Benzophenone-antioxidant

Figure 6. Inhibition of discoloration with benzophenone-antioxidant combination—Fade-ometer exposure...

Kellum [115] has described a class-selective oxidation chemistry procedure for the quantitative determination of secondary antioxidants in extracts of PE and PP with great precision (better than 1 %). Diorgano sulfides and tertiary phosphites can be quantitatively oxidised with /-chloropcroxybenzoic acid to the corresponding sulfones and phosphates with no interference from other stabilisers or additives. Hindered phenols, benzophenones, triazoles, fatty acid amides, and stearate... 

As already shown, it is technically possible to incorporate additive functional groups within the structure of a polymer itself, thus dispensing with easily extractable small-molecular additives. However, the various attempts of incorporation of additive functionalities into the polymer chain, by copolymerisation or free radical initiated grafting, have not yet led to widespread practical use, mainly for economical reasons. Many macromolecular stabiliser-functionalised systems and reactive stabiliser-functionalised monomers have been described (cf. ref. [576]). Examples are bound-in chromophores, e.g. the benzotriazole moiety incorporated into polymers [577,578], but also copolymerisation with special monomers containing an inhibitor structural unit, leading to the incorporation of the antioxidant into the polymer chain. Copolymers of styrene and benzophenone-type UV stabilisers have been described [579]. Chemical combination of an antioxidant with the polymer leads to a high degree of resistance to (oil) extraction. 

Polystyrene light stabilization has been achieved with a variety of ulfravioler absorbers including the benzophenones, benzotriazoles. and salicylates. While yellowing of polystyrene occurs in many applications, it is particularly noticeable in diffusers used with fluorescent lights. This problem has been effectively solved by using ultraviolet light absorbers. In this instance, superior stabilization is achieved when the ultraviolet absorber is used in conjunction wirh specific antioxidants. 

The stabilizers chosen for evaluation include different types of heat and light stabilizers selected to represent different mechanisms of action as well as chemical compositions (ArJi). Types of stabilizers evaluated include benzotriazole and benzophenone light stabilizers [ultraviolet (UV) light absorbers], hindered amine light stabilizers (HALS, catalytic radical scavengers), hindered phenol heat stabilizers (antioxidant radical scavengers), and thioester heat stabilizers (antioxidant hydroperoxide decomposers). 

Poly[styrene-co-(2-hydroxy-4 -vinylbenzophenone)] was less efficient in PS than 2-hydroxy-4-methoxybenzophenone [334]. Similarly, PE films doped with 4-dodecyloxy-2-hydroxybenzophenone (0.1 mol%) were more stable than PE doped with copolymers of ethylene with polymerisable benzophenones having a comparable content of chromophores [54]. The efficiency of a SAN type LS, a terpolymer of 2-hydroxy-4-(4-vinylbenzyloxy)benzophenone with acrylonitrile and styrene did not exceed that of conventional LS [84]. No efficiency loss of 2-hydroxy-4-methacryloyloxybenzophenone in ABS was observed after bonding into a terpolymer with styrene and acrylonitrile. The homopolymer was slightly inferior to both the monomer and terpolymer [84]. A better protection of PP was provided by poly[(2-hydroxy-3-allyl-4-methoxyphenylbenzophenone)-co-dibutyl maleate] than with 2-hydroxy-3-allyl-4-methoxybenzophenone [335] (stabilization tests were performed in the presence of phenolic antioxidants). A comparable or better light stabilizing efficiency of poly[vinyl acetate-co-(5-methylacryloyloxy salicylate)] or poly(2-allylphenyl salicylate-co-dioctyl maleate) than that of alkyl-phenyl salicylates was observed in polyolefins [335]. 

The variety of substances used as additives in polymers is considerable. For example, the fillers may include china clay, various forms of calcium carbonate, talc, silicas (diatomaceous silica), silicates, carbon black, etc. The impact modifiers typically include other polymers. Plasticizers include certain polymers with low (oligomers), dialkyl phthalates, dialkyl sebacates, chlorinated paraffin waxes, liquid paraffinic fractions, oil extracts, etc. Heat stabilizers include heavy metals salts such as basic lead carbonate, basic lead sulfate, dibasic lead phosphite (also acting as a light stabilizer), dibasic lead phthalate, stearates, ricinoleates, palmitates and octanoates of cadmium and barium, epoxide resins and oils, amines, diphenylurea, 2-phenylindole, aminocrotonates. The antioxidants include tris-nonyl phenyl phosphite, 2,6-di-ferf-butyl-p-cresol (BHT), octadecyl-3,5-di-terf-butyl-4-hydroxyhydrocinnamate, etc. The UV stabilizers include modified benzophenones and benzotriazoles. Processing lubricants include calcium stearate, stearic acid, lead stearate, various wax derivatives, glyceryl esters and long-chain acids. Fire retardants include antimony oxide, some pyrophosphates, etc. 

The free-radical-scavenging activity of compounds was evaluated in the TEAC and CL assays. The first measures the relative abiUty of antioxidant substances to scavenge the radical cation 2,2 -azinobis(3-ethylbenzothiozoline-6-sulfonate) (ABTS" ) as compared to a standard amount of the synthetic antioxidant Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid). The CL assay measures the inhibition of iodophenol-enhanced chemiluminescence by a horseradish peroxidase/perborate/luminol system. Trolox was used as the reference antioxidant. The results showed that xanthones exhibited free-radical-scavenging activity at potency levels comparable to those of reference antioxidant compounds quercetin and rutin, while the benzophenone and phloroglucinol type compoimds had more moderate activities [87]. 

Direct grafting of antioxidants on polypropylene has been accomplished by treatment with 3,5-di- erf-butyl-4-hydroxylbenzyl acrylate and a photoactivator such as benzophenone (7). 

Commingled polyolefins are re-stabilized using about 0.06 wt% of a hindered phenol antioxidant, and about 0.09 wt% phosphite. Acids present in the mixture should be neutralized by addition of a sufficient amount of CalOH). For other compositions of PCW, other stabilizers, viz., thio-propionic acid, benzophenones, oxalides, benzo-triazoles, or sterically hindered amines may have to be used [Pauquet et al., 1993]. 

For possible migrants in HDPE, there are traces of complex organometallic catalysts (which can be reduced to a minimum by repeated washing), traces of stabilisers [1-5] as well as solvents that are left in the system. However, animal tests showed that no toxic effects are involved in general [6, 7]. It is recommended that benzophenone-based UV absorbents and antioxidants are not used in HDPE designed for packaging foods that contain fat, especially corn oil [3-5]. 

Suggestions have also been made that better overall performance can be achieved by the use of more than one benzophenone [37], or combinations with other classes of stabiliser such as benzotriazoles or cinnamates [36], or in combination with antioxidants [41, 42]. 

Additive packages containing benzotriazoles along with other co-additives are also known. These include combinations with benzophenones and/or cinnamate-types [36] with antioxidants [41, 42] with fatty acid salts of manganese [55] combinations of polyoxyalkyene-based benzotriazoles and PEN used in PET [61] and benzotriazole plus poly(isobornyl acrylate) for the protection of polyalkylene naphthalates [62]. 

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