Nanomodified wire enamels and enamelled wire

FIELD: chemistry.

SUBSTANCE: invention relates to use of nanomaterials in wire enamel for improving thermal properties of enamel. The nanomodified wire enamels are usually used in making insulated winding wire. The polymer base of wire enamel is selected from a group comprising polyamideimide, polyester, polyesterimide, polyurethane and mixtures thereof. The nanomaterial is selected from a group comprising nano-oxides, metal nano-oxides, metal oxides or hydroxides of aluminium, tin, born, germanium, gallium, lead, transition metals, lanthanides, actinides and mixtures thereof. The nanomaterial is also selected from a group comprising nano-oxides, metal nano-oxides, metal oxides and hydroxides of aluminium, silicon, titanium, zinc, yttrium, vanadium, zirconium, nickel and mixtures thereof. After applying enamel on the wire and curing thereof, the wire exhibits improved thermal and mechanical properties.

EFFECT: improved thermal properties of enamel.

8 cl, 6 tbl

 

The present invention relates to a method for nanomodified (on the nanoscale) enamel wire, based compositions (formulations), which are well known and typically used in the manufacture of insulated winding wires, preferably, based on polyesters, polyetherimides, polyamideimides and/or polyurethanes, including the addition of nanomaterials. Obtained in this method, enamel, used for the production of winding wires with improved thermal and mechanical properties.

Wire with enamel insulation used in electrical or electronic devices are exposed to high temperatures due to heat according to Joule, during the flow of electric current, resulting in a magnetic field. In order to avoid the degradation and deformation of the wire with enamel insulation must be heat resistant. In addition, due to the continuous size reduction of the above devices, adverse conditions, which must run a separate motors or coils of the electrical components of vehicles, such as high temperatures or significant overcurrent, appeared an increasing demand for wire with a higher resistance to thermal influences.

From ur is VNA techniques known to use wire with polyimide insulation, demonstrates the superior thermal properties of the polyimides were declared and described, for example, in GB 898651, US 3207728, EP 0274602 and EP 0274121.

Also known inorganic modified polyimides (JP 2001351440, JP 2002304915), insulated wire of which also showed higher thermostability. However, wires insulated with polyimide also have several disadvantages: they are less resistant to abrasive wear unlike other types of wires (for example, wires insulated with polyvinyl (PVF) or wires with a protective coating of nylon); they are highly susceptible to hydrolysis in moist hermetic systems; they are subject to cracking by the action of solvents until, until you dropped voltage in the winding (for example, by heat treatment); they are very difficult to remove insulation, requiring highly corrosive means for removing insulation; as for the content of dry matter, with respect to their suitability for the job is very limited (very low compared to enamels other types).

Other coatings, demonstrating high heat stability, these coatings based on inorganic materials (JP 2006143543, JP 2003123551, US 20060228548). Such materials also have disadvantages, as they require a special application of technology and with rasaut the lifetime of a device for coating, since the latter are subject to a continuous abrasive action on the part of the inorganic component. In addition, the coating of the wires may be damaged during operation of the coil, in which the wires are subjected to mechanical stresses such as compression, extension or friction. In addition, ceramic enamels have a high tendency to cracking during thermodynamic cycles, remove the insulation from the wire.

The basis of the present invention lies in the task of developing a method of producing compositions of enamel wire with a higher resistance to thermal stress, get wire with enamel insulation from the modified traditionally used enamels, such as enamel based on polyesters, polyetherimides, polyurethanes and polyamidimide, which exhibit higher mechanical and thermal properties compared to traditional enamels. Enamel wire according to the present invention does not require any other conditions of application, non-standard conditions, and do not involve increased maintenance devices for enameling, compared with their normal maintenance.

The task of the present invention are achieved by a method of producing compositions of enamel wire with a higher resistance to teplovi the impacts consisting in adding nanomaterials for polymer-based composition of the enamel to the wire before applying the enamel on the wire, enamel wire and the use of nanomaterials in enamels for the wires to get the enamel with improved thermal properties.

Hereinafter the invention will be disclosed in more detail.

Enamel wire on the basis of polyester resins include condensation products of aromatic and/or aliphatic polyvalent carboxylic acids and their anhydrides, aromatic and/or aliphatic polyvalent alcohols and/or Tris-(2-hydroxyethyl) isocyanurate (THEIC)dissolved using a solvent-based Krasilovka acid. In addition, they usually contain solvent-naphtha and one or more catalysts for cross-linking; a more detailed description see US 3342780, US 3249578, EP 0144281 and WO 92/02776. All of the above products are products manufactured by the industry, well-known specialists in this field of technology. Usually the enamel on the basis of the polyesters used in the systems with two-layer coating as a ground layer, over which is applied a layer of polyamidimide.

Enamel-based polyetherimide used for the wires, as a rule, contain polyetherimide resin, dissolved in a mixture Kreinovich acids with event-nafta. In addition, they contain curing catalysts and additives. Polyetherimide resin is a condensation product of aromatic and/or aliphatic polyvalent carboxylic acids and their anhydrides, dicarboxylic acid is obtained as reaction product trimellitic anhydride (TMA) and an aromatic or aliphatic diamine, preferably, diaminodiphenylmethane, aromatic and/or aliphatic polyvalent alcohols and/or Tris(2 hydroxyethyl)isocyanurate (THEIC). A more detailed description can be found in such patents as DE 1445263, DE 1495100, WO 91/07469, WO 90/01911 that describe the current level of technology.

