RU2206582C1 - Method of production of prepreg for winding heat- shielding and/or anti-static internal shells for glass plastic tubes-envelopes of various classes and purposes - Google Patents

Abstract

FIELD: laminar composite materials; production of prepreg for aeronautical and space engineering and shipbuilding. SUBSTANCE: proposed method includes operations of simultaneous and/or parallel preparation of hybrid binder on base of resins whose types are indicated in Specification and woven fillers formed from polycaproamide (caprone) , polyphene and/or carbon filaments (strands or cords) coated with cover material made from copolymer of tetrafluoroethylene with vinylidene fluoride and/or commercial carbon with anti-static soot and/or carbon graphite and/or metallized mixtures and antipyrine additives: antimony trioxide, hexachlorobenzene , carbon tetrachloride CCl₄, trichloroethyl phosphate and/or chladon. Anti-static and antipyrine additives are also introduced in hybrid binder for impregnation of fabric fillers. Other powder fillers, for example oxides and/or nitrides of metals are introduced in hybrid binder for enhancing their physico-mechanical, thermal and anti-static properties, such as specific impact viscosity, shear, compressive and breaking-off strength. Impregnation of woven fillers at rate of continuous motion of 1-3 m/min, tension of 0.1 to 1.5 kg per centimeter of prepreg width; drying of binder is performed in drying chamber at temperature of 90-210 C. EFFECT: enhanced efficiency; improved anti-static and adhesive properties. 9 cl, 12 dwg, 21 tbl, 9 ex

Description

 The invention relates to layered composite fibrous materials and relates to a method for producing a prepreg (or prepregs) for the manufacture of plastics with high sublimation, antistatic and heat-protective properties.

 The present invention can find wide application in rocket and space technology, aircraft manufacturing, in various fields of machine and shipbuilding, as well as in other sectors of the national economy.

 In particular, it can be used as a facing material for the protection of structural fiberglass pipes-shells, such as chimneys, compartments of mine wells, cargo and launch containers, fairings, internal and (or) external heat protection of oil and gas products, etc.

 A known method of producing a prepreg based on fiberglass and a binder containing an alcohol solution of phenolamine resin (ed. Certificate. SU 323340, class C 08 G 8/04, 1972).

 The fiberglass obtained in accordance with this method have low antistatic properties. In addition, they also have low heat-shielding properties: fire resistance, heat resistance and thermal stability. And, in addition, obtained in accordance with ed. testimonial. SU 322340 prepregs are not technologically advanced enough to process them into structural products, and plastics based on them are prone to aging and therefore have low operational reliability.

 There is also known a method of producing a prepreg based on fiberglass and a binder containing a phenolamine resin, modified with methyl tris- (β-hydroxyethyl) -ammonium methyl sulfate (ed. Certificate SU 468936, class C 08 G 8/28, 1975).

 Fiberglass, obtained on the basis of this method of producing a prepreg, also have insufficiently high physical, mechanical and thermophysical properties. They have low antistatic properties and, in addition, do not have high operational reliability, since they are prone to aging.

 The method according to ed. testimonial. SU 468936 (class C 08 G 8/04) is not technologically advanced and practically unsuitable for the manufacture of serial batches of engineering plastic products, since prepregs prepared in accordance with this method are made only by solid impregnation with a limited thickness of 0.8-1 mm.

A closer analogue of the proposed method is a technical solution according to ed. testimonial. SU 690041 for μL ² C 08 L 61/14, C 08 J 5/24, 32 V 27/42. In accordance with this method, the prepreg is made on the basis of fiberglass and a binder containing a solution of phenolamine resin modified with methyl tris- (β-hydroxyethyl) -ammonium methyl sulfate in ethylene glycol monoethyl ether.

To increase the physico-mechanical properties of this prepreg and at the same time maintain high antistatic properties of fiberglass based on it, a bakelite varnish is additionally introduced into the solution of the modified phenolamine resin in the following ratio of components, parts by weight:
Modified Phenolamine Resin Solution - 18-28
Bakelite varnish - 9-16
Fiberglass - 60-70
This analogue has the disadvantages inherent in the above analogues. In addition, plastics made in accordance with the proposed method have low fire resistance and do not have thermal stability.

 A close analogue of the claimed technical solution is the method of obtaining prepregs by ed. testimonial. SU 226146, class C 08 L 63/00, 1968. In this analogue, an ETF epoxytriphenol resin (70 parts by weight) was taken as the basis of a hybrid binder for tissue prepregs, and AFP aniline-formaldehyde resin (30 parts by weight) was used as a hardener. The disadvantages of this technical solution is the low transverse (tear-off) strength and shear strength at elevated temperatures.

The closest analogue of the claimed technical solution is a method of obtaining a prepreg by ed. testimonial. SU 726137, μL ² C 08 L 63/04, C 08 J 5/24. According to this method, in order to increase the viability of the prepregs and at the same time increase the interlayer (adhesive) and transversal strength of the plastics based on them, the glass fabric is impregnated with a hybrid binder based on ETF epoxy resin (base resin - 60-70 parts by weight) dissolved in aniline-formaldehyde (10 -20 parts by weight) and phenol-formaldehyde novolac (10-20 parts by weight) resins.

 Aniline-formaldehyde resin (AFP) in this hybrid binder is used as a hardener, phenol-formaldehyde novolac resin is used in this hybrid binder to increase its heat resistance. It was noted (author's certificate SU 726137) that with an increase in the content of novolac resin in the hybrid binder more than 20 parts by weight there is a sharp decrease in the heat resistance and strength of mechanical reinforced plastics (based on prepregs of fiberglass and a hybrid binder) at elevated temperatures. In addition, it was noted that when reducing novolac phenol-formaldehyde resin in a hybrid binder to 10 wt.h. and less in plastics (based on it and fiberglass), a sharp decrease in the transfer (tear-off) strength begins to occur, during the machining of such plastics, defects such as cracking and delamination of the material begin to be observed, and the shelf life of the prepregs is sharply reduced. With the optimal amount of novolac phenol-formaldehyde resin in a hybrid binder (10-20 parts by weight), it is possible to significantly increase the viability of the prepregs (up to 10 times) and increase the transverse strength of large-sized structural products made from these prepregs by winding by 10-20%.

The disadvantage of this method of producing prepregs is the same, it does not provide a comprehensive solution to the issue, that is, obtaining prepregs that provide both their high viability and high heat resistance and thermal stability of plastics based on them under conditions of their long-term operation (at temperatures above 180 ^o C and short-term the effects of high-speed gas flows).

 The prototype of the invention, the authors chose patent RU 2028334 C1, C 08 L 63/00, C 08 K 5/00, 32 V 27/38 // C 08 K 5/00, 5/05, 5/07, 5/47 , with priority 09.08.91, published on 02.02.93. In the technical solution according to patent RU 2028334, the same tasks were practically solved as in the previously described analogues - it is flammability, fire resistance, heat resistance, thermal stability, immunity of plastic to accumulation of charges on its surfaces static electricity.

In this basic solution (in comparison with the claimed one), a hybrid binder containing three epoxy resins - ETF (19 ± 0.1 wt.%) Was used to create prepreg compositions with electrical conductive properties and high fire resistance (meaning the properties of plastics based on these prepregs) hours), KDA (19 ± 0.1 parts by weight) and UP-631U (19 ± 0.1 parts by weight), taken in equal proportions (1: 1: 1), if a hardener is present in the composition ( 3.1 ± 0.05) and the nickel-chlorine complex (NiZ ₂ Cl ₂ ) diluted in an alcohol-acetone solution with a solvent ratio of 1: 0.7 (alcohol 24 ± 0.1, acetone 16 ± 0.1).

 The given composition of the hybrid binder, as well as all the above-described analogues, is intended for the preparation of prepregs using glass-carbon-organo-reinforcing fillers as power fillers in them.

 The main disadvantage of the prototype is that its hybrid binder uses UP-631U bromine-containing resin, which allows (according to the developers of this hybrid binder) to reduce the ignition rate of plastics based on it and increase their oxygen index (up to 35-38%) and heat resistance .

 Usually, the bromine content in plastics is determined by the requirement of their fire resistance. In such binders, the content of bromine-containing components (substances) is from 2 to 20%. However, it is known that fiberglass based on a binder with such a bromine content have low heat resistance, thermal stability and resistance to high temperature erosion currents (see auth. Certificate SU 730753), that is, the task of increasing thermal stability and thermal stability.

 In addition, it is also known that many developers, trying to increase heat resistance and thermal stability (while maintaining fire resistance), tried to go the other way - by eliminating bromine-containing epoxy resins from the composition of hybrid binders to obtain prepregs and plastics based on them having simultaneously high physical and mechanical and thermophysical properties, high manufacturability of their processing into structural products by winding methods (for example, patent RU 2148598 C1, C 08 L 63/00, C 08 J 5/24, 32 V 27/38, C 08 K 5/56 // C 08 L 63/00, 61/11, published 10.05.2000 g.).

 The authors of the present invention believe that the presence of bromine-containing components in the prototype complicates the hybrid binder formulation itself and the technology for preparing prepregs from it, and the technology for processing the prepregs themselves directly into structural power products.

 Therefore, the authors of the technical solution claimed as an invention, as well as the developers of the patent RU 2148598, also took the path of eliminating bromine-containing epoxy resins in prepregs.

 The method proposed by the authors for producing a prepreg for winding heat-shielding and (or) antistatic inner shells of pipe shells is significantly different from all the above methods for producing prepregs (and plastics based on them).

 In all of the above technical solutions, the improvements concerned only the composition of the hybrid binder needed to obtain prepregs and the methods for its preparation.

 None of the known above solutions address issues related to the simultaneous improvement and composition of the hybrid binder and the composition of the filler, that is, a comprehensive simultaneous selection of materials (for both filler and binder).

 The proposed method involves the preparation of prepregs from carbon, polycaproamide (kapron) and (or) polyphene fabrics and a hybrid binder consisting of three resins - two epoxy (ETF and DEG-1) and one phenol-formaldehyde SF-340A, used by the authors as a hardener.

 The method includes operations of preparing a hybrid binder and operations of combining it with a woven filler consisting of polycaproamide (kapron) and (or) polyphene, and (or) carbon filaments lined with a coating material from a tetrafluoroethylene copolymer with vinylidene fluoride and (or) carbon black containing its composition is antistatic and flame retardant additives. Exactly the same additives are introduced into the hybrid binder, and thus a hybrid prepreg is prepared from the filler and the binder having the same structural composition. Plastics obtained from such prepregs are uniform in composition, have very high cohesive and adhesive strength and interact well with each other - both in terms of removing static electricity charges, and in terms of increasing fire resistance, and in terms of increasing heat resistance and thermal stability under long-term operation under high-speed heat fluxes.

 A hybrid binder for prepregs is created by mechanical mixing of epoxy (ETF and DEG-1) and phenol-formaldehyde (SF-340A) resins (binders) in an acetone-alcohol-toluene solvent. Then the fabric filler is impregnated and dried, consisting of polycaproamide (kapron), carbon and (or) polyphene yarns, coated with a coating of a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black with additives to the state of prepreg on an impregnation-drying machine and continuous rewinding prepreg on coils and (or) bobbins with obtaining from it a fabric prepreg spiral.

