PL91703B1 - - Google Patents

Description

The invention relates to a manufacturing process suitable, especially for solid application unmelted, varnish insulating resins for coating wires, especially wires.

Insulating varnish resins have been known for a long time for wires, containing exclusively kwTa radicals of terephthalic acid and / or isophthalic acid, both alcohol more than dihydric alcohol and one of the dihydric alcohol and which, after dissolving them released in solvent mixtures containing cresol, with the addition of hardeners, e.g. alkyl titanates burn out on the wires insulating.

It is also known to coat this type of resin in the molten state without the participation of dissolving czalników (Yu. I. Linin, Tr. Tomsk. Nauch., Issled.

Inst. Cable. Ferry. 1969, No. 1, 231-39). This is done method compared to coating with solution the creation has a number of remarkable benefits, it should be especially emphasized that, dykally prevents air pollution when firing with evaporated cresol solution solvent.

Resins of the given composition on iso-conductors however, they give coatings that do not sleep eggs to the fullest extent required. Therefore, he asked it has already been repeated to replace the whole in these products completely or partially terephthalic acid radicals- it and / or isophthalic acid with diacid radicals carboxylic acid containing two imido groups we, with the general formula shown in the figure, where = N - R - N = denotes a di- primary diamine, preferably 4,4 '- diaminodiphenylmethane.

This dicarboxylic acid containing two imide groups can also be obtained in situ in the presence of all or part of the usual material Resin-forming starting material, in progress resins from trimellitic anhydride and di amines in a molar ratio of about 2: 1 and con- dense it. You can find out about this method see, for example, published patents German Rep. Fed. DOS 1520061 and 1495456.

A further known step in this field is use of tri (hydroxyethyl) isocyanurate as a multifunctional alcohol in resins graded day in the introduction given and (cf. eg DOS 1590442).

Resins corresponding to the present state of the art The radicals therefore contain the radicals mentioned above a dicarboxylic acid containing two imide groups, possibly also radicals therein terephthalic acid, further isocyanurate radicals tri (hydroxyethyl), and ethylene glycol. Te¬ of the same kind of products in a dissolved and stable state data on hardeners can be found in the trade as insulating varnishes for wires and to a large extent meet the requirements for such varnishes (see for example DOS 1645435). Resins about it they have a relatively high temperature in store softening, which rises with increasing intensity 91 703917 3 the degree of condensation. Therefore, it is difficult to transmit up to melt coating because at a relatively low temperature of 140 ° -160 ° C have too high melt viscosity, and in higher temperature of about 160 ° -180 ° C, due to B. further condensation, their viscosity in the molten state nym changes over time. In order to remove of this bad state, it has already been proposed to do so treat the type of resin with a small amount of dilution or produce it in its presence 10 ci, so that at exclusion temperature downstream condensation to obtain a sufficiently low viscosity at molten state (DOS 2135157).

However, this method is scarce for two reasons beneficial. Once, that the mentioned 15 is not removed in the introduction to the problem of air pollution, and it only reduces it. Second, the viscosity of the resin with a molten solvent changes with time due to evaporation of the evaporation of solvent at fusing temperature, at least less when the molten resin is in open tank, as is customary in traditional wire coating equipment.

It has now been found that the above-mentioned disadvantages can be removed to obtain iso-M varnish resins coatings for wire coating, and especially wires, perfectly suitable for application in molten state, if in the first stage it is dimethyl terephthalate is used in excess of carbon ethylene colum and tri - isocyanurate (hydro- xyethyl) in the presence of 0.3-1.5% of an alkoxide titanium, zirconium, or vanadium, or them of the mixture, based on the weight of the total of all resin-forming monomers, possibly in the presence of catalytic amounts of others known esterification catalysts such as zinc acetate cerium heptane carboxylate, lead oxide, etc., followed by adding trimellitic anhydride and esterifies it to such an extent that about 50-45% three carboxyl groups of trimellitic acid equivalent to trimellitic anhydride taps in an esterified form, then ends The esterification reactions took place by immediate addition give you all of the diamine, around 1 moles to 2 moles of trimellitic anhydride, and pro¬ prevents polycondensation with drainage and / or ethylene glycol until molten a mass at a temperature of 140 ° -160 ° C will have a viscosity suitable for stand coating vertical. The range of viscosity of the molten melt is suitable The sy for the melt coating is generally M not from about 5,000 to 20,000 cP.

Alkoxides are preferably those of the formula general value Ti (OR) Ai Zr (OR) 4 and O = V (OR) 8, wherein R is cycloalkyl or dec a branched or unbranched alkyl radical as M with up to 5 carbon atoms. Alcoholates can also, possibly, to hydrate and possibly with condensation into oligomers.

It is best to use titanate, zirconate or n-butyl and isopropyl vanadate, in particular in tetra-n-butyl titanate or tetra- isopropyl.