Enamel-based polyurethanes used for the wires, as a rule, contain high molecular weight resin on the basis of a complex of the polyester and a blocked polyisocyanate. They usually dissolved in a mixture Krasilovka acid with solvent-naphtha; as curing catalysts are usually used tertiary amines, organic salts of tin, zinc, iron and other metals. Complex polyester, as a rule, represents the condensation products of aromatic and/or aliphatic polyvalent acids and their anhydrides, aromatic and/or aliphatic mnogovalentnykh alcohols. In some enamels based polyurethanes used for the wires, instead of the polyesters used the form of polyetherimide. The blocked polyisocyanate is the reaction product of aromatic diisocyanates or polyisocyanates with Krasilovka acid or phenol. More detailed information can be found in such patents as DE 144749, DE-957157, DE 2840352, DE 2545912 and WO 90/01911.

Polyesters, polyetherimide and polyurethanes, particularly soluble in Kreinovich acids, being mixtures of phenol from 1 to 90%, Cresols from 1 to 99%, xylenols from 1 to 99%, three-METHYLPHENOL from 0 to 30%, ethylphenol from 0 to 20%, anisoles and other alkyl phenols and low molecular weight (2<<5). Crazylove acid as solvents for paints for wires, usually used in a mixture with a high-boiling aromatic hydrocarbons, for example, solventfree, xylene, Solvesso 100, Solvesso 150 and others. In some cases you can also use other solvents, such as high-boiling alcohols or high-boiling ethers, glycol, and other.

Enamel wire on the basis of polyamidimide contain polyamidimide resin, dissolved in a mixture of polar aprotic organic solvents. Tar get direct reaction of the anhydride tricarboxylic acid with a diisocyanate. As traditionally used tricarboxylic anhydride acid preference should be given trimellitate anhydride. As traditionally used is used isocyanates should be the preferred aromatic diisocyanates, (such as 4,4'-difenilmetana diisocyanate, colorvision. As solvents typically use N-methyl-2-pyrrolidone (NRM), N-ethyl-2-pyrrolidone (NEP), N,N'-dimethylacetamide, N,N'-dimethylformamide with xylene, solvent-naphtha and other hydrocarbons. The prior art is described in such patents as US 3554984, DE 2441020, DE 2556523, DE 1266427 and DE 1956512.

The authors of the present invention found that modified at the nanoscale enamel wire, obtained by adding nanomaterials for polymer-based composition of enamel before applying the enamel on the wire, exhibit improved properties compared to non-modified enamels. In particular, such modified enamel demonstrate high mechanical and especially thermal properties compared to traditional enamels and do not require special conditions of application compared to standard conditions, thanks to the description size of the used inorganic material. In addition, each type of enamel basically can be modified at the nanoscale, using the method described in this invention; however, the standard properties of the enamel will not deteriorate and will either improve or remain unchanged.

Nanomaterials, as a rule, are of inorganic materials with particles, the average radius of which is from 1 to ascolichen nanometers (nm). These materials are produced by manufacturers such as Degussa AG, Nanophase Technologies Corporation and other companies. Nanomaterials in the adulteration of various plastics or films lead to significant improvements in mechanical properties such as resistance to scratching and the rigidity of the film (reports on "Nanocomposite 2001", Baltimore 2001; "Second Annual Wood Coatings and Substrates Conference, Greensboro, 2006).

Nanoparticles, which can be used according to the method disclosed in the present invention, are particles, the average radius which is from 1 to 300 nm, preferably from 2 to 100 nm, even more preferably from 5 to 65 nm. Examples of preferred nanoparticles include: nanooxides, nanooxides metals, metal oxides or hydroxides of aluminum, tin, boron, germanium, gallium, lead, the transition metals and the lanthanides and actinides, in particular from the series comprising aluminum, silicon, titanium, zinc, yttrium, vanadium, zirconium and/or Nickel, preferably, aluminum, silicon, titanium and/or zirconium, which have the nano in the dispersed phase and can be used separately or in combination. Among nanooxides of the most preferred metals are different nanooxides aluminum. As examples of nanooxides aluminium brand name: BYK®-LP X 20693 and NanoBYK 3610, manufactured by BYK-Chemie GmbH, Nycol A120SD manufactured by the company Nycol Nano Technolgies Inc., Dispal X-25 SRu SRL, Disperal P2, P3, OS1 and OS2, manufactured by Sasol Germany GmbH. Among nanooxides aluminum are preferred ceramic particles of aluminum oxide, pre-dispersed in a polar solvent such as BYK®-LP X 20693 and NanoBYK 3610 company BYK-Chemie GmbH.

In a preferred embodiment of the present invention, the nanoparticles can be used together with binders. As binders it is possible to use any known functional alkoxy - or arelatively. Among functional silanes are preferred: (isocyanatomethyl)tralkoxydim, (aminoalkyl)tralkoxydim, (tralkoxydim)the alkyl anhydrides and oligomeric diamino-silane systems. Alkylsalicylate group and alkoxygroup functional silane is from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms. The above alkyl and alkoxygroup can continue to have the replacement group. As binders it is also advisable to use the titanates and/or zirconate. Can be any conventional esters orthotitanate or zirconium acid, such as, for example, tetraisopropyl, tetrabutyl, acetylacetone, esters acetoxy acid, diethanolamine, triethanolamine, titanate or lead zirconate of kresila.

