Process for producing power-like furan resin

The present invention relates to processes for producing powder-like furna resine.
FIELD OF APPLICATION OF THE INVENTION
Furan powder-like resins are employed for the manufacture of construction parts, e.g. for heat-exchangers; protective anti-corrosion coatings (foamed plastics), in the production of structural members of electroinsulation fixture, pipelines, reactors.
Articles from powder-like compression-moulding materials based on powder-like furan resins may be manufactured by a continuous process. Protection coatings based on furan powder-like resins may be applied by the gas-flame spraying method as well as by deposition in an electrostatic field or in a fluidized bed. Manufacture of laminates and coatings with the use of a powder-like furna resin makes it possible to obviate the use of a solvent in the process.
BACKGROUND OF THE INVENTION
Known in the art are phenol-formaldehyde, polyester and epoxy resins employed as binders for the manufacture of foamed plastics, laminated plastics, graphitized plastics, compression-moulding powders, spray-deposited coatings. However, said resins do not satisfy the requirements imposed on the final articles in respect of their heat-resistance and chemical resistance. Furthermore, powder-like resinous products based on epoxy and polyester resins are rather expensive.
Known in the art is a process for producing powder-like furan resins comprising heating a ketone of the furan series such as crystalline difurfurylidene acetone at the temperature of 220.degree. C. for 6 hours. The resulting resin is stable against the effect of aggressive media at temperatures of at most 80.degree. C. Furthermore, Martens yield temperature of the prior art resin does not exceed 250.degree. C. The desired product yield ensured by the prior art process is only 45 to 55%. Moreover, the resin produced by said process is not stable against oxidizing agents. The thus-produced resin is suitable only for the manufacture of a construction graphite-reinforced plastic.
Also known in the art is a process for producing powder-like furna resins comprising heating difurfurylidene acetone in a current of an inert gas at the temperature of 200.degree. C. for the period of 4 hours. The resulting resin has but a limited resistance in respect of aggressive media; it is not resistant against oxidizing agents and its Martens yield temperature does not exceed 270.degree. C. The desired product yield in this process is equal to 70%. This process is also suitable for the manufacture of resins for a construction graphite-reinforced plastic.
It is an object of the present invention to overcome the above-mentioned disadvantages.
It is also an object of the present invention to provide such a process which would enable the production of a powder-like furan resin possessing an increased chemical resistance relative to the effect of highly-aggressive media and oxidizing agents at elevated temperatures.
It is another object of the present to provide such a process which would make it possible to produce a powder-like furan resin possessing high yield temperature.
It is still another object of the present invention to provide such a process for producing a powder-like furan resin which would enable a high yield of the desired product.
These objects are accomplished by that in the production of a powder-like furan resin by way of heating a ketone of the furan series, in accordance with the present invention, the process is conducted at a temperature within the range of from 130.degree. to 200.degree. C. in the presence of a phenol-formaldehyde resin, the weight ratio between said ketone of the furane series and said phenol-formaldehyde resin is 10:3-15 respectively.
The process for producing a powder-like furan resin makes it possible to obtain a resin possessing an increased resistance to the effect of highly-aggressive media at a temperature of up to 120.degree. C. and oxidizing agents at a temperature of up to 80.degree. C. with a Martens yield temperature as high as 300.degree. C. The resin yield is ensured at about 93%.
To reduce the process duration down to 1-2 hours, it is advisable to maintain the process temperature, in accordance with the present invention, within the range of from 180.degree. to 200.degree. C.
Besides, in accordance with the present invention it is also advisable to use, as the ketone of the furan series, monofurfurylidene acetone, difurfurylidene acetone, a mixture of monofurfurylidene acetone and difurfurylidene acetone in a ratio therebetween of from 7:3 to 7:7 respectively, difurfurylidene cyclohexanone, 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5, 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3 or mixtures thereof.