A distinctive feature of the method is that as a hybrid binder for the preparation of the prepreg (or prepregs), solutions (mixtures) of two epoxy - epoxytriphenol (ETF) and epoxyaliphatic (DEG-1) resins and one phenol-formaldehyde resol resin (SF-340A) are used at the following ratio of components by weight:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol formaldehyde resole resin SF-340A (hardener) - 34
Acetone - 90
Technical alcohol - 46
Toluene (petroleum or coal) - 10
and at the same time, the hybrid binder for the prepreg is prepared in three stages - at the first initial stage, the epoxytriphenol (ETF) and epoxyaliphatic (DEG-1) resins are separately heated to a temperature of 180-200 ^° C and the process of uniform heating of the ETF binder is carried out for 24 hours and the binder DEG-1 - for 2 hours, and then mix and dissolve them in each other in the reactor for 3-5 hours per ton of composition at temperatures of 35-60 ^o C, which are obtained by introducing into the reactor with there with resins (ETF and DEG-1) acetone alcohol ol solvent in a ratio of 1: 0.51: 0.11, introduced into the reactor at temperatures of 18-30 ^o C, the second stage of preparation of the binder to the reactor in an already dissolved together in a solvent TFE resin and DEG-1 was added and the crumb (or ) particles (pieces) of solid, milled into pieces of 1-3 mm in size SF-340A phenol-formaldehyde resin and again heat the newly obtained consistency of resins to a temperature of 35-60 ^o C and complete dissolution of phenol-formaldehyde resin SF-340A in previously dissolved among themselves in epoxy solvent ETF and DEG-1 moles by co-mixing in the reactor for 3-5 hours per ton of the obtained new hybrid binder composition, and at the last stage of the preparation of the hybrid binder, it is filtered to remove all solid particles of the binder and (or) foreign particles that are not dissolved in the reactor , for example, by passing a hybrid binder through one and (or) several layers of rarefied Excelsior fiberglass and bring the consistency of a new hybrid binder of three resins - ETF, DEG-1 and SF-340A to a density of 9 60-1100 kg / m ³ by additionally introducing into the binder an alcohol-acetone mixture taken in a ratio of 1: 2, and mixing it with it for 20-30 minutes, bringing the temperature of the new binder due to the alcohol-toluene mixture additionally introduced into it to a temperature of 18- 35 ^o C and then warmed through hybrid binder located, e.g., in the impregnating bath of the machine, is passed woven filler polycapramide (nylon) and (or) polifenovyh and (or) carbon fibers coated with a copolymer of tetrafluoroethylene and vinylidene fluoride ( l) carbon black (with a volume ratio of coating material and filament from 0.3: 1 to 0.7: 1), followed by pressing it on the support rolls of the impregnation machine and bringing the mass fraction of soluble resin to 90 ± 1% and the mass fraction of volatile substances and moisture from 0.8 to 4% due to giving the speed of the filler moving through the hybrid binder from 1 to 3 m / min, filler tension from 0.1 to 1.5 kgf per centimeter of web and temperature drying of the binder-filled filler in the impregnation zones machines from 90 to 210 ^o C.

A distinctive feature of the method is the fact that as a hybrid binder for the preparation of the prepreg, a mixture of three resins (ETF, DEG-1 and SF-340A) dissolved in each other and in an acetone-alcohol toluene solvent and carbon black and / or carbon-graphite mixture is used in the following ratio of components wt.h .:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol-formaldehyde resin SF-340A (hardener) - 34
Soot and (or) carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 - 15
Acetone - 90
Technical alcohol - 46
Toluene (petroleum or coal) - 10
A distinctive feature of the method is that, as a binder for preparing the prepreg, a mixture or solution of three resins ETF, DEG-1 and SF-340A dissolved in each other and in a solvent with flame retardant and antistatic additives in the form of antimony trioxide, hexachlorobenzene is used (used) and carbon black and (or) carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 in the following ratio of ingredients, parts by weight:
ETF epoxytriphenol resin (base binder base) - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol formaldehyde resole resin SF-340A (hardener) - 34
Acetone - 90
Technical alcohol - 46
Toluene (petroleum or coal) - 10
Soot and (or) carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 - 10
Antimony trioxide - 10
Hexachlorobenzene - 15
A distinctive feature of the method is the fact that as a hybrid binder for preparing the prepreg, a mixture of three resins (ETF, DEG-1 and SF-340A) dissolved in each other and in an acetone-alcohol toluene solvent and mixed in a binder is used in the following ratio of components wt.h .:
ETF Epoxytriphenol Resin (Hybrid Binder Base) - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol formaldehyde resin SF-340A - 34
Soot and (or) carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 (antistatic) - 10-15
Antimony trioxide (flame retardant) - 5-10
Hexachlorobenzene (flame retardant) - 5-10
Carbon tetrachloride (CCl ₄ ) (flame retardant) - 5-10
A distinctive feature of the method is that as a hybrid binder for the preparation of a prepreg, a mixture of three ETF, DEG-1 and SF-340A resins, which are soluble in each other and in an acetone-alcohol toluene solvent, and antistatic and (or) flame retardant additives mixed in it are used in the following ratio ingredients, parts by weight:
ETF Epoxytriphenol Resin (Hybrid Binder Base) - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol-formaldehyde resin SF-340A (hardener) - 34
Soot and (or) carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 (antistatic) - 5-15
Antimony trioxide (flame retardant) - 5-10
Hexachlorobenzene (flame retardant) - 5-10
Freon (flame retardant) - 5-10
A distinctive feature of the proposed method is that as a hybrid binder to obtain a prepreg, a mixture of three resins dissolved in each other and acetone-alcohol toluene solvent - ETF, DEG-1 and SF-340A, into which antistatic additives are introduced:
- carbon-graphite fine mixture (antistatic) and (or) soot, for example, grade PN-100 and fine powder mixture of flame retardants - hexachlorobenzene, antimony trioxide and (or) microencapsulated additives: carbon tetrachloride (CCl ₄ ) and refrigerant in the following ratio of ingredients, parts by weight:
ETF Epoxytriphenol Resin (Hybrid Binder Base) - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol formaldehyde resole resin SF-340A (hardener) - 34
Acetone - 90
Technical alcohol - 46
Toluene (petroleum or coal) - 10
Carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1 (antistatic) - 5-10
Soot (PN-100) (antistatic) - 5-10
Hexachlorobenzene and (or) antimony trioxide (flame retardants) and (or) mixtures thereof in a ratio of 1: 3-3: 1 - 10
Carbon tetrachloride CCl ₄ and (or) freon (flame retardants) (or mixtures thereof in a ratio of 1: 3-3: 1) - 10
A distinctive feature of the proposed method consists in the fact that as a hybrid binder to create a prepreg, a mixture of three ETF, DEG-1 and SF-340A resins is used and dispersed mixtures of metal powders - copper, nickel oxides, are introduced into it as antistatic and flame retardant additives iron and (or) aluminum (or their solutions, suspensions) in the following ratio of ingredients, parts by weight:
ETF Epoxytriphenol Resin (Hybrid Binder Base) - 100
Epoxyaliphatic resin DEG-1 (diluent-plasticizer) - 12
Phenol formaldehyde resole resin SF-340A (hardener) - 34
Acetone - 90
Technical alcohol - 46
Toluene (petroleum or coal) - 10
- finely dispersed mixtures (solutions) of powders and (or) suspensions of metal oxides, for example, copper, nickel, iron and (or) aluminum.

A distinctive feature of the proposed method consists in the fact that as a coating (facing) material for the threads forming the base fabric of the prepreg, for example polycaproamide (kapron), polyphene and (or) carbon, a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black is used with additives introduced into it: antistatic (carbon black, carbon-graphite powders and (or) their mixtures, metal powder materials consisting of metal oxides, for example copper, nickel, iron or aluminum) and (or) antip irene (antimony trioxide, hexachlorobenzene, carbon tetrachloride CCl ₄ , freon) additives introduced into the hybrid binder (ETF, DEG-1, SF-340A) in the same proportional ratio.

 Figure 1 of this description shows a schematic diagram of the preparation of prepregs from various tissues formed from polycaproamide (kapron), polyphene and (or) carbon fibers (or combinations thereof) and a hybrid binder based on ETF, DEG-1 and SF-340A resins, designed in accordance with the proposed method.

 Figure 2 and 3 shows the individual fragments of the formation of the prepreg (or prepregs) at the individual stages of their formation.

 Figure 4-8 shows fundamentally possible schemes for processing prepregs obtained in accordance with the proposed method directly into heat-protective layers of structural products.

 The impregnated fabric 3 (polycaproamide (kapron), polyphene and (or) carbon) pre-rewound onto coil 1, forming continuous coils 2 on the coil in the form of a spiral, is mounted on the rigid frame 5 of the impregnating machine (Fig. 1) and fixed on it by means of threaded connections and faceplates (figure 2).

Non-impregnated fabric 3 (any: polycaproamide (kapron), polyphene and (or) carbon, consisting of any combination of polycaproamide (kapron), polyphene and (or) carbon threads) from reel 1 of the release mechanism 5 (Fig. 1 and 2) through the tension the roller 6 and the additional brake mechanism 7 enters the first drying chamber-shaft 20, equipped with electric heating elements, where at a temperature of 35-60 ^o With the heating of the woven filler. The fabric 3 with the release mechanism (figures 1 and 2) through the tension roller 6 and the brake mechanism 7 of the impregnation machine through the supporting-leading (and (or) pass) shafts 8-10 passes the first chamber-shaft 20, where under the influence created by electric heating devices temperatures (35-60 ^o C) there is a pre-preparation of the fabric for impregnation with a hybrid binder. Then the fabric 3 passes through the rollers 17 mounted in the impregnation bath 16, where it is impregnated with a hybrid binder 18 (ETF + DEG-1 + SF-340A) and then through the squeezing rollers 19, which regulate the application of the binder to the fabric (or fabrics) and enters the drying chambers 21 and 22, in which, under the influence of high temperatures, from 90-120 ^o С (at the inlet and outlet of the drying chambers) and up to 190-210 ^o С (in the upper zones of the drying chambers), the volatile components of the hybrid binder (acetone, alcohol) are removed , toluene and other components) and education as proposed m method of "dry" tissue prepreg from polycaproamide (kapron), polyphene and (or) carbon filaments. Then, through the lower pass shaft 12 and the feed mechanism 13 of the impregnation machine, the finished prepreg enters the coils 14 of the receiving device 23 of the impregnation machine, where it is finally formed into the prepreg fabric spiral 15 in the form of continuous spiral turns 24 (Figs. 1, 3). The holiday (Fig. 1, 2) and receiving (Fig. 1, 3) mechanisms of the impregnation machine for producing the prepreg are almost identical in design, that is, from the point of view of the interchangeability of individual nodes and parts, they have the same geometric dimensions and the shape of the nodes and parts.

 The difference in the (tempering and receiving) mechanisms consists only in the fact that the receiving mechanism of the impregnating machine (Figs. 1, 3) is equipped with an electric drive 25, and the tempering mechanism of the impregnating machine contains a brake drum 26 having brake pads (they are not shown in Fig. 2 ), by means of which the shaft 27 is braked, due to which the fabric (or tissues) is pretensioned 3. It should be noted here that the prepreg fabrics (Figs. 4-7) are tensioned when they are converted into structural products by namo methods webs with exactly the same tension mechanisms.

 Coil 1 (for the release mechanism) and coil 14 (for the receive mechanism) are interchangeable. They are mounted on the shafts 27 and secured against axial displacement (or skew) by special threaded plates 28 that are moved along the axis of the shaft 27 by means of threads 29 and 30 made on the pre-end sections of the shaft 27. The shaft end parts 31 are mounted in the thrust bearings 33 fixed in the holes brackets and pads tempering 5 (figure 2) and receiving 23 (figure 3) mechanisms of the impregnating machine, which are also for reasons of interchangeability made exactly the same.

