Abstract:
A method of producing furan-epoxy powder-like binder comprising reacting the product of the polycondensation of epichlorohydrin with diphenylpropane (100 weight parts) with a ketone containing a furfurylidene group (33-200 weight parts) and a nitrogen-containing compound (8-100 weight parts). As examples of the ketone containing a furfurylidene group monofurfurylideneacetone, difurfurylideneacetone, difurfurylidenecyclohexanone, a mixture of monofurfurylideneacetone with difurfurylideneacetone in a ratio (weight parts from 1:1 to 1.4:1; 1,9-di-(α-furyl)nonanetetracene-1,3,6,8-one-5 or 1,5 -di-(α-furyl)-2,4-dimethylpentadiene-1, 4-one-3 may be mentioned. Triethanolamine, 3-methyl-5-furylpyrazoline, trifurylimidazoline, hexamethylenediamine, and low molecular polyamides with molecular weight of 2000-10000 or polyethylenepolyamine with molecular weight of 1000 are used as a nitrogen-containing compound. The reaction is performed at 130°-200° C. in the presence, if necessary, of trifurfurylborate (1-12 weight parts). The obtained product is cooled down to a temperature not exceeding 30° C. and ground to a powder state. The furan-epoxy binder does not cake for 60 days and retains its properties upon storing for a long period of time (up to 12 months). Heat distortion temperature of polymer  materials based on the above-cited binder is 250° C. according to the Vicat method. Polymer materials formed from said binder can be combustible and incombustible or display ability to self-extinction.

Description:
FIELD OF APPLICATION OF THE INVENTION 
     The present invention relates to producing furan-epoxy powder-like binder used in manufacturing moulding materials, adhesives, polymer coatings, foam plastics, laminated plastics, and the like. 
     BACKGROUND OF THE INVENTION 
     Known in the art is a method of producing furan-epoxy powder-like binder by reacting the product of the polycondensation of epichlorohydrin with bis(hydroxyphenyl)propane (hereinafter polycondensation resin) with difurfurylideneacetone and a nitrogen-containing compound, namely, furfuramide at 140° C. and at the following ratio between the components (weight parts): 
     polycondensation: 100 
     difurfurylidenacetone: 50-150 
     furfuramide: 95-100; 
     the obtained product is cooled down to a temperature not exceeding than 30° C. and ground to a powder state. 
     A binder obtained by the known method has a high tendency to caking (is caked after 30 days) and loses its initial properties, solubility and fusibility, upon short-time storage (not more than 3 months). Heat distortion temperature of the polymer materials based on known furan-epoxy binder does not exceed 208° C. according to the Vicat Method. Besides, polymer materials based on the known binder are combustible. 
     BRIEF DESCRIPTION OF THE INVENTION 
     It is an object of the invention to provide a method of producing furan-epoxy powder-like binder which will ensure the production of a binder with enhanced non-caking. 
     Another object of the invention is to provide a method of producing furan-epoxy powder-like binder which will ensure the production of a binder retaining its initial properties upon prolonged storage. 
     It is also an object of the invention to increase heat distortion temperature of polymer materials based on the furan-epoxy binder. 
     A still further object of the invention is to impart to polymer materials, based on the furan-epoxy powderous binder, incombustibility or tendency to self-extinction. 
     In accordance with these and other objects the invention resides in a method of producing furan-epoxy powder-like binder by interacting the reaction product of the polycondensation of epichlorohydrin with diphenylpropane with a furan-carrying ketone and a nitrogen-containing compound upon heating with subsequent cooling of the obtained product down to a temperature not exceeding 30° C. and grinding to a powder state. According to the invention, a furfurylidene-containing ketone can be made from monofurfurylideneacetone, difurfurylideneacetone, difurfurylidenecyclohexanone, a mixture of monofurfurylideneacetone, with difurfurylideneacetone at a ratio (weight parts) of from 1:1 to 1.4:1, 1,9-di-(α-furyl)-nonantetraene-1,3,6,8-one-5or 1,5-di (-α-furyl)-2,4-dimethylpentadiene-1,4-one-3. As the nitrogen-containing compound, triethanolamine, 3-methyl-5-furylpyrazoline, trifuryl-imidazoline, hexamethylenediamine, low molecular polyamides with molecular weight of 2,000-10,000 or polyethylenepolyamine with molecular weight of 1000 may be used, the reaction being performed at 130°-200° C. and in the following ratio of said components (weight parts): 
     Polycondensation: 100 
     furfurylidene-containing ketone: 33-200 
     nitrogen-containing compound: 8-100. 
