Source: http://www.google.com/patents/US4420535?dq=5,815,794
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Patent US4420535 - Bondable polyamide - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsSelf-bondable polyamides are prepared by reacting an aromatic diisocyanate or diamine with a mixture of terephthalic acid and an aliphatic dibasic acid having at least 6 carbon atoms. These self-bondable amides can also be used as topcoats for wires having basecoats of another polymer, e.g. a polyester,...http://www.google.com/patents/US4420535?utm_source=gb-gplus-sharePatent US4420535 - Bondable polyamideAdvanced Patent SearchPublication numberUS4420535 APublication typeGrantApplication numberUS 06/311,385Publication dateDec 13, 1983Filing dateOct 14, 1981Priority dateOct 14, 1981Fee statusPaidPublication number06311385, 311385, US 4420535 A, US 4420535A, US-A-4420535, US4420535 A, US4420535AInventorsScott D. Smith, George A. WalrathOriginal AssigneeSchenectady Chemicals, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (8), Referenced by (15), Classifications (24), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetBondable polyamideUS 4420535 AAbstract Self-bondable polyamides are prepared by reacting an aromatic diisocyanate or diamine with a mixture of terephthalic acid and an aliphatic dibasic acid having at least 6 carbon atoms. These self-bondable amides can also be used as topcoats for wires having basecoats of another polymer, e.g. a polyester, polyester-imide, or polyamideimide.
What is claimed is: 1. A self bondable insulated wire comprising a conductor and an insulating layer of a copolyamide having the recurring unit ##STR4## where AL is the divalent hydrocarbon residue of an unsubstituted aliphatic dicarboxylic acid having at least 6 carbon atoms, R is tolylene, phenylene, ##STR5## where F is O, CH.sub.2, or SO.sub.2 or is a cycloaliphatic hydrocarbon, Ar is p-phenylene, y is 35 to 80% of the recurring units and z is 65 to 20% of the recurring units.
2. A self-bondable insulated wire according to claim 1 where the conductor is copper.
3. A self-bondable insulated wire according to claim 1 where the copolyamide is directly on the bare wire.
4. A self-bondable insulated wire according to claim 1 where the copolyamide is a topcoat over an insulating basecoat.
5. A self-bondable insulated wire according to claim 4 wherein the basecoat is a polyester, polyester-imide, or an amide-imide.
6. An insulated wire according to claim 1 where y is 35 to 70% of the recurring units.
7. An insulated wire according to claim 6 where y is 40 to 70% of the recurring units.
8. An insulated wire according to claim 7 where y is 60 to 70% of the recurring units.
9. An insulated wire according to claim 8 where y is about 65% of the recurring units.
10. An insulated wire according to claim 1 where R is tolylene, 4,4'-methylene diphenylene or a mixture thereof.
11. An insulated wire according to claim 10 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
12. An insulated wire according to claim 8 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
13. An insulated wire according to claim 1 where AL is (CH.sub.2).sub.x where x is 4 to 34.
14. An insulated wire according to claim 13 where y is 35 to 70% of the recurring units.
15. An insulated wire according to claim 14 where y is 40 to 70% of the recurring units.
16. An insulated wire according to claim 15 where y is 60 to 70% of the recurring units.
17. An insulated wire according to claim 16 where y is about 65% of the recurring units.
18. An insulated wire according to claim 17 where R is tolylene, 4,4'-methylene diphenylene or a mixture thereof.
19. An insulated wire according to claim 18 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
20. An insulated wire according to claim 16 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
21. An insulated wire according to claim 13 where x is 6 to 12.
22. An insulated wire according to claim 21 where y is 35 to 70% of the recurring units.
23. An insulated wire according to claim 22 where y is 40 to 70% of the recurring units.
24. An insulated wire according to claim 23 where y is 60 to 70% of the recurring units.
25. An insulated wire according to claim 24 where y is about 65% of the recurring units.
26. An insulated wire according to claim 25 where R is tolylene, 4,4'-methylene diphenylene or a mixture thereof.
27. An insulated wire according to claim 26 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
28. An insulated wire according to claim 24 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
29. An insulated wire according to claim 21 where x is 10.
30. An insulated wire according to claim 29 where y is 35 to 70% of the recurring units.
31. An insulated wire according to claim 30 where y is 40 to 70% of the recurring units.
32. An insulated wire according to claim 31 where y is 60 to 70% of the recurring units.
33. An insulated wire according to claim 32 where y is about 65% of the recurring units.
34. An insulated wire according to claim 33 where R is tolylene, 4,4'-methylene diphenylene or a mixture thereof.
35. An insulated wire according to claim 34 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
36. An insulated wire according to claim 32 where R has the mole percent ratio of 4-methyl-m-phenylene, 2-methyl-m-phenylene, 4,4'-methylene diphenylene of 40/10/50 to 80/20/0.
