Hindered amine light stabilizer effectiveness

Bauer I, Habicher W D, Korner S and Al-Malaika S (1997) Antioxidant interaction between organic phosphites and hindered amine light stabilizers effect during photooxidation of polypropylene, Folym Degrad Stab 55>217-224. 

Oligomeric hindered amine light stabilizers are effective thermal antioxidants for polypropylene. Thus 0.1% of A[,Af-bis(2,2,6,6-tetramethyl-4-piperadinyl)-l,6-hexanediamine polymer, with 2,4,6-trichloro-l,3,5-triazine and 2,4,4-trimethyl-2-pentaneainine [70624-18-9] (35) (Fig. 5), protects polypropylene multifilaments against oxidation when exposed at 120°C in a forced-air oven (22) for 47 days. 3,5-Di-/ l -butyl-4-hydroxytoluene [128-37-0] (0.1%) affords protection for only 14 days. 

UV absorbers have been found to be quite effective for stabilization of polymers and are very much in demand. They function by the absorption and harmless dissipation of the sunlight or UV-rich artificial radiation, which would have otherwise initiated degradation of a polymer material. Meyer and Geurhart reported, for the first time in 1945 [10], the use of UV absorber in a polymer. They found that the outdoor life of cellulose acetate film was greatly prolonged by adding phenyl salicylate (salol) [10]. After that, resorcinol monobenzoate, a much more effective absorber, was introduced in 1951 [11] for stabilization of PP, but salol continued to be the only important commercial stabilizer for several years. The 2,4-dihydroxybenzophenone was marketed in 1953, followed shortly by 2-hydroxy-4-methoxybenzophenone and other derivatives. Of the more commonly known UV absorbers, the 2-hydroxybenzophenones, 2-hy-droxy-phenyl-triazines, derivatives of phenol salicylates, its metal chelates, and hindered amine light stabilizers (HALS) are widely used in the polymer industry. 

In the present study possible modes of action of a relatively new class of light stabilizers, the Hindered Amine Light Stabilizers (HALS, tetramethylpiperidine derivatives, TMP) will be discussed. Certain members of this group have a light stabilizing effect superior in many fields of application to that of previous additives. They are effective in both thick layers and fibers13 12. 

The Good-rite 3125 was also combined with the Chimassorb 944LD and Cyanox STDP to evaluate possible synergistic effects between combinations of a hindered phenol stabilizer with first a thioester and then a hindered amine light stabilizer (HALS). 

Set B Based on the results of set A discussed below, a third set. Set B, was prepared (Table IV). Cyasorb 531 (a benzophenone UV light absorber) was found to be the most effective stabilizer in Set A. It was therefore rerun at an even lower add-on in Set B, and since it was the only UV light absorber included in Set A, a second type of UV absorber, Tinuvin 327 (a benzotriazole) was included in Set B. Two new non-polymeric hindered amine light stabilizers (HALS) Tinuvin 770 and Tinuvin 765 were also evaluated in Set B with the hope that they might be more effective than the polymeric HALS (Chimassorb 944LD) included in Set A which was quite detrimental to the heat stability. Combinations of these four additives were also applied in Set B. The three new compounds evaluated have been reported to be effective light stabilizers for polyester and polyamide fibers (Capocci, G., Ciba Geigy Corporation, Ardsley, NY, personal communication, 1986). 

Exposure to solar irradiation (sunlight) may alter their chemical integrity and in due course some physical properties such as mechanical strength (e.g. brittleness) or color (e.g. fading) as well. Additives like industrial ultra violet (UV)-absorbers, hindered amine light stabilizers, radical scavengers and antioxidants are incorporated or applied in these products to effectively reduce or delay such radiation induced deteriorations. 

As with thermal stabilizers, photostabilizers must satisfy basic chemical and physical requirements (see the section titled ""Antioxidant permanence effects of chemical and physical factors ). In addition, they must be photo-stable, i.e., stable to UV-light, to withstand continuous periods of UV-exposure, without being prematurely destroyed or effectively transformed into sensitizing products. There are essentially three classes of compounds that are categorized as photostabilizers/ photoantioxidants UV-absorbers and pigments, peroxide decomposers including nickel complexes, and sterically hindered amine light stabilizers. 

Thioethers increase long-term stability in conjunction with phenolic antioxidants. Their use is limited to applications where possible effect on odour or taste and negative interaction with HALS (hindered amine light stabilizers) is not important. 

It is well known that HALS compounds (sterically hindered amine light stabilizers) exert excellent photostabilizing effect on polyolefins (1-3). Most of the authors agree that N-oxyl radicals formed from HALS compounds play an important role in the photostabilizing process (4-6). 

A number of antioxidants were examined for solubility in the monomer, effect upon the photoinitiator, UV stability, effect upon physical properties of the cured coating and their effectiveness as stabilizers. The addition of hydrogen donors, HD-2 or HD-3, or a hindered amine light stabilizer, HALS-1, improves the stability of a cured epoxy acrylate system with a minimal change in the physical properties of the resin. DSC and oxygen absorption measurements show that the secondary hindered amine, HALS-1, imparts the best stability to the resin. 

The most important classes of UV stabilizers are UV absorbers (U VAs), quenchers and hindered amine light stabilizers. In this chapter an overview is given about the types of UV stabilizers in use, their mechanisms of action as well as possible synergistic and antagonistic effects. In the last part for a selected number of polymers the effectiveness of different stabilizers is shown. The chemicals structures of all stabilizers mentioned in this chapter are shown in Appendix 17.9. 

S.W. Bigger and O. Delatycki, The effect of hindered amine light stabilizers on the photoxidative stability of high density polyethylene, J. Polym. Sci. A Polym. Chem. 1989, 27, 63-73. 

The light stabilizer category, hindered amine light stabilizers (HALS) are very effective stabilizers for urethane coatings. These compounds, developed primarily by Ciba-Geigy, do not act as UV absorbers but act by Inhibiting the degradation of the binder that is already in an excited state. 

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