Polyetheramideimide Resins and Electrical Conductors Insulated Therewith

The present invention relates to polyetheramideimide resins and to electrical conductors coated therewith. More particularly it relates to polyetheramideimides derived from a combination of a dianhydride of a diphenolic compound and a tribasic acid anhydride and a diisocyanate and/or a diamine.

Polyetherimides comprising the reaction products of a dianhydride of a diphenolic compound and a diamine, e.g., methylenedianiline are known to form useful resinous coatings for electrical conductors. See, for example, Heath and Wirth, U.S. Pat. No. 3,847,867. Furthermore, polyamideimides comprising the reaction products of a carboxylic acid anhydride, a diamine and a diisocyanate are known to form useful coatings for electrical conductors. See, for example, Pauze and Holub, U.S. Pat. No. 3,817,926. In addition, polyamideimide resins comprising the reaction products of a tribasic acid anhydride and a diisocyanate are known to form useful insulating coatings from Nakano and Koyama, U.S. Pat. No. 3,541,038. Moreover, it is disclosed in Y. G. L. Lee's copending, commonly filed U.S. patent applicaton Ser. No. 137,991, filed Apr. 7, 1980 now abandoned, assigned to the assignee herein, that useful insulating coatings comprise the polycondensation product of a dianhydride of a diphenolic compound and a diisocyanate. The contents of the foregoing patents and application are incorporated herein by reference.

It has now been discovered that uniquely useful reaction products comprising polyetheramideimide resins can be formed from the reaction of (A) a combination of a dianhydride of a diphenolic compound and a tribasic acid anhydride and (B) a diisocyanate and/or a diamine. Such products are preferred for use as insulating coatings for electrical conductors, e.g., magnet wire and magnet strip, because they are safer, better and more economical. The resins are preferably applied as compositions diluted in an organic solvent.

According to the present invention there are provided high molecular weight polyetheramideimide resins prepared by subjecting

(A) a combination of anhydrides comprising:

(i) from 1 to 99 parts by weight of a dianhydride of the formula ##STR1## or a mixture thereof with at least one other dianhydride of an organic tetracarboxylic acid, and

(ii) from 99 to 1 parts by weight of a tribasic acid anhydride and

(B) 0.99 to 1.01 moles, per mole of the anhydride, of a difunctional organic nitrogen compound of the formula

(i) O.dbd.C.dbd.N--R--N.dbd.C.dbd.O,

(ii) H.sub.2 N--R--NH.sub.2, or

(iii) a mixture of (i) and (ii) wherein

R is divalent alkylene of 2 to 20 carbon atoms, ##STR2## or a mixture thereof, to polycondensation at a temperature of about 60.degree. to 200.degree. C. in the presence of the inert solvent.

It is also contemplated to provide electrical conductors having an insulating coating thereon comprising a resin as above defined.

In preferred features, the resin will be prepared in the presence of a catalytic amount, preferably, from a trace to about 10 mole percent (based on the anhydrides) of 2-methylimidazole. Preferably, the difunctional organic nitrogen compound will be diphenylmethanediisocyanate and/or diaminodiphenylmethane.

The dianhydride component (A)(i), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, also known as bisphenol-A dianhydride, is described in the above-mentioned Heath and Wirth, U.S. Pat. No. 3,847,867, and can be made by hydrolyzing, followed by dehydrating, the reaction product of a nitro-substituted phenyl dinitrite with a metal salt of a dihydric aryl compound in the presence of a dipolar aprotic solvent.

The organic diisocyanate and the organic diamines, (B)(i) and (ii) can be prepared in ways known to those skilled in this art, and they are also commercially available.

The term tribasic acid anhydride is used in the art-recognized sense set out in the above-mentioned U.S. Pat. No. 3,817,926 and 3,541,038. In general, it includes aromatic, alicyclic and aliphatic tribasic anhydrides, such as, for example, trimellitic anhydride (which is preferred), hemimellitic anhydride, aconitic anhydride, and the like.

The advantageous properties of the polymers of the invention can be varied by substituting for up to 50 mole percent of the bisphenol-A dianhydride one or more dianhydrides of tetracarboxylic acids, which may be either aromatic dianhydrides or aliphatic dianhydrides, as follows:

The aromatic dianhydrides that are useful in this invention are those having the formula: ##STR3## wherein R is a tetravalent radical containing at least one ring of 6 carbon atoms and having benzenoid unsaturation, each pair of carboxyl groups being attached to a different adjacent carbon atoms. These dianhydrides include, for example,

pyromellitic dianhydride,

2,3,6,7-naphthalenetetracarboxylic dianhydride,

3,3',4,4'-benzophenonetetracacarboxylic dianhydride,

benzene-1,2,3,4-tetracarboxylic dianhydride,

bis (3,4-dicarboxyphenyl) sulfone dianhydride,

bis (2,3-dicarboxyphenyl) methane dianhydride,

2,6-dichloronapthalene-1,4,5,8-tetracarboxylic dianhydride,

2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,

2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,

naphthalene-1,4,5,8-tetracarboxylic dianhydride,

naphthalene-1,4,5,8-tetracarboxylic dianhydride,

naphthalene-1,2,4,5-tetracarboxylic dianhydride,

3,3',4,4'-diphenyltetracarboxylic dianhydride,

1,2,5,6-naphthalenetetracarboxylic dianhydride,

2,2',2,2'-diphenyltetracarboxylic dianhydride,

2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,

3,4,9,10-phenylenetetracarboxylic dianhydride,

bis (3,4-dicarboxyphenyl) ether dianhydride,

2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,

1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,

1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride, and the like.