A preferred variant the options proposed in the present invention the method is characterized by that the composition of the enamel wire includes:

a) from 10 to 80 wt.%, preferably from 20 to 70 wt.%, particularly preferably from 25 to 60 wt.% polymer base;

b) from 0.01 to 50 wt.%, preferably from 0.2 to 20 wt.%, particularly preferably from 1.0 to 10 wt.% nanomaterial;

in) from 19 to 90 wt.%, preferably from 29 to 80 wt.%, particularly preferably from 39 to 74 wt.% solvents, curing catalysts, binders and additives; in the basis of the percentages is the mass of the whole enamel wire, component, in any case, in the amount of 100%.

A method of obtaining modified at the nanoscale enamels for the wires can be implemented in several ways.

The nanoparticles can be dispersed in a suitable for this purpose solvent at different temperatures. The obtained dispersion system then add in the enamel wire.

It is also possible dispersion of nanomaterials in solvents with a synthetic resin in this dispersed system.

To improve the dispersion of nanoparticles in polymer solution such binders as functional silanes, titanates or zirconate can be added directly to the dispersion system with nanoparticles and mixed in the system before the system is added to the solution of a polymeric resin, or can be added directly to p the polymer solution, to add a dispersive system with nanoparticles. Alternatively, the binder can be mixed into the polymer solution prior to adding the dispersion system with nanoparticles to obtain a closer link between organic and inorganic components. The mixture of polymer solution with the binder may be mixed at room temperature or under conditions of relatively low temperature for several hours before adding solution nanooxide metal.

The present invention also relates to the manufacture of wire with enamel insulation when using disclosed in the present invention compositions obtained as described above.

Application and curing proposed in the present invention the composition does not require any special procedures for the application, non-standard procedures. On the wire to be used, whose type and diameter of the same type and diameter of the wires used for the application of unmodified enamel insulation may be covered with a coating layer of 0.005 to 6 mm Under acceptable wires understand traditional metal wire, preferably copper, aluminum wire or wires of their alloys. In the form of wires there are no limits, in particular, can use the matching wire round and of rectangular cross-section.

Proposed in the present invention the composition may be applied one layer, two layers or multiple layers. With regard to the application of two layers or more layers, enamel, modified at the nanoscale, can be applied together with the non-modified enamels. Preference is given to application of nano-modified enamels for each coating layer.

When applying the composition, the thickness of the applied layer can be standard, while the thickness of the layer in a dry form corresponds to the standardized values of the thickness of the wires for both small and large diameters.

The composition of the present invention is applied to the wire and utverjdayut in the furnace with horizontal or vertical heating channels.

The wire can be covered with one layer with its curing or more layers, followed by curing each layer. As for the temperature of curing, its acceptable limit can vary from 300 to 800°C in accordance with the traditional parameters used for the corresponding unmodified enamels, and the wire material, which is coated. Such conditions enameling, as the number of passes, the rate of deposition and the temperature of the furnace depends on the wire material, which is coated.

Made Prov is Yes with enamel insulation tested in accordance with IEC 60851.

It was found that the formulation of enamel wire, prepared in accordance with the above description, when applied to the wire, followed by curing exhibit higher thermal stability compared to conventional non-modified enamels. In particular, a higher resistance to elevated temperatures were determined as the higher strength at break. Also improved this property, as heat stroke, which allows the wire insulated with enamel, modified at the nanoscale, to withstand higher temperatures for a certain period of time without cracking wound wire. In addition, the coatings obtained using enamels, modified at the nanoscale, according to the present invention exhibit higher wear resistance, and sometimes higher flexibility compared to conventional coatings.

The present invention also covers the use of nanomaterials in enamels for the wires in order to improve thermal properties of enamels, in particular in the enamel wire obtained by the above method.

The present invention will be described below in more detail based on examples below, although it is not limited to only these options implementation.

When the career

Preparation of protective coatings for wires according to the prior art.

Example 1 (polyamidimide for comparison).

In chetyrehosnuju flask with a volume of 2 liters with a stirrer, a cooling tube and a tube with calcium chloride, loaded USD 192.1 g of anhydride trimellitic acid (TMA), 250,3 g methylenediphenyl 4,4'-diisocyanate (MDI) and 668 g of N-methyl-2-pyrrolidone (NRM). The resulting mixture reacts for 2 hours at a temperature of 80°C, followed by heating to 140°C. and stirring at this temperature until, until stopped the formation of carbon dioxide. Then the reaction mixture was cooled to a temperature of 50°C and to it was added 257 g of xylene. According to the above procedure was obtained a solution polyamidimide resin concentration of the resin of 33.0 wt.% and a viscosity of 900 CPS (at 20°C.

Example 2 (complex polyester for comparison).

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device was downloaded 54 g of ethylene glycol together with 179 g of Tris(2 hydroxyethyl)isocyanurate (THEIC), 177 g of dimethyl terephthalate (DMT) and 0.33 g of tetrabutyltin orthotitanate acid (tetramethylsilane). The resulting mixture was heated to 210°C and continued mixing until until it was whisked 55 g of methanol. The obtained complex polyester was then cooled and mixed with 13 g of tetrabutyltin and a sufficient number of CME and, consisting of 80 parts Kreinovich acid and 20 parts of solvent-naphtha, obtaining a solution with a dry matter content of up 37.0 wt.%.

