Para-tertiary-butylphenol Research Articles

Assessment of Contact Allergens in "Hypoallergenic" Athletic Shoes by Mass Spectrometry.

Background: Identification of athletic shoes for patients with contact allergy is difficult. Company reports of allergen content are often incorrect. Objectives: To determine whether chemical analysis of 4 athletic shoes, previously reported to be free of the most common contact allergens, contain quantifiable allergen levels. Methods: Samples from the uppers and insoles of 4 shoes believed to be free of common allergens were assessed by mass spectrometry. A total of 4 rubber accelerators and 2 adhesives were directly quantified and additional 7 rubber accelerators were assessed using semiquantitative measures. Results: Aside from carbamates (assayed as 59 ppm zinc in insoles) in SeaVee's Sixty-Six sneakers, para-tertiarybutylphenol formaldehyde resin (PTBFR) (assayed as 7.6 ppm paratertiary butylphenol or 4-tertiary butylphenol [4TBP] in uppers) in Allbirds Tree Runners and rosin (assayed as 628 ppm sodium abietate in uppers) and carbamates (24 ppm zinc in uppers) in Saucony Jazz sneakers, these shoes had low levels of all allergens assayed in this study. Tom's Carlo sneakers contained rosin (127 ppm sodium abietate in insoles), PTBFR (6.5 ppm 4TBP in uppers), and carbamates (112 ppm sodium abietate in insoles) but had low levels of all other assayed allergens. Conclusions: Although identifying allergen-free shoes is challenging, the results of this analysis will help patch testing physicians recommend athletic shoes to patients with specific allergies.

Improvement of the unit for obtaining a commercial product of the para-tertiary butylphenol synthesis unit

Improvement of the unit for obtaining a commercial product of the para-tertiary butylphenol synthesis unit

Novel ionic liquid-templated ordered mesoporous aluminosilicates: Synthesis, characterization and catalytic properties

Abstract Highly crystalline ordered mesoporous aluminosilicates with hexagonal AlIITM-41 and cubic AlIITM-48 pore symmetries with varying silicon-to-aluminium ratios were hydrothermally synthesized, for the first time, using long-chain ionic-liquid (IL) such as 1-hexadecyl-3-methylimidazolium chloride (HDMIC), as structure directing agent. The prepared materials were systematically characterized by various analytical, spectroscopic and imaging techniques, viz., XRD, BET, TEM and XRF. In addition, the extent of aluminium incorporation and the nature of acid sites were deduced from 27 Al MAS-NMR and NH 3 -TPD measurements. The structural and physico-chemical properties of both AlIITM-41 and AlIITM-48 were compared with analogous AlMCM-41 and AlMCM-48, respectively prepared using hexadecyltrimethylammonium bromide (CTAB). It was found that all the ionic liquid-templated materials, viz., AlIITM-41 and AlIITM-48, and exhibited large surface area, high crystallinity and thicker pore walls. The observed superior orderness of AlIITM-41 and AlIITM-48 could attribute to a well distributed positive charge and π-π stacking of aromatic imidazolium head group of ionic-liquid. In addition, it also assisted in the incorporation of all the aluminium species exclusively in the tetrahedral silicate framework even after the calcination as confirmed by 27 Al MAS NMR. AlIITM-41 and AlIITM-48 possess more medium and strong Bronsted acid sites due to their thicker walls, high crystallinity and presence of tetrahedral aluminium in the framework, due to which they exhibited higher catalytic activity towards tertiary butylation of phenol with a good Para tertiary butyl phenol selectivity compared to commonly used aluminosilicates, H-AlMCM-41 and H-AlMCM-48.

