FI57964C - BRAENNLACK INNEHAOLLANDE ORGANIC LOESNINGSMEDEL OCH KVAEVEHALTIGA MODIFIERADE POLYESTERHARTSER - Google Patents

Description

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Patent and Registration Office / 44) Date of issue and date of issue. -

Patent · och registerstyrelaen 'Amok »utiagd och utUkrutm pubiicurad 31.07.80 (32) (33) (31) Requested priority priority ** 29.07.71

Federal Republic of Germany a-Fö rbun dsrepubliken Tyskland (DE) P 2137884.7 (71) Herberts Gesellschaft mit beschränkter Haftung, Christbusch 25 ,.

D-5600 Wuppertal 2, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Hans-Dieter Hille, Rath b. Nörvenich, Arnold Dobbelstein, Junkersdorf b. Köln, Suresh Merchant, Wuppertal-Elberfeld, Federal Republic of Germany-Förbundsr (74) Berggren Oy Ab (54) The present invention relates to organic solvents and nitrogen-containing modified polyester resins.

It is known to make polyester imide resins suitable for varnishing electrical conductors. (English patents 937,377, 1,082,181, 1,067,541, 1,067,542 and 1,127,214; Belgian patent 663,429; French patent 1,391,834; East German patent 30,838; West German patent applications 1,494,434, 1,493 182, 1 495 192, 1 520 06l and 1 494 413.)

Varnish films of known polyester-imide resins obtained by heating on copper wire show excellent thermal stability, good resilience, good solvent resistance and also good resistance to thermal shock. The pencil hardness of these lacquer films is usually between 3 ~ 4 H, and this hardness can hardly be increased without a significant decrease in elasticity. Admittedly, pencil hardnesses in excess of 5 H are desirable, as the requirements for the lacquer surfaces of wires, due to modern feeding methods in the manufacture of motors and rotors, 2 have risen very strongly. 5 79 64

British Patent 1,171,710 discloses a process in which polyester resins are modified on the basis of terephthalic acid and / or isophthalic acid, glycol and at least a 3-functional polyhydric alcohol in the direction that the polyester resin will contain primary or secondary hydrazide groups. The starting materials for these prior art polyesters do not contain at least two ortho-carboxyl groups, so that a ring-forming reaction cannot take place between such ortho-carboxyl groups and hydrazide groups. These prior art polyester resins are regularly inferior in properties to polyester imide resins and have not reached any practical significance.

Linear unmodified polymers made from pyromellitic acid dianhydride and bifunctional acid hydrates have become known from Die Makromolekulare Chemie, 1966, pages 11 * 1-123. These compounds are very sparingly soluble, dissolving in up to polar solvents. They only produce brittle films. When terephthalic acid dihydrazide is used as a starting material, it is not possible to prepare a polymer with a sufficiently high molecular weight as would be necessary to obtain film-forming properties. The compounds disclosed in this literature reference are therefore not suitable for the preparation of coatings and moldings.

Furthermore, it has already been proposed to modify polyester imide resins so that they are prepared as polyvalent amines using amines comprising 5 to 100 molar? of the total amount of polyvalent amines used, such compounds or mixtures thereof are prepared by reacting dicyandiamide with hydrazine in a molar ratio of between 0.8: 1 and 1: 5 at a temperature between room temperature and 280 ° C (German Application No. 1,937,311). The polyester imide resins produced by this method have excellent and vastly better properties than previously known polyester imide resins, especially in that the fired lacquer films have hardnesses of 7-8 H, which values have not previously been possible in high temperature resistant coatings.

It is also already known to use itaconic acid and / or its isomers as a reaction component in the preparation of modified polyester resins, as in the above-mentioned embodiments. However, itaconic acid was reacted with 3,57964 amino compounds in which the NH 2 group is attached to a carbon atom (French Patent 1,581,397; West German Patent Applications 1,924,808 and 1,928,934). However, the fuel lacquer insulators obtained by this technology have not proved to be better in hardness than those made from known polyester imides, while retaining their other good properties, or the hardness is improved somewhat, while other properties deteriorate.

It is an object of the present invention to provide novel nitrogen-containing polyester resins which, after firing on the surface of electrical conductors, form coatings with improved hardness and which can be produced both in a technically very safe and simple manner with maximum yields and easily processed.

Surprisingly, it has now been found that this object can be achieved by preserving other good properties of known resins by incorporating compounds containing one or more carbohydrazide groups into the polyester resin, these carbohydrazide groups being at least partially attached to Itaconic acid and / or its isomers.

