Abstract:
A process for producing a furan-epoxy powder-like binder comprising reaction of an epoxy diane resin (100 parts by weight) with a ketone of the furan series (40 to 500 parts by weight) and a modifying agent (60 to 500 parts by weight). As the ketone of the furan series use is made of monofurfurylideneacetone, difurfurylideneacetone, difurfurylidenecyclohexanone, a mixture of monofurfurylidenacetone with difurfurylidenacetone, 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, or 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3. As the modifying agent use is made of a phenolformaldehyde resin or anhydrides of dibasic carboxylic acids. The reaction is carried out at a temperature within the range of from 130° to 180° C. in the presence, when required, of trifurylborate (10 to 30 parts by weight). The resulting product is cooled to a temperature of at most 30° C. and disintegrated to a powder-like condition. The furan-epoxy binder according to the present invention is not clogging for 60 days; it is also capable of being stored for long periods, up to 12 months, without losing its initial properties. Strain heat-resistance of polymeric materials based on this binder is as high as 320° C. according to Vicat. Polymeric materials based on the binder of this invention can be both inflammable and non-inflammable or can have self-extinguishing properties.

Description:
FIELD OF THE INVENTION 
     The present invention relates to the art of production of furan-epoxy powder-like binders adapted to be used in the manufacture of spray coatings, laminates, moulding compositions, adhesives, foamed plastics. 
     BACKGROUND OF THE INVENTION 
     Known in the art is a process for producing a furanepoxy binder by reacting an epoxy diane resin (a product of polycondensation of epichlorohydrin with diphenylolpropane) with difurfurylideneacetone and a modifying agent, viz. furfuramide, at the temperature of 140° C. at the following proportions of the epoxy diane resin, difurfurylideneacetone and furfuramide, parts by weight: 
     epoxy diane resin:100 
     difurfurylideneacetone:50-150 
     furfuramide:95-100; 
     The resultant product is cooled to a temperature of at most 30° C. and disintegrated to a powder-like condition. 
     The binder produced by this prior art process has an increased clogging (becomes clogged after 30 days) and cannot be stored for long periods (more than 3 months) without loss of its initial properties (solubility and meltability). Vicat heat-resistance of polymeric materials prepared from said furan-epoxy polymeric powder-like binder does not exceed 208° C. Moreover, polymeric materials prepared on the basis of said binder are inflammable. These disadvantages restrict the field of application of the furan-epoxy polymeric binder. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide such a process which would make it possible to prepare a furan-epoxy powder-like binder which would feature an increased non-clogging ability. 
     It is another object of the present invention to provide such a process which would make it possible to prepare a furan-epoxy powder-like binder which would be capable of being stored for long periods without alteration of its initial properties. 
     It is a further object of the present invention to increase the strain heat-resistance of polymeric materials based on a furan-epoxy powder-like binder. 
     Still another object of the present invention is to impart, to polymeric materials on the basis of a furan-epoxy powder-like binder, the property of inflammability of selfextinction. 
     These and other objects of the present invention are accomplished by a process for producing a furan-epoxy powder-like binder by way of reacting an epoxy diane resin with a ketone of the furan series and a modifying agent upon heating, followed by cooling the resulting product to a temperature of at most 30° C. and disintergration to a powder-like condition, wherein, in accordance with the present invention, as the ketone of the furan series use is made of monofurfurylideneacetone, difurfurylideneacetone, difurfurylidenecyclohexanone, a mixture of monofurfurylideneacetone and difurfurylideneacetone at a weight ratio therebetween of from 1:1 to 1.4:1 (parts by weight); 1,9-di-(α-furyl)-nonantetraene-1,3,6,8-one-5 or 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3; as the modifying agent use is made of a phenol-formaldehyde resin or anhydrides of dibasic carboxylic acids; the interaction is effected at a temperature within the range of from 130° to 180° C. and at the following proportions of the above-mentioned components, parts by weight: 
     epoxy diane resin:100 
     ketone of the furan series:40 to 50 
     phenol-formaldehyde resin or anhydrides of dibasic carboxylic acids:60 to 500. 