The aliphatic dianhydrides that are useful in this invention are those having the formula: ##STR4## where R' is a straight-chain or alicyclic tetravalent radical having from 1 to 10 carbon atoms. These dianhydrides include, for example:

methanetetracarboxylic dianhydride,

ethanetetracarboxylic dianhydride,

propanetetracarboxylic dianhydride,

butanetetracarboxylic dianhydride,

hexanetetracarboxylic dianhydride,

cyclohexanetetracarboxylic dianhydride, and the like.

The polymers are prepared from the reaction of mixed bisphenol-A dianhydride (BPA-DA) and, e.g., trimellitic anhydride and diphenylmethane diisocyanate (MDI), diphenyletherdiisocyanate, methylenedianiline (MDA), diaminodiphenyl ether, or a mixture of any of the foregoing, in the presence or absence of 2-methylimidazole (2-MeIM) catalyst, in an organic solvent, such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), an aromatic hydrocarbon, e.g., of 6 to 40 carbon atoms, e.g., xylene, or a proprietary aromatic hydrocarbon solvent, e.g., Solvesso 100, or in mixtures thereof, such as NMP-DMAC, NMP-xylene, NMP-DMAC-xylene or Solvesso 100, etc.

One typical reaction pathway is as follows: ##STR5##

Another typical reaction pathway is as follows: ##STR6## where R is as defined above.

The resulting resins can be random copolymers or random block copolymers.

The optimum mole ratio of MDI or MDA, BPA-DA and TMA (trimellitic anhydride) is (1.98-2.02):1.00:1.00 and the catalyst is 0-10 mole %, based on the mixed anhydrides. To make a coating composition the resin can be prepared in the organic solvent, e.g., NMP, NMP-DMAC, NMP-XYLENE or Solvesso 100, etc., or the resin can be isolated, then redissolved in such solvents, or in methylene chloride, dimethyl formamide, cresylic acid, phenol, and the like.

Conventional preparative methods are used. See, for example, the above-mentioned U.S. Pat. No. 3,541,038, which sets forth reaction times, temperatures, etc.

In one manner of proceeding, the BPA-DA and TMA are reacted with MDI (or MDA) in the presence of a mixture of N-methylpyrrolidone and the organic liquid hydrocarbon Solvesso 100 at a temperature of 135.degree. C. for about 5 hours. During the first period of reaction, the carbon dioxide (or water) is continuously evolved. Later, the solution gradually increases in viscosity and by-product (CO.sub.2 or water, as the case may be) evolution substantially ceases. A suitable termination point is a Gardner viscosity of Z2. Such an enamel can be used as a sole coat on a wire conductor or it can be used as a top coat over a polyester or polyesterimide base coat.

In accord with conventional practices, other additives may be formulated into the compositions, such as, without limitation, minor proportions of aliphatic amino compounds, conventional phenolic resins, titanate esters, blocked polyisocyanates, and the like.

In the drawing, the figure shows a section of magnet wire made according to this invention.

In the figure a magnet wire indicated generally by the numeral 10 and has a conductor 11 covered with a layer 12 of a resinous polyetheramideimide of bisphenol-A dianhydride and trimellitic anhydride and a diisocyanate and/or a diamine. Although the drawing illustrates a conductor 11 that is circular in section, it will be understood that the square or rectangular conductors in the form of strips or foils may also be used without departing from the invention.

A suitable polyetheramideimide for layer 12 can be made following Examples 1-5.

On mole (520 g.) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 1 mole (192 g.) of trimellitic anhydride, 2 mole (500 g.) of methylenediisocyanate, 0.1 mole (8.2 g.) of 2-methylimidazole, 1300.9 g. of N-methylpyrrolidone and 565.6 g. of aromatic hydrocarbon solvent (Solvesso 100) are added to a five liter, three neck, round bottomed flask equipped with a stirrer, thermometer, condenser, and a nitrogen inlet. The mixture is heated from room temperature to 135.degree. C. in approximately two hours and held at 135.degree. C. for 3.25 hours until a Gardner viscosity of Z2 is obtained. In this reaction, the solution changes from yellow, orange to clear red and clear dark red during the first two hours of heating, and carbon dioxide is nearly completely removed after 11/2 hour reaction at 135.degree. C. Thereafter, the solution viscosity gradually increases with continued very minor evolution of CO.sub.2. The solids content is about 40% in the organic solvent, and the composition can be used as an electrical conductor coating composition. If desired, the resin from this, and the other examples, can be isolated by pouring the cooled reaction mixture into methanol to precipitate the polymer.

Although diphenylmethanediisocyanate is shown, it can be partially a completely replaced by diphenylether diisocyanate. Moreover, the catalyst can be omitted.