The use of ketones belonging to the furane series or mixtures thereof makes it possible to perform the process for producing a furan powder-like resin of various grades thus imparting thereto a whole range of specific properties for a further processing thereof to articles. Depending on the field of application of a resin, the latter is produced with a required melting point or dropping point.
To produce a furan resin suitable for the manufacture of coatings, compression-moulded articles, construction materials in accordance with the present invention it is advisable to conduct the process at a temperature within the range of from 130.degree. to 180.degree. C. in the presence of furfurol at a weight ratio of the furan-series ketone, phenolformaldehyde resin and furfurol ranging from 10:3:2 to 10:15:5 respectively.
The resin produced by the process according to the present invention is stable against highly-aggressive media at elevated temperatures, its Martens yield point is as high as 320.degree. C., and impact strength is up to 4 kgf.cm/cm.sup.2.
An embodiment of the present invention resides in that the process is performed at a weight ratio of the furan-series ketone, phenolformaldehyde resin and furfurol equal to 10:5:5 respectively at the process temperature varied within the range of from 130.degree. to 140.degree. C.
Owing to the present invention it is now possible to produce a furan resin suitable for the production of a structural graphite-reinforced plastic, a laminated plastic.
Incorporation of furfurol into the reaction mixture makes it possible to lower the process temperature down to 130.degree.-140.degree. C. In accordance with the present invention, it is advisable to perform the process in the presence of 1-3% by weight of a catalyst (calculated for the weight of the starting components) comprising a mixture of tin dichloride and hexamethylene diamine employed in a weight ratio of from 7:3 to 3:7 respectively. Performance of the process in the presence of the catalyst makes it possible to reduce the process duration down to 1-3 hours.
In order to impart the property of non-inflammation or self-extinction to the resin, it is advisable to incorporate, into the starting mixture of the components, triphenylphosphate taken in a weight ratio of the ketone of the furan series of from 10:0.5 to 10:3 respectively.
To increase impact resistance of the resulting resin by 1.6 times, it is advisable, in accordance with the present invention, to conduct the process in the presence of tetraethoxysilane taken in a weight ratio to the ketone of the furane series within the range of from 10:3 to 10:6 respectively.
DETAILED DESCRIPTION OF THE INVENTION
Other objects and advantages of the present invention will now become more fully apparent from the following detailed description of the process for producing a powder-like furan resin and Examples illustrating same.
The process for producing powder-like furan resins in accordance with the present invention is based on the use of ketones belonging to the furan series, phenolformaldehyde resins and furfurol.
As the ketones of the furan series use may be made of difurfurylidene acetone, monofurfurylidene acetone, difurfurylidene cyclohexane, 1,9-di-(.alpha.-furyl)-nonane-tetraen-1,3,6,8-one-5, 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3, mixtures of said compounds such as a mixture of monofurfurylidene acetone and difurfurylidene acetone taken in equal amounts, a mixture of difurfurylidene acetone and 1,5-di-(.alpha.-furyl)-2,4-dimethylpentaiden-1,4-one-3, a mixture of monofurfurylidene acetone and difurfurylidene acetone taken in a weight ratio ranging from 7:3 to 7:7 respectively. For example, the mixture of monofurfurylidene acetone and difurfurylidene acetone may be prepared by mixing the starting components or by condensation of furfurol and acetone in the presence of an alkali catalyst.
The phenolformaldehyde resin employed as the starting component in the process according to the present invention comprises a product of condensation of phenol and formaldehyde in the presence of an alkali catalyst or an acidic catalyst.
The process according to the present invention makes it possible to produce, from the above-cited range of the starting compounds, resins possessing sufficiently broad range of properties which have been impossible to obtain by the hitherto-known processes.
In accordance with the process of the present invention, temperature of the process for producing a powder-like furan resin is varied within the range of from 130.degree. to 200.degree. C.
