CN102861867A - Method for producing self-hardened furan resin for casting by modifying furfuryl alcohol through pentose compound - Google Patents
Method for producing self-hardened furan resin for casting by modifying furfuryl alcohol through pentose compound Download PDFInfo
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Abstract
The invention relates to a preparation method of self-hardened furan resin for casting, in particular to a method for producing the self-hardened furan resin for casting by partially modifying furfuryl alcohol through a pentose compound. The method comprises the following steps of: taking the furfuryl alcohol and the pentose compound in a weight ratio of (50-60): (5-35) as raw materials to prepare a furfuryl alcohol modified component to replace a large amount of the furfuryl alcohol needed by the prior art, so that the use amount of the furfuryl alcohol is reduced; compared with the traditional production of the furan resin, the preparation method provided by the invention has the advantages that the production cost is reduced, the damages to an environment are reduced and the large-scale production is easy to realize; meanwhile, pentose compound molecules contain an aldehyde group and a polyhydroxy structure; and in a process of preparing the furan resin, the cross-linking point of resin curing is increased, a net-shaped structure is easy to form in a curing process of the resin, the strength of resin sand is improved and the content of free formaldehyde can be effectively reduced.
Description
Technical field
The present invention relates to a kind of preparation method who casts with self-hardening furan resin, be specifically related to a kind of preparation technology who casts take pentose compounds Partial Replacement furfuryl alcohol as material modification production with self-hardening furan resin.
Background technology
Furane resins refer to have the furfuryl alcohol of furan nucleus and the general name that furfural is made the resinae of raw material production, and it is cured as insoluble and molten solid content under the strong acid effect, and kind has furfuryl alcohol resin, furfural resin, furfural acetone resin, chaff ketone--formaldehyde resin etc.Furfuryl alcohol resin is that main body and formaldehyde condensation polymer form (modified product has added again urea) by furfuryl alcohol, outward appearance is that dark brown is to the liquid or solid of black, heat resistance and resistance to water are all fine, chemical resistance is extremely strong, acid, alkali, salt and organic solution are had good resistance, are good anticorrisive agents.Casting is a kind of of furfuryl alcohol resin with self-hardening furan resin, refer at room temperature can make sand mold (core) sclerosis by acid catalysis, and in structure, contain furan nucleus, have furfuryl alcohol, formaldehyde, urea and or the synthetic thermosetting resin such as phenol, be generally faint yellow to brown transparent or semitransparent uniform liquid.Casting is high with self-hardening furan resin intensity, is the good binding agents such as timber, rubber, metal and pottery, also can be used for producing coating.Casting is to make core binder in the casting technique of mechanical industry with an important use of self-hardening resin, is specially adapted to large-scale, large batch of machine-building, such as the production of automobile military project, internal combustion engine, diesel engine, sewing machine etc.When being used for the binding agent of casting sand core, casting has following characteristics with self-hardening resin: curing rate is fast, normal temperature strength is low, decomposition temperature is high; According to the phosphorus content of different foundry goods, can select the resin of different nitrogen contents; Get angry little, elevated temperature strength is high, thermal expansivity is moderate, fragility is large, pore tendency is little, hygroscopicity is large, is widely used as binding agent in industries such as timber, rubber, metal, potteries, in mechanical industry, also play an important role.Especially after adding is urea-modified, can require to produce according to difference the furfuryl alcohol resin of different nitrogen contents, to satisfy the requirement of cast steel, cast iron and other non-ferrous metals casting techniques.
In the prior art, general conventional cast with the synthesis technique of self-hardening furan resin is: add formaldehyde (15-25 part) in reactor, and start stirring a period of time, then add part urea (5-8 part) dissolving, and regulate pH and under alkali condition, react certain hour; Adding a part of furfuryl alcohol (15-20 part) according to the requirement of the nitrogen content of required production resin again reacts; At first regulate pH behind the adding furfuryl alcohol and under alkali condition, react a period of time, then adjust again the pH value of material system and react for acidity; Add subsequently remaining part urea (1-3 part) to reduce the free formaldehyde in the resin, again whole material system is dewatered under vacuum condition, and add the furfuryl alcohol (40-75 part) of remaining part in the system after the dehydration, and stir, namely get required casting self-hardening furan resin product.
