DE1922316C3 - Polyamidimidamides and a process for producing a polymer composition therefrom - Google Patents

Description

at room temperature, where R "is a tetravalent, organic radical which contains at least two carbon atoms and where χ is a number from 1 to 20.

2. Polyamidimidsäureamide according to claim 1, characterized in that the dianhydride to the heated reaction product of trimellitic anhydride and diamine is added.

3. A method for producing a polymer mass from the gelled product according to claim 1, characterized in that characterized in that the gel is kept at a temperature of about 100-150 ° C for at least one hour is heated.

The invention relates to polyamideimidamides obtained by reacting a reaction product of χ moles of trimellitic anhydride and χ + 1 mole of at least one diamine of the general formula

H ₂ N - R '- NH ₂

wherein R 'denotes a divalent aromatic radical with at least one dianhydride of the formula

at room temperature, where R "is a tetravalent, organic radical which contains at least two carbon atoms and where χ is a number from 1 to 20.

FR-PS 14 21 681 generally describes polymeric aromatic imidamides and their preparation by reacting a trimellitic acid halide anhydride or a trimellitic acid monoester dihalide with a diamine. Specifically in Example 7 of this FR-PS, however, the production of a polyamidimidamide is described, 68 g of 3, ^ - diaminobenzanilide being reacted at 10 to 20 ° C with 78 g of the dichloride of trimellitic acid monomethyl ester in the presence of dimethylacetamide, Na ₂ CO ₃ and xylene . The resulting solution containing about 20% resin solids is at room temperature with

ίο 1.256 g of pyromellitic dianhydride implemented, whereby an almost clear, slightly yellow solution with a solids content of 20.6% and a viscosity of 850 Centistokes at 23 ° C.

In US-PS 31 79 635 linear polymeric amide-modified polyimides and methods for their Manufacture described. These amide-modified polyimides known from US Pat. No. 3,179,635 are reaction products from an aromatic dianhydride, an aromatic diamine and an aromatic diacyl halide, wherein the products according to this US-PS both by conversion of a reaction product the aromatic diamine and the aromatic diacyl halide with an aromatic dianhydride, such as by reacting the reaction product of aromatic diamine and aromatic dianhydride with an aromatic diacyl halide are available. Thus, according to Example 1, m-phenylenediamine is first used reacted with a mixture of isophthalic and terephthalic acid chloride, whereupon the obtained Reacts product according to Example 2 with pyromellitic acid dianhydride In contrast, Example 9 describes the reaction of 19.8 g of 4,4'-methylenedianiline with 10.8 g of pyromellitic acid dianhydride and the other Reaction of the product obtained with isophthalic acid chloride to give the desired amide-modified product. As is evident from the entire disclosure of US Pat. No. 3,179,635, it is necessary that the structural units of the product the residue of an aromatic dianhydride, d. H. a dianhydride an aromatic Contain tetracarboxylic acid.

In US Pat. No. 3,260,691, coating compositions are made from condensation products of aromatic primary diamines and aromatic tricarboxylic acid compounds. It is true that the proportions of the reactants from 5% molar excess of the tricarboxylic acid compound to 70% molar excess of the primary Diamines vary, but chemical equivalency is preferred when the product has maximum linearity and so that it should have solubility. And obviously the equimolar use of the reactants is preferred, because in The examples are always based on the product of Example 1, in which a reaction product from equimolar amounts of trimellitic anhydride monoacid chloride and methylenedianiline.

In FR-PS 14 36 252 a reaction lacquer for electrical wires is described, which consists of a reaction product from 1 mole of trimellitic acid and 1-1.7, preferably 1.4-1.6, moles of aromatic diamines consists.

The polyamideimidamides according to the invention give after their curing polyamideimidides mi * very good properties including good ductility, toughness and good electrical and other physical properties.

The diamines that can be used include those in US Pat. No. 3,179,614 and others Place listed diamines in which the two amino groups are bonded to separate carbon atoms,

including benzidine, methylenediamine (MDA), oxydianiline (ODA), m-phenylenediamine (MPDA), p-phenylenediamine (PPDA) and diaminodiphenyl sulfone.

During the preparation of the reaction product, the diamine is reacted with trimellitic anhydride (TMA) in such molar ratios that the molar ratio of diamine to anhydride is always greater than 1 and that χ mol of anhydride are reacted with x + 1 mol of diamine. Usable products are obtained when χ is a number from 1 to 20. The reaction product can be prepared in the melt, but preferably in a solvent such as phenol, cresol, dimethylacetamide, dimethylformamide and N-methylpyrrolidone (NMP) or other high-boiling solvents which do not react with the starting materials. The preparation of the reaction product is complete when, after refluxing, the theoretical amount of water has been obtained. These reaction products can also be referred to as amino-terminated polyamide-imides.