The use of the process temperature below 130.degree. C. results in the production of a resin having a non-uniform composition. Its Martens yield temperature does not exceed 170.degree.-180.degree. C. The resin does not withstand the effect of aggressive media even at room temperature. The process temperature above 200.degree. C. results in the production of a non-soluble and non-melting resin which does not lend itself to further processing into articles. The process of the resin production is difficult to control and gives a foamed resin with a substantial evolution of gases. The resin yield ranges from 60 to 70%.
It has been found that the preparation of a furan resin from phenolformaldehyde resin and difurfurylidene acetone by way of heating the components should be preferably conducted at a temperature within the range of from 180.degree. to 200.degree. C. Said starting compounds should be taken in such a weight ratio that 3 to 15 parts by weight of phenolformaldehyde resin be used for every 10 parts by weight of the ketone of the furan series. The thus-produced furan resin is a foamed plastic.
Production of the furan resin according to the present invention should be preferably performed in the presence of 1 to 3% by weight of a catalyst (as calculated for the weight of the starting components) comprising a mixture of tin dichloride and hexamethylenediamine taken in a weight ratio of from 7:3 to 3:7 respectively.
The use of the catalyst in the production of the resin makes it possible to substantially reduce the process duration. The resin produced in the presence of the catalyst has a higher mechanical strength and chemical resistance. Thus, Martens yield temperature is as high as 320.degree. C. and impact strength is of about 4 kgf.cm/cm.sup.2. Chemical resistance of the resin produced in the presence of the catalyst against aggressive media is 1.3 to 1.6 times higher than that of a resin produced without the catalyst.
The above-mentioned ratios between the catalyst components are selected with the proviso that an increased ratio of tin dichloride to hexamethylene diamine exceeding the one mentioned hereinbefore results in the formation of a refuse product and frequently in the formation of a foamed mass unsuitable for a further use, lowering said ratio between tin dichloride and hexamethylenediamine results in the formation of the final product having a low chemical resistance.
It should be noted that the furan resins produced from the above-mentioned two starting compounds in the presence of the catalyst according to the present invention may be used for the production of laminated plastics, spray-deposited coatings and have a high heat-resistance and chemical stability.
The process according to the present invention makes it possible to produce powder-like furan resins possessing, as it has been already mentioned, a high heat-resistance chemical stability and suitable for the manufacture of graphite-reinforced plastics, construction plastics, laminated plastics using three starting compounds, namely: a ketone of the furan series, a phenol formaldehyde resin and furfurol in the presence of the above-described catalyst.
It has also been found that with the use of a ketone of the furan series, phenolformaldehyde resin and furfurol taken in a weight ratio of from 10:3:2 to 10:15:5 and preferably of 10:5:5 respectively, the process should be conducted in the presence of the above-mentioned catalyst at a temperature within the range of from 130.degree. to 180.degree. C. and preferably from 130.degree. to 180.degree. C. to obtain a powder-like furan resin suitable for the manufacture of spray-deposited coatings, compression-moulding powders, structural materials.
It should be noted that the above-mentioned ratios of the starting components make it possible to produce a resin possessing predetermined properties. A higher ratio of said ketone and phenolformaldehyde resin and of the ketone and furfurol exceeding the one mentioned hereinbefore results in a lowered impact strength of the final products. The resin has an increased brittleness and becomes broken under the influence of aggressive media and elevated temperatures.
Amounts of the incorporated phenolformaldehyde resin exceeding the corresponding amounts of other components in the starting mixture result in a lowered stability of the resin in aggressive media and at an elevated temperature. The yield of the desired product is decreased to 70%.
An increased amount of the incorporated furfurol relative to other components gives a resin having impaired processability. The resin becomes tacky, sticks to parts of the comminuting and processing equipment. Chemical resistance and heat-resistance of the resulting resin are lower than those of the prior art resins.
In accordance with the present invention, it is advantageous to introduce, into the starting mixture, in addition to the above-mentioned compounds, triphenylphosphite which imparts to the resulting resin the properties of self-extinction and non-combustibility. Triphenylphosphite is added into the mixture of the starting components in an amount ensuring a weight ratio of triphenyl and the ketone of the furan series ranging from 10:0.5 to 10:3 respectively.