Example 3 (polyetherimide for comparison).

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device was downloaded 300 g Kreinovich acids together with 62,0 g of ethylene glycol and 261,1 g THEIS, 194,2 g DMT and 0.35 g of tetrabutyltin. The resulting mixture was heated to a temperature of 200°C and continue mixing until until it was driven into 60 g of methanol. After cooling to a temperature of 140°C was added USD 192.1 g TMA and a 99.0 g of DDM, then the solution was heated to 205°C for 2 hours and continued mixing until until it was whisked 33 g of water. The resulting polymer mixture was then cooled and under continuous stirring was mixed with 23 g of tetrabutyltin and 110 g phenolaldehyde resin. Then, the solution was diluted with sufficient amount of a mixture consisting of 70 parts Kreinovich acid and 30 parts of solvent-naphtha with obtaining enamel wire with a dry matter content of up 37.0 wt.%.

Example 4 (polyurethane for comparison).

Preparation of high molecular weight resin on the basis of a complex of the polyester.

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device was downloaded 194,1 g DMT, 170,0 g of ethylene glycol, of 92.1 g of glycerin and 0.06 g of lead acetate. Received mesh was heated to a temperature of 220°C and continued mixing for several hours, until then, until it was driven into 64 g of methanol. Then into the hot resin was added a sufficient amount of Krasilovka acid to obtain a solution of high molecular weight resin on the basis of a complex of the polyester with a dry matter content of 44,8 wt.%.

Preparation of blocked polyisocyanate:

In chetyrehosnuju flask with a volume of 2 liters, with a stirrer, a cooling tube and a tube with calcium chloride was loaded with 150 g of phenol, 150 g xylenols, 174 g colordistance, (TDI), produced by industry, and 44.7 g of trimethylolpropane (TMP). The resulting mixture was heated with continuous stirring to a temperature of 120°C and kept at this temperature until, while in the reaction mixture does not remain isocyanate. Then, upon cooling, to the mixture was added 120 g of a solvent-naphtha. According to the above procedure was obtained a resin solution on the basis of the isocyanate concentration of the resin is 46.5%.

Preparation of enamel wire polyurethane-based.

In dvuhgolosy flask with a volume of 2 liters with a stirrer were added 30 parts prepared with high molecular weight resin on the basis of a complex of the polyester and 70 parts prepared resin-based MDI. This mixture was mixed with a sufficient quantity of a solvent mixture consisting of 40 parts of phenol, 20 parts xylenols, 20 parts of xylene and 20 parts of solvent-naphtha. The resulting enamel is the wires on the basis of polyurethane had a dry matter content of 33.0 wt.%.

Preparation of protective coatings for wires in accordance with the present invention

Example 1A. (Preparation of polyamidimide modified at the nanoscale).

In chetyrehosnuju flask with a volume of 2 liters with a stirrer, a tube for cooling, with a tube with calcium chloride was downloaded 33,0 g BYK-LP X 20693 and 77.0 g of N-methylpyrrolidone (NRM). Then the mixture was stirred at 40°C for 2 hours, after which the above-mentioned flask was added to 1000 g of the solution polyamidimide resin from Example 1, the concentration of 33 wt.%. The resulting mixture was stirred at room temperature for several hours; then the solution was filtered to remove random solids, with the receipt of polyamidimide modified at the nanoscale, with dry matter content of 32.2 wt.%. In this case, the content of aluminum oxide (Al2O3) amounted to 5 wt.%.

Example 1B. (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A Example 1B was prepared using NANOBYK 3610 (company BYK Chemie) with the receipt of polyamidimide modified at the nanoscale, with dry matter content and 32.3 wt.%. In this case, the content of aluminum oxide (Al2O3) amounted to 5 wt.%.

Example 1B. (Preparation of polyamidimide modified at the nanoscale).

As is written in Example 1A, Example 1B was prepared using Disperal P2 (Sasol) with the receipt of polyamidimide modified at the nanoscale, with dry matter content 32,4 wt.%. In this case, the content of aluminum oxide (Al2O3) amounted to 5 wt.%.

Example g (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A, Example 1G was prepared using Nycol AL20SD (company Nycol) obtaining polyamidimide modified at the nanoscale, with dry matter content 32,4 wt.%. In this case, the content of aluminum oxide (Al2O3) amounted to 5 wt.%.

Enamel and testing

As conductors conductor insulation used copper wire with a thickness of the exposed wires of 0.71 mm Enamel was applied and utverjdali when heated 14 times in the machine for enameling MAG HEL 4/5, with recirculation of air at a temperature of 520°C, with a speed of 32 m/min; as a system for coating used dies. The resulting layer thickness was 0,070 mm

Table 1
The test results of polyamidimide modified at the nanoscale, with different nanoparticles.
Example 1AExample 1BExample 1BExample 1GExample 1 (comparative)
NontobaccoBYK LP X 20693NANOBY TO 3610Disperal P2Nycol A120OSD-
Flexibility (1×D, % pre-strain)2015151515
One-sided directional wear (N)1819181716
Tan Delta (°C)275273272269270
Strength at break (°C)450440430430410
Thermal shock (30 min at 240°C): 3/32/32/32/32/3

From table 1 it is evident that the products modified at the nanoscale, have a higher breakdown strength than the comparative example. Achieved a higher wear resistance. Enamel from Example 1A (3 subjects sample of three), fully withstands thermal shock tests on at a temperature of 240°C.

