DE2230165A1 - POLYAMIDE-IMIDE-HYDANTOINE, PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

Polyamide-imide-hydantoine, process for their production and their use

The invention relates to polyamide-imide-hydantoins, processes for their production and their use as wire enamels for electrical conductors.

According to the invention, new polyamide-imide-hydantoins are proposed which are characterized in that the essentially linear molecules consist of about 5 to 95% of hydantoin units, the amide units making up 20 to 80 % of the total of the amide and imide groups, and that the Hydantoin units of the general formula

Ri

C = O

N N

O = C C

I I

"V

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Ar

ORIGINAL INSPECTED

correspond, in the areines optionally by halogen, nitro, alkyl, alkoxy, dialkylamino, acyl, carbalkoxy aromatic radical substituted by cyano groups, Y a radical corresponding to the definition of Ar or an alkylene group with 4 to 10 carbon atoms, oxyalkylene group with 4 to 10 C atoms or thioalkylene group with 4 to 10 C atoms and Rj. Denote a hydrogen atom or an alkyl group, and that the hydantoin units by reacting a Glycinderi derivatives of the general formula

Ar- (NH-C-COR ₉ )

in which R_ is a dialkylamino, alkoxy or aryloxy group and χ is an integer from 2 to 4 with one in turn by reacting (1) trimellitic anhydride or (2) one Mixture of trimellitic anhydride with a dibasic acid, a dianhydride or tribasic acid with (a) a Diisocyanate or (b) a diisocyanate and an organic titanate made polyamideimide having terminal isocyanate groups can be obtained.

Due to the complexity of the polymer molecules, a exact structural formula not given; but the polymeric compounds can be expressed by the formula

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-H-II-AI-AA-H-AI-H-AI-H-AI-AI-H-AI-AA-H-AI-II-H-

reproduce, in the AI an amide-imide unit, AA an amide-amide unit, H is a hydantoin unit and II is an imide-imide unit indicates. The polymers of the invention exhibit a substantially uniform distribution of the amide-imide and of the hydantoin units, with essentially none form larger blocks of amide-imide units or hydantoin units.

The hydantoin units correspond to the general formula

_{R c c = 0 0} _ _{c c R}

⁴ II -Il ⁴

N _N _ γ ν ν Ar

Il Il

O O

in the Ar one optionally by halogen atoms such as chlorine or bromine atoms, nitro or alkoxy groups such as, for example Methoxy or ethoxy groups, alkyl groups such as Methyl, ethyl or butyl groups, dialkylamino groups such as dimethylamino groups, acyl groups such as Acetyl or propionyl groups, carbalkoxy groups such as carbmethoxy or carbethoxy groups or Aromatic radical substituted by cyano groups. Of the

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Optionally substituted aromatic radical can be derived from benzene, naphthalene, anthracene, diphenyl or from substituted aromatic compounds such as triphenylmethane, diphenylalkanes such as diphenylmethane, diphenylethane or diphenylpropane, from diphenylalkenes such as stilbene, from diphenyl ether, diphenylthioether, diphenyl sulfone or a polyphenyl sulfone. In the general formula of the hydantoins, Rj. Denotes a hydrogen atom or an alkyl group with preferably 1 to 6 carbon atoms and Y corresponds to the definition of Ar or denotes an alkylene group with k to 10 carbon atoms, an oxyalkylene group with k to 10 carbon atoms or a thioalkylene group with ¹ J to 10 C atoms.

The polymers according to the invention have at least 5 % of the bonds in the form of hydantoin groups and are soluble in cresol-like solvents such as, for example, 3> ^ - cresol or cresolic acid. In general, preferably from 20 to 60 % of the linkages are in the form of hydantoin groups.

The polymers according to the invention are preferably used as wire enamels for electrical conductors. The ones made from it Wire enamels show after application on the conductor and especially when used in hermetically sealed Systems have excellent chemical resistance to fluorinated

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Hydrocarbons such as against hydrocarbons of the trademarks "Preon". They also show wire enamels significantly higher values for breakdown temperatures and higher values in the general electric abrasion scrape resistance test than conventional wire enamels that are soluble in cresol-like solvents.

The polyamide-imide-hydantoins according to the invention are prepared by reacting a diisocyanate with trimellitic anhydride, preferably in the solid state, in accordance with British Patent 1,220,590, an amide-imide prepolymer with terminal isocyanate groups being formed, the reaction in the solid state excluding side reactions with cresol-like solvents . This amide-imide prepolymer usually has 20 to 80 % and preferably 30 to 70 % amide groups and 80 to 20 and preferably 70 to 30 % imide groups.

