SU1050566A3 - Process for preparing polyamidoimides - Google Patents

Abstract

THE METHOD OF OBTAINING POLYAMIDOIMIDES by the reaction of trimellitic anhydride and an aromatic or aliphatic diamine when ripe in an organic solvent medium followed by the interaction of the obtained product with a diisocyanate. in order to improve the processability of the process, the molar ratio of trimellitic anhydride. acid, diamine and diisocyanate is 1:

Description

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The invention relates to the production of high molecular weight polymers that can be used as enamels, which protect against conductive metallic wires, such as copper. Polymers are also used to prepare various heat-resistant insulating films, coatings and cast products. The starting polymers may have a low molecular weight; they are not combined into high molecular weight polymers, since they are obtained as a result of an unbalance reaction with a residual excess of carboxylic acid groups. A characteristic advantage of this new reaction is that the off-balance process is carried out with great care in such a way as to maintain the molar ratio in a definite range. The closest to the proposed technical essence and the achieved result is a method of producing polyamidoimides by the reaction of trimellitic anhydride and an aromatic or aliphatic diamine at a molar ratio of 2: 1 while heating in an organic solvent medium followed by the interaction of the resulting product with the L1 J diisocyanate, polyamide imides are produced by ordered structures and high molecular weight, in connection with which they are difficult to process. For formation operations where it is necessary to melt or plasticize polymers, high melting points require energy consumption. The purpose of the invention is to improve the process technology, increase its efficiency. This goal is achieved by the fact that when polyamidoimides are obtained by reacting trimellitic anhydride and an aromatic or aliphatic diamine when heated in an organic solvent followed by reacting the resulting product with diisocyanates, the molar ratio of trimellitic anhydride, diamine and diisocyanate is 1: (0 , 9): (Oh, 1 0.75). 66 The reaction between trimellitic anhydride and diamine is carried out at a temperature of 210-250 ° C, preferably at 220-230 ° C, at atmospheric pressure. To the resulting product, diisocyanate is added at a temperature ranging from room temperature to 125 ° G. The reaction temperature can be 120 -155 ° C. It is best if the reaction starts at room temperature and ends at about 135 ° C. The reaction to form the starting polyamide imide polymers is usually carried out in the same solvent that is used to prepare enamels for. wires. This uses predominantly nitrogen-containing or sulfur oxide alkyl organic polar solvents or substituted phenols. The following solvents are used: M-methylpyrrolidone, technical creao v, p-cresol, m-cresol, dimethyl sulfoxide, M-methyl caprolactam, dimethyl sulfone cyclohexane and phenol. N-methylpyrrolidone is considered the best solvent. At the stage of completion of the formation of the starting polymers, diluents may be added. Representative diluents are M-methylpyrrolidone, dimethylacetamide (DMAC, DMAS), dimethylformamide or mixtures of the listed components with strands of aromatic hydrocarbons, such as Soiveso 100 and ISO, xylenes and toluene. Yes. Aliphatic diamines are hexamethylene, ethylenediamine, pentamethylenediamine. and dodecamethylenediamine. Aromatic diamines include methylene-di- (aniline), k-diaminodiphenylmethane, hydroxy-di- (aniline),, 4-diaminodiphenyl ether, benzidine, m-phenylenediamine, p-phenylenediamine, 2, -, and 2,6-toluene diamine, (and . of their mixture), 3,3-diaminodiphenyl, 1,4-diaminonaphthalene, -diaminodiphenyl ketone, k, k-diaminodiphenylsulfone, di - (- aminophenyl) -1,1 - ethylene. Aromatic diisocyanates on | methylene-di- (-phenyl isocyanate), 1,5-naphthalene diisocyanate. m-phenyldiisocyanate, hydroxy-bis- (h-finalisocyanate), mesitylene diisocyanate. durylene diisocyanate, toluene diisocyanate, it, C-dirksitoluene di-oxiene, axi, di-oxitolyl diisocyan, methoxy-1, 3 phenylene diisocyanate, A-chloro-1, 3 fe; nylene diisocyanate, 3.3-dimethyl, a-chloro-1, 3 fe; -diisocyanate, k -diisocyanatodiphenylsulfone, AlkylenodisoCyanates include hexamethylene diisocyanate, ethylene diisocyanate, dodecamethylene diisocyanate, and pentamethylene diisocyanate. Polyamidoimides are used as enamels for wires in stretch. Systems of the listed solvents. They are used for electrical conductors such as copper, silver, aluminum or stainless steel by conventional means, for example, by free dipping or application. The speed of the wire may be 6–12.2 m / s with a maximum temperature of 205–82 ° C, and in this the final temperature is usually 2 ° C. The polyamide-imide enamel applied to the wire may have a thickness of 0.033-0.122 cm, preferably 0.007-0.009 cm. If this is done, the wire is passed through one or more times until the desired thickness is obtained. By coating is meant the ubiquitous increase in the diameter over a hollow wire. Soluble popyamidoimida can be turned into hard, non-meltable and insoluble resin. With great advantages, this is used in the formation of films, coatings, impregnated fibers and cast products. For example, a solution of a substance that is polyamidoimide is applied to a wire or other surface and heated to a temperature of 200-U20 ° C, preferably up to 300 ° Or ° C (for coatings for PR9VODO), for a time sufficient to evaporate the solvents and form insoluble polyamidoimide. About 1 minute is usually sufficient while about 2 minutes is required for this. Thus, coatings such as surfaces, sheets, etc., made from various metals, such as copper, steel, aluminum, copper, or various alloys, can be made. In this way, products are produced that have multiple layers joined together with polyamide on the material with which is carried out in contact with polyamidoimide. The layering is carried out by placing the treatment object in polyamidoimide dissolved in an organic solvent, and then keeping each layer at an elevated temperature. After holding one layer of polyamidoimide, the subject of the treatment is to be put back into the polymer solution, and the process continues. Glass or asbestos fibers can be coated by applying polyamidoimide in solution to these Materials and then holding them at a temperature. Polyamidoimides have a viscosity of 0.3 dl / g (in DIAC, with). The properties of polyamidoimide obtained in the form of a film show that it has a tensile strength at 25 C, kg / cm and an elongation at 10-25%, except In addition, excellent electrical performance and heat resistance. PRI me R 1. 8 vessel equipped with a nitrogen purge, a stirrer, a condenser with a trap, placed 1059.0 parts of trimellitic anhydride, 717.0 parts of N-methylpyrrolidone and 68.0 parts of pseudocumene. The mixture was warmed to tOO-110 ° C, 87.0 parts of methylene bis (aniline) were added at intervals of 5-10 minutes. After a three-hour period, peraturu brought up to 225C. The water layer is continuously withdrawn from the trap. The solution is kept at 225 for 5 hours, then the heating is removed in minutes. 0 minutes is added thereto. N-methylpyrrolidone and the solution is allowed to cool. When adding 286.0 parts of isonate 12 $ mf (Isonate 125 mf) was added and the mixture was stirred for 30 minutes. The solution is heated before and kept for 1 hour, then heated to 135 and again maintained for 1 hour. After a 2-hour period, an additional isonate 125 mf is added until then. until Gardiner Holt viscosity (Gardner-HoVt) reaches 2-6-7. At 25 ° C viscosity, according to Brookfield (Brookfild) 238 P with 32.5% of solids. a.) 333.3 parts of xylene are added to the tOOO of this solution;

