyl halide and (c) phosgene, a dialkyl carbonate or an alkylene carbonate, (2) A 4-tertiary - amino - 4 - hydrocarbyloxymethyl - 2,6 - dioxacyclohexanone or 4-tertiary amino-4-acyloxymethyl - 2,6 - dioxacyclohexanone may be prepared by (a) catalytic hydrogenation of the product of (1b) above followed (b) by alkylation.  (3) A 4-nitro-4-hydrocarbyl-2,6-dioxacyclohexanone or a 4-tertiary-amino-4-hydrocarbyl - 2,6 - dioxacyclohexanone may be prepared by carrying out reaction (1) or (2) above replacing the nitromethane with a substituted nitromethane.  (4) A 4,4-dihydrocarbyl - 2,6 - dioxacyclohexanone is prepared by reacting an aldehyde having one a -hydrogen atom with (a) HCHO and (b) a cyclizing agent as in (1c).  (5) A 4-hydrocarbyl-4-hydrocarbyl-oxymethyl - 2,6 - dioxacyclohexanone or a 4 - hydrocarbyl - 4 - acyloxymethyl-2, 6-dioxacyclohexanone may be prepared by treating an aldehyde containing 2 alpha hydrogen atoms with (a) HCHO, (b) a hydrocarbyl halide and (c) a cyclizing agent as in (1c).  (6) A 4,4-di(hydrocarbylmethyl) - 2,6 - dioxacyclohexanone or a 4,4 - di(acyloxymethyl) - 2,6 - dioxacyclohexanone may be prepared by reacting pentaerythritol with (a) a hydrocarbyl halide and (b) a cyclizing agent.  (7) 3-oxa-2,4-dioxaspiro[5.5]-undecane may be prepared (a) by carrying out a Diels-Alder reaction between butadiene and acrolein and treating the product with (b) formaldehyde, (c) H2/catalyst and (d) a cyclizing agent.  (8) The carbonates of bicyclo[2.2.1]-heptane - 2,2 - dimethanols or bicyclo[2.2.2]-octane-2,2-dimethanols may be prepared by (a) carrying out a Diels-Alder reaction between a cyclohexa- or penta-diene and acrolein and treating the product with (b) formaldehyde, (c) H2/catalyst and (d) a cyclizing agent. (9) 3 - oxo - 2,4,8 - trioxaspiro[5,3]nonane may be prepared by reacting pentaerythritol monochloride with (a) dilute alkali and (b) a cyclizing agent.  (10) 3-oxo-8-thia-2,4-dioxaspiro[5.3]-nonane may be prepared by reacting pentaerythritol dichloride with (a) Na2S and (b) a cyclizing agent. (11) 1-oxo-8-thia-2,4-dioxaspiro[5.3]nonae-8-oxide may be prepared by treating 3,3-dimethylol thietane with (a) peracetic acid and (b) a cyclizing agent.  (12) 3-oxa - 8 - thia - 2,4 - dioxaspiro[5.3]nonane - 8 - dioxide may be prepared by reacting 3,3-dimethylol thietane with (a) excess peracetic acid and (b) a cyclizing agent.  (13) 3-oxo-2,4,8,10-tetraoxaspiro[5.3]undecanes may be prepared by reacting a monocarbonyl compound with (a) pentaerythritol and (b) a cyclizing agent.  If the carbonyl compound is acrolein dimer and the product is hydrogenated prior to cyclization there is obtained 3-oxo-2,4,8,10-tetraoxaspiro-[5.5]undecane - 9 - (21 - tetrahydropyran).  (14) 3 - oxo - 2,4,8,10 - tetraoxa - 9 - thiaspiro[5.5]-undecane-9-oxide may be prepared by reacting pentaerythritol with (a) sulphonyl chloride and (b) a cyclizing agent.  (15) 4-substituted-4-cyanoalkoxymethyl - 2,6 - dioxacyclohexanones wherein the 4-substituent is hydrocarbyl, nitro or tertiary amino may be prepared by reacting 1 - hydrocarbyl - 1,1,1 - trimethylolmethane or the corresponding 1 nitro compound with (a) an a ,b -unsaturated nitrile and (b) a cyclizing agent.  The nitro-group may be hydrogenated and alkylated before cyclization. (16) 4,4-di-(cyanoalkoxymethyl) - 2,6 - dioxacyclohexanones may be prepared by reacting pentaerythritol with (a) an alkenyl nitrile and (b) a cyclizing agent.  (17) 3-oxo-2,4,7-trioxaspiro-[5.5]undecane may be prepared by treating acrolein dimer with (a) formaldehyde and (b) a cyclizing agent.  3-oxo-2,4,7-trioxaspiro[5.4]-decane and 3-oxo-2,4-dioxaspiro[5.4]decane may be prepared by reacting tetrahydrofurfural and cyclopentane aldehyde as in (17).  (18) 4,4-di-(halomethyl)-2,6-dioxacyclohexanones may be prepared by reacting pentaerythritol dichloride with a dialkyl carbonate. (19) 4,4-di(cyanomethyl) - 2,6 - dioxacyclohexanone may be prepared by treating pentaerythritol dichloride with (a) an alkali metal cyanide and (b) a cyclizing agent.  (20) 3-chloromethyl-2,6-dioxacyclohexanone and 3-cyanomethyl-2,6-dioxacyclohexanone can be prepared by cyclizing 4-chloro - 1,3 - butane diol and 4 - cyano - 1,3 - butane diol.