In the preparation of the polyamide-imide acid amide, the polyamide-imide-polyamine reaction product is used as Intermediate reacted with a tetracarboxylic acid dianhydride of the general formula

Il c

R "

in which R "represents a tetravalent organic radical which has at least two carbon atoms and is selected from substituted and unsubstituted, aliphatic, cycloaliphatic, heterocyclic, aromatic groups and combinations of these groups. The anhydrides which can be used for this purpose include
Pyromellitic acid dianhydride (PM DA),
2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
meso-l ^ .i ^ -Butane-tetracarboxylic acid-

dianhydride (TCBA),

p-phenylene bis (trimellitic acid) dianhydride,
! ^, ö-naphthalene-tetracarboxylic acid dianhydride,
2,2 ', 3,3'-diphenyl-tetracarboxylic acid dianhydride,
2,2-bis- (3,4-dicarboxyphenyl) propane dianhydride,
Bis (3,4-dicarboxyphenyl) sulfonic dianhydride,
Perylene-3,4,9,10-tetracarboxylic acid dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride,
Naphthalene-1,2,4,5-tetracarboxylic acid dianhydride,
2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
1,1 bis (2,3-carboxyphenyl) ethane dianhydride,
l, l-bis (3,4-dicarboxyphenyl) ethane dianhydride,
Bis (2,3-dicarboxyphenyl) methane dianhydride,
Bis (3,4-dicarboxyphenvl) methane dianhydride,
Benzene-l ^^ - tetracarboxylic acid dianhydride,
Pyrazine ^^ Aö-tetracarboxylic acid dianhydride,
Thiophene ^ AS-tetracarboxylic acid dianhydride and ß / U '.'T'-Benzophenone tetracarboxylic acid dianhydride. The reaction between the dianhydride and the reaction product is generally carried out in that the dianhydride is added to the solution of the reaction product and the reaction is carried out for up to several hours at room temperature.

door to progress This leads to a gel the one has high imide content wherein the ratio of a + 1 to χ is less than about 5 to 4

In order to obtain useful products, the gel obtained as a reaction mixture the anhydride must be heated for about one hour to about iOO to 150 ⁰ C, so that a soluble substance is obtained, which does not solidify on cooling to the gel and stable at room temperature can optionally also be added to the heated solution of the reaction product.

The polymer solution with a high content of imide groups obtained in this way can be used for covering wires, for casting in films, as an adhesive or for other desired purposes. It becomes insoluble and infusible if it is ^{heated to more than 150 °} C., preferably more than 200 ^° C., for 1 to 10 hours, or is dehydrated by other generally known measures.

Preparation of the reaction product (A)

Under a nitrogen atmosphere and with exclusion of moisture, a mixture of methylenedianiline (188 g, 0.94 mol), trimellitic anhydride (90 g, 0.47 mol), N-methylpyrrolidone (65 g) and xylene (70 ml) was gradually stirred to 128 Heated to 220 ° C by removing parts of the xylene at various times until 17 ml of water had accumulated. The reaction product was diluted with 1053 g of N-methylpyrrolidone and gave a solution which contained 19% solids. The molar ratio of x + 1 to at was 2: 1.

example 1

A solution prepared as above (1361 g, 19% solids) was reacted at room temperature with meso-1,2,3,4-butanetetracarboxylic acid dianhydride (90.5 g) which was added all at once. The mixture was placed on a roller for 1/2 hour, after which time a clear gel had formed. The gel was kept in an oven at 105 ^° C. for 5 hours and the liquid polymer solution obtained was then cooled. The cooled reaction product was filtered, diluted with 235 g of a 1: 1 SoIvesso 100: 120 mixture with stirring and placed on a roller for 1/2 hour.

The inherent viscosity was 0.21 (dl / g) at 25 ° C (0.5% in N-methylpyrrolidone) and it became one elastic film produced by curing at 100, 200 and 240 ° C for one hour. That

so Polyamidimidsäureamid was applied to a 0.45 mm thick copper wire and in six passes in a wire tower having a temperature of 340 ⁰ C and at the bottom a temperature of 325 ° C had to the ceiling, to a 0.075 mm thick pad

hardened. The elasticity of the coating, as measured at room temperature and 25% elongation was 1 χ and showed no failure, for example by breaking, was wound as the stretched wire around a mandrel having the same diameter as the wire. The tear-Dehn test was passed successfully, the individual abrasion was measured by standard methods and found to be 1560 g and the duration of abrasion 76. was Examination of the thermal shock resistance at 220 ⁰ C for one hour, the wire was wound around a mandrel without stretching, of the the same diameter as the wire. The result was satisfactory. The severing temperature was between

around 360 and 373 ° C, and according to IEEE No. 57 measured thermal life at 227 "C was 20,000 hours.