To increase impact strength of the furan resin, into the starting mixture of the components tetraethoxysilane should be preferably added in an amount ensuring a weight ratio thereof to the ketone of the furan series ranging from 10:3 to 10:6 respectively.
Said additives may be introduced either in combination or separately.
It has been found that the incorporated additives affect neither the process duration nor the yield of the desired product.
The powder-like furan resin produced by the process according to the present invention is resistant to highly aggressive media at a temperature of up to 120.degree. C.; Martens yield temperature of the resulting resins is as high as 320.degree. C., while their impact strength is up to 4 kgf.cm/cm.sup.2.

EXAMPLE 1
Into a reactor provided with a stirring means, a heater and a reflux condenser there are charged 10 parts by weight of difurfurylidene acetone, 3 parts by weight of resol formaldehyde resin having Ubbelohde dropping point of 80.degree. C. The process is conducted at the temperature of 130.degree. C. for the period of 3 hours. The final resin is drained and cooled to the temperature of 15.degree. C. After cooling the resin becomes a solid mass. The resin yield is 90%. Properties of the resin are shown in Table 1 hereinbelow.
To produce an article, 1 kg of dry resin produced as described hereinabove and 50 g of anhydrous iron chloride are charged into a comminuting unit and a mixture is then prepared with a required particle size. The comminuted mixture is rolled at the temperature of 120.degree..+-.20.degree. C., crushed and subjected to compression-moulding. The mass is compressed at the temperature of 200.degree..+-.10.degree. C. under the pressure of 500 kgf/cm.sup.2 with the residence time of 1 minute per every mm of the article thickness. Properties of the article are shown in Table 2 hereinbelow.
EXAMPLE 2
Into a reactor similar to that described in the foregoing Example 1 there are charged 10 parts by weight of difurfurylidene acetone, 5 parts by weight of novolac phenol-formaldehyde resin with the Ubbelohde dropping point of 95.degree. C. and 0.5 part by weight of triphenylphosphite. The process is conducted at the temperature of 180.degree. C. for two hours. The yield of the resin is 92%. Manufacture of an article is performed following the procedure described in Example 1 hereinabove. Properties of the resin and of the article made therefrom are shown in Tables 1 and 2.
EXAMPLE 3
Into a reactor similar to that described in Example 1 there are charged 10 parts by weight of difurfurylidene acetone, 6 parts by weight of novolac phenol-formaldehyde resin with the Ubbelohde dropping point of 135.degree. C., 30 parts by weight of triphenylphosphite, 30 parts by weight of tetraethoxysilane. The process is conducted at the temperature of 200.degree. C. for one hour. The final resin is cooled to the temperature of 30.degree. C. The resin yield is 93%. Manufacture of the articles is performed following the procedure of Example 1. Properties of the resin and those of the article made therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 4
Into a reactor described in the foregoing Example 1 there are charged 10 parts by weight of difurfurylidene acetone, 5 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 5 parts by weight of furfurol, 1.0 parts by weight of triphenylphosphite, 6 parts by weight of tetraethoxysilane and 3% (0.81 part by weight) as calculated for the weight of the starting components of the catalyst comprising a mixture of 3.0 parts by weight of tin dichloride and 7 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 130.degree. C. for one hour. The final resin is drained and cooled to the temperature of 20.degree. C. The yield of the resin is 90%. Properties of the resin and of the article produced therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 5
Into a reactor similar to that described in Example 1 hereinbefore there are charged 10 parts by weight of difurfurylidene acetone, 5 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 5 parts by weight of furfurol, 1.5 part by weight of triphenylphosphite, 3.0 parts by weight of tetraethoxysilane and 2% (0.45 parts by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 5.0 parts by weight of tin dichloride and 5.0 parts by weight of hexamethylenediamine. The process is conducted at the temperature of 180.degree. C. for 0.5 hour. The final resin is drained and cooled to the temperature of 30.degree. C. The resin yield is equal to 93%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 6
Into a reactor similar to that described in the foregoing Example 1 there are charged 10 parts by weight of novolac phenol-formaldehyde resin with the Ubbelohde dropping point of 135.degree. C., 3.0 parts by weight of triphenylphosphite and 1% (0.23 part by weight), as calculated by weight of the starting components, of a catalyst comprising a mixture of 7.0 parts by weight of tin dichloride and 3.0 parts by weight of hexamethylenediamine. The process is conducted at the temperature of 140.degree. C. for one hour. The final resin is drained, cooled to the temperature of 15.degree. C. The resin yield is equal to 93%. Properties of the resin and of the articles manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 7