 Obtained on the coil 14 woven prepregs (or prepreg) together with the coils are removed from the receiving device of the impregnating machine and rearranged on the frame device of the winding machines (Figs. 4-9), where the brake drums 26 (Fig. 2) and pads are tensioned already prepreg fabrics in the process of their processing into structural layers of plastic structural products created by the methods of direct circumferential winding (PN) or combined (Fig. 8), where initially on the mandrel 34 heat-insulating inner layers are formed with an overlap of layers ( if necessary - and sealing layers) structure, and for them already is forming the structural strength of products, carried by more advanced (in comparison with Mo) methods - DPU and (or) CH (8).

 The description, in the opinion of the authors of the present invention, would not be complete if they did not present reasoning evidence of the advantages of the proposed method for producing prepreg (or prepregs) in comparison with the previously described analogues and prototype.

 For the first time, a mixture of three resins - ETF, DEG-1 and SF-340A in an acetone-alcohol-to-toluene diluent, proposed and used to obtain prepreg (or prepregs), was not chosen by chance, but as a result of an inventive concept, extensive experience in this field, thoroughly conducted patent research, and also based on experimental and theoretical studies conducted by the authors regarding optimization of the structures of the prepregs they create. The basic epoxytriphenol binder ETF was chosen for the following reasons: after curing, it is non-toxic, at ordinary temperature ETF is a viscous liquid with a low molecular weight (350-700), which is especially important with the technology of forming large-sized plastic products.

 Possessing a high content of epoxy groups (from 13 to 27%), this resin is very reactive and can be cured in the presence of amine-type hardeners even without heating, practically emitting a very small amount of volatile products (up to 2.5%).

Lateral hydroxyl groups in the molecule of ETF resin allow another curing mechanism to be realized, for example, when using the resol type phenol-formaldehyde resin SF-340A as a hardener, which is carried out at elevated temperatures (from 160 ^o С and above).

The hot curing of this resin used by the authors made it possible to obtain a more durable and tough product. Due to its viscosity, ETF epoxy resin can be effectively used for the impregnation of any fibrous materials, including fabrics made of polycaproamide (kapron), polyphene and (or) carbon fibers. ETF resin is well compatible with active plasticizer diluents such as DEG-1 epoxyaliphatic resin, which has a low dynamic viscosity (0.07 Pa • s at a temperature of 25 ± 2 ^o С) and a low molecular weight of 240-320 and a sufficiently high content of epoxy groups (for DEG-1 resins, the content of epoxy groups ranges from 19 to 29%) and with solvents such as acetone-alcohol-to-toluene mixtures.

 The advantage of a bond of ETF and DEG-1 resins is the high stability of their properties even under long-term storage (up to 10 years). The use of phenol-formaldehyde resole resin SF-340A as a hardener in a hybrid binder was also not chosen by chance. Firstly, the use of resin SF-340A as a hardener made it possible to replace bromine-containing resins commonly used to increase the fire resistance of plastics.

 The burning time of such resins after the removal of the flame should be no more than 5 seconds, and the oxygen index is 35-38%. In foreign practice (and in RU too), in such binders, the bromine content is at least 2-22% and plastics with such a bromine content have low indices for heat resistance and thermal stability.

 Replacement of the bromine-containing resin UP-631U (see prototype, RU 2028334) with phenol-formaldehyde resole (SF-340A) allowed the authors to reduce the bromine content to zero values and due to this only increase (up to 10-30%) the heat resistance and thermal stability of plastics based on the prepregs.

 At the same time, the plastics obtained on the basis of the created prepregs retained high fire resistance, and this, apparently, is also associated with the influence of phenol-formaldehyde resole resin SF-340A, which enhances the fire-extinguishing characteristics of plastics during their combustion due to the release of coal.

 In conclusion of the foregoing, it should be added here that the exclusion of the bromine-containing resin (in comparison with the prototype) from the hybrid binder allowed us to simplify its formulation and the technology for preparing prepreg (or prepregs), and the technology for its processing into plastic products. The presence of bromine-containing resin (see prototype, RU 2028334), as a rule, creates significant difficulties in the production of heat-protective composite materials (apparently, this is due to some features of its physical and mechanical properties).

 Introduction to the hybrid binder of ETF, DEG-1 and SF-340A resins, antistatic additives (carbon black, carbon-graphite mixtures, metal powders (or powders) from metal oxides or nitrides, for example nickel, copper, iron and (or) aluminum and others), made plastics based on the obtained prepregs, formed in accordance with the proposed manufacturing method, electrically conductive, that is, plastics began to have high antistatic properties - the ability not to accumulate static charges on their surfaces during their operation. In addition, the presence of these antistatic additives in a hybrid binder has increased the heat resistance and thermal stability of plastics based on it, in particular, based on polycaproamide (kapron), polyphene and (or) carbon fabrics.

The introduction into the hybrid binder of flame retardant additives - hexachlorobenzene, antimony trioxide, chladone, carbon tetrachloride (CCl ₄ ) increased the heat resistance, thermal stability and fire resistance of structural products based on it even more.

 The use of flame retardants in a hybrid binder (ETF + DEG-1 + SF-340A) and in the lining of polycaproamide (kapron) and (or) polyphene and (or) carbon filaments formed from a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black, dramatically increases the fire resistance of plastics based on the created prepregs, they increase the heat resistance of plastics and their thermal stability, that is, resistance to aging.

 The flame retardants used in the method — antimony trioxide, hexachlorobenzene, carbon tetrachloride and chladone — slow down the burning of plastics due to endothermic effects during their thermal decomposition, releasing gases - carbon dioxide, chlorine, ammonia, phosphoric and chloride anhydrides, water vapor, etc. . Antimony oxides, and hexachlorobenzene, and carbon tetrachloride, etc. also impede the burning of plastics. According to the authors of the present invention, the total amount of flame retardants introduced into prepregs (and further into the composition of plastics based on them) should not exceed 3-10% of the total mass prepregs. At the same time, powder fillers from metal oxides or nitrides introduced into the hybrid binder additionally increase the impact strength of plastics based on it.

 The introduction of finely divided fillers in the composition of the hybrid binder and in the composition of the coating lining of the thread reinforcement of polycaproamide (kapron), polyphene and (or) carbon filaments made it possible to reduce the exothermic effect during curing of the compositions. This, in turn, led to a decrease in shrinkage of plastics, an improvement in their mechanical and some thermophysical characteristics. In addition, the use of finely dispersed conductive powder mixtures made it possible to improve a number of specific properties of plastics based on the obtained prepregs (or prepreg), namely, resistance to fire, radiation, and aging. Due to the introduction of finely dispersed mixtures into the composition, such indicators of plastics as electrical conductivity, long-term resistance to the appearance of electrostatic charges on their surfaces, etc. were improved. In addition, the use of finely dispersed mixtures allowed to reduce (in some cases up to 5-10% or more) the cost of products made on the basis of the proposed method for producing prepregs (or prepreg).

 The use of finely dispersed powdery fillers, for example, from metal oxides or nitrides, made it possible to improve some physicomechanical properties of plastic compositions, in particular, to increase transverse strength (tensile and interlayer shear strength).

 The amount of powder as well as discrete fibrous fillers introduced into the prepreg composition, according to the authors, should not exceed 10-30% of the total mass of fillers.

 Studies on a number of prepregs based on a hybrid binder (ETF + DEG-1 + SF-340A) showed that the introduction of powder carbon-graphite, metal and discrete finely dispersed mixtures in most cases can increase (up to 5-10% or more) the toughness of plastics based on these prepregs.

 However, the authors of the present invention should draw the attention of the developers of composite materials to the fact that the introduction of finely dispersed mixtures into the compositions of the prepregs developed by them must be strictly metered in each case, because with an overdose in plastics, undesirable effects, such as a change in the hygroscopicity and gas permeability of plastics, can occur , a significant slowdown or, conversely, acceleration of the curing of the binder, an increase in the viscosity of the binder and the resulting technological skie difficulties associated with the processing of prepregs directly in construction and (or) heat-shielding layer packages of products.

 According to the authors of the present invention, in the preparation of prepregs developed in accordance with the proposed method, special attention should be paid to the technological properties of the hybrid binder - its viscosity, viability and gelation period, as well as the amount of released volatile products and shrinkage. The first three characteristics (viscosity, viability and gelation period), to which the ability of the hybrid binder to wet the surface of the fibers should be added, ultimately determine the quality of the impregnation of the filler and the quality of the plastics obtained on their basis. The quality of the impregnation significantly affects the nature of the internal stresses in the material and, consequently, the number of cracks formed.

 The impregnation of prepreg fillers - tissues - largely depends on maintaining the optimal viscosity of the binder, at least during the first stages of prepreg formation. In most cases, hybrid resins with a low dynamic viscosity turn out to be more technologically advanced, since more liquid binders more easily penetrate the inter-filament (and inter-fiber) spaces of woven fillers.

 The optimal viscosity of the binder used to impregnate the prepregs lies in the range from 0.1 to 1 Pa • s. A binder with such a viscosity easily fills pores with a diameter of even 5-6 microns.

ETF epoxytriphenol resin produced at the Avangard Production Association is characterized by a rather wide range of viscosity properties: from 0.1 to 15 • 10 ³ MPa. The dynamic viscosity of the DEG-1 resin, which acts as a plasticizer diluent in a hybrid binder, is much lower and amounts to only 0.07 Pa • s at a temperature of 25 ^o C. This resin belongs to the category of low-viscosity resins with a molecular weight of 240-320 (whereas ETF resin has a molecular weight in the range of 350-700).

 The viscosity of phenol-formaldehyde binders, representing aqueous or alcoholic solutions, varies from 0.04 to 10 Pa • s with a solvent content of up to 35-55%. In particular, the dynamic viscosity of the resin solution SF-340A (GOST 18694-80) is only 10-20 MPa • s.

Therefore, when mixing ETF, DEG-1 and SF-340A resins, it is possible to lower the viscosity of the hybrid binder to the required limits of 0.1 to 5 Pa • s. The viscosity of the hybrid binder 18 can be reduced by 10-20% by heating it to 35-60 ^o C in the bath 16 of the impregnating machine (figure 1) by using heating elements 11.

That is why the method developed by the authors proposes to introduce into the impregnation process the heating of the hybrid binder they created from 35 to 60 ^o C. Heating the hybrid binder in the bath of the impregnation machine (Fig. 1) within its operating temperature significantly improves the tissue impregnation for the resulting prepreg even at lower the amount of binder applied to the reinforcement, which allows some control of the volumetric content of the fibrous filler in polycaproamide (kapron), polyphene and (or) carbon filaments in the composition tion.

 According to the authors, some attention should be paid to the shrinkage occurring in the hybrid binder during curing.

 Binder shrinkage is a consequence of the formation of the three-dimensional structure of the polymer during curing, when the chemical interaction changes the distance between the monomer molecules and the flame retardant and antistatic components introduced into it.

 The presence of a reinforcing filler (tissue) in the composition prevents the free shrinkage of the binder, leads to the formation of internal stresses, the most significant at the phase boundary. The introduction into the composition of the hybrid binder finely divided flame retardant and antistatic and discrete additives listed above significantly reduces the negative interaction of shrinkage, but does not completely eliminate it.

 Note. Unfortunately, the authors of the present invention do not have the opportunity, within the framework of the claimed solution, to more widely disclose the topics related to the formation of residual stresses in plastics formed on the basis of the prepregs (and plastics based on them) created by them and methods for their preparation.

 However, the authors consider it necessary to give a more detailed assessment of the complex of physicomechanical, thermophysical and technological properties of the obtained (or obtained) in accordance with the proposed method of prepreg (or prepregs) in the presented description.

 In the table. 1-12, the main properties of plastics obtained on the basis of prepregs from a hybrid binder (ETF + DEG-1 + SF-340A) and fillers from polycaproamide (nylon), polyphene and (or) carbon filaments (strands or bundles) are given.

