Polyolefins aromatic amines

The metal coordination complexes of both sahcylaldehyde phenyhiydrazone (91) and sahcylaldoxime provide antioxidant (92) protection and uv stabihty to polyolefins (see Antioxidants). In addition, the imines resulting from the reaction of sahcylaldehyde and aromatic amines, eg, p- am in oph en o1 or a-naphthylamine, can be used at very low levels as heat stabiLizers (qv) in polyolefins (93). 

Low surface energy substrates, such as polyethylene or polypropylene, are generally difficult to bond with adhesives. However, cyanoacrylate-based adhesives can be effectively utilized to bond polyolefins with the use of the proper primer/activa-tor on the surface. Primer materials include tertiary aliphatic and aromatic amines, trialkyl ammonium carboxylate salts, tetraalkyl ammonium salts, phosphines, and organometallic compounds, which are initiators for alkyl cyanoacrylate polymerization [33-36]. The primer is applied as a dilute solution to the polyolefin surface, solvent is allowed to evaporate, and the specimens are assembled with a small amount of the adhesive. With the use of primers, adhesive strength can be so strong that substrate failure occurs during the course of the shear tests, as shown in Fig. 11. 

Naugard 445 is non-discoloring aromatic amine antioxidant that works synergistically with phosphites and phenolic antioxidants as a thermal stabilizer in polyolefins, styrenics, polyols, hot melt adhesives, lubricants, and polyamides. 

It was noted that the efficiency is increased in the presence of amines (Scott, 1993b), so the effectiveness in conjunction with aromatic amine free-radical (CB-D) stabilizers or the amine end groups of nylon would be expected. It is also noted that cuprous salts are often used as the iodide, and the effective alkyl-scavenging ability of iodo compounds has been demonstrated (Henman, 1979). Copper salts are also effective in the melt stabilization of polyesters, but in this case the effectiveness is improved by using a hindered phenol antioxidant. This performance is in contrast to the strong prodegradant effect of copper and other transition metals on the polyolefins as discussed later. 

Secondary aromatic amines are effective antioxidants in the protection of saturated hydrocarbon polymers (polyolefins) against autooxidation. Their role in the stabilization of unsaturated hydrocarbon polymers (rubbers) is more complex depending on their structure, they impart protection against autooxidation, metal catalyzed oxidation, flex-cracking, and ozonation. The understanding of antioxidant, antiflex-cracking and antiozonant processes together with involved mechanistic relations are of both scientific and economic interest. 

The same technique can be used to dye a material that is otherwise difficult to dye. An ethylene-propylene copolymer rubber was reacted first with maleic anhydride, then with an aromatic amine dye in an extruder to produce a dyed rubber.81 Dye sites can also be inserted into polyolefins by grafting them with dimethylaminoethyl methacrylate, using azo or peroxide catalysts in an extruder.82 jV-Vinylimidazole has been grafted to polyethylene in an extruder with the help of dicumylperoxide.83 The product was mixed with an acrylic acid-modified polypropylene and used to compatibilize polyethylene and polypropylene. This could be helpful in the recycling of mixed polyolefins from municipal solid waste. Recycling of cross-linked (thermoset) polymers is more of a problem because they cannot be remelted in an extruder. However, they can be if... 

The presence of the above-mentioned metal ions increases the decomposition rate of hydroperoxides and the overall oxidation rate in the autoxidation of a hydrocarbon to such an extent that even in the presence of antioxidants, the induction period of oxygen uptake is drastically shortened. In such a case, sterically hindered phenols or aromatic amines even at rather high concentrations, do not retard the oxidation rate satisfactorily. A much more efficient inhibition is then achieved hy using metal deactivators, together with antioxidants. Metal deactivators are also known as copper inhihitors, because, in practice, the copper-catalyzed oxidation of polyolefins is by far of greatest importance. This is due to the fact that polyolefins are the preferred insulation material for communication wire and power cables, which generally contain copper conductors. 

The additional reaction of additives in the polyolefin due to an increased temperature or light providing more efficient stabilizer. Example aromatic amines + mercaptobenzimidazol. 

A redox mechanism in an oxidized polyolefin mediated by, e.g., hydroperoxides which oxidize more efficient component of the synergistic mixture that is reduced back by a less reactive component. Example aromatic amines + phenols. 

Oxidation at moderate temperatures (thermal oxidation) or by UV radiation (photo-oxidation) can lead to a lowering of MW by chain scission and to a deterioration of mechanical properties. The thermal oxidation of polyolefins was a serious fault with, for instance, polyolefin-insulated copper wire. It was shown that peroxide radicals were responsible. The damaging effects of these radicals were overcome by adding antioxidants which had a greater affinity for the radical than the polyolefin chain. Typical antioxidants are hindered phenols and aromatic amines which act as radical scavengers. 

As mentioned in the previous section, R-, RO-, and RO2 radicals and hydroperoxides are the main products of hydrocarbon oxidation. For this reason, easily oxidized polymers (polyolefins, polyamides, polystyrene, etc.) are stabilized by compounds that can react directly with peroxide radicals or directly with hydroperoxides. They are substituted phenols, aromatic amines, mercaptans, organic sulfides, etc. they are called antioxidants. 

The combined introduction of an inhibitor, which terminates chains, and a substance, which decomposes hydroperoxides, is widely used for the more efficient retardation of oxidation processes in polyolefins, resins, lubricants, and other materials. Various phenols, bisphenols, and aromatic amines are applied as an acceptor of RO 2, and aryl phosphites, esters of thiopropionic acid, dialkyl dithiopropionates and thiophosphates of zinc and nickel, and other similar compounds are introduced to... 

The chemical mechanisms involved in the action of antioxidants have been discussed in a number of reviews [8,11-18] and the reader is directed to these and the references they contain for more detailed information. Two complementary antioxidant mechanisms are frequently used synergistically in polyolefins. The first is the kinetic chain-breaking hydrogen donor process, (CB-D) summarised in reaction (3). The relatively stable radicals (A) produced (e.g. phenoxyl from phenols and aminoxyl from aromatic amines) carmot continue the kinetic chain and disappear from the system by coupling with other or the same free radicals. However, it should be noted that this process is stoichiometric and hydroperoxides... 

Hydroxybenzamines of the general formula have been claimed to improve the adhesion of a wide range of coatings to zinc and cadmium and other metallic substrates when used as either pretreatment primers or additives [63]. Ethylenically unsaturated hydroxy-functional amines have been claimed to improve the adhesion of water-based systems [64], and amines have been examined as adhesion promoters for aromatic isocyanate cured adhesives on glass and other substrates [65]. Primary aliphatic amines are claimed to improve the bondability of polyolefines [66] and an oxyethylated polyethylene... 

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