The present invention thus relates to a fuel lacquer containing organic solvents and nitrogen-containing modified polyester resins formed from itaconic acid and / or its isomers and other polybasic carboxylic acids, polyhydric alcohols and compounds containing at least three of these compounds, optionally in addition to conventional lacquer additives and / or hardeners, which combustion lacquer is characterized in that the polyester resins contain, as condensed NHg-containing compounds, 5 to 100 mol of the total number of NH4-containing compounds used having carbohydrazide-containing compounds of the general formula

(A -R - (- CONH - NH2) n I

wherein m is 0 or an integer from 1 to 3 and n is an integer from 1 to 3, wherein m + n is at least 2, and R represents an aliphatic, aromatic or araliphatic group or also a direct bond, wherein n is 1 or 2 and m is 0 or 1 and m + n is at least 2, and A is an atomic grouping comprising at least one functional group of 4 57964, the carbohydrazide groups of the compounds of general formula I being reacted with itaconic acid in a range of 20 to 100?, But all itaconic acid molecules being completely reacted react with NH 4 groups.

Thus, the nitrogen-containing polyester resins used in accordance with this invention differ from the modified polyester resins of the prior art in that they contain coupling products of the compounds of general formula I condensed with itaconic acid and / or its isomers. These affiliates are likely to contain one or both of the following groupings

0 L

li Ai

- C - NH - N

N_Lcooh ϊ ^ NH— \

- c - C00H

o

Other condensed components or starting materials may be the same as those used in prior art nitrogen-containing polyester resins, especially those containing five-membered imide rings. In this context, reference is made to the above-mentioned literature references. Therefore, this description does not provide a detailed list of possible reaction components.

According to the invention, combustion varnishes comprising polyester resins are preferably used which contain the compounds of the formula I in an amount of from 20 to 100 molar, in particular from 20 to 60 molar, condensed. The total amount of compounds containing NHg groups was 57964. If the polyester resins contain compounds containing NH 4 groups condensed in part via five-membered imide rings, then these five-membered imide rings should preferably be formed between the NHL groups and trimellitic acid.

The most preferred starting materials are those compounds of the formula I in which the symbol R represents a benzene ring or also a naphthalene or diphenyl ring or an atomic grouping of the following formula: -O '- * - O- in which X is oxygen, sulfur, -SO -, -CH 2 - or -C (CH 2) 2.

As indicated above, the symbol n in formula I should contain "one of the numbers 1, 2 and 3 · In principle, it is also possible to use compounds of formula I in which the symbol n has a value greater than 3 · Such compounds are relatively difficult to obtain and do not have the same is true for mark m, the value of mark m is preferably 0, 1 or 2. As mentioned, the sum of the numbers n and m should be at least 2, which means that the group R must contain at least two a functional group through which it can be attached to the polyester molecule.

The symbol A denotes an atomic grouping comprising at least one functional group. For the purposes of the present invention, functional groups are understood to mean those groups which are capable of forming a bond, in particular an ester, amide or imide bond, with other groups of starting materials used for the preparation of nitrogen-containing polyester resins. Examples of such functional groups are a hydroxyl, amino, amido or carboxyl group or derivatives capable of a condensation reaction of such groups, for example a carbomethoxy group. The group R, when n is at least the number 2, can also be a direct bond. Furthermore, the group R may be an aliphatic saturated hydrocarbon radical having 1 to 6, preferably 1 to 4 carbon atoms. Examples of such particularly suitable compounds of the formula I are oxalic acid mono- and bis-hydrazide and adipic acid mono- and bis-hydrazide. These compounds are very readily available and provide very good properties to combustion varnish insulators.

Of the compounds of formula I in which R represents an aromatic group, terephthalic acid or iso- 6,57964 phthalic acid mono- or bis-hydrazide are particularly preferred because they are readily available and give good results.

The compounds of formula I are partly known. They can be prepared, for example, by reacting hydrazine with an acid chloride of the formula I, an acid amide or an ester of such a day. The reaction can take place under heating. If desired, it is possible to work in a solvent. The desired compounds of formula I precipitate extensively during the reaction and can be easily isolated in high purity.

The compounds of formula I do not need to be isolated prior to their use in the preparation of the polyester resins of the invention.

They can also be prepared in the same reaction vessel as where the process of the invention is carried out and introduced in the form of a reaction solution. This procedure greatly simplifies the production of the desired polyester resins.

When a polyhydric carboxylic acid containing at least two ortho-carboxyl groups and in addition at least one functional group is used as starting material, trimellitic acid and / or its anhydride are best used, as in the prior art. The same groups as described above are also considered to be functional groups.