 Table 1 presents the thermophysical characteristics of plastics based on prepregs from a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers from polycaproamide (kapron), polyphene and (or) carbon filaments (strands or bundles) in comparison with the known plastics formed on the basis of prepregs according to ed. testimonial. SU 730753.

 Table 2 shows the heat-shielding properties of plastics formed on the basis of a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers of polycaproamide (kapron), polyphene and (or) carbon filaments (strands or bundles) in comparison with the known plastics formed on the basis of prepregs according to ed. testimonial. SU 730753.

 Table 3 shows the physical and some other thermophysical properties of plastics formed on the basis of a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers from polycaproamide (kapron), polyphene and (or) carbon filaments.

 In the table. Figure 4 shows the average heat-shielding and antistatic properties of plastics formed on the basis of prepregs from a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers from polycaproamide (kapron), polyphene and (or) carbon fibers coated with a tetrafluoroethylene-vinylidene fluoride copolymer and (or) carbon black with antistatic and flame retardant additives introduced into it.

 Table 5 shows the comparative electrical characteristics of plastics based on prepregs formed in accordance with the proposed production method, namely, on the basis of a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers made of polycaproamide (kapron), polyphene and (or) carbon fibers lined with a coating material from a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black with antistatic and flame retardant additives - soot PN-100, hexachlorobenzene and antimony trioxide.

 In the table. Figure 6 shows the comparative electrostatic properties of plastics based on prepregs from a hybrid binder (ETF + DEG-1 + SF-340A) with antistatic additives (soot) and woven fillers formed from polycaproamide (kapron), polyphene and (or) carbon fibers lined with a copolymer from tetrafluoroethylene with vinylidene fluoride and (or) carbon black with antistatic additives introduced into the copolymer — carbon black and (or) carbon-graphite mixture in a ratio of 1: 5 to 5: 1.

 Note. As a basis for comparison, we used plastics formed from prepregs based on a hybrid binder consisting of ED-16 epoxy resin (45:55 parts by weight), UP-631U epoxy tetrabromodian resin, and SF-010 novolac phenol-formaldehyde resin and a filler made of fiberglass E-01 plain weaving of threads (ed. certificate. SU 730753).

 In the table. 7 shows data on the study of the performance of structural plastic model products (200 mm in diameter) manufactured by direct fabric winding with an overlap of tissue layers from 10 to 30 mm. The inner plastic heat-and-erosion-protective layers of these products were wound from prepregs formed from a hybrid binder (ETF + DEG-1 + SF-340A) and woven linen fillers from polycaproamide (capron), polyphene and (or) carbon threads lined with a vinyl tetrafluoroethylene copolymer and (or) carbon black with antistatic (soot) and flame retardant (antimony trioxide and hexachlorobenzene) added.

 In the table. Figure 8 presents an analysis of the basic physical and mechanical characteristics of wound plastics formed from a hybrid binder (ETF + DEG-1 + SF-340A) and linen woven fillers from polycaproamide (kapron), polyphene and (or) carbon filaments lined with a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black with antistatic (soot and carbon-graphite mixture with a ratio of components from 1: 5 to 5: 1) and flame retardant additives, and ordinary woven fillers from aluminoborosilicate and (or) organic threads type ZHSVM.

In the table. Figure 9 shows the physicomechanical characteristics of plastics formed from a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers from polycaproamide (kapron), polyphene and (or) carbon filaments at a test temperature of 20 ± 5 ^o C; in this embodiment, polyphene yarns are lined with a tetrafluoroethylene coating material with vinylidene fluoride and (or) carbon black with flame retardants added (hexachlorobenzene and antimony trioxide); powder fillers from metal oxides or nitrides were added to the hybrid binder formed from ETF + DEG-1 + SF-340A resins, which increase the transverse (tear-off) strength of plastics created with the proposed technical solution in relation to other widely known structural plastics of the type SKN-21, SKN-24, SKN-25, SKN-28 (OST 3-485-77) obtained by winding from conventional fabric prepregs based on fiberglass T-10, T-13, T-25VM, TSU-8 / 3-VM-78 and epoxyphenolic varnish EP-5122 TU 16-504.010-87, manufactured by the Electroisolit plant, Khotkovo Mosk ova region.

In the table. 10 presents the properties of plastics obtained on the basis of a hybrid binder ETF + DEG-1 + SF-340A and various woven fillers from glass, polycaproamide (kapron), polyphene and (or) carbon fibers, obtained by two methods
molding - by winding and pressing at a temperature of 20 ^o C.

 And finally, in the table. 11 and 12 show the recommended processing regimes for prepregs formed from woven polycaproamide (kapron), polyphene and (or) carbon materials and a hybrid binder ETF + DEG-1 + SF-340A, obtained by two methods: winding and (or) pressing followed by curing hybrid binder and converting it into a cured polymer matrix.

 In FIG. 10 and 11, the authors of the invention in addition to those presented earlier in the description of the table. 1-12, there are also data on the relative thermal expansion of plastics formed on the basis of a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers of polycaproamide (kapron) (Fig. 11), polyphene and (or) carbon (Fig. .10) filaments lined with a coating of a tetrafluoroethylene copolymer with vinylidene fluoride and (or) carbon black and antistatic (carbon black) and flame retardant (hexachlorobenzene and antimony trioxide) additives.

 In FIG. 12 shows the dependence of temperature on time in sublimation coatings based on a hybrid binder ETF + DEG-1 + SF-340A and fabrics made of polycaproamide (kapron), polyphene and (or) carbon fibers at various depths of plastic products.

 The results of studies conducted by the authors showed the following: on the surfaces of plastics formed from prepregs based on a hybrid binder (ETF, DEG-1 and SF-340A) and woven fillers from polycaproamide (kapron), polyphene and (or) carbon fibers lined with a copolymer with additives, the accumulation of charges of static electricity does not occur (see tab. 5, 6), the electric charges on the surfaces of the above plastics disappear earlier than it is practically possible to determine them and therefore these plastic materials are made According to the proposed method, can be attributed to the class of electrically conductive antistatic composites. Further studies showed that the above plastics during long-term operation lose their electrical and electrostatic characteristics in very small limits, which are: when simulating storage in a heated room for 10 years, no more than 20%; when simulating storage in an unheated room for 10 years, no more than 10%.

They quite actively absorb a large amount of heat during decomposition, have a high enthalpy. The average ablation rate of these materials (determined by weight loss, in mm / s) is for plastics made of carbon fabric yarns and a hybrid binder ETF + DEG-1 + SF-340A (with threads lined with a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black with flame retardants - hexachlorobenzene and antimony trioxide) 0.51 mm / s, for similar plastics from polycaproamide (kapron) fabrics the average ablation rate is already 0.54 mm / s, for similar plastics from polyphene fibers the average ablation rate is S THE already ≈0,75 mm / s (see Table 7 below.), and for plastics on the basis of the usual glass E-01 and known hybrid binder - ED-16, DP-631U and SF-010 Auto. testimonial. SU 730753 (ED-16), the ablation is already more than 1 mm / s (see table 7). The sublimation temperatures of the above plastics vary significantly and for a heat flux of 3.6 • 10 ⁶ W / m ² they have the following meanings: for fabrics made of polycaproamide (kapron) filaments with flame retardants, they are 300 ^o С, for fabrics made of polyphenic yarns they are 600 ^o C, for fabrics with carbon filaments they are more than 650 ^o C. The analysis of the tests (see table 1-7) shows that both the heat-protective and antistatic properties of the resulting plastics formed in accordance with the proposed method are more effective, than famous pla tic obtained by the technology described in the author. testimonial. SU 730753.

It should also be added here that as a result of the experimental data presented by the authors, it was found that plastics based on polyphenic fabrics have a higher density and thermal conductivity than plastics based on polycaproamide (kapron) fabrics, however, from the point of view of heat-shielding properties, composites based on polyphenic fabrics yarns are somewhat more effective than fabric composites from polycaproamide (kapron) yarns (by about 10-15%), since the thermal diffusivity of these compositions is slightly lower and amounts to 1,32 • this July ¹⁰ m ² / cek, whereas composites based on polycaproamide (nylon) tissue it is as 1,52 • July ¹⁰ m ² / sec (see. Table 1).

However, if we evaluate the performance of the above plastics under the influence of high-enthalpy heat gas flows (with heat flux values ≈3.6 • 10 ⁶ W / m ² ), then it is already preferable to use plastics made of polycaproamide (kapron) woven fillers, since they have more high thermal resistance [4.3 sec / (kg / m ² ) - for plastics from polycaproamide (kapron) fabrics, 2.3 sec / (kg / m ² ) - for plastics from polyphenic fabrics].

 Plastics made of polycaproamide (kapron) fabrics with a coating of a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black with flame retardants (antimony trioxide and hexachlorobenzene) have a lower ablation rate: 0.55 mm / sec for polycaproamide (capron) plastics tissues, 4.75 mm / s - for plastics from polyphenic fabrics (with the same hybrid binder (ETF-DEG-1-SF-340A).

Plastics based on fabrics made of carbon filaments lined with a similar copolymer coating have higher values of these parameters (the ablation rate at a heat flux of 3.6 • 10 ⁶ W / m ² for carbon plastics is 0.51 m / s), i.e., in comparison with plastics based on polycaproamide (kapron) and (or) polyphene based plastics these plastics are 10-20% more effective in the ablation rate. Especially noticeable they differ by sublimation temperature, which for the plastics manufactured according to the proposed technical solution is: for plastics of carbon prepregs ≈700 ^o C for from plastics polifenovyh prepregs ≈600 ^o C, and for plastics of polycapramide (nylon) prepregs ≈300 ^o С, whereas in ordinary plastics, for example, based on the hybrid binder ED-16, UP-631U and SF-010, the sublimation temperature is less than 200 ^o С. However, we should not forget the laws of a market economy, i.e. our case estoimost plastics production teploognezaschitnogo and (or) an antistatic purpose.

 In this indicator, plastics made of polycaproamide (kapron) fabrics and a hybrid binder are significantly superior to similar plastics made of polyphene and, especially, carbon filaments with a coating lining of a copolymer of tetrafluoroethylene with vinylidene fluoride and (or) carbon black (in comparison with plastics made of polyphene filaments - in 1 5-3 times, compared with plastics made of carbon filaments - an order of magnitude or more).

 According to the authors of the present invention, when designing structural products, the values of thermal deformations that these plastics admit must be taken into account. Although the nature of thermal deformations in all the studied plastics - from carbon, polycaproamide (kapron) and polyphene fabrics - is the same (see Figs. 11 and 12), however, the thermal deformations of these materials are significantly different, the thermal deformation of plastics based on fabrics from polyphene fabrics is significantly higher than that of plastics based on fabrics made of polycaproamide (kapron) and especially carbon fibers.

 However, all plastics obtained on the basis of polycaproamide (kapron), polyphene and even more carbon fabrics and a hybrid binder (ETF + DEG-1 + SF-340A) in this indicator, as well as in terms of thermal resistance and thermal stability, are significantly superior to plastics described in known analogues and prototype.

 Significantly they surpass the known plastics in aging, that is, from the point of view of preserving their properties under long-term operation.

Below are preliminary data on the reduction in the performance of plastics made in accordance with the proposed method for producing prepreg (or prepregs) during their long-term storage. Imitation of storage - 10 years in the conditions of storage of products in warehouses at a temperature of 18-25 ^o C, and in an unheated room - a shelf life of up to 5 years.

The conducted studies yielded the following result:
decrease in basic physical and mechanical characteristics (except shear and transverse strength) - no change;
reduction of thermophysical characteristics in% - no more than 10;
decrease in heat-shielding characteristics in% - no more than 15;
decrease in electrical characteristics - 20;
stress reduction when separated from other structural plastics that are in conjunction with the obtained plastics (formed by winding methods):
SKN-21 - 10,
SKN-24 - 15,
SKN-25 - 15,
SKN-28 - 20.