Example 1D. (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A, Example 1D was prepared using the BYK-LP X 20693 in such quantity that the resulting polyamideimide modified at the nanoscale, had a dry matter content is 32.8 wt.% and the content of aluminum oxide (Al2O3) - 2 wt.%.

Example 1E. (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A, Example 1E was prepared using the BYK-LP X 20693 in such quantity that the resulting polyamideimide modified at the nanoscale, had a dry solids content of 32.1 wt.% and the content of aluminum oxide (Al2O3) - 7.5 wt.%.

Example 1G. (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A, Example 1G was prepared using the BYK-LP X 20693 in such quantity that the resulting polyamideimide, modified at the nanoscale, had a dry matter content of 31.8 wt.% and the content of aluminum oxide (Al2O3) - 10 wt.%.

Table 2
The test results of polyamidimide modified at the nanoscale, with different amounts of nanoparticles.
Example 1DExample 1aExample 1EExample 1GExample 1 (comparative)
NontobaccoBYK LP X 20693BYK LP X 20693BYK LP X 20693BYK LP X 20693-
The percentage of aluminum oxide (Al2O3, %)257,510
Flexibility (1×D,% pre-strain)1520201515
Unilateral is e aimed wear (N) 2018181716
Tan Delta (°C)270275277273270
Strength at break (°C)420450490480410
Thermal shock (30 min at 240°C)2/33/33/33/32/3

Table 2 shows that the optimal number of nanoparticles present in the tested system, is 7.5%. The product from Example 1E has an ultrahigh strength at break, higher wear resistance and higher resistance to thermal shock.

Example 1H. (Preparation of polyamidimide modified at the nanoscale).

As described in Example 1A, Example 1H was prepared using the BYK-LP X 20693 and (3-aminopropyl)triethoxysilane. The silane pre-mixed in the NRM together with nanooxides aluminum for 4 hours at 4°C. Polyamidimide modified at the nanoscale, had a dry matter content of 33.0 wt.%, the content of aluminum oxide (Al2O3) - 7.5 wt.% and silane - 0.5 wt.%.

Table 3
The test results of polyamidimide modified at the nanoscale, illustrating the influence of the binder.
Example 1EExample 1ZExample 1 (comparative)
NontobaccoBYK LP X 20693BYK LP X 20693-
The percentage of aluminum oxide (Al2O3, %)7,57,5-
Functional silane (%)-0,5
Flexibility (1×D, % pre-strain)202015
One-sided directional wear (N)18 19,616
Tan Delta (°C)277285270
Strength at break (°C)490500410
Thermal shock (30 min at 240°C)3/33/32/3

Table 3 shows that when using a binder, it continues to improve properties such as strength at break and tan Delta.

Example 2A. (Preparation of a complex of the polyester modified at the nanoscale).

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device, downloaded 37,0 g BYK-LP X 20693, 1.85 g (3-aminopropyl)triethoxysilane and to 172.6 g Kreinovich acids. Then the resulting mixture was stirred for 4 hours at 40°C, followed by adding 1000 gr. the resin solution on the basis of the complex of the polyester from Example 2. After that, the mixture was stirred for 2 hours at a temperature of 40°C To produce a complex of the polyester modified at the nanoscale, with a dry matter content of 36.7 wt.%. In this case, the content of the silane was 0.5 wt.%, and the content of nanooxide is luminia - 5 wt.%.

Example 3A. (Preparation of polyetherimide modified at the nanoscale).

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device was downloaded 37,0 g BYK-LP X 20693, 1.85 g (3-aminopropyl)triethoxysilane and to 172.6 g Kreinovich acids. Then the resulting mixture was stirred for 4 hours at 40°C, followed by adding 1000 g of the solution polyetherimide resin from Example 3. After that, the mixture was stirred for 2 hours at 40°C with getting polyetherimide modified at the nanoscale, with dry matter content to 36.8 wt.%. In this case, the content of the silane was 0.5 wt.%, and the content of nanooxide aluminum - 5 wt.%.

Table 4
The results of the tests of complex polyester and polyetherimide modified at the nanoscale
Example 2AExample 2 (comparative)Example 3AExample 3 (comparative)
NontobaccoBYK LP X 20693-BYK LP X 20693-
The percentage of aluminum oxide (Al2O3, %)5-5-
Functional silane (%)0,5-0,5-
Flexibility (1×D, % pre-strain)30302525
One-sided directional wear (N)1814
Tan Delta (°C)188182207204
Strength at break (°C)470440440420
Thermal shock (30 min at 240°C)2/31/32/31/3

From Table 4 it is seen that the products modified at the nanoscale, there is tons higher strength at break, than in the comparative example. Achieved higher durability.

Example 2B. (Preparation of a complex of the polyester modified at the nanoscale).

As described in Example 2A, Example 1B was prepared using N-dimethoxy(methyl)millimeter-O-methyl-carbamate, 0.5 wt.%. The results of applying the enamel is equivalent to Example 2A.

Wire with enamel insulation tested in accordance with the positions of Table 5, were made of copper wires when the thickness of the exposed wires of 0.71 mm Enamel was applied: first, a complex polyester or polyetherimide, as a primer layer (11 layers), plus 3 of the top layer of polyamidimide.