For the production of this prepolymer aromatic, aliphatic or cycloaliphatic diisocyanates are used. Suitable compounds are, for example, 4,4'-methylenediphenyl diisocyanate, 2,4-toluene diisocyanate, isophorone diisocyanate, 2,6-toluene diisocyanate, ethylbenzene diisocyanate, Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, Octamethylene diisocyanate, decamethylene

30) 808/1315

diisocyanate, diisopropylbenzene diisocyanate, tri-isopropylbenzene diisocyanate, 2-chloro-p-phenylene diisocyanate, naphthalene diisocyanate, glycol di-Cp-isocyanato-phenyl ester), 4,4'-diisocyanato-diphenyl ether, 1,2- Bis-p-isocyanato-phenylethane, 4,4'-diisocyanato-stilbene, 4,4'-diphenylsulfone diisocyanate, 3,5,6-trichlorotolylene diisocyanate, xylylene diisocyanate, propylbenzene diisocyanate, m-phenylene diisocyanate, p- Phenylene diisocyanate, dodecamethylene diisocyanate, tetrachloro-m-phenylene diisocyanate, ^, ^ '- bis-o-tolylene diisocyanate, i <, 4'-methylene-di- (o-tolyl isocyanate), il-methoxy-1 , 3-phenylene diisocyanate, 4-chloro-l, 3-phenylene diisocyanate, 4-isopropyl-l, 3-phenylene diisocyanate, 2, ¹ I '-diisocyanatodiphenyl ether, 3,3'-dimethy1-4,4' -diisocyanato-diphenylmethane, mesitylene diisocyanate and durol diisocyanate.

The amide-imide prepolymer with terminal isocyanate groups is then in a mostly cresol-like solvent such as p-cresol, o-cresol, m-cresol, cresol acid or dissolved in phenol with or without the addition of a hydrocarbon diluent and with a glycine ester of the general

formula

MR..

Ar- (NC-COR _p )

implemented in the Ar and Rh the meaning already given have, where the R ^ groups can be the same or different,

3 0 9808/1315

and FL is a dialkylamino, alkoxy or aryloxy group and χ is an integer from 2 to ¹ I. Suitable glycine derivatives are described, for example, in British Patent 1,106. These compounds include, for example, methylene bis (N-phenyl glycine ethyl ester), methylene bis (N-phenyl glycine methyl ester), methylene bis (N-phenyl glycine propyl ester), methylene bis ( N-phenyl-glycine isopropyl ester), methylene bis (N-phenyl glycine butyl ester), methylene bis (N-phenyl glycine sec. Butyl ester), methylene bis (N-phenyl glycine hexyl ester) , Methylene-bis- (N-phenyl-glycine-cyclohexyl ester), methylene-bis- (N-phenyl-glycine-isooctyl ester), methylene-bis- (N-phenyl-glycine), methylene-bis- (N-phenyl- N ', N'-dimethylglycine amide), methylene-bis- (N-phenyl-N', N'-dibutyl-glycine amide), methylene-bis- (N-phenyl-glycine-phenyl ester), methylenebis- (N-phenyl- glycine-p-tolyl ester), Ν, Ν'-bis-carboxymethyl-4, H '-diaminobenzene, oxybis- (N-phenyl-glycine-ethyl ester), oxybis- (N-phenyl-glycine-methyl ester), thiobis- ( N-phenylglycine ethyl ester), thiobis (N-phenyl glycine butyl ester), sulfon bis (N-phenyl glycine ethyl ester), oxybis (N-3-chlorophenyl glycine ethyl ester), oxybis ( N-2-chlorophenyl-glycine methyl ester), ethyl en-bis- (N-phenyl-glycine-ethyl ester), tetramethylene-bis-iN-phenyl-glycine-amyl ester), hexamethylene-bis- (N-phenyl-glycine-methyl ester) , decamethylene-bis- (N-phenylglycine- ethyl ester), diphenyl-lJjlJ'-bis- (glycine-ethy ester),

3 0 9 8 0 8/1 3 1 B.

Stüben-4,4'-bis-Cglycine-ethyl ester), Ν, Ν'-bis-carboxymethyl-2,2'-diaminobenzene, N, N'-bis (methoxycarbonyldimethyl-methyl) -4, ¹ J'-diamino -diphenylmethane, ethylidene-bis (N-phenyl-glycine ethyl ester), isopropylidene-bis (N-phenyl-glycine-ethyl ester), butylidene-bis (N-phenyl-glycine propyl ester), tridecane-6,6-bis - (N-phenyl-glycine-ethyl ester), N, N'-bis (methoxycarbonyldimethyl-methyl) -m-phenylene-diamine, N, N ¹ , N ^1! -Tris- (ethoxycarbonyl-methyD-ί} , H ' , H "-triamino-triphenyl-methane, N, N ^f , N ¹ ' -Tris- (ethoxycarbonyl-methyl) -2, '] _> i | '-triamino-triphenyl and azobis- (N-phenyl-1-methyl-glycine-ethyl ester).