37. A self-bondable insulated wire according to claim 6 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
38. A self-bondable insulated wire according to claim 7 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
39. A self-bondable insulated wire according to claim 8 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
40. A self-bondable insulated wire according to claim 9 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
41. A self-bondable insulated wire according to claim 10 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
42. A self-bondable insulated wire according to claim 11 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
43. A self-bondable insulated wire according to claim 12 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
44. A self-bondable insulated wire according to claim 13 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
45. A self-bondable insulated wire according to claim 14 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
46. A self-bondable insulated wire according to claim 15 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
47. A self-bondable insulated wire according to claim 16 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
48. A self-bondable insulated wire according to claim 17 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
49. A self-bondable insulated wire according to claim 18 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
50. A self-bondable insulated wire according to claim 19 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
51. A self-bondable insulated wire according to claim 20 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
52. A self-bondable insulated wire according to claim 21 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
53. A self-bondable insulated wire according to claim 22 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
54. A self-bondable insulated wire according to claim 23 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
55. A self-bondable insulated wire according to claim 24 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
56. A self-bondable insulated wire according to claim 25 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
57. A self-bondable insulated wire according to claim 26 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
58. A self-bondable insulated wire according to claim 27 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
59. A self-bondable insulated wire according to claim 28 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
60. A self-bondable insulated wire according to claim 29 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
61. A self-bondable insulated wire according to claim 30 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
62. A self-bondable insulated wire according to claim 31 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
63. A self-bondable insulated wire according to claim 32 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
64. A self-bondable insulted wire according to claim 33 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
65. A self-bondable insulated wire according to claim 34 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
66. A self-bondable insulated wire according to claim 35 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
67. A self-bondable insulated wire according to claim 36 comprising the copolyamide as a topcoat over an insulating basecoat which is a polyester, polyester-imide, or an amide-imide.
68. A self-bondable insulated wire according to claim 67 wherein the basecoat is a polyester of tris(2-hydroxyethyl)isocyanurate, ethylene glycol, and terephthalic acid.
69. A self-bondable insulated wire according to claim 67 wherein the basecoat is a polyester-imide made of tris(2-hydroxyethyl) isocyanurate, ethylene glycol, terephthalic acid, methylene dianiline or methylene diphenyl diisocyanate, and trimellitic anhydride.
70. A self-bondable insulated wire coating to claim 67 wherein the basecoat is a polyamide-imide made of trimellitic anhydride and methylene diphenyl diisocyanate or methylenedianiline.
71. A self-bondable insulated wire according to claim 67 wherein the basecoat is a polyester of tris(2-hydroxyethyl isocyanurate, ethylene glycol and terephthalic acid overcoated with a polyamide-imide.
72. A self-bondable insulated wire according to claim 1 which is film wrapped wire and the bondable copolyamide is a coating over the film.
73. An insulated wire according to claim 1 where the copolyamide has the recurring unit ##STR6## where AL is the divalent hydrocarbon residue of an unsubstituted aliphatic dicarboxylic acid having at least 6 carbon atoms, R is tolylene, phenylene or ##STR7## where F is O, CH.sub.2, or SO.sub.2, Ar is p-phenylene, y is 35 to 80% of the recurring units and z is 65 to 20% of the recurring units.
BACKGROUND OF THE INVENTION The present invention relates to a novel self bondable aromatic aliphatic polyamide.
An all-aromatic polyamide as made in accordance with Allard U.S. Pat. No. 3,642,715 does not exhibit self-bonding characteristics even when tested via the NEMA Bonding Test No. 57.1.1.2. at temperatures up to 260 C. The all-aliphatic polyamides as described by the work of Otis U.S. Pat. No. 4,216,263 and Kawaguchi U.S. Pat. No. 4,163,826 are thermoplastic in nature and exhibit good bonding characteristics but do not offer the excellent humidity resistance and resistance to attack by refrigerants as do the aromatic-aliphatic polyamides of the present invention.