Example 2

A solution of the reaction product A (348 g, 34% solids content) was cooled to 110 ° C. and taken under Stir with 38.4 g of 1,2,3,4-butane-tetracarboxylic acid dianhydride treated In the course of 5 minutes, the temperature rose to 125 ° C, whereupon the polymer solution rose Room temperature was cooled. No gel formed because the polyamine solution was hot. the end this polymer solution with 40% solids content was hardened for one hour at 100, 200 and 240 ° C produced an elastic film. The inherent viscosity was 0.135 (dl / g) at 25 ° C (0.5% in N-methylpyrrolidone).

Example 3

A solution of reaction product A (138.2 g, 10% solids content) was treated with 5.3 g of pyromellitic dianhydride. A gel formed almost immediately and was placed in an oven ^{at HO 0 C for one hour.} The resulting liquid polymer solution exhibited an inherent viscosity of 0.49 (dl / g) at 25 ° C and after curing for one hour at 100, 200 and 240 ° C, yielded an elastic film. A wire coated with it according to Example 2 had a severing temperature of 520 ° C. Its extensibility was 25% elongation and its internal space was 5 λ.

Example 4

A solution of reaction product A (263 g, 20% solids content) was mixed all at once with 29.9 g of benzophenone tetracarboxylic acid dianhydride treated. After 15 minutes on a shaker, the product went in the Gelzusiand over. It was mn N-methylpyrrolidone to 20% solids content diluted, for 3 hours in left in an oven at 110 ° C to give a flowable polymer solution. This polymer showed an inherent viscosity of 0.585 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone.

This sample showed a cutting temperature of 450 ° C, an extensibility at 25% elongation of 5 times after it had been applied to a copper wire and cured on a wire tower as in Example 2 (elongation of an insulated conductor with a diameter of χ by 75% and winding around a mandrel with a diameter of 5 x).

Example 5

A solution of reaction product A (138.0 g, 20% solids content) was heated to 85 ° C. with stirring and nitrogen. Then, in the course of 67 minutes, 22.44 g of p-phenylene-bis (trimellitate) dianhydride were added in portions as a suspension in 100 g of pyrrolidone. During this time the temperature was maintained for 55 minutes in the Pereich 105-150 ⁰ C so that the gel formed was dissolved. The then "? Cooled liquid polymer" was treated with a fi! ...-. :: ... "agent and filtered off on a pressure filter. Inextensible films were made therefrom and cured at 240 and 300 ° C. The inherent viscosity of the solution was 0.555 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone.

This polymer solution was applied as a coating to a copper wire as in Example 1 and showed severing temperatures of 380 to 385 ° C. and an extensibility of 2 × at 0% elongation.

Example 6

In the preparation of the reaction product A, 10 mol% of the trimellitic anhydride were replaced by azelaic acid and a polyamine in pyrrolidone with a solids content of 20% was obtained as a result. This solution of 584.5 g was diluted with 183.2 g of pyrrolidone. The solution was heated to 100 ° C. with stirring and under nitrogen and treated with 45.8 g of pyromellitic acid dianhydride. A gel forms, but this is caused by heating Dissolved no more than 127 ° C over a period of 18 minutes. The flowable product was cooled rapidly and the solids content was determined to be 19.3%. The inherent viscosity was 0.592 (dl / g) at 25 ° C. (0.5% solution in pyrrolidone). By curing both at 240 ° C, as described above, and at 300 ° C, as in Example 3, strain-free films were obtained. Applied to copper wire, this wire enamel solution exhibited a ductility at 25% elongation of 4 χ and a through separation temperature on 440 to 450 ° C

Example 7

In the preparation of the reaction product A, the methylenedianiline was replaced by Oxydianiiin and a Polyamine obtained with 20% solids content in pyrrolidone.

A portion of 111.40 g was diluted with 72.55 g of pyrrolidone and heated to 100 ° C. With stirring and nitrogen was added 18.14 g of p-phenylene bis (trimellitic acid) dianhydride was added was formed almost immediately a gel at 145 ⁰ C gave a flowable product after 15 minutes of heating. The product was cooled rapidly. The inherent viscosity was 0.395 (dl / g) at 25 ⁰ C; 0.5% in N-methylpyrrolidone) and hardened tough films were produced from it.

Example 8

A portion of 111.4g of the polyamine solution of the Example 7 was diluted with pyrrolidone (34.5 g), heated to 100 ° C. with stirring and added with 8.62 g of pyromellitic dianhydride treated. A gel step occurred, but this was caused by brief heating to 130 to 155 ° C could be resolved. The polymer was cooled to room temperature in an ice bath and gave free, hardened and tough films. The solution exhibited an inherent viscosity of 0.297 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone).