     The proposed method ensures the production of a furan-epoxy binder which does not cake for 60 days and can be stored for a long time (up to 12 months) without a change in the initial properties. Heat distortion temperature of polymer materials based on said binder is 250° C. according to Vicat Method. 
     It is recommended to perform the reaction of the above-cited components in the presence of trifurfurylborate at a ratio of trifurfurylborate and polycondensation resin (in weight parts) equal to 1-12:100 respectively. As a result, a furan-epoxy binder is obtained which imparts incombustibility and tendency to self-extinguish to polymer materials based on said binder. The proposed method is technologically simple and does not require complicated equipment. The method ensures a high yield (up to 95%) of the end product. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The polycondensation resin, the furfuryl-containing ketone, a nitrogen-containing compound, and, if necessary, trifurfuryl borate, are placed in a required ratio into a reactor fitted with a heating device, a reflux condenser, a thermometer, and a stirrer. The reaction mixture is heated up to 130°-200° C. and the process is run at this temperature for 1-3 hours. The obtained furan-epoxy binder is poured out from the reactor on a tray, cooled to a temperature not exceeding 30° C., for example, to room temperature, and ground to a powder with the required particle size (depending on the field of application of the binder). It is not expedient to cool the binder to a temperature above 30° C., since in this case the binder being ground may adhere to the component parts of the grinding device. 
     Low molecular weight polyamides with molecular weight of 2000-10000 used in the proposed method are obtained by the known method comprising polycondensation of dimerized fatty acids (for instance, dimerized linseed oil, dimerized oleic, linoleic, or linolenic acid) with polyethylenepolyamine having molecular weight of 1000 (see, for example Encyclopaedia of Polymers, Moscow, 1974, vol. 2, pp. 736-746). 
     Polyethylenepolyamine with the above-cited molecular weight also used in the proposed invention is obtained by the known method comprising polycondensation of dichloroethane with ammonia (see, for example, Encyclopaedia of Polymers, Moscow, 1974, vol. 2, pp. 747-749). 
     A mixture of monofurfurylideneacetone with difurfurylideneacetone used in the proposed method can be obtained by condensation of furfurol with acetone in the presence of a catalyst (an alkali) at 60°-90° C. (see, for example, Orobchenko E.V. &#34;Furan Resins&#34;, Kiev, 1963, pp. 64-70). 
    
    
     For a better understanding of the present invention specific examples of realizing thereof are given hereinbelow by way of illustration. The properties of the furan-epoxy powder-like binder and a polymer based thereon are given in Tables 1 and 2, respectively, after the Examples. 
     EXAMPLE 1 
     200 g of polycondensation resin with the number of epoxy groups 14-16% on a weight basis, 100 g of difurfurylideneacetone, 10 g of trifurylborate and 200 g of trifurylimidazoline are put into a reactor fitted with a heating device, a reflux condenser, a thermometer, and a stirrer. The ratio of the above-cited components is 100:50:5:100, respectively. The temperature in the reactor is raised up to 140° C. and the process is run at this temperature for 1.5 hours. The obtained furan-epoxy binder (yield 92%) is poured out from the reactor, cooled to 30° C. and ground to a powder state. 
     EXAMPLE 2 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 66 g of difurfurylideneacetone, 14 g of trifurylborate, and 200 g of trifurylimidazoline are put into the reactor similar to that described in Example 1. The ratio of the abovecited components (in weight parts) is 100:33:7:100, respectively. The process is run at 130° C. for 2 hours. The obtained product (yield 95%) is poured from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 3 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 260 g of difurfurylideneacetone, 24 g of trifurfurylborate, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the above-cited components is 100:130:12:100, respectively. The process is run at 140° C. for 2.5 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 20° C. and ground to a powder state. 
     EXAMPLE 4 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 200 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone in a ratio (weight parts) of 1:1, 2 g of trifurfurylborate, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the above-cited components in weight parts is 100:100:1:100, respectively. The process is run at 145° C. for 1.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 15° C. and ground to a powder state. 