The percentage of aluminum oxide (Al2O3, %)
Table 5
The results of the test wires with double coverage.
Example 2A (primer) + 1H (top layer)Example 2 + Example 1 (comparative)Example 3A + 1ZSample 3 + Sample 1 (comparative)
NontobaccoBYK LP X 20693-BYK LP X 20693-
5 (primer) + 7,5 (upper layer)-5 (primer) + 7,5 (upper layer)-
Functional silane (%)0,5 (primer) + 0,5 (upper layer)-0,5 (primer) + 0,5 (upper layer)-
Flexibility (1×D, % pre-strain)20152015
One-sided directional wear (N)22192219
Tan Delta (°C)181178208205
Strength at break (°C)460410450400
Thermal shock (30 min at 240°C)3/3 1/33/32/3

From Table 5 it is seen that system, modified nano material and having a double coating, in both cases, their properties superior to the properties of the unmodified products. In all cases, all of the improved properties.

Example 4A. (Preparation of polyurethane modified at the nanoscale).

In a three-neck flask with a volume of 2 liters, with a thermometer, a stirrer and a distillation device was downloaded 33,0 g BYK-LP X 20693, of 1.65 g of (3-aminopropyl)triethoxysilane and 154 g Kreinovich acids. Then the resulting mixture was stirred for 4 hours at 40°C, followed by adding 1000 g of the solution of polyurethane resin of Example 4. After that, the mixture was stirred for 2 hours at a temperature of 40°C To produce polyurethane, modified at the nanoscale, with a dry matter content of 33.3 wt.%. In this case, the content of the silane was 0.5 wt.%, and the content of nanooxide aluminum - 5 wt.%.

Example 4B. (Preparation of polyurethane modified at the nanoscale).

As described in Example 4A Example 4B was prepared using the BYK-LP X 20693 and (3-aminopropyl)triethoxysilane in such quantity that the resulting polyurethane, modified at the nanoscale, had a dry matter content of 33.3 wt.%, the content of aluminum oxide (A 2O3) - 2 wt.% and silane - 0.2 wt.%.

Example 4B. (Preparation of polyurethane modified at the nanoscale).

As described in Example 4A Example 4B was prepared using the BYK-LP X 20693 and (3-aminopropyl)triethoxysilane in such quantity that the resulting polyurethane, modified at the nanoscale, had a dry matter content of 33.3 wt.%, the content of aluminum oxide (Al2O3) - 1 wt.% and silane - 0.1 wt.%.

Table 6
The results of the testing of enamels for the wires on the basis of polyurethane, modified at the nanoscale.
Example 4AExample 4BExample 4BExample 4 (comparative)
NontobaccoBYK LP X 20693BYK LP X 20693BYK LP X 20693-
The percentage of aluminum oxide (Al2O3, %)521-
Functional silane (%) 0,50,20,1-
Solderability (seconds at 380°C)2,52,52,32,5
One-sided directional wear (N)15141312
Tan Delta (°C)176181182185
Strength at break (°C)270280270260
Thermal shock (30 min at 240°C)2/31/31/30/3

From Table 6 it is seen that there is an optimum content of nanoparticles, equal to 2%, leading to a significant increase in the durability test, without compromising paemst copper wire (thickness of 0.71 mm) with a coating of polyurethane. Also substantially improved resistance to thermal shock.

1. The use of nanomaterials in enamel for wires is to improve thermal properties of enamel.

2. The use according to claim 1, in which the polymer base of the enamel wire is chosen from the group comprising polyamidimide, complex polyester, polyetherimide, polyurethane and mixtures thereof.

3. The use according to claim 1, in which a nanomaterial selected from the group including nanooxides, nanooxides metals, metal oxides or hydroxides of aluminum, tin, boron, germanium, gallium, lead, the transition metals, lanthanides, actinides, and mixtures thereof.

4. The use according to claim 1, in which a nanomaterial selected from the group including nanooxides, nanooxides metals, metal oxides or hydroxides of aluminum, silicon, titanium, zinc, yttrium, vanadium, zirconium, Nickel and mixtures thereof.

5. The use according to claim 1, in which a nanomaterial selected from the group including nanooxides aluminum.

6. The use according to claim 1, in which the radius of the nanoparticles is in the range from 1 to 300 nm, preferably from 2 to 100 nm, particularly preferably from 5 to 65 nm.

7. The use according to claim 1, in which the nanomaterial is treated with one or more binders.

8. The use according to claim 7, characterized in that the binder is chosen from the group comprising alkoxy - or arelatively, (isocyanatomethyl)tralkoxydim, (aminoalkyl)tralkoxydim, (tralkoxydim)alkyl anhydrides, oligomeric diaminoethane, titanates, zirconate and mixtures thereof.

9. The use according to claim 1, in which the EMA is ü wire includes:
a) from 10 to 80 wt.%, preferably from 20 to 70 wt.%, particularly preferably from 25 to 60 wt.% polymer basis;
b) from 0.01 to 50 wt.%, preferably from 0.2 to 20 wt.%, particularly preferably from 1.0 to 10 wt.% nanomaterial;
in) from 19 to 90 wt.%, preferably from 29 to 80 wt.%, particularly preferably from 39 to 74 wt.% solvents, curing catalysts, binders and additives
where the basis of percentages taken the whole mass of the enamel component in the sum in any case 100%.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing a dispersion of silicon dioxide particles with a modified surface, having mean diameter of not more than 100 nm, via high-pressure grinding of a pre-dispersion containing a) 10-50 wt % silicon dioxide particles with a modified surface, b) at least one glycol monoether of general formula H3C(CH2)m-O-(CH2)n-[O-(CH2)o]p-OH (A), c) at least one carboxylic ester of general formula H2x+1Cx-O-CH2-(CHR)-[O-CHR]y-O-C(=O)-CzH2z+1 (B), where the molar ratio A/B ranges from 10:90 to 40:60 and m, n, o, p, x, y and z do not depend on each other. Also disclosed is a dispersion obtained using the disclosed method, a method of producing granules of silicon dioxide particles with a modified surface by separating the liquid phase of the dispersion, granules obtained using the disclosed method and use of the dispersion and granules in coating materials.

