Method of producing epoxy resin curing agents. RU patent 2507226.
 Polymer composition / 2506291Present invention relates to production of polymer compositions based on epoxy resins and modified amine curing agents, intended for producing high-strength composite materials with high resistance to thermal deformation. Described is a polymer composition based on epoxy resin, active epoxy diluents and nitrogen-containing curing agents intended for producing high-strength composite materials with high resistance to thermal deformation, characterised by that the curing agent is a product of reaction of an amine component with monocarboxylic acids, using as the amine component a mixture consisting of a primary aromatic amine or a mixture of aromatic amines (A), a secondary aliphatic amino alcohol (B) and a tertiary aliphatic amino alcohol (C) in weight ratio A:B:C from 98:0.2:1.8 to 80:5:15, and a monocarboxylic acid (D) is added in form of a 25-80% solution to the monoatomic aliphatic or aromatic alcohol, or ester thereof with a mono- or dicarboxylic acid, in ratio (A+B+C):D from 90:10 to 60:40 per 100% acid, followed by reaction by mixing in a reactor at temperature ranging from 50 to 130°C for 20 to 120 minutes and mixer speed of 100 to 3000 rpm, and additionally contains a thickener, a pigment or a dye, wherein the composition contains the following in pts.wt: epoxy resin - 100, active epoxy diluent - 5-130, curing agent - 15-110, thickener - 5-50, pigment and dye - 0.5-25. |
 Epoxy binder for reinforced plastic / 2505568Binder contains the following, pts.wt: 70-90 polyglycidyl derivative of low-molecular weight phenol-formaldehyde novolac, 10-30 epoxy-diane resin, 3-6 boron trifluoride and benzylamine complex, 60-80 2,2'-bis-(3,5-di-bromo-4-hydroxyphenyl)-propane, 1-3 bis-[3-(3,5-di-tert-butyl-4-oxyphenyl) propyl]phthalate and 90-160 alcohol-acetone mixture with weight ratio of alcohol to acetone of 1:1. |
| Press material for sealing integrated microcircuits / 2505567 Press material for sealing integrated microcircuits contains binder - o-cresol novolac epoxy resin with softening point of 50-65°C, a curing agent - cyan-acetic ester and diglycidyl ether of 1,4-butanediol, an accelerating atent - N1-(3,4-dichlorophenyl)-N,N-dimethylurea, filler - ground quartz, glycidyloxypropyltrimethoxy silane finishing agent, lubricant - oxidised polyethylene wax. |
| Method of making articles from composite / 2505403 Proposed method comprises preparing binder directly before impregnation of fibrous filler. Epoxy-novolac binder with number-average molecular weight of 300 a.u. and weight fraction of epoxy groups of 8-11 are produced by loading 10-28 wt % of product into reactor, said product being obtained by epoxidation of hydroxyphenyl oligomer from alkyl resorcinol, 47-80 wt % of diane epoxy resin and 10-25 wt % of modifier, and by boiling at 60-250°C for 30-180 minutes. Article is shaped by drawing fibrous filler impregnated with binder and hardener via replacement die and helical winding on reinforcing bundle core. |
 Thermosetting epoxy polymer, composite material, method of moulding article from composite material, mould and method of making mould / 2499013Composite material contains a matrix phase made of thermosetting epoxy polymer with magnetite particles and a reinforcing phase made of carbon fibre. The mould for moulding an article from composite material has a housing made of material which is substantially permeable for microwave radiation, with a surface or a back surface which is coated with a layer containing material which is substantially permeable for microwave radiation. |
 Thermosetting resin-based polymer composite material and fibre-filled material containing said resin / 2495056Invention relates to a thermosetting resin-based polymer composite material and fibre-filled material based thereon. The polymer composite material contains thermosetting resol phenol-formaldehyde resin and additionally thermosetting epoxy resin and a thermosetting polyester resin in the following ratio, wt %: thermosetting resol phenol-formaldehyde resin 48-83; thermosetting epoxy resin 3-13; thermosetting polyester resin 14-39. The fibre-filled material contains a thermosetting resin-based polymer composite material and fibre. The fibre used is polyacrylonitrile fibre or glass fibre in the following ratio, pts.wt: thermosetting resin-based polymer composite material 3.2-5.2; fibre 1.0. |
