CS220979B1 - Electroisolating solventless impregnant and method of making the same - Google Patents

Description

The invention relates to the field of production of electrical insulating materials for the motor industry. The problem of solvent-free impregnants based on unsaturated polyesterimide resins, suitable for impregnation of windings of electric machines and devices with a permanent temperature load up to 155 ° C, is addressed, the solution being specifically focused. Needs related to the application of soaking technology or melting. at atmospheric pressure, possibly under vacuum.

The solution is a suitable type of solvent-free impregnant, which is formed on the basis of a specific modified unsaturated oligoesterimide resin, obtained by the reaction of special polyestriimidyl diols with acidic ricinomaleinate and maleic anhydride, and as a resin component with the other components of the impregnant. , with specified proportions of unsaturated monomer, inhibitor and initiator of the copolymerization reaction.

(Immediate use of the invention is possible for manufacturers of electroinsulating varnishes and impregnants, and the product is used for the production of electric motors and in the repair shops of relevant electrical equipment and devices.

The invention relates to the field of electroinsulating materials, solves the problem of electrolytic solvent-free impregnants based on modified unsaturated polyeisteirimide resins, whose permanent temperature resistance is 155 ° C and are particularly suitable for impregnation of windings of electric rotating machines, apparatuses and coils of transformers, in particular atmospheric pressure, under vacuum. The solution is to enable the production and application of impregnants of a given type with higher ¹ technical and technological parameters and, in particular, to a long time possible to process them.

The curing of the solvent-free impregnants based on the unsaturated polyesters results from copolymerization reactions by double bonding of the unsaturated polyester and the unsaturated monomer in the presence of free radical initiators, possibly also in the presence of various types of accelerators. The reaction mechanism of curing of the bis-solvent impregnants and the fact that it contains no inert solvents brings a number of technical and economic advantages. In particular, it is their substantially shorter time, curing and the possibility of achieving the same increment of bituminous mass in the winding by up to a single impregnation - as opposed to the otherwise necessary two to three times the impregnation in the case of impregnating varnishes. The impregnating lacquers comprise inert solvents in an amount of 50 to 65% by weight of peireent, which amounts need to be evaporated in the hardening process. When applying solvent free IMPREGNANTE these lapses, thereby achieving a significant increase in productivity, significant energy savings, production tation areas, significant decreases prácnoisť, air pollution © ¹ and the working environment.

For impregnation of windings of temperature-stressed systems above 1310 ° C, in which, at the same time, the resistance of the hardened impregnant to resistance to cyclic temperature changes and to pulse overheating is required, solvent-free impregnates based on ¹ unsaturated polyesters having 5-compound compounds. imidocycles into the structure of the unsaturated polyester chain. Despite these solvent-free impregnates, they are currently widely used in impregnating windings of electro-rotating rotary machines, devices and trainformers with a permanent heat resistance of 1.55 ° C.

A number of raw materials are known for use in the preparation of unsaturated polyesterimides, and various processes for their production are known, which can explain a relatively large assortment of iso-solvent impregnants on this basis with different application focuses, which differ in functional and processing properties. the chemical structure and the method of production are, in this case, solvent-free polyester, imide impregnants intended for impregnating the windings of the teohinology or the soaking or flooding respectively. The high demands here arise from the need for simultaneous fulfillment of several functional properties, i.e. high temperature resistance, which should appear to be a small component of electrical strength, and insulation resistance, from temperature and low shrinkage of electrical strength to long-term temperature aging, good mechanical reinforcement at operating temperatures and temperature cycling and thermal overload, as well as the necessary application properties, in particular the longer processing time of the initiated impregnant at 23 ° C to 2 ° C, at the same time short gel time ® at 100 ° C, and short curing time and low impregnation viscosity.

The aforementioned functional and application properties depend on the composition and method of manufacture of the bis-solvent impregnant based on unsaturated polyesiterimides, but are not directly proportional, since the achievement of the necessary value for some functional or processing properties usually results in unacceptable deterioration in others or most other vapor. Therefore, due to the necessary compromise, the properties of even top-quality impregnants of this kind for a given purpose differ and are only narrowly applicable, since they only have some of the desired properties.