Onder U.S. Pat. No. 4,072,665 discloses a novel copolymer of the formula ##STR1## where R is 60 to 85 percent of an aliphatic dibasic carboxylic acid with (CH.sub.2).sub.x recurring units and x being an integer of 7 to 12 inclusive, the remaining 15 to 40 percent of R being m-phenylene. The proportions are indicated to be critical in Onder. Onder also indicates on column 6, lines 43-52 that a portion of the recurring units up to 10% can have R from a different dicarboxylic acid, e.g. terephthalic acid. Onder uses his products for many things including wire coatings, column 6, lines 11-22. However, Onder makes no mention of a solution cast film which is baked and yet retains self-sealing or adhesive properties.
SUMMARY OF THE INVENTION There have now been prepared random aromatic-aliphatic copolyamides having the recurring unit ##STR2## where AL is the divalent hydrocarbon residue of an unsubstituted aliphatic dicarboxylic acid having 6 to 36 carbon atoms or more, usually AL is (CH.sub.2).sub.x where x is 4 to 34, preferably 6 to 12, most preferably 10. However, AL can be the residue of an unsaturated dicarboxylic acid, e.g. dimerized linoleic acid or dimerized oleic acid or dimerized tall oil. R is tolylene, phenyl, ##STR3## where F is O, CH.sub.2 or SO.sub.2. Less preferably all or a part of R can be cycloaliphatic, e.g. cyclohexylene or methylenedicyclohexyl, Ar is p-phenylene, y is 35 to 80% of the recurring units and z is 65 to 20% of the recurring units. Usually y is 40 to 70% of the recurring units and preferably y is about 60 to 70%, most preferably 65% of the recurring units. If y is above 70% there is a tendency to gel on standing.
The copolyamides can be prepared in conventional manner by reacting a mixture of the dicarboxylic acids, e.g. dodecanedioic acid and terephthalic acid with a diisocyanate, e.g. toluene diisocyanate or methylene diphenyldiisocyanate, or with the corresponding diamine, e.g. toluene diamine, 4,4'-methylene diphenyl diamine (methylene dianiline), oxydianiline, phenylene diamine, diaminodiphenyl sulfone, or a mixture of such diisocyanates or of such diamines. As indicated there can also be employed a minor amount of 4,4'-methylene diphenyl diamine or cyclohexyl diamine. In reacting with the diamine rather than the diisocyanate it is of course possible to employ other acylating agents than the acid, e.g. there can be used the acyl halides, e.g. the dichloride or dibromide of dodecandioic acid or the lower alkyl esters, e.g. dimethyl dodecandioate, diethyl dodecandioate, and dibutyl dodecanedioate.
It was previously pointed out that the copolyamides of the present invention are superior, in humidity resistance and resistance to attack by refrigerants, to the products of Otis U.S. Pat. No. 4,216,263. Thus when a sample of a polyamide as described in Otis is subjected to a 100 percent humidity at 70 370,000 megohms. After aging one week, the megohm resistance was about 280,000 megohms; after two weeks, the resistance had dropped to about 160,000 megohms. The aromatic-aliphatic polyamide of the present invention (based on Mondur TD-80, 4,4-methylene diphenylenediisocyanate, terephthalic acid and dodecanedioic acid), when submitted to this test, gave the following results:
______________________________________       After          AfterInitial     One Week       Two Weeks______________________________________422,000 megohms       900,000 megohms                      820,000 megohms______________________________________
The dielectrics of the all-aliphatic polyamides of Otis were reduced by 50 percent after two weeks at 100 percent relative humidity and 70 The aromatic-aliphatic polyamides of this invention, however, did not significantly change after the two-week aging. The all-aliphatic nylons are true thermoplastics, unlike the aromatic-aliphatic polyamides of the invention which, when initially bonded at 200 strength at 200 invention, when coated over a polyester of the type described by Meyer in U.S. Pat. Nos. 3,201,276 and 3,211,585, will upgrade the base polyester to a NEMA Class 155 entire disclosure of the Meyer patents are hereby incorporated by reference and relied upon. When coated over other wire enamels or wire enamel systems, the inherent properties of the coated wire are not adversely effected. The aliphatic-aromatic polyamides of this invention will self-bond at temperatures of 170 accordance with NEMA Test Specification 57.1.1.2 with resulting bond strengths of greater than seven pounds when broken at 180
(1) The wire coating is bondable at 200 bond strength at 180 above the apparent glass transition temperature of the aromatic-aliphatic polyamide, the apparent glass transition temperature increases, thus giving some thermoset properties to the coating.