Provoking factors, including chemicals, in Dutch patients with vitiligo

In vitiligo, many provoking factors have been described, but epidemiological data, especially on the role of contact with chemicals, are scarce. To obtain an insight into the patient-reported factors provoking vitiligo, including contact with chemicals. A retrospective cohort study was conducted on all 1264 patients with vitiligo who visited the Netherlands Institute for Pigment disorders from January 2003 to December 2007. Patients for whom an exogenous provoking factor was recorded were sent a questionnaire. Subsequently, patients who mentioned a chemical provoking factor were contacted to elucidate the alleged causal relationship between exposure to the chemical and the onset of vitiligo. A total of 300 out of the 1264 patients indicated that provoking factors had played a role in their disease. Two hundred and forty-six patients were sent a questionnaire, which was returned by 177 (response rate of 72%). Emotional stress was indicated as a provoking factor in 98 patients (55.4%), 51 patients (28.8%) recorded sunburn, 34 patients (19.2%) recorded mechanical factors and 20 patients (11.3%) other factors. Of 29 patients (16.4%) who indicated a chemical factor, a presumed causal relationship could be corroborated in four. The chemicals involved were para-tertiary butylphenol (n = 2), captan (n = 1) and diphencyprone (n = 1). The majority of the patients with vitiligo from this study did not mention provoking factors, but the ones who did point to emotional stress in more than half of the cases. Of the 29 patients who assigned chemical provoking factors, solvents were mainly indicated. However, a presumed relationship with the chemical could be corroborated in only four patients.

10 years' experience of patch testing with a shoe series in 230 patients: which allergens are important?

Over a 10-year period, 230 patients with foot dermatitis were patch tested to a shoe series of allergens. About 54 (23%) had relevant allergic positive reactions to one or more allergens. The commonest relevant allergens groups were, in order, chromate, medicaments, rubber chemicals, dyes and cosmetic constituents, with the most frequent individual allergens being chromate (4%), neomycin (3%), rubber chemicals (> 3%), paraphenylenediamine (2%) and tixocortyl pivolate (2%). Some allergens previously thought to be important, e.g. certain plastic and adhesive chemicals, did not show any positives over the period of study. In addition, para-tertiary butyl phenol formaldehyde resin was a relatively unimportant allergen in this series. The main practical points to emerge from this study are that, in patients with foot dermatitis, chromate is still the principal allergen, and that medicament and cosmetic allergens may be prominent.

Allergic contact dermatitis in Iran

The frequency of sensitization to contact allergens varies in different countries because of both genetic and, more importantly, allergen exposure variations. The objective is to determine the frequency of sensitization to contact allergens in Iranian patients with dermatitis. 250 patients with a clinical diagnosis of contact dermatitis and/or atopic dermatitis were evaluated with a 28-allergen screening series recommended by the German Contact Dermatitis Research Group from September 2002 to April 2004 in Tehran, Iran. The patches were applied on the back of the patients, removed after 24 hr and the readings were taken on 24 hr, 48 hr and 72 hr after application. 126 patients (50.4%) showed at least 1 positive reaction, and 23 patients (9.2%) had more than 2 positive reactions. 189 (84.4%) of 224 positive reactions had past and/or present clinical relevance. The 5 most common allergens were nickel sulfate 70 (28.0%), cobalt chloride 32 (12.8%), para-tertiarybutyl phenol formaldehyde resin 20 (8.0%), potassium dichromate 13 (5.2%) and colophony 13 (5.2%). Contact allergy to nickel sulfate was significantly more common in female patients and in patients under 40 years of age (P < 0.05). Nickel sulfate is the most common contact allergen in Iran, mostly affecting women and younger patients probably because of more exposure.

Vapor-Phase Tertiary Butylation of Phenol Over Mesoporous Gallosilicate Molecular Sieves

Isomorphously substituted GaMCM-41 molecular sieves with different Si:Ga ratio were synthesized and characterized systematically by various analytical and spectroscopic techniques. Temperature-programmed desorption of ammonia was used to identify the nature of acidic sites. For the first time, the vapor-phase tertiary butylation of phenol reaction was carried out over protonated GaMCM-41. The catalysts showed higher (phenol) conversion and good (para-tertiary butyl phenol) selectivity over the Al- and Fe-analogs of MCM-41. Further, the gallosilicates showed good stability both before and after the reaction compared to the aluminosilicates or ferrisilicates.

Active sensitization and occupational allergic contact dermatitis caused by para-tertiary-butylcatechol.

Para-tertiary-butylcatechol (PTBC) is a rare allergen which is used in the rubber, paint and petroleum industries. We present 9 patients who were sensitized to PTBC and examined at the Finnish Institute of Occupational Health (FIOH) between 1974 and 1995. 3 of the patients had been exposed to PTBC in their work. 2 of them also had allergic reactions to para-tertiary-butylphenol (PTBP)-formaldehyde resin and to PTBP. 5 of the patients became sensitized to PTBC from patch testing. PTBC was found to be one of the most common causes of active sensitization in our clinic. Accordingly, at the FIOH, the patch test concentration of PTBC was lowered to 0.25% and this lower concentration is recommended for general use.