It is known that the greater the number of heterocyclic imide ring bifunctional compounds incorporated by an esterification reaction into the structure of an unsaturated polyester, the more advantageous it is to achieve a higher temperature resistance and a lower temperature dependence of its dielectric properties. The use of bifunctional imide compounds simultaneously provides the possibility, together with other bifunctional or even multifunctional polyols and, bifunctional or multifunctional carboxylic acids, and at least one bifunctional unsaturated acid or anhydride thereof, of preparing high molecular weight unsaturated polyesterimides with high molecular weight polyimides. 70 ° to 100 ° C and with good mechanical properties in the cured state after copolymerization with unsaturated imionomers, for example styrene, in the presence of peroxide initiators. However, these high-molecular-weight unsaturated polyesterimides, which at normal temperature are hard materials with a melt temperature above 70 ° C, cannot be used as a conventional, safe method of preparing impregnants with solvent and melt homogenization of stabilized unsaturated poiyesterimide in styrene at 100-120 ° C. it does not give rise to undesired gelling and thus depreciates the impregnant in its manufacture.

Instead, the unsaturated polyesterimide treiba cools down to the nor has! temperature, 23 ° C, crushed, crushed, and dissolved in portions in powder form in styrene. This process is cumbersome and requires additional equipment for cooling, grinding and dissolving unsaturated polyesterimide. Another disadvantage is undesirable. high viscosity of such styrene solution for winding impregnation purposes. It is possible to reduce this viscosity by increasing. styrene concentration, but this results in a deterioration of the mechanical efficiency of the impregnated winding at the nominal temperature and application, treat the impreginatot due to the disadvantageous, less buildup of bitumen in the winding after hardening and due to the higher styrene losses it becomes technologically and economically disadvantageous.

Disadvantages dcterajšieho state of the ISA of the invention remove the solution, which is characterized in that the resin component reactive mixed impnegnantu form a change down 40 to hmiptnostných percent of a modified unsaturated oltgoesterimidu of the formula I '' by 7 ^ R G ~ C ~ C-COOR ~ _Rb (?) v kitorom

R 5 represents a trifunctional residue of an unsaturated castor oil ester, - of ricomialeinate, in an amount of 15 to 35% by weight of pencemi,

R represents a twenty-two oligoeisterimiddiol radical of formula

-W in an amount of 55 to 75% by weight, but less confusing is the content of at least 80% by weight of diols of the type (III) and in the formulas (II, III).

R 1, the notion is a residue of a bifunctional or trifunctional polyol, preferably

CH3

- -CII2 — C — Clls-CH3 or a proportion of these in the mixture,

R 2 is an alkylene of up to 3 carbons, n is equal to 1 to> 4, and the unsaturated portion of the modified oligo orthoesterite (I) structure constitutes 8 to 14 weight percent of maleic anhydride or other alpha, non-dicarboxylic acid beta non-anisate and those a) from 0.025 to 0.1% by weight of the radicals of the radical copolymerization inhibitor, preferably hydroquinone, and the other component of the reactive or mixed impregnant comprises a proportion of 40 to 55% by weight of the unsaturated monomer, preferably styrene; the impregnant contains 0.8 to 1.2 parts by weight of the peroxydroxy compound, preferably a 3-methylbenzyl perbenzoate, as the initiator of the curing copolymer of the isolation reaction, in an amount calculated per 100 parts by weight of the bitumen component solution in non-greasy monomer. an optional constituent in the impregnation is ai the proportion of accelerators of the type of metal salts of organic acids, preferably cobialite-fumate in an amount of -0-, 100 to 2500 parts of cobalt gravity parts, also calculated per 100 parts by weight of the nutrient solution solution. monomer.

The impregnant according to the invention is preferably produced in such a way that a modified unsaturated oiligoesterlimide bile is prepared by a two-stage synthesis, which is carried out as follows. It dissolves in the tertiary stage in an unsaturated monomer, preferably in styrene, following a series of operations such that the tertiary carboxylic acid anhydride is reacted with the aminoalkobyl acid, preferably 2,2-diimethyliproipan, in the first stage. olom-1,3 at 130 to 200 ° C to form oligooisterimide diol containing 10- to 12-weight peroxy-oxy groups which are, in the next second stage, dispersed in the presence of a r-adical copolymieirls inhibitor, preferably hydroquinone with pre-prepared ricin maleate and anhydride, maleic acid, optionally having an alpha, beta n-ensaturated dicarboxylic acid content and their anhydrides or mixtures thereof at ISO to 220 ° C, or into the reaction mixture oiigoesterilmii didioles are added with castor oil and malleic acid anhydride, and some of the anhydride is at least as low as hydroxyl groups at a temperature of 1-40 to 150 [deg.] C., the resulting racemialeineate is saturated with the remainder of the α-maleic anhydride with oligoesterimide diols at 50 [deg.] C ^; 0 to 210 [deg.] C., wherein the modified n-ensaturated oligoesterinimide resin is then dissolved at 100 to 120 [deg.] C. in an unsaturated monomer, preferably in styrene, and the resulting styrene resin solution is at a maximum of 25 ° C, the peroxide initiator cures the reaction of the preferred tertiary butyl peryl benzoate and, optionally, the accelerator-based metal salts of organic acids, preferably cobalt, before use.

