Patent GB-1474753-A (GB)
Title: Process for the manufacture of curable and thermosetting  synthetic resins containing nitrogen and boron
IPC: F16D69/02
Filed: 1974-08-02
Abstract: 1474753 Thermosetting synthetic resin containing boron and nitrogen HOECHST AG 2 Aug 1974 [28 Sept 1973 19 April 1974] 34208/74 Heading C3R A process for the manufacture of a curable and thermosetting synthetic resin containing nitrogen and boron is charcterized in that (a) phenol and/or a bisphenol or a mixture of phenol and/or a bisphenol and at least one substituted phenol having a hydrogen atom at least in the O-position on the phenol nucleus capable of reacting with formaldehyde, the substituted phenol being selected from C 1 -C 30 -alkylphenols, C 5 -C 10 -cycloalkylphenols, C 5 -C 10  cycloalkenylphenols, the alkenyl and cycloalkenyl radicals being mono- or bi-cyclic, C 2 -C 30 -alkenylphenols, aryl-substituted phenols and aralkylsubstituted phenols with one aromatic ring in the substituent, halogen-substituted phenols and amino-substituted phenols, (b) at least one esterifiable boron compound, (c) at least one primary and/or secondary aliphatic saturated C 2 -C 5 -monoalcohol, (d) hexamethylenetetramine, and (e) formaldehyde and/or paraformaldehyde and/or triozane, are reacted conjointly using an excess of (e) or stepwise, with removal of water, and in the conjoint reaction of (a), (b), (c), (d) and (e) the water of reaction is removed by azeotropic distillation in the presence of a water-entraining agent, by heating to a maximum of 110‹ C., and the further volatile constituents are then removed at 110-150‹ C. and heating is discontinued when the synthetic resin reaches a B-time of 30 seconds to 6 minutes at 160‹ C.; or in the stepwise reaction (I) first components (b) and (c) optionally in the presence of a water-entraining agent are reacted in a molar ratio of 1 : 1 to 1 : 4, component (b) being calculated as boron, to give an aliphatic boric acid ester (be), or an aliphatic boric acid ester (bc<SP>1</SP>) is employed, the alcohol radical of which from a primary and/or secondary aliphatic C 1 - C 5  monoalcohol; or (Ia) first components (b) and (c) are reacted in a molar ratio of 1 : 1 to 1: 4, component (b) being calculated as boron, to give the ester (bc), in the presence of component (a) and optionally a water-entraining agent at 120-150‹ C., components (a) and (b) being present in a weight ratio of 100 : 5 to 100 : 20, (b) now being calculated as boron oxide; and (II) the ester (be) or (bc<SP>1</SP>) from stage (I) is reacted with components (a), (d) and (e) by heating to 95-100‹ C., the molar ratio of (a) to (e) being from 1 : 1 to 1 : 2À5, and of (b) : (d) being from 1 : 0À1 to 1 : 1, (b) being calculated as boron and (d) as nitrogen, the molar ratio (b) : (d) not exceeding a value of 1 : 0À5 if the weight ratio of (a) : (be) or (bc<SP>1</SP>) respectively is 100 : # 7, where (be) and (bc<SP>1</SP>) are calculated as boron oxide, and wherein (a) and (be) or (bc<SP>1</SP>) are present in a weight ratio of 100 : 5 to 100 : 20, where (be) or (bc<SP>1</SP>) are calculated as boron oxide, or (IIa) the reaction mixture from stage (Ia) is reacted with components (d) and (e) at 95-100‹ C., wherein the molar ratio of (a) to (e) is from 1 : 1 to 1 : 2À5, the molar ratio of (b) : (d) is from 1 : 0À1 to 1À1, (b) being calculated as boron and (d) as nitrogen, and wherein the molar ratio of (b) : (d) does not exceed 1 : 0À5 if the weight ratio of (a) : (b) is 100 : #7, (b) being calculated as boron oxide; and (III) the batches from (II) or (IIa) are then heated under reduced pressure to 110-150‹ C. with removal of the volatile constituents, until the synthetic resin has a B-time of 30 seconds to 6 minutes at 160‹ C. Component (a) may also be employed as a semi-formal. The reaction may be carried out in the presence of an inorganic or organic acid of pK less than 2À5. Suitable substituted phenols (a) are m-cresol, 3,4-, 3,5- and 2,5-dimethylphenol, m-ethyl, or -butyl, or -propyl-phenol, o- and/or p-n- and/or -isopropenylphenol, o- and/or p-allylphenol, phenylphenol, o- and/or p-aminophenols, o- and/or -p- α- and/or -#-phenylethylphenol or phenylisopropylphenol or methylphenylethylphenol and technical alkylation products of olefins and phenols. Suitable bisphenols are dihydroxydiphenylalkane derivatives such as bisphenol A. Suitable components (b) or (bc<SP>1</SP>) are boric acid, boron trioxide, boron trichloride or trifluoride, and the reaction product of boric acid and acetic anhydride. Preferred components (c) are isobutanol and n - butanol. Preferred waterentraining agents are toluene, benzene or xylene. The resins can be used as binders for compression moulding compositions, resin impregnated papers and brake linings.