Patent Grant
10778058
This application is a U.S. National Stage Application of International Application No. PCT/EP2017/052721 filed Feb. 8, 2017, which designates the United States of America, and claims priority to DE Application No. 10 2016 203 867.2 filed Mar. 9, 2016, the contents of which are hereby incorporated by reference in their entirety.
The present disclosure relates to insulation. Various embodiments may include a solid insulation material, especially in tape form, the use thereof in a vacuum impregnation process, and/or an insulation system produced therewith and also an electrical machine having the insulation system, especially for the medium- and high-voltage sector, namely for medium- and high-voltage machines, especially rotating electrical machines in the medium- and high-voltage sector and also semifinished products for electrical switchgear.
Electrical machines (motors, generators) typically have, in the majority of the longitudinal grooves of their stator laminate stacks, special types of coil windings or conductor bars, generally made from copper or another material of high conductivity. In the case of an electric motor, by supplying current in a time-selective manner, a magnetic field propagating in all directions is generated, and this drives the freely rotating rotor suspended in the stator cavity, and the rotor reacts to the induced magnetic field in the form of forced rotation, for example owing to a multitude of applied permanent magnets, and hence converts electrical energy to kinetic energy. In electrical terms, the laminate stack is at ground potential, but the coils are at high kilovolt potential. The coils fitted into the stator grooves must accordingly be electrically insulated with respect to ground potential. For this purpose, each and every coil is insulated, for example, with a special tape, for example mica tape, repeatedly and with defined overlap.
Mica is commonly used since, being a particulate inorganic barrier material, especially in platelet form, it is capable of retarding electrical erosion under electrical partial discharges effectively and for a long period, for example over the entire lifetime of the machine, and has good chemical and thermal stability. Mica tapes consist of mica paper and one or more carriers, for example fabrics, film(s), bonded to one another via a tape adhesive. Mica tapes are necessary since mica paper alone does not have the mechanical strength needed for an insulation process. According to the application, additives may be added to the tape adhesive, for example curing catalysts, which have an initiating effect on the thermal curing of an externally applied impregnating agent: after the mica tape-insulated coils have been fitted into the stator laminate stacks and electrically connected, for avoidance of partial discharges during later operation, the air in the cavities of the windings and especially in the groove gaps of the stator laminate stack is eliminated. Since this distance from current-carrying insulated coil to the laminate stack is generally kept as small as possible, field strengths of several kV/mm there are not unusual. There is corresponding stress on the insulation material.
Impregnating agents according to the prior art that have been found to be suitable for vacuum impregnation processes are thermally curable epoxy resin/anhydride mixtures. They are used for impregnation of the stators of the electrical machines, composed of the individual parts thereof, with the fitted and mica tape-insulated coils, or for individual coil or conductor bar impregnation. During a VPI (vacuum pressure impregnation) process, these stators or coils are usually wholly flooded with a mobile epoxy resin/phthalic anhydride formulation in a vacuum chamber and then impregnated under pressure. The final curing is generally effected under standard pressure in an industrial oven.
The function of the curing catalyst is for the mobile impregnating agent, usually composed of epoxy resin and phthalic anhydride, to gelate within a particular period at a given temperature. The industrial standard impregnating agent in this regard has to date been a mixture of distilled bisphenol A diglycidyl ether and methylhexahydrophthalic anhydride. This mixture is sufficiently mobile to assure the complete impregnation of the tape insulation on the one hand and, in the absence of curing catalysts, sufficient storage stability on the other hand. The curing catalyst is generally at least also present in the solid insulation material, for example mica tape. This mica tape is held together by the tape adhesive, and so it is essential that the tape adhesive and the curing catalyst are inert to one another.
Typically, all three components, i.e. tape adhesive, curing catalyst, and charged impregnating agent, do not react until the moment they encounter one another during the VPI process. In this way, the best possible crosslinking and attachment, compatibility and freedom of the insulation from cavities are achieved, which leads in turn to an optimized lifetime of the “main insulation” of the electrical machine formed thereafter in the course of curing. Owing to toxicological concerns about the unrestricted use of phthalic anhydrides, impregnating agents used in the future will be phthalic anhydride-free or completely anhydride-free epoxy-based impregnating agents, which are polymerized using curing catalysts.