(3) The aromatic-aliphatic polyamide, when coated over ISONEL 200, yields a Class 155 shock, displays Class 180
When coated over ISOMID, excellent properties as a Class 180 magnet wire are observed.
(4) The aromatic-aliphatic polyamide coated over ISONEL 200 pases the A. O. Smith Freon Blister Test; conventional Nylon 6,6 coated over ISONEL 200 fails this test.
As indicated above the enamels of the invention exhibit good bond strengths when coated over ISONEL 200 and ISOMID wire enamel. Thus when bonded at 200 lbs. and even up to 7.4 pounds at 180 wire properties by application of the bond coat.
1. a glycerine or other aliphatic polyhydric alcohol polyester, e.g. glycerineethylene glycol terephthalate polymer as in Precopio U.S. Pat. No. 2,936,296,
2. tris(2-hydroxyethyl)isocyanurate polyester, e.g. tris(2-hydroxyethyl) isocyanurate(THEIC)ethylene glycol-terephthalate polymer as in Meyer U.S. Pat. No. 3,342,780,
3. a polyester coated with an amide-imide polymer, e.g. the polyester of Precopio or Meyer 3,342,780 coated with an amide-imide polymer as shown in Koerner U.S. Pat. No. 3,022,200 and Standard Oil British Pat. No. 1,056,564.
5. amide-imide coated polyester-imide as in the Koerner and Standard Oil patents,
9. conventional Formvar (polyvinyl formal), epoxy (e.g. bisphenol A-epichlorohydrin), urethane, and nylon top coated urethane. The entire disclosures of the Meyer Pat. No. 3,342,780, Precopio, Koerner, Standard Oil, Keating, Meyer U.S. Pat. No. 3,426,098, and the Edwards patents are hereby incorporated by reference and relied upon.
1. Kapton--a polyimide film of DuPont as in the Edwards patents
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of bond strength vs. percent of aliphatic dibasic acid (dodecanedioic acid); and
______________________________________                     LoadRaw Materials             in Grams______________________________________(1)   N--methyl-2-pyrrolidone 4168(2)   Toluene diisocyanate (Mondur TD-80)*                         1033(3)   4,4' Methylene diphenyldiisocyanate                          637(4)   Terephthalic Acid        494(5)   Dodecanedioic Acid      1267(6)   Xylene                  2243(7)   N--methyl-2-pyrrolidone 1050______________________________________ *Mondur TD80 is a 80/20 blend of 4methyl-m-phenylene diisocyanate and 2methyl-m-phenylene diisocyanate and is commercially available from Mobay Chemical Company, Pittsburgh, Pennsylvania.
Parts one through three charged at room temperature into a 12-liter, round-bottom reaction flask, equipped with an agitator, a thermometer, an inert gas purge, and a water-cooled condenser fitted with a flexible tube which was immersed in a flask containing a mixture of water and denatured ethyl alcohol. (The reaction by-products carried through the condenser by the carbon dioxide and nitrogen are trapped in the water-alcohol solution). Parts four and five were added at room temperature with agitation and a blanket of nitrogen was applied over the reaction. The temperature was raised slowly by use of an electric heating mantel to approximately 75 external heat was then reduced and the temperature of the batch was allowed to rise over a four-hour time period to approximately 170 C. At about 80 four-hour hold at 170 to cool slowly to room temperature over night. The next morning the reaction mixture was sampled and a 60 percent solution in N-methyl-2-pyrrolidone was determined to have a viscosity at 25 on the Gardner-Holdt scale of W 1/2. Parts six and seven were then added. The final viscosity of the solution at 25 Gardner-Holdt scale, or 2,500 centipoises as measured by a Brookfield RVT Viscometer.
The percent non-volatiles of the solution were determined to be 27 percent by baking a two-gram sample for two hours at 200 gravity of the solution was determined to be 1.025 at 25 solution was then used to overcoat a commercially available polyester (ISONEL 200)**. The test properties were as shown in Table One. It was also coated over a commercially available polyester-imide (ISOMID)*** and tested as shown in Table One.
