SU582769A3 - Method of manufacturing lacquer resin for wire insulation - Google Patents

Description

(54) METHOD OF OBTAINING VARNISH RESIN FOR INSULATION

WIRES

varnishes for insulation wires. Resins of this composition have a relatively high softening point, which increases with increasing condensation temperature. They are not suitable for melt deposition, since at temperatures t yes-16 o C they have too high melt viscosity and at higher melting points (about 160-180 ° C) due to continued condensation their melt viscosity changes.

The closest in technical essence to the invention is a method for producing a resin varnish for the insulation of wires by perezterifikatsii dimethyl etnlenglikolem trisgidroksietilizotsianuratom and in the presence of catalysts of this esterification product pereeterifikatsiiJ -trimellitovoy acid anhydride and adding 4,4-diaminodiphenylmethane in a molar ratio of trimellitic anhydride and a diamine 2: 1 followed by polycondensation 3.

However, this method does not completely solve the contamination problem, but only partially, and the viscosity of resins containing diluents at melting temperatures changes with time due to evaporation of the diluent, since the melt is in open tanks, as is the case with conventional wire coating machines The resulting resins have a high melt viscosity at 140–160 ° C, so it is nevral to apply them to the wires from the melt.

The aim of the invention is to obtain a lacquer resin suitable for applying it to wires from a melt.

This is achieved by using 0.3–1.5% of the weight of all resin-forming titanium and / or vanadium and / or zirconium monomers as the transesterification catalyst; the esterification of trimellitic acid anhydride is stopped by adding the total amount of diamine with a degree of esterification of 42.5 -50%, and polycondensation is carried out before obtaining a resin having a viscosity of 140-160 ° C at 140-160 ° C.

The process of the invention is carried out by transesterification of dimethyl terephthalate with excess ethylene glycol and trishydroxyethylisocyanurato in the presence of 0.3-1.5% titanium, zirconium or vanadium alcoholate or their mixtures by weight of all resin-forming monomers, in the presence of catalytic amounts of other known transesterification agents, such as zinc acetate, ceroctate, lead oxide, etc., after which trimellitic acid anhydride was added, and subsequently etherification until

until approximately 42.5-50% of the carboxyl groups of trimellitic acid, equivalent to trimellitic anhydride, are obtained in the esterified form, ending the esterification reaction by immediately adding the total amount of diamine and continuing polyxdensation with water removal and / or lythylene glycol until the resin becomes refluxing; 140-160 ° C; viscosity 5000-20000 spz.

Compounds of the general formula 11SO3, 2 GN) are used as alcohols, as well as 0V10L) h; Preferably, such compounds are used in which E is cycloalkyl or is a branched or unbranched alkyl radical with up to 5 carbon atoms.

Preferably n-buty and isopropyl titanates, zirconates and vanadates are used, especially tetra-n-butyl titanate or tetraisopropyl titanate.

The proposed dyeing method for producing a lacquer resin has several unexpected effects: the alcoholate present in the reaction in significant amounts, for example, titanium, during the formation of the reaction water from diamine and the trimethylic acid partial ester is not transformed by samination into titanium dioxide, causing turbidity, and the resin remains completely transparent (turbidity always occurs while titanium alcohol is added during the resin production process);

the presence of relatively large amounts of alcoholate at 140–160 ° C does not affect the melting stability of the final products;

the introduction of an alcoholate into the resin leads to the fact that the degree of condensation in order to achieve a sufficiently low viscosity for melt deposition can be kept at extremely low levels. If, however, similarly formulated resins are condensed, for example, without adding titanium alcohol to a low level of polycondensation, dissolve them in cresol / solvent-naphthic mixtures in the usual way and add the above mentioned amount of alcoholate, then after application by hot drying on Copper wires are coated with properties that are unsatisfactory for technical use (see Example 2).