The method according to the invention has several effects inconceivable from the constant nu technique. First, it was impossible to predict 4 child that already present in considerable amounts in re¬ an action alcoholate, e.g. titanium alkoxide, in progress the formation of water from the reaction of diamine and part the ester of trimellitic acid did not sapwood to titanium dioxide, causing a thickening, and that the resin will remain completely transparent; the disturbing cloudiness is rather against expectations, always when added titanium alkoxide in any subsequent when the resin is produced. Still not expecting it is important that the presence of relatively large amounts of al koholan did not affect the product stability in a molten state at 140 ° - 160 ° C. In the end, it was also impossible to predict implies that the introduction of the alcoholate into the resin is implies that it will be possible to maintain a lot low degree of polycondensation in order to obtain nothing low viscosities are for melt coating.

If resins with an analogous composition, e.g. condenses without the addition of titanium alkoxide to the same low degree of polycondensate dissolve them in the usual manner while stirring no cresol and solvent - kerosene and to the solution of this the alcohol amounts mentioned in the introduction are added titanium nu, then after firing it is obtained on copper wire coating with insufficient technical and utility properties (cf. clade II), The method of producing the appropriate, especially for melt application of lacquer coatings insulating ropes for coating wires, a especially wires, in the way of dimethyl phthalate isocyanurate with tri (hy- droxyethyl) and ethylene glycol as present catalysts, nitrification, transesterification of the total product with trimellitic anhydride on pre-product containing carboxyl groups we, adding 4,4H-diaminodiphenylmethane in the molar ratio of trimellitic anhydride and a diamine of about 2: 1 and the next lycondensation, according to the invention, consists in that 0.3 is added to the test mixture —1.5% of titanium and / or vanadium alkoxide and / or zirconium based on the weight of the lice resin-forming monomers, further e- The stratification of trimellitic anhydride is interrupted off suddenly by quickly adding the whole amount diamines and conducts polycondensation as long as until the resin is at 140 ° -160 ° C with a consistency suitable for coating in molten state.

However, lacquer insulating resins for produced in the manner indicated above, are worthy of weights especially from the point of view of coating w molten state, they can also be dissolved in mixture of cresol and solvent - kerosene and solution These are preferably made without adding any further hardening whether to apply in a conventional manner to varnish cutting electric wires. This method the use generally also takes precedence over the usual varnishes of the same composition that the property of the man chanical insulation cables practically broken they remain unchanged to a very large extent firing conditions. Possibly broad border the production procedure is understandable91703 very desirable reasons, because it is very much degree excludes a manufacturing error.

Example 1 In a 2-liter round bottom flask, provided with an agitator, an inert gas supply solution and distillation cooler are weighed 290 g (1.50 mole) dimethyl terephthalate, 289 g (1.1 mole) tr- (hydroxyethyl) isocyanurate, 105 g (1.7 mole) of ethylene glycol, 3 g of heptanecarboxyl- cerium oxide and 0.2 g of zinc acetate dihydrate and melts it. After melting and at temperature inside at 130 ° C is added while stirring g of tetra-n-butyl titanate, then w for about 5 hours at 150 ° -200 ° C 95 g of methanol are distilled off. Now he adds Another 170 g (2.74 mol) of ethylene glycol is added [adding glycol in 2 steps is advisable because it forces to participate in the esterification reaction oji isocyanurate. tr- (hydroxyethyl)] and 410 g (2.14 moles) of trimellitic anhydride by mixing.

The temperature, lowered as a result, increases up to 180 ° C while distilling off the water from the esterification process. After getting 16 ml of water, in the shortest possible time (about 5 minutes) 211 g (1.5 mol) of 4,4'-diamino are added with stirring n-diphenylmethane and thus interrupts the re esterification actions. Then the stop is brought in temperature up to 215 ° C and keeps it up to time until the water stops flowing. Then the pod a vacuum of about 50 lines is connected and maintained temperature 200 ° -205 ° C until the viscosity reg encapsulated, marked in a capillary viscometer at 25 ° C, with an Ig weight of the resin w 100 ml of a solution containing 60% by weight of alcohol nol and 40% by weight of 1,1,2,2-tetrachloroethane, o- will hit 0.095. Then the vein is poured vice and the condensation reaction is completed.

The coagulated resin melts again and at the temperature At 150 ° C it has a viscosity of 10,000 cps. That sticky guy bone of resin in a molten state at temperature 150 ° C in 8 hours practically does not change Aug.

If the experience changes like this that butyl titanate is added a) after completion niu esterification, b) after completion of cleavage water formed from the imide formation reaction, then you get fine resins that won't work neither dissolve clearly nor dissolve to clear solutions.

In contrast, tetra-n-butyl titanate in the above the same amount can be replaced with the 19 40 45 50 of vanadyl tri-n-butoxide or zirconate tetra-n-butyl, with no noticeable visible peculiarities of plrepa / rate or deviation, meaning muon values, technical-utility - second varnished with these resins.

Example II. The procedure is as in the example And with the difference that no titanate is added to it low-.

Example III. It is done as in a guide day And with the difference that diamine is added no in about 5 minutes, only slowly over a period extended to about 30 imminutes.

