SU663315A3 - Polymer composition - Google Patents

Description

(54) POLYMER COMPOSITION a) a liquid epoxy resin axes ve bisphenol A with an epoxy content of at least 4.5 eq / kg or other polar nizkomapekul aromatiches FIR diglycidyl compounds, e.g. rozortsindiglitsidilovogo ether fenolftaleindiglitsidilovogo ether, halogenated diglycidyl compounds and b) a small amount of aromatic or, in the case of necessity, also cycloaliphatic diamine, for example, di-di-di-diphenide sulfone, diamine is single-phenyl methane and a. As hardeners, one can use solid forpoiimers from ;. a) aroma such as the diayinov minutes Cesc diamynodifvni methane dia 1inoditolnlmotan, diaminodiphenylsulfone, 0-, m-, p -fonilendiamin, diahmynodifenilovy ether, benzidine, stilbene diamine, 4,4 - diamino-biphenyl and 3,3-dimethyl. , b), a small amount of a diepoxy compound, for example, a liquid bisphenol h low molecular weight resin, epichlorohydrin with an epoxide content of more. 4, eq. / Kg of simple dpglitsilovy ethers, friend

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Двух,,,,, n,,,,,,, g g n g, n-n, N, N, N-N-N-diglycidyl compounds, for example, N, N, N-N-glycidyl, glyphyl, or Bisphenol A., The hardener is obtained preferably in the absence of solvents in the reaction vessel, usually at 50200 G, preferably Tel'nykh 120-170 ° C, and a1 to 1nosoedine sho portionwise or continuously 1I {} imeshivayut epoxy compound or both. The main components are continuously refined in a suitable heated reactor, and then they are reacted, and the reaction of the preliminary reaction under these conditions proceeds almost quantitatively and gives irradiated products with good. in the process of waving .. The reaction proceeds approximately according to the following scheme:

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The ratio between amino and epoxy groups: in the initial mixture is 1.5-2.5, in most cases it is 1.75-2.25, and accordingly it gives about products with different softening points.

The softening points of epoxy resin and prepolymers of amine hardeners are 45–120 ° C, preferably 30–30 ° C, their melting points are 55–15 ° C 0 The temperature difference between the softening points and the melting points of the components should be 5–30 s.