In recent years, fast development along with China's foundry industry, casting a large amount of employings of self-hardening furan resin sand technique, so that its demand progressively increases, although its good casting property, but the price of raw material furfuryl alcohol remained on very high level in these several years always, and then caused the price of the furane resins produced also relatively high, and certain restriction inhibition has been played in this extensive use for furane resins.At present, seek a kind of cheap furfuryl alcohol alternative materials production casting and become the foundry industry problem demanding prompt solution with self-hardening furan resin.
Summary of the invention
For this reason, technical problem to be solved by this invention is in the prior art that casting causes the higher problem of production cost with a large amount of furfuryl alcohol of preparation need of production consumption of self-hardening furan resin, and then provides a kind of and partly substitute furfuryl alcohol production with the pentose compounds and cast with self-hardening furan resin with the casting that reduces production costs self-hardening furan resin preparation method.
Second technical problem to be solved by this invention is to provide the more widely new method for preparing furane resins of a kind of raw material sources.
For solving the problems of the technologies described above, the invention discloses a kind of pentose compounds and replace furfuryl alcohol to cast with the application in the self-hardening furan resin in preparation.
The invention also discloses a kind of pentose compounds modification furfuryl alcohol production casting with the method for self-hardening furan resin, comprise the steps:,
(1) gets furfuryl alcohol and regulate pH to highly acid, add subsequently pentose and control temperature 70-85 ℃ and react, reach 17-40 during second (25 ℃ are coated with cup viscosity-No. 4) to material viscosity and stop reaction, the weight part ratio of described furfuryl alcohol and described pentose compounds is 65-95:5-35;
(2) reactant that obtains in the step (1) is regulated pH to neutral, and dewatered under vacuum state stop reaction when moisture content is lower than 1.0%, it is for subsequent use to obtain the furfuryl alcohol modified component;
(3) in reactor, add formaldehyde 15-20 part, and 5-8 part urea stirs, and to regulate pH be alkaline reaction, adds subsequently the furfuryl alcohol modified component that obtains in 15-20 part step (2) and reacts, and to adjust system pH be acid, controls 80-100 ℃ of reaction of reaction temperature;
(4) again add while hot 1-3 part urea, and to adjust the material system pH be alkalescent, then 70-85 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed, and adds the furfuryl alcohol modified component that obtains in 65-80 part step (2), stirs, and namely gets required product;
The above umber is parts by weight.
The method of detection material viscosity of the present invention adopts the viscosity data when being coated with-No. 4 flow cups and detecting 25 ℃, and when pentose compounds addition was taken off limit value, viscosity was also got the lower limit of measurement; During pentose compounds addition capping value, viscosity is also got the higher limit of measured value.
Described pentose compounds comprises wood sugar, arabinose, xylitol, come one or more the mixture in crisp sweets, the ribose.
In the described step (1), adjusting pH is 1.0-3.0.
In the described step (2), adjusting pH is 6.5-7.5.
In the described step (3), the adjusting alkaline pH is 8.0-10.0.
In the described step (3), adjustment of acidity pH is 2.5-5.5.
In the described step (4), adjusting pH is 7.5-9.5.
In the described step (5), described processed is carried out under vacuum condition.
In the described step (5), described processed is dewatered reactant to moisture content and is lower than 20%.
In the described step (1), described formaldehyde is preferably 37% formalin.
The invention also discloses another pentose compounds and substitute furfuryl alcohol production casting with the method for self-hardening furan resin, comprise the steps:
(1) in reactor, adds formaldehyde 15-25 part, reach 5-8 part urea and stir, and regulate pH value 8.0-10.0 and react;
(2) add 15-20 part furfuryl alcohol and react, and to adjust system pH be 2.5-5.5,80-100 ℃ of reaction of control reaction temperature;
(3) add 1-3 part urea in the reactant that again obtains in the step (2), and to adjust the material system pH be 7.5-9.5, then 70-85 ℃ of control reaction temperature be cooled to system 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, and adds 5-35 part pentose compounds and 35-40 part furfuryl alcohol, stirs, and namely gets required product;
Above umber is parts by weight.
