DE3113925A1 - "POLYAETHERAMIDIMIDE RESIN AND ISOLATED ELECTRICAL LADDER" - Google Patents

Description

The invention relates to polyether amide imide resins and electrical conductors coated therewith, in particular on polyether amide imides which are composed of a combination of a dianhydride a diphenol compound and a tribasic acid anhydride and a diisocyanate and / or a diamine come.

Polyetherimides, which are the reaction products of a dianhydride a diphenol compound and a diamine such as methylenedianiline are known to form useful ones Resin coatings for electrical conductors, see, for example, US Pat. No. 3,847,867. It is also known that polyamide-imides, comprising the reaction products of a carboxylic acid anhydride, a diamine and a diisocyanate are useful coatings for electrical conductors, see, for example, U.S. Patent 3,817,926. It is also known that polyamide-imide resins, which are the reaction products a tri-basic acid anhydride and a diisocyanate form useful insulating coatings, See US Pat. No. 3,541,038. Furthermore, patent application P .... (6OIN-63O), filed at the same time, discloses that useful insulating coatings are the polycondensation product of a dianhydride, a diphenol compound and a diisocyanate include. By referring to the aforementioned patent specifications and the application, their disclosure content becomes included in the present application.

It has now been found that uniquely useful reaction products the polyether amide imide resins comprise, from the reaction of (A) a combination of a dianhydride one Diphenol compound and a tri-basic acid anhydride and (B) a diisocyanate and / or a diamine can be. Such products are preferred as insulating coatings for electrical conductors, e.g. magnetic wire and magnetic strips, used because they are safer, better and more economical

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are lighter. The resins are preferably used as an organic Solvent diluted agents applied or applied.

According to the invention, high molecular weight polyether amide imide resins are created, produced by polycondensation of (A) a combination of anhydrides with

(i) 1 to 99 parts by weight of a dianhydride of the formula

or a mixture thereof with at least one other dianhydride of an organic tetracarboxylic acid and (ii) 99 to 1 parts by weight of a tribasic acid anhydride with

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

(i) O = C = NRN = C = O,
(ii) H ₂ NR-NH ₂ or
(iii) a mixture of (i) and (ii), where R

or their mixture, at a temperature of about 60 to 200 ° C in the presence of an inert solvent,

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The invention also provides electrical conductors with an insulating coating, comprising a resin as defined above.

The invention also relates to coating agents which a polyether amide imide resin as defined above dissolved in an organic solvent.

According to a preferred embodiment, the resin is in the presence a catalytic amount, preferably from a trace up to about 10 mol% (based on the anhydrides), 2-methylimidazole produced. Preferably is the difunctional organic nitrogen compound diphenylmethane diisocyanate 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 in the aforementioned U.S. patent 3,847,867 and can by hydrolyzing and then dehydrating the reaction product of a nitro-substituted phenyl dinitrite with a metal salt of a divalent aryl compound in the presence of a dipolar, aprotic solvent.

organic diisocyanate and the organic diamines (B) (i) and (ii) can in a manner known to the person skilled in the art and are also commercially available.

The term tribasic acid anhydride is used in the art recognized sense, such as in those above mentioned U.S. Patents 3,817,926 and 3,541,038. In general, it includes aromatic, alicyclic and aliphatic tribasic anhydrides, such as trimellitic anhydride (preferred), hemimellitic anhydride, Aconitic anhydride and the like.

130067/0718

The advantageous properties of the polymers according to the invention can be varied by adding up to 50 mol% of the bisphenol A dianhydride one or more dianhydrides of other tetracarboxylic acids used, either aromatic or aliphatic Can be dianhydrides. The following of the aforementioned dianhydrides can be used:

The aromatic which can be used in the context of the present invention Dianhydrides are those of the following formula

O O

wherein R is a tetravalent radical containing at least one ring of 6 carbon atoms and benzene unsaturation with each pair of carboxyl groups bonded to other adjacent carbon atoms. Examples for these aromatic dianhydrides are the following: pyromellitic dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, Benzene-1,2,3,4-tetracarboxylic acid dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, Bis (2,3-dicarboxyphenyl) methane dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-i, 4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, Naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, Naphthalene-1,2,4,5-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2 ', 2,2 · -Diphenyltetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-phenylenetetracarboxylic dianhydride,

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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 etc.

