DE2155678A1 - Polyamide-imide compositions - Google Patents

Description

Dr. rer. η at. Horst Schuler PATENT ADVOCATE

Frärikfurf / Μαίη X, aen g « _ov 1074 Niddasfraße 52 Dr. Sb , / he

Telephone [06K) 237220 Postscheck-Könta: 282420 Pranfcfuff / M, Bank-Konfo: 225/0389 Deofsche Bank AG, Frankfurt / M.

ÖENEHÄL ELECTRIC COMPANY 1 River Road

N.Y / ü.S.A

The present invention relates to; Polyamide imides with properties that make them useful for various high temperature applications such as insulation and writing. In particular, the invention relates to unsaturated anhydride-blocked polyimides with free Garböxyl «and Awingruppen * which are reacted with poly» isööyanat to give an improved hardened end product »

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Chain-blocked polyamide-imides of the type mentioned above can can be prepared by first combining a material with a three carboxyl acid with an organic polyamine in a suitable solvent, where an amide " ijiid materlal is created, which is then combined with an unsaturated anhydride treated and hardened by heating. It does exist, however a need for materials of the above kind that make flexible films and other products that have good high temperature and others have physical properties, and accordingly it is a primary object of the present invention to provide such improved materials to accomplish. Further objects and advantages of the invention can be found in the description below.

The present invention creates new and improved polymers by reacting a tricarboxyellian material with an organic polyamine or an amine which contains more than one amine group and adding an unsaturated anhydride to the resulting reaction product and the subsequent reaction with polyisocyanate and curing, ura the desired Improve physical properties.

There are believed to be unreacted carboxyl and amine groups in the known materials of the type described above, the just the opposite effect on the physical properties of the hardened product have * The implementation of the polyisocyanate, so it is believed that having some or all of the unreacted groups creates the resulting improved properties.

The three carboxyl groups acid and the polyamine in an inert solvent under nitrogen Generally speaking, heated to a reflux temperature, which is generally between i8ö to 2JJO ⁰ C, namely until little or no water accumulates more by azeotropic distillation, or a carboxy group titration shows no or only a very slow reduction in the concentration of carboxyls. The tricarboxyclic

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The material and the polyamine can be used in stoichiometric amounts. However, if desired, the amine can be employed up to 1 mole or more in excess of the stoichiometric amount. After cooling to room temperature, the unsaturated anhydride is added in an amount which is more or less equivalent to the calculated amount of free amine. To this solution, which also contains free carboxyl groups, is added the polyisocyanate and the mixture heated to a temperature in the range from 60 ⁰ C to the reflux temperature, in order to facilitate the reaction with all the free acid and amine groups which may be present. The unsaturated anhydride and isocyanate can also be added together. On the other hand, after the addition of the unsaturated anhydride, the solution can also be heated in order to close the rings, after which the isocyanate is then added with heating.

Although trimellitic anhydride is the preferred tricarboxyclic acid material, any of a number of suitable tricarboxyclic acid materials can be used, such as 2,6,7-naphthalenetricarboxylic anhydride, 3,3 ', ^ -diphenyltricarboxylic anhydride, 3 »3', M-benzophenonic tricarboxylic acid, 3, iJ-Cyclopentantricarboxylsäureanhydrid, 2.2 x, 3-Diphenyltricarboxylsäureanhydrid, diphenyl-3,3 ^1, JJ-tricarboxylsäureanhydridj-diphenylisopropylidene ^, 3 '' ^ - tr carboxylic acid anhydride, 3,4,10-Preylentricarboxylsäureanhydfid, 3, ¹ J -Dicarboxyphenyl-3-carboxyphenyl ether anhydride, ethylene tricarboxylic acid anhydride, 1,2,5-naphthalenetricarboxylic acid anhydride, 1,2, iJ-butane-carboxy isic anhydride, etc. The tricarboxy ^ lischen acid materials can be characterized by the following formula:

HOOC _R

Il
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- 4 _ where R is a trivalent organic radical.