Described pentose compounds comprises wood sugar, arabinose, xylitol, lyxose, ribose or its mixture.
In the described step (1), described formaldehyde is preferably 37% formalin.
The invention also discloses the third pentose compounds and substitute furfuryl alcohol production casting with the method for self-hardening furan resin, comprise the steps:
(1) add formaldehyde 15-25 part in the reactor, and to regulate pH is that 8.0-10.0 reacts, adds subsequently pentose compounds 5-35 part, 80-100 ℃ of reaction of control temperature;
(2) add while hot 5-8 part urea in the reactor and stir, and add 15-20 part furfuryl alcohol and react, and to adjust system pH be 2.5-5.5 that 80-100 ℃ of control reaction temperature reacted;
(3) again add 1-3 part urea, and to adjust material system pH value be 7.5-9.5, then 70-85 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 35-40 part furfuryl alcohol, stir, namely get required product;
The above umber is parts by weight.
In the described step (1), described formaldehyde is 37% formalin.
More than pentose compounds described in each method comprise wood sugar, arabinose, xylitol, lyxose, ribose or its mixture.
The used dilute acid soln of adjustment of acidity pH can be the solution of the 5-25% such as sulfuric acid, hydrochloric acid, oxalic acid, sulfonic acid in the above procedure, take oxalic acid as best; Regulating the used alkaline solution of alkaline pH in the building-up process can be the solution of NaOH, sodium carbonate, sodium acid carbonate etc., take NaOH as best.
The invention also discloses by the standby casting self-hardening furan resin that obtains of above-mentioned each side legal system.
Technique scheme of the present invention has the following advantages compared to existing technology, 1, of the present invention with the technique of pentose compounds replacement furfuryl alcohol production casting with self-hardening furan resin, with the cheap expensive furfuryl alcohol of pentose compounds Partial Replacement, thereby reduce the consumption of furfuryl alcohol, compare with the production of traditional furane resins, reduce production cost, and the harmfulness of environment has been reduced, be conducive to large-scale production; 2, technology utilization pentose compounds of the present invention is participated in the synthetic reaction of furane resins directly, simplify elder generation and be cyclized into furfural by pentose, generate furfuryl alcohol by furfural hydrogenation again, participate in the technique that reaction generates furane resins by furfuryl alcohol at last, saved production cost; 3, utilize in the technique of the present invention and contain aldehyde radical and polyhydroxy structure in the pentose compounds molecule, in the process of preparation furane resins, increased the crosslinking points of resin solidification, be conducive to resin and in solidification process, form network structure, improve the intensity of resin sand, in addition because pentose belongs to polyhydroxy aldehyde, can also with free formaldehyde generation aldol reaction in the reaction system, and then unreacted formaldehyde consumed during Lauxite is synthetic, thereby had reduced the content of free formaldehyde; 4, method of the present invention is directly used self-hardening furan resin with the pentose compounds that occurring in nature extensively exists as raw material production casting, and the synthetic more widely new way of a kind of raw material sources that provides of furane resins is provided; 5, the prepared product of the technique of production furfuryl alcohol resin of the present invention is compared with product of the prior art, and nitrogen content and free formaldehyde content all meet national standard, are applicable in the required technique.
The specific embodiment
Embodiment 1
Raw material form: formaldehyde 200Kg(20 part), and urea 100Kg(10 part).