 Epoxy resins and composite materials exhibiting improved combustion properties / 2494126Invention relates to epoxy resin-based composite materials. The epoxy resin-based composition contains: a) 50-70 wt % of a component which is an epoxy resin containing one or more epoxy resins; b) 15-35 wt % of a mixture of thermoplastic materials containing polyetherimide and polyamideimide, where the weight ratio of polyetherimide to polyamideimide ranges from 5:1 to 1:5; and c) 5-25 wt % of a component which is a curing agent, where the epoxy resin composition has sulphur dioxide release level below 100 ppm. Also disclosed is a method of preparing a composition, a component made from an uncured composite, a component made from the composite, where a matrix of the epoxy resin is cured, and a method of producing a prepreg. |
| Composition to reinforce building structures / 2493337 Composition comprises glass or basalt roving in amount of 90-100 wt parts, impregnated with polymer binder based on epoxide-diane resin in the amount of 18÷20 wt parts. The polymer binder additionally contains a magnetic-susceptible metal-containing carbon nanostructure in the amount of 0.001÷1.5 wt parts. |
 Thermally hardened compositions based on epoxy resins, which contain non-aromatic ureas as accelerants / 2491309Claimed invention relates to thermally hardened composition based on epoxy resins, which contains: (a) at least one epoxy resin A, which has on average more than one epoxy group per molecule; (b) at least one hardener B of opoxy resin, which is activated at increased temperature and represents amine, amide, anhydride of carboxylic acid or polyphenol; and (c) at least one accelerant C of formula (Ia) or (Ib), where R1 represents H or n-valent aliphatic, or araliphatic residue; R2 and R3 represent each independently on each other alkyl group; R1' represents n'-atom aliphatic residue; R2' represents alkyl group; R3' independently on each other represent H, or alkyl group, or aralkyl group; and n and n' - each has value from 1 to 4, in particular, 1 or 2; and d) at least one viscosity modifier D. Invention also relates to application of such composition in form of one-component thermally hardened glue, for obtaining coatings and for obtaining structural foam for reinforcement of cavities, as well as to method of gluing heat-resistant materials with application of composition by invention and to glued together/glued to product, thus obtained, and to vehicle or vehicle component, which contain such foamed product. Also described is application of accelerant of formula (Ia) or (Ib) for increasing viscosity of claimed compositions based on epoxy resins. |
| Epoxide composition for making articles from polymer composite materials by vacuum infusion / 2488612 Invention relates to cold curing epoxide compositions and can be used in making structures, including large-sized structures, from polymer composite materials by vacuum infusion in engineering fields. The epoxide composition includes an epoxide base containing epoxy-diane resin, an active diluent and a curing system based on an amine curing agent and a surfactant, characterised by that the epoxy-diane resin used is a resin or a mixture of resins with molecular weight 340-430, the active diluent used has viscosity of up to 0.1 Pa·s, the amine curing agent is a mixture of a curing agent basedd on an aromatic amine and a cold curing catalyst, and the curing system further includes a heterocyclic imidazole-type compound and a nanomodifier. The technical result is preparation of a high-technology epoxy composition, curable without the need for additional heat and without a large exothermic effect, and characterised by improved physical and mechanical properties. |
| Thermally curable binder for composite materials / 2250241 Invention relates to epoxide compositions, in particular to preparation of hot-molded thermally curable epoxide compositions used as binders in manufacture of composite materials and products thereof. Binder comprises 60-70% 4,4'-isopropylidenediphenol epoxide resin, amine-type curing agent, and additionally 5-15% aliphatic epoxide resin (DEG-1) and 1-5% phenyl glycidyl ether. Curing agent (utilized in balancing amounts) is aniline-formaldehyde condensation product, condensation being carried out in presence of acid catalyst and giving aminobenzylaniline as main condensation product. |
 Epoxyde composition and method for production the same / 2251560Claimed composition contains epoxy-dianic resin with molecular weight at most 390, aliphatic epoxy resin, and triethyleneamin as curing agent. Composition is obtained by addition of 5-10 mass pts of aliphatic epoxy resin to 100 mass pts of epoxy-dianic resin and mixture is blended to obtain homogeneous mass. Then 13-14 mass pts of triethyleneamin as reduced to 100 mass pts of resin is admixed and cured at room temperature for one day followed by auxiliary curing at 100-120°C for 3-5 h. Composition of present invention is useful in production of heat resistant polymeric constructional materials for aerospace and machine industry. |