Example IV. As shown in the example And 425 g (2.19 mol) of tere is esterified dimethyl phthalate, 407 g (1.56 moles) of isocyanurate tri- (hydroxyethyl) janurate and 120 g (1.93 mo a) ethylene glycol in the presence of 3 g of heptane ceric carboxylate, 0.2 g acetate dihydrate of zinc and 12 g of tetra-n-butyl titanate, then a further 155 g (2.5 moles) of glyco are added ethylene oxide and 384 g (2.0 mol) anhydride of trimellite1, 10 ml of water from the pro- the esterification process, interrupts the esterification reaction by adding 198 g of diniminodiphenyl methane and will polycondensate until the viscous condition molten at a temperature of 150 ° C will be equal 12,000 cP.

Example V. The procedure is as in the example I or IV, the amounts of raw material used being half given in the order of the addition: 140 g (0.72 mole) te dimethyl phthalate, 207 g (0.8 mole) of isocyanurate tri- (hydroxyethyl) janurate, 177 g (2.85 m Ia) ethylene glycol, 3.5 g of heptane carboxyl- cerium oxide, 0.22 g of zinc acetate dihydrate 13 g of tetra-n-butyl titanate, 150 g (2.4 mol) ethylene glycol, 487 g (2.54 mol) trimellitic anhydride and 252 g (1.27 mol) diaminodiphenylmethane. Viscosity able the melt temperature determined at 150 ° C is 15,000 cP.

From the resins according to examples I-V are prepared 32% by weight solutions in a mixture of cresol and salt vent - kerosene and without any other additives burns them on 0.6 mm copper wire in 7 passes by an oven with a temperature of 500 ° C and a length of 2.5 m for a paint coat with a thickness of 35- ^ 15 | x.

A suitable device is described, for example, in the brochure of W. Aumann K. G., Espelkamp - Mittwald, "FLK Feindrahltlackiermaschinen, \ O- The following subfetal exclusions were taken niki: Example No. Drag speed (m / min) VD (%>) VD / HS 180 ° C 2 hours

(• / •) Thermal pressure as per German standard DlN 46453 (° C) HS, 30 min (° C) ii 11— * 17 - & 5 J20 330- ^ 350 i2oo — aio II -. - « -and - ^ ~ * PI —14 —10 360 190 IV 11-46 Ml 350-360 20d V 11-17 (320-330 20091 703 8 The drag speed here means the range the speed of the wire at which it is achieved crack-free coatings.

VD stands for lacquered pre-stretching wire, on which it can still be rolled into glue bang around a spindle with a diameter of an ordinary clean wire without cracks on the varnish layer.

HS stands for Shock Resistance temperature which (at a given load temperature / time) gives the admissible preliminary values stretching without cracking the wire, varnish wound in a bundle around the mandrel with a diameter of plain plain wire (VD / HS), or gives the maximum temperature within 30 minutes nut which withstands the same fluff produced in the same way made of painted wire initially not pulled out, without breakage basin on the lacquered surface (HS, 30 min.).

With the product prepared in example II at all stresses during cutting cracks were forming. It happened too when 1% by weight was added to this varnish of tetra-n-butyl titanate (with reference to to the amount of resin it contains).

Paint tank, open at the top of the device painting of a conventional structure, it is now equipped with electric heating not adjustable with reed thermometer in the tank. In the tank the varnish was fitted with a drive agitator a motor that keeps the molten paint in circulation chu. The coating nozzles have been replaced with electrically heated and varnish during treatment wania may temperature 170-180 ° C. An oily wire immediately before the first entry into the reservoir the lacquer is pulled through the heating zone in which it is heated to the initial temperature 70 ° -100 ° C. The tank for varnish will be loaded the resin in the molten state, heated to the temperature 31 temperature 150 ° C and applies an insulating layer with a thickness of of 35-45 "and by dipping the wire four times here. The oven temperature is 500 ° C.

The lacquer wires produced under these conditions important practically have the same properties as wires varnished with appropriate solutions. IN In the case of example I, the painting is carried out continuously for 8 hours, alive vice melted replenishes from time to time fresh product heated to temperature 150 ° C. During this service life it does not turn off no disturbances step by, as well as varnish properties wire during this time remains practical not unchanged.

Claims (1)

Claim 1. A method of producing insulating lacquer resins suitable for the coating of conductors, especially wires, especially for melt-coating, by conversion of dimethyl steel with isocyanurate with trihydroxyethyl isocyanurate and ethylene glycol in the presence of catalysts, esterification esterification. - the product with trimellitic anhydride into a pre-product containing carboxyl groups, the addition of 4,4'-diaminodiphenylmethane in a molar ratio of trimellitic anhydride: diamine of about 2: 1, and a further poly-condensation, characterized in that it is stable for 0.3-1.5% of titanium and / or vanadium and / or zirconium alkoxide based on the weight of all resin-forming monomers are added to the mixture, further esterification of trimellitic anhydride is stopped abruptly by the rapid addition of all diamine and polycondensation is carried out as long as the resin at 140-160 ° C will have consistency suitable for melt coating. what H00C -y \ y / oc> n-r-n; co oc "C00H \ Hz.ó zor LZG Z-d No. 2 order 565/77 110 copies A4 C« for PLN 10