The aromatic polyamines useful in the present invention are known and have the following general formula:

χ Rf - (NHg) _n -

where R 'is an organic radical and η is at least 2 and X is hydrogen, an amino group or an organic radical including those containing at least one amino group. Examples for those usable in the present invention alone or in admixture Amines are the following:

4,4-diamino-2,2'-sulfonediphenylmethane ethylenediamine
Benzoguanamine
m-phenylenediamine
p-phenylenediamine
^F 4,4-diamino-dipheny! Propane 4,4'-diamino-diphenyl methane benzidine

4,4'-diamino diphenyl sulfide 4,4'-diamino-diphenyl sulfone 3,3'-diamino-diphenyl sulfone

4,4'-diamino-diphenyl ether

2,6-diamino-pyridine bis (4-aminophenyl) diethylsilane bis (4-aminophenyl) diphenylsilane bis (4-aminophenyl) phosphine oxide 4,4'-diaminobenzophenone bis (4-aminophenyl) -N -methylamine bis (4-aminobutyl) tetramethyldisiloxane 1,5-diaminonaphthalene 3,3'-dimethyl, 4,4'-diamino-biphenyl ^f 3.3.-dimethoxy ^ J3enzidin 2J4-bis (beta-amino-t-butyl )toluene

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Toluene diamine

Up to Cpara-beta-amino-t-butyl-phenyl) Ä.ther

p-Bis (2-methyl-4-amine Q-pentyl} benzene

p-Bis (1, t-dimethyl-5-amine Q-pentyl) benz Ql

ra-xylyl-diamine

p-xylyl diamine

Bis (^ -amino-cyclohexyl > rae than.

Hexaraethylene-diamine Heptamethylene-diamine Qetamethylene-diamine Nanamethylene-diaraine Decamethylene-diaiffitn 3-Met hy 1-hep camnetbylen-diainine Λ, ² I '"üimethyllßptamethylene-diamine 2,11-Diaiaino-dodecane 1,2-bis- (3- amino-propoxy) ätiiaii 2 ₁ 2-Diiaethyl propylenediamine 3-MefehQxy-. hexamethylenediamine 2 »5-Dimethylh.examethylenediaiaine 2j5-Dimethylheptamethylenediamine 5-Methylnonamethylenediamine 1, ^ - öiamino-eyelohexane 1,12-Diamino-octadecane 2» 5-Diamino-octadecane 2 »5-Diamino-octadecane i »3 * 4-oxadiazole

Pölyme thylenpo; J- * aBtin (C ur ithan) and their mixtures.

Among the unsaturated anhydrides are useful "in the present invention include, for example, substituted and un3ubstituiertes maleic anhydride, ItaeansäureanhydrId _s

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Ci trac onsäureanhydr id and Endo-cis-5-norbornene-2,3-dicarboxylic anhydride, the methy! -substituted material and tetrahydrophthalic anhydride. These anhydrides can be expressed by the following formula:

R ¹ * O

ι V

where R "is a divalent, aliphatically unsaturated, organic one Radical or contains a carbon-carbon double bond. Other anhydrides are known to those skilled in the art.

All polyisocyanates, such as R ^Fti (NCO), which contain two or more isocyanate groups, whether blocked or unblocked, can be used. In the last-mentioned formula, R ^rf * is an organic radical and y is at least 2. Blocked isocyanates, which contain phenols or alcohols as a blocking component, or complexed isocyanates, can be used and generally lead to an end product with a higher molecular weight, which is advantageous for paints, for example is. On the other hand, unblocked isocyanates result in more flexible end products. In any case, the blocking material must be evaporated as much as possible, and from the standpoint of the reaction there is no advantage in using the blocked material, except in the above-mentioned case. An example of the blocked polyisocyanates is Mondur S, which contains mixtures of 2 »^ - wiü 2,6-toluene dilsoxyanate reacted with methylolpropane and blocks the esterification, ialfe phenol in the ratio of 3 moles of isocyanate 1 mole of ethylolpropane and 3 moles of phenol In Mondur SH, the isocyanate groups from mixed 2,4- and 2,6-T © lu © l isoeyanate are blocked, for example by esterification with cresol or phenol. Of the polyisocyanates, for example, the following can be used alone or in a mixture: Ö3S0