The temperature of coating the wires in all of the examples was 370
EXAMPLE 2 ______________________________________                     LoadRaw Materials             in Grams______________________________________(1)   N--methyl-2-pyrrolidone 4168(2)   Toluene diisocyanate (Mondur TD-80)                         1033(3)   4,4-Methylene diphenyldiisocyanate                          637(4)   Terephthalic Acid        494(5)   Dodecanedioic Acid      1267(6)   Xylene                  1982(7)   N--methyl-2-pyrrolidone  910______________________________________
The reaction was carried out much in the same fashion as described in example one, with the exception of the over night cooling step. The reaction medium was sampled after a three-hour hold at 165 180 viscosity of V 1/2 at 25 was then reduced with six and seven to a final viscosity of Y 1/4 at 25 determined as described in Example One.
The material was then coated over a polyester (ISONEL 200), a polyester imide (ISOMID), a polyester overcoated with a polyamide-imide, (ISONEL 200 overcoated with trimellitic anhydride-methylene dianiline polymer), a polyamide-imide (trimellitic anhydride-methylene dianiline polymer) wire coating and as a monolithic enamel. The results of the testing on the coated conductors are as shown in Table one.
______________________________________Example     3       4      5     6    7     8______________________________________Reactants    Batch weight______________________________________(1) N--methyl-2-           644     611  623   633  655   664    pyrrolidone(2) Toluene     159     159  159   159  159   159    diisocyanate(3) 4,4'-methylene            98      98   98    98   98    98    diphenyl    diisocyanate(4) Terephthalic            76     141  118    97   54    32    Acid(5) Dodecanedioic           194     104  135   164  224   254    Acid(6) Xylene      327     382  346   331  335   366(7) N--methyl-2-           119     140  241   140  126   210    pyrrolidone    Gardner-Holdt           Y3/4    X1/2 Y+    Z+   Y1/4  Y    Viscosity @ 25    Percent Non-           27.8    24.9 25.2  26.8 23.8  25.7    Volatiles    Determined    2 gm., 2 hr.,    200______________________________________
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       600(2)  Toluene diisocyanate   171(3)  4,4' Methylene diphenyldiisocyanate                       105(4)  Terephthalic Acid       81(5)  Adipic Acid            133(6)  Xylene                 257Gardner-Holdt Viscosity (25                       W1/2Determined Percent Non-Volatiles                       32.4(2 grams, 2 hours, 200______________________________________
EXAMPLE 10 This example describes the use of an aliphatic diacid as described in the disclosure where X equals seven.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       622(2)  Toluene diisocyanate   165(3)  4,4' Methylene diphenyl diisocyanate                       161(4)  Terephthalic Acid       78(5)  Azelaic Acid           165(6)  N--methyl-2-pyrrolidone                       198(7)  Xylene                 412Gardner-Holdt Viscosity (@ 25                       X3/4Determined percent Non-Volatiles                       22.9(2 grams, 2 hours, 200______________________________________
This example was prepared in the same fashion as Example One. This enamel was applied on 18-AWG copper wire over ISOMID. The electrical test properties are as shown in Table one.
EXAMPLE 11 This example demonstrates the use of a diabasic acid where X equals eight.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       560(2)  Toluene diisocyanate   145(3)  4,4' Methylene diphenyl diisocyanate                        89(4)  Terephthalic Acid       69(5)  Sebacic Acid           156(6)  N--methyl-2-pyrrolidone                       207(7)  Xylene                 411Gardner-Holdt Viscosity (@ 25                       X1/2Determined percent Non-Volatiles                       24.2(2 grams, 2 hours, 200______________________________________
This example was prepared in accordance with the procedure described in Example One. The test results obtained when this enamel was applied over 18-AWG copper wire coated with ISOMID are shown in Table One.
EXAMPLE 12 This example indicates that the allowable number of methylene groups between the two carboxyl groups of the aliphatic diacid may not have an upper limit.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       585(2)  Toluene diisocyanate    94(3)  4,4' methylene diphenyl diisocyanate                        68(4)  Terephthalic Acid       45(5)  Empol 1010*            283(6)  N--methyl-2-pyrrolidone                       140(7)  Xylene                 310Gardner-Holdt Viscosity (@ 25                       Y1/4Determined percent Non-Volatiles                       29.4(2 grams, 2 hours, 200______________________________________ *Empol 1010 is a C.sub.36 dimerized fatty acid available from Emery Industries, Inc., Cincinnati, Ohio.