 Epoxy composition / 2252229Claimed composition contains at least one epoxydianic resin or mixture thereof with resins comprising one or two epoxy groups; anhydrite or polyanhydrite or mixture thereof as curing agent; and curing catalyst. As curing catalyst composition contains quaternary ammonium salt or mixture of quaternary ammonium salts of general formula: , wherein R1, R2, and R3 are aliphatic hydrocarbon radical; at least one R1, R2, and R3 has 8-20 of carbon atoms, and the rest ones has not more than 2 of carbon atoms; R4-H, CH3, C2H5, benzyl; A- is Cl- or Br-. Compositions of present invention are useful as binder in composite (e.g., reinforced plastics) production. Invention may be used in automobile, spacecraft, electric industry, etc. |
 Low density thermoreactive material and method for production thereof / 2252230Claimed method includes blending of aluminum silicate hole beads with powder of epoxy or polyester resin in ratio of (2/3-1/3) pts vol. of aluminum silicate to (1/3-2/3) pts vol. of resin. Mixture is formed and heat treated at 200°C for 0.5-1.5 h. Powder of epoxy or polyester resin represents waste from powder coating or hot-drying varnishing and has particle size of 30 mum or less. Aluminum silicate hole beads have diameter of 10-100 mum. Obtained articles have bulk mass of 0.4-0.5 kg/dm3 and compression strength of 10-20 N/cm2. |
 Composition for manufacturing thermocontracting products / 2253659Invention concerns epoxide composition for manufacturing thermocontracting connection elements during construction and restoration of gas ducts and water ducts, joining of pipelines and rod structures of dissimilar materials in mechanical engineering, communication, etc. Polymer composition contains 80-90% 4,4'-isopropylidenediphenol epoxide resin, 10-20% modifier, and epoxy hardener in stoichiometric amount. Modifier is selected from group comprising particular types of oligoepoxyurethane and low-molecular rubbers and hardener is selected from diethylenenriaminomethylphenol, triethanolamine titanate, and isomethyltetrahydrophthalic anhydride. |
 Amino-derivatives of c60-fullerene and composition material comprising indicated amino-derivatives / 2254329Invention relates to polymeric composition materials used in construction members in aviation and cosmic technique. Amino-derivatives of C60-fullerene combine functions of polyamine hardening agent, electron-active nanomodifying agent of permolecular structure of matrix, function of plasticizer reducing fragility of matrix, function of microcrack stopper and function of reinforcing members. Invention provides preparing amino-derivatives of C60-fullerene - products of chemical interaction of C60-fullerene with benzylamine (BA) of the empirical formula C60(BA)n wherein n = 4-6, and the composition material made from epoxy-base polymeric binding agent and fibrous filling agent wherein polymeric binding agent comprises additionally indicated amino-derivatives of C60-fullerene in the amount 10.2-60.6 mas. p. p. per 100 mas. p. p. of epoxy base. |
 Composition material / 2255097Composition materials are prepared from composition based on hybrid binding of hot hardening - epoxy vinyl ester resin in the amount 100 mas. p. p. with peroxide hardening initiating agent, modifying agent and reinforcing filling agent. Modifying agent comprises at least one epoxy resin in the amount 70-110 mas. p. p. with anhydride hardening agent in their ratio in the mixture from 100:75 to 100:100, and imidazole hardening catalyst in the amount 0.4-0.9 mas. p. Invention provides improving technological indices, for example, to enhance working ability and wetting capacity of binding agent, to reduce its viscosity, to increase broach rate and to improve mechanical indices of composition material in storage and some increase of level of its physical-chemical properties, in particular, heat stability, chemical and hydrolytic resistance. Proposed composition materials can be used in building, aircraft, automobile, aerospace, railway and other branches of industry. |