Fillers and lubricants can be added to the composition. As a 65

Fillers can use quartz flour, shale flour, roasted kaolin, powdered chalk, wollastonite, mica, alkali trihydrate, diopside, crushed dolomite, talc, barium sulfate, graphite, wood flour, pigments, etc., in addition, substances that simultaneously serve as forces, such as asbestos, glass, carbon, and boron fibers, organic fibers such as cellulose, polyamide, polyester, polyacrylonitrile, etc. Mixtures of such fillers may also be used. Stearates, for example, magnesium, calcium and zinc stearate, stearate acid, beeswax, carnauch wax, paraffin and synthetic socks, for example, based on polyethylene or silicone, can be used as lubricants. Compositions can be obtained in the following way. Mix the adduct obtained from a small amount of epoxy resin and cycloaliphatic or aromatic with the addition of inorganic and organic fillers, lubricants, and, if necessary, accelerate using a ball mill, which can be cooled, or using similar plants suitable for grinding. and mixing of the part: the press masses, and during the mixing and grinding process, no more than just the surface fusion of the resin particles and from the verditel should occur. Consequently, the resin and the hardener in the finished press mass are preferably in the form of separate particles; they are mixed and react only when they are melted under the influence of heat and pressure in the process or worm casting machine used for processing. The obtained fine powder product is used as such or it is granulated and then processed using various conventional methods (by pressing, injection molding, casting under pressure, etc.). The resulting compositions have the following advantages: high storage stability, as a result of which it is often possible to do without storage and transport in an isothermal container; high curing speed, as a result of which the pressing time becomes shorter and the processing is more profitable; better and more precisely controlled flowability, as a result of which during processing it reduces the scrap rate; high homogeneity and better surface quality of the obtained press products. Prepolymer G. .. UOOOO g of bisphenol A-based liquid epoxy resin with a content of 5.35 eq. epoxy groups per kg and viscosity 13,500 сP at 25С. In the reaction vessel: with a capacity of 2 liters and in an oil bath heated to 140 ° C. 100 g of 4,4-diaminerdiphenylmethane (10.00 eq. N. / kg) are mixed in the molten form at 45 ° C for 45 minutes at 100 ° C. The feed rate is adjusted so that the temperature of the reaction mixture does not exceed. . After a further 30 minutes at the same temperature, cool the resulting liquid and crush the yellow, resinous and fragile product. Product properties are listed below. Equivalent epoxy {groups / kgJ, o Softening point (Kofper), ° C58 Melting point (Kofler), ° C72 Prepolymer J) 1000 g of the resin used to make adduct 1 is heated to and for 1 hour at this temperature 120 g of 4,4-diaminodiphenylsulfone (8.00 eq. NHj / Kr) are added and mixed in portions. By regulating the heating and feed rate of the amine, the temperature of the mixture is maintained so that it does not exceed 185C. Then the viscous liquid is kept at 170 ° C for 30 minutes and the reaction is completed. Then the resin is cooled and crushed in a spruce mill. Resin properties are listed below. Softening point, ° C 55 Melting point, ° C74 Equivalent to epoxy groups / kg2.95 Prepolymer 1 1000 g of epoxy resin used for the production of duct I epoxy resin are fed to a 2 liter reaction vessel. During 0 min, stirring constantly, 115 g of 4,4-diamio-3, 3-dimethyldicyclohexylmethane (8.4 eq. Iv / kg) are added at a rate that did not exceed 40 ° C. further ten-minute exposure at the same temperature is cooled and the product is ground. Product properties are listed below. Equivalents of epoxy groups / kg 3.06 Softener point, ° C 58. Melting point, ° C73 Prepolymer {Y 500 g of epoxy resin used to produce duct I is fed into a 1 liter reaction vessel and heated to 80 ° C . Then, at one time, 50 g of aspalted one having a temperature of .4, 4-diamneenylmethane is mixed in and the bath temperature is raised to 140 ° C for 2 hours and kept at that temperature for another 30 minutes. The resulting viscous product is cooled and. crushed. Product properties are listed below. Equivalents of epoxy groups / kg2.95 Softening point, C 60 Melting point, C76 Fort polymer -V

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663315 500 g of epoxidized phenolphthalein (epoxy equivalent / kg 4.15, softening point) is melted in a 1 L reaction vessel and heated to 140 ° C. Within 60 minutes, constantly stirring, 20 g of 4,4-diaminodiphenylmethane (10.00 eq. Amino groups / kg) are added dropwise in the molten state at such a rate that the temperature of the mixture does not exceed 160 ° After further heating cool and crush the product for 20 minutes. The properties of the product are shown below. Equivalent to epoxy -groups / kg3.2 Softening point, c85 Melting point, C97 Production of hardeners. Hardener A. 1300 g of 4,4-diaminodiphenylmethane are fed into the reaction vessel with a capacity of Zli heated to 140 s. Over 50 minutes, 1000 g of bisphenol A-based liquid epoxy resin with a content of 5.35 eq of epoxy, groups / kg and a viscosity of 13,500 cP at 25 ° C are added dropwise to the mixture, continuously stirring to ensure that the temperature of the mixture does not exceed 170 ° C. . After a further 30 minutes, the extracts are cooled and the product, whose properties are given below, is shallowed. Equivalents, amino groups / kg4.45. Softening point, ° C57 Melting point; "C70 Hardener B.. 1000 g of 4,4-diaminodiphenylmethane is fed into the reaction vessel. The Zlie tank is heated to 140 ° C. For 50 minutes, with constant stirring, 1000 g of resin used for the preparation of hardener A are mixed in, and the temperature of the mixture should not exceed 170 ° C. . . After a further thirty minutes soaking at this temperature, cool and crush the product, the properties of which are given below. Equivalent amino groups / kg3, Softening point. ° C67 Melting point, ° C80 Hardener B. 4,4-Diaminodiphenylmethane (Yu equiv. IVHg / Kr) and the resin used to obtain Sealant A, heated to 100 ° C, by weight, the ratio 1.2:: 1.0 is fed to a discontinuously operating reactor heated to 170 ° C, in which the reaction takes place under continuous refilling by means of a worm. The product flowing out of the reactor is cooled and crushed. Its properties are given below. Equivalent amino groups / kg 4.2