The described pentose compounds of present embodiment modification furfuryl alcohol production casting comprises the steps: with the method for self-hardening furan resin
(1) gets furfuryl alcohol and also regulate pH to 1.0-1.4 with 20% oxalic acid solution, add subsequently wood sugar and control temperature 75-80 ℃ and react, to material viscosity reach 35-40 during second (25 ℃ are coated with flow cup viscosity-No. 4) stop reaction, the weight part ratio of described furfuryl alcohol and described wood sugar is 50:35
(2) with 15% sodium hydroxide solution the reactant that obtains in the step (1) is regulated pH to 6.5-7.0, and dewater under vacuum state stop reaction when the resin moisture content is lower than 1.0%, the furfuryl alcohol modified component that obtains q.s is for subsequent use;
(3) in reactor, add 20 parts in formaldehyde, and 8 parts of urea stir, and to regulate pH with 15% sodium hydroxide solution be the 9.0-9.2 reaction, adding subsequently the furfuryl alcohol modified component that obtains in 15 parts of steps (2) reacts, and to adjust system pH with 20% oxalic acid solution be 2.5-3.5,80-85 ℃ of reaction of control reaction temperature;
(4) again add while hot 2 parts of urea, and to adjust the material system pH with 15% sodium hydroxide solution be 7.8-8.0, then 70-75 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds the furfuryl alcohol modified component that obtains in 75 parts of steps (2), stirs, and blowing namely gets about required product 960Kg.
Embodiment 2
Raw material form: formaldehyde (concentration 37%) 250Kg(25 part), and urea 110Kg(11 part).
The described pentose compounds of present embodiment modification furfuryl alcohol production casting comprises the steps: with the method for self-hardening furan resin
(1) gets furfuryl alcohol and regulate pH to 2.5-3.0 with 20% hydrochloric acid solution, add subsequently the mixture of arabinose and xylitol and control temperature 70-75 ℃ and react, reach (25 ℃ of 20-22 seconds to material viscosity, be coated with cup viscosity-No. 4) make stop the reaction, the weight part ratio of the mixture of described furfuryl alcohol and described arabinose and xylitol is 60:35;
(2) with rare sodium bicarbonate solution the reactant that obtains in the step (1) is regulated pH to 7.0-7.5, and dewater under vacuum state stop reaction when moisture content is lower than 1.0%, the furfuryl alcohol modified component that obtains q.s is for subsequent use;
(3) in reactor, add 25 parts in formaldehyde, and 8 parts of urea stir, and rare sodium bicarbonate solution adjusting pH is the 9.8-10.0 reaction, adding subsequently 200Kg(20 part) the furfuryl alcohol modified component that obtains in the step (2) reacts, and adjust system pH as 5.0-5.5,95-100 ℃ of reaction of control reaction temperature take 20% hydrochloric acid solution;
(4) again add while hot 3 parts of urea, and adjust the material system pH as 7.5-8.0 take rare sodium bicarbonate solution, then 80-85 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 400Kg(40 part) the furfuryl alcohol modified component that obtains in the step (2), stir, blowing namely gets about required product 1100Kg.
Embodiment 3
Raw material form: polyformaldehyde (concentration 37%) 150Kg(15 part), and urea 80Kg(8 part).
The described pentose compounds of present embodiment modification furfuryl alcohol production casting comprises the steps: with the method for self-hardening furan resin
(1) gets furfuryl alcohol and regulate pH to 2.0-2.5 with 10% formic acid solution, add subsequently xylitol and control temperature 80-85 ℃ and react, stop reaction when material viscosity reaches 20-22 second (25 ℃ are coated with cup viscosity-No. 4), the weight part ratio of described furfuryl alcohol and described xylitol is 50:5;
(2) with rare sodium carbonate liquor the reactant that obtains in the step (1) is regulated pH to 6.5-7.5, and dewater under vacuum state stop reaction when moisture content is lower than 1.0%, the furfuryl alcohol modified component that obtains q.s is for subsequent use;
(3) in reactor, add 15 parts of polyformaldehyde solution, and 6 parts of urea stir, and rare sodium carbonate liquor adjusting pH is the 9.2-9.5 reaction, adding subsequently 150Kg(15 part) the furfuryl alcohol modified component that obtains in the step (2) reacts, and adjust system pH as 4.5-5.5,85-90 ℃ of reaction of control reaction temperature take 10% formic acid solution;
(4) again add while hot 2 parts of urea, and rare sodium carbonate liquor to adjust the material system pH be 8.5-9.5, then 75-80 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 600Kg(60 part) the furfuryl alcohol modified component that obtains in the step (2), stir, blowing namely gets about required product 1100Kg.
