Modification of acetophenone—formaldehyde and cyclohexanone—formaldehyde resins

Abstract

SYNOPSISCyclohexanone-formaldehyde and acetophenone-formaldehyde resin were in situ modified with phenol, Bisphenols, and substituted acetophenones. Furthermore, acetophenoneformaldehyde, cyclohexanon-formaldehyde, and in situ-modified resins were modified with anhydrides such as acetic anhydride, maleic anhydride, dodecenylsuccinic anhydride, 3,434'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphtalic anhydride. Modification of these resins with hydroxyl amine, semicarbazide, and phenyl hydrazine were also studied. Melting points, solubilities in organic solvents, FTIR, and NMR spectrum of the modified resins were determined. 0 1996 John Wiley & Sons, Inc. I NTRO DU CTI 0 NModification of cyclohexanone-formaldehyde resin and acetophenone-formaldehyde resin have been previously studied.'.' Hydroxyl groups were reacted with acetyl chloride, benzoyl chloride, phatalic anhydride, and carbonyl groups with hydroxylamine, semicarbazide, and phenylhydrazine.Furthermore, in situ modification of acetophenone-formaldehyde resin was carried out using phen01,~ p-c~mylphenol,~ p-cresol? and Bisphenols' as the modifier compounds. Cyclohexanone-formaldehyde resin was also in situ modified using methyl isobutyl ketone: methyl ethyl ketone,6 methyl cyclohexanone: acetaldehyde,6 propion-aldehyde,6 cinnamaldehyde,6 di~ynadiamide,~ arninotria~ine,~ and phen01.~ In this work, cyclohexanone-formaldehyde resin (CF resin) and acetophenone-formaldehyde resin (AF resin) were modified during resin preparation by the addition of a modifier compound/formaldehyde mixture to the polymerization media. Modifier compounds were phenol, l,l-di(4-hydroxy phenyl)cyclododecane, 1 -phenyl-1,l -di( 4-hydroxy phenyl)etan, 2,4-dichloroacetophenone, and 4-bromoacetophenone. AF resin, in situ-modified AF res-* To whom correspondence should be addressed. ins, and in situ-modified CF resins were modified via their hydroxyl, phenolic hydroxyl, and carbonyl groups. EXPERIMENTALIR spectra were recorded on a Jasco FTIR-5300 Fourier transform infrared spectrometer. 'H-NMR spectra were obtained for the CDC13 solution on a Bruker AC (200 MHz). GPC chromatograms were obtained using a Knauer M64 instrument equipped with a differential refractometer. The preparations of these resins were carried out as described previously.

Ladder type polymers from dihydroxyaromatic compounds and dialdehydes

“…2,2-Di(4-hydroxyphenyl)propane, (Bisphe-nol-A) 5) , 1,1-di(4-hydroxyphenyl)cyclohexanone (Bisphenol-C) 6) , and 1-phenyl-1,1-di(4-hydroxyphenyl)ethane (Bisphenol-ACP) 7) were synthesized as described in the literature. 2,2-Di(4-hydroxyphenyl)propane, (Bisphe-nol-A) 5) , 1,1-di(4-hydroxyphenyl)cyclohexanone (Bisphenol-C) 6) , and 1-phenyl-1,1-di(4-hydroxyphenyl)ethane (Bisphenol-ACP) 7) were synthesized as described in the literature.…”

Chain extended cyclohexanone-formaldehyde and acetophenone-formaldehyde resins

“…Cyclohexanone-formaldehyde (CF, 10) and acetophenone-formaldehyde (AF, 20) resins (Scheme 1) were modified via their hydroxyl and carbonyl groups in earlier studies. [1][2][3] The type of modifying compound had a marked affect on the melting point and solubilities of the modified resins. The molecular weights of the ketonic resins were not increased considerably by the modification reactions.…”

“…[1][2][3] For example, when the molar ratio of hydroxyl to anhydride was about 1, all the hydroxyl groups of the ketonic resin reacted with phthalic anhydride to give a modified ketonic resin containing free carboxylic acid groups in place of the hydroxyl groups. If this ratio was 9 : 1, a dimeric chain extended CF resin was produced 3 because each CF-resin molecule contained approximately nine hydroxyl groups. Chain extensions of ketonic resins with an extender reagent such as anhydrides, dimethyl dichlorosilane, phosphorus oxychloride, or toluene-2,4-diisocyanate (TDI) were achieved and preliminary results were obtained.…”

Chain extension of ketonic resins

“…Furthermore, the reaction of hydroxyl groups of ketonic resins with phthalic anhydride (Ref. 3 In this work, the chain extension of ketonic resins by the reaction of their hydroxyl groups with dimethyldichlorosilane, phosphorus oxychloride, toluene-2,4-diisocyanate, phthalic anhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, tetrahydro phthalic anhydride, have been carried out in order to modify their physical properties such as solubilities in organic solvents, melting point , adhesive properties and flammability.…”