In connection with the above-mentioned production process, however, it is necessary to ascertain, in the context of the present invention, that the glass-making process is approached in such a way that the mixture of the proportions of oligoeSt-erimiddioles, acidic unsaturated a tri-functional ester of castor oil and maleic anhydride or i-ne-alpha, a beta-unsaturated dicarboxylic acid having a carbon number of 4- to 5 or a mixture thereof, is reacted in the same proportion of the components to per mole of hydroxyl groups, 0-6-5 to 0-8-5 preferred 0-0.05 to 0.88 carboxylic acid groups after converting the amhydride groups to carboxyl groups. The unsaturated oligo-esteirimide containing from 0.0215 to 0.1% by weight of the radical copolymer inhibitor is prepared by such a process that the riajiscuir is reacted with the trilbaric acid anhydride with aimin-oalkool, preferably 1,2-amhydrol. -id 1,2,4-beinzéntrikiarboxyliovej of the aminoalkyl-shaved, preferably with monoettamol-aimini dvojfun kčnýimi-polyoxyethylene-limit, for example eitylénglykol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl ^and thyl- 2-n-propylpropanediol-1,3,3-preferred-with 2,2-dymethyl-prop-an-diotom-1,3 'and trifunctional polyilyl such as glycerin, trimethylolpropane and tris (2-Hydroxyitylisocyanurate) at a temperature of 130 to 200 ° C to produce oligoeister-1-middiol-ol containing HO to 12 weight percent p-ercent hydroxyl groups.

The solution according to the invention makes it possible to obtain an electro-insulating anti-solvent or admixture which satisfies the demanding requirements for the need, the low viscosity when applied, the high storage stability and the operation, in conjunction with short-time incursions and with increased heat resistance are achieved.

Compared with the prior art, the solution according to the invention represents a significant improvement in terms of both economical and technical aspects of the manufacture of the γpr-egnan and its application. The impregnation resin component, a high-molecular-weight unsaturated ciligoesterimide s-a dissolves directly in monosylene at temperatures of 10 ° C to 120 ° C without the danger of gelling the reaction mixture. The costs and time losses resulting from the prior art technology, such as crushing, milling and pulverulent pulverulent resins in the moinoistyrene, are eliminated. Production. it is even easier and more reproducible due to the temporal improvement of the control and control of the polycondensation state of the unsaturated oligoeistertmide, which is associated with a significant reduction in the risk of gelling in the reaction apparatus prior to addition. styrene.

Dal-show advantages of the present invention is the fact that in solutions -nenasýtenýcb ollgoiesterimi dov-in four-ene The viscosity and the less significant m dlihšlm time-sípracova'telnosi ^1:, which is particularly advantageous for the winding iimpregnáci.u .technológiou Macan. In contrast to the known and comparable types, the impregnation in accordance with the invention is more advantageous in application properties, which appear, for example, in an average of 10 minutes less gel time at 100 [deg.] C. at the same time longer sp-racibility. In addition, an impregnant of this type cured under the same conditions, i.e. 3 hours at IfltteC, as opposed to analogs or other types of cure which also cure at 4 ° C at 140 ° C. C, this type exhibits several technical improvements, higher parameters, for example higher electrical strength, in particular at an elevated temperature of 155 ° C, in particular 70- to ΙιΟ-Q kV / mm - oprcih do-current-values. 55-7-Cl! kV / mm, more dimensional stability to mechanical stresses at elevated temperatures, at a temperature of -20 ° C, and a higher temperature resistance of n-oist -o-10 ° C, characterized by temperature index 170 ° C.