When the trimellitic anhydride is reacted with the isocyanate, part of the trimellitic anhydride can be replaced by a dicarboxylic acid or a difunctional anhydride, i.e. a carboxylic dianhydride, in amounts of 0.1 to 50 mol, based on the moles of trimellitic anhydride used. Suitable dicarboxylic acids and dianhydrides are, for example, isophthalic acid (preferably in amounts of 15 mol $), terephthalic acid (preferably in amounts of not more than 20 mol and especially in amounts of 8 mol), phenylindanedicarboxylic acid, adipic acid, pimelic acid, h, k '- Dicarboxy-diphenyl ethers, ^, H ¹ - dicarboxy-diphenylsulfone, benzophenone-carboxylic acid dianhydride, cyclopentanecarboxylic acid dianhydride or pyromellitic acid dianhydride. However, dicarboxylic acids that are

0 ^ 808/131 Γ>

Can form imides with amines or isocyanates, such as for example o-phthalic acid or glutaric acid, cannot be used.

A small part of the total trimellitic anhydride used can also be replaced by a trifunctional carboxylic acid to achieve a slight branching by for example up to about 10 moles of trimesic acid, based on the total content of trimellitic anhydride, with processed will.

The molar ratio of acids and anhydrides to methylenebis (N-phenyl-glycine-ethyl ester) or another compound capable of hydantoin formation can be about 95 % to 5 % to about 5 % to 95 % .

In general, the implementation partners are used in the following quantities:

(1) Diisocyanate 0.85 to 1.05 moles (preferably 1.00 moles)

(2) Aminoethyl ester 0.05 to 0.95 mol (preferably 0. ^ 0 mol)

(3) trimellitic anhydride 0.05 to 0.01 mol (preferably 0.1 to 0.5 mol)

Dicarboxylic acid 0.0 to 0.3 mol (preferably 0.15 mol)

(5) dianhydride 0.0 to 0.3 moles (preferably 0.2 moles)

(6) tricarboxylic acid 0.0 to 0.05 moles (preferably 0.033 moles)

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(7) Organometallic compounds, especially organic titanates 0.0 to 1.0 mol (preferably 0.0 to 0.06 mol)

The total amount from (2), (3), ( ¹ I), (5) and (6) should be about 1.05 to 0.95 mol and preferably 1.00 mol, so that the amounts of diisocyanate or diisocyanate used of the diisocyanate and the organotitanium compound correspond approximately to the amounts of the other reaction partners used.

The reaction temperature is generally about 80 to 500 ^° C., since hydantoin formation takes place at these temperatures, depending on the starting material.

The solvents used are preferably cresol-like solvents such as so-called cresolic acid or individual cresols, their mixtures or mixtures with phenol, xylenol, chlorophenol and similar compounds. Hydrocarbons can be added as diluents in amounts up to 6.5 vol. # Or above and preferably in amounts of about 10 to 25 vol. #. Suitable diluents are, for example, xylene, toluene, wire enamel naphtha, aromatic naphtha with a boiling range of about 160 to 171 ° C (Solvesso 100), aromatic naphtha with a boiling range of about 185 to 20 ¹ I ⁰ C (Solvesso 150) or aromatic naphthenes with a Boiling range from about 188 to 260 ° C (N-150).

3.0 Π 808/1 3 1 5

Unless otherwise stated, all parts and percentages relate to weight.

The polyamide-imide-hydantoins according to the invention can be applied as wire enamels for electrical conductors made, for example, of copper, silver, aluminum or stainless steel in a conventional manner, for example by the method described in US Pat. No. 3,201. The wire speeds can be approximately 9 to 15 m / min or more at wire tower temperatures of approximately 120 to ¹ IJO ⁰ C, the final temperature in the wire tower generally being above 260 ° C. The layer thickness of the coating, i.e. the increase in the total diameter in relation to the wire diameter without coating, the polyamide-imide-hydantoin varnish can be about 0.012 to 0.025 and preferably about 0.005 to 0.01 cm when using a wire Nr..l8 make up, whereby the wire can be coated one or more times with the lacquer to achieve the desired layer thickness.