Erythema Multiformlike Contact Dermatitis: Report of Four Cases

Four women patients developed an erythema multiformlike eruption associated with an allergic contact dermatitis. The responsible allergens included povidone-iodine, hair dyes, paratertiary butylphenol formaldehyde resin, disperse blue 124, and hair lotion. The pathogenesis of the secondary polymorphic reactions associated with allergic eczematous dermatitis remains obscure. According to the new pathogenetic classification of eczemas recently proposed by Happle, these reactions may be included in the group of paraptic eczema.

Allergic contact dermatitis of the lip margins from para‐tertiary‐butylphenol in a lip liner

We describe the use of gas chromatography with mass spectrometry (GC-MS) in the investigation of a case of allergic contact dermatitis of the lip margins caused by a lip liner. Patch testing identified sensitization to para-tertiary-butylphenol-formaldehyde resin (PTBP-FR), a resin glue frequently used in leather work but rarely found in cosmetics. Investigation specified the para-tertiary-butylphenol (PTBP) component of the resin as the hapten responsible for the allergic contact dermatitis, as well as for associated depigmentation.

Contact depigmentation from free para‐tertiary‐butylphenol in bindi adhesive

100 consecutive cases of contact depigmentation due to bindi during a period of 11 months were studied. Bindi adhesive material was found to contain 80% para-tertiary-butylphenol (PTBP), by thin-layer chromatography, infrared spectrophotometry and high-pressure liquid chromatography. The possibility of hypersensitivity to PTBP was ruled out as none of the 15 patients tested with 2% PTBP and 1% para-tertiary-butylphenol-formaldehyde resin gave any positive reactions. Development of depigmentation could have been due either to individual susceptibility or to constant use for a prolonged period. The area of contact being very small, generalised vitiligo as a result of systemic absorption appeared to be a remote possibility.

Clinical aspects of para‐tertiary‐ butylphenolformaldehyde resin (PTBP‐FR) allergy

Sensitization by para-tertiary-butylphenolformaldehyde resin (PTBP-FR), which is particularly useful as a leather glue, has been known for 30 years. We retrospectively studied the clinical aspects of those patients with a PTBP-FR allergy among 1966 patients in whom contact dermatitis was confirmed by patch testing. A positive patch test to PTBP-FR was present in 30 patients (1.5%), 24 of whom were women. Exposure to PTBP-FR as a cause of the dermatitis was "certain" in 7, "very likely" in 6 and "unclear" in 17. 67.7% of the patients had a multiple allergy. In 43.3% of the patients, a history of atopy was found. No clear association of PTBP-FR sensitization with allergies to phenolformaldehyde resin (P-FR) or free para-tertiary-butylphenol (PTBP) emerged in this group of 30 patients. This study supports the hypothesis that PTBP-FR and P-FR do not contain the same sensitizers. Follow-up of 26 of the 30 patients showed a favourable course, dependent on identification of the source of exposure, avoidance of further contact and absence of sensitization to multiple allergens.

Acute Toxicity and Primary Irritation of Para-Tertiary Butylphenol

Para-tertiary butylphenol [(PTBP); the Union Carbide Corporation trademark for this chemical is UCAR Butylphenol 4-T Flake] has applications as a raw material in the manufacture of resins and also as an industrial intermediate. Acute peroral LD50 values (95% confidence limits) of 5.4 (3.6-7.9) g/kg and 3.6 (3.0-4.4) g/kg were obtained for male and female albino rats, respectively. Occluded cutaneous applications of moistened PTBP at 16 g/kg for 24 hr produced no mortalities in male or female rabbits, but signs of local toxicity and irritation were apparent at the site of application. A 6 hr exposure to a substantially saturated vapor under static conditions produced no mortality, while a 4 hr exposure to a dynamically generated respirable dust aerosol at a concentration of 5.6 mg/L produced 20% mortality. Occluded dermal contact (4 hr) with 0.5 g moistened PTBP produced a range of effects from no reaction to necrosis. PTBP placed in the conjunctival sac of rabbits produced severe ocular injury which generally persisted for 21 days after exposure. The major hazard associated with acute exposure to PTBP appears to be the irritation produced by dermal or ocular contact.

Demonstration of contact sensitizers in resins and products based on phenol-formaldehyde.