The novel curing catalysts are matched to the anhydride-free impregnating agents. There is increasing use of anhydride-free impregnating agents, as known from the prior applications DE 102015214872.6 and DE 102015213534.9, the disclosure content of which is hereby incorporated into the present description. These propose the use on the one hand of imidazoles and/or pyrazoles and the derivatives thereof as curing catalysts, and on the other hand covalently bridged diimidazole derivatives and/or covalently bridged dipyrazole derivatives as curing catalysts which, for example, are condensation products and/or addition products. These are curing catalysts in solid insulating materials which, by virtue of the molecular enlargement and possible additional interactions at the formerly electrophilic center, have a lower volatility than the simple (alkyl)imidazoles. In spite of this lower volatility, the reactivity with respect to acid anhydride-free impregnating resins based on epoxy resin is adversely affected only insubstantially, or not at all, in comparison to simple (alkyl)imidazoles. Consequently, these systems represent excellent curing catalysts for acid anhydride-free impregnating resins based on epoxy resin.
There is still a requirement for novel curing catalysts for anhydride-free glycidyl ether epoxy resins and glycidyl ester epoxy resins, especially for those which can be produced from readily-available raw materials in a manner suitable for mass production, and/or which have better chemical compatibility with epoxy resins than the imidazoles, diimidazoles, pyrazoles, and/or dipyrazoles known from the prior art. The teachings of the present disclosure may be embodied in a solid insulation material with a curing catalyst, which overcomes the disadvantages of the prior art, with the use of the organic acid anhydrides and/or the phthalic anhydrides which sensitize the respiratory pathway generally being avoided.
For example, some embodiments may include a solid insulation material which can be used together with an anhydride-free impregnating agent for the preparation of an insulation system in a vacuum impregnation process, wherein said solid insulation material comprises a carrier, a barrier material, a curing catalyst and a tape adhesive, the curing catalyst and the tape adhesive being inert to one another but, under the conditions of the vacuum impregnation, reacting with an anhydride-free impregnating agent with gelling times of 1 h to 15 h at the impregnation temperature, the curing catalyst being obtainable by reaction of at least one 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups.
In some embodiments, the compound containing oxirane groups has n=1 to 4 oxirane functionalities per molecule.
In some embodiments, the compound containing oxirane groups is a glycidyl compound.
In some embodiments, the compound containing oxirane groups is liquid at room temperature.
In some embodiments, the curing catalyst is a compound which is an adduct of one and/or more 1H-acid dinitrogen heterocycles and/or 1H-acid trinitrogen heterocycles with a compound containing oxirane groups.
In some embodiments, the compound containing oxirane groups is a compound selected from the following group of compounds:
In some embodiments, the curing catalyst has a nitrogen density D in the range from, for example, 1 to 15 mmol/g.
In some embodiments, the curing catalyst is an adduct of a
In some embodiments, the curing catalyst additionally has n=1-4 covalently bonded hydroxyl groups per molecule.
In some embodiments, the tape adhesive comprises an addition product of a bisphenol, diol, triol and/or higher alcohol, subsequently referred to as “A(OH)n” segment, with cyclohexene oxide and/or a cyclohexene oxide derivative, subsequently referred to as “Cy” segment, wherein A(OH)n is selected from the following group of compounds:
In some embodiments, the tape adhesive comprises a compound selected from the following group of compounds:
In some embodiments, the curing catalyst is present in an amount of less than 10 wt %.
In some embodiments, the tape adhesive is present in an amount in the range from 1 to 30 wt %.
In some embodiments, there is a carrier in the form of a woven material, nonwoven material and/or film.
In some embodiments, there is a perforated film.
In some embodiments, there is a particulate barrier material.
In some embodiments, the particulate barrier material comprises at least partially platelet-shaped barrier material particles.
In some embodiments, the particles of the barrier material are coated.
In some embodiments, the coating comprises a metal oxide.
In some embodiments, the coating is doped.
As another example, some embodiments include the use of an insulation system, produced by vacuum impregnation with a solid insulation material as described above, in medium- and high-voltage machines, especially rotating electrical machines in the medium- and high-voltage sector, and also in electrical switchgear, medium- and high-voltage applications, bushings, transformer bushings, generator bushings and/or HVDC bushings, and in corresponding semifinished products.