The described method is a method of producing polyethers, in which titanium compounds can be used as a catheter of esterification or transesterification. These compounds should be applied in very small quantities, otherwise the equilibrium is shifted.

whereby the polycondensation reaction continues. Thus, melt viscosity stability cannot be achieved.

Known transesterificacin catalysts should generally be present, because the titanium, zirconium or vanadium compounds added by the proposed method do not sufficiently reduce the transesterification reaction at temperatures within the boiling point of ethylene glycol, as a result of which the pare esterification would last too long in the absence of the known catalysts. .

Although the lacquer resins for insulating wires obtained in the manner described above, especially from the point of view of their melt application, are of interest, it is quite easy to dissolve them in cresol / SALT-naphthic mixtures and these solutions are used without further addition of hardeners for lacquering electrical wires . This method of application has the advantage over ordinary varnishes of the same composition that the mechanical properties of insulated wires under conditions of hot drying practically remain CONSTANT). Preferably, they are operated with the highest possible wire feed pitch, Tc (K, technical defects are excluded.

Example 1. In a switchgear, a single flask with a capacity of 2 liters with fuel oil, with an inert gas supply and a descending hoe. 290 g (1 5 mol of dimethyl terephthalate, 289 g (1.1 mol) of trishydroxyethyl isocyanurate, 105 g (1.7 mol) ethylene rvHi amount, 3 g of ceroctoate and 0.2 g of zinc acetate dihydrate. After melting at a temperature, enter 10 g (O, -9 wt.%) of tetra- and -butyl titanag and then 95 g of methanol is distilled off at 150-200 ° C for about 5 hours. Then another 170 g (2.7 mol) of ethylene glycol is added (add glycol for 2 h so as not to cause the fate of tris-hydroxyethyl isocyanurate in the transesterification reaction) and mix 410 g (2.14 mol) of trimellitic anhydride lots. The temperature is lowered again and the water is distilled off from the transesterification. As a result of the resulting 16 ml of water (degree of esterification of 47%), 211 g (1.05 mol) is mixed in as quickly as possible (approximately 5 minutes). A) 4,4-diaminodiphenylmethane and the esterification reaction is stopped, after which the temperature is increased to 2.15 ° C and maintained at this level until the distillation of water stops. Then create vacuum up to 50 Torr and maintain a temperature of 200 Hp, while

the viscosity, measured by capillary, using the PRI method with a 1 g gum of resin in 100 ml of solution (with the diluent consisting of a mixture of fiO wt.% phenol and 40 wt.% 1,1,2,2-tetrachloroethane), will not reach 0.095. After that, the resin is poured and the condensation reaction is completed. The resulting resin is melted, the melt at 150 ° C has a viscosity of 10,000 sps. This value of the melt viscosity remains almost unchanged for 8 hours at 150 ° C.

If butyl titanate is added at the end of the transesterification or after the removal of water arising during the desalting, turbid resins are obtained which cannot be made transparent either by melting or by dissolution.

In the above example, tetra-n-butyl titanate can be replaced by the same amount of vanadyl t-n-butylate or tetra-n-butyl zirconate.

PRI mme R 2. Experience Conducted according to example 1 with the difference that butyl titanate during the process does not

add.

PRI me R 3,

OnFiiT is carried out according to Example 1, Example i with the difference that the addition of diamine is not made within 5 minutes, but gradually over about 30 minutes.

P 1 m er 4. In Example 1, a transesterification of 425 g (2.19 mol) of dimethyl terephthalate, 407 g (1.5 b mol) of trishydroxyethyl isocyanurate and 120 g (1.9 of mol) of ethylene glycol in the presence of 3 g of teroctoate, 0.2 g of acetate dihydrate is carried out. zinc and 12 g (0.95 re;% T tetraH-butyl titanate, then another 155 g (2.5 mol) of ethylene glycol and 384 g of trimellitic anhydride are added, 10 ml of reaction water are distilled off (degree of esterification 42.5%), the esterification reaction is interrupted by the addition of 198 g of diaminodiphylmethane and polycondensation is carried out until the melt viscosity measured NPA when not amount to 12,000 cps..