EFFECT: disclosed dispersion and particles can be used in transparent coating compositions.

10 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of cyclohexane dicarboxylic acid diesters, wherein ester groups contain residues selected from a group of branched and straight substituted and unsubstituted alkyl residues, for producing coating materials for the method of coating roll or sheet metallic materials. The coating method is realised by continuously depositing onto one or both sides of a tape at least one fluid coating material and then thermally treating the layers. The coating material contains at least one said cyclohexane dicarboxylic acid diester, at least one paste-like polyvinyl chloride with mean grain diameter of 1-15 mcm and at least one extender polyvinyl chloride with mean grain diameter of 25-35 mcm. The invention also relates to production of three-dimensional moulded articles from the coated roll or sheet material, obtained by moulding from this material.

EFFECT: coated sheets, as well as their coating have improved weather resistance, particularly resistance to UV radiation.

21 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a resin paint composition for high internal permeability cationic electrodeposition and can be used as a primer coat. The composition contains a basic resin which contains products of reaction of polysulphide compounds with epoxy compounds and products of reaction of amine compounds and epoxy compounds; a resin curing agent which contains products of reaction of modified polyol compounds; aromatic sulphonic acid; and a substance which provides rheologic properties, containing a urethane functional group.

EFFECT: composition has high stability of aqueous dispersion, coating uniformity, antibacterial properties, plasticity and anticorrosion properties.

8 cl, 11 tbl

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: additives are used in compositions which are applied on transparent panel bases, e.g., used in windows. The coating composition additive contains an agent for improving functioning of the coating composition, containing a Michael reaction siloxane product, also containing one or more active hydrogen-containing functional radicals with two or more acrylate groups and a compound containing an acid radical which is a carboxylic acid. The invention also relates to an article obtained using the following method. The base-coating method involves mixing the coating composition with said additive, depositing the mixture onto the base and adhesion of the deposited mixture. The invention relates to a coating composition which contains a resin selected from epoxy, acrylic, polyurethane or any combination thereof, a dye and said additive.

EFFECT: articles with the coating composition are characterised by prolonged use.

9 cl, 5 tbl

Pigment dispersion // 2455326

FIELD: chemistry.

SUBSTANCE: described is a method of producing an essentially aqueous pigment dispersion which is essentially free from organic binder and dispersions obtained using said method. The method involves mixing a water-soluble or water-dispersable silane compound and particles of colloidal silicon dioxide with weight ratio of silane to silicon dioxide from 0.25 to 1.5 to form particles of silanised colloidal silicon dioxide in an aqueous dispersion. Said particles of colloidal silicon dioxide are further mixed with an organic and/or inorganic pigment with weight ratio of silicon dioxide to pigment from about 0.001 to about 0.8, to form said essentially aqueous pigment dispersion. Described also is use of the disclosed pigment dispersion when applying coatings and for reducing formation of bubbles on non-absorbent substrates.

EFFECT: disclosed pigment dispersion has high resistance to flocculation and high stability over time.

20 cl, 5 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: described are novel benzotriazole UV-absorbers, having absorption spectrum shifted towards the long-wave side with considerable absorption in the region up to 410-420 nm, having general formulae (a)-(k) (structural formula and values of radicals are given in the description), composition which is stabilised with respect to UV radiation and containing novel UV-absorbers, and use of the novel compounds as UV light stabilisers for organic materials.

EFFECT: obtaining novel benzotriazole UV-absorbers, having absorption spectrum shifted towards the long-wave side.

13 cl, 23 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: coating composition has a latex component and a volatile coalescing solvent substituting agent. The agent has the formula: X(AO)nH, where X is a group from C6 to C16, selected from a group of linear chains, branched chains, aromatic rings and combinations thereof, AO is an alkyleneoxy group selected from ethyleneoxy groups, 1,2-propyleneoxy groups, 1,2-butyleneoxy groups and combinations thereof, and n varies from 3 to 14. The coating composition has content of volatile organic compounds less than or equal to 150 g/l. The volatile coalescing solvent substituting agent has little or no contribution into the total level of the volatile organic compounds in the coating composition.

EFFECT: obtaining a coating composition with high continuity and restorability, suitable low-temperature coalescence, resistance to adhesion and operational parameters in freezing and thawing conditions.

25 cl, 11 tbl

FIELD: chemistry.

SUBSTANCE: electroplating composition contains cyclic guanidine and a polymer which contains a functional group. Said polymer contains a functional group which reacts with said cyclic guanidine and said functional group includes an epoxy group. In the composition, said polymer with cyclic guanidine forms a reaction product. Said cyclic guanidine is 1,5,7-triazabicyclo[4.4.0]dec-5-ene. Use of cyclic guanidine in said composition can cut and/or completely eliminate the need for metallic catalysts such as tin and/or bismuth.