The composition is further diluted with a mixture of 4 parts of NMP to 1.74 parts of Solvesso 100 and coating compositions containing 36 and 37% of solids are also obtained.

The composition of Example 1 (40% solids) is applied to 0.0403" copper wire as a sole coat in a commercial wire tower. A build of 2.8-3.3 mils is obtained. The following properties are observed:

Excellent quality coated conductors are obtained.

The composition of Example 1 is applied to 0.0403 copper wire as an overcoat over an ethylene glycol-tris(2-hydroxyethyl)isocyanate-terephthalate undercoat (Schenectady Chemical's ISONEL 678). A final build of 2.9 to 3.1 is obtained. The following properties are observed from 40% solids as a topcoat:

Excellent coated conductors are obtained.

The general procedure of Example 1 is repeated with 416g. (0.8 mole) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 307.4 g. (1.6 moles) of trimelletic anhydride, 606 g. (2.42 moles) of diphenylmethane diisocyanate 9.84 g. (0.12 mole) of 2-methylimidazole, 1098.8 g. of N-methylpyrrolidone and 477.7 g. of xylene. The viscosity after 1 hour is 8970 centistokes. The resin composition is cut with 293.6 g. of NMP and 127.7 g. of xylene. The heating is continued for 0.5 hour (viscosity 3390 centistokes). At room temperature, the viscosity is 3530 centistokes. Heating at 135.degree. C. is resumed for 2 hours and 15 minutes. Final viscosity is Gardner Z3+. Solids content is 35.78% average.

The composition of Example 2 is applied to 0.0403" copper wire as a sole coat in a commercial wire tower. A build of 2.8-3.3 mils. is obtained. The following properties are observed:

The composition of Example 2 is applied to 0.0403 copper wire as an overcoat over an ethylene glycol-tris (2-hydroxyethyl)isocyanate terephthalate undercoat (Schenectady Chemical's ISONEL 678). A final build of 2.9-3.2 mils. is obtained. The following properties are observed:

Excellent coated conductors are obtained.

Following the general procedure of Example 1, a polyetheramideimide is made using methylenedianiline (MDA) instead of diphenylmethanediisocyanate (MDI). There are used 520 g. (1 mole) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 192 g. (1 mole) of trimellitic anhydride, 400.5 g. (2.02 mole) of MDA, 1277 g. of N-methyl pyrrolidone and 555.6 g. of aromatic hydrocarbon (Solvesso 100). No 2-methylimidazole is used. The temperature reaches 180.degree. C. during heating. When70.5 mls. of water has been collected, the very viscous reaction mixture is filtered. The very viscous liquid is 40% solids. Seven hundred grams of the viscous composition is mixed with 97 g. of N-methylpyrrolidone and 44.7 g. of Solvesso 100 hydrocarbon solvent to produce a resin composition suitable for coating electrical conductors.

Following the general procedure of Example 1, a polyetheramideimide is prepared, substituting 20 mole percent of the 2,2 bis[4-(3,4-dicarboxyphenoxy)phenyl]propane (BPA-DA) with benzophenonetetracarboxylic dianhydride (BTDA). There are used 416 g. (0.8 mole) of BPA, 64.45 g. (0.2 mole) of BTDA, 192 g. (1 mole) of trimellitic anhydride, 505 g. (2.02 moles) of MDI, 1278 g. of NMP, 556 g. of Solvesso 100, and 8.2 g. (0.1 mole) 2-methylimidazole. The temperature never exceeds 135.degree. C., and after 3 hours a viscosity of Gardner Z31/2 (about 1760 centistokes) is obtained. Part of this composition is cut with a solvent mixture, 80 g. NMP and 35 g. Solvesso 100, then mixed at room temperature for two hours. Final viscosity is Gardner Z2. Solids content is 36.9%. This composition is labeled A.

The remaining portion is further reacted at 135.degree. C. until a Gardner viscosity of Z5 is reached. This is cut with a solvent mixture, 200 g. NMP and 87 g. Solvesso 100 to obtain a Gardner viscosity of Z3/4 and a solids content of 33.25%. This composition is labeled B.

Both enamels are applied to 0.0403" copper wire as a sole coat in a commercial wire tower. In both cases a build of 2.9-3.1 mils are obtained. The following properties were observed:

The general procedure of Example 4 is repeated, except that 20 mole percent of the 2,2 bis[4-(3,4-dicarboxyphen oxy)phenyl]propane (BPA-DA) is replaced with pyromellitic dianhydride (PMDA) instead of benzophenonetetracarboxylic dianhydride. 43.6 g. (0.2 mole) of the PMDA are used; all other amounts are the same as in Example 4. The final enamels obtained, labeled A' and B', had respective Gardner viscosities of Z11/2 and Z1, and had respective solids contents of 38.5% and 32.2%.

These enamels were also applied to 0.0403" copper wire as a sole coat in a commercial wire tower to builds of 2.9-3.1 mils. The following properties were observed:

Many variations will suggest themselves to those skilled in this art in light of the above-detailed description. All such modifications are within the full intended scope of the appended claims.