As another example, some embodiments include an electrical machine, e.g., rotating electrical machine in the medium- and high-voltage sector and electrical switchgear, medium- and high-voltage application, bushing, transformer bushing, generator bushing and/or HVDC bushing, and corresponding semifinished product, comprising an insulation system produced from a solid insulation material as described above.
Some embodiments of the teachings herein may include a solid insulation material which can be used together with an anhydride-free impregnating agent for the preparation of an insulation system in a vacuum impregnation process, wherein said solid insulation material comprises a carrier, a barrier material, a curing catalyst and a tape adhesive, the curing catalyst and the tape adhesive being inert to one another but, under the conditions of the vacuum impregnation, reacting with an anhydride-free impregnating agent with gelling times of 1 h to 15 h at the impregnation temperature, the curing catalyst being obtainable by reaction of at least one 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups. Some embodiments may include the use of the insulation system produced in this way in electrical machines, e.g., in rotating electrical machines in the medium- and high-voltage sector, and also in electrical switchgear, medium- and high-voltage applications, bushings, transformer bushings, generator bushings and/or HVDC bushings, and in corresponding semifinished products. Finally, electrical machines in the medium- and high-voltage sector and electrical switchgear, medium- and high-voltage applications, bushings, transformer bushings, generator bushings and/or HVDC bushings, and corresponding semifinished products, may include such an insulation system.
Although the curing catalyst can be obtained by reaction at least of a 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups, it can also be produced according to other desired synthesis routes. The curing catalyst is for example merely the adduct of a 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups. In some embodiments, the curing catalyst, which is for example an adduct of a 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups, has a nitrogen density D in the range from, for example, 1 to 15 mmol/g; D is especially in the range from
Structure I: Conventional curing catalyst according to the prior art
can be determined as follows: the molar mass of the molecule depicted, which represents a conventional curing catalyst according to the prior art, is M=638.89 g/mol. It has 3 nitrogen electron pairs capable of polymerization and hence for example the reference nitrogen density of 3 mol/638.89 g=4.7.10−3=1/g.
In some embodiments, a curing catalyst is an adduct of a 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups. It is possible to produce a curing catalyst in mica papers containing binder which can be modified such that it becomes vacuum-stable at temperatures from 50-80° C. For example, such a curing catalyst has a vapor pressure of less than 10−4 mbar at 70° C., and also a suitable dynamic viscosity.
In some embodiments, the curing catalyst exhibits a dynamic viscosity in the range from 1 to 10 000 Pa·s, especially from 5 to 5000 Pa·s, or in the range from 10 to 3000 Pa·s.
In some embodiments, the curing catalyst exhibits a vapor pressure at the impregnation temperature of less than 10−1 mbar, especially at 70° C. in the range from 10−2 mbar to 10−8 mbar, from 10−3 mbar to 10−7 mbar, or from 10−4 mbar to 10−6 mbar.
A curing catalyst can be obtained by reaction at least of a 1H-imidazole and/or 1H-imidazole derivative with a compound containing oxirane groups, such as obtained via an addition reaction, as represented schematically below:
Reaction Equation I: Imidazole Derivative Addition Reaction
Wherein, n=1-4; R1, R2, R3=hydrogen, alkyl and/or aryl; R is the molecular radical of the compound containing oxirane groups, i.e. for example a glycidyl reactant compound.
Reaction equation II: Pyrazole derivative addition reaction wherein, n=1-4; R1, R2, R3=hydrogen, alkyl and/or aryl; R is the molecular radical of the compound containing oxirane groups, i.e. for example the glycidyl reactant compound.
The table below shows a summary of possible reactants for preparing the curing catalyst, for example according to one of the mechanisms shown in the reaction equations I and/or II. The rows in the table give exemplary reactants containing oxirane groups and the columns give exemplary 1H-imidazole and/or 1H-imidazole derivatives: In particular, the abbreviations used in the columns have the following meanings:
Im: 1H-imidazole;
2m-Im: 1H-2-methylimidazole;
2e-Im: 1H-2-ethylimidazole;
2e-4m-Im: 1H-2-ethyl-4-methylimidazole;
4e-2Ph-Im: 1H-4-ethyl-2-phenylimidazole, and
3,5m-Pyr: 1H-3,5-dimethylpyrazole.