The following examples are intended to explain the invention in more detail.

example 1

1) iJ, iJ'-methylene-diphenyl-diisocyanate (1.0 mol) 250 g

2) Trimellitic anhydride (0.5 mole) 96 g Terephthalic acid (0.1 mol) 16 g

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3) methylene bis (N-phenyl-glycine-ethyl ester)

(0.4 mole) 11 * 8 g

4) N-methyl-2-pyrrolidone i | 0 g

5) 3,4-cresol 2 * »6 g C.P. phenol i »94 g o-cresol 146 g

6) cresolic acid 582 g xylene 120 g Phenol 200 g

1) was placed in a kettle equipped with a stirrer, reflux condenser, thermometer and inert gas inlet tube, then 2) was added slowly while the temperature was increased to 166 ^° C. The reaction mixture was kept HO minutes at a temperature of 166-171 ° C, then was added 4), followed immediately entered a fast COP development. 200 g of 5) were then added and the addition of 3) was started at a temperature of 171 ° C., the temperature of the reaction mixture being about 199 ° C. at the end of the addition. After the addition of the remaining portion of 5), the temperature dropped to about 116 ° C., the reaction mixture was then heated again to 193 ° C., left at this temperature and 6) was added. The reaction mixture was then cooled and filtered to give a wire enamel designated "Wire Enamel 1" having a final viscosity of X on the Gardner-Holdt scale.

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250 ε 20th S. 96 G 185 ε 246 G 494 ε 146 ε 582 ε 420 ε

Example 2

1) 4,4'-methylene-diphenyl diisocyanate (1.0 mole)

N-methyl-2-pyrrolidone

2) trimellitic anhydride (0.5 moles)

3) methylene bis (N-phenyl-glycine ethyl ester) (0.5 moles)

4) 3,4-cresol C.P. phenol o-cresol

5) cresolic acid Xylene

In the kettle described in Example 1, 1) and 2) were reacted according to the processes described there, with vigorous COp evolution taking place at a temperature of 171 ° C. The reaction mixture heated to 199 ° ^{C. and} was then diluted with 4), heated again to 138 ° C. and then quickly added 3). The mixture was then kept at a temperature of 193 ° C. until 27 ε ethanol had distilled off, then 5) was added and the mixture was cooled and filtered. The wire enamel thus obtained, referred to as "wire enamel 2", had a final viscosity with a pesticide content of 17.5 % of Zl ⁺ according to the Gardner-Holdt scale.

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- Ill -

250 G ? 6 ε 185 G 246 6th 494 G 146 G 20th G 382 G 120 ε 200 G

Example 3

1) 4,4'-methylene-diphenyl-diisocyanate (1.0 mol)

2) trimellitic anhydride (0.5 moles)

3) methylene bis (N-phenyl-glycine-ethyl ester) (0.5 moles)

4) 3,4-cresol CP.-phenol o-cresol

5) 4,4'-methylene-diphenyl diisocyanate

6) cresolic acid xylene

C.P. phenol

In the described process, 1) was slowly added with 2), a maximum temperature of 171 ° C was observed. The reaction mixture was one hour and 15 minutes at leave this temperature, then with half of 3)> then with 4) and after the temperature has risen again from 82 ° C to 115 ° C with the remainder of 3). The reaction temperature was then increased to 193 ° C and kept constant, only 16 ml of ethanol were distilled off in two hours. At the stated temperature, 5) was then added to the reaction mixture and a further 1 to 2 hours at leave the specified temperature, no further amounts of ethanol distilling off. The mixture was then cooled and filtered and after addition of 6) gave a wire enamel designated as "wire enamel 3" with a final viscosity

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20th ε 96 G 148 G 1000 G IiOO G 182 G 64 G

a 20 # solids content of R on the Gardner-Holdt scale.

Example 4

1) 4.4 ¹ -methylene-diphenyl-diisocyanate (1.0 mol) 250 g of N-methyl-2-pyrrclidone

2) trimellitic anhydride

3) methylene bis (N-phenyl-glycine-ethyl ester) (0.4 moles)

4) cresolic acid ADP-14

5) Solvesso 100

6) Solvesso 100 cresolic acid

In the course of half an hour, 2) to 1) was added at a temperature of about 121 ° C., then the temperature was increased to 171 ° C., an exothermic reaction with a further increase in temperature to 183 ° C. occurring. At this temperature, 200 g of 4) were added, the cooled reaction mixture was heated again to 177 ° C. and 3) was slowly added. The temperature was then increased to 193 ° ^C. and after 14 g of ethanol had been distilled off, the remaining amount of 4) was added. The temperature was then increased to 199 ° C. and 5) and 6) were added. The reaction mixture was then cooled and filtered to give a

3 C) M 8 0 8/1 3 1 δ

Wire enamel designated as "wire enamel 4" with a final viscosity at 20 tiger pesticide content of X ⁺ according to the Gardner-Holdt scale.