8 Softening point, C Melting point, C Hardener G. 1100 g 4,4-diaminodiphenyl sulfide (thioaniline) 9.2 eq. ) is heated to the reaction vessel with a mixture of 3 liters. In the course of 60 minutes, 1000 g of the wiper is used. resins; after further aging for 30 minutes at the same temperature, the product is cooled and crushed. Its properties are listed below. Equivalent amino groups / kg3.5 Softening point, C70 Melting point, C85 Hardener D. 1000 gm-phenylenediamine (18.4 eq. NHg / kg) are heated to 130 ° C in a 3-liter reaction vessel, then constantly stirred for 30 min, 975 g of cyclohexylamine glycide (7.38 epoxy equiv. / kg) are mixed in portions. After further thirty-minute exposure at this temperature, cool and grind the product, the properties of which are given below. Equivalent amino groups / kg7.38 Softening point, ° C67 Melting point, C82 Hardener E. 1000 g of 4, 4-diaminoditoluylmethane (8.8 eq. NNe / kg) are fed into a 3 l reaction vessel and heated to, then for 40 615 g of diglycidyl terephthalate (7.18 eq. epoxy groups / kg) are added dropwise for a minute, and after complete mixing, the mixture is kept at 140 ° C for an additional hour. The product is cooled and crushed. Its properties are given below. Equivalent amino groups / kg4.08 Softener point, ° C65 Melting point, C79 Hardener J. 309 g 4,4-diaminodiphenylmethane, (10.0 equiv. NHg / kg is fed into a 2 L reaction vessel and heated to. Within 1 h 500 g of bromine ester ester based on tetrabrombisphenol A with 3.16 equiv. of epoxy groups / kg and 40 wt.% bromine in the melted form are added dropwise to the melt (temperature and mixed with constant stirring so that the temperature does not exceed 155 ° C. After further aging at this temperature for 30 minutes, cool and grind t viscous product, the properties of which are given below: Equivalent amino groups / kg 2.9 Softening point, C70 Melting point, -os85 Preparation of press mass. Example 1. 225 g of ground prepolymer are ground for 15 h in a ball mill with a capacity of 4 , 5 liters, together with 75 g of hardener A, 300 g of talc, 380 g of kaolin, 10 g of zinc stearate and 10 g of gaseous s. The resulting fine-mass press is pelletized, the tablet tablets and the preheated tapes are processed into molds heated to. Test specimens are listed below. Flexural strength (DiNJ, kg / cm 700 Impact viscosity (DiN), SMKG / SM2b Martens heat resistance, C112 Water absorption (DIN), mg 8 Electrical volume resistance, ohm-cm. Dielectric loss coefficient tgS / lO Hz 0, 01 Comparative Experiment. Compare the stability during storage of the press mass according to Example 1 with the press mass, which is obtained by the following method (stage B): 300 g of talc, 380 g of kaolin, 10 g of zinc stearate and 10 g of carbon black for 30 min is stirred in a two-blade two-liter mixer with a capacity of 5 liters. Then 65 g of molten heated about 10 (Ps of 4,4-diaminodiphenylmethane, admixing to 235 g of bisphenol A epoxy resin heated to 50 ° C, 5.35 equivalents of epoxy groups / kg, the mixture is fed into the mixer for 15 minutes, mixed and mixed with a powdery fraction. The resulting viscous, dough mous by heating to translate into a solid state and then grind. The comparison is made by the method of determining the yield in a molding mold with a spiral channel, and the figures are in inches: Baseline hfess mass Example 1 stage After daily storage at 13 1/2 .8 After daily storage at 50 ° C9 1/2 Example 2. 250 g of resin prepolymer II are mixed for 7 hours and crushed with 100 g of hardener B, 10 g of calcium stearate, 10 gaseous jars and 630 g of quartz flour in a 4.5-liter ball mill. The resulting press mass is processed further according to Example 1. The properties of the product are given below Bending Flexural Strength, kg / cm 1000 Impact Viscosity, cmcg / cm 9