EXAMPLE 13 This working example demonstrates the use of a cyclic aliphatic diisocyanate to replace a portion of the aromatic diisocyanate.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       600(2)  Toluene diisocyanate   146(3)  Desmondur W*            97(4)  Dodecanedioic Acid     179(5)  Terephthalic Acid       76(6)  N--methyl-2-pyrrolidone                       155(7)  Xylene                 323Gardner-Holdt Viscosity (@ 25                       Z1/4Determined Percent Non-Volatiles                       27.5(2 grams, 2 hours, 200______________________________________ *Desmondur W is a cycloaliphatic diisocyanate available from Mobay Chemical Company, Pittsburgh, Pennsylvania.
EXAMPLE 14 This example shows the use of all toluene diisocyanate to make an acceptable bond coat.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       606(2)  Toluene diisocyanate   226(3)  Dodecanedioic Acid     194(4)  Terephthalic Acid       76(5)  N--methyl-2-pyrrolidone                       210(6)  Xylene                 350Gardner-Holdt Viscosity (@ 25                       X1/4Determined percent Non-Volatiles                       27.2(2 grams, 2 hours, 200______________________________________
This example was prepared using the procedure described in Example One. However, as indicated no 4,4'-methylene diphenyl diisocyanate was employed. When coated over 18-AWG ISOMID coated wire, the bond coat gave the properties as shown in Table One.
EXAMPLE 15 This example defines the lower preferred limit of toluene diisocyanate in the bond coat.
______________________________________Reactants               Batch Weight______________________________________(1)  N--methyl-2-pyrrolidone                       615(2)  Toluene diisocyanate   150(3)  4,4' Methylene diphenyl diisocyanate                       179(4)  Dodecanedioic Acid      70(5)  Terephthalic Acid      140(6)  N--methyl-2-pyrrolidone                        35(7)  Xylene                 280Gardner-Holdt Viscosity (@ 25                       YDetermined Percent Non-Volatiles                       31.4(2 grams, 2 hours, 220______________________________________
This enamel was also cooked as described in Example One. It was then applied to ISOMID coated 18-AWG copper wire giving the test results as reported in Table One.
COMPARATIVE EXAMPLE 2 A solution of Nylon 11 was prepared in accordance with U.S. Pat. No. 4,216,263 by Otis. The viscosity of this solution was approximately Z5 1/2 on the Gardner-Holdt Scale at 25 the solution was determined to be 16.1 percent by baking a two-gram sample for two hours at 200 polyester-imide of the ISOMID type on AWG-24 copper wire. The electrical and bonding test results are shown in Table One.
COMPARATIVE EXAMPLE 3 A solution of Nylon 11 was prepared in accordance with U.S. Pat. No. 4,216,263 by Otis. The viscosity of the solution was approximately Z2 3/4 on the Gardner-Holdt Scale at 25 non-volatiles determined as in Example One. This enamel was coated over a polyesterimide wire coating, namely ISOMID on 18-AWG copper wire. The test results are shown on Table One. A comparison of the bond strength of this example to the preferred composition of this disclosure as described by Example One is shown on Graph Number Two.
COMPARATIVE EXAMPLE 4 A solution of Nylon 11 was prepared in accordance with U.S. Pat. No. 4,216,263 Otis. The viscosity of this solution was approximately Z3 1/2 on the Gardner-Holdt Scale at 25 determined as in Example One were 16.8 percent. This enamel was coated over a polyester wire coating, namely ISONEL 200 on 18-AWG copper wire. The electrical and bonding test results are as shown in Table One.