     EXAMPLE 5 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 300 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone in a ratio of 1.2:1 (in weight parts), 14 g of trifurfurylborate, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the above-cited components is 100:150:7:100, respectively. The process is run at 140° C. for 1.5 hours. The obtained product (yield 91%) is poured out from the reactor, cooled to 20° C. and ground to a powder state. 
     EXAMPLE 6 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 66 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone at a ratio of 1.4:1 (in weight parts), respectively, 24 g of trifurfurylborate, and 100 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the above-cited components is 100:33:12:50, respectively. The process is run at 140° C. for 1.5 hours. The obtained product (yield 88%) is poured out form the reactor, cooled to 25° C. and ground to a powder state. 
     EXAMPLE 7 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 200 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, 2 g of trifurfurylborate, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the above-cited components is 100:100:1:100, respectively. The process is run at 140° C. for 1.5 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 8 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 200 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, 20 g of trifurfurylborate, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:10:100, respectively. The process is run at 130° C. for 2 hours. The obtained product (yield 95%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 9 
     200 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 66 g of difurfurylideneacetone, 3.4 g of trifurfurylborate, and 80 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:1.7:40,  respectively. The process is run at 140° C. for 2 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 15° C. and ground to a powder state. 
     EXAMPLE 10 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 200 g of difurfurylideneacetone, 18 g of trifurfurylborate, and 200 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:9:100, respectively. The process is run at 160° C. for 1 hour. The obtained product (yield 93%) is poured out from the reactor, cooled to 25° C. and ground to a powder state. 
     EXAMPLE 11 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 300 g of difurfurylideneacetone, 24 g of trifurfurylborate, and 180 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:150:12:90, respectively. The process is run at 180° C. for 1.5 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 12 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 200 g of a mixture of monofurfurylideneacetone with difurfurylidene acetone in a ratio of 1.4:1 weight parts, respectively, 24 g of trifurfurylborate, and 200 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:12:100, respectively. The process is run at 150° C. for 1.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 13 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 200 g of monofurfurylideneacetone, 24 g of trifurfurylborate, and 200 g of 3-methyl-5-furyl-pyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:12:100, respectively. The process is run at 150° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 14 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 200 g of difurfurylideneacetone, 24 g of trifurfurylborate, and 200 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:12:100, respectively. The process is run at 150° C. for 1.5 hours. The obtained product (yield 94%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 15 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 200 g of difurfurylidenecyclohexanone, 20 g of trifurfurylborate, and 100 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:10:50, respectively. The process is run at 180° C. for 2 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 16 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 200 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, 24 g of trifurfurylborate, and 200 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:12:100. The process is run at 150° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 17 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 400 g of difurfurylideneacetone, and 16 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:200:8, respectively. The process is run at 200° C. for 1 hour. The obtained product (yield 88%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 18 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 66 g of difurfurylidenecyclohexanone, and 16 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:8, respectively. The process is run at 190° C. for 1 hour. The obtained product (yield 90%) is poured out from the reactor, cooled to a temperature 20° C., and ground to a powder state. 
     EXAMPLE 19 
     200 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, and 200 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:100, respectively. The process is run at 170° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 20 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 66 g of difurfurylidenecyclohexanone, 10 g of trifurfurylborate, and 100 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:5:50, respectively. The process is run at 160° C. for 1.5 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 21 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 100 g of a mixture of monofurfurylideneacetone with difurfurylidenacetone at a ratio in weight parts of 1.4:1, 2 g of trifurfurylborate, and 40 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of said components in weight parts is 100:50:1:20, respectively. The process is run at 150° C. for 3 hours. The obtained product (yield 91%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 22 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of difurfurylidenecyclohexanone, 7 g of trifurfurylborate, and 100 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:200:7:100, respectively. The process is run at 160° C. for 2 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 23 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 100 g of difurfurylideneacetone, 24 g of trifurfurylborate, and 100 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:50:12:50, respectively. The process is run at 140° C. for 3 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 24 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 66 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone at a weight ratio of 1:1, and 16 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:8, respectively. The process is run at 200° C. for 2.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 15° C. and ground to a powder state. 
     EXAMPLE 25 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of difurfurylideneacetone, 12 g of trifurfurylborate, and 100 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of said components in weight parts is 100:200:12:100, respectively. The process is run at 130° C. for 2 hours. The obtained product (yield 95%) is poured out from the reactor, cooled to 30° C. and ground to a powder state. 