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V tetramethylene hexamethylene diisocyanate 1,4-phenylene 1,3-Phenylendlisocyanat 1,4-Cytiohexylendiisocyanat 2,4-tolylene diisocyanate 2,5-tolylene diisocyanate 2 j6-tolylene diisocyanate 3,5-tolylene diisocyanate ⁱ l-chloro-l, 3-phenylene l-methoxy -2, ⁱ -phenylene diisocyanate 1,3,5-triethyl-2, iJ-phenylene diisocyanate, l-methyl-3,5-diethyl-2, ⁱ »-phenylene diisocyanate, l-methyl-3j5-diethyl-6-chloro-2, ¹ l-phenylene diisocyanate 6-methyl-2, ⁱ l-diethyl-5-nitro-1,3-phenylene diisocyanate p-xylyl diisocyanate m-xylyl diisocyanate 4,6-dimethyl-1,3-xylyl diisocyanate 1,3-dimethyl- ¹ J, 6-bls- (b-isocyanate ethyl) benzene 3- (a-isocyanate ethyl) phenyl isocyanate l-methyl-2, ⁱ l-cyclohexylene ^{diisocyanate 1} I, H '-biphenylene diisocyanate 3,3' -dimethyl- ¹ !, ¹ I ' -biphenylene diisocyanate 3,3 · -Dime thoxy- ¹ 1,4 '-biphenylene diisocyanate 3,3'-diethoxy-4, il-biphenylene diisocyanate 1,1-bis- (4-isocyanafcphenyl) cyclohexane Ü, ¹ ^ * i) iisocyanate- diphenyl ether ^, il'-diisocyanate-dicyclohexylmethane 4,4'-diisocyanate-diphenylmetha n 4,4'-diisocyanate-3,3'-dimethyldiphenylmethane 4 j 4'-diisocyanate-3>3'-dichlorodiphenylmethane4,4'-diisocyanate-diphenyldimethylmethane 1,5-naphthylene diisocyanate I ₃ 4r-naphthylene diisocyanate 4,4 ', 4-triisocyanate triphenylmethane 1-methyl-3,5-diethyl-2,6-phenylenedilsocyanate 209822/0990

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2,4,4'-triisocyanate diphenyl ether

2,4,6-triisocyanate-1-methyl-j5,5-diethylbenzene

o-tolidine -4,4'-diisocyanate

m-tolidine-4,4'-diisocyanate

Benzophenone ¹ !, 4 ^f -diisocyanate

Biuret triisocyanates

Polymethylene polyphenyl isocyanate

Generally speaking, the organic solvents that are used to prepare the materials according to the invention are polar organic solvents, such as N-methylpyrrolidone, pyridinedimethylsulfone, dirnethylacetamide, tetramethylene sulfone, tetramethylurea, dimethyl sulfoxide, dimethylformamide, all of which do not react with the other constituents under the reaction conditions. Up to 100 % cresol can be used. If desired, the above solvent to hO wt.% With high-boiling petroleum fractions such as Solvessomaterialien, various ketones such as methyl ethyl ketone, alcohols and the like may be diluted.

While it is preferred for some applications because of the properties of the end product to use tricarboxyclic materials such as P trimellitic anhydride and the like, the carboxyclic reactant can also be partially or entirely an aromatic, two carboxyl group-containing acid or a corresponding anhydride, such as terephthalic acid or isophthalic acid materials and benzophenone dianhydride. Furthermore, up to 80 % of such dicarboxyclic materials can be replaced by aliphatic, dicarboxyclic materials, such as adipic, sabacic, azelaic, suberic, pimelic, oxalic, maleic, succinic, glufcaric, dodecanedicarboxylic and fumaric acid.

While the aromatic polyamines are preferred, the aliphatic polyamines can also be used where the lower temperatures

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2155673

temperature properties along with improved flexibility be desired.

Below are some examples in which the invention is explained in more detail will.

example 1

380 g of N-methylpyrrolidone and 594 g (3 moles) of p-methylenedianine were poured into a flask fitted with a Vigreaux flask, a Dean Stark trap and condensation vessel, a stirrer and a thermometer contents were heated "to check a solution had formed and then 518.4 g (2.7 moles) of trimellitic anhydride were added together with 40 ς xylene" After a? -stündigen heating to 215 ⁰ C and collecting the resulting Wasseis was a viscous A solution is obtained to which another 1135 g of N-methylpyrrolidone are added. The carboxyl content was 2.46 %, the solution was allowed to cool to room temperature and 58.8 g (0.6 mol) of maleic anhydride were slowly added, the mixture was stirred and heated to 90 °, at which temperature 6.7 g of S ^ -TQlyldiisQesy / anat were added «öas. The resulting gelling was eliminated by heating to 2QQ ° G for hours. The remaining € 4, 8 g of the iso-

at a temperature of 11Q ^Q G added »which developed .. From this material one poured one

free film on an aluminum plate and hardened this at IQQ ⁰ G, 15Q ° G >> 20Q ¹⁹ G and at 25Q ° G for 1 hour each