     The process according to the present invention makes it possible to produce a furan-epoxy powder-like resin which is not clogged for 60 days and capable of being stored for as long as 12 months without changing its initial properties. Strain heat-resistance of polymeric materials prepared on the basis of said binder is as high as 320° C. (according to Vicat). 
     It is advisable to perform the interaction of said components in the presence of trifurylborate at a ratio thereof to the epoxy diane resin (expressed in parts by weight) equal to 10-30:100 respectively. In this case there is obtained a furan-epoxy binder which imparts, to polymeric materials, based thereon, the property of inflammability or self-extinction. 
     The process according to the present invention is simple in both technology and equipment employed. It enables the preparation of the desired product at a high yield of up to 95%. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Into a reactor provided with a heating means, a reflux condenser, thermometer and a stirrer there are charged specified amounts of an epoxy diane resin, a ketone of the furan series, a modifying agent and, when required, trifurylborate. The reaction mixture is heated to a temperature within the range of from 130° to 180° C. and the process is conducted for a period of from 1 to 3 hours. Then the resulting furanepoxy binder is poured from the reactor onto a griddle, cooled to a temperature of at most 30° C., for example, to room temperature and ground to a powder with a specified particle size (depending on the end use of the binder). It is undesirable to cool the binder to a temperature above 30° C., since in this case the binder, upon its disintegration, adheres to the parts of the disintegration means. 
     The mixture of monofurfurylideneacetone and difurfurylideneacetone as used in the process of the present invention may be prepared by condensation of furfural with acetone in the presence of a catalyst, viz. an alkali, at a temperature within the range of from 60° to 90° C. (cf. E. V. Orobchenko &#34;Furan Resins&#34;, Kiev, 1963, pp. 64-70). 
    
    
     For a better understanding of the present invention some specific Examples of its particular embodiments are given hereinbelow. Properties of the furan-epoxy powder-like binder and those of polymers prepared therefrom are shown in Tables 1 and 2 respectively which are given after the Examples. 
     EXAMPLE 1 
     Into a reactor provided with a heating means, reflux condenser, thermometer and a stirrer there are charged 200 g of an epoxy diane resin (the product of polycondensation of epichlorohydrin with diphenylolpropane) with a number of epoxy groups of 14 to 16%, 80 g of difurfurylideneacetone, 20 g of trifurylborate and 120 g of maleic anhydride. The ratio between the components expressed in parts by weight is equal to 100:40:10:60 respectively. Temperature in the reactor is elevated to 130° C. and the process is conducted at this temperature for 2 hours. The resulting furan-epoxy binder (the yield is equal to 88%) is poured from the reactor, cooled to the temperature of 30° C. and disintegrated to powder with a predetermined particle size. 