Into a reactor similar to that described in the foregoing Example 1 there are charged 10 parts by weight of monofurfurylidene acetone, 3 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 2 parts by weight of furfurol and 2% (0.3 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 5.0 parts by weight of tin dichloride and 5.0 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 140.degree. C. for one hour. The final resin is drained and cooled to the temperature of 30.degree. C. The resin yield is equal to 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 8
Under the conditions similar to those described in Example 1 hereinbefore into a reactor there are charged 10 parts by weight of monofurfurylidene acetone, 9.0 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 110.degree. C., 3.5 parts by weight of furfurol and 2% (0.45 part by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 5.0 parts by weight of tin dichloride and 5.0 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 140.degree. C. for one hour. The final resin is drained and cooled to the temperature of 20.degree. C. The resin yield is 91%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 9
Under the conditions similar to those described in the foregoing Example 1 into a reactor there are charged 10 parts by weight of monofurfurylidene acetone, 15 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 80.degree. C., 6 parts by weight of tetraethoxysilane, 3 parts by weight of triphenylphosphite and 3% (1.02 parts by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 3.0 parts by weight of tin dichloride and 7.0 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 130.degree. C. for one hour. The final resin is drained and cooled to 15.degree. C. The resin yield is 93%. Properties of the resin and of the articles made therefrom are shown in Tables 1 and 2.
EXAMPLE 10
Under the conditions similar to those described in the foregoing Example 1 into a reactor there are charged 10 parts by weight of a mixture of monofurfurylidene acetone and difurfurylidene acetone in the weight ratio of 7:3 respectively 3 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 135.degree. C., 3 parts by weight of triphenylphosphite, 2 parts by weight of furfurol and 1% (0.18 part by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 7.0 parts by weight of tin dichloride and 3.0 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 140.degree. C. for 1.5 hour. The final resin is drained and cooled to the temperature of 20.degree. C. The resin yield is equal to 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 11
Into a reactor similar to that described in the foregoing Example 1 there are charged 10 parts by weight of a mixture of monofurfurylidene acetone and difurfurylidene acetone taken in the weight ratio of 7:5 respectively, 9 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 80.degree. C., 4 parts by weight of furfurol, 1 part by weight of triphenylphosphite, 3 parts by weight of tetraethoxysilane and 2% (0.54 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 3.0 parts by weight of tin dichloride and 7.0 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 150.degree. C. for two hours. The final resin is drained and cooled to the temperature of 25.degree. C. The resin yield is 91%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2.
EXAMPLE 12
Into a reactor similar to that described in Example 1 there are charged 10 parts by weight of a mixture of monofurfurylidene acetone and difurfurylidene acetone taken in the weight ratio of 7:7 respectively, 15 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 5 parts by weight of furfurol, 5 parts by weight of triphenylphosphite, 4.5 parts by weight of tetraethoxysilane and 3% (1.125 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 5 parts by weight of tin dichloride and 5 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 180.degree. C. for one hour. The final resin is drained and cooled to the temperature of 30.degree. C. The resin yield is 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 13
Into a reactor similar to that of Example 13 there are charged 10 parts by weight of difurfurylidene cyclohexanone, 3 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 135.degree. C., 2 parts by weight of furfurol and 1% (0.15 part by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 7 parts by weight of tin dichloride and 3 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 180.degree. C. for three hours. The final resin is drained and cooled to the temperature of 15.degree. C. The resin yield is equal to 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2.