______________________________________Abbreviation Key for Table 1______________________________________F.O.M.      Figure of MeritHrs.        HoursFPM         Feet per MinuteVPM         Volts per MilBase Coat:PE          Polyester of the ISONEL PEI         Polyester-imide of the ISOMID PAI         Aromatic polyamide-imidePAI/PE      Polyamide imide based upon       4,4' methylene diphenyl diisocyanate       and trimellitic anhydride over-       coated over a polyester of the       ISONEL None        Indicates the bond coat was applied       in eight passes to obtain a three-       mil buildBuild       total increase in the wire diameter       as a result of the coating.Wire Size   All AWG sizesSpeed       The rate the wire traveled as it       was coated in multiple passes and baked       in a 15-foot, gas-fired oven. -Appearance:G           Indicates good or smooth surface.VSW         Indicates smooth surface with a       very slight wave.SW          Indicates minor flaws in the coating       surfaceHeavy Grain Indicates a rough surface without       blistersRough       Is an indication the coating is       unacceptable as it may contain       blisters, or a very heavy grain,       or an extreme wave.(+)         Indicates slightly better than given       rating(-)         Indicates slightly worse than given       ratingSnap        Measured in accordance with NEMA       Standards Publication Part 3,       paragraph 3.1.1.Mandrel After Snap       Smallest mandrel around which wire       which has been "snapped" as above can       be wound without exhibiting surface       cracks.Abrasion    Measured in accordance with NEMAUnilateral  Standard Publication Part 3,Scrape      paragraph 59.1.1.Windability 1500 volts are passed through a       six foot long wire sample which is       wrapped around a specified mandrel.       The mandrel moves along the wire       at fixed rate elongating and       abrading the wire. Failure is       described when three shorts occur       along the surface of the sample.Cut Through Measured in accordance with NEMA       Standards Publication Part 3,       paragraph 50.1.1.2.Heat Shock  Tested in accordance with NEMA       Standards Publication, Part 3,       paragraph 4.1.1.Burn Out    Tested in accordance with NEMA       Standards Publication, Part 3,       paragraph 53.1.1.4. F.O.M. is       Figure of Merit calculated as       described in NEMA Standards       Publication, Part 3, paragraph       53.1.1.3.A. O. Smith A five-foot sample of wire isFreon Blister       wound into a coil which producesTest        four to six percent stretch, baked for       two hours at 150       to room temperature. The samples       are then placed in a freon bomb       charged with Freon 22        pressure in the bomb is brought up       to 600 pounds per square inch by       heating and held six hours. After       the six-hour hold, the pressure is       immediately released and coils are       placed in an oven at 150       four hours. The coils are then       removed from the oven and checked       for blistering. One large blister,       or two medium, or five small blister       constitutes a failure. The wire is       then wrapped around a five times       mandrel for ten turns and checked       for cracks or peeling. If the       coating cracks or peels, it is       a failure. Finally, the wire is       made into a twisted pair and       dielectrics are determined in       accordance with NEMA Standards       Publication, Part 3, paragraph       7.1.1.3.Dielectrics:Dry         Determined in accordance with NEMA       Standards Publication, Part 3,       paragraph 7.1.1.3.Wet         After soaking in water for 24 hours,       the samples are tested as described       above.Bonding     Determined following the procedure       described in NEMA Standards Publication       Part 3, paragraph 57.1.1.2. at the       temperature stated under Bonding       Temperature.Dissipation Factor       Tested in accordance with NEMA       Standards Publication, Part 3,       Paragraph 9.1.1.2.Heat Aging  Number of hours up to 168 (at 180at 180       required for a sample to be baked       to fail a post winding of around a       one times mandrel.