EFFECT: invention enables to form a coating which endows a substrate with corrosion resistance, wear resistance, resistance to damages caused by impact, fire resistance and heat resistance, chemical resistance, resistance to UV light and structural integrity.

67 cl, 33 ex

FIELD: chemistry.

SUBSTANCE: acrylic lacquer contains an acrylic copolymer dispersion Primal AC-4800ER, a coalescent additive Nexcoat NX-795, a wax additive Aquacer 502, Orotan 681 dispersant, a polyurethane thickener Acrisol RM-2020, a neutraliser - 20% aqueous ammonia solution, an antifoaming agent Nopko NXZ, a preservative Kathon LXE and water.

EFFECT: with the given combination of components, the acrylic lacquer is characterised by good working characteristics and forms a high-lustre transparent coating on wooden articles.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: varnish contains a varnish base, a functional additive which increases coating hardness, siccative HF and methyl ethyl ketoxime radical polymerisation inhibitor. The varnish base is an oligomer with strongly polar chromane rings. The oligomer is obtained by reacting tung oil and 101L phenol-formaldehyde resin, taken in equivalent ratio of 1:0.15-0.18, respectively, while heating said mixture for 60 minutes at temperature 160°C. After extracting water, temperature is raised to 182°C until achieving viscosity of 25-36 s. The oligomer is added to the composition in 50% xylene solution. The functional additive used is rosin ester with glycerine. Components are in the following ratio, wt %: oligomer - 31.0-36.2, rosin ester with glycerine - 9.0-3.8, siccative HF - 2.00, methyl ethyl ketoxime - 0.60, xylene - the balance.

EFFECT: wider raw material base, replacing molten amber, which is not produced on an industrial scale, with rosin ester with glycerine, high content of non-volatile substances, elasticity and electrical strength of the coating.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed insulating coating composition, containing bitumen in amount 90-100 wt fractions, fluorocarbon polymer 32 LN in amount 10-15 wt fractions, butyl acetate in amount 40-45 wt fractions, acetone in amount 40-45 wt fractions and mica in amount 2-3 wt fractions.

EFFECT: improved insulating properties, mechanical strength and chemical stability.

1 tbl, 1 ex

FIELD: polymer materials.

SUBSTANCE: insulating varnish for coating enameled wires contains polyester resin, titanium catalyst, and organic solvents, titanium catalyst being, in particular, tetrabutoxytitanium and organic solvents being petroleum solvent and cresol solvent recovered by treatment coal oil and consisting of phenol, o-, m-, and p-cresols, and xylenols, which has following fraction composition (by volume): up to 180°C not more than 3%, 190-205°C at least 70% and up to 210°C at least 85%.

EFFECT: lowered cost price of varnish and improved quality of finished product.

1 tbl, 9 ex

FIELD: polymer materials.

SUBSTANCE: insulating varnish for coating enameled wires contains polyesteramide resin cresol solvent, petroleum solvent, and tetrabutoxytitanium, said cresol solvent being the one recovered by treatment coal oil and consisting of phenol, o-, m-, and p-cresols, and xylenols, which has following fraction composition (by volume): up to 180°C not more than 3%, 190-205°C at least 70% and up to 210°C at least 85%.

EFFECT: lowered cost price of varnish and improved quality of finished product.

1 tbl, 9 ex

The invention relates to the field of compositions intended for sealing electrical connectors between the contacts and the insulator

The invention relates to the field of construction and repair of metal pipes with insulating coating, such as underground experiencing simultaneous effects of dynamic and static loads, corrosive environments, low temperatures, microorganisms

The invention relates to the insulation of the surfaces of metal products, mainly jewelry, at local, predominantly electrochemical and chemical processes, and is intended for use in the jewelry industry, instrument-making, machine-building and local industry

The invention relates to electrical engineering, and in particular to compositions insulating coatings and impregnation of windings of electrical machines and devices operating at high temperatures

The invention relates to the production of insulating coatings on electrical steel used in the magnetic circuits of electrical machines, apparatus and instruments

FIELD: chemistry.

SUBSTANCE: composition for fixing wrapping articles contains A) 1-60 wt % of at lest one resin of α,β-unsaturated polyether based on at least one unsaturated mono-, di- or tricarboxylic acid and/or substance containing molecules with mono-, di- or tricarboxylic acid groups, at least one polyol, B) 0.1-80 wt % of at least one inorganic and/or an organic-inorganic hybrid component, having functional groups for reaction with components A) and C), where said hybrid components are polymers or colloidal solutions based on silicon, titanium or zirconium and oxygen atoms, which contain hydroxyl and/or alkoxy groups and/or hydroxyalkyloxy groups and/or organic fragments, which have epoxy and/or isocyanate and/or unsaturated groups, C) 2-80 wt % of at least one monomer and/or oligomeric unsaturated component, which is styrene, vinyl toluene, hexanediol dimethacrylate, butanediol dimethacrylate and/or (meth)acrylates of products of a polyaddition reaction of ethylene oxide with trimethylolpropane capable of reaction with components A and B, and D) 0-15 wt % conventional additives, where wt % is calculated relative the total weight of the composition.

EFFECT: excellent heat conductivity properties and high level of electrical insulation along with excellent adhesion and thermal stability.

6 cl, 1 tbl, 2 ex

Up!