Example 1 and d 1

A 125 g 2, 2 ' -dimethylpyridine-1 ' 3 was weighed into an orifice flask equipped with a stirrer, a control thermometer, a needle column, and an ehillaldicide. The best of the gradual introduction of an inert gas, was added in amounts ekviivadentých · 192, 1 g of trimellitic anhydride in the same time to perform multiple 61 g of monoethanolamine at such a rate that the temperature was heated to LL3! 0 ^IQ ,, did not exceed 135 C. C. After completion of the exo-thermic reaction, the temperature was raised to 2100 ° C and. the reaction mixture was condensed until the refractive index determined at 150 ° C between 1.6395 and 1.5445 was reached, and until it reached the refractive index. the carboxyl group content did not decrease to 0.1 - 0.3 mol / kg. The obtained oligoeisteriin dihydrochloride mixture had a hydroxyl group content of 10-12%, while 33-34 g of water was separated from the reaction mixture.

142 g of ricinomaileinate, 58.6 g of maleic anhydride and 0.25 g of hydroquinone were added to the. The reaction mixture was condensed at 200 ° C to a viscosity of 18-2-6 Pa. s at 95 ° C. The unsaturated oligoeisterimide obtained was cooled to 100-120 ° C and thereto was added in an amount of 405 g of styrene, which was inhibited by 10-25 ppm of tertiary butyl pyrroquinoline. After cooling the solution, 7.4 parts by weight of tertiary buityl perbenzoate were added.

Example 2

125 g of 2,2‘-dimethylipro, pandiol-1,3i and an amount of 61 g of monoethylamino amine were weighed into the apparatus as in Example 1. After the inert gas was introduced, a portion of 192 g of trimellitic anhydride was gradually added while heating the mixture to 200 µl. ° 'C. At this temperature, the mixture was condensed until the refractive index determined at 50 ° C in the range of 1.3395 to 1.5445 was reached and the carboxyl group content dropped to 0.1 to 0.3 mol / kg. A further procedure for preparing unsaturated oligoesterimide and its solution in styrene was similar to Example 1.

EXAMPLE 1 a d 3

112.7 pbw of castor oil, 88 g of maleic anhydride and 0.39 g of hydroquinone were added to the cligceserimidioles prepared according to the procedure of Examples 1 and 2. The reaction mixture was condensed at 200 ° C to a viscosity of 18-26 Pa · s at 95 ° C. The obtained unsaturated oligoesteirilmide was cooled to 100-120 ° C and styrene was added thereto in an amount of 425 g which was inhibited by 10-25-25 ppm tertiary butylpyrocatechlinoim. After cooling the solution, 7.55 parts by weight of tertiary butyl perhenzoate was added.

By impregnating the impregnant, this was mixed with an appropriate proportion of initiator, eventually an accelerator, and poured into a storage tank, where the possibility of mixing and cooling was allowed at 10 ° C.

When using the impregnants for winding electric rotating machines, apparatus and equipment, the objects are impregnated in the impregnation tank by immersion or flooding at atmospheric pressure or under vacuum. When the impregnant is left, the impregnant is pumped from the storage tank to the impregnation tank and then the objects are immersed in it, for example in a continuous impregnation.

During flooding, objects are pre-loaded into the impregnation tank and flooded from below with impregnant by pumping under vacuum or hydrostatic pressure. The temperature of the impregnant in the impregnation tank should preferably be in the range of 18-23 ° C. To ensure unlimited impregnated workability · 110 - 15% of the impregnant content should be consumed weekly and replaced with initiated clarification. The impregnated objects are placed in an oven pre-heated to 140-180 ° C and cured for 3 hours after reaching a temperature of 130 ° C in the winding.

The solvent-free implants according to the invention can be used for impregnating the stator and rotor windings of general-purpose electric rotary machines, as well as for machines operating in harsh operating conditions such as mines, huts, agricultural and high-humidity environments, as well as impregnation. . astermalocers and circulating oil, where resistance to transformer oils is required.

Solvent-free impregnants according to Examples 1, 2 and 3 for impregnating the windings of electric rotary machines, apparatuses and transformer coils cured for 3 hours at a heat of 1,3,0 ^and C exhibited the following characteristics:

11 220979 12 Consistency, 20 ° C, 4 nm / s 45-75 CSN 67, 3013 Gel time, 100 ° C / min 1.5-25 DIN 10945 workability time, 29 with the criterion 23 + 1 ° C / weeks is krateniia ča- Electrical strength, kV / rnim 213 ° C 80-130 su gélovanla at 100 ° C to 1/3 of the original value CSN 67 3150 155 ° C 70-100 Art. 10 after 24 h in science 27-35 Internal resistivity / Ohm.m CSN '67 3150 Deň: 18 ° C 1O ⁴⁴ Art. 13 156 [deg.] C 109—10 ^1θ thickness samples after 96 h in water 10 ¹⁴ ke 2 mim Top floor for lacquered wires complies e.g. CSN 67 31:50 LCIA does not show Art. 11 decline eleiktir le- metčda B Heat index - calculated at 15i5 ° C after impreignant suspension for β · hours at 130 ° C from baseline CSN 34 6501 from a decrease in electrical strength after aging of lacquered fabrics at 180, 190 ', 200' and 220 ° C 170 ^C C Strengthening test, coils CSN 67 3150 impiregnainfom, number "ib" Art. 12 2L3 '° iC 9-12 155 ° C 1.3-1.7

The possibility of immediate utilization of the solution of the invention is given to producers of electroinsulating materials of the given type, to producers of electro-insulating impregnations of other varnishes supplying to the motor industry.

Claims (2)

SUBJECT 1. Electro-insulating solvent-free impregnant for winding of electrical machines and devices, which is a reactive mixture of a modified unsaturated oligoesterlmide with an unsaturated monomer, an inhibitor and a initiator of a copolymerization reaction, and optionally with an accelerator of the copolymerizing reactivity, 40 to 60 weight percent of a modified unsaturated oligoesterimide of formula I OF THE INVENTION in which form R 5 represents a tri-functional residue of an unsaturated castor oil ester, ronine-maleate, in an amount of 15 to 35% by weight, R represents the bivalent radical of the olefinestrine dihydroxide of general formulas Η H R i i / R-O-C-OC-C-O-R (I) in an amount of 55-75% by weight, containing at least 80% by weight of the parts of the third general formula (III). and in the above general formulas (II. III) R 1 represents an excess of a bifunctional or tri-functional polyol, preferably GHg — CH2-C — CH2-. I CH 3 or a proportion of these in the mixture. R 2 represents alkylene with a number of! carbons 2 to 3, n is equal to 1 to 4 and the unsaturated part of the modified polyester esterimide structure (II) constitutes 8 to 14% by weight of maileinic anhydride or other alpha, beta unsaturated d-carboxylic acid and their arihydirides having a carbon number of 4 to 5, or their amides and the unsaturated oligoesterimide further comprises 0.025 to 0.1 wt. 2 parts by weight of a compound peroxidoveij, competitive · tereiáirného butylperbenzoáitu, initiator 'kojooilymeirizačnei curing reaction, and ¹ in an amount, calculated on 100 parts of the solution of component živlčnej nenasýtenoím momomer, wherein the other optional ingredients in the imp also the proportion of the metal salt organic acid accelerator, preferably cobalt naphthinate in an amount of 0.00215 to 0.00135 parts by weight of cobalt, also calculated on (tm) 100 parts by weight of a bitumen solution solution in an unsaturated motor. "Second The process for producing a solvent-free impregnation according to item 1, characterized in that a modified non-saturated oligocsterimide resin is prepared by a two-step synthesis, which is dissolved in the unsaturated ¹ moiety, preferably in styrene, in a subsequent step. In the first step, tricarboxylic acid anhydride is reacted with aiminoalcohol, preferably 2,2-diimieltylpiropanediol-1S at a temperature of 130 ° C to 200 ° C to form a mixture of oligoeisterimidiol diol containing 10 to 12% by weight of hydroxyl groups which are condensed in the next step copolymerization, preferably hydroquinanotone with preformed ricinomalieinate and maleic anhydride, optionally with a partial proportion of alpha, be unsaturated dicarboxylic acid and their arihydride or mixtures thereof, 180 to 220 ° C, but . castor oil and maleic anhydride are added to the reaction mixture of oligoeisterimide diol, a portion of which is initially aduro to the hydroxyl groups at a temperature of 140-150 ° C, formed by the ricinomaleinaphthate, polycondensated with the remaining portion of maleic anhydride with an oligoesterimide of 15 ° C to 10 ° C, the modified non-fatty oligdesterimide resin obtained thereafter is then dissolved at 100 DEG to 120 DEG C. in unsaturated mono-monosulfides, preferably in styrene, by adding to the final solution of the styrene bitumen product at a maximum of 25 DEG C. a petroxide curing reaction initiator before use, preferably a tertiary butyl perbenzoate and optionally an accelerator based on metallic salts of organic acids, preferably cobalt.