Di-nonylphenol

Dialkylation of phenol with nonene (propylene trimer) produces di-nonylphenol. It is used in the manufacture of specialty surfactants. The volume of this product is extremely limited. The latter (i.e., Structures 3.8 and 3.9) has been extensively used within surfactant mixtures (Structures 3.8 and 3.9) aimed for laundry detergents in the late 1960s. 

The most widely used alkylphenols in the manufacture of nonionic surfactants are described as follows in the order of their importance. APEs derived from p-nonylphenol account approximately 80% of the total market whereas those derived from octyl phenol account for 15-20%. Dodecyl phenol, di-nonylphenol, and DSBP ethoxylates run a poor third at <5%. 

Alkylphenols di-nonylphenol and 2,6-DSBP are both building blocks for specialty nonionic surfactants through polyethoxylation for use in specialty niche applications. The only significant usage for DSBP, for example, is in emulsifying liquid agrochemicals (see Structures 3.7 and 3.9 found on p. 52). 

Figure 12.7 Cliromatograms of a polycarbonate sample (a) microcolumn SEC ti ace (b) capillary GC ti ace of inti oduced fractions. SEC conditions fused-silica (30 cm X 250 mm i.d.) packed with PL-GEL (50 A pore size, 5 mm particle diameter) eluent, THE at aElow rate of 2.0ml/min injection size, 200 NL UV detection at 254 nm x represents the polymer additive fraction ti ansfeired to EC system (ca. 6 p-L). GC conditions DB-1 column (15m X 0.25 mm i.d., 0.25 pm film thickness) deactivated fused-silica uncoated inlet (5 m X 0.32 mm i.d.) temperature program, 100 °C for 8 min, rising to 350 °C at a rate of 12°C/min flame ionization detection. Peak identification is as follows 1, 2,4-rert-butylphenol 2, nonylphenol isomers 3, di(4-tert-butylphenyl) carbonate 4, Tinuvin 329 5, solvent impurity 6, Ii gaphos 168 (oxidized). Reprinted with permission from Ref. (14).

Cortes et al. [634] have recently used /rSEC-GC/LC in a comparative quantitative study of dissolution and dissolution/precipitation of PC/(2,4-di-f-butylphenol, nonylphenol isomers, Tinuvin 329, Irgafos 168) and ABS/(nonylphenol isomers, Tinuvin P, BBP, Vanox 2246, Tinuvin 328/770, Topanol CA, Acrawax). For the ABS sample the dissolution approach determined a four-fold higher concentration for Vanox 2246 than by dissolution/precipitation of the sample, indicating that precipitation can yield low (incorrect) results for additives which exhibit solubility dependence. Using both sample preparations equivalent concentrations were observed for the additives of the PC sample, except for Tinuvin 329. 

As to the main limitation of MS vs. FTIR detection, namely the inability to distinguish closely related isomers, this rarely plays a role in additive analysis. Notable examples of isomeric additives are the bifunctional stabilisers C22H30O2S as 4,4 -thio-bis-(6-t-butyl-m-cresol), 2,2 -thio-bis-(4-methyl-6-f-butylphenol) and 4,4 -thio-bis-(2-methyl-6-f-butylphenol) (Section 6.3.6), the bisphenolic antioxidants C23H32O2 (Plastanox 2246 and Ethanox 720) and the phenolic antioxidants C15H24O (nonylphenol and di-f-butyl-p-cresol). 

Table 1 Concentrations of nonylphenol and nonylphenol mono- and di-ethoxylates in sewage sludge... 

Di Corcia A, Costantino A, Crescenzi C, Marinoni E, Samperi R (1998) Characterization of recalcitrant intermediates from biotransformation of the branched alkyl side chain of nonylphenol ethoxylate surfactants. Environ Sci Technol 32 2401-2409... 

Aparicio I, Santos JL, Alonso E (2007) Simultaneous sonication-assisted extraction, and determination by gas chromatography-mass spectrometry, of di-(2-ethylhexyl)phthalate, nonylphenol, nonylphenol ethoxylates and polychlorinated biphenyls in sludge from waste-water treatment plants. Anal Chim Acta 584 455 161... 