Note. Here SKN-21 is a structural winding plastic based on T-13 plain fiberglass and binder EP-5122;
SKN-24 - structural winding plastic based on TSU-8/3-VM-78 twill fiberglass fabric and EP-5122 binder;
SKN-25 - structural winding plastic based on cord fiberglass T-25VM and binder EP-5122;
SKN-28 - structural winding plastic based on satin fabric T-10 and a binder EP-5122;
EP-5122 is an epoxy binder, most used in the production of structural plastic products (TU 16-504.010-87).

Presented in the description of the data on the physico-mechanical, thermophysical and antistatic properties of plastics based on prepreg (or prepregs) obtained in accordance with the claimed method, have significant advantages over similar characteristics of plastics obtained in accordance with the methods described in the known analogues and prototype:
- the obtained plastics can be attributed to the class of electrically conductive composites on the surfaces of plastics based on a hybrid binder ETF + DEG-1 + SF-340A with antistatic and flame retardant additives and fabrics made of polycaproamide (kapron), polyphene and (or) carbon fibers lined with a tetrafluoroethylene copolymer with vinylidene fluoride and (or) carbon black with similar antistatic and flame retardant additives, there is no accumulation of charges of static electricity - the electric charge disappears earlier than its practical ski unable to determine. The above plastics described in analogues and prototype do not possess such properties;
- the obtained flame retardant plastics have a high enthalpy, absorb a large amount of heat during decomposition, work well as sublimators, they are more effective in terms of heat-shielding and antistatic properties compared to known sublimators obtained, for example, based on hybrid binders containing bromine-containing resins (ed. certificate SU 730753 and patent RU 2028334);
- prepregs obtained in accordance with the proposed method are more technologically advanced when processing into composites, while the production cycles of products based on them are reduced and the working conditions of workers are significantly improved;
- the resulting plastics based on the proposed method have higher ultimate shear and tearing stresses (up to 10-40%), higher impact strength (up to 10-15%) (see table 10);
- the resulting plastics in structural products have a lower level of residual stresses, they are less prone to the formation of cracks, swellings, delaminations;
- plastics obtained on the basis of the proposed method have a significant advantage over the known ones from the point of view of their operational reliability - their main physical and mechanical characteristics do not change during long-term operation (up to 5 years), in conditions of storage these characteristics do not change during 10 years.

 As for the inevitable loss of thermophysical, heat-shielding and electrical characteristics and losses of transversal strength (up to 10-20% during a ten-year period of operation or storage in warehouses), they, according to the authors, are, firstly, inevitable, and secondly, not so significant in comparison with the plastics described in the analogues and prototype.

However, it should be noted that the main physical and mechanical characteristics of plastics made by the proposed method have lower (several times in comparison with analogues and prototype) tensile and tensile stresses along the warp and weft of fabrics, these characteristics are significantly lower (by an order of magnitude and more) and the tensile modulus of elasticity in the direction of warp and weft: E _in ^k = 0.18 GPa, E _in ^OS = 0.2 GPa (see table 10).

All of the above reasoning suggests that the prepregs obtained in accordance with the developed method (and plastics based on them) can be used with a high degree of efficiency both as flame-retardant materials and as sublimators that work well in carrying away the material from the action of the heat flux 3.6 • 10 ⁶ W / m ² (the average linear ablation of plastics at these speeds is from 0.5 to 0.75 mm / s, for plastics manufactured in accordance with the prototype, this figure is more than 1 mm / s).

 However, as the main structural strength materials, the plastics obtained in accordance with the proposed method are not effective and not applicable; for these purposes, it is more efficient to use the presented hybrid binder (ETF + DEG-1 + SF-340A) in combination with ordinary fiberglass plain fabrics, satin, twill and even cord weaves or unidirectional ribbons processed by conventional winding methods - PN, PPN, SN, SPN, etc. (see tab. 10).

 Prepregs obtained in accordance with the proposed method can be processed into heat-protective (or antistatic) layers of products only by direct ring winding methods (Fig. 7), with an overlap of layers up to 10-30 mm and with very low nominal tensions - from 0.1 kgf / cm (when refueling) up to 1-1.5 kgf per centimeter of prepreg width (when winding).

 The mass fraction of the hybrid binder (ETF + DEG-1 + SF-340A) in the prepreg is 40-50%, the mass fraction of moisture and volatile substances is 3.5-5.5%, and the warranty period of storage of the prepreg is not more than 6 days.

 The above data indicate that the prepregs obtained in accordance with the proposed method cannot be used as structural strength material for technological reasons, and for reasons of economic feasibility.

 Too many structural large-sized products made by winding methods have long production periods of up to 5-30 days or more, while the guaranteed shelf life of the obtained prepregs is only 6 days, even for storage reasons prepared for winding prepregs must be used for 3- 6 days no more, and therefore it is more expedient to use them as initial layers of structural products, for example, either in the form of antistatic, or in the form of heat and flame retardant, or sculpt features antistatic and sublimator simultaneously.

 However, the above disadvantages of plastic composites obtained from prepregs in accordance with the claimed method of their manufacture, do not reduce their advantages in comparison with known analogues and prototype. According to the authors of the present invention, composite antistatic, anticorrosive plastics, first created on the basis of the above-described prepregs, in addition to the above advantages, also have high heat and flame retardant, sublimation and technological properties. In addition, almost all of their physico-mechanical, heat-shielding, electrostatic and some other characteristics are not prone to aging and keep their properties constant (up to 10 years of operation) under the influence of atmospheric precipitation, solar radiation and aggressive environments.

 The proposed method for producing prepregs from fabrics containing polycaproamide (nylon), polyphene and (or) carbon fibers, allows to obtain prepregs with various weaves of threads - linen, satin, twill and others with different volume contents of the binder and filler in plastics, and with different contents volatile substances - up to 2.5%.

 The method is high-tech, its reproduction does not require large economic costs and the use of highly qualified labor, the reproduction cycle is only several tens of hours (taking into account all the preparatory operations).

 The method involves an almost continuous cycle of manufacturing products - from the beginning of the preparation of the hybrid binder to the impregnation of fillers, their drying, rewinding to produce prepreg (or prepregs) and its (them) processing directly into heat-protective and (or) antistatic layers of large-sized products obtained from composite fibrous materials by winding methods (see figure 4-9).

The proposed method for producing prepregs from polycaproamide (kapron), polyphene and (or) carbon fabrics and a hybrid binder containing the same number of antistatic and flame retardant additives (and with the same ratio of flame retardant and conductive components in these additives), when introduced into industrial production can give a big economic effect, which even in the conditions of continuous loading of only one plant - GP Avangard - can give a big direct economic effect, which will be:
- in the conditions of pilot and small-scale production, tens of millions of rubles;
- in the conditions of mass production, several hundred million rubles;
- In conditions of large-scale and mass production, tens and hundreds of billions of rubles.

Direct economic effect from the implementation of the proposed method is achieved:
- by reducing the energy complexity of the manufacture of prepregs and products based on them;
- by reducing the manufacturing cycles of prepregs and products based on them;
- by reducing the costs used in the production of raw materials, including by reducing production waste;
- by improving the operational characteristics (parameters) of manufactured products, including by improving their quality and operational reliability.

 The economic effect of the proposed technical solution can be achieved at various stages of obtaining the prepreg (or prepregs) and its (them) processing into products by winding and (or) pressing methods.

 At present, the enterprise GP Avangard has carried out not only research work on creating prepregs, but also has created a basis for their industrial use. In particular, reactors for the production of a hybrid binder (ETF + DEG-1 + SF-340A), impregnation machines, mandrels for molding structural products of various nomenclature and geometric sizes were designed and manufactured. At the same time, technological equipment was also created for processing flexible tape prepregs obtained in accordance with the proposed method for both winding and pressing methods, heat chambers for heat treatment of plastic products based on them, and means for controlling the reproduction of all technological operations of their processing into structural products.

The work was carried out in several directions at the same time:
- in the direction of studying the possibility of using tape prepregs for the manufacture of structural products or their surface heat-shielding or antistatic facings;
- in the direction of the search for the most optimal modes of their formation, impregnation, drying and processing;
- in the direction of improving technological equipment and winding machines to obtain flexible tape prepregs from KVM and their processing into structural products;
- in the direction of studying the physicomechanical, thermophysical, sublimating, operational and other properties of materials obtained from flexible tape prepregs by winding and (or) pressing methods;
- in the direction of studying the processes of obtaining copolymer coatings for threads, strands or bundles and the effect of introducing into them and into a hybrid binder one or another type of antistatic and (or) flame retardant additives on the strength, stiffness, thermophysical, electrostatic and operational properties obtained from flexible tape prepregs plastic composites.

 The research and development work carried out and currently being carried out at the Avangard GP software company and research and development center shows the high efficiency of the proposed method for manufacturing tape prepreg (or prepregs) from KVM. Currently, at the Avangard Production Association, in accordance with the technical solutions presented in this description, for preparing flexible tape prepregs and the modes of their processing into structural products, experimental batches of structural products — chimneys, containers, oil and gas pipelines, high-pressure cylinders, and other products — have been made and tested. .

 Tests of experimental model tubular specimens and full-scale products manufactured in accordance with the technological winding schemes given in the description were performed at the Avangard GP software company and gave a positive result.

 The greatest economic effect from the implementation of the proposed technical solution is expected by increasing the operational properties of structural products made from flexible tape prepregs, as well as improving their quality, operational reliability and durability.

 Thus, the proposed technical solution is new and more effective in comparison with the prior art. The scope of the invention should be understood more broadly than its specific implementation, presented in the materials of this description and in the drawings. It should be borne in mind that the forms of the invention described above in the application materials are not only possible options for its implementation, but can be used by other, maybe more advanced embodiments of the invention in the direction of choosing hybrid binders and tissue fillers for flexible tape prepregs, as well as constructions of impregnating apparatuses, modes of forming flexible tape prepregs, their drying, rewinding and processing.

 It should be borne in mind that the technological modes of forming tape prepregs from KVM described above, the modes of their processing into structural products, the technological properties of tape prepregs and technological modes of their processing will be effective only when using materials of the above compositions and structure, as well as the volumetric content of polycaproamide ( nylon), polyphene and (or) carbon filaments and a hybrid binder (ETF + DEG-1 + SF-340A). When using other fabric fillers, for example, cord, knitting-stitched and from other threads (and threads with a different facing copolymer structure and other binders, for example, more fluid or more viscous), to obtain flexible tape prepregs from KVM, it will be necessary to introduce: a significant adjustment of the modes obtaining flexible tape prepregs (in terms of their speeds of movement, tension, heating and drying, used for prepregs of fillers and a binder) and significant structural changes in the layout of the impregnating device and winding equipment.

 In conclusion of the presented description of the invention, it should be noted that its implementation is not limited to its use only for receiving plastic tubular products - chimneys, containers, pipelines, facing materials, plate elements, etc. It can be used, for example, in the manufacture of flexible tape spirals used to repair pipes and pipelines, as well as other spirals, for example with "elastic memory", with enhanced thermophysical, antistatic and anticorrosion properties.

 At the enterprise GP Avangard, in accordance with the proposed method for the manufacture of prepreg (or prepregs), large-scale research work has been carried out - research and development. Currently, in accordance with the proposed method for the preparation of prepregs (or prepregs), a large number of technological equipment and equipment has been designed, manufactured and tested (including with the involvement of contractors): mixing reactors with thermostatic devices for producing a binder and mixing them, heating devices individual resins before mixing, impregnation machines, mandrels for processing the prepreg (or prepregs) directly into structural products, winding devices and, including , winding machines with program control and means of control of separately carried out operations of the method, heat chambers for heat treatment of products, etc.