Example 5

1) 4,4'-methylene-diphenyl-diisocyanate (1.0 mol) 250 g trimellitic anhydride (0.6 mol)
N-methyl-2-pyrrolidone

2) 3,4-cresol

3) methylene bis (N-phenyl-glycine-ethyl ester) (0.4 mol -2 g)

4) cresolic acid ADF-14

5) Solvesso 100

6) 3,4-cresol

1) was heated slowly to 171 ° C, an exothermic reaction started at a temperature rise to 196 ⁰ C. At this temperature 2) was added, whereupon the temperature dropped to 162 ° C., then the total amount of 3) was added all at once. The temperature was increased again and 4) was slowly added so that the reaction temperature was 193 ° C. at the end of the addition. At this temperature 5) and 6) were added, then the reaction mixture was cooled and filtered to give a wire enamel designated as "wire enamel 5" and having a final viscosity

116 G 30th G 200 G 146 G 848 G 424 G 224 G

3 0 9 8 Π a / 1 3 1 B

20 tigern solids content of X-Y on the Gardner-Holdt scale.

Example 6

1) 4 _i 4 ^t "methylene diphenyl diisocyanate (1 mol) trimellitic anhydride (0.6 mol)

2) N-methyl-2-pyrrolidone

3) C.P. phenol

k ) methylene bis (N-pheny1-glycine ethyl ester) (0.4 mol)

§) C, P.-Phenol o-cresol 3,4-cresol

β) 4,4'-methylene-diphenyl-diisocyanate 7) xylene

1) was heated to 210 ⁰ C, then the temperature to 171 ° C was lowered and added to 2). After the temperature had increased to 182 ° C., 3) and immediately thereafter 4) together with 250 g of 5) were added. The reaction temperature was then increased to 199 ° C. and, after addition of 6), kept constant for a further hour. The reaction mixture was then diluted with the remaining amounts of 5) and 7). The wire enamel referred to as "wire enamel 6" had a final viscosity of X according to the GardnertiOldt scale with a solids content of 17.5%,

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250 ε 115 ε 40 ε 200 ε 148 ε 654 ε ' 256 ε 598 ε 15th G 256 ε

Example 7

1) 4,4'-methylene diphenyl diisocyanate

(1 mole + 5g) 255g

Trimellitic anhydride (0.6 mole) 109 g

Trimesic acid (0.033 mole) 7 g

2) N-methyl-2-pyrrolidone 40 g

3) cresolic acid 200 g

4) methylene bis (N-phenyl-glycine-ethyl ester)

<0.1 »mol) 148 g

5) cresolic acid 1173 g

6) Solvesso 100 343 g

1) Was slowly warmed to 193 ° C and after the fall of the Temperature to 177 ° C. was 2) added, the temperature increased again to 193 ° C. and 3) added. After the temperature has dropped

o / ^with

temperature to 177 C was added 4) together 500 g of 5), the The reaction mixture is heated again to 193 ° C. and a further 250 g of 5) are added at this temperature. Afterward the temperature was increased to 2O4 ° C. and the remaining amount of 5) and 6) were added to the reaction mixture. The mixture was cooled and filtered, leaving a wire enamel designated "wire enamel 7" with a final viscosity at 20/6 pesticide content of Z2 on the Gardner-Holdt scale revealed.

The wire enamels produced in this way were applied to a copper wire No. 18 applied and examined. The results are in the table

compiled.

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Wire coating speed play in thickness No. m / min in to

Table 1

Plexibility- Resistant-

ity test passability against G.E.-

(Core winding impact heat- Polyftuor-KW abrasion-

after the temperature shock ("Preon" / ₀ firm-

Appearance stretching) in ⁰ C (260 ° C) 42.4 kg / cnT) speed

1 12.2 2 12.2 σ 8 08 t 3 io, 7 4th 10.7 sn 5 10.7 6th 9.1 7th 12.2

73.66-76.2

71.12

76.2
71.12

71.12 68.58 66.04

Well

very little wavy, medium grain

good, weak grain

very little wavy, medium grain size 2X 2X

3X 3X

3X 2X 2X

421-400 50-90-
100-lCO resistant 69 300-400 0-90-
100-100 ^ 52 420-410 0-50-
90-100 ___ 30th 380-450 + 0-50-
70-70 resistant 312 415-405 0-50-
60-80 70 399-388 O-6O-
80-90 147 370-382 20-70-
9Ο-9Ο 43

250 G 96 G 16 G 8th G 5 G 700 G

Example 8

1) 4,4'-methylene-diphenyl-diisocyanate (1.0 mol) Trimellitic anhydride (0.5 mol) benzophenonecarboxylic acid dianhydride (0.05 mol) isophthalic acid (0.05 mol)

2) tributylamine

3) cresolic acid

4) methylene bis (N-phenyl-glycine-ethyl ester)