This is carried out according to examples 1 and 4, and the following quantities of the starting components are used in the sequence

additions: 140 g (0.72 mol) of dimethyl terephthalate, 207 g (0.8 mol) of trishydroxyethylisocyanurate, 177 g (2.85 mol) of ethylene glycol, 3.5 g of teroctoates, 0.22 g of zinc acetate dihydrate, 13 g (1 , 2 wt.%) Tetra-n-butyl titanate, 150 g (2.4 mol) eti7 glycol, 487 g (2.54 mol) of trimellitic anhydride and 252 I- (1.27 mol) diaminodiphenylmethane. Diamine Diffusion TmJap is added at

Degree of sterication 50 ,. Viscosity

the melt measured at is 15,000 spu.

From the resins according to examples 1-5, half of the solutions in cresol / solvent-naphthic mixtures containing about 32% by weight of resin, which without post-sponge additives are applied by hot drying with 0.6 millimeter copper wire in 7 passes at a furnace temperature and length furnace 2.5 m in the form of a lacquer film with a thickness of 35-45 microns.

The feed pitch is determined, which means the wire feed speed within which the coatings were obtained without breaking; preliminary elongation of varnished wire (pr elongation), after which it is almost impossible to obtain a turn of the coating around the bare wire core without gaps in the lacquer layer; resistance to thermal shock (temperature / time under load) indicates the elongation of the varnished wire of the coating around rod diameter of bare wire (eg. lengthening / resistance to thermal shock) or the maximum temperature for 30 minutes, which this kind of coil can withstand, in the same way, on a pre-stretched varnished wire, without gaps in the lacquer layer (resistance to thermal shock for 30 minutes).

Thermal pressure resistance according to DIN 46 453 is defined as follows:

2 varnished wires, between which an alternating voltage of 100 + 10 V and a frequency of 50 Hz is applied, are placed at an angle of 90 one above the other in a test device, which ensures the application of load to the wire crossing point. The test apparatus is preheated to the test temperature. The wires located one above the other are not loaded for 1 min and then pressed one against the other under a pressure of 900 gf for 2 min. At the same time, the resistance to heat pressure corresponds to the test temperature at which, under these conditions, a current of about 5 mA between the two wires does not flow.

At the same time receive the results presented in table 1.

Table 1

bone to heat

hit (h),%

Heat pressure

according to DIN 46453, C

Resistance to thermal shock (30 min),

lt

The wire obtained according to Example 2 has gaps at all values of the feed steps. This is also the case when 1 wt.% Of tetra-AND-butyl titanate (relative to the amount of resin contained in it) is added to the varnish.

1525

350-360 320-330

200

200

Example Example 1 is repeated with the difference that butyl titanate

3.5 g (0.3% by weight) and 16 g (1.45% by weight), respectively, are added in an amount.

Get the results presented in table 2. An example of the lacquer obtained by the proposed method from its solution is given only in evidence that the obtained lacquer can be applied to the wire and from its solution even at such a high working speed at which a known varnish cannot be processed into a high-quality coating (see Table 1 and 2). The application of the lacquer resin to the wires from the melt is carried out as follows. An open top lacquer tank of a conventional type of lacquering machine is equipped with an electrical heating device that is adjustable by means of a contact thermometer / inserted into the tank. An agitator is provided in the lacquer tank, driven by engine 8 and indexes.

bone to heat stroke 180 ° С "2 h,%

Heat pressure according to DIN 46453, ° С

Resistance to thermal shock (30 min), ° C

Example 8. When using the resin of example 6 and applied from the melt to the wire described above.

table 2

Table 3

Properties of resin coatings by example

14 23 352-360 320-335 200 200

method get the results presented in table 4. to keep the melt in motion. The nozzles for applying the melt are replaced by electrically heated ones with the possibility of keeping the temperature during the 170ISO C varnishing process. The bare wire passes directly in front of the entrance to the varnishing tank through a preheating zone, in which it is heated for about 70-100 ° C. The varnishing tank is filled with resin melt heated to 150 ° C and a 34-cm thick layer of resin is applied to it by multiple immersion of the wire -45 microns. Oven temperature. PRI me R 7. The resins of examples 1 and 3-5 are used to apply varnish to the melt wire in the manner described above. Get the results presented in table.3.