12 phenol-formaldehyde resins were investigated with regard to the presence of 14 contact sensitizers by using high-pressure liquid chromatography. The allergens consisted of simple methylol phenols, dihydroxydiphenyl methanes, 4,4(1)-dihydroxy-(hydroxymethyl)-diphenyl methanes and 2,4(1)-dihydroxy-(hydroxymethyl)-diphenyl methanes. Four substances, 2,4-dimethylol phenol, 2,6-dimethylol phenol, 4,4(1)-dihydroxydiphenyl methane and 2,4(1)-dihydroxydiphenyl methane, were isolated from a resol resin and identified by mass-spectrometry and nuclear magnetic resonance spectrometry. The highest concentrations (up to 15% w/w) of allergens were noted for methylol phenols in resol resins based on phenol and formaldehyde. The corresponding novolak resins showed a high content of dihydroxydiphenyl methanes. There was great variation in concentration of the sensitizers between the resins. None of these sensitizers were demonstrated in the resin based on paratertiary-butyl phenol. Products based on phenol-formaldehyde resins were also investigated for the presence of allergens. Uncured impregnated paper for laminate production and uncured mineral wool contained the same concentrations of the sensitizers as some of the resins studied. The curing process decreased the content of all the allergens investigated in all products, but the sensitizers did not disappear, and they may thus be present in finished products.

Contact allergy to phenol-formaldehyde resins.

Adverse reactions to phenol-formaldehyde resins include depigmentation, irritant dermatitis, chemical burns and allergic contact dermatitis. Allergic contact dermatitis from phenol-formaldehyde resin has mainly been ascribed to resins based on paratertiary-butyl phenol and formaldehyde, and such a resin is included in the ICDRG standard patch test series. When 1220 patients were patch tested with this resin as well as with 2 other phenol-formaldehyde resins, based on phenol and formaldehyde, 26 patients were positive to at least 1 resin. The figures for positive reactions to paratertiary-butyl phenol-formaldehyde resin and the 2 other resins were 0.8%, 1.0% and 3.0% (440 tested subjects), respectively. Therefore, a battery of phenol-formaldehyde resins should be used for screening purposes, since patch testing with the paratertiary-butyl phenol-formaldehyde resin is not sufficient to identify patients with contact allergy to phenol-formaldehyde resins. Several of the 26 patients were patch tested with the basic substances phenol, formaldehyde and paratertiary-butyl phenol, but only 1 positive reaction to formaldehyde was noted. The sensitizing capacity of 2-methylol phenol, 4-methylol phenol and 2,4,6-trimethylol phenol, all 3 compounds being possible ingredients of resins based on phenol and formaldehyde, was demonstrated; 5 of 14 resin positive patients reacted to at least 1 of these methylol phenols.

Occupational Vitiligo Caused by Paratertiary Butylphenol

To the Editor.— Occupational vitiligo caused by paratertiary butylphenol (ptBP) has been reported in the United States, the USSR, Japan, and the Netherlands. In three cases reported recently in West Germany, 1-3 there were hepatic dysfunctions, with slight increases in the serum glutamic oxaloacetic transaminase and serum glutamic pyruvic transaminase levels and with distinct increases in the retention of sulfobromophthalein sodium. Polymorphism of the hepatocytes and disintegration of the cytoplasm were seen in liver biopsy specimens from all three patients; specimens from two patients showed disseminated fatty degeneration. With the use of scintigraphy, enlargement of the spleen was seen in two of the patients. In all three cases, the presence of diffuse strumas was confirmed scintigraphically. Extensive functional evaluation, with the use of long-acting thyroid stimulator, disclosed intrathyroidal disorders of thyroid hormone synthesis. Antibody evaluations were positive. I believe that these are the first three cases to be reported of

Resin Dermatitis in a Car Factory

An outbreak of dermatitis in a car assembly factory is described; it affected 50 workers who handled rubber weatherstrips coated with an adhesive. The adhesive was found to contain para-tertiary butyl phenol (P.T.B.P.) formaldehyde resin. Of those patch tested 70% gave positive reactions to the adhesive and 65% to the resin. Improved methods of handling and personal protection succeeded in arresting the occurrence of dermatitis. Barrier creams gave no protection in these circumstances. The episode illustrates the different preventive control methods which have to be tried when dealing with a simple skin hazard which cannot be abolished.

Occupational eczema due to para-tertiary butylphenol in a shoe adhesive.

Occupational eczema due to para-tertiary butylphenol in a shoe adhesive.