     EXAMPLE 26 
     100 g of polycondensation resin with the number of epoxy groups 16-18%, by weight, 100 g of difurfurylidenecyclohexanone, 5 g of trifurfurylborate, and 50 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:5:50, respectively. The process is run at 150° C. for 2 hours. The obtained product is poured out from the reactor, cooled to 25° C. and ground to a powder state. 
     EXAMPLE 27 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 66 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone at a ratio in weight parts of 1.2:1, and 16 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:8, respectively. The process is run at 160° C. for 2.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 28 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 100 g of difurfurylidenecyclohexanone, 12 g of trifurfurylborate, and 100 g of low molecular polyamide with molecular weight of 2000, which is a product of polycondensation of dimerized linseed oil and polyethylenepolyamine with molecular weight of 1000, are put into a reactor similar to that described in Example 1. The ratio of said components in weight parts is 100:100:12:100, respectively. The process is run at 130° C. for 3 hours. The obtained product (yield 94%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 29 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 100 g of difurfurylidenecyclohexanone, 10 g of trifurfurylborate, and 100 g of low molecular polyamide with molecular weight of 3500, which is a product of polycondensation of dimerized oleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:50:5:50, respectively. The process is run at 160° C. for 2 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 20° C. and ground to a powder state. 
     EXAMPLE 30 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 66 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone at a ratio in weight parts of 1.4:1,2 g of trifurfurylborate, and 16 g of low molecular polyamide with molecular weight of 10000, which is a product of polycondensation of dimerized linoleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:33:1:8, respectively. The process is run at 200° C. for 1.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 30° C. and ground to a powder state. 
     EXAMPLE 31 
     200 g of polycondensation resin with number of epoxy groups 20-22% by weight, 140 g of difurfurylideneacetone, and 140 g of low molecular polyamide with molecular weight of 2700, which is a product of polycondensation of dimerized linoleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of said components is 100:70:70, respectively. The process is run at 170° C. for 2.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 15° C. and ground to a powder state. 
     EXAMPLE 32 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 200 g of difurfurylidenecyclohexanone, 24 g of trifurfurylborate, and 200 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:12:100, respectively. The process is run at 160° C. for 2 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 33 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 66 g of a mixture of monofurfurylideneacetone with difurfurylideneacetone at a ratio in weight parts of 1.2:1, 10 g of trifurfurylborate, and 16 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:5:8, respectively. The process is run at 200° C. for 2.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 30° C. and ground to a powder state. 
     EXAMPLE 34 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of difurfurylideneacetone, and 50 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components is 100:200:50, respectively. The process is run at 180° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 35 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 66 g of 1,9-di(α-furyl)-nonanetetraene-1,3,6,8-one-5, 24 g of trifurfurylborate and 16 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:12:8, respectively. The process is run at 150° C. for 2 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 36 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 200 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, 20 g of trifurfurylborate, and 100 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of said components in weight parts is 100:100:10:50, respectively. The process is run at 160° C. for 1 hour. The obtained product (yield 94%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 37 
     100 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 100 g of 1,9-di(α-furyl)-nonanetetraene-1,3,6,8-one-5, and 100 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:100, respectively. The process is run at 130° C. for 1.5 hours. The obtained product (yield 95%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 38 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 100 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, 10 g of trifurfurylborate, and 100 g of low molecular polyamide with molecular weight of 2000 which is a product of polycondensation of dimerized linseed oil and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of said components is 100:50:5:50, respectively. The process is run at 140° C. for 2 hours. The obtained product (yield 95%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 39 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, and 100 g of low molecular polyamide with molecular weight of 3500 which is a product of polycondensation of dimerized oleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:200:100, respectively. The process is run at 160° C. for 2.5 hours. The obtained product (yield 93%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 40 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 66 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, 24 g of trifurfurylborate, and 16 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:12:8, respectively. The process is run at 200° C. for 1.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 41 
