GB1475804A - Process for the manufacture of curable and thermosetting syn thetic resins containing nitrogen and boron - Google Patents

Abstract

1475804 Thermosetting resin containing boron and nitrogen HOECHST AG 2 Aug 1974 [28 Sept 1973 19 April 1974 (2)] 34207/74 Heading C3R A process for the manufacture of a curable and thermosetting synthetic resin containing nitrogen and boron is characterized in that (a) phenol alone or in admixture with at least one substituted phenol having a hydrogen atom at least in the ortho-position on the phenol nucleus, the substituted phenol being selected from C 1 -C 30 alkyl-phenols, C 5 -C 10 cycloalkylphenols, C 2 -C 30 -alkenylphenols, C 5 -C 10 cycloalkenyl-phenols, the cycloalkyl and cycloalkenyl radicals being monocyclic or bicyclic, aryl-substituted phenols and aralkyl-substituted phenols with one aromatic ring in the substituent, and halogen-substituted phenols; (b) at least one nitrogen compound having a basic reaction; (c) formaldehyde and/or paraformaldehyde and/or trioxane; (d) at least one esterifiable boron compound and (e) at least one primary and/or secondary aliphatic saturated C 2 -C 5 monoalcohol are reacted stepwise with removal of the water of reaction and (I) first components (a), (b) and (c) are reacted at 68- 110‹ C. to give a nitrogen-containing condensate with complete incorporation of components (b) and (c), the molar ratio of (a) to (c) being 1 : 0À5-0À8, and of (b) to (c) being 1 : 1, based on the equivalents of active H atoms on (b), the molar ratio of (b) to (d) being from 0À1- 0À5 : 1, based on the mols of N in (b) and the mols of boron in (d); (II) the resulting condensate is reacted in the presence of components (d) and (e) and a water-entraining agent, with azeotropic removal of the water of reaction at 120-150‹ C., the weight ratio of (a) to (d) being from 100 : 5 to 100 : 20 ((d) calculated as boron oxide), and the molar ratio of (d) to (e) being from 1 : 1 to 1 : 4; or (IIa) the resulting condensate from (I) is freed from water by heating in vacuo, and is then mixed with an ester obtained by reacting components (d) and (e) and/or an aliphatic boric acid ester (de<SP>1</SP>) the alcohol radical of which consists of primary and/or secondary saturated C 1 -C 5 monoalcohols, the weight ratio of (a) to the ester (de) or (de<SP>1</SP>) calculated as boron oxide being from 100 : 5 to 100 : 20; and (III) the resulting batch from (II) or (IIa) is reacted with additional formaldehyde and/or paraformaldehyde and/or trioxane at 95-100‹ C. and is then heated under reduced pressure at 100-150‹ C., with removal of the volatile constituents, until the resin obtained has reached a B-time of 30 seconds to 6 minutes at 160‹ C. Suitable substituted phenols (a) are m-cresol, 3,4-, 3,5- and 2,5-dimethylphenol, m-ethyl or propyl or -butyl - phenol, o- and/or p - n - and/or isopropenylphenol, o- and/or p-allylphenol, phenyl-phenol, o- and/or p-a- and/or -#- phenylethylphenol or - phenylisopropylphenol or .methylphenylethylphenol, and technical alkylation products of olefins and phenols. Suitable components (b) are ammonia, hydrazine, methylamine, propylamine, aniline, toluidine, di - (p - aminophenyl) - sulphide, di - (paminophenyl)-methane and ethylene diamine. Suitable components (d) and (de<SP>1</SP>) are boric acid, boron trioxide and trimethyl borate. Preferred components (e) are iso- or n-butanol. Suitable water-entraining agents are benzene, toluene or xylene. The reaction may be carried out in the presence of an inorganic or organic acid of pK less than 2À5. In the examples resins are prepared as above using as component (a) phenol alone and in admixture with phenylethylphenol; as component (b) NH 3 , aniline, hydrazine hydrate, methylamine or di-(p-aminophenyl)- sulphide; as component (c) in step (I) aqueous HCHO and in step (III) paraformaldehyde, trioxane or a butanol solution of HCHO; as component (d) or (de<SP>1</SP>) boric acid, boron oxide or trimethylborate; as component (e) iso- or nbutanol or amylalcohol; as water-entraining agent toluene or xylene. Other examples are described. Uses.-Binders for compression-moulding compositions, resin-impregnated papers and brake linings.