 In addition, a large number of flame retardant and antistatic additives have been tested, used to give the hybrid binder and fillers various technological properties, and plastics from them - operational properties.

 A large technological refinement of the proposed technical solution in laboratory conditions and directly in industrial production was also carried out. So, for example, additional studies were carried out to determine the effect of the shift of individual turns of the spiral prepreg relative to each other and the ovality of the spiral prepregs on the quality of the windings of structural products obtained from them.

 The authors of the present invention found that the shift of the turns of the tape prepreg when rewinding it to the coil of the receiving device of the impregnating machine should be no more than 5 mm, and its ovality in the annular cross section should be no more than 20 mm.

 Failure to comply with the above technological parameters of the prepregs significantly reduces the quality of obtained from them by winding structural products. For example, the shift of the coils in the prepreg helix of more than 5 mm relative to each other worsens the conditions for obtaining the calculated overlap (or overlaps) of the prepreg filler webs placed on rotating mandrels with an overlap of 10 to 30 mm. The molding of blanks of full-scale plastic products from the aforementioned prepregs with increased ovality (over 20 mm in the annular section) does not allow laying on the mandrel with the specified tension and speed. Structural products molded with such parameters have unstable structures, and therefore unstable strength, stiffness, thermophysical, electrical, electrostatic, and other characteristics. Such products are more prone to the formation of residual stresses and, therefore, have low performance, in particular shear, transverse and dynamic strength.

 Currently, in accordance with the proposed method, the production of pilot batches of plastic pipes-shells and parts of various classes and purposes, in particular containers, pipes, pipelines, tanks, oil storage tanks, high-pressure plastic cylinders for the oil and gas industry, smoke pipes and parts for them, has begun thermal stations and boiler rooms, various structural products and parts for them aerospace technology.

 A new technical solution presented in FIPS as the proposed invention meets the criteria of "Novelty" and "Industrial utility".

Example 1
1. We heat the epoxytriphenol resin ETF (TU 2225-316-09201208-94) in an amount of 365.6 kg to a temperature of 180-200 ^o C for 24 hours - 100 wt. h

 2. We heat the epoxyaliphatic resin DEG-1 (TU 2225-027-00203306-97) for 2 hours (it is allowed not to heat the resin DEG-1) - 12 parts by weight

 3. We prepare acetone-alcohol-toluene solvent in a quantitative ratio of 301.6: 168.2: 36.5 kg (acetone - GOST 2603-79 or GOST 2768-84 - 90 parts by weight; ethyl alcohol - GOST 17299-76 or GOST 18300- 72 - 46 parts by weight; toluene (oil or coal shale) - GOST 98-8-76 - 10 parts by weight).

 4. Pour the heated epoxy binder ETF, DEG-1 and acetone-alcohol toluene solvent into the reactor-mixer.

5. The mixture of the above components is mixed at a temperature of 35-55 ^o C for 3-5 hours per ton of composition.

 6. Grind phenol-formaldehyde resole resin brand SF-340A, GOST 18694-80, in the amount of 124.3 kg into pieces to a value of 1-3 mm (34 parts by weight) and add to the reactor-mixer into the already dissolved among themselves in acetone-alcohol-toluene solvent epoxy resins ETF and DEG-1.

7. We heat the newly obtained consistency of resins to a temperature of 40-60 ^o C for 3-5 hours by mixing them together in a reactor-mixer.

8. We bring the consistency of the hybrid binder to a density of 950-1010 kg / m ³ by introducing 20 kg alcohol-acetone solvent into it in a ratio of 1: 2 and mix it with a hybrid binder at temperatures of 18-35 ^o C for 30-40 minutes.

 9. We filter the hybrid binder through a filter or several layers of diluted Excelsior fabric in order to remove all particles of phenol-formaldehyde resol binder SF-340A that do not dissolve in the reactor.

10. A hybrid binder based on ETF epoxy resin, DEG-1 epoxy aliphatic resin, and SF-340A phenol-formaldehyde resole resin, dissolved together in a combined acetone-alcohol-toluene solvent, must meet the following requirements:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing foreign inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 50-63;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 950-1010;
g) gelation time at a temperature of 160 ± 2 ^o C, min - 4-5;
11. We fill in the impregnation machine woven filler, heated to a temperature of 40-60 ^o C.

12. Set the temperature in the shaft of the impregnation machine 90-130 ^o With at the inlet and outlet of the drying chamber and 130-210 ^o With in its main working areas.

 13. Pour the hybrid binder into the bath of the impregnation machine.

 14. We impregnate the woven filler with a hybrid binder at a speed of 1-3 m / min and a tension of 0.5-1.5 kg per centimeter of web width, followed by removing excess hybrid binder on the squeeze rolls of the impregnation machine.

15. Upon reaching the impregnated and dried to the state of the prepreg tissue filler of the receiving mechanism of the impregnation machine, cut off the strip from the filler and check for compliance with the following requirements:
a) mass fraction of resin,% - 35-55;
b) mass fraction of volatile substances and moisture,% - 0.8-5.5;
c) mass fraction of soluble hybrid resin,% - 88-92.

 16. We make full-scale products or samples by winding or pressing on the basis of prepregs from a hybrid binder (ETF + DEG-1 + SF-340A) and woven fillers, from the product allowances we cut out test samples and obtain the characteristics of the PCB, given in Table 1.

Example 2 (the implementation of the method according to p. 2 claims according to the application 2002101670/04)
1. In the prepared consistent formation - a hybrid binder ETF + DEG-1 + SF-340A, having the properties of clause 10 of Example 1, add carbon black or carbon-graphite mixture (per ton of hybrid binder up to 100 kg of carbon black or carbon-black graphite) and mix for 10-15 minutes.

2. The hybrid binder must meet the following requirements:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 57-72;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 950-1050;
g) gelation time at a temperature of 160 ± 2 ^o C, min - 4-6.

3. We impregnate the woven filler with a hybrid binder according to claim 1, analogously to example 1 and check for compliance with the following requirements:
a) mass fraction of resin,% - 37-58;
b) mass fraction of volatile substances and moisture,% - 1.0-6.0;
c) mass fraction of soluble resin,% - 80-90.

4. We make the product by winding or pressing from a hybrid binder (ETF + DEG-1 + SF-340A + carbon black (or carbon-graphite mixture) and woven fillers at a temperature of +20 ^o C and we obtain plastic characteristics similar to example 1, except: increases density by 10%; physical and mechanical characteristics are reduced by 8%; antifriction properties are improved, namely, the friction-slip coefficient is increased to 0.094, in addition, some other properties of plastic are also improved:
- the coefficient of thermal diffusivity increases, • 10 ⁶ , m ² / s - 0.9-1.35;
- the coefficient of thermal conductivity increases, W / m • K - 0.19-0.4;
- the specific heat increases, kJ / (kg • K ^-1 ) - 0.95-1.4;
- the antistatic properties of plastic are improved (plastics do not accumulate static charges during operation).

Example 3 (the implementation of the method according to claim 3 of the claims according to the application 2002101670/04)
1. In the prepared hybrid binder ETF + DEG-1 + SF-340A, having the properties of clause 10 of Example 1, we add carbon black or carbon-graphite mixture, antimony trioxide, hexachlorobenzene (per ton of hybrid binder, up to 36.5 kg of carbon black or carbon-graphite mixture, up to 45 kg of antimony trioxide and up to 45 kg of hexachlorobenzene) and mix for 15-20 minutes.

2. The resulting hybrid binder must meet the following requirements:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 56-73;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 950-1060;
g) gelation time at a temperature of 160 ± 2 ^o C, min - 4-7.

3. We impregnate the woven filler with a hybrid binder according to claim 1, analogously to example 1 and check for compliance with the following requirements:
a) mass fraction of resin,% - 35-60;
b) mass fraction of volatile substances and moisture,% - 1.0-6.1;
c) mass fraction of soluble resin,% - 60-90.

4. We make the product by winding or pressing from a hybrid binder (ETF + DEG-1 + SF-340A + carbon black (or carbon-graphite mixture) + antimony trioxide + hexachlorobenzene and woven fillers at a temperature of +20 ^o C and obtain plastic characteristics similar to example 1 , with the exception of:
- increase in density by 5%;
- reduction of physical and mechanical characteristics by 6% (in comparison with table 1 of example 1).

In addition, a number of other properties of plastics also change:
- improved anti-friction properties analogously to example 2;
- electrical characteristics are improved (the degree of flammability of plastic is reduced by 10-30%, see table. A);
- the antistatic properties of plastics are improved (during operation, plastics do not accumulate static charges).

Example 4 (the implementation of the method according to claim 4 of the claims according to the application 2002101670/04)
1. In the prepared hybrid binder ETF + DEG-1 + SF-340A, having the properties of clause 10 of Example 1, add carbon black or carbon-graphite mixture, antimony trioxide, hexachlorobenzene, carbon tetrachloride CCl ₄ , freon (per ton of hybrid binder up to 36, 5 kg of carbon black or carbon-graphite mixture, up to 45 kg of carbon tetrachloride CCl ₄ and up to 45 kg of freon), mix for 15-20 minutes (the reactor-mixer must be grounded).

2. The resulting hybrid binder must meet the following requirements:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 56-72;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 950-1000;
g) gelation time at a temperature of 160 ± 2 ^o C, min - 4-8.

3. We impregnate the woven filler with a hybrid binder according to claim 1 (the impregnating machine must be grounded) similarly to example 1 and check for compliance with the following requirements:
a) mass fraction of resin,% - 35-56;
b) mass fraction of volatile substances and moisture,% - 1.0-6.2;
c) mass fraction of soluble resin,% - 80-88.

4. We make the product by winding or pressing from a hybrid binder (ETF-DEG-1 + SF-340A + soot (or carbon-graphite mixture) + antimony trioxide + hexachlorobenzene + carbon tetrachloride CCl ₄ + cold) and woven fillers at a temperature of +20 ^o С and get the characteristics of the plastic, similar to example 1, except:
- water absorption increases and reaches up to 2%;
- reduced physical and mechanical characteristics by 7% (compared with table 1 of example 1);
- improved anti-friction characteristics as in example 2;
- improve electrical characteristics as in example 3;
- thermophysical and antistatic properties are improved:
effective enthalpy, • 10 ⁶ , J / kg - 3.24-3.82,
average linear ablation at a gas flow velocity of 500 m / s - not more than 0.7,
sublimation temperature, ^o С - 300,
specific volume resistance, Ohm • m (Ohm • cm) - not more than 1.1 (0.11 • 10 ³ ).

Example 5 (the implementation of the method according to claim 5 of the claims according to the application 2002101670/04)
1. In the prepared hybrid binder ETF + DEG-1 + SF-340A, with the properties of clause 10 of Example 1, we add carbon tetrachloride CCl ₄ and freon (per ton of hybrid binder: up to 90 kg of carbon tetrachloride CCl ₄ and up to 45 kg of freon ), mix for 10-15 minutes (the reactor-mixer must be grounded).

2. The resulting hybrid binder must meet the following requirements:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 57-70;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 950-1000;
g) gelation time at a temperature of 160 ± 2 ^o C - 4-8 minutes

3. We impregnate the woven filler with a hybrid binder according to claim 1 (the impregnating machine must be grounded) similarly to example 1 and check for compliance with the following requirements:
a) mass fraction of resin,% - 35-57;
b) mass fraction of volatile substances and moisture,% - 1.0-6.0;
c) mass fraction of soluble resin,% - 86-92.

