Patent GB-826979-A (GB)
Title: Improvements in or relating to polymeric materials
IPC: C08G85/00
Filed: 1956-08-16
Abstract: The Specification describes the preparation of the following compounds containing a cyclobutene ring for use as intermediates in the manufacture of condensation polymers (see Group IV (a)): (a) 1-methyl-1-cyclobutene-2 : 3-dicarbonyl chloride is prepared from 1-methylenecyclobutene - 2 : 3 - dicarboxylic anhydride (the adduct of allene and maleic anhydride) by hydrolysing and isomerizing it with aqueous alkali and then acidifying with HCl to form the free cyclobutene dicarboxylic acid which is then treated with thionyl chloride; (b) 1-cyano-1-cyclobutene-3 : 4-dicarboxylic acid anhydride is prepared from 3-methylenecyclobutane-1 : 2-dicarboxylic acid anhydride (the adduct of allene and maleic anhydride) by treating it with ozone to convert the methylene group into the O= group, treating this compound with hydrogen cyanide and ammonia to give 3-amino-3-cyanocyclobutane-1 : 2-dicarboxylic anhydride, forming the trimethylammonium iodide salt of this compound and heating it with aqueous alkali; (c) 3-hydroxymethyl-1-carboxy-1-cyclobutene is made from 3-methylenecyclobutene-1-carbonitrile (the adduct of allene and acrylonitrile) by adding bromine to the double bond, hydrolysing with aqueous NaOH and neutralizing with HCl; (d) 1-methyl-3 : 3-dicarboethoxy-1-cyclobutene is made by adding isobutylene dibromide to diethyl malonate to form 1 - methylene - 3 : 3 - dicarboethoxycyclobutane, treating this compound with HI to give 1 - iodo - 1 - methyl - 3 : 3 - dicarboethoxycyclobutane and dehydrohalogenating the latter with triethylamine; (e) 1 : 1-di-(aminomethyl)-2-cyclobutene is made by reacting 1-bromo-3-chloropropane with dicyanomethane to form 1 : 1-dicyanocyclobutane, treating this compound with chlorine to give 2- and 3-chloro-1 : 1-dicyanocyclobutane, treating the mixture of isomers with triethylamine to give 1 : 1-dicyano-2-cyclobutene and reducing the latter with lithium aluminium hydride; (f) 3-(aminomethyl) - 1 - carbomethoxy - 1 - cyclobutene is made by the peroxide catalysed addition of hydrogen bromide to 3-methylene-1-cyclobutane-1-carbonitrile which is then reacted with ammonia to form 3-aminocyclobutane-1-carbonitrile, the free amino group of which is acetylated and the compound brominated in the position alphato the nitrile group.  The resulting bromo compound is then hydrolysed with aqueous NaOH to the sodium salt of 3-(aminomethyl) - 1 - carboxy - 1 - cyclobutene which is converted to the ester by neutralization with HCl followed by esterification with methanol; (g) the N-carboanhydride of 1-amino-1-carboxy-2-cyclobutene is made by treating 1-methylene - 3 - cyclobutyltrimethylammonium iodide with ozone to convert the methylene group to the =O group and reacting the resulting compound with hydrogen cyanide and p  ammonium chloride to form the 1-amino-1-cyano derivative.  This compound is hydrolysed with HCl to form the hydrochloride of 1 - amino - 1 - carboxy - 3 - cyclobutyltrimethylammonium chloride, the quaternary ammonium radical of which is removed by heating with aqueous NaOH. After neutralization, the resulting 1-amino-1-carboxy-2-cyclobutene is converted to the N-carboanhydride by treatment with phosgene; (h) 1 : 2-di-(aminomethyl)-1-cyclobutene is made by treating the corresponding chloromethyl compound with ammonia.  Specification 805,664 is referred to.ALSO:A cross-linkable condensation polyester, polyamide, polyurethane or polyurea has a chain structure containing recurring cyclobutene rings intralineal with the chain. Cross-linking, due to opening of the cyclobutene ring, is effected by heating the polymer at 100-325 DEG  C.  The cross-linking may be applied to the polymer when in the form of a shaped article, a fibre, a coating on a surface, an adhesive between lamin  or as printed matter.  The following polymers are exemplified:-  Polyesters obtained from (a) dimethyl-1-cyclobutene-1:2-dicarboxylate and diphenylol propane, N,N-diethanol-aniline or ethylene-, triethylene-, trimethylene-, tetramethylene-, hexamethylene- or decamethylene-glycol; (b) the dimethyl ester of 3-methyl-1-cyclobutene-1:2-dicarboxylic acid, the dimethyl ester of 3:3-diethyl-1-cyclobutene-1:2-dicarboxylic acid or the dimethyl ester of 3:4-dimethyl-1-cyclobutene-1:2-dicarboxylic acid and hexamethylene glycol; (c) 1-methyl-1-cyclobutene-2:3-dicarbonyl chloride, sebacyl chloride and diphenylol propane; (d) 1-methyl-1-cyclobutene-2:3-dicarbonyl chloride and ethylene glycol; (e) 1 - methyl - 1 - cyclobutene - 2:3 - dicarbonyl chloride, terephthaloyl chloride and ethylene glycol; (f) 1-methyl-1-cyclobutene-2:3-dicarboxylic acid and ethylene glycol; (g) 1 - cyano - 1 - cyclobutene - 3:4 - dicarboxylic anhydride and ethylene glycol; (h) 1:2-di-(hydroxymethyl) - 1 - cyclobutene and malonic, succinic, maleic, adipic, suberic, terephthalic, p-phenylene diacetic or thioldibutyric acid or ester-forming derivatives thereof; (i) a hydroxyethylated 1:2-dihydroxymethyl-1-cyclobutene and adipic acid; (j) 3-hydroxymethyl-1-carboxy-1-cyclobutene.  Polyamides obtained from (a) dimethyl-1-cyclobutene-1:2-dicarboxylate and ethylene-, hexamethylene-, 3 - methylhexamethylene-, decamethylene- or m-phenylene-diamine; (h) 1 - methyl - 1 - cyclobutene - 2:3 - dicarbonyl chloride, sebacyl chloride and 2-methoxymethyl-5 - methylhexamethylenediamine; (c) 1-methyl-1 - cyclobutene - 2:3 - dicarboxylic acid, 3:3-diethyl - 1 - cyclobutene - 1:2 - dicarboxylic acid or 3:4 - dimethyl - 1 - cyclobutene - 1:2 - dicarboxylic acid (or amide-forming derivatives thereof) and hexamethylene diamine; (d) 1-methyl - 3:3 - dicarboethoxy - 1 - cyclobutene and ethylene diamine; (e) 1:1-di(aminomethyl)-2-cyclobutene and adipyl chloride; (f) 3 - (aminomethyl) - 1 - carbomethoxy - 1 - cyclobutene; (g) the N-carboanhydride of 1-amino - 1 - carboxy - 2 - cyclobutene. Polyurethanes obtained from (a) 1:2-di-(hydroxymethyl) - 1 - cyclobutene and hexamethylene diisocyanate; (b) 3-methyl-2-cyclobutene-1,2-bis-methanol and hexamethylene diisocyanate; (c) 3-methyl-2-cyclobutene-1.2-bis-methanol, ethylene glycol and 3-methyl-2-cyclobutene-1,2-bismethanol; (d) a diisocyanate having a cyclobutene ring and a glycol (both unspecified).  Polyureas obtained from 1:2-di-(aminomethyl) - 1 - cyclobutene and hexamethylene diisocyanate.  Specification 805,664 is referred to.