obtaining a solution at 23.5% in 32. The solution is applied to 18-gauge copper-wire. Test data are given in the table.

b. B, part of the solution prepared according to Example 1, 18.3 parts of xylene, 9.0 parts of TiO, 3.0 hours of yellow nickel titanate and 1 hour, 8 parts of N-methylpyrrolidone are added. All materials overnight are mixed in a ball mill. A sample of the mixture was applied to a Bonderite 37 steel panel (Bpnderite 37) and held for 15 minutes at. Test data: Aged film thickness 0 mm

Pencil hardness Hardness of a wedge 27 Adhesion at shuffling,% 100 Flexion on a conical mandrel, 1/8,% of shelf life 100 Shock viscosity at direct impact, cm / kg 2.950 Shock viscosity at return impact, cm / kg 2,950 o

c} To 10 parts of the solution prepared according to Example 1, 3.3 hours of N-methylpyrrolidone are added and the solution is injected into distilled water. Lenka is maintained at a temperature for 5 minutes, as a result of which we have produced strands that can be bound.

d) Use as a binder ..

Small portions of the product prepared according to Example 1 are applied to cold rolled steel (Bonderite P.-100 Bonderite R-100 treatment) and kept under vacuum for 8 hours and 16 hours (to check the T-peeling during adhesion) in the same way. hot rolled steel (1, 25 mm), purified with chloroethane, and made in such a way for shear tests. T-shelling poi adhesion K2b kg / cm; a shift of 112.5 kg / cm.

Test specimens prepared using 15 second activation 1, k kg / cm at

 on protective thermal coating Sentinel.

PRI mme R 2. In a vessel equipped with a nitrogen purge, a stirrer, a condenser with a trap, 38.2 parts of trimellitic anhydride, 183.8 parts of m-phenylenediamine, .260.0 parts of m-methylpyrrolide, and Zb, 6 hours pseudocumene. The mixture is heated to 220s

during the hour period and kept at this temperature for 5 hours. At the same time, the water layer is constantly removed from the trap. After a 5-hour exposure at 220 ° C through

15 minutes was added 2000 parts of dimethylacetamide, after which the solution was allowed to cool. At 25 s, 65.0 parts of m-phenylene diisocyanate was added, after which the mixture was stirred for 30 minutes. The temperature was raised to 135 ° C for 1.5 hours. After 45 minutes at this temperature, 15.0 parts of m-phenylenediisocyanate was added and heating continued for 30 minutes.

With a Brookfield viscosity of 62 P and a 2.3% solids content. The product has an intrinsic viscosity of 0.38 dl / g (DMAC, at 25 s ;. a) 500 hours of the prepared solution is precipitated in 1500 hours of distilled water in an industrial mixer (War ing-Blender). The product is filtered, washed, dried and pressed. Wherein

use a form 8.5 inches (21.6 cm) in diameter and 1.75 inches (", 44 cm) thick. The nest form has inches (.14 cm) in diameter. 3 form is filled with 78 parts of the polymer and heated.

to (about 326 ° C. The sample is pressed according to the following schedule: Time, min. Pressure, TN 40O (contact pressure)

22.5

25

110I

425

1, 50.

525

Then the form is cooled to 282 C and the product is removed.

Tensile strength 782 kg / cm. Elongation 4.0%.

Approx. In a vessel equipped according to examples 1 and 2, placed 192, 11h. trimellitic anhydride, 100.0 parts of hexamethylenediamine, 130.0 parts of N-methylpyrrolidone and 3b, 6 hours

pseudocumene. The mixture is heated for up to an hour and kept at this temperature for 5 hours. At the same time, the aqueous layer is continuously removed from the trap. Then heating is termed and after 20 min, 800 parts of N-methylpyrrolidone are added. The solution is then allowed to cool. 25 ° C. Was added PM (Multrafhan M), after which the mixture was stirred for 30 minutes, the temperature was raised to 135 ° C. After an hour, 18.0 parts of multirate on M (Multrathan M) are added and heating is continued for 30 minutes. The resulting product has a Brookfield viscosity (ori)} it3 The content of solid inclusions is 26.9%. A hard flexible film can be prepared by applying a portion of the solution to the glass and then holding at 315 for -3 min.

Test wire coatings.

In this example, the enamel is deposited on a wire in a 15-foot two-zone, vertical with forced air circulation furnace for enameling the General. Electric To obtain insulation of sufficient thickness, six layers of coating are applied. The thickness of the wire (copper) 18 AUG (l8 caliber according to American wire gauge corresponds to 1.02). Magnetic wire is coated in such a way tested according to ASTH D-1676 (ASTM D-T676) American Standard for film thickness, plasticity, adhesion strength and resistance to scaling.

The heat resistance or burnout time is determined from the overload test system given in HEMA MJVIOOO.

Plasticity and adhesion tested according to ASTM D-1976. To verify the ability of automatic winding and normal handling during production, the wire must go through a full crimping cycle. This means that it must be capable of fast stretching without RIPPING8, orienting this, the stretched areas of the coating on the wire must remain intact, i.e. they should not have cracks (brittleness), the coating should not have a tubular effect or should not separate from the base (poor adhesion). In addition to testing for adhesion during stretching, it is desirable not to stretch a portion of the wire, either stretched or

20 of its original length (20% Terk jerk), either. up to the point of rupture (full stretching) is capable of winding on the smallest possible mandrel. In this case, mandrels of 1-3 and t, d are used. Hens (Nepse), and the terminology in assessing the properties of plasticity is a magnet (the wire is a full stretch - or ZOlg - jerk + SPM). Smallest passing mandrel is the smallest mandrel for winding during the tests. 5 are considered to be a higher category, 20% jerk and SPM 2 are recognized as very good category, SPM 3 is acceptable, SPM is extremely acceptable, and SPM 5 is a marriage.