Embodiment 4
Raw material form: formaldehyde (concentration 37%) 220Kg(22 part), and urea 90Kg(9 part).
The described pentose compounds of present embodiment modification furfuryl alcohol production casting comprises the steps: with the method for self-hardening furan resin
(1) gets furfuryl alcohol and regulate pH to 1.5-2.0 with 15% sulfuric acid solution, add subsequently the mixture of lyxose and wood sugar and control temperature 70-80 ℃ and react, reach (25 ℃ of 17-20 seconds to material viscosity, be coated with cup viscosity-No. 4) time stop the reaction, the weight part ratio of the mixture of described furfuryl alcohol and described lyxose and wood sugar is 60:5;
(2) with rare sodium hydroxide solution the reactant that obtains in the step (1) is regulated pH to 6.5-6.8, and dewater under vacuum state stop reaction when moisture content is lower than 1.0%, the furfuryl alcohol modified component that obtains q.s is for subsequent use;
(3) in reactor, add 22 parts in formaldehyde, and 7 parts of urea stir, and take rare sodium hydroxide solution adjusting pH as the 9.5-10.0 reaction, adding subsequently 180Kg(18 part) the furfuryl alcohol modified component that obtains in the step (2) reacts, and adjust system pH as 4.5-5.5,90-95 ℃ of reaction of control reaction temperature take 5% sulfuric acid solution;
(4) again add while hot 2 parts of urea, and adjust the material system pH as 8.0-8.5 take rare sodium hydroxide solution, then 75-80 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 500Kg(50 part) the furfuryl alcohol modified component that obtains in the step (2), stir, blowing namely gets about required product 1150Kg.
Embodiment 5
Raw material form: formaldehyde (concentration 37%) 180Kg(18 part), and urea 60Kg(60 part).
The described pentose compounds of present embodiment modification furfuryl alcohol production casting comprises the steps: with the method for self-hardening furan resin
(1) gets furfuryl alcohol and regulate pH to 1.2-1.5 with 12% sulfonic acid solutions, add subsequently ribose and control temperature 70-85 ℃ and react, stop reaction when material viscosity reaches 30-40 second (25 ℃ are coated with cup viscosity-No. 4), the weight part ratio of described furfuryl alcohol and described ribose is 60:5;
(2) with rare sodium bicarbonate solution the reactant that obtains in the step (1) is regulated pH to 6.8-7.2, and dewater under vacuum state stop reaction when moisture content is lower than 1.0%, the furfuryl alcohol modified component that obtains q.s is for subsequent use;
(3) in reactor, add 18 parts in formaldehyde, and 5 parts of urea stir, and take rare sodium bicarbonate solution adjusting pH as the 9.0-9.5 reaction, adding subsequently 170Kg(17 part) the furfuryl alcohol modified component that obtains in the step (2) reacts, and adjust system pH as 5.0-5.5,80-85 ℃ of reaction of control reaction temperature take 12% sulfonic acid solutions;
(4) again add while hot 1 part of urea, and adjust the material system pH as 8.0-9.0 take rare sodium bicarbonate solution, then 72-78 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 700Kg(70 part) the furfuryl alcohol modified component that obtains in the step (2), stir, blowing namely gets about required product 1130Kg.
Comparative Examples 1
Raw material form: formaldehyde (concentration 37%) 200Kg(20 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with art methods, comprises the steps:
(1) in reactor, adds 20 parts in formaldehyde, and 8 parts of urea stir, and to regulate pH with 15% sodium hydroxide solution be that 9.0-9.2 reacts, and add subsequently 15 parts of furfuryl alcohol components and react, and to adjust system pH with 20% oxalic acid solution be 2.5-3.5,80-85 ℃ of reaction of control reaction temperature;
(2) again add while hot 2 parts of urea, and to adjust the material system pH with 15% sodium hydroxide solution be 7.8-8.0, then 70-75 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(3) reactant that step (2) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 75 parts of furfuryl alcohol components, stirs, and blowing namely gets about required product 960Kg.