______________________________________
TABLE 1  Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple 1 2 3 4 5 6 7 8    PAI/ Basecoat PE PEI PE PEI PEI PEI PE PAI None None PEI PEI PEI P EI PEI PEI Build (mils) bondcoat/basecoat 1.0/2.0 1.0/2.0 1.0/2.1 0.9/1.9 1.0/2.0 1.0/2.0 1.1/ 1.0/2.0   1.0/2.0 1.0/2.0 1.0/2.0 1.0/2.0 1.0/2.0 1.0/2.1        0.7/2.3 Wire Size (AWG) 18 18 18 24 24 24 18 18 18 18 18 18 18 18 18 18 Wire Speed (fpm) 50 50 50 100 120 130 50 50 40 50 50 50 50 50 50 50 Appearance, bondcoat/basecoat VSW/ VSW/ VSW/ VSW/ VSW/ VSW-/ VSW/ VSW/   VSW/ VSW/ VSW/ VSW/ VSW/ VSW-/  VSW VSW VSW+ VSW VSW VSW VSW/ VSW   VSW VSW VSW VSW VSW VSW        VSW MECHANICAL PROPERTIES Mandrel, before snap 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X Snap (OK or Fail) OK OK OK OK OK OK OK OK OK OK OK OK OK OK OK OK Mandrel, after snap 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X Abrasion (gms.) 2000+ 2000+ 1933 1000+ 1000+ 1000+ 2000+ 1816 2000+ 2000+ 1883 1866 1800 1950 2000+ 1933 Windability 25 20     17 14 Helical Coil Bonding; Bond Temp.,  200 200 200 200 200 200 200 Bond Str., lbs. @ 25 6.6 9.7 9.2 19.80 18.65  --  -- 21.7 0.4 1.0 2.9 16.2 12.5 150 C. 6.40 10.88  4.9 5.2 5.6  --  --  --  -- 10.9 0.0 1.0 2.0 8.0 5.2 180 4.7 1.5 200 0.0 1.4 2.2 1.1 THERMAL PROPERTIES Cut Through Temp.,  355 342 318 316 385 325 280 260 Heat Shock, 1X 50 80 70 80 60 70 80 70 80 80 (1/2 Hr. at test, 2X 80 90 80 90 80 80 90 90 90 90 temp., 20%, 3X 100 100 100 100 100 100 100 100 100 100 pre-stretch), 4X 100 100 100 100 100 100 100 100 100 100 Heat Shock Test Temp.,  200 200 200 260 260 260 260 Burnout (F.O.M.) 5.4 6.67      8.51 2.46 1.13 Heat Aging (hrs.) 168-OK ELECTRICAL PROPERTIES Dielectric Strength, dry 14.6 15.6     15.9 11.5 (vpm), wet 11.1 11.1     14.5 11.2 Dissipatio n Factor 11.5 4.92  3.34 3.16 5.45 28.72 22.26 453.0 1874.0 CHEMICAL PROPERTIES A. O. Smith Freon Test; appearance/flexibility Fail OK/OK dielectric after test (VPM)   Compara- Compara- Compara- Compara- tive tive tive tive Exam- Exam- Exam- Exam- Exam- Exam- Exam-  Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple ple ple 9 10 11 12 13 14 15 1 2 3 4   Basecoat PEI PEI PEI PEI PEI PEI PEI PE PEI PEI PEI PE Build (mils) bondcoat/basecoat 1.0/2.0 1.0/2.0 1.0/2.0 1.0/2.1 1.0/2.1 1.0/2.1 1.0/2.1 1.0/2.0 1.0/2.0 1.0/2.0 1.0/2.1 1.0/2.0 Wire Size (AWG) 18 18 18 18 18 18 18 18 18 24 18 18 Wire Speed (fpm) 50 50 50 50 50 50 50 50 50 90 50 50 Appearance, bondcoat/basecoat Wavy/ VSW/ VSW/ VSW-/ SW/ Hvy. Grain/ Hvy. Grain/ VSW-/ VSW-/ SW/ VSW-/ SW/  VSW VSW VSW+ VSW VSW VSW VSW VSW VSW VSW VSW VSW MECHANICAL PROPERTIES Mandrel, before snap  1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X Snap (OK or Fail) Fail OK OK OK OK OK OK OK OK OK OK OK Mandrel, after snap  -- 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X 1X Abrasion (gms.)  -- 1833 1808 1708 1950 2000+ 2000+ 2000+  1916 1000+ 1750 1608 Windability Helical Coil Bonding; Bond Temp.,  200 200 200 200 200 200 200 200 200 200 200 Bond Str., lbs. @ 25 C.  --  --  --  --  --  --  -- 0.0 0.0 4.7 22.4 21.7 150 --  --  --  --  --  --  --  -- 0.8 11.0 180 6.3 5.5 3.6 0.0 0.0 0.2 2.8 200 --  --  -- 0.4 THERMAL PROPERTIES Cut Through Temp.,  280 285 334 315 395 Heat Shock, 1X        80 90 50 90 20 (1/2Hr. at test, 2X        90 100 70 100 30 Temp., 20%, 3X        100 100 80 100 40 pre-stretch), 4X        100 100 100 100 40 Heat Shock Test Temp.,  5.46 Heat Aging (hrs.) ELECTRICAL PROPERTIES Dielectric Strength, dry   11.1 (vpm), wet Dissipation Factor CHEMICAL PROPERTIES A. O. Smith Freon Test; appearance/flexibility   OK/OK dielectric after test (VPM)
Examples 1 and 3 which are within the present invention both employ a 65/35 molar mixture of dodecanedioic acid and terephthalic acid. The bond strength of Comparative Example 5, Comparative Example 6, Example 1, and Example 3 were tested by coating their resultant enamel solutions on top of ISOMID-coated wire at 50 ft./min., followed by bonding at 200 C. for 20 minutes under 1-kg load. The results were as set forth in Table 2:
TABLE 2______________________________________Test              Bond Strength,Specimen          Lbs. at 180______________________________________Comparative Example 5             4.75Comparative Example 6             3.2Example 1         5.9Example 3         6.2______________________________________
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