In the preparation of the modified polyester resins contained in the fire varnishes according to the invention, at least some of the compounds of the general formula I in the above-mentioned relative amounts are reacted with itaconic acid and / or its isomers to form coupling products likely to contain the above five- or six-membered rings. These coupling products can be reacted with other starting materials in the same reaction vessel without prior isolation. In this case, it is advantageous to react any starting materials containing HH2 groups which may still be present with carboxylic acids which contain at least two carboxyl groups in the ortho position and, in addition, at least one other functional group. As previously mentioned, the most suitable such carboxylic acid is trimellitic acid and / or its anhydride. In this reaction, five-membered imide rings are formed.

As already mentioned, any remaining itaconic acid molecules which have not reacted with the compounds of general formula I to form said coupling products must be completely reacted with the compounds containing N 1 groups before they are condensed into the poly-57964 7 ester molecule. The reason for this is that the double bond contained in itaconic acid or its isomers, if possible, must no longer be present in the polyester resins, otherwise the effect on the properties of the resin will be unfavorable. When itaconic acid or its isomers are reacted with compounds containing Ni 2 groups, the coupling takes place in a similar manner as between itaconic acid and the compounds of the formula I, the double bond becoming a modified single bond.

The polyester resin lacquers of the invention can be used to make insulating coatings on electrical conductors by coating the conductors with a thermosetting lacquer solution and heating the lacquer-coated conductors to an elevated temperature. The preparation of polyester resins and / or the preparation of insulating coatings by heating at elevated temperatures can take place in a known manner, optionally in the presence of known catalysts and / or other auxiliaries. Detailed listing is also unnecessary in this case, as such catalysts and / or auxiliaries are carefully described in the above-mentioned patent publications on this technique. It is further possible to mix the polyester resins of this invention with other resins, and to prepare such mixtures or solutions thereof using fuel lacquer insulators for electrical conductors.

Insulation coatings applied to electrical conductors using the lacquers according to the invention have the same good properties as known polyester imide resins, but have an improved hardness of 5-8 H and / or a considerably improved winding strength, i.e. resilience, compared to the latter. This is very surprising because hardness and resilience are opposite properties. Therefore, known products with good elasticity generally have poor hardness and vice versa. The combustion varnishes according to the present invention, on the other hand, have very high values of hardness and resilience, which have not previously been considered even possible.

The following examples illustrate the invention.

Example 1 19 g (1.0 mole) of dimethyl terephthalate 287 g (1.1 moles) of tris- (2-hydroxyethyl) isocyanurate 130 g (2.1 moles) of ethylene glycol 8 57964 and 30 g of technical cresol are introduced into a three-necked flask which is equipped with a stirrer, thermometer and column. After adding 1 g of zinc acetate, the mixture is heated under a nitrogen atmosphere. At a temperature of about 140-150 ° C, distillation of the methanol liberated by transesterification begins. After about 3 hours, 64 g of methanol have distilled off; at a temperature of 220 ° C. After cooling to about 150 [deg.] C., 130 g (1.0 mol) of itaconic acid and 97 g (0.5 mol) of terephthalic acid bis-hydrazide are added to the mixture, and the mixture is reheated until 36 g of water have distilled off.

To the mixture cooled to about 150 ° C are repeatedly added 130 g (1.0 mol) of itaconic acid and 97 g (0.5 mol) of terephthalic acid bis-hydrazide and the mixture is further condensed until again 36 g of water have distilled off. Stir for a further 2 hours at 200-210 ° C, after which the mixture is diluted with technical cresol to a 50% solution.

Example 2 194 g (1.0 moles) of dimethyl terephthalate 287 g (1.1 moles) of tris- (2-hydroxyethyl) isocyanurate 130 g (2.1 moles) of ethylene glycol are reacted in the same manner as in Example 1. To a mixture cooled to 150 ° C 130 g (1.0 mol) of itaconic acid are added 87 g (0.5 mol) of adipic acid bis-hydrazide. By reheating to 220 ° C, 36 g of water are distilled off. To the melt cooled to 150 ° C, 130 g (1.0 mol) of itaconic acid and 37 g (0.5 mol) of adipic acid bis-hydrazide are repeatedly added, and the mixture is further condensed until 36 g of water have distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol to a 50 # solution. Example 3 194 g (1.0 moles) of dimethyl terephthalate 237 g (1.1 moles) of tris- (2-hydroxyethyl) isocyanurate 130 g (2.1 moles) of ethylene glycol are reacted in the same manner as in Example 1. To a mixture cooled to 150 ° C 9,57964 (130 moles) of itaconic acid and 39 g (0.5 moles) of oxalic acid bis-hydratide are added.