     100 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 100 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3,5 g of trifurfurylborate, and 100 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:5:100, respectively. The process is run at 150° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 42 
     100 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 200 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, and 100 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:200:100, respectively. The process is run at 160° C. for 2 hours. The obtained product (yield 94%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 43 
     200 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 66 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, 2 g of trifurfurylborate, and 16 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:33:1:8, respectively. The process is run at 170° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 44 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 100 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, and 100 g of 3-methyl-5-furylpyrazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:100, respectively. The process is run at 130° C. for 3 hours. The obtained product (yield 95%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 45 
     100 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 200 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, 7 g of trifurfurylborate, and 100 g of low molecular polyamide with molecular weight of 2000, which is a product of polycondensation of dimerized linseed oil and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:200:7:100, respectively. The process is run at 150° C. for 2 hours. The obtained product (yield 93%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 46 
     100 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 100 g of difurfurylideneacetone, and 50 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:50, respectively. The process is run at 180° C. for 2.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 47 
     200 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 66 g of monofurfurylideneacetone, 24 g of trifurfurylborate, and 16 g of trifurylimidazoline are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:12:8, respectively. The process is run at 170° C. for 2 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 48 
     100 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 100 g of monofurfurylideneacetone, 5 g of trifurfurylborate, and 100 g of hexamethylenediamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:100:5:100, respectively. The process is run at 150° C. for 1.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     EXAMPLE 49 
     100 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 200 g of monofurfurylideneacetone, 1 g of trifurfurylborate, and 50 g of polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of said components in weight parts is 100:200:1:50, respectively. The process is run at 160° C. for 1 hour. The obtained product (yield 88%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 50 
     200 g of polycondensation resin with the number of epoxy groups 16-18% by weight, 100 g of monofurfurylidenacetone, and 200 g of low molecular polyamide with molecular weight of 3500, which is a product of polycondensation of dimerized oleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components is 100:50:100, respectively. The process is run at 170° C. for 2 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 15° C. and ground to a powder state. 
     EXAMPLE 51 
     200 g of polycondensation resin with the number of epoxy groups 18-20% by weight, 66 g of monofurfurylideneacetone, 20 g of trifurfurylborate, and 100 g of low molecular polyamide with molecular weight of 2000, which is a product of polycondensation of dimerized linseed oil and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:10:50, respectively. The process is run at 140° C. for 3 hours. The obtained product (yield 93%) is poured out from the reactor, cooled to 25° C., and ground to a powder state. 
     EXAMPLE 52 
     100 g of polycondensation resin with the number of epoxy groups 20-22% by weight, 200 g of monofurfurylideneacetone, 12 g of trifurfurylborate, and 100 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:200:12:100, respectively. The process is run at 130° C. for 3 hours. The obtained product (yield 92%) is poured out from the reactor, cooled to 15° C., and ground to a powder state. 
     EXAMPLE 53 
     100 g of polycondensation resin with the number of epoxy groups 22-24% by weight, 200 g of monofurfurylideneacetone, and 8 g of low molecular polyamide with molecular weight of 10000, which is a product of polycondensation of dimerized linoleic acid and polyethylenepolyamine with molecular weight of 1000 are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:200:8, respectively. The process is run at 200° C. for 1.5 hours. The obtained product (yield 88%) is poured out from the reactor, cooled to 30° C., and ground to a powder state. 
     EXAMPLE 54 
     200 g of polycondensation resin with the number of epoxy groups 14-16% by weight, 66 g of difurfurylidenecyclohexanone, 14 g of trifurfurylborate, and 16 g of triethanolamine are put into a reactor similar to that described in Example 1. The ratio of the components in weight parts is 100:33:7:8, respectively. The process is run at 180° C. for 2.5 hours. The obtained product (yield 90%) is poured out from the reactor, cooled to 20° C., and ground to a powder state. 
     Table 1 illustrates the properties of the furan-epoxy powder-like binder obtained by the proposed method according to Examples 1-54 and by the known method. 