Example 9

A portion of 111.4 g of that prepared in Example 7 The solution was diluted with 51 g of pyrrolidone, stirred, heated to 100 ° C. and treated with 12.7 g of benzophenone tetracarboxylic acid dianhydride treated and gave a clear gel step. By briefly heating to 155 to The gel was dissolved at 171 ° C. The system was cooled to room temperature and cured at 240 and 300 ° C stretch-free films. The solution exhibited an inherent viscosity of 0.297 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone.

Example 10

_b 5 A portion of 22.08 g of reaction product A (20% solution) was treated with 0.4740 g of commercially available polymethylene polyaniline. It was a slurry of 1.9800 g of 1,2,3,4-butane-tetracarbon-

acid dianhydride in 9.816 g of pyrrolidone was added. The mixture was allowed to react for 30 minutes to give a homogeneous solution. After standing for 10 minutes at room temperature, a clear gel step occurred. By heating this product for 70 minutes at 104 ^° C., it became flowable. Stretchable films were made in the manner described above and cured as above at 240 and 300 ° C. The inherent viscosity of the solution was 0.28 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone.

In another approach, in which the proportion of the polymethylene polyamine is 20% by weight of the polyamine content the polymer solution obtained had an inherent viscosity of 0.51 (dl / g) at 25 ° C; 0.5% in N-methylpyrrolidone and gave stretchable films.

Example 11

It was a mixture of 198 g (1.0 mol) of MDA, 153.6 g (0.8 mol) of TMA, 88.0 g of NMP and 50 g of xylene with stirring and nitrogen for a total of 11 hours at a temperature of Held at 216 ° C. A total of 28.7 g of water (99.7% of theory) was collected in a trap. The ratio of x + 1 to χ was 5 to 4. The mixture was then diluted with 664 g of NMP and resulted in a solution of the intermediate product with a solids content of 30%.

a) To a portion of 107.5 g of the above solution, 32.78 g of NMP and 3.92 g of TCBA were added. After stirring for several minutes, the mixture turned into a gel state. After 6 hours When heated at 110 ° C, the gel dissolved and a viscous polymer solution was obtained. At this point the polymer had an inherent viscosity of 0.31 (dL / g) at 25 ° C; 0.5% in N-methylpyrrolidone.

Films cast from this material on aluminum plates were each cast for 1 hour at 100, 200, Cured 240 ° C and an additional half hour at 300 ° C and gave tough and stretchable films. This material was applied to copper wire and cured in a wire tower.

b) To a second portion of 107.5 g of the above Solution were 297 g of NMP and 9.07 g of p-phenylene

bis (trimellitate) dianhydride was added. The mixture immediately went into the gel state, which however dissolved again by heating for a period of 21 hours at 110 ° C and a viscous polymer solution with an inherent viscosity of 0.51 (dl / g) at 25 ° C; 0.5% in N-methylpyrrolidone yielded.
The films cast from this solution were tough and ductile after curing.

Example 12

A mixture of 198 g (1.0 mole) of MDA, 172.8 g (0.9 mole) of TMA, 132 g of NMP and 50 g of xylene was used for 7 hours heated to 211 "C for a long time under nitrogen. The ratio of x + lzux was 10 to 9. In one case, a Total amount of 32.6 g of water (100% of theory) collected. The mixture was made with 123 g of NMP diluted and gave a solution of the intermediate product with 20% solids content.

a) 1.78 g of TCBA were added to a portion of 169.5 g of the above solution. The mixture was stirred for one hour and gave a viscous polymer solution with an inherent viscosity of 0.31 (dl / g) at 25 ^° C .; 0.5% in N-methylpyrrolidone.

A film made from this material and cured as in the above examples was tough and stretchy.

b) 1.92 g of PMDA were added to a second portion of 169.5 g of the above solution. To After stirring for one hour, a viscous polymer solution having an inherent viscosity was obtained of 0.40 (dl / g) at 25 ° C; 0.5% in N-methylpyrrolidone, from which a tough and stretchable film was obtained. This sample was applied to a copper wire and a wire tower hardened.

c) To a third portion of 169.5 g of the above solution were 4.03 g of p-phenylene-bis (trimellitate) dianhydride added.

After stirring for one hour, the viscous polymer solution showed an inherent viscosity of 0.36 (dl / g) at 25 ^° C .; 0.5% in N-methylpyrrolidone and, after curing to 300 ^° C., resulted in a tough and stretchable film.

# 30 249/13

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Claims (1)

Patent claims: 1. Polyamidimidsamides, obtained by reacting a reaction product of χ mol of trimethyl anhydride and χ + 1 mol of at least one diamine of the general formula H ₂ N-RZ-NH ₂ wherein R 'denotes a divalent aromatic radical with at least one dianhydride formula