EXAMPLE 14
Into a reactor similar to that of Example 1 there are charged 10 parts by weight of difurfurylidene cyclohexanone, 9 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 80.degree. C., 3.5 parts by weight of furfurol, 0.5 part by weight of triphenylphosphite, 6 parts by weight of tetraethoxysilane and 3% (0.87 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 3 parts by weight of tin dichloride and 7 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 130.degree. C. for the period of two hours. The final resin is drained and cooled to the temperature of 30.degree. C. The resin yield is equal to 93%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 15
Into a reactor similar to that of Example 1 there are charged 10 parts by weight of difurfurylidene cyclohexanone. 15 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 120.degree. C., 5 parts by weight of furfurol, 1.5 parts by weight of triphenylphosphite, 3 parts by weight of tetraethoxysilane and 2% (0.68 part by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 5 parts by weight of tin dichloride and 5 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 200.degree. C. for one hour. The final resin is drained and cooled to the temperature of 20.degree. C. The resin yield is equal to 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 16
Into a reactor similar to that of Example 1 there are charged 10 parts by weight of 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one5,3 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 2 parts by weight of furfurol, 3 parts by weight of triphenylphosphite, 6 parts by weight of tetraethoxysilane and 1% (0.24 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 7 parts by weight of tin dichloride and 3 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 200.degree. C. for 1.5 hours. The final resin is drained and cooled to the temperature of 15.degree. C. The resin yield is equal to 92%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 17
Into a reactor similar to that of Example 1 there are charged 10 parts by weight of 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5, 9 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 100.degree. C., 3.5 parts by weight of furfurol, and 2% (0.51 part by weight), as calculated for the weight of the starting components, of a catalyst comprising a mixture of 3 parts by weight of tin dichloride and 7 parts by weight of hexamethylene diamine. The process of conducted at the temperature of 180.degree. C. for two hours. The final resin is drained and cooled to the temperature of 20.degree. C. The resin yield is equal to 93%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 18
Into a reactor there are charged, by following the procedure of the foregoing Example 1, 10 parts by weight of 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5, 15 parts by weight of resol phenolformaldehyde resin with the Ubbelohde dropping point of 85.degree. C., 5 parts by weight of furfurol, 0.5 part by weight of triphenylphosphite, 6 parts by weight of tetraethoxysilane and 3% (1.095 parts by weight), as calculated for the starting components, of a catalyst consisting of a mixture of 5 parts by weight of tin dichloride and 5 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 130.degree. C. for the period of 3 hours. The final resin is drained and cooled to the temperature of 30.degree. C. The resin yield is equal to 93%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2.
EXAMPLE 19
Into a reactor similar to that of Example 1 there are charged 10 parts by weight of 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3, 3 parts by weight of novolac phenol formaldehyde resin with the Ubbelohde dropping point of 95.degree. C., 2 parts by weight of furfurol and 1% (0.15 part by weight), as calculated for the starting components, of a catalyst consisting of a mixture of 7 parts by weight of tin dichloride and 3 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 130.degree. C. for two hours. The resulting resin is drained and cooled to the temperatures of 30.degree. C. The resin yield is equal to 91%. Properties of the resin and of the article manufactured therefrom are shown in the following Tables 1 and 2.