     
                                           TABLE 1__________________________________________________________________________Furan-epoxy   Propertiespowder-like                      Stability    Contentbinder obtain-   Melting                 U.sub.below                       Solubility                            upon stor-   of epoxyed by the pro-   Appear-  point,                 drop point,                       in   age,  Non-caking                                         groups, %posed method   ance     °C.                 °C.                       acetone                            months                                  days   by weight1       2        3    4     5    6     7      8__________________________________________________________________________By folloiwngExample 1   Powder coloured            86   117   Complete                            9     40     3.8Example 2   from yellow            84   112   &#34;    9     40     4.2Example 3   to brown 88   118   &#34;    9     40     3.1Example 4        88   121   &#34;    10    45     2.9Example 5        92   125   &#34;    12    60     1.8Example 6        83   110   &#34;    9     45     3.7Example 7        86   117   &#34;    10    45     2.1Example 8        82   109   &#34;    9     40     2.7Example 9        80   101   &#34;    9     40     4.5Example 10       98   130   &#34;    12    60     3.6Example 11       103  135   &#34;    12    60     1.8Example 12       92   121   &#34;    12    60     2.9Example 13       86   114   &#34;    10    50     2.6Example 14       85   112   &#34;    10    45     2.7Example 15       101  132   &#34;    12    60     1.9Example 16       87   115   &#34;    10    40     2.1Example 17       105  137   &#34;    12    60     1.6Example 18       103  129   &#34;    12    60     3.9Example 19       98   127   &#34;    12    60     2.3Example 20       95   123   &#34;    12    60     3.7Example 21       89   118   &#34;    12    60     4.3Example 22       98   125   &#34;    12    60     1.9Example 23       87   118   &#34;    10    45     4.5Example 24       96   120   &#34;    10    45     3.9Example 25       91   116   &#34;    9     40     4.7Example 26       92   119   &#34;    7     35     3.7Example 27       98   124   &#34;    12    60     2.8Example 28       82   103   &#34;    7     35     4.4Example 29       88   111   &#34;    10    40     2.1Example 30       105  130   &#34;    12    60     2.2Example 31       102  125   &#34;    12    60     2.8Example 32       98   121   &#34;    12    60     2.4Example 33       105  135   &#34;    12    60     4.1Example 34       103  131   &#34;    12    60     1.9Example 35       97   121   &#34;    10    45     3.9Example 36       99   132   &#34;    12    60     2.1Example 37       85   114   &#34;    9     50     2.0Example 38       82   109   &#34;    7     35     4.2Example 39       91   123   &#34;    10    50     1.8Example 40       101  128   &#34;    12    60     3.7Example 41       95   118   &#34;    10    45     1.9Example 42       97   121   &#34;    12    60     1.8Example 43       101  133   &#34;    12    60     2.8Example 44       82   108   &#34;    10    50     1.7Example 45       85   112   &#34;    10    50     1.9Example 46       103  135   &#34;    12    60     1.6Example 47       101  132   &#34;    12    60     2.5Example 48       91   119   &#34;    10    50     2.1Example 49       95   126   &#34;    12    60     1.8Example 50       98   133   &#34;    12    60     2.4Example 51       84   112   &#34;    10    50     4.5Example 52       80   106   &#34;    7     35     2.1Example 53       105  132   &#34;    12    60     4.3Example 54       103  135   &#34;    12    60     3.2Binder obtain-ed by known   Dark-brown            92   114   &#34;    3     30     --method__________________________________________________________________________ 
    
     Table 2 illustrates the properties of the polymer based on the furan-epoxy powder-like binder obtained by the proposed method. The polymer is obtained by hardening the binder by step heat treatment within the temperature range of from 120° to 200° C. with a 6-hr exposure and 20° C. increments. 
     
                       TABLE 2______________________________________Properties            Value  1                   2______________________________________Heat distortion temperature,according to Vicat method, °C.                 212-250Compression strength, kgf/cm.sup.2                 800-1500Static bending strength, kgf/cm.sup.2                 300-800Impact strength, kgf.cm/cm.sup.2                 2-10Brinnel hardness, kgf/cm.sup.2                 3000-3800Coking value, %       35-60Power factor at 50 Hz and 20° C.                 22.10.sup.-3 -30.10.sup.-3Chemical stability towards:alkali                stableacids                 stableCombustibility:of the polymer based on the binderobtained by following Examples 17-1924, 27, 31, 34, 37, 39, 42, 44, 46,50, 53                combustibleof the polymer based on the binderobtained by following Examples 4,7, 9, 21, 30, 43, 49  self-extinction                 abilityof the polymer based on the binderobtained by following Examples 1-3, 5,6, 8, 10-16, 20, 22, 23, 25, 26, 28,29, 32, 33, 35, 36, 38, 40, 41, 45,47, 48, 51, 52, 54    incombustible______________________________________