By reheating to 220 ° C, 36 g of water are distilled off. To the melt cooled to 150 ° C, 130 g (1.0 mol) of itaconic acid and 59 S (0.5 mol) of oxalic acid bis-hydrazide are repeatedly added, and the mixture is further condensed until 36 g of water have distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol to a 5 ° solution. Example 4 ^ 194 g (1.0 moles) of dimethyl terephthalate 287 g (1.1 moles) of tris- (2-hydroxyethyl) isocyanurate 130 g (2.1 moles) of ethylene glycol are reacted in the same manner as in Example 1. After cooling to 150 ° C, 130 g (1.0 mol) of itaconic acid are added to the mixture, 75.5 g (0.5 mol) of p-aminobenzhydrazide and the mixture is further condensed until 36 g of water have distilled off. To the melt cooled to 150 ° C, 130 g (1.0 mol) of itaconic acid and 75.5 2 (0.5 mol) of p-aminobenzhydrazide are repeatedly added, and the mixture is condensed until 36 g of water have distilled off again. The mixture is stirred for a further 2 hours at 200-210 ° C, after which it is diluted with technical cresol to a 50% solution.

Example 5 200 g of technical cresol and 93 S (1.5 moles) of 80 # hydrazine hydrate are heated to 60 ° C in a three-necked flask equipped with a stirrer, thermometer and column. Five 39 g portions of dimethyl terephthalate (1.0 mol in total) are then added to the mixture every 30 minutes. The temperature is now slowly raised to 110 ° C, whereupon 48 g of the methanol released when the hydrazide is formed are distilled off. During that time, a white crystalline terephthalic acid bis-hydrazide precipitate has formed. To a mixture cooled to 80 ° C, 195 E (1.5 moles) of itaconic acid are added. The mixture is now heated to 150 ° C within 2 hours, at which point the precipitate slowly disappears. The temperature is further raised until 10 g of water have distilled off. In this case, the temperature is 180 ° C. 10 5 79 6 4 316 g (1.2 moles) of tris- (2-hydroxyethyl) isocyanurate and 93 g (1.5 moles) of ethylene glycol are now added to the mixture, and the mixture is further condensed by adding 1 g of zinc acetate until 30 g of water is distilled off. To the mixture cooled to 150 ° C are added 192 g (1.0 mole) of trimellitic anhydride and 99 g (0.3 mole) of 4,4'-diaminodiphenylmethane, and the mixture is further condensed until 36 g of water has distilled off. To the mixture cooled to 150 ° C are added 192 g (1.0 mol) of trimellitic anhydride and 99 g (0.3 mol) of 4,4'-diaminodiphenylmethane, and the mixture is condensed until 36 g of water have distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol to a 50% solution.

Example 6 388 g (2.0 moles) of dimethyl terephthalate 427 g (1.64 moles) of tris- (2-hydroxyethyl) isocyanurate and 186 g (3.0 moles) of ethylene glycol are reacted as in Example 1. After cooling to 150 ° C, 192 g (1.0 mol) of trimellitic anhydride are added to the mixture, 97 g (0.5 mol) of terephthalic acid bis-hydrazide, and the mixture is heated until 36 g of water <n is distilled off. To the mixture cooled to 150 ° C are added 130 g (1.0 mole) of itaconic acid and 97 g (0.5 mole) of terephthalic acid bis-hydrazide, and the mixture is further condensed until 36 g of water has distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol 50%. sex solution.

Example 7 388 g (2.0 moles) of dimethyl terephthalate 326 g (1.25 moles) of tris- (2-hydroxyethyl) isocyanurate 30 g (4.5 moles) of ethylene glycol are reacted as in Example 1. To a mixture cooled to 150 ° C 192 g (1.0 mol) of trimellitic anhydride are added, 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane, and the mixture is condensed until 36 g of water have distilled off. To the mixture cooled to 150 ° C are repeatedly added 192 g (1.0 mol) of trimellitic anhydride and 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane, 11 5 7964, and the mixture is further condensed until J> G g of water has distilled off. . To the mixture cooled to 150 ° C are added 97.3 g (0.79 moles) of itaconic acid and 3 g (0.25 moles) of trimesic acid tris-hydrazide, and the mixture is condensed until 27 g of water has distilled off. 97.3 g (0.73 mol) of itaconic acid and 63 g (0.25 mol) of trimesic acid tris-hydrazide are repeatedly added to the mixture cooled to 150 [deg.] C., and the mixture is further condensed until 27 g of water have distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol to a 50% solution.

