Bisphenol-type compounds

Bisphenol A is used as a raw material to make polycarbonate and epoxy adhesives and can coatings. It is also used in flame-retardants, in unsaturated polyesters and in polyacrylate resins. Many foodstuff containers are made of these resins, including containers for oven and microwave cooking. Recent studies have shown that bisphenol type compounds have both mutagenic and cytotoxic properties [84]. Nerin et al. developed a fast screening method based on SPME and HPLC with fluorescence detection suitable for the analysis of several bisphenol derivatives and their degradation products in aqueous canned foods such as tuna, olives and corn [85]. The best results were obtained with carbowax and PDMS/DVB fibers. The detection limits were between 0.7 and 2.4ngmL while RSDs were between 14 and 32%. After the extraction parameters were optimized, the method was applied to... 

It is of interest that when aluminum porphyrin is used, oligomers or polymers of controlled molecular weight distribution can be produced by using bisphenol A or related bisphenol-type compounds as chain transfer agents. 

Internal mixing is widely used with fluorocarbon elastomers. Gumstocks and compounds that are particularly successful fall in the viscosity ranges discussed earlier, and use both incorporated bisphenol-type and peroxide cure systems. A typical internal mix cycle mns 6—8 min with a drop temperature of 90—120°C. The typical formulations in Tables 4 and 7 are readily mixed in an internal mixer. 

Lattimer and co-workers [25] have applied mass spectrometry (MS) to the determination of antioxidants and antiozonants in rubber vulcanisates. Direct thermal desorption was used with three different ionisation methods [electron impact (El), chemical ionisation (Cl), field ionisation (FI)]. The vulcanisates were also examined by direct fast atom bombardment mass spectrometry (FAB-MS) as a means for surface desorption/ionisation. Rubber extracts were examined directly by these four ionisation methods. Of the various vaporisation/ionisation methods, it appears that field ionisation is the most efficient for identifying organic additives in the rubber vulcanisates. Other ionisation methods may be required, however, for detection of specific types of additives. There was no clear advantage for direct analysis as compared to extract analysis. Antiozonants examined include aromatic amines and a hindered bisphenol. These compounds could be identified quite readily by either extraction or direct analysis and by use of any vaporisation/ionisation method. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

Whereas Sears and Darby (7) found many types of compounds which would plasticize bisphenol A polycarbonate when the plasticizer concentration was 25 to 30%, the norbornane-tvpe polycarbonates could be plasticized only with larger amounts of plasticizer. When present in concentrations of 20 to 30%, conventional plasticizers acted as diluents—that is, the tensile modulus and tensile strength were depressed, as occurs with plasticizers, but the elongation was not appreciably increased. The antiplasticizers also acted similarly and became diluents after their peak antiplasticizing action was reached. 

In a similar way as has been described for syntheses of type al, the majority of examples of type b involve polycondensation of a,ea bifunctional, small molecule reaction partners. Some examples are the reaction of AIBN or AIBN derivatives with 1,4-cyclohexane bismethyl diamine78), 1,2-ethylene diamine78), 1,6-hexamethylene diamine 78-80 , bisphenol A 78,81 and mono-, di- and tetraethylene glycol 55-64 . In almost all case using the AIBN derivative 4,4 -azobis(4-cyano valeryl chloride), an interfacial polymerization was employed. These polymeric azo compounds could be used as initiators for radical block copolymerizations. 

Of all the compounds prepared in this work, these latter compounds, the ortho-linked compounds derived from dimercaptans, come the closest to realizing our objective of structures with the activity of a bisphenol and the nondiscoloring characteristics of a monocyclic phenol. For example, Table IV shows some results in cw-polybutadiene which demonstrate that a compound of the type XXVI is superior as a heat stabilizer to both 2,6-di-terf-butyl-4-methylphenol and 2,2 -methylenebis(4-methyl-6-ferf-butylphenol) in both activity and color. Screening results in cis-... 

The main decomposition product of poly(bisphenot A carbonate) during flash pyrolysis, which is detected using the separation on a Carbowax column, is phenol. Bisphenol A (which has the base peak at 213 a.u. and the molecular ion at 228 a.u.) is not detected in the pyrogram, although other studies indicate its presence in the pyrolysate as a major component. Very likely, bisphenol A does not elute in the experimental conditions used for the pyrolysate separation. A broad peak in the pyrogram tentatively identified as diethylene glycol dibenzoate may be the result of the presence of an additive. These Py-GC/MS results are in agreement with various studies on thermal decomposition of poly(bisphenol A carbonate) [16]. The formation of C02 in the thermal decomposition of these compounds can be explained by reactions of the type ... 

We have investigated the recovered glassfiber-resin powder for its properties as a filler for epoxy resin compounds which are used as paints or adhesives, and compared it to conventional fillers, such as talc and calcium carbonate. The epoxy resin compound, composed of bisphenol A type epoxy resin (50.0wt%), aliphatic polyamine type hardener (18.0wt%) and filler (32.0%), was prepared. Strength and thermal expansion properties were measured for the molded epoxy resin compound cured 23°C for 7 days. Viscosity was measured for the epoxy resin compound before adding the hardener. Adhesive strength was measured by tearing two ferric boards bonded with the epoxy resin compound which was composed of bisphenol A type epoxy resin (49.2wt%), polyaminoamide type hardener (18.0wt %), and filler (32.8wt%), and was cured at 23°C for 7 days. 

At least some of the ways toward which other chemicals have turned to capture the researcher s attention are clearly shown in a few specific examples. Functionality in the new product is most important where the ultimate application involves its use as an intermediate or as a monomer. Development of bisphenol, epichlorohydrin, and peroxygenated compounds are examples resting upon this type of situation. Our own diallylmelamine is a similar example. 

Other types of polycarbonates have also been made using a very different approach from that involving bisphenol A and related compounds. For example, the reaction between phosgene and allyl alcohol (CH2=CHCH2OH) produces a monomer with carbon-carbon double bonds at both ends of the molecule that can be used for polymerization. Interestingly enough, the polycarbonate produced by this process has very different physical properties from the traditional bisphenol A polymer. The allyl polymer is a clear, transparent, flexible plastic whose primary use is in the production of eyeglass lenses. 

Another use of 4-/ i octylphenol is in the production of uv stabilizers. 4-/ f-Octylphenol reacts with sulfur dichloride to yield the thio-bisphenol derivative, which then reacts with nickel acetate to form 2,2 -thiobis(4-/ octylphenolate)-A -butylamine nickel [14516-71-3]. This type of stabilizer is widely used in the production of outdoor carpeting based on polypropylene fibers. Nickel compounds give a green discoloration which limits their applications. A second class of uv stabilizers based on the benzotriazole stmcture. 2-(2 -hydroxy-5 -/ f2 octylphenyl)benzotriazole [3147-75-9] is produced from 4-/ y-octylphenol (55). 

The appearance of an intense peak at m/e = 119 signifies the presence of a styryl moiety (which typically appears in bisphenol A type structures). This appears in the MS spectra of IV and V, but is absent in the MS spectra of compounds VI, VII, and VIII. 

Bisphenol A is produced by the condensation reaction of excess phenol with acetone in the presence of an acidic catalyst. Sulfur compounds that may be used as a cocatalyst include alkyl mercaptans, such as methyl mercaptan, ethyl mercaptan and thioglycol acid. Recently, a catalyst composed of an acid-type ion exchange resin, which is modified in part with a sulfur-... 

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