SU524526A3 - The method of obtaining thermosetting polymers - Google Patents

Description

(54) METHOD FOR OBTAINING THERMORACTIVE POLYMERS

This invention relates to the chemistry of highly molecular compounds, the synthesis of new thermosetting polymers and the preparation of products based on them. A method of producing thermosetting polymers by reacting N, N-bisimides of unsaturated dicarboxylic acids and polyamines when heated in the presence of a catalyst is known. According to the invention, in order to increase the heat resistance, a method for producing thermosetting polymers is proposed, which consists in the interaction of N, N-bisimides of unsaturated dicarboxylic acids of the general formula OO and U d. B VA-N- where A is a bivalent organic radical with a minimum of 2 and maximum AOR carbon atoms and B is a radical of the formula and azomethins of the formula K- (NR iB-C T5-AS CK iij PO-N CR- (W; IIRR where I is a hydrogen atom or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, and T and I have the same meaning as R, at temperatures from 100 to 280 ° C and in the presence of a catalyst. The proposed method allows to obtain a solidified reaction product by heating to 135 With a mixture of, K, N-bismaleimide and azomethine after 13O minutes It contains: a) bisimides, where A is the radical of the formulas, ..g or (CH), in which n 2-8; B is a vinale radical; b) the azomethins of formulas I and 11, where there is a hydrogen atom, and each of R and H is a phenyl radical, and A has the same meaning as A in the preferably used bimimides. Bisimides are a known class of compounds that can be prepared as described in U.S. Patent 2,444,536 and in Great Britain Patent 1,137,592 to methods of reacting the corresponding diamines with unsaturated dicarboxylic anhydrides in a polar solvent and in the presence of a catalyst. As examples of Bisimo, you can learn how to use the following languages; , 4-biphenylsulfonbismaleinN, N -4.4-Dicyclohexylmethanbismalemedicians sn , 4-diphenylcyclohexane bismaleimide. The azomethins of the formulas 1.31 and 111 can be obtained by known methods with the mutual influence of aldehydes or ketones with monoamides or diamines in equivalent amounts and, if necessary, in the presence of a catalyst. These methods are described, for example, B Noyet - Wevt / Metoden dei- og grantschen Chemie Volume 11 (2) 1958 p. 73. As the azomethins according to the invention, the following are preferred: N, N-Bis- (benzylidene) -hexamethylenediamine N, N - Bis- (benzylidene) -paraphenylene diamine N, N-Bis- (benzylidene) -1,3-di- (8-aminopropyl) -5,5-dimethylhydantoin N, C-Bis- (furfurylidene) -hexamethylenediamine. A mixture in which there are more than two imide groups on one C ' N-group cures faster and gives products with better mechanical properties, especially heat resistance. This is confirmed by the data given in table. 1, which shows the curing time of various mixtures of bmalemaleimide with azomethines and only bmalemaleimide at 135 and 160 ° C. In curable mixtures according to the invention, the molar ratio of N, N-bisimides and azomethines of formula I can vary from 1: 1 to 3 : 1, aN, N-bisimides and azomethins of the formula 11 or III FROM 2: 1 to 6: 1. The curing of the proposed mixtures is carried out by heating them to a temperature of 1OO280 ° C, preferably 150-250 ° C, at gQ, than the mixture, without the formation of volatile reaction products, is converted into crosslinked insoluble and non-meltable products. For some technical purposes, the addition of a curing catalyst is advantageous. Doggles, for example, a small amount of organic peroxide or suprasalt reach faster curing. For this purpose, compounds such as di-tert-butyl peroxide, dilauryl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide or tert-butyl peroxoate can be used in a concentration of 0.01-5%, preferably O, 250, 5% based on on the total weight of the cured mixture. However, it is also possible to use other non-peroxide curing accelerators or additives which have a beneficial effect on curing. The polymers obtained by the proposed method are used as coatings for protecting surfaces in electrical engineering, for the manufacture of layers and in construction. Depending on the purpose of their application, they can be used in the filled or unfilled state in the form of solutions or emulsions, such as varnishes, press materials, sintering powders, resins for coating by dipping, casting resins, pressurized material, impregnating resins, binding materials and binders for layered plastics.

well a

to et o & f Example 1, 31.7 g (0.1125 mol) of N, N-bis- (benzylidene) -hexamethyldiamine and 86.6 g (0.225 mol) of N, N -4.4-diphenylmethane-bismaleimide (bisimide B) stir thoroughly and melt in a round bottom flask at 145 ° C and 12 mm Hg. and the gas is removed. The melt is poured into molds for testing with dimensions of 150x150x4 and 150x150x2 mm, then cured at 5 hours at 140 ° C, 1.5 hours at 160 ° C, 1.5 hours at 180 ° C and 15 minutes at 2OO C. The results obtained are given in tab. 2

Example 2. 22.5 g (O, OBO mol) of N, N -bis- (benzylidene) -hexamethylenediamine and 86.0 g (0.240 mol) of bisimideB Union of Swiss Machine Builders. The international organization for standards and Example 4. 27.1 g (0.725 mol) of N, N -bis (benzylidene) -4,4-diamino is thoroughly mixed, melted at 150 C and 15 mm Hg in a round bottom flask. and the gas is removed. The melt is poured into forms according to example 1 and cured.

The results are shown in Table. 2

Example 3. 16.9 g (O, O 60 mol) N, N-bis- (b ensylidene) -hexamethyl endiamine and 86.0 g (0.240 mol) of bisimide B were carefully biased, melted in a round bottom flask at 145 ° C and removed gas. The melt is poured into molds and cured as in Example 1.