The aliphatic which can be used in the context of the present invention Dianhydrides are those of the following formula:

0 0

H N

η η 0 0

wherein R ^{1 is} a straight-chain or alicyclic tetravalent radical having 1 to 10 carbon atoms. Examples of these aliphatic dianhydrides are the following: methane tetracarboxylic dianhydride,
Ethane tetracarboxylic acid diynhydride,
Propane tetracarboxylic dianhydride,
Butanetetracarboxylic dianhydride,
Hexanetetracarboxylic dianhydride,
Cyclohexanetetracarboxylic acid dianhydride, etc.

The polymers are made by reacting mixtures of bisphenol-A-dianhydride (BPA-DA) and, for example, trimellitic anhydride and diphenylmethane diisocyanate (MDI), diphenyl ether diisocyanate, methylenedianiline (MDA) , diaminodiphenyl ether or a mixture of any of the aforementioned compounds in the presence or absence of 2-methylimidazole (2-MeIM) as a catalyst in an organic solvent such as N-methylpyrrolidone (NMP) , dimethylacetamide (DMAC), an aromatic hydrocarbon, for example with 6 to 40 carbon atoms, for example xylene, or a

aromatic brand hydrocarbon solvents , e.g. Solvesso 100, or in their mixtures, such as NMP-DMAC, NMP-xylene, NMP-DMAC-xylene or Solveeeo 100, etc.

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(2X) O = C = N-R-N = C = O

(X)

(X)

2-MeIM
■ ψ (catalytic converter)

+ (4X) CO ₂ C *)

Etc.

H-

(E ff

H-

H O 3 (ß t-n O

Q (D

wherein

or a mixture of these.

OO CD K)

Another typical reaction path is as follows:

—Ο

CM

2 CM

ο = .ο

U = O

Μ> Ν>

P Ul • Η

• Η M O

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

The optimal molar ratio of MDI or MDA, BPA-DA and TMA (Trimellitic Anhydride) is (1.98-2.02): 1.00: 1.00 and the catalyst accounts for 0 to 10 mol% based on the mixed anhydrides. For the production of a coating agent the resin can be in the organic solvent, e.g. NMP, NMP-DMAC, NMP-xylene or Solvesso 100 etc. be prepared, or the resin can be isolated, then in such solvents or in methylene chloride, dimethylformamide, Carbolic acid, phenol and the like. Be redissolved.

Conventional preparative methods are used, cf. the above-mentioned US Pat. No. 3,541,038, the reaction times, Indicating temperatures, etc.

In one approach, the BPA-DA and TMA are mixed with MDI (or MDA) in the presence of a mixture of N-methylpyrrolidone and the liquid organic hydrocarbon solvent Solvesso 100 at a temperature of 135 ° C for about 5 h implemented. During the first reaction time, carbon dioxide (or water) is continuously evolved. later the viscosity of the solution gradually increases and the development of the by-product (CO or water, depending on) practically stops. A suitable end point is a Gardner viscosity Z2. Such a paint can be the only one Coating on a conductor wire or used as a topcoat over a polyester or polyesterimide base coat will.

In accordance with conventional practice, further additives can be added to the agents, such as small amounts of aliphatic Amino compounds, conventional phenolic resins, titanate esters, blocked polyisocyanates and the like, without to be limited to this.

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The figure shows a sectional view of a magnet wire produced according to the invention.

In the figure, a magnet wire generally designated by the reference numeral 10 has a conductor 11, which is marked with a layer 12 of a polyether amide imide resin made from ßisphenol-A-dianhydride and trimellitic anhydride and a diisocyanate and / or a diamine is covered. Although the figure illustrates a conductor 11 of circular cross-section, it is clear that it is square or rectangular Conductors in the form of strips or foils can also be used without departing from the scope of the invention.

