Patent GB-996705-A (GB)
Title: New polyaddition resins
IPC: C08G75/04
Filed: 1961-11-14
Abstract: In examples:  (16( adipic acid-bis-(2,3-dihydro-4H-pyran-2-yl-methyl ester is prepared from the corresponding alcohol and adipic acid dichloride.  (18) Bis-(2,3-dihydro-4H-pyran-2-yl) formal is prepared from divinyl formal and acrolein; (19) Ethylene glycol-bis-(2,3-dihydro-4H-pyran-2-yl) ether is prepared from ethylene glycol divinyl ether and acrolein; (22) Oxalic acid - bis - (2,3 - dihydro - 4H - pyran - 2 - yl-methyl) ester is prepared from oxalalyl chloride and the corresponding methanol derivation; (23) and (24) The succinic acid di-ester and the tri-phosphate are similarly prepared; (25) Bis - (2,3 - dihydro - 4H - pyran - 2 - yl - methyl) carbonate is prepared from phosgene and the appropriate methanol derivative; (28) Toluene-2,4 - bis - (carbamic acid - 21,31 - dihydro - 41H-pyran-21-yl-methyl ester) is prepared from toluene-2,4-diisocyanate and 2,3-dihydro-4H-pyran-2-yl-methanol; (29) Ethylene diamine-bis-(2,3-dihydro - 4H - pyran - 2 - methyl - 2 - carboxylic acid) amide is prepared from ethylene diamine and 2,3 - dihydro - 4H - pyran - 2 8 methyl - 2-carboxylic acid methyl ester; (30) and (31) Ethylene glycol - bis - (2,3 - dihydro - 4H - pyran-2-methyl-2-carboxylic acid) ester is prepared from ethylene glycol and 2,3-dihydro-4H-pyran-2-methyl-2-carboxyli acid methyl ester, and Hexanetriol - bis - (2,3 - dihydro - 4H - pyran-2-methyl-2-carboxylic acid) ester and pentaery-thritol - bis - (2,3 - dihydro - 4H - pyran - 2 - methyl-2-carboxylic acid) ester are prepared from hexanetriol or pentaerythritol and the same methyl ester.ALSO:Polyaddition resins are prepared by reacting (1) a compound of the general formula <FORM:0996705/C3/1> in which R is H or CH3; n=2 to 6; and Z is either -COOCH2- (in which case n=2); or -[-COO-]-nY, where Y is the hydrocarbon residue of a polyol; or -[-CH2O-]-nX, where X is the ester residue of a polycarboxylic or inorganic acid of basicity n, or an alkylidene group (in which case n=2), or the hydrocarbon residue of a polyol; or -[-O-]-nR1, where R1 is the hydrocarbon residue of a polyol or an alkylidene group (in which case n=2); or -[-OCONH-]-nR2, or -[-CH2OCONH-]-nR2, where R2 is a hydrocarbon radical of valency n, with (2) a compound containing at least two groups chosen from hydroxyl, mercapto, carboxyl, amide, acetal and ortho-ester groups.  Preferably, an acid catalyst is used, unless compound (2) above is strongly acidic. Suitable starting materials are listed.  If desired, a precondensate may first be formed, and cured by further reaction, e.g. with polyols, polyesters, phenolic or epoxy resins. Products may be linear or cross-linked. Conventional additives, e.g. fillers, plasticizers or colouring matters may be added before curing. In Examples 1-15, 20, 21, compound (1) is 2,3-dihydro - 4H - pyran - 2 - carboxylic acid-(21,31-dihydro - 41H - pyran - 21 - yl) - methyl ester. It is reacted with: Example 1. Ethylene glycol. 2. Glycerol.  3. A polyester from glycerol and phthalic anhydride.  4. Oxalic acid.  5. A polyester from adipic acid and glycol.  6. A hexanetriol-phthalate resin.  7. A mixture of 1,2,6-hexanetriol and phenol.  8. A mixture of trimethylolpropane and 1,1 - bis - (41 - hydroxyphenyl) ethane. 9. A hydroxylated ester from ethylene glycol, trimethylol ethane, and succinic anhydride. 10. A mixture of 1,4-bis-(hydroxymethyl) - benzene, phenol and diglycerol. 11. A mixture of glyoxal-tetramethylacetal and trimethylolpropane.  12. A mixture of a hydroxylated ester from ethylene glycol, trimethylol ethane, and succinic anhydride, with a liquid polymeric polysulphide known as "Thiokol LP-3" (Registered Trade Mark).  13. A mixture of thiourea and glycerol. 14. A mixture of trimethylolpropane and e -caprolactam. 15. A mixture of trimethylolpropane and an epoxy resin from 2,2-bis-(p-hydroxyphenyl)-propane and epichlorhydrin.  20. A mixture of trimethylol propane and e -caprolactone.  21. Polyvinyl alcohol. The other examples are as follows: 16. Adipic acid-bis-(2,3-dihydro-4H -pyran-2-yl-methyl ester) is reacted with e -caprolactone and trimethylolpropane.  17. Excess 2,3 - dihydro - 4H - pyran - 2 - carboxylic acid - (21,31 - hydro - 41H - pyran - 21 - yl) methyl ester is reacted with ethylene glycol-di-(2 -hydroxypropyl) ether.  The product may be subsequently reacted with the hydroxylated ester of Example 9. 18. Bis-(2,3-dihydro-4H -pyran-2-yl)-formal is reacted with the hydroxylated ester of Example 9.  19. Ethylene glycolbis - (2,3 - dihydro - 4H - pyran - 2 - yl) ether is reacted with a mixture of phenol and 1,2,6-hexanetriol. 22. Oxalic acid bis-(2,3-dihydro - 4H - pyran - 2 - yl - methyl) ester is reacted with (a) 1,2,6-hexanetriol, or (b) trimethylolpropane. Other examples use succinic acid-bis -(2,3 - dihydro - 4H - pyran - 2 - yl - methyl) ester; tri - (2,3 - dihydro - 4H - pyran - 2 - yl - methyl) phosphate; bis - (2,3 - dihydro - 4H - pyran - 2 - yl - methyl) carbonate; diphenyl-di -(2,3 - dihydro - 4H - pyran - 2 - yl - methyl) orthosilicate (prepared from 2,3-dihydro-4H -pyran-2-yl-methanol and diphenoxy dichlorosilane; a urethane prepared from an adduct of hexanetriol and m-phenylene diisocyanate, and 2,3 - dihydro - 4H - pyran - 2 - yl - methanol; toluene - 2,4 - bis - (carbamic acid - 21,31 - di - hydro - 41H - pyran - 21 - yl - methyl ester); Ethylene diamine - bis - (2,3 - dihydro - 4H - pyran - 2 - methyl - 2 - carboxylic acid)-amide; ethylene glycol - bis - (2,3 - dihydro - 4H-pyran -2 - methyl - 2 - carboxylic acid) ester; hexane triol - bis - (2,3 - dihydro - 4H - pyran - 2 - methyl - 2 - carboxylic acid) ester; and pentaerythritol - bis - (2,3 - dihydro - 4H - pyran - 2 - methyl - 2 - carboxylic acid) ester.ALSO:In Example 3, a glycerol-phthalic anhydride resin is dissolved in isobutyl acetate and 213-dihydro-4H-pyran-2-carboxylic acid-[2131-dihydro-41H-pyran-21-yl] -methyl ester and hydrochloric acid is added.  The solution is distributed over an aluminium sheet, solvent evaporated and the lacquer coat stoved.