     EXAMPLE 2 
     Into the reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 16-18%, 200 g of monofurfurylideneacetone, 24 g of trifurylborate and 200 g of phthalic anhydride. Ratio between said components, expressed in parts by weight, is equal to 100:100:12:100 respectively. The process is conducted at the temperature of 160° C. for 2 hours. The resulting product (the yield is equal to 88%) is poured from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 3 
     Into a reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 200 g of a mixture of monofurfurylideneacetone and difurfurylideneacetone at the ratio therebetween of 1:1 and 400 g of a resol phenol-formaldehyde resin (Ubbelohde drop point is 88°-90° C.). Ratio between said components, expressed in parts by weight, is equal to 100:100:200 respectively. The process is conducted at the temperature of 140° C. for 1 hour. The resulting product (the yield is equal to 95%) is poured from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 4 
     Into the reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 20-22%, 200 g of difurfurylideneacetone, 60 g of trifurylborate and 200 g of a novolac phenolformaldehyde resin (Ubbelohde drop point is 105°-115° C.). The ratio between said components, expressed in parts by weight is equal to 100:100:30:100 respectively. The process is conducted at the temperature of 140° C. for one hour. The resulting product (the yield is 95%) is poured from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 5 
     Into the reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 22-24%, 100 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5 and 460 g of a novolac phenolformaldehyde resin (Ubbelohde drop point is 115°-120° C.). The ratio between said components, expressed in parts by weight, is equal to 100:200:300 respectively. The process is conducted at the temperature of 150° C. for two hours. The resulting product (the yield is 94%) is discharged from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 6 
     Into the reactor described in Example 1 hereinbefore there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 16-18%, 400 g of difurfurylidenecyclohexanone and 460 g of methyltetrahydrophthalic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:400:460 respectively. The process is conducted at the temperature of 180° C. for three hours. The resulting product (the yield is equal to 88%) is discharged from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 7 
     Into the reactor described in Example 1 hereinbefore there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 20-22%, 100 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3 and 500 g of a novolac phenol-formaldehyde resin (Ubbelohde drop point is 120°-130° C.). The ratio between said components expressed in parts by weight is equal to 100:100:500 respectively. The process is conducted at the temperature of 180° C. for two hours. The resulting product (the yield is equal to 90%) is discharged from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 8 
     Into the reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 200 g of a mixture of monofurfurylideneacetone and difurfurylideneacetone at the ratio therebetween (expressed in parts by weight) of 1.4:1, 60 g of trifurylborate and 120 g of a novolac phenol-formaldehyde resin (Ubbelohde drop point is 95°-105° C.). The ratio between said components, expressed in parts by weight, is equal to 100:100:30:60 respectively. The process is conducted at the temperature of 130° C. for 1.5 hour. The resulting product (the yield is equal to 92%) is discharged from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 9 
     Into the reactor described in Example 1 hereinbefore there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 14-16%, 200 g of a mixture of monofurfurylideneacetone and difurfurylideneacetone at the weight ratio therebetween of 1.2:1 (expressed in parts by weight) and 200 g of phthalic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:100:100 respectively. The process is conducted at the temperature of 180° C. for 1.5 hour. The resulting product (the yield is equal to 88%) is discharged from the reactor, cooled to the temperature of 30° C. and ground to a powder-like condition. 
     EXAMPLE 10 
     Into the reactor described in Example 1, there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 400 g of difurfurylideneacetone, 30 g of trifurylborate and 400 g of a novolac phenol-formaldehyde resin (Ubbelohde drop point is 105°-115° C.). The ratio between said components, expressed in parts by weight, is equal to 100:400:30:400 respectively. The process is conducted at the temperature of 140° C. for two hours. The resulting product (the yield is equal to 95%) is discharged from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 11 
     Into the reactor described in Example 1 hereinbefore there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 400 g of monofurfurylideneacetone, 30 g of trifurylborate and 400 g of a novolac phenolformaldehyde resin (Ubbelohde drop point is 115°-120° C.). The ratio between said components, expressed in parts by weight, is equal to 100:400:30:400 respectively. The process is conducted at the temperature of 140° C. for 1.5 hour. The resulting product (the yield is equal to 92%) is discharged from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 12 
     Into the reactor described in Example 1 there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 20-22%, 200 g of monofurfurylideneacetone and 60 g of maleic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:200:60 respectively. The process is conducted at the temperature of 150° C. for two hours. The resulting product (the yield is equal to 90%) is discharged from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 13 
     Into the reactor described in Example 1 hereinbefore there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 14-16%, 200 g of monofurfurylideneacetone, 30 g of trifurylborate and 120 g of methyltetrahydrophthalic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:100:15:60 respectively. The process is conducted at the temperature of 170° C. for two hours. The resulting product (the yield is equal to 88%) is discharged from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 14 
     Into the reactor described in the foregoing Example 1 there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 400 g of 1,9-di-(α-furyl)-nonanetetraene-1,3,6,8-one-5, 30 g of trifurylborate and 200 g of a resol phenol-formaldehyde resin (Ubbelohde drop point is equal to 85°-88° C.). The ratio between said components, expressed in parts by weight, is equal to 100:400:30:200 respectively. The process is conducted at the temperature of 180° C. for two hours. The resulting product (the yield is equal to 88%) is poured from the reactor, cooled to the temperature of 30° C. and ground to a powder-like condition. 