A suitable polyether amide imide for layer 12 can be prepared according to Examples 1-5.

example 1

One mole (520 g) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, 1 mole (192 g) of trimellitic anhydride, 2 moles (500 g) of methylene diisocyanate, 0.1 mole (8.2 g) 2-methylimidazole, 1300.9 g of N-methylpyrrolidone and 565.6 g of aromatic hydrocarbon solvent (Solvesso 100) are placed in a 5-liter round-neck flask equipped with a stirrer, thermometer, condenser and nitrogen supply line. The mixture is heated from room temperature to 135 ° C. in about 2 hours and held at 135 ° C. for 3.25 hours until a Gardner viscosity of Z2 is reached. In this reaction, the color of the solution changes from yellow, orange to a clear red and a clear ounce red during the first two hours of heating and after a reaction time of 1.5 hours at 135 ° C. , the carbon dioxide is almost completely removed. Thereafter, the viscosity of the solution increases gradually with further, very little evolution of CO ₂ . The festival-

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substance content is about 40 t in the organic solvent, and the agent can be used as a coating agent for electrical conductors. If desired, the resin can do this and the further examples by pouring the cooled reaction mixture into methanol to precipitate the polymer to be isolated.

While diphenylmethane diisocyanate is illustrated, this can be partially or completely replaced by diphenylether diisocyanate be replaced. Furthermore, the catalyst can be omitted.

The agent is further diluted with a mixture of 4 parts of NMP to 1.74 parts of Solvesso 100 and a coating agent 36 and 32% solids are also obtained.

The composition of Example 1 (40% solids) is used as the only coating on a commercial wire tower 1.024 mm (0.0403 ") copper wire applied. One 0.071-0.084 mm (2.8-3.3 mils) layer is obtained. The following properties are observed:

Speed, m / min (ft / min)

Flexibility 25+

Thermal shock -20% -30'-260 C.

Cutting temperature, C at 2000 g

Values after deposition from a 32% solids composition applied as a topcoat over polyester (ISONEL 678).

12.19
(40) 13.72
(45) 15.24
(50) 1X 1X 1X 1X * IX * 2X
IX 1X
2 X * not be
Right 378 376 not be 415 * 403 * Right

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Conductors with coatings of excellent quality are obtained.

The agent of Example 1 is applied as a top coat over an ethylene glycol tris (2-hydroxyethyl) isocyanurate terephthalate base coat (Schenectady Chemical's ISONEL 678) on a copper wire of 1.024 mm (0.04O3 ^M ). A 0.074-0.079 mm (2.9-3.1 mils) layer is obtained. A top coat made from a 40% solids composition exhibits the following properties:

Speed, 12.19 13.72

m / min (ft / min) (40) (45)

Flexibility 25+ 1X 1X

Thermal shock

-20% -30'-260 ° C 1X 1X

Intersecting

temperature, ° C at 2000 g 407 412

Excellent coated conductors are obtained. Example 2

The general procedure of Example 1 is carried out with 416 g (0.8 mol) of 2,2-bisf4- (3,4-dicarboxyphenoxy) phenyl} propane, 307.4 g (1.6 mol) of trimellitic anhydride, 606 g (2, 42 mol) of diphenylmethane diisocyanate, 9.84 g (0.12 mol) of 2-methylimidazole, 1098.8 g of N-methylpyrrolidone and 477.7 g of xylene were repeated. The viscosity after 1 hour is 89.70 cm ² / s (8970 cSt). The resin agent is blended with 293.6 g of NMP and 127.7 g of xylene. Heating is continued for half an hour (viscosity 33.90 cm ² / · or 3390 cSt). The viscosity at room temperature is 35.30 cm ² / s (3530 cSt). The mixture is again heated to 135 ° C. for 2.25 h. The final Gardner viscosity is Z3 +. The average solids content is 35.78%.

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The agent of Example 2 is the only coating in a commercial wire tower on a copper wire from 1.024 mm (0.0403 ") is applied. A 0.071-0.084 mm (2.8-3.3 rails) layer is obtained. The following Properties are observed:

Speed, 10.67

m / min (ft / min) (35)

Flexibility 25+ 2X

Thermal shock -20% -30'-26O ° C 3X

Cutting temperature /

° C at 2000 g 474

The agent of Example 2 is used as a top coat over an ethylene glycol tris (2-hydroxyethyl) isocyanate terephthalate and coating (Schenectady Chemical's ISONEL 678) is applied to 1.024 mm (0.0403 ") copper wire. It is obtained a final layer thickness of 0.074-0.081 mm (2.9-3.2 mils). The following properties are observed:

Speed, m / min (ft / min)