4. We manufacture the product by winding or pressing from a hybrid binder (ETF + DEG-1 + SF-340A + carbon tetrachloride CCl ₄ + freon) and woven fillers at a temperature of +20 ^o С and we obtain plastic characteristics similar to example 1, with the exception of:
- water absorption increases to 1%,
- improved thermophysical and antistatic properties (identical to example 4);
- electrical characteristics are improved;
- the degree of flammability of the plastic is reduced by 10-40%.

Example 6 (the implementation of the method according to p. 6 claims according to the application 2002101670/04)
1. In the prepared hybrid binder ETF + DEG-1 + SF-340A, having the properties of claim 10 of Example 1, we add a powder or a powder mixture of metal oxides or nitrides - magnesium oxide, aluminum oxide, titanium oxide, iron oxide, nickel oxide or boron nitride (per ton of hybrid binder up to 160 kg of powder or a powder mixture of metal oxides or nitrides), mix for 10-15 minutes.

2. The resulting hybrid binder must meet the following characteristics:
a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;
b) mass fraction of non-volatile substances,% - 55-72;
c) the density of the hybrid binder at a temperature of 20 ± 1 ^o C, kg / m ³ - 980-1100;
g) gelation time at a temperature of 160 ± 2 ^o C, min - 4-8.

3. We impregnate the woven filler with a hybrid binder according to claim 1, analogously to example 1 and check for compliance with the following requirements:
a) mass fraction of resin,% - 35-55;
b) mass fraction of volatile substances and moisture,% - 0.8-5.6;
c) mass fraction of soluble resin,% - 80-90.

4. We make the product by winding or pressing from a hybrid binder (ETF + DEG-1 + SF-340A + powder or a powder mixture of metal oxides or nitrides) and woven fillers at a temperature of +20 ^o С and we obtain plastic characteristics similar to Table 1 Example 1, with the exception of:
- increase the rate of heat resistance according to Martenson, K - up to 850;
- improving the antistatic properties of plastics;
- improving the thermophysical properties of plastics (thermal conductivity up to 10%, thermal diffusivity up to 25%, heat capacity up to 20% - in comparison with the data of example 4).

 In addition, the introduction of finely divided powder fillers in the composition of the hybrid binder allows to reduce the exothermic effect during curing, as well as reduce shrinkage, improve mechanical properties (for example, impact strength - up to 10-15%).

 However, powdered fine fillers can also cause undesirable effects, such as a change in the hygroscopicity and gas permeability of reinforced plastics, a significant slowdown (for example, due to the introduction of a hybrid binder of magnesium oxides in the composition), or, conversely, acceleration or acceleration of the curing of the binder (for example, due to the introduction of aluminum oxide binder).

 The disadvantages of using powder fillers in a hybrid binder include the increase in its viscosity and the resulting technological difficulties associated, for example, with the difficulties of impregnation of fabrics and their processing by winding into structural products.

Example 7 (the implementation of the method according to claim 7 of the claims according to the application 2002101670/04)
1. We prepare a hybrid binder (ETF + DEG-1 + SF-340A) and impregnate the woven filler in accordance with example 1.

 2. We prepare a coating material consisting of a copolymer of tetrafluoroethylene with vinylidene fluoride and carbon black with carbon black or carbon-graphite mixture introduced into them (copolymer of tetrafluoroethylene with vinylidene fluorine 25 kg, carbon black up to 20 kg, carbon black or carbon-graphite mixture 15 kg).

3. We mix the coating material in any container for 20-30 minutes at a temperature of 50-70 ^o C until the components are completely combined.

4. We issue coating material for winding and process it at a temperature of 60 ± 5 ^o C for no more than 4 hours.

 5. Pour the coating material into the bath, fill the woven filler, impregnated with a hybrid binder, and manufacture the product according to the technological schemes presented in figures 4-8 of the application description 2002101670/04.

6. We obtain plastic characteristics similar to example 1, with the exception of:
- increased water absorption up to 1%;
- improved anti-friction characteristics as in example 2;
- improved thermophysical and antistatic properties as in example 4.

Example 8 (the implementation of the method according to claim 8 of the claims according to the application 2002101670/04)
1. In the coating material prepared according to claim 2 of Example 7, we additionally introduce antimony trioxide and hexachlorobenzene (antimony trioxide 12 kg and hexachlorobenzene 12 kg).

 2. Perform the operations of p. 3, 4, 5 of example 7.

3. We obtain plastic characteristics similar to examples 1 and 7, with the exception of:
- improve the electrical characteristics of plastics by 20-50% (in comparison with the data of example 3);
- decreases the combustibility of plastics by 20-60% (in comparison with the data of example 3).

Example 9 (the implementation of the method according to p. 9 of the claims according to the application 2002101670/04)
1. In the coating material prepared according to claim 2 of Example 7, we additionally introduce a powder filler in the form of metal or silicon oxides or nitrides (14 kg).

 2. Perform the operations p. 3, 4, 5 of example 7.

 3. We obtain the characteristics of the plastic, similar to examples 1, 6, 7.

Conclusions and recommendations
Analysis of the data given in examples 7-9 shows:
- the introduction into the composition of the coating copolymers of tissue fillers of plastics carbon black, carbon black and / or carbon-graphite mixture significantly increases the antistatic effect of plastics (10-20% in comparison with examples 1-4);
- the simultaneous introduction into the compositions of coating copolymers of fabric fillers of antistatic agents (carbon black, soot or carbon-graphite mixture) and flame retardants (antimony trioxide, hexachlorobenzene) significantly improves the antistatic properties of plastics by 10-30% and reduces their combustibility to 40% (example 8);
- the introduction into the copolymers of coating materials of fabrics of powder fillers from metal oxides and boron nitrides by 30-40% increases the dynamic strength of plastics (example 9);
- the introduction into the composition of the copolymers of coating materials of woven fillers of silicon oxides significantly (10-30%) increases the heat resistance of plastics, as well as their chemical resistance and radio transparency. Note: data on the chemical resistance, water resistance and heat resistance of the above plastics with the powdered compositions of silicon oxides introduced into them are not available in the application materials, since their consideration is beyond the scope of the claims of this application.

 Preliminary studies of this type of plastic (with silicon oxide fabrics introduced into the composition of the hybrid binder and copolymers of coating materials) showed that they have low adhesive strength, high brittleness and instability of physico-mechanical and thermophysical properties; in addition, such plastics have a significant cost.

 In conclusion of this section of the answer, it should be said that the use of ETF + DEG-1 + SF-340A composite hybrid binder in plastics with antistatic (soot, carbon-graphite powder mixtures), flame retardant (chladone, hexachlorobenzene, carbon tetrachloride, antimony trioxide) simultaneously introduced into it , anti-shock (metal oxides) and anti-acid (silicon oxides) powder components and woven fillers made of polyphene, polycaproamide and carbon filaments can significantly use the advantages their constituent elements (and components) and avoid their inherent disadvantages.

 The ETF resin used in the hybrid binder, due to its low molecular weight (350-600), is a viscous liquid, which is especially important in the molding of large-sized large-tonnage products. Having a high content of epoxy groups (13-29%), this resin is very reactive and can be cured in the presence of phenol-formaldehyde resin SF-340A, practically not emitting volatile products (up to 2.5%).

 The hot curing of these resins together with woven fillers from polyphene, polyamide and carbon filaments allows to obtain more durable and rigid plastics with a wide range of physico-mechanical, thermophysical, antistatic, shockproof and other properties.

 The DEG-1 resin used in this method for producing prepregs relates to low-viscosity epoxy resins with a molecular weight of 240-320. It has good compatibility with the active acetone-alcohol-toluene diluents used in the method.

 Due to the low viscosity, the hybrid binder used in the method can be widely used for impregnation and preparation of prepregs from any fibrous materials, including woven fillers from polyphene, polycaproamide, and carbon fibers, including fibers coated with copolymers of tetrafluoroethylene with vinylidene fluoride, technical carbon and powder fillers of the above types.

 The advantage of the method is the high stability of the properties of the resins ETF, DEG-1 and SF-340A, which are part of the hybrid binders, even under conditions of their long-term storage (up to three years).

Clarifications to the examples presented in this letter of reply on application 2002101670/04
In the table. 1 of this answer, explaining the essence of the invention according to the application 2002101670/04, in section 2 fiberglass fabrics with a linen weave structure and thread thickness from 8 to 15 μm are indicated, it is such fabrics (fabrics of grades E-01 or T-13) were used to create prepregs from a hybrid polymer binder according to ed. testimonial. 730753, Mcl ² C 08 L 63/02, taken by the authors of this application for the prototype.

The composition of the hybrid binder prototype used:
- epoxy diane resin ED-16, GOST 10587-84 (45-55 parts by weight);
- bromine-containing epoxy resin UP 631, TU 6-05-1689-79 (45-55 parts by weight), which is a product of epichlorohydrin with tetrabromodefinylolpropane;
- phenol-formaldehyde resin SF-010, GOST 18694-80, the closest in composition to the ingredients phenol-formaldehyde resin SF-340A, used by the inventors according to application 2002101670/04 (002143) as a resin - hardener of its hybrid binder to create new prepregs.

 In general, the proposed method for preparing prepregs involves the use of plain, satin, twill and even cord weave. However, since the prototype is taken as the basic object of comparison - ed. testimonial. 730753, in which prepregs obtained on the basis of plain weave fabrics (fabrics E-01, T-13, etc.) are taken as fillers, then in the future, to compare the physicomechanical and thermophysical properties, the properties of prepregs formed from woven structures will be considered plain weaving of threads and a hybrid binder (ETF + DEG-1 + SF-340A).

 In fabrics with plain weave, warp and weft threads are mutually interwoven, the ratio of warp and weft fabrics is ≈2: 1, therefore, the physicomechanical characteristics of plastics made from prepreg fabrics with plain weave warp and weft are significantly different (≈ 2 times), with the exception of compressive strengths, where these limits in the direction of the warp and weft of plastic are approximately equal and amount to 170-200 MPa (for example, for plastics formed from prepregs based on fiberglass plain fillers (ty PA fiberglass T-13) and a hybrid binder).

 Fabrics with plain weave of threads have a strength in the direction of reinforcement (base) slightly less (by 10-20%) than fabrics of satin weave, but prepregs with plain weave of threads have higher flexibility, and therefore are more technological and effective in the manufacture of plastic products ; they simply fit better on the surface of the mandrels without gaps; thereby increasing the transversal strength of the shell structures of multilayer products.

 In addition, fabrics with plain weave of threads are much cheaper than fabrics with satin, twill and cord weave of threads, which, ceteris paribus (along with manufacturability) gives them a significant advantage when conducting research work on the creation of new prepregs and their industrial introduction to large-scale production.

 Therefore, as an example, table. 1 of this letter, to obtain new prepregs, fabrics with plain weave were used - both power (table 1 to the examples) and heat-protective (table 2-5).

 In section 2 of the table. 1 shows the characteristics of fiberglass, formed on the basis of fiberglass fabrics with plain weaving of type T-13 or E-01 and a hybrid binder ETF + DEG-1 + SF-340A.

 These fiberglass plastics incorporate 35 ± 5 parts by weight. hybrid binder and 70 ± 5 wt. including fiberglass plain filler (the most optimal composition of fiberglass in terms of their rigidity and strength).