EXAMPLE 20
Into a reactor similar to that described in Example 1 there are charged 10 parts by weight of 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3, 9 parts of resol phenol-formaldehyde resin with the Ubbelohde dropping point of 80.degree. C., 3.5 parts by weight of furfurol, 1.5 parts by weight of triphenylphosphite, 3 parts by weight of tetraethoxysilane and 2% (0.54 part by weight), as calculated for the weight of the starting components, of a catalyst consisting of a mixture of 5 parts by weight of tin dichloride, and 5 parts by weight of hexamethylelene diamine. The process is conducted for 1.5 hours at the temperature of 180.degree. C. The resulting resin is drained and cooled to the temperature of 20.degree. C. The resin yield is equal to 93%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 21
Using the equipment and techniques similar to those described in the foregoing Example 1, into a reactor there are charged 10 parts by weight of 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3, 15 parts by weight of novolac phenolformaldehyde resin with the Ubbelohde dropping point of 135.degree. C., 5 parts by weight of furfurol, 3 parts by weight of triphenylphosphite, 6 parts by weight of tetraethoxysilane and 3% (1.17 parts by weight), as calculated for the weight of starting components, of a catalyst consisting of a mixture of 3 parts by weight of tin dichloride and 7 parts by weight of hexamethylene diamine. The process is conducted at the temperature of 200.degree. C. for the period of one hour. The resulting resin is drained and cooled to the temperature of 15.degree. C. The resin yield is equal to 91%. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 22
The process is conducted under the conditions similar to those described in Example 5 hereinbefore, except that as the ketone use is made of a mixture of difurfurylidene acetone and difurfurylidene cyclohexanone in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 23
The process is conducted under conditions similar to those described in Example 16 hereinbefore, with the only exception that as the ketone use is made of a mixture of difurfurylidene acetone and 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5 in the ratio of 5:5 (parts by weight) respectively. The properties of the resin and those of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 24
The process is conducted under conditions similar to those described in the foregoing Example 21, with the only exception that as the ketone use is made of a mixture of difurfurylidene acetone and 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3 in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2.
EXAMPLE 25
The process is conducted under conditions similar to those described in the foregoing Example 3, except only that as the ketone use is made of a mixture of difurfurylidene cyclohexanone and 1,9-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5 in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 26
The process is conducted under conditions similar to those described in Example 13 hereinbefore, with the only exception that as the ketone use is made of a mixture of difurfurylidene cyclohexanone and 1,5-di-(.alpha.-furyl)-2,4-methylpentadien-1,4-one-3 in the ratio of 5:5 parts by weight respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 27
The process is conducted under conditions similar to those described in Example 17 hereinbefore, with the only exception that as the ketone use is made of a mixture of 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3 and 1,9-di-(.alpha.-furyl)-nonanetetraene-1,3,6,8-one-5 in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 28
The process is conducted under conditions similar to those described in Example 12 hereinabove, with the only exception that as the ketone use is made of a mixture of monofurfurylidene acetone and difurfurylidene acetone in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 29
The process is conducted under conditions similar to those described in Example 20 hereinbefore, except that as the ketone use is made of a mixture of monofurfurylidene acetone and 1,9-di-(.alpha.-furyl)-nonanetetraen-1,3,6,8-one-5 in the ratio of 5:5 (parts by weight) respectively. Properties of the resulting resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
EXAMPLE 30
The process is conducted under conditions similar to those described in Example 8 hereinbefore, with the only exception that as the ketone use is made of a mixture of monofurfurylidene acetone and 1,5-di-(.alpha.-furyl)-2,4-dimethylpentadien-1,4-one-3 in the ratio of 5:5 (parts by weight) respectively. Properties of the resin and of the article manufactured therefrom are shown in Tables 1 and 2 hereinbelow.