Example 8 19 * 1 g (1.0 mol) of dimethyl terephthalate ^ 122 g (1.33 mol) of glycerol 288 g (3.67 mol) of ethylene glycol are reacted in the same manner as in Example 1. To a mixture cooled to 150 ° C is added 192 g (1 mol) of .0 moles) of trimellitic anhydride and 99 g (0.5 moles) of 4,4'-diaminodiphenylmethane, and the mixture is condensed until 36 g of water has distilled off. To the mixture cooled to 150 ° C are repeatedly added 192 g (1.0 mol) of trimellitic anhydride and 99 S (0.5 mol) of k, * J'-diaminodiphenylmethane, and the mixture is further condensed until 38 g of water has distilled off. To the mixture cooled to 150 ° C are added 130 g (1.0 mole) of itaconic acid and 37 g (0.5 mole) of adipic acid bis-hydrazide, and the mixture is heated until 36 g of water has distilled off. To the mixture cooled to 150 ° C, ^130 g (1.0 mole) of itaconic acid and ja7 g (0.5 mole) of adipic acid bis-hydrazide are repeatedly added, and the mixture is further heated until 36 g of water has distilled off. The mixture is stirred for a further 2 hours at 200-210 ° C, after which it is diluted with technical cresol to a 50% solution.

Example 9 338 g (2.0 moles) of dimethyl terephthalate 382 g (1.5 moles) of tris- (2-hydroxyethyl) isocyanurate 217 g (3.33 moles) of ethylene glycol are reacted in the same manner as in Example 1. To a mixture cooled to 150 ° C 12,57964,192 g (1.0 mol) of trimellitic anhydride are added to 97 ° C (0.5 mol) of terephthalic acid bis-hydrazide, and the mixture is condensed until 36 S of water have distilled off. To the mixture cooled to 150 ° C are repeatedly added 192 g (1.0 mol) of trimellitic anhydride and 97 g (0.5 mol) of terephthalic acid bis-hydrazide, and the mixture is condensed until again 36 g of water have distilled off. To the mixture cooled to 150 ° C are added 65 g (0.5 moles) of itaconic acid and 43 g (0.25 moles) of terephthalic acid bis-hydrazide, and the mixture is condensed until 18 g of water has distilled off. After stirring for 2 hours at 200-210 ° C, the mixture is diluted with technical cresol to a £ 50 solution.

Example 10

From the resin solutions of Examples 1-9, varnishes are prepared using the following recipe: 60.00 parts of a £ 50 resin cresol solution 15.00 parts of technical cresol 15.00 parts of solvent naphtha 9.70 parts of xylene 0.30 parts of polymeric butyl titanate 100.00 parts

Varnishing takes place in a manner known per se in a horizontal, 3 m long wire varnishing furnace by brushing the varnish in 6 layers on the surface of a 0.8 mm diameter copper wire and curing the coating at a temperature of 400-450 ° C. The varnishing speed is 9-14 m / min.

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Claims (8)

1. Fuel varnish containing organic solvents and nitrogen-containing modified polyester resins formed from itaconic acid and / or its isomers and other polybasic carboxylic acids, polyhydric alcohols and compounds containing N1 groups or reactive derivatives of said compounds, wherein at least three , and, in addition, any customary lacquer additives and / or curing agents, characterized in that the polyester resins contain as uncondensed NH 2 groups containing compounds 5-100 mol% of the total amount of NH 2 groups containing compounds of the hydrocarbon groups containing the compounds containing the A + - R -fCONH - NH 2 also a direct bond wherein n is 1 or 2 and m is 0 or 1 and m + n is at least 2 and A is an atomic group containing at least one functional group, wherein the carbohydrazide groups in the compounds of the general formula I are reacted 20-20% with itaconic acid, but all itaconic acid molecules are reacted completely with NH 2 groups. 2. A fire varnish according to claim 1, characterized in that the polyester resins contain the condensed compound of the general formula I in an amount of 20-100 mole, in particular 20-60 mole, of the total amount of NH2 groups containing compounds. 3. A burning lacquer according to claim 1, characterized in that the polyester resins contain such uncondensed compounds of general formula I in which R is a benzene ring. . Fire lacquer according to claims 1-3, characterized in that the polyester resins contain such uncondensed compounds.