Feed step, m / min Extention,%

Extending / resistance to thermal shock 2 h,%

Heat pressure according to DIN 46453, s

Resistance to thermal shock (30 min), “C

PRI me R 9. Get the resin of example 1 with the only difference that they use 0.6 wt.% Tetramethyltitanate. Viscosity at 18,000 sp.

This resin is melted onto the wire in the manner described.

The results are presented in table 1c. five.

I'll try it on. Get the resin of example 1 with the only difference that they use 1.0 weight.% Of a mixture of 0.4 weight. tetraethyl titanate and 0.6 wt.% trine-vanadyl butylate. Viscosity at 13,000 sps. This resin is melted onto the wire in the manner described.

The results are presented in table.5.

Example 11. A resin is prepared as in example 1 with the only difference that 1.5 wt.% Of an ISO mixture is used, bves. vanadyl trimethyl and 0.9 wt.% zirconium tetraethylate. Viscosity at 160 ° C 16,000 cps.

This resin is melted onto the wire in the manner described.

The results are presented in table.5. Thermal pressure according to DIN 46453, 350-360360. Resistance to thermal shock (30 min), 195190-200

Table 4

11-16

15

15

350

200

Example 12. Get the resin of example 1 with the only difference that they use 1.2 wt.% A mixture of 0.5 wt.% Tetrabutyltin, 0.3 weight. tri-n-propane vanadyl and 0.4 wt.% tetramethyl zirconate. Viscosity at 140 ° C 19,500 cps.

This resin is melted onto the wire in the manner described.

The results are presented in table.5.

Ex. And measure 13. The resin of Example 1 is obtained with the only difference that 0.9% by weight of a mixture of 0.5% by weight of tetra-m-propyl titanate and 0.4% by weight of tetraethyl circulant is used.

Viscosity at 150s 14,500 cps.

This resin is applied from the melt to the wire in the manner described.

The results are presented in table.5.

Example 14. The resin is prepared according to Example 1 with the only difference that 0.8 weight% tetraisoamyl titanate is used.

Viscosity at 12,000 sps.

This resin is melted onto the wire in the manner described above.

The results are presented in table.5.

Claims (3)

Table 5 320-340 350-360 340 320-340 190-200 200 200-210 210 The proposed method allows to obtain lacquer resins for insulating wires, suitable for ironing and on the wire from the melt. Claims. A method of obtaining a lacquer resin for insulating wires by re-ethering dimethyl terephthalate with ethylene glycol and trishydroxyethyl eocycium urate in the presence of a re-esterification catalyst, etherification}} of this product with trimellitic acid anhydride and using a speed setting, but not to go; followed by a polycondensate, characterized in that, in order to obtain a lacquer resin suitable for applying it to the wires from the melt, as a transesterification catalyst 0.3-1.5% of the weight of all resin-forming titanium and / or vanadium and / or zirconium monomer monomers is used, the esterification of trimellitic acid anhydride is prekrgitsayut adding the total amount of diamine. At a degree of esterixia 42.5-50%, and the polycondensation is carried out to obtain a resin having at 140-160 ° C a viscosity of 5,000,2,000 cps. Sources of information taken into account during the examination: 1.Linin YI, TRUD№ Tomsk Research Institute of the cable industry, 1969, №1, p.231-239. 2. For Germany 1520061 Cl. 20/30, 1969. 3. For the war of FRG 2135157, cl. 21 from 7/02, 1972.