 In the table. Clause 1, Clause 3 shows the physicomechanical and thermophysical properties of plastic formed from polycompromide fabric with plain weaving (TU 06-31-121-76), consisting of multicomplex electrically conductive threads of the MKEN-k brand (TU 06-31-121-76 ) and the ETF-DEG-1 + SF-340A hybrid binder in accordance with Example 1 (the plastic is formed by winding methods), the weight of the hybrid binder being 30 ± 5 parts by weight, and the content of the polycarbide filler with plain weaving of MKEN-k threads - 70 ± 5 wt. h

 In the table. 1, p. 4 shows the physicomechanical characteristics of plastic formed from polyphene fabric, consisting of multicomplex electrically conductive fibers MKEN-p (TU 06-31-121-76) and a hybrid binder ETF + DEG-1 + SF-340A in accordance with an example 1 (the plastic is formed by winding methods), while the weight content of the hybrid binder in plastic is 35 ± 5 parts by weight, the content of polyphene woven filler with plain weaving of threads 70 ± 5 parts by weight

 In sections 5-7 of the table. 1 shows the physicomechanical and thermophysical characteristics of the above-described plastics of the same structure and composition (p. 5 - fiberglass, p. 6 - polycompromide plastic, p. 7 - polyphene plastic made by extrusion).

 Note. In the table. 1 above the line shows the physico-mechanical and thermophysical characteristics of plastics in the direction of the basics of tissue fillers, and below the line shows the physical-mechanical and thermophysical characteristics of plastics in the direction of the weft of tissue fillers.

 Data analysis table. 1 shows that the prepregs made in accordance with the proposed method from a hybrid binder ETF + DEG-1 + SF-340A and polycompromide or polyphene fabrics with plain weave of threads allow to obtain plastics (textolites) with very low physical and mechanical characteristics (3 or more times smaller than in fiberglass, obtained on the basis of the same hybrid binder from fiberglass plain weave).

 Therefore, these prepregs cannot be recommended by the inventors to obtain plastics of power parts of products; on the other hand, these prepregs make it possible to obtain plastics with high physical and thermophysical properties that effectively protect the power plastics of products from the simultaneous effects of high-speed heat fluxes.

 In the table. 3 and 4 are examples of the performance of heat-protective plastic coatings made of prepregs formed in accordance with the proposed method.

 It should be noted (Tables 2 and 3 of the examples below) that the greatest heat-shielding effect is observed in plastics with a content of hybrid binder ETF + DEG-1 + SF-340A 40-50 wt.h. and capromide or polyphene woven fillers with plain weave of caproamide (kapron) or polyphene fibers MKEN-k or MKEN-p 50-60 wt.h.

The advantages of plastics from prepregs developed in accordance with the proposed method according to the application 2002101670/04
The physical, thermophysical, physico-mechanical and other characteristics of plastics made on the basis of the proposed method for producing prepregs given in the description materials and examples of the response letter of the application 2002101670/04 show:
a) all three materials (based on the hybrid binder ETF + DEG-1 + SF-340A and fabrics made from threads of the MKEN-p and MKEN-k brands and carbon fabrics of the UT-900-2.5 type) have a number of significant advantages over materials, given in the prototype - ed. testimonial. 730753;
b) they have higher sublimation properties and receive a greater amount of heat during decomposition, that is, they have a higher enthalpy in comparison with the enthalpy of the prototype (Tables 2-4, 7 and 8);
c) all plastics are electrically conductive materials, they do not accumulate static electricity on their surface, that is, they have high antistatic properties (prototype plastics do not have such properties);
d) all materials are technologically advanced when processed into composites, their use reduces the cycles of manufacturing products from KVM by winding methods; sharply improving working conditions in the manufacture of such products by winding methods.

 Table 8 presents the average values of the test results of plastics made from prepregs in accordance with the developed method, and plastics made in accordance with the prototype.

 All plastics in comparison with the plastics of the prototype (table. 8) have higher performance under the influence of highly enthalpic gas flows; all plastics work both as sublimators, that is, have high enthalpy (they absorb a large amount of heat during decomposition), and as antistatic agents, that is, they can protect KVM products from the accumulation of electrostatic charges.

 In addition, all plastics obtained from prepregs in accordance with the proposed method are more technologically advanced in comparison with other known paste-like sublimators of the SSP type.

In comparison with them, plastics obtained in accordance with the proposed method have a number of significant advantages, namely:
- the molding of plastics on the inner (or outer) surfaces of KVM products is carried out by the dry winding method, which makes it possible to shorten the production cycle of KVM products and have more stable thicknesses of their heat-protective coatings, since their sizes are provided only by the number of prepreg layers when forming products from KVM by winding and the geometry of tooling (mandrels).

In addition, in the manufacture of KVM products coated with heat-protective plastics made of prepregs in accordance with the proposed method of their formation, there are other significant advantages, namely:
- excludes the operation of measuring the thickness of the heat-protective coatings of products from KVM;
- simplified operations for the repair of heat-protective coatings of products from KVM (in case of burnout and / or mechanical damage);
- high quality of internal or external surfaces of products from KVM is provided;
- no special safety measures are required in the formation of heat-protective coatings of products from KVM and their repair.

Claims (2)

1. A method of producing a prepreg for winding heat-shielding and / or antistatic inner and / or outer layers or shells of pipe shells for structural purposes, including the preparation and impregnation of woven material consisting of polycaproamide, polyphene and / or carbon fibers, a hybrid binder containing a mixture epoxytriphenol ETF, epoxyaliphatic DEG-1 and rezol phenol-formaldehyde SF-340A resins dissolved in a combined acetone-alcohol-toluene solvent, with the following components, wt. .:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 1-12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
drying the woven material to the state of prepreg and rewinding the coils of the impregnation machine, the epoxy binder for the prepreg being prepared in four stages: at the first stage, the resins are heated separately in epoxytriphenol ETF and epoxyaliphatic DEG-1 to 180-200 ^° C and the epoxytriphenol is uniformly heated ETF binder is produced within 24 hours, and epoxyaliphatic binder DEG-1 is produced within 2 hours; at the second stage, both separately heated epoxy binders ETF and DEG-1 are mixed and dissolved in the reactor-mixer for 3-5 hours per 1 ton of the composition at temperatures of 35-55 ^o C, which are obtained by pouring ETF and DEG- resins into the composition 1 acetone-alcohol-toluene solvent in a ratio of 1: 0.51: 0.11 introduced into the reactor at 18-30 ^° C; at the third stage, crumb of solid milled particles 1-3 mm in size of phenol-formaldehyde resol resin SF-340A is added to already dissolved ETF and DEG-1 epoxy resins, the newly obtained consistency of resins is again heated to 40-60 ^o C and complete dissolution phenol-formaldehyde resin SF-340A in ETF and DEG-1 acetone-alcohol-toluene epoxy resins previously dissolved among themselves in a combined solvent by mixing them in the reactor for 3-5 hours per 1 ton of hybrid binder; and at the fourth stage of preparation of the hybrid binder, it is filtered to remove all particles of the phenol-formaldehyde binder SF-340A that are not dissolved in the reactor by passing the hybrid binder through a filter and / or several layers of diluted Excelsior fiberglass and bring the consistency of the hybrid binder to a density of 950-1010 kg / m ³ by additionally introducing into the hybrid binder an alcohol-acetone mixture in a ratio of 1: 2, mixing it with a hybrid binder for 30-40 minutes and adjusting the temperature of the hybrid the second binder due to the alcohol-acetone solvent introduced into it up to 18-35 ^o C, and then the prepared hybrid composition is poured into the bath of the impregnation machine and through it at a speed of 1-3 m / min and a tension of 0.5-1.5 kg per 1 cm web widths allow woven filler heated up to 40-60 ^° C preformed from polycaproamide, polyphene and / or carbon filaments coated with a tetrafluoroethylene copolymer with vinylidene fluoride and / or carbon black with a coating copolymer to filament volume ratio from 0.3: 1 to 0.7: 1 s after by removing excess hybrid binder on squeeze rollers and adjusting the mass fraction of the hybrid binder in the prepreg to 35-55%, the mass fraction of soluble resin 88-92% and the mass fraction of volatile substances and moisture 0.8-5.5% due to its drying in the chambers of the impregnation machine at 90-130 ^o С at the inlet and outlet of the drying chamber and 130-210 ^o С in its main working temperature zones. 2. The method according to claim 1, characterized in that the epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde resole SF-340A resins with antistatic additives introduced into them, for example, from carbon black and dissolved in acetone-alcohol-to-toluene solution, are used as a hybrid binder to obtain a prepreg / or carbon-graphite mixture in the following ratios of components, parts by weight:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
Soot and / or carbon-graphite mixture in the ratio from 1: 5 to 5: 1 - 10-15
3. The method according to claim 1, characterized in that the epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde resolved SF-340A resins dissolved in the acetospirtotoluene solvent are used as the hybrid binder to prepare the prepreg in the following ratio of components wt.h .:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
Soot and / or carbon-graphite mixture in the ratio from 1: 5 to 5: 1 - 10-15
Antimony trioxide - 10-15
Hexachlorobenzene - 10-15
4. The method according to claim 1, characterized in that the epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde resolved SF-340A resins dissolved in the acetospirtotoluene solvent are used in the hybrid binder to prepare the prepreg in the following ratio of components wt.h .:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
Soot and / or carbon-graphite mixture in the ratio from 1: 5 to 5: 1 - 10-15
Antimony trioxide - 5-10
Hexachlorobenzene - 5-10
Carbon tetrachloride CCL ₄ - 5-10
Freon - 5-10
5. The method according to claim 1, characterized in that the epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde resolved SF-340A resins dissolved in the acetospirtotoluene solvent are used as the hybrid binder to prepare the prepreg in the following ratio of components wt.h .:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
Carbon tetrachloride CCL ₄ - 10-20
Freon - 10-15
6. The method according to claim 1, characterized in that the epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde resol SF-340A resins dissolved in the acetospirtotoluene solvent are used as the hybrid binder to prepare the prepreg; metal nitrides in the following ratio of components, parts by weight:
Epoxytriphenol resin ETF - 100
Epoxyaliphatic resin DEG-1 - 12
Phenol formaldehyde resole resin SF-340A - 34
Acetone - 90
Technical alcohol - 46
Toluene - 10
Powder and / or powder mixtures of metal oxides and / or nitrides - magnesium oxide, aluminum oxide, copper oxide, nickel oxide, iron oxide and / or boron nitride - 10-40
7. The method according to claim 1, characterized in that as a coating material for polycaproamide polyphene and / or carbon fibers in the prepreg copolymers of tetrafluoroethylene with vinylidene fluoride and carbon black are introduced with carbon black and / or carbon-graphite mixture 1: 1 introduced into them in the following ratio components in copolymers, parts by weight:
Tetrafluoroethylene copolymer with vinylidene fluoride and carbon black - 45-55
Soot and / or carbon-graphite powder mixture in a ratio of 1: 1 - 15-20
8. The method according to claim 1, characterized in that copolymers of tetrafluoroethylene with vinylidene fluoride and carbon black with antistatic additives introduced into them, carbon black and / or carbon-graphite mixtures in the coating material, are used as coating material for polycompromide, polyphenic and / or carbon fibers. flame retardant in the following ratio of components in parts by weight:
Tetrafluoroethylene copolymer with vinylidene fluoride and carbon black - 45-55
Soot and / or carbon-graphite mixture in a ratio of 1: 5 to 5: 1 - 10-20
Antimony trioxide - 10
Hexachlorobenzene - 10
9. The method according to claim 1, characterized in that as a coating material for polycaproamide, polyphene and / or carbon fibers for the woven filler of the prepreg, tetrafluoroethylene copolymers with vinylidene fluoride and carbon black and with antistatic powder fillers introduced in them in the form of oxides and / or nitrides of materials and silicon in the following ratio of components in the copolymer, parts by weight:
Tetrafluoroethylene copolymer with vinylidene fluoride and carbon black - 45-55
Powder filler of magnesium oxide and / or alumina and / or titanium oxide and / or silicon oxide and / or copper oxide and / or iron oxide and / or boron nitride BN - 10-20i

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