Compositions – Preservative agents – Anti-oxidants or chemical change inhibitants
Reexamination Certificate
2001-08-22
2003-04-29
Moore, Margaret G. (Department: 1712)
Compositions
Preservative agents
Anti-oxidants or chemical change inhibitants
C252S404000, C252S405000, C252S406000, C525S533000, C528S112000, C528S113000
Reexamination Certificate
active
06555023
ABSTRACT:
FIELD OF THE INVENTION
This invention relates polymeric materials used in air-cooled generators and a method of forming same, and more particularly, this invention relates to polymeric materials used with electrical insulation, tapes, coatings and similar applications which are more resistant than conventional materials to the effects of corrosive byproducts, e.g., ozone, peroxy free radicals, produced by partial discharges within an electrical generator.
BACKGROUND OF THE INVENTION
One critical factor that determines the long-term performance of electrical insulation and other materials used in air-cooled generators is the stability of the polymeric materials to thermal, mechanical and electrical stresses. The resistance of organic polymeric materials to oxidative degradation, particularly at elevated temperatures, is a key requirement for obtaining satisfactory, long-term performance.
Some polymers, however, oxidize more readily than others. For example, high aliphatic content polyesters tend to degrade more readily than epoxies, resulting in a loss of key properties, such as adhesion, flexibility, tensile strength, dielectric strength, and other similar properties. Thermal oxidative degradation of polymeric insulation materials also leads to degraded operating properties in motor and generator insulation, including partial discharges, increasing tan ∂ “tip-up” of delamination, fracture and embrittlement. The attack from ozone and other reactive peroxy radical species resulting from partial discharges in the generator are particularly harmful.
Some electrical utilities have aggressively tested these electrical components under thermal stressed conditions. These studies have shown that under aggressive conditions, in an air ambient, premature coil degradation can occur, as evidenced by decreased voltage-loss tangent tip-up and increased power factor measurements. If failure is defined as a measured decrease in tip-up and increased power factor, then these coils have experienced an increased failure rate under these more stressful conditions.
There is also a concern with electric utilities and power generator manufacturers that the epoxy resins tend to degrade in air via an “autocatalytic” free radical chain process where runaway degradation occurs. There is also a potential for the high electric fields to enhance this degradation process via discharge and polarization effects. This enhances electrochemically induced reactions. The present uncertainty of the chemical reactions in air is highlighted by a possible competing mechanism where polarization effects may retard degradation. For example, some prior art studies have noted the aging of epoxy based rotor insulation in air (20% O
2
)and in 5% O
2
.
The exact mechanism that is responsible for the thermo-oxidative degradation of resins, such as epoxies, is not understood in great detail. It is generally believed, however, by many skilled in the art, that the chemical species responsible for thermal degradation are free radicals, i.e., very reactive transient compounds, which are derived from atmospheric oxygen and breakdown fragments from the polymer resin. In the case of a bisphenol “A” epoxy resin, it has been found that the
ether linkage and isopropylidene group are weak links
for free radical attack. It has been found that the combination of temperature and oxygen produces an “autocatalytic” effect, which causes more rapid polymer degradation than some thermal effects. By controlling or “trapping” the free radical species responsible for degradation, improved thermo-oxidative stability composition of polymers could be developed, such as epoxies and polyesters.
It has been known to add “antioxidant” additives for controlling oxidation of polymers and plastics. These additives have been used commercially in different materials, such as polyethylene, polypropylene, neoprene, and other thermoplastics and elastomers. They have not had widespread use in thermoset materials, e.g., polyesters and epoxies, because of a perception that thermosets are more resistant to oxidative attack. Although this may be true for “normal” use, it is not true for the harsher, stressful environments found with high voltage electrical insulation, particularly with ozone present in elevated temperature oxidative environments of air-cooled generators.
Any selected antioxidant materials should be “compatible” with insulation resins such as epoxies and polyesters. “Compatible” would indicate that these additives have no deleterious effect on the long-term performance and properties of insulation polymers (e.g., electrical, mechanical, and chemical properties). These additives should also not have any adverse effect on the processing characteristics of the resins, for example, the gel time, viscosity, tank stability, post-cure and “wetting” of mica. Most commercially available antioxidants would have adverse effects on these polymers. This would be particularly true of amine and organometallic based compounds.
Another problem associated with common, prior art antioxidants is migration from the polymer composition over time because of elevated temperatures, causing the polymer to lose its protection. This migration of antioxidant, however, can be controlled by chemically bonding the antioxidant to the polymer structure and preventing loss of the additive.
For suitability in high voltage insulation, any antioxidants should have the following characteristics:
1. They should be compatible with the resin and have no deleterious effect on long-term performance or on the processing characteristics.
2. They should be “non-fugitive” in nature, i.e., they should not migrate out of the polymer structure.
3. They should be easily reacted into the polymer structure before final processing and the cure of the insulation resin.
4. They should be used at the lowest possible con centrations preferably less than 0.5% w/w, to minimize the effects on electrical properties, including the dielectric constant and dissipation factor, and tensile properties, including tensile strength and flexural modulus.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an antioxidant suitable for use in insulation resins, such as epoxies, that is compatible with the resins and has no deleterious effect on long-term performance or on the processing and characteristics of the resin.
It is yet another object of the present invention to provide an antioxidant used with insulation resins, such as epoxies, that is non-fugitive, reacted into a polymer structure before final processing and cure of the insulation resin, and used at a low concentration to minimize the effects on electrical and tensile properties.
The present invention is advantageous and provides a high voltage capable, insulating and resinous composition such as used with electrical coils and the like. In one aspect of the invention, it is formed from an epoxy-anhydride resin that has been prereacted with an antioxidant oligomer selected from the group consisting of organophosphorus compounds, sterically-hindered alkylated phenolics, alkyl and aryl thio-esters, alkyl and aryl thio-phosphites, thiazoles, lactones, hydroxylamines, and maleimides. In another aspect of the present invention, the organophosphorus compounds are formed from one of 2-phenyl-1-1-1,3,2-dioxaphosphepane, Deoxophostone, Vinylphosphonic acid, or Vinylphosphonic acid dimethyl ester. The sterically-hindered alkylated phenolics can be one of 2,6-di-butyl-4-hydroxymethyl phenol, and N-butyl-p-aminophenol. The alkyl and aryl thio-esters could be Trilauryl trithiophosphite. The thiazoles could include 3-(N-salicyloyl)-amino,2,3-thiazole, and the lactone could be one of Benzofuranones or 3-aryl benzofuran-2-one. The hydroxylamines can be N-(2-hydroxypropyl) ethylenediamine, Hydroxy ethyldiethylenetriamine, or N-(2-hydroxy, 2,4,4-trimethylpentyl) diethylene triamine. The maleimides can include 1,1 (Methylene-4,1-Phenylene) Bis-Maleimide.
In yet another aspect of the present invention, the epoxy-anhydride resin consists essentia
Aylward D.
Moore Margaret G.
Siemens Westinghouse Power Corporation
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