Flexibility 25+ thermal shock -20% -30'-260 ° C Cutting temperature

° C at 2000 g 420

Excellent coated conductors are obtained. Example 3

Following the general procedure of Example 1, a polyether amide imide is made using methylenedianiline

12.19
(40) 13.72
(45) 1X 1X 1X 1X

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(MDA) instead of diphenylmethane diisocyanate (MDI) manufactured. There are 520 g (1 mol) of 2,2-bis f4- (3,4-dicarboxyphenoxy) phenyl] propanedlanhydride, 192 grams (1 mole) of trimellitic anhydride, 400.5 grams (2.02 moles) of MDA, 1277.9 grams of N-methylpyrrolidone, and 555.6 grams of aromatic Hydrocarbon (Solvesso 100) used. 2-methylimidazole is not used. The temperature reached when heated to 180 ° C. When 70.5 ml of water is collected have been, the very viscous reaction mixture is filtered. It contains 40% pesticides. 700 g of the viscous mass are added with 97 g of N-methylpyrrolidone and 44.7 g of hydrocarbon solvent Solvesso 100 mixed with a resin compound that is suitable for covering electrical conductors.

Example 4

Following the general procedure of Example 1, a polyether amide imide was obtained prepared by adding 20 mole percent of the 2,2-bis-C4- (3,4-dicarboxyphenoxy) phenyl) propane (BPA) was replaced by benzophenone tetracarboxylic acid dianhydride (BTDA). There were 416 g (0.8 mol) of BPA, 64.45 g (0.2 mol) of BTDA, 192 g (1 mol) Trimellitic anhydride, 505 g (2.02 mol) MDI, 1278 g NMP, 556 g Solvesso 100 and 8.2 g (0.1 mol) 2-methylimidazole were used. The temperature never exceeded 135 ° C and after 3 hours a Gardner viscosity of 3 1/2 (about 1760 centistokes) was obtained. Part of this mass was blended with a solvent mixture of 80 g of NMP and 35 g of Solvesso 100 and mixed for 2 hours at room temperature. The final viscosity was Z2 according to Gardner, the solids content 36.9%, and this mass was designated "A".

The remaining part was further reacted at 135 ° C until one Gardner-Viskos! Tat was achieved by Z5. Then you blended the mixture with a solvent mixture of 200 g NMP and 87 g Solvesso 100, to a Gardner viscosity of 2 3/4 and to obtain a solids content of 33.25%. This mass was designated "B".

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Both wire lacquers were used as the only coating in a commercial Wire tower applied to 1.024 mm (0.0403 ") thick copper wire. A coating thickness was used in both cases from 0.074 to 0.079 mm (2.9-3.1 mils). The coatings had the following properties:

Wire enamel A 13.72
(45) 15.24
(50) speed
m / min (ft / min) 12.19
(40) 2X 1X Flexibility 25% + 3X Loss factor

5.0 12.3 14.7

Thermal shock (20% -

30 min at 24O ° C) 1X 2X 2X

Cut through temperature

in ⁰ C at 2000 g 403 444 374

Dielectric strength (KV) 12.1 9.9 9.2

Wire enamel B 13.72
(45) 15.24
(50) speed
m / min (ft / min) 12.19
(40) 1X 1X Flexibility 25% + 1X 12.0 13.1 Loss factor
(26O ° C) 7.5

Thermal shock (20% -

30 min at 240 ^° C.) 1X 1X 1X

Cutting temperature

in ° C at 2000 g 471 403 394

Dielectric strength (KV) 9.3 9.7 11.9

Example 5

The general procedure of Example 4 was repeated except that 20 mole percent of the 2,2-bis 4- (3,4-dicarboxyphenoxy) phenyl propane (BPA) were replaced by pyromellitic dianhydride (PMDA) instead of benzophenone tetracarboxylic acid dianhydride. 43.6 g (0.2 mol) of the PMDA were used. All other amounts were the same as in Example 4. The

1 30067/0718

Wire enamels finally obtained, which are designated "A ¹ " and "B ¹ ", had Gardner viscosities of Z 1 1/2 and Z1 and solids contents of 38.5% and 32.2%, respectively.

