Contact Allergy to Trimers in <i>p-tert</i>-Butylphenol-Formaldehyde Resin

Abstract

Allergy to p-tert-butylphenol formaldehyde resin (PTBP-F-R) is not rare. More knowledge about the sensitizers in the resin can contribute to the development of diagnosis and prevention. The objective was to study some trimers in PTBP-F-R. Preparative and analytical high-pressure liquid chromatography, nuclear magnetic resonance spectrometry, mass spectrometry and patch testing in patients hypersensitive to PTBP-F-R were used. Four trimers were isolated and identified: 4-tert-butyl-2,6- bis-(5-tert-butyl-2-hydroxy-3-hydroxymethyl-benzyloxy-methyl)-phenol (XIII), 4-tert-butyl-2-(5-tert-butyl-2-hydroxy-benzyloxymethyl)-6-(5-tert-butyl-2-hydroxy-3-hydroxymethyl-benzyloxymethyl)-phenol (XIVa), 9,17,25-tri-tert-butyl-27,28,29-trihydroxy-2,3,4,5,12,13,20,21-octahomo-3,5,13,21-tetraoxacalix[3]arene (XVIIa) and 7,15,23-tri-tert-butyl-25,26,27-trihydroxy-2,3,10,11,18,19-hexahomo-3,11,19-trioxacalix[3]arene (XVIII). Six patients hypersensitive to PTBP-F-R were patch tested with serial dilutions of XIII, XIVa, XVIIa and XVIII. Six 6, 1 and 0 patients reacted positively to XIII, XIVa, XVIIa and XVIII, respectively. No control patient reacted positively to XIII or XIVa. Positive patch test reactions were seen down to 0.025 mmol × 1^–1 for XIII and XIVa. The study shows that XIII and XIVa are allergens in PTBP-F-R and strongly argues that XVIIa is also one.

Sensitizing capacity of some trimers in p‐tert‐butylphenol‐formaldehyde resin

“…The purpose of this study was to determine the sensitizing capacities of 3 PTBP‐F‐R trimers and to investigate the cross‐reaction patterns using the guinea pig for sensitization. The isolation of the trimers from PTBP‐F‐R has recently been published by our group (5). The substances are 4‐ tert ‐ butyl‐ 2,6 ‐bis‐ (5 ‐ tert ‐butyl‐ 2 ‐hydroxy‐ 3 ‐hydroxymethyl‐benzyloxy‐methyl)‐phenol (XIII), 4‐ tert ‐ butyl‐ 2 ‐ (5 ‐ tert ‐butyl‐ 2 ‐hydroxy‐benzyloxymethyl)‐ 6 ‐ (5 ‐ tert ‐butyl‐ 2 ‐hydroxy‐ 3 ‐hydroxymethyl‐benzyl oxymethyl)‐phenol (XIVa) and 7,15,23‐tri‐ tert ‐butyl‐25,26,27‐trihydroxy‐2,3,10,11,18,19‐hexahomo‐3,11,19‐trioxacalix(3)arene (XVIII).…”

Is p‐tert‐butylphenol‐formaldehyde resin (PTBP‐FR) in TRUE Test® (Mekos test) sensitizing the tested patients?

“…We know from other studies that the concentration of one of the main sensitizers (substance 2) can vary more than 10-fold in different PTBP-FRs (16). When comparing the concentrations of some monomers, Corresponding values published previously for two other PTBP-FRs (PTBP-FR 1 and 2) are given for comparison (2,5,13). 1, 4-tert-butyl-2,6-bis-hydroxymethyl-phenol; 2, 4-tert-butyl-2- dimers and trimers in the TRUE Test ® resin, and in the resins used for patch testing at the Malmö department, we found higher concentrations of these substances in the TRUE Test ® resin, indicating that this resin has a lower degree of polymerization or condensation.…”

“…Previously determined and published concentrations of these substances in two other PTBP-FRs are given for comparison (2,5,13). The concentrations of monomers, dimers and trimers were generally higher in the TRUE Test ® resin.…”

“…Previously isolated and identified samples of the different low molecular weight PTBP-FR constituents, substances 1, 2, 4, and 5 ( Fig. 1), served as reference substances for determination of the amounts of these substances in PTBP-FR (3,5,6,13). No reference was available for substance 3 at the time.…”

Concentration variability of potent allergens of p-tert-butylphenol-formaldehyde resin (PTBP-FR) in patch test preparations and commercially available PTBP-FR

“…Two main allergens in the resin with high sensitizing capacity in guinea pigs have been isolated and described 35–40 . Elicitation studies in sensitized patients have demonstrated that these allergens play a vital role in contact allergy to PTBP‐FR in humans 41–44 . The allergens are the dimers, 4‐ tert ‐butyl‐2‐(5‐ tert ‐butyl‐2‐hydroxy‐3‐hydroxymethyl‐benzyloxymethyl)‐6‐hydroxymethylphenol and 4‐ tert ‐butyl‐2‐(5‐ tert ‐butyl‐2‐hydroxy‐benzyloxymethyl)‐6‐hydroxymethylphenol.…”