Film was clear and slh and could be bent at 18O ^Q G without lerstörung * Mn lhnlisher FiIm ^ afeer no manufactured "wurd © \ ^ ttat ¥ erb4egen feet %% Q? Q

If: a mt% a polyesterimide: coated masnet wire spiral coil is treated with the product of this example, and it is up to a thickness of about 10 to % Z $ micron, (Ψ * 5 rotls) then the bond strength is in the range ^VQR about 25 kg (55 pounds) at 25 ⁰ G up to about 5.4 kg (12 pounds)

Example 2

765 g of the product from Example 1 with a pest body content of 56 % together with 9.3 g of diallyl were placed in a glass flask.

isophthalate and 38O g of dimethylformamide-xylene solution in a volume ratio 1: 1 given. A plate was immersed in the stirred material, then left about 1/2 Run for hour and cured at temperatures of 100 and 150 ° C for one hour each. After that, the plate wore one Copolymer film with good wetting properties and a good one Flexibility that survived bending over a mandrel approximately 3 mm (1/8 inch) thick.

Example 3

A flask equipped as described in Example 1 was charged with 768 g (k moles) of trimellitic anhydride, 798 g (4 moles) of methylenedianiline, 668 g of N-methylpyrrolidone and 40 g of xylene. As in Example 1, the contents were heated for about 5 hours to a carboxy content of 3.3 % and a total of 7380 g of N-methylpyrrolidone were added to the mixture.

500 grams of the above material was added to 19.7 grams (0.11 moles) of Endocis-5-boron-2,3-dicarboxylic anhydride. Then it was added for 3 hours in which; the temperature was gradually increased to 140 ⁰ C, small fractions of a total of 19 * 25 g of Sj ^ -Tolwoldiisoeyanat added. Finally, 56O ml of N, methyl pyrrolidone were added. A plate was immersed in the resulting material, dried and, as in Example 2, cured, and a clear, flexible coating which passed the mandrel bending structure described in Example 2 resulted.

example k

Example! 3 was repeated except that instead of the worboom 16j? 2 g (0.11 moles) of tetrahydrophthalic anhydride and total

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32.6 g of 2,4-toluene diisocyanate were used. A stainless steel plate was immersed in the solution as above and removed at a rate of about 10 cm (4 inches) per minute; it was allowed to drain off until it was sticky and then hardened at 100, 150 and 200 ^° C. for one hour each and at 300 ^° C. for 15 minutes. The resulting material passed the mandrel bending test described above.

Example 5

A flask equipped as in Example 1 was charged with 768 g (4 moles) of trimellitic anhydride, 792 g (4 moles) of methylenedianiline, 668 g of N-methylpyrrolidone and 40 g of xylene. ^{The contents were heated to about 220 °} C. for about 7 hours and then still had a free carboxyl group content of 2.7%. Then 900 g of dimethylformamide and 1150 g of xylene were added to the solution. After cooling to room temperature, 83.3 g (0.85 moles) of maleic anhydride are added, the contents being stirred and allowed to react. Finally, 172.5 g 2 added ¹ I-ToIuOldiisocyanat were, in small portions over about 10 hours. 60 g of propanol were added to give a final product with a viscosity of 2480 centipoise at a solids content of 32%. The product was tested according to IEEE Test No. 57 as a layer over commercially available polyamide-imide and as a layer under a polyester-imide on a magnet wire. In both tests, an endurance rating of 40,000 hours at 213 ° C was carried out. This example demonstrated the good solubility of the amide imide in a solvent system with a relatively high hydrocarbon content; it was further stabilized by blocking free isocyanates with alcohol.

Example 6

A flask equipped as in Example 1 was loaded with 24Q g N-methylpyrrolidone, 297g (1.5Mol) methylenedianiline, 259.2g

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(1.35 moles) of trimellitic anhydride and 40 g of xylene. The constituents were heated to a temperature of 210 ^° C. until the theoretical amount of water had been distilled off for complete conversion. The contents were then diluted with further N-methylpyrrolidone to a concentration of about 30 % solids. 39.2 g (0.40 mol) of maleic anhydride were added to the solution at room temperature, the contents were stirred further and finally 120 ml of N-methylpyrrolidone were added.

^{A total of 16 gp, p f} -diphenylmethane diisocyanate were added to 333 g of the resulting solution over a period of 4 hours and at temperatures of about 90 to 140.degree. A sample of the material thus obtained was cured on a hot plate at 220 ° C. for 1 hour and gave a tough, flexible film.