These wire enamels were also used in a commercial wire tower as the only coating on a copper wire of 1.024 mm (0.0403 ") Thickness applied. The coating thickness was 0.074 to 0.079 mm (2.9 to 3.1 mils). The coating had the following Characteristics:

Wire enamel A ¹

Speed 12.19 13.72 15.24

m / min (ft / min) (40) (45) (50)

Flexibility 25% + 1X 1X 1X

Loss factor
(260 ° C) 9.5 10.9 11.6

Thermal shock (20% -

30 min at 24O ° C) 1X 1X 1X

Cutting temperature

in ⁰ C at 2000 g 461 422 395

Dielectric strength (KV) 12.4 12.9 10.4

Wire enamel B ¹ 13.72
(45) 15.24
(50) speed
m / min (ft / min) 12.19
(40) 1X 1X Flexibility 25% + 1X 9.0 13.3 Loss factor
(26O ° C) 7.5 1X 1X Thermal shock (20% -
30 min at 24O ° C) 1X 436 384 Average temperature
in ⁰ C at 2000 g 463 9.9 12.2 Dielectric strength
ability (KV) 9.7

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Claims (16)

Dr. rer. near Horst Schüler PATENTANWALT 6000 Frankfurt / Main 1, 6.4.81 Kaiierstraße 41 Dr. Sb / Rg Telephone (0611) 235555 Telex ι 04-16759 mapa »d Poitschedc account: 282420-602 Franltfurt-M. Bank account! 225/0389 Deutsche Bank AG, Frankfurt / M. 8658-6OIN-629 GENERAL ELECTRIC COMPANY 1 River Road Schenectady, N.Y./U.S.A. Polyether amide imide resins and electrical conductors insulated with them 1. High molecular weight polyether amide imide resin produced by polycondensation of
(A) a combination of anhydrides with (i) 1 to 99 parts by weight of a dianhydride of the formula 130067/0710 or a mixture thereof with at least one other dianhydride of an organic tetracarboxylic acid and (ii) 99 to 1 parts by weight of a tribasic acid anhydride with
(B) 0.99 to 1.01 moles, per mole of the anhydride, a difunctional organic nitrogen compound of formula (i) O = C = N-R-N = C = O, (ii) H ₂ NR-NH ₂ or
(iii) a mixture of (i) and (ii), where R or their mixture, at a temperature of about 60 to 200 C in the presence of an inert solvent. 2. Polyether amide imide resin according to claim 1, made by Polycondensation in the presence of a catalytic amount of 2-methylimidazole. J. Polyether amide imide resin according to claim 2, wherein the amount of 2-methylimidazole trace amounts up to about 10 mol%, based on the anhydride component (A). 4. polyether amide imide resin according to claim 1, wherein at component (A) component (i) is 40 to 60 parts by weight and component (ii) is 60 to 40 parts by weight. 130067/07 1 «. Q - 5. polyether amide imide resin according to claim 1, wherein the difunctional Component (B) (i) R. 6. polyether amide imide resin according to claim 1, wherein the difunctional Component (B) (ii) R. 7. Polyätheramidimidharz according to claim 1, wherein the inert Solvents N-methylpyrrolidone, dimethylacetamide aromatic hydrocarbon or a mixture of any of the aforementioned solvents. 8. Polyether amide imide resin according to claim 1, wherein in component (A) constituent (i) the other dianhydride benzophenone tetracarboxylic dianhydride is. 9. polyether amide imide resin according to claim 1, wherein at component (A) Component (i) the other dianhydride pyromellitic dianhydride is. 10. An electrical conductor having an insulating resin coating comprising a resin according to claim 1. 11. Electrical conductor with an insulating resin coating according to Claim 5. 130067/0718 12. Electrical conductor with an insulating resin coating according to
Claim 6. 13. coating composition with one in an organic solvent dissolved polyether amide imide resin according to claim 1. 14. Coating composition according to claim 13, the organic solvent thereof among N-methylpyrrolidone, dimethylacetamide, an aromatic hydrocarbon, or a mixture of any the aforementioned solvent is selected. 15. An electrical conductor with an insulating resin coating consisting only of a resin according to claim 1. 16. An electrical conductor with an insulating resin coating consisting of a base coating of a polyester or polyesterimide and a top coat made of a resin according to claim 1. 130067 / 071ö