Fig. 2.11.15. General structural formulae of (I) di-nonylphenolethoxy carboxylates (di-NPEC CnIIl9)2-C6H3-0-(CIl2-CH2-())I-CIl2-C02), (II) nonylphenoldiethoxysulfo-nates (NP(EO)2-S03 C9H19-C6H4-0-(CH2-CH2-0)2-CH2-S03), (III) nonylphenol-ethoxy sulfates (NPEO-SO4 C -Ce -O-fCHa-CHa-O -SOgH), and (IV) nonylphenolethoxy phosphate (NPEO-PO4 O9II19—CBII/ —G—(CH2-CH2-0)x-...

Rudel et al. (2001) reported concentrations of nonylphenol and its mono- and di-ethoxylates up to 14 mg kg 1 in house dust for a 7-sample pilot study in the USA. Concentrations of ethoxylated octylphenols did not exceed 5 mg kg"1. Of the more than 30 phenols analyzed only 4-nonylphenol was found in air with concentrations up to 0.118pgm"3. Wilson, Chuang and Lyu (2001) reported the nonylphenol content of dust samples from 10 child care centers (USA) to be 4.16-13. Smgkg 1 the Bisphenol A content to be 1.04—4.51 mgkg 1, respectively. In their study concentrations in air amounted to 0.052-0.527 ggm 3 for nonylphenol and up to 0.0018ggm 3 for Bisphenol A. 

Phenols/cresols Phenol, 2,5-dimethylphenol, 3,5-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, o,m,p-cresol, p-tetramethylbutylphenol, nonylphenols, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4 -butyliden-bis-(6-tert-butyl) -m-cresol, C-8-alkylphenols, C-9-alkylphenols... 

Organic chemicals that are susceptible to oxidation and are of concern from the perspective of contamination and environmental degradation include aliphatic and aromatic hydrocarbons, alcohols, aldehydes, and ketones phenols, polyphenols, and hydroquinones sulfides (thiols) and sulfoxides nitriles, amines, and diamines nitrogen and sulfur heterocyclic compounds mono- and di-halogenated aliphatics linear alkybenzene-sulfonate and nonylphenol polyethoxylate surfactants and thiophosphate esters. Table... 

Pumiliotoxin B has both cardiotonic and myotonic activity in isolated atrial or rat phrenic nerve diaphragm preparations (97). The cardiotonic activity is markedly dependent on the structure of the pumiliotoxin (95). Subsequent studies on the activity of pumiliotoxin B in neuromuscular preparations were interpreted as due to an apparent facilitation of calcium translocation from internal storage sites (99 see review in Ref. 5). Inhibitory effects on the calcium-dependent ATPase of sarcoplasmic reticulum were shown to be due not to pumiliotoxin B, but to phenolic impurities, namely, fcis(2-hydroxy-3-terf-butyl-5-methylphenyl)methane, 3,5-di-/ert-butyl-4-hydroxytoluene (BHT), and nonylphenols (100). 

Environmental chemicals such as p-nonylphenol (NP), 4-ferf.-octylphenol (OP), 4-ferf.-pentylphenol (TPP), bisphenol-A (BPA), tetrabromobisphenol-A (TBBA), butylbenzylphthalate (BBP), di- -butylphthalate (DBP), butylated hydroxyanisole (BHA), p-chloro-ra-cresol, p-chloro-o-cresol, ds-nonachlor, frans-nonachlor, and the herbicide alachlor [2-chloro-iV-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide] have been discovered to be weakly estrogenic [128,129,137,138]. 

Ferguson et al. [40] reported the analysis of APEO metabolites in estuarine water and sediments. Compounds like nonylphenols, octylphenols, their mono-, di-, and triethoxylates, halogenated nonylphenols, and NPEC were found in water samples after SPE. Individual APEO metabolite concentrations of 1-320 ng/1 in water and 5-2000 ng/g in sediment were found. 

Chlorfenvinphos, Chlorpyrifos, Di(2-ethylhexyl)phthalate (DEHP), Endosulfan, Fluoranthene, Hexachlorobenzene, Hexachlorobutadiene, Hexachlorocyclohexane, Naphthalene, Nonylphenols, Octylphenols, Pentachlorobenzene, Pentachlorophenol, Polyaromatic hydrocarbons, Tributyltin compounds, Trichlorobenzenes, Trifluralin... 

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