Patent GB-1056821-A (GB)
Title: Improvements in and relating to ester isocyanates
IPC: C08G18/70
Filed: 1963-07-22
Abstract: Curable coating compositions are obtained by reacting diisocyanate esters of formula <FORM:1056821/C4-C5/1> wherein R is a divalent substituted or unsubstituted, saturated or unsaturated aromatic group; and R1 is a divalent group <FORM:1056821/C4-C5/2> (see Division C2) with a drying oil or a diene of formula <FORM:1056821/C4-C5/3> where each R6 and R8 is hydrogen or a substituted or unsubstituted aliphatic group or one of R6 and R8 together are a methylene or phenylene group or an oxo bridge; and R7 is hydrogen or a substituted or unsubstituted aliphatic group or both R7's taken together are part of the same six-membered cycloaliphatic or aromatic group.  Diene compounds mentioned are tung, oiticica, corn, linseed, safflower seed, soybean or dehydrated castor oils. The compositions may include driers, e.g. cobalt naphthenate, lead octanoate, dibutyl tin dilaurate, diamines and aminetin complexes, fillers and pigments and yield transparent flexible coatings. Examples describe the reaction of tung oil, oiticica oil or tung oil modified with a pentaerythritol ester of rosin, oiticica oil modified with a rosin acid ester of tricyclo-[4.3.12,5.01,6]-undecane-4,8,9-triol, dehydrated castor, linseed and oiticica oils and bis-(2-iso-cyanatoethyl) fumarate which yield air-drying and moisture cured film coatings.ALSO:The invention comprises ester isocyanates of formula <FORM:1056821/C2/1> wherein R is a divalent substituted or unsubstituted, saturated or unsaturated aliphatic or alicyclic group or a substituted or unsubstituted aromatic group and R1 is a divalent group of formula <FORM:1056821/C2/2> wherein B is a divalent organic group containing a 2-butylene group which forms a six-membered ring; R2 is hydrogen or alkyl with the proviso that when both R's are alkylene R1 is not a cis-vinylene group.  Particular groups of compounds mentioned are those of formula <FORM:1056821/C2/3> wherein R3 represents an alkylene, alkenylene, alkynylene, cycloalkylalkylene, cycloalkenylalkylene, or aralkylene groups with 2-10 C atoms, e.g. bis-(2-isocyanatoethyl), bis-(2,2-dimethyl - 3 - isocyanatopropyl), bis - (9-isocyanatononyl), bis - (5,6,7 - triethyl - 9 - isocyanatononyl), 2 - methyl - 3 - isocyanatopropyl 2-isocyanatoethyl and 4-ethyl-7-isoheptyl 6-isocyanato fumarates; of formula <FORM:1056821/C2/4> where R4 is a cycloalkylene, cycloalkenylenes, cycloalkynylene, alkylcycloalkylene, alkylcycloalkenylene, alkylcycloalkynylene, or cycloalkylenealkylene group with 4-10 C atoms, e.g. bis-(2-isocyanatocyclobutyl) maleate, bis-(3-isocyanatocyclopentyl) fumarate, bis-(5-isocyanato-6-cycloheptamyl) maleate, bis-(3-isocyanato cyclopentylmethyl) fumarate and bis-(3 - isocyanato - 5 - methylcyclohexyl) fumarate; where R4 represents a divalent substituted or unsubstituted aromatic group with 6-12 C atoms or a fused cycloaliphatic or aromatic ring, e.g. bis-(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate or bicyclic or heterocyclic ester isocyanates, e.g. bis-(2-isocyanatoethyl)-5-norbornene - 2,3 - dicarboxylate or bis - (2-isocyanatoethyl) - 3,6 - endo - oxo - 4 - cyclohexene - 1,2 - dicarboxylate; or compounds obtained by the Diels-Alder reaction of a drying oil with an olefinically unsaturated ester isocyanate. The ester isocyanates are prepared by reacting a carbonyl dihalide, e.g. phosgene with the corresponding olefinically unsaturated ester diamines or diamine salts, in an inert liquid organic solvent at between 100 DEG  and 225 DEG  C.  Examples describe the preparation of bis-(2-isocyanatoethyl) fumarate; bis-(a -isocyanatoethyl) fumarate; bis - 2 - isocyanatoethyl) - 5 - norbornene - 2,3 - dicarboxylate, bis - (2 - isocyanato) - 4 - cyclohexene - 1,2-dicarboxylate; bis - (2 - isocyanatoethyl)-trans - 9,10 - dihydroanthracene - 9,10 - endo-a ,b  - succinate; bis - (2 - isocyanatoethyl) - 4-methylcyclo - hex - 4 - ene - 1,2 - dicarboxylate; and bis - (2 - isocyanatoethyl) - 4,5 - dimethylcyclohex - 4 - ene - 1,2 - dicarboxylate.  Compounds of the formula <FORM:1056821/C2/5> are prepared by the additional step of adding a diene to the unsaturated ester isocyanate. Dienes are listed and preferred are the triglycerides of fatty acids with at least one conjugated unsaturation or unsaturation capable of reaction. Examples describe the Diels-Alder reaction of tung oil, oil modified with a rosin-pentaerythritol ester, oiticica oil modified with a rosin acid ester of tricyclo-[4,3,12,5,01,6] undecane - 4,8,9 - triol, dehydrated castor oil and linseed oil with bis-(2-isocyanatoethyl) fumarate and the products yield cured films of improved protective properties.