Comparative Examples 2
Raw material form: formaldehyde (concentration 37%) 250Kg(25 part), urea 110Kg(11 part), furfuryl alcohol 600Kg(60 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with art methods, comprises the steps:
(1) in reactor, adds 25 parts in formaldehyde, and 8 parts of urea stir, and rare sodium bicarbonate solution adjusting pH is the 9.8-10.0 reaction, adding subsequently 200Kg(20 part) the furfuryl alcohol component reacts, and adjust system pH as 5.0-5.5,95-100 ℃ of reaction of control reaction temperature take 20% hydrochloric acid solution;
(2) again add while hot 3 parts of urea, and adjust the material system pH as 7.5-8.0 take rare sodium bicarbonate solution, then 80-85 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(3) reactant that step (2) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 400Kg(40 part) the furfuryl alcohol component, stir, blowing namely gets about required product 1100Kg.
Comparative Examples 3
Raw material form: polyformaldehyde (concentration 37%) 150Kg(15 part), urea 80Kg(8 part), furfuryl alcohol 750Kg(75 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with art methods, comprises the steps:
(1) in reactor, adds 15 parts of polyformaldehyde solution, and 6 parts of urea stir, and rare sodium carbonate liquor adjusting pH is the 9.2-9.5 reaction, adding subsequently 150Kg(15 part) the furfuryl alcohol component reacts, and adjust system pH as 4.5-5.5,85-90 ℃ of reaction of control reaction temperature take 10% formic acid solution;
(2) again add while hot 2 parts of urea, and rare sodium carbonate liquor to adjust the material system pH be 8.5-9.5, then 75-80 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(3) reactant that step (4) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 600Kg(60 part) the furfuryl alcohol component, stir, blowing namely gets about required product 1100Kg.
Comparative Examples 4
Raw material form: formaldehyde (concentration 37%) 220Kg(22 part), urea 90Kg(9 part), furfuryl alcohol 680Kg(68 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with art methods, comprises the steps:
(1) in reactor, adds 22 parts in formaldehyde, and 7 parts of urea stir, and take rare sodium hydroxide solution adjusting pH as the 9.5-10.0 reaction, adding subsequently 180Kg(18 part) the furfuryl alcohol component reacts, and adjust system pH as 4.5-5.5,90-95 ℃ of reaction of control reaction temperature take 5% sulfuric acid solution;
(2) again add while hot 2 parts of urea, and adjust the material system pH as 8.0-8.5 take rare sodium hydroxide solution, then 75-80 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(3) reactant that step (2) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 500Kg(50 part) the furfuryl alcohol component, stir, blowing namely gets about required product 1150Kg.
Comparative Examples 5
Raw material form: formaldehyde (concentration 37%) 180Kg(18 part), urea 60Kg(60 part), furfuryl alcohol 870Kg(87 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with art methods, comprises the steps:
(1) in reactor, adds 18 parts in formaldehyde, and 5 parts of urea stir, and take rare sodium bicarbonate solution adjusting pH as the 9.0-9.5 reaction, adding subsequently 170Kg(17 part) the furfuryl alcohol component reacts, and adjust system pH as 5.0-5.5,80-85 ℃ of reaction of control reaction temperature take 12% sulfonic acid solutions;
(2) again add while hot 1 part of urea, and adjust the material system pH as 8.0-9.0 take rare sodium bicarbonate solution, then 72-78 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(3) reactant that step (2) is obtained carries out processed to moisture content and is lower than 20% under vacuum condition, and adds 700Kg(70 part) the furfuryl alcohol component, stir, blowing namely gets about required product 1130Kg.
More than the index comparing result of synthetic furane resins sees Table 1.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-2008 " casting self-hardening furan resin " and carry out.
The index determining result of table 1 embodiment 1-5 and Comparative Examples 1-5
| Project | Nitrogen content (%) | Free formaldehyde (%) | The normal temperature tension is intensity (MPa) just | The whole intensity (MPa) of normal temperature tension |
| Embodiment 1 | 3.951 | 0.252 | 0.63 | 1.71 |
| Embodiment 2 | 3.478 | 0.196 | 0.69 | 1.70 |
| Embodiment 3 | 3.387 | 0.262 | 0.59 | 1.