The results are shown in Table. 2

Table 2 of standards of phenylmethane and 10.4.2 g (0.290 mol) of bis imide B is carefully displaced and melted at 160 ° C in a round bottom flask, then the gas is removed, the melt is poured into molds and cured according to example 1. The resulting molded product has an ISO heat resistance / R 75 307 C. PRI mme R 5. 42.6 g (0.150 mol) of N, N-bis- (b enzilidei) -paraphenylene diam and 107.5 (0.30 mol) of bisimide B are thoroughly mixed and melted in a round bottom flask at 170 ° C and 13 mm Hg, then gas was removed. The melt is analogous to Example 1 and is molded and solidified. The heat bone nolSO / R 75 of the obtained molded article 257 C. Example b, 22.7 g (0.08 mol) of N, N - bis - (benzylidene) - paraphenylene diamine and 128.3 g of bisimide B are thoroughly mixed and melted in a round bottom the flask at 17 ° C and 12 mm Hg, then the gas is removed. The melt is poured into molds and cured according to example 1, the resulting molded product has heat resistance ISO / K 7,298 ° C. Example 7. 20.6 g (0.114 mol) of benzalaniline and 81.6 g (0.223 mol) of bi-imide B are thoroughly mixed and melted in a round bottom flask at 145 ° C and 12 mm Hg. and the gas is removed. The melt is poured into molds and cured as in Example 1. The resulting molded product has a heat resistance of no ISO / R 75,298 ° C. Comparative Example For comparison, according to French Patent No. 1555564, 19.8 g (0.10 mol) of 4,4-diaminodiphenylmethane and 72.0 g (0.2 O mol) of bimimide B are carefully biased and the mixture is melted in a round bottom flask at 150 ° C and 12 mm Hg then the gas is removed. The melt is poured into molds and cured according to example 1. The indicators of the obtained molded products are given in table. 2. From table. 2 var; o, that molded products made of polymers obtained by the proposed method have good properties. Molded products obtained from the polymers of example 1 are characterized by better tensile strength and better heat resistance than products made from the polymer obtained in the comparative example. The flexural strength and the tensile strength of the bending of polymer products of Examples 2 and 3, although they have lower values, however, their heat resistance is higher. Products from polymers of examples 4-7 also have excellent heat resistance. The results obtained in Example 1 also confirm the excellent electrical properties of the new products. The dielectric loss coefficient and dielectric constant have a constant value within the temperature range of 23-220 ° C, and the specific breakdown resistance within these temperatures decreases only by two tenth degrees. Example 8. 34.5 g of M, H bis (benzylidene) -1.6 hexanediol-di-C -amnopropyl ether) and 60.5 g of bisimide B are carefully displaced, melted in a round bottom flask at 160 ° C and the gas is removed . The melt is analogous to example 1 poured into molds and cured. The indicators obtained molded product are given in table. 3. Example 9. 36.9 g (0, O88 mol) N, N-bis- (benzylidene) -, 3-di- (f -aminopropyl) -5,5-dimethylhydantoin and 63.1 g (0.176 mol) Bisimide B is carefully biased, melted at 160 ° C and 12 mm Hg. and the gas is removed. The melt is poured into molds and cured as in Example 1. The indicators of the obtained molded product are given in table. 3. Example 1O. 27, 30g of N, N-bis- (benzylidene) ethylene diamine and 82.7 g of bisimide B are thoroughly mixed, melted in a round-bottom flask at 16 ° C and the gas is removed. The melt is poured into molds and cured as in Example 1. The indicators of the obtained molded product are given in table. Example 11. 31.8 g of N, N-bis- (benzylidene) -hexamethylenediamine and 78.2 g of N, N-4,4-diphenyl ether-bis-maleimide are carefully displaced, melted in a round bottom flask at 16 ° C remove the gas. The melt is poured into forms and cured according to example 1. The indicators of the obtained molded product are given in table. 3. Example 12. 31.2 g of N, N-bis (benzylidene) paraxilylenediamine and 71.6 g of bisimide B are thoroughly mixed, melted in a round bottom flask at 16 ° C and the gas is removed. The melt is poured into molds and cured according to example 1. The indicators of the obtained molded product are shown in Table 3

eleven

Identical to the example table. 2

Example 13. Thoroughly mix 30.7 g of bisimide B, 9.3 g of bis- {furfurylidene) -hexamethylenediamine, 1 g of zinc stearate and 59 g of glass fibers. This mixture at 180 ° C and a pressure of 100 atm is pressed for 8 minutes into disk-shaped molded products with a thickness of 2 mm and a diameter of 8 mm, which are additionally cured for 6 hours at 2OO C.

Electrical properties of the products obtained: 2

a) tg; 10 at 23 C and frequency, Hz:

500,47

36

, 02

b) Dielectric constant at and frequency, Hz:

504.2

1034.4

10b3,7

c) specific breakdown resistance.

OMVCM:

in a dry state after daily storage. and in water at 23 ° C

624526

12

Table 3

g) Surface resistivity, OMG

2.1-1О

in a dry state

after daily storage of 4.1-1012

in water at 23 C

Example 14. 7.20 g of H, N-diaminodiphenyl ether bismaleine imide and 2.84 g of terephthalmide amide are thoroughly mixed, then fbrmut under pressure of approximately 5 atm for 15 min. N, the molded product is cured, after which it is additionally cured for another 24 hours.

Example 15. 5.68 g of N, N-metaphenylene bismaleimide and 2.76 g of bis- (cycpohexylidene) - hexamethylenediamine as in example 14 are converted into a cured molded product.

The films obtained in examples 14 and 15 are subjected to thermogravimetric testing in a dry air atmosphere using a Mettler Recording Vacuum ThemoanalvierrA-l with a weight of 50 mg and a heating rate of 2 C per minute.

These thermogravimetric analysis are given in table. four.

Table 4