The numerical values given correspond in each case to the nitrogen density D of the curing catalyst, i.e. of the respective addition product, as described above. As compounds containing oxirane groups, for example glycidyl ether and/or glycidyl ester compounds are used. Exemplary compounds are listed in the following table, with ester derivatives and/or other derivatives of the compounds containing oxirane groups mentioned by way of example here that are obvious to those skilled in the art in all cases also being incorporated within.
Technical grade trimethylolpropane triglycidyl ether in 5% molar deficiency relative to the 1H-imidazole derivative were added slowly dropwise by means of a dropping funnel, with stirring, into a three-necked flask with reflux condenser in which 5 g of 1H-2-methylimidazole had been initially charged in 20 ml toluene at room temperature and had been dissolved under reflux for 10 min at 130° C.
The mixture was then refluxed for a few hours. Subsequently, an orange-colored, clear, highly viscous liquid was able to be obtained, which was dried under vacuum at 50-100° C.
A 5% (w/w) admixture to distilled Bisphenol A diglycidyl ether at 70° C. gave gelation and anionic curing. The same procedure was carried out with trimethylolpropane triglycidyl ether-tris(1H-2-ethyl-4-methylimidazole) reactant, neopentyl diglycidyl ether-bis(1H-2-ethyl-4-methylimidazole) reactant and bisphenol F diglycidyl ether-bis(1H-2-methylimidazole) reactant, with the distilled bisphenol F diglycidyl ether also being predissolved in toluene.
As tape adhesive, in the presence of the abovementioned reactants 1H-imidazole and/or 1H-imidazole derivatives with compounds containing oxirane groups as curing catalyst, use is preferably made of a tape adhesive as described in DE 102015205328.8, the disclosure content of which is hereby incorporated into the subject matter of the present description. Furthermore, for example a compound selected from the following group may be used in the solid insulation material:
The tape adhesive connects the at least one carrier and the barrier material in the solid insulation material. It is present in the solid insulation material in an amount in the range from 1 to 30 wt %, 2 to 15 wt %, or 5 to 10 wt %. The carrier in the solid insulation material is in the form of a woven material, such as glass fiber woven material, or a nonwoven material, especially a polyester nonwoven, paper and/or film. The carrier may also be in the form of a perforated film.
In some embodiments, the particulate barrier material is located at, in and/or on this carrier in the solid insulation material. The barrier material may be at least partially in platelet form. Mica can especially be used as barrier material. In some embodiments, a coated particulate barrier material is used. This can especially be a metal oxide-coated particulate barrier material, for example tin oxide, zinc oxide or titanium oxide-coated particles.
In some embodiments, a doped coating of the particulate, especially platelet-shaped barrier material is provided. The tape adhesive connects the at least one carrier and the barrier material in the solid insulation material. It is present in the solid insulation material in an amount in the range from 1 to 30 wt %, 2 to 15 wt %, or 5 to 10 wt %.
In some embodiments, the curing catalyst, also referred to as “tape curing catalyst” or “tape accelerator” is present in the solid insulation material in a concentration of less than 10 wt %, for example from 0.001 wt % to 7.5 wt %, in the range from 0.01 wt % to 5 wt %, or from 0.1 wt % to 3.5 wt %, such that gelling times of several hours can be produced.
In some embodiments, the curing catalyst initiates the polymerization of the impregnation resin at temperatures in the range from 20° C. to 100° C., from 50° C. to 80° C., or from 55° C. to 75° C.
In order to achieve the targeted storage stability in the solid insulation material, for example at room temperature and especially for several hours of continuously maintained vacuum and impregnation temperature, the curing catalyst is comparatively inert to the tape adhesive material. This is especially also the case under the conditions of maintained vacuum and/or impregnation temperature, which are for example in the range between 20° C. and 100° C., between 50° C. to 80° C., or between 55° C. to 75° C. Suitable as tape adhesive are, for example, diols, triols and/or polyols.
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| WO2017/153113 | 9/14/2017 | WO | A |
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