(0.4 mole) 148 g

5) cresolic acid 1079 g Solvesso 100 (15 % of the solvent) 319 g

1) was placed in a 3 liter kettle, then the temperature was increased to 188 ° C over a period of 70 minutes, and 2) added dropwise while maintaining the mixture at a minimum temperature of 182 ° C for 50 minutes. Then 3) was added to dissolve the polymer formed, after a complete solution had formed, 4) was added at a temperature of 149 C. The reaction mixture was then heated to 204 ° C., left at this temperature for 5 hours and then diluted with 5). The finished wire enamel showed a final viscosity of X 3 / ^ according to the Gardner-Holdt scale with a solids content of 17%.

The test of the wire enamel properties resulted in the following values:

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Wire speed 10.7 m / min 12.2 m / min Appearance Well Well Flexibility test HX 2X Breakdown temperature 391- ¹ UQ ⁰ C 302-378 ^O C Heat shock (26O ° C) 20-60-90-100 5O-90-IOO-IOO Resistance to "Preon" (42.2 kg / cm ² ) resistant resistant G.E. abrasion resistance 181 126

Example 9

1) -AjiJ'-methylene-diphenyl-diisocyanate - 8000 g Trimellitic anhydride 3072 g of benzophenonecarboxylic acid dianhydride. 1024 g

2) Tributylamine 160 g

3) cresolic acid 30400 g

4) methylene bis (N-pheriyl-glycine-ethyl ester) 4736 g

5) C.P. phenol 13623 g

6) Solvesso 100 10240 g

7) cresolic acid 21888 g

1) Was in a 56 liter kettle for 3 hours at a temperature of 195 ° C., then 2) was added over a period of minutes and the reaction mixture was added for a further 15 minutes leave at the specified temperature. By adding 3), the polymer formed was completely dissolved, then was the temperature lowered to 149 ° C. and 4) added. The reaction mixture was 7 hours at a maximum temperature

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223Q165

heated by 205 ° C until at least 1000 ml of ethanol distilled off and a 25 wt / sige solution in cresolic acid had a viscosity of N on the Gardner-Holdt scale. Finally the reaction mixture was diluted with 5) »6) and 7) .: The Examination of the wire enamel gave the following results:

Wire speed 10.7 m / min 12.2 m / min

Look good, mean good, mean

Flexibility test 3X grain _2χ grain

Breakdown temperature 420-421 ⁰ C 319-36O ⁰ C

Heat shock test (260 ° C) 20-70-90-100 40-80-100-100

Example 10

1) 4.4 ^t -methylene diphenyl diisocyanate (1.0 mol) 250 g trimellitic anhydride (0.4 mol) benzophenonecarboxylic acid dianhydride (0.2 mol)

2) tributylamine

3) cresolic acid

4) methylene bis (N-phenyl-glycine-ethyl ester) (0.4 moles)

5) cresolic acid

6) C.P. phenol

7) Solvesso 100

1) Was in a 3 liter kettle with stirring for 2 hours heated to a maximum temperature of 213 ° C., then became slow

77 G 64 G 5 G 700 6th 148 G 646 G 431 G 323 G

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2) and then 3) added. After the polymer formed had dissolved in 3), ¹ J) was added at a temperature of 154 ° C. and the reaction mixture was heated to 208 ° C. for 10 hours and then diluted with 5) >> 6) and 7).

The examination of the wire enamel gave the following results:

Wire speed 12.2 m / min

Coating thickness 68.58 ^ µm

Flexibility test 2X

Looks good

Breakdown temperature. 385-388 C

Heat shock test (260 ⁰ C) 5O-9O-9O-IOO

G.E. Abrasion Resistance 49

Example 11

1) 4,4'-methylene-diphenyl diisocyanate (0.4 mol) 225 g trimellitic anhydride (0.4 mol) 77 g Benzophenonecarboxylic acid dianhydride (0.2 mol) 64 g

2) Tributylamine 5 g 3.) Cresolic acid 1000 g

4) methylene bis (N-phenyl-glycine-ethyl ester)

', (0.4 mole) 148 g

5) cresolic acid 475 g

6) Ethyl cellosolve (5 % of the solvent) 87 g

7) Solvesso 100 (10 % of the solvent) 17 ¹ I g

8) Tetraisopropyl titanate 18 g

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The wire enamel was produced according to the method described in Example 8, the mixture of 5), 6) and 7) being used for thinning and 8) being added after thinning. The pesticide content was adjusted to 17.5% , in
to which 269 g of cresolic acid, 39 g of Solvesso 100 and 12 g of ethyl cellosolve were added. The wire enamel had a final viscosity of Z on the Gardner-Holdt scale. The examination of the wire enamel gave the following results:

Wire speed Coating thickness flexibility test

Braise resistance (33 Amp, 4 min)

Schmorfestigkeit (at 40 Amp in min) Dielectric temperature heat shock test (26O ⁰ C) Resistance to "Preon" GE-abrasion resistance (42,2 kg / cm2, 72 h) Emerson scratch resistance

12.2 m / min

73.6-76.2 / µm

2X

10.1 KV

15+ min

450+ - i »50 + ° C

40-90-100-100

constant 33 strokes

13.7 m / min 73.6-76.2 / µm 2X

9.3 KV

15+ min

450+ - 45O + ° C 70-100-100-100

constant 24 lines 26 lines

Example 12

1) 4,4'-methylene-diphenyl-diisocyanate (0.9 mol)
Trimellitic anhydride (0.4 mol)
Benzophenonecarboxylic acid dianhydride (0.2 mol)

2) tributylamine

225 g 77 g 64 g

5 g

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3) cresolic acid 1000 g

4) methylene bis (N-phenyl-glycine-ethyl ester)

(0.4 mole) 148 g

5) cresolic acid 134 g

6) CP phenol (20 % of the solvent) 350 g

7) Solvesso 100 (15 % of the solvent) 264 g

8) Tetraisopropyl titanate 18 g

The production was carried out according to the method given in Example 11. The final viscosity at a solids content of 20 % was YI / 2 according to the Gardner-Holdt scale. The examination of the coated wire gave the following results:

Wire speed 12.2 m / min 13 j7 m / mm Coating thickness 71.1 µm 68.6 µm Flexibility test 3X 3X Breakdown temperature 450+ - 45O + ° C 450+ - 45O + ° C Heat shock test (26O ° C) 30-80-100-100 20-80-100-100 Resistance to "Freon" (42.2 kg / cm ² , 72 h) resistant resistant G.E. abrasion resistance 51 strokes 19 lines Emerson scratch resistance 24 lines

Braise resistance

(33 Amp, 4 min) 1O ₅ O KV 7.8 KV

The main modification in Examples 11 and 12 is in that only 0.9 mol of 4,4'-methylene-diphenyl diisocyanate were used and the remaining 0.1 mol through

309808/1315

Tetraisopropyl titanate were replaced. Instead of tetraisopropyl titanate other titanates such as alkyl or aryl titanates such as tetramethyl titanate, tetrabutyl titanate, Tetrapropyl titanate, tetrahexyl titanate, tetraphenyl titanate or tetracresyl titanate or, if appropriate, other titanates such as titanium glycolate or tetra-triethanolamine titanium can be used.

The wire enamels produced in Examples 11 and 12 show particular advantages:

(1) higher wire speeds in the wire tower

(2) much higher breakdown temperatures

(3) better flexibility in core winding after drawing

(4) higher braising resistance when exposed to ^ 1 minute exposure 33 amps

(5) higher braising strength in seconds at ¹ IO amps

(6) better results in the Emerson scratch resistance test

When using a mole of the titanate, care must be taken that only 3 equivalents are available, as one of the organic Groups is very difficult to split off.

309808/1315

In order to demonstrate the particular advantages of the polymers according to the invention, a series of comparative tests were carried out with a wire enamel according to the information in the British patent 1 106 915 carried out. In an attempt to use the polymer des Preparing example 37 of this patent specification has been found to that one is insoluble in the recommended solvents, dimethyl sulfoxide and diethylacetamide in a weight ratio of 1: 1 Polymer was obtained. The polymeric compounds of Examples 33 and 3 * f of the British patent were reworked and the polymers applied as wire enamel. The following results were obtained:

Wire speed appearance

flexibility
Breakdown temperature heat shock test (26O ° C)

Braise resistance (H min, 33 Amp)

Resistance to "Preon" (42.2 kg / cm2, 72 h) G.E. abrasion resistance

Wire speed appearance

Flexibility test

Example 33 of British PS 1 106 915

10.7 m / min 12.2 m / min very little wavy very little wavy,

occasional stains

2X

32O-315 ° C

5O-8O-IOO-IOO

5.3 KV

resistant
99 lines

282-290 ° C 60-80-100-100

2.0 KV '

consistently 102 lines

Example 3 ** of the British PS 1 IO6 915

10.7 m / min 12.2 m / min

very little wavy, very little wavy, occasional spots

2X

309808/131 5

223016

example ^ k the British PS 1 106

Breakdown temperature heat shock test (26O ° C)

Braise resistance (4 min, 33 amp)

G.E. abrasion resistance

282-29O ⁰ C 70-100-100

1.9 KV

73 strokes

The hydantoins according to British Patent 1 106 915 and the polyamide-imide-hydantoins according to the invention were made using investigated by gel chromatography, it was found that accordingly the polyamide-imide-hydantoine according to the invention have a slightly larger molecular weight.