PRI and MER. In the appropriate vessel equipped with a stirrer, nitrogen purge, thermometer, condenser trap placed, 2 h, tripledBoJ acid; 317.2-hour meti tylen-bis- (aniline), 260.6 parts, N-Methylpyrrolidone and 38.7 parts (AO ml) pseed doctumal The mixture is then heated

0 to 2.5 hours, during which some amount of water is removed from the trap.

The solution is kept at 220-g225. within 5h In this case,

5 is a very small amount of traffic. Heating is removed and after 20 minutes, 1500 hours, K1-methylpyrrolide. When the temperature drops to about 13, 800 parts of xylene are added. The solution is allowed to cool while stirring. At 100.0 parts of isonate 125 mflgEE) is added, and the mixture is brought to 155 ° C after 2 hours. After 60 minutes at 155 ° C, viscosity according to Gardy5 nehru-Holdt F (F). After 95 minutes, an additional 3.5 hours of isonate 125 mf (isonate 125 mf) was added, giving an I + (Y +) viscosity. The product test gave the following results.

0 tats:

Brookfield viscosity, P2 Content of solid inclusions,% 2, 5 Intrinsic viscosity (solution of DMAC) 0, dl / g 0.5 g per 0 ml ml DMAC ,.

A. A sample of a substance is applied to a copper wire using an epigastric layer, four layers on isonel 200 XBEigO (isonel 200 E 490) with polyester, modified with trihydroxy ethyl isocyanurate (manufactured by Shenecti Chemical Co.). The solution prepared according to Example 4 is applied 2 times. 8. A portion of the substance prepared according to Example A is injected in a wet state into distilled water using syringes. Half shush is kept for 5 minutes at 315 ,. The fiber is drsato but flexible and can be used. C. Coverage. The following substances were loaded into a ball mill: substances of Example 1, 8.0 m. TiOt 2.5 parts of yellow titanate nickel, H, f NMP (N-MP) (N-methyl pyrrolidone). Test data are given in table 2. The mixture is treated overnight and then applied to Bonderite 37 steel panel. After aging for 12 minutes at 2 ° C, the panel test (coating) gave the following results: Film thickness after exposure, mm 0.0256 Hardness QA Note: Line A shows the characteristics for an individual coating, and line B shows a quality mixed coating. For experiment A, 6 layers of individual coating were applied.

For experience B, 4 layers of Isonel 200 polyether substrate modified with trihydroxyethyl isocyanurate (manufactured by Shenectady Chemical Co.), + 2 sZu of the same amidoimide as in test A. Impact viscosity during direct impact, kg / cm, 950 Impact viscosity at reverse shock, g / cm 2,350 D. Use as a binder: T-peeling (T-Re) 1) - samples of the product prepared according to example 4, are applied to cold-rolled steel (Bonderite R-1000 treatment) and then kept under vacuum at 80 ° C for 1b. h (for T-peeling during adhesion), and applied in the same way on hot rolling steel 1, 25 mm (purified chloroethane) with the same exposure for shear tests. T-peeling during adhesion, kg / cm 1.0688 Shift, kg / cm 90 Test specimens were prepared with a 15-second activation of -1.4 kg / cm with thermal cover Sentinel, behind a protective thermal coating. E. The film. A sample of the product obtained in example 4, deposited on the glass and aged for 2 hours at

.Table 2

Claims (1)

METHOD FOR PRODUCING POLYAMIDIMOIMIDES by reacting trimellitic acid anhydride and aromatic or aliphatic diamine by heating an organic solvent in a medium with subsequent interaction of the obtained product with diisocyanate, which consists in that, in order to improve the processability, the molar ratio of trimellitic anhydride. acid, diamine and diisocyanate is 1: (0.7-0.9) :( 0.1-0.75). 1 1050566 2