     EXAMPLE 15 
     Into the reactor described in Example 1 there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 20-22%, 500 g of 1,5-di-(α-furyl)-2,4-dimethylpentadiene-1,4-one-3, 30 g of trifurylborate and 500 g of phthalic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:500:30:500 respectively. The process is conducted at the temperature of 160° C. for two hours. The resulting product (the yield is equal to 88%) is discharged from the reactor, cooled to the temperature of 25° C. and ground to a powder-like condition. 
     EXAMPLE 16 
     Into the reactor described in Example 1 hereinbefore there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 80 g of difurfurylidenecyclohexanone, 20 g of trifurylborate and 400 g of a novolac phenol-formaldehyde resin (Ubbelohde drop point is 95°-105° C.). The ratio between said components, expressed in parts by weight, is equal to 100:40:10:200 respectively. The process is conducted at the temperature of 160° C. for three hours. The resulting product (the yield is equal to 95%) is discharged from the reactor, cooled to the temperature of 20° C. and ground to a powder-like condition. 
     EXAMPLE 17 
     Into the reactor described in the foregoing Example 1 there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 22-24%, 80 g of monofurfurylideneacetone, 20 g of trifurylborate and 120 g of phthalic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:40:10:60 respectively. The process is conducted at the temperature of 170° C. for two hours. The resulting product (the yield is equal to 88%) is discharged from the reactor, cooled to the temperature of 15° C. and disintegrated to a powder-like condition. 
     EXAMPLE 18 
     Into the reactor described in Example 1 hereinbefore there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 500 g of a mixture of monofurfurylideneacetone and difurfurylideneacetone at the ratio therebetween (expressed in parts by weight) of 1.4:1, 30 g of trifurylborate and 500 g of maleic anhydride. The ratio between said components, expressed in parts by weight, is equal to 100:500:30:500 respectively. The process is conducted at the temperature of 160° C. for two hours. The resulting product (the yield is equal to 90%) is discharged from the reactor, cooled to the temperature of 20° C. and disintegrated to a powder-like condition. 
     EXAMPLE 19 
     Into the reactor of Example 1 there are charged 80 g of an epoxy diane resin with a number of epoxy groups of 22-24%, 400 g of difurfurylideneacetone and 400 g of a resol phenol-formaldehyde resin (Ubbelohde drop point is 78°-80° C.). The ratio between said components is equal to 100:500:500 respectively (in parts by weight). The process is conducted at the temperature of 150° C. for 1.5 hour. The resulting product (the yield is equal to 92%) is discharged from the reactor, cooled to the temperature of 25° C. and disintegrated to a powder-like condition. 
     EXAMPLE 20 
     Into the reactor described in Example 1 hereinbefore there are charged 200 g of an epoxy diane resin with a number of epoxy groups of 16-18%, 80 g of difurfurylideneacetone, 30 g of trifurylborate and 120 g of a resol phenolformaldehyde resin (Ubbelohde drop point is 88°-90° C.). The ratio between the components, expressed in parts by weight is equal to 100:40:15:60 respectively. The process is conducted at the temperature of 160° C. for one hour. The resulting product (the yield is equal to 90%) is discharged from the reactor, cooled to the temperature of 20° C. and disintegrated to a powder-like condition. 