Example 7

Into a flask equipped as in Example 1 were placed 768 g (4 moles) of trimellitic anhydride, 792 g (4 moles) of methylenedianiline, and 668 g of N-methylpyrrolidone and 40 g of xylene. The contents were heated to 220 ⁰ C until the carboxyl group content of 3.5% and the solids content was 45.3% djwa. To this solution, 108 g (1.1 moles) of maleic anhydride was added and the contents reacted with stirring. 60 g of 2,4-toluene diisocyanate were added to the reaction mixture obtained at 50 ° C. and the mixture was allowed to react overnight. The viscous solution obtained was diluted to a solids content of 30.8% with N-methylpyrrolidone. 60 g of propanol were added to this solution and the material was precipitated by pouring the mixture into a mixer containing water, the precipitate was washed with ether and dried. The powder thus obtained was dissolved in dimethylformamide to form a solution with a viscosity of 33 seconds in a No. 2 Zahn cup. the

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amber solution was pigmented on a clean aluminum plate sprayed and at 100, 200 and 3O2 ° C each 15 Cured minutes and gave a clear, greenish colored film that passed an impact test weighing 22.5 kg.

Example 8

In a flask equipped as in Example 1, 248 g (µmol) of diaminodiphenyl sulfone, 192 g (1 mol) of trimellitic anhydride, 167 g of N-methylpyrrolidone and 40 g of xylene were placed. The contents were heated to about 220 ° C. for about 15 hours and then had a carboxyl group content of about 3.2% . The contents were then diluted by adding a further 650 g of N-methylpyrrolidone and added 28.4 g to the solution at room temperature (0.29 mol) maleic anhydride was added and the mixture was stirred for 1 hour. The solution was heated to 180 ° C. for 1 hour and developed the theoretical amount of water. At 70 ° C., 15 g of 2,4-toluene diisocyanate were then added over the course of 6 hours and a temperature of 145 ° C. was set. 66 g of Mondur SH were added to this solution. Produced on a film of a metal plate, in each case 1 hour at I80, cured 200 and 250 ⁰ C, was clear, tough, infusible and flexible.

The present invention provides polyamide-imides whose chains are blocked by unsaturated anhydrides, wherein some or all of the free amine or carboxyl groups are reacted with polyisocyanate during manufacture in order to obtain a cured material with good high temperature properties. As explained above, the products are available as wire enamels, impregnating varnishes, paints and for the production of flexible films suitable. They are also useful as adhesives and impregnating agents for fibrous and other base materials, such as mica-like material for the manufacture of composites. They can also be precipitated and used in known fashion for compression molding and other applications.

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Claims (12)

- 14 patent cap claims Reaction product from a) the reaction product of a three carboxyl group Acid material and a polyamine, b) an aliphatically unsaturated anhydride and c) a polyisocyanate. 2. Product according to claim 1, characterized shows that the three carboxyl group acid material is trimellitic anhydride. 3. Product according to claim 1, characterized in that that the aliphatically unsaturated anhydride is selected from substituted and unsubstituted maleic anhydride, Itaconic anhydride, citraconic anhydride, Endo-cis-S-norbornene-ZjS-dicarboxylic acid anhydride, tetrahydr © phthalic anhydride and their mixtures. 4. Product according to claim 1, characterized z e rejects that part of the three carboxyl groups Acid material is replaced by an acid material bearing two carboxyl groups. 5. Product according to claim I _9, characterized in that the acid material containing three carboxyl groups is trimellitic anhydride, that the polyamine is methylenedianiline, that the aliphatically unsaturated anhydride is endocis-5-norbornene-2,3-dicarboxylic anhydride and that the polyisocyanate is 2, 4-toluene diisocyanate is. 6. Product according to claim 5 _S characterized by z e i c h η e t that the aliphatically unsaturated anhydride Is tetrahydrophthalic anhydride. 209822/0990 7. reaction product according to claim 1, characterized in that g ekennzelch. net that the aliphatically unsaturated anhydride is maleic anhydride. 8. The cured reaction product of claim 9. An electrical conductor coated with the cured product of claim 1. 10. Base material impregnated with the product according to claim 11. A film made from the product of claim 12. Product according to claim 1, characterized in that that it is copolymerized with other unsaturated monomer materials. 209822/0990