 Epoxy binding agent for reinforced plastics (variants) and method for its preparing / 2260022Invention relates to hybrid binding agents based on epoxy triphenolic resin designated for reinforced plastics with enhanced corrosion resistance and thermal stability and to methods for their preparing. A binding agent comprises epoxy triphenolic resin, plasticizing agent as a diluting agent representing resin DEG-1, resol-phenolformaldehyde resin SF-340A as a hardening agent and mixture of acetone, ethyl alcohol and petroleum and/or coal toluene as a solvent. Anti-static additive, antipyrene additive, crystalline sodium alumosilicate and a filling agent can be added to the binding agent composition additionally. A filling agent can be in forms of monolith or hollow thread-like crystals, finely divided powder-like filling of monolith, hollow, scaly and fibrous particles. The combination of components taken in the definite ratios and carrying out a method for preparing a binding agent at enhanced temperatures and in the definite sequence of addition of components into reactor and assigned temperature-temporal regimens of their stirring and dissolving provides the improvement of properties of the binding agent. Monolith composites as product of hardening binding agents elicit improved physical-mechanical, heat-physical, electric and anti-static properties with the density value 0.96-1.1 g/cm3, the mass content of nonvolatile substances 55-63% and the gelatinizing time 4-8 min at temperature 160-200°C. The claimed invention can be used in preparing prepregs by impregnation method of glass-organo-coal-filled filling agents, among them caproamide, basalt, polyphene and fibers with different lubricants, dressings and other coatings. |
 Gluing composition / 2261885Invention relates to high-strength glues of cold hardening able to harden in the range of temperatures 10-15°C under conditions of enhanced moisture and on wetted surfaces. Invention proposes a glue composition comprising the following components, mas. p. p.: epoxydiane resin, 100; polyamide resin (product of condensation of polyethylene polyamine with higher unsaturated synthetic dicarboxylic acid methyl esters), 14-16; organosilicon amine, 1.15-1.30, and, additionally, chlorine-containing resin, 14-30; amine hardening agent, 8-22, and catalyst, 0.5-1.6. For improving the technological effectiveness the composition can comprise additionally mineral filling agent (titanium dioxide, asbestos or synthetic corundum) in the amount 5-20 mas. p. p. Prepared gluing composition can be used for repair work of glued constructions, articles and aviation technique aggregates in field conditions, and for gluing metallic and nonmetallic materials and aviation and other branches of machine engineering. Invention provides enhancing strength in shift, exfoliation and break off, enhanced water proofing, in tropic climate, possibility for hardening and retaining strength properties after hardening in the range of temperature 10-15°C under conditions of enhanced moisture and on wetted surfaces. |
| Binder for prepregs, prepreg and article made from it / 2263690 Proposed binder for prepreg contains the following components, parts by mass: epoxy triphenol resin, 40-60;low-molecular epoxy diane resin, 25-35; high-molecular epoxy diane resin, 3-6; dicyanodiamide, 5.5-7.0 and bis-(N,N'-dimethyl carbamide) of diphenyl methane, 0.05-2.0; solvent, 0-90; silicon dioxide, 1-6. Prepreg contains also 30-42 mass-% of epoxy binder and 58-70 mass-% of fibrous filler. Articles are made from prepreg by molding. |
FIELD: chemistry.
SUBSTANCE: invention relates to production of epoxy resin curing agents used to prepare epoxy compositions with improved processing properties and minimal toxicity, which enable to produce composite materials with high strength, thermophysical and dielectric properties. The method of producing epoxy resin curing agents involves reacting a liquid or molten aromatic, aliphatic, cycloaliphatic or alkylene aromatic di- or polyamine (B) with cycloaliphatic or aliphatic-cycloaliphatic dioxides (A) with excess amine, after which acrylate (V) and amino alcohol (G) are added to the obtained mixture and the reaction mixture is stirred for 20-180 minutes at T=30-180°C.
EFFECT: high stability of the obtained curing agents during storage and transportation and improved dielectric properties at high temperature.
2 tbl, 8 ex
The invention relates to the field of production of epoxy resins, hardeners, used for the manufacture of epoxy compositions with improved technological properties and minimal toxicity, providing preparation of composite materials with enhanced strength, thermal and dielectric properties.
A method of obtaining an epoxy resins, hardeners (adducts) through interaction amines aromatic or aliphatic, with or aliphatic resin, synthesized by the method of indirect epoxidation, i.e. with the use of epichlorohydrin, 4-6 fold molar excess Amin (see « on plastic masses» under the editorship of V. Kataev and other M 1975. Publishing house «Chemistry», .219. Prototype).
The disadvantage of this method is limited tasks. It allows to reduce volatility and toxicity hardeners, but does not increase the viability of epoxy compositions and does not improve the operational characteristics of the goods received, in addition, hardeners, obtained by this method have a small storage period from 0.5 to 3 months.
The aim of the proposed method is to obtain hardeners with high stability at storage and transportation in various climatic conditions and provide improvement of dielectric properties at elevated temperatures and after prolonged exposure to hot and hot water.
The goal is achieved by the fact that as epoxy compounds used or - obtained by the oxidation of unsaturated compounds (As), and in the process of obtaining hardeners in the reactor first introduced liquid or molten di - or polyamine - aliphatic, aromatic, cycloaliphatic or (B), and then add to it dioxide at the rate of 3 to 20 times the molar excess Amin, then enter acrylate () and (G) in the ratio of (A+B):In:G from 99,8:0,1:0.1 to 60:30:10 and the reaction mixture was stirred for 20 to 180 minutes at T = 30 up to 180 degrees C.
Example 1.
In the reactor, equipped with heating, cooling and a high-speed mixer download 500 mass parts molten 4,4' (T p =82 OC) (component B), and to see him for 10 minutes, add 100 mass parts , containing 45% of epoxy groups (As), that is 10 fold molar excess of Amin. The temperature in the reactor was raised to 105 OC and add 90 mass parts of butyl methacrylate () and 40 mass parts - (G), the ratio of (A+B):A:D=80:15:5. The process of interaction of lead with 105°by stirring for 85 minutes at 1000 rpm running stirrers. The resulting product is cooled to 20 OC and poured into the metal tank.
Examples of 2 to 8 perform similarly to example 1, but with the view change , Amina, the ratio of components and parameters in accordance with table 1. Properties hardeners, obtained by example 1-8 and epoxy compositions with their use are presented in table 2.
Table 2Properties hardener obtained by the present method and them epoxy Dianova pitch mark ED-20 (examples 1 to 8)
№ itemName of indicators
1 2 3 4 5 6 7 8 1The valid storage period hardener in warehouse environments
Not less than 1 year
2Viscosity hardener when VZ-4, at 20 C, with
100 100 100 100 100 250 60 100Compositions on the base of resin ed-20 and hardener
1Curing of the resin, in parts by weight of 200 g
- at 20oC
90 min 90 min 90 min 90 min 90 min 90 min 60 min 120 min- at 120 C
10 min 10 min 10 min 10 min 10 min 10 min 7 min 20 min 2Heat according to Martens, AC
210 180 190 200 210 200 220 220 3Volume resistivity:
- at 20 C, Ohm·cm
4·10 15 6·10 15 7·10 15 6·10 15 4·10 15 6·10 15 6·10 15 4·10 15- at 150 C, Ohm·cm
6·10 14 5·10 14 4·10 14 2·10 14 6·10 14 5·10 14 6·10 14 7·10 14- at 200 OC, Ohm·cm
8·10 12 6·10 12 8·10 12 7·10 12 6·10 12 2·10 12 4·10 12 6·10 12So after staying within 24 hours
in boiling water, Ohm·cm
4·10 13 6·10 13 9·10 12 8·10 13 2·10 13 4·10 13 6·10 13 8·10 12- in the superheated water to 120 C, Ohm·cm
8·10 12 6·10 12 4·10 12 9·10 11 6·10 12 3·10 13 4·10 13 4·10 12Method of receipt of epoxy resins, hardeners, including operation of interaction epoxy connection with a surplus of di - or polyamine, characterized in that in the capacity of epoxy compounds used or - obtained by the oxidation of unsaturated compounds (As), and in the process of obtaining hardeners in the reactor first introduced liquid or molten di - or polyamine-aliphatic, aromatic, cycloaliphatic or (B), and then add to it dioxide from the calculation of 3-20 times the molar excess Amin, then enter acrylate () and (G) in the ratio of (A+B):In:G from 99,8:0,1:0.1 to 60:30:10, the reaction mixture was stirred for 20 to 180 min at the temperature from 30 up to 180 degrees C.