     EXAMPLE 21 
     Into the reactor described in Example 1 there are charged 100 g of an epoxy diane resin with a number of epoxy groups of 18-20%, 250 g of difurfurylideneacetone, 30 g of trifurylborate and 250 g of a resol phenol-formaldehyde resin (Ubbelohde drop point is 85°-88° C.). The ratio between said components, expressed in parts by weight, is equal to 100:250:30:250 respectively. The process is conducted at the temperature of 130° C. for 2.5 hours. The resulting product (the yield is equal to 95%) is discharged from the reactor, cooled to the temperature of 15° C. and disintegrated to a powder-like condition. 
     Properties of the furan-epoxy powder-like binder produced by the process of the present invention in Examples 1 through 21 and by the prior art process are given in the following Table 1. 
     
                                           Table 1__________________________________________________________________________Furan-epoxypowder-likebinderproducedby thePropertiesprocess                      Stabi-of the                       lity                            Non-present   Melt-         Ubbeloh-  Content                        upon                            clogg-inven-Appe-     ing de drop              Solubi-                   of epo-                        stora-                            ing abi-tion, asaran-     point,         point,              lity in                   xy gro-                        ge, lity,of   ce   °C.         °C.              acetone                   ups, %                        months                            days1    2    3   4    5    6    7   8__________________________________________________________________________Exam-Pow-ple 1der  82  109  Total                   2.8  6   35Exam-ofple 2yel- 102 123  &#34;    2.0  10  50Exam-lowple 3to   85  112  &#34;    3.2  9   45Exam-darkple 4brown     80  103  &#34;    4.2  12  60colourExam-ple 5     103 127  Total                   2.6  8   40Exam-ple 6     95  118  &#34;    2.1  10  50Exam-ple 7     105 130  &#34;    2.0  12  60Exam-Pow-ple 8der  81  97   &#34;    4.6  7   40Exam-ofple 9yel- 102 127  &#34;    2.3  11  45Exam-lowple 10to   88  109  &#34;    2.4  9   45Exam-darkple 11brown     84  103  &#34;    2.9  8   40colourExam-ple 12    81  101  &#34;    4.1  7   35Exam-ple 13    92  115  &#34;    2.7  12  60Exam-ple 14    106 131  &#34;    2.1  12  60Exam-ple 15    87  108  &#34;    2.1  9   40Exam-ple 16    90  114  &#34;    2.9  12  60Exam-ple 17    94  116  &#34;    4.0  8   35Exam-ple 18    106 131  Total                   2.2  12  60Exam-ple 19    98  127  &#34;    1.8  8   60Exam-ple 20    83  109  &#34;    3.9  7   60Exam-ple 21    100 129  &#34;    4.2  7   60Binderdark-     92  114  &#34;    --   3   30producedbrownby thepowderprior artprocess__________________________________________________________________________ 
    
     Properties of a polymer produced from the furan-epoxy powder-like binder according to the present invention are shown in the following Table 2. The polymer is prepared by curing of the binder according to a step-wise schedule at a temperature within the range of from 140° to 200° C. with the interval of 6 hours after every 20° C. 
     
                       Table 2______________________________________Properties             Value______________________________________Vicat strain heat-resistance, °C.                  215-320Ultimate compression strength, kgf/cm.sup.2                  800-1,400Ultimate strength at static bending,                  350-600kgf/cm.sup.2Resilience, kgf.cm/cm.sup.2                  2-8Brinnel hardness, kgf/cm.sup.2                  3,000-4,500Coke number, %         35-60Dielectric loss angle at 50 Hz and                  25.10.sup.-3 -30.10.sup.-320° C.Chemical resistance:against alkalis        Resistantagainst acids          ResistantInflammability:of the polymer produced from the binder                  Inflammableof Examples 3, 5, 6, 7, 9, 12, 19of the polymer produced from the                  Capable of self-binder of Examples 1, 2, 16, 17                  extinguishingof the polymer produced from the                  Non-inflammablebinder of Examples 4, 8, 10, 11, 13,14, 15, 18, 20, 21______________________________________