Table 1__________________________________________________________________________Properties of the resin produced by the processaccording to the present invention and that pro-duced by the prior art process ContentProcedure for Ubbelohde Ubbeloh- of hy-producing the Solubi- melting de drop- droxylresin accord- lity in point, ping po- groups,ing to Appearance acetone .degree.C. int, .degree.C. %1 2 3 4 5 6__________________________________________________________________________Example 1 Powder of total 87 105 2.20 yellow to dark-brown colourExample 2 " " 102 123 2.0Example 3 " " 105 129 1.90Example 4 " " 82 101 1.80Example 5 " " 104 127 1.95Example 6 " " 92 115 2.1Example 7 " " 85 108 1.75Example 8 " " 90 113 1.85Example 9 " " 96 120 2.5Example 10 " " 80 103 1.75Example 11 " " 85 109 1.92Example 12 Powder of yel- Total 92 117 2.35 low to dark- brown colourExample 13 " " 105 131 1.65Example 14 " " 109 136 1.60Example 15 " " 83 105 1.70Example 16 " " 88 113 1.90Example 17 " " 91 118 2.45Example 18 " " 84 109 1.95Example 19 " " 93 118 2.2Example 20 " " 99 123 2.15Example 21 " " 86 109 1.9Example 22 " " 103 125 2.0Example 23 " " 85 110 1.85Example 24 " " 84 106 1.92Example 25 " " 107 126 1.95Example 26 " " 104 127 1.70Example 27 " " 89 110 2.50Example 28 " " 93 119 2.30Example 29 " " 97 120 2.20Example 30 " " 91 115 1.90Prior art process " " 102 125 --__________________________________________________________________________
Table 2__________________________________________________________________________Properties of the article manufactured by theprocess according to the present invention andby the prior art process Resistance against Mixture of 50% H.sub.2 SO.sub.4 and 60% nit- 30% HNO.sub.3,Articles pro- Impact Martens 93% sulphur- ric acid 20% ofduced from the resi- yield ic acid at at a tem- water atresin prepar- lience, tempe- combus- a tempera- perature a tempe-ed by the pro- kgf.cm/ rature, tibi- ture of up up to rature ofcedure of cm.sup.2 .degree.C. lity to 120.degree. C. 60.degree. C. up to 60.degree. C.1 2 3 4 5 6 7__________________________________________________________________________Example 1 3.0 270 combustible resistant resistant resistantExample 2 3.2 280 self-extinc- " " "Example 3 4.2 310 non-combust- " " " ibleExample 4 6.3 315 self-extinc- " " " tionExample 5 6.3 320 non-combust- " " " ibleExample 6 3.9 310 non-combust- " " " ibleExample 7 3.0 300 combustible " " "Example 8 3.9 300 combustible " " "Example 9 6.3 320 non-combustible " " "Example 10 3.9 310 non-combustible " " "Example 11 4.3 315 self-extinction " " "Example 12 5.3 310 non-combustible " " "Example 13 3.9 316 combustible resistant resis- resis- tant tantExample 14 6.3 320 self-extinction " " "Example 15 5.3 312 non-combustible " " "Example 16 6.3 320 non-combustible " " "Example 17 5.2 300 combustible " " "Example 18 6.2 320 self-extinction resist- resist- resist- ant ant antExample 19 3.0 295 combustible " " "Example 20 5.4 305 non-combustible " " "Example 21 6.3 320 non-combustible " " "Example 22 6.3 320 non-combustible " " "Example 23 6.2 318 non-combustible " " "Example 24 6.3 320 non-combustible " " "Example 25 4.3 310 non-combustible " " "Example 26 3.8 312 combustible " " "Example 27 5.0 295 combustible " " "Example 28 5.4 312 non-combustible " " "Example 29 5.3 308 non-combustible " " "Example 30 3.8 302 combustible " " "Prior art limitedlyprocess 2.5 250 combustible resist- non- non- ant resist- resi- ant stant__________________________________________________________________________

Number	Date	Country
2513610	Jun 1977	SUX
2517037	Aug 1977	SUX
2593551	Apr 1978	SUX

Number	Name	Date
1591999	Redman	Oct 1924
1716665	Redman et al.	Jun 1929
2561814	Novotny et al.	Jul 1951
2600403	Harvey	Jun 1952
2776266	Harvey	Jan 1957
2803618	Harvey	Aug 1957
2970121	Schmittberger	Jan 1961
3074972	Harvey et al.	Jan 1963
3725333	Adkins et al.	Apr 1973
4051301	Laitar	Sep 1977

Process for producing power-like furan resin

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