309808/1315

Claims (1)

Claims 1. Polyamide-imide-hydantoins, characterized in that the hydantoin units make up about 5 - 95% of the total units, that the amide groups form 20 - 80 % of the total of amide and imide units, that the hydantoin units of the following general formula ^R H ^R R C C = O O = C C ^k II II N N Y N I I I N N Y N N Ar. C C Ä ° correspond, in which Ar is an aromatic radical optionally substituted by halogen, nitro, alkyl, alkoxy, dialkylamino, acyl, carbalkoxy or cyano groups, Y is Ar or alkylene groups having 4 to 10 carbon atoms , Oxyalkylene groups with Ί to 10 carbon atoms or thioalkylene groups with ¹ I to 10 carbon atoms and R ₁ , a hydrogen atom or alkyl groups, the hydantoin units by reaction of a glycine derivative of the general-Meineη formula Ar- (NH-C-CORp)
1 3 0q8 0 8/1315 in which R_ is a dialkylamino, alkoxy or aryloxy group and χ is an integer from 2 to 4, with one in turn by reaction of (1) trimellitic anhydride or (2) a mixture of trimellitic anhydride with a dibasic acid, a dianhydride, or tribasic Acid with (a) a diisocyanate or (b) a diisocyanate and an organic titanate polyamide-imide with terminal isocyanate groups have been formed. 2. Polyamide-imide-hydantoin, characterized in that at least 30 % of the total units of the molecule consist of hydantoin units. 3. polyamide-imide-hydantoin according to claim 1, characterized in that that Ar and Y are each aromatic hydrocarbons and that the diisocyanate is an aromatic diisocyanate is. ¹ I. Polyamide-imide-hydantoin according to Claims 1 to 3> characterized in that the polymer is produced by reacting (1) 0.85 to 1.05 mol of diisocyanate, (2) 0.005 to 0.995 mol of a glycine derivative, (3) 0 , 95 to 0.01 moles of trimellitic anhydride, ( ¹ J) 0.0 to 0.3 moles of a dicarboxylic acid, (5) 0.0 to 0.3 moles of a carboxylic acid dianhydride, and (6) 0.0 to 0.05 moles of a Tricarboxylic acid and (7) 0.0 to 1.0 moles of one 0 9 8 0 8/1315 has been prepared organic ** titanate, wherein the total amount of (2), (3), ⁽¹ O, (5) and (6) 1.05 to 0.95 mole matters. 5. polyamide-imide-hydantoin according to claim ¹ I, characterized in that the total amount of (3), ( ¹ Oj (5) and (6) consists of 100% trimellitic anhydride. 6. polyamide-imide-hydantoin according to claim ¹ I, characterized in that the total amount of (3) »( ¹ O » (5) and (6) consists of 99> 9 to 50% of trimellitic anhydride. 7. polyamide-imide-hydantoin according to claim 4, characterized in that the total amount of (3), (^) _s (5) · and (6) consists of 60 to 100% of trimellitic anhydride. 8. Polyamide-imide-hydantoin according to claim 7rxlakter characterized that the content of trimellitic anhydride is 0.5 to 0.6 mol. 9-polyamide-imide-hydantoin according to Claim 7 _S, characterized in that no tricarboxylic acid is present. 10. polyamide-imide-hydantoin according to claim 7, characterized in that that in the general formula all R ^ groups are hydrogen atoms. 3 0 9 8 0 8/1315 11. polyamide-imide-hydantoin according to claim 10, characterized draws that the polymer from methylene-bis-tN-phenylglycine-alkyl ester) is made with lower alkyl groups. 12. polyamide-imide-hydantoin according to claim 10, characterized shows that in the general formula Y and Ar both denote methylene-bis-phenyl groups. 13 · Process for the production of polyamide-imide-hydantoins according to claims 1 to 12, characterized in that a glycine derivative of the general formula Ar- (NH-C-COR ₉ ) with a preformed polyamide-imide with terminal Isocyanate groups is implemented. 14. The method according to claim 13 » characterized in that smaller amounts of an organic titanate are added to the reaction mixture. 15. The method according to claim 13 or 1Ί, characterized in, that the titanate is used in amounts of about 15 equivalent percent of the diisocyanate. 309808 / 131S Ιδ. Use äev Falyamiü-im ± a-hyaa.nta & ne: naeBi A up to 12 in a preferably cresol-like solution area if necessary, an old age of apsmatiscken! Koiilenals D ^ aiitlaeke for eleicfeFisciie head «