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Claims (2)

66331.5 Martens Heat Resistance (DiN), с 120 Water Absorption (D1N), mg 7 Electrical Volume Resistance, ohm-cm 2-10 Dielectric Loss Ratio tgS / lO-, G 0.008 Example 3. 183 g of prepolymer are ground for 10 h with 67 g verditel B, 730 g shale oil, 10 g of titanium oxide and 10 g of zinc steate in a 5 l ball mill and the resulting fine powder oukkt processed according to priru 1. The properties of the product are given below. Flexural strength (DiN), kg / cm 550 Shock viscosity (DiN), cm.kg / cm 4.5 Heat resistance according to Martens (DIM), ° С 108 Water absorption (eN), mg12 Electrical volume resistance, cm 10 Dielectric loss factor tgS / lO r 0.03 Example 4, 260 g of prepoly IV for 15 hours are ground O g of hardener G, 610 g of shredded glass fibers, g of zinc stearate and 10 g of gas-shrink B ball mill. The resulting powder is processed further as in Example 1. The properties of the product are given below. Flexural strength (DiN), kg / cm 1200 Impact .: viscosity (DiN), cm.kg / cm 212 Heat resistance according to Martens (DiN), 1200 Water absorption (DiN), mg 8 Electrical volume 1 resistance, ohm-cm Yu Dielectric loss factor, tgS / lO g 0.003 Example 5. 223 g of prefoli-a are crushed within 15 hours from g of hardener B, 695 g of chamothian kaolin, 2 g of wax and gas soot in a 4.5-liter ball mill. The resulting press masses are pelletized and abatted further according to an example. The properties of the product are shown below. Flexural strength (DiN), kg / cm 1350 Impact viscosity (DiN), see g / cm 10 Heat resistance according to Martens (DiN), ° С125 Water absorption, (DiN), mg 7 electrical resistivity, ohm cm 5-10 Dielectric loss factor tg (S750 G0.006 Approx. 180 g of prepolymer I is ground for 12 hours with 70 g of hardener B, 50 g of high molecular weight epoxy resin based on bisphenol A / 1.1 eq, epoxy groups / kg , 693 g of calcium silicate (wollastonite), 4 g of wax and 3 g of carbon black in a 4.5-liter ball mill. Then, powdered powder is granulated. It is manufactured according to Example 1. The properties of the product are given below: Flexural Strength (DiN), kg / cm 100 Impact Viscosity (DiN), cm.kg / cm Martens Heat Resistance (DIN), С Water Absorption. (DiN), mg Electrical bulk resistance, ohm-cm Dielectric loss factor tgB / lO G Example 7. 246 g of prepolymer I are ground for 13 hours with 124 g of hardener G, 564 g of crushed glass fibers, 50 g of antimony polyoxide, 5 g of titanium white ( rutile), 1g chromophthalic sin and 10 g of carnauba wax in a 4.5 L ball mill; further processing is carried out analogously to example 1. The properties of the product are given below The Flexural Strength, (DiN), kg / cm Shock Viscosity (DiN), see kg / cm2 Martens Heat Resistance (DiN), ° C Water Absorption (DiN), mg Electrical volumetric resistance, Dielectric loss factor, tgS / lOS G 0.004 Example 8. 158 g of prepolymer I are ground for 10 h together with 103 g of hardener B and 70 g of a prepolymer of triglycidylzocyanurate and hexahydrophthalic. “Islota, 5.7 eq. epoxy groups / kg, 300 g of crushed glass fibers, 350 g of voplastonite 7 g of wax OP and 3 g of gas soot in a 4.5 l ball mill, and processed further like for example 1. The properties of the product are given below Strength at bending (DiN), kg Shock viscosity (DIN), cm kg / cm2. Martens' heat resistance (DIN), ° C15 Approx. 9. 196 g of Vanmy cresol novolac glycidilir (epoxy equivalent / kg 4.65, dryness point 62 ° C) is stirred and crushed for 8 hours with 104 g of hardener B, 393 g of chamoised kaolin, 300 g of glass fibers, 4 g of OR wax and 3 g of carbon black in a 4.5-liter ball mill. Then the powdered product is processed further anaogically to example 1. The properties of the product are shown below. Strength, bending, (DiN), kg / cm 900 Impact viscosity (DiN), cm.kg / cm 6 Heat resistance according to Martens (DiN), C175 Water absorption (DiN), mg 8 Electrical resistance, ohm “cm . Dielectric loss coefficient,, 009. I'll try it on. 186 g of glycidylated phenol novolak (epoxy equivalents / kg 5.4, softening point 53С) are sutured for 8 hours and crushed with 114 g of hardener B adduct, 693 g of fireclay kaolin, 4 g of OR wax and 3 g of carbon black in a ball mill 4.5 liters Then the powdered product is processed further analogously to example 1. The properties of the product are shown below. Flexural strength (DiN), kg / cm 1140 Impact viscosity (), cm.kg / cm 8 Heat resistance according to Martens (DiN), C205 Water absorption (DiN), mg 5 Electrical volume resistance, ohm cm Dielectric loss factor, 10 G0.007. Approx. 11. 207 g of glycidyl alcohol of phenolphthalein (epoxy equivalents / kg 5.15, softening point 55 ° С) are mixed for 6 hours and ground with 95 g of hardener adduct, 685 g of quartz flour, 10 g of zinc stearate and 5 g gas soot in a 4.5 liter ball mill. Then the powdered product is processed further analogously to example 1. The properties of the product are shown below. Flexural strength (DiN), 700, Impact viscosity (DiN), s. Kg / cm Marten-Martens heat resistance (DiN), ° С 137 Water absorption (DiN), mg 5 Electrical volume resistance, ohm-cm (Coefficient dielectric loss tg S, Example 12: 163 g of terephthalate diglyc (epoxy equivalent / kg 6.10, softening point) are mixed and ground with 137 g of hardener adduct, 0.05 g of ash, 675 g of calcined kaolin, 10 g of titanium white, 5 g of iron oxide and 10 g of zinc stearate in a 4.5-liter ball mill. Then the product is further processed in the same way as at 1. The properties of the product are given below the Flexural Flexural Limit, kg / cm Impact Viscosity, cmkg / cm Martens Heat Resistance (DiN), “с Water Absorption (DiN), Mr. Electrical Volume Resistance, with n-cm Dielectric Loss Coefficient, , 10 g. Example 13. 223 g of prepolymer 1 for 10 hours grind 77t of hardener B, 300 g of crushed glass fibers, 390 g of kaolin, 2 g of carbon black and IP wax OP in a ball mixture of 4.5 liters. The obtained powdered press mass of granules up to the grain size from 0.2 to 2.0 mm and the granulate is mixed with 0.6 g of wax op. This product :. suitable for injection molding. The properties of the product are houriena below the Flexural Yield Limit (1) W), kg / cm 900 Impact Viscosity, cmkg / cm 9 2-10 0.01 Martens Heat Resistance (DIN,), C118 Water Absorption (DiN), mg12 Electrical. volume resistance, ohm-cm4 10 Dielectric loss factor, tg, South 0.025. The invention has a polymer composition comprising an epoxy resin, which is an epoxy resin prepolymer and a diamine resin, having a softening temperature of 4-5-120 seconds and a melting point at the bsue softening temperature, and a hardener, which is an fs amine and epoxy polymer resin, in which the ratio of the number of reactive nitrogen atoms of the amine to the number of epoxy groups is 3-5: 1, about t and h and so that, in order to increase resistance to long-term heating and arc resistance, the composition contains as As a hardener, the Frplimerp arsenic amine and epoxy resin hardener has a softening temperature of 4-5-120 ° C and a melting point higher than the softening temperature at the following component ratio, parts by weight: (JiopnonBMepv epoxy resin and diamine30-80 Answer Yaytel 10-20. Istrian information, taken on the attention of expert examination 1, Vatheit Switzerland 498171, 08 g 30/14, published 1970. 2. Authors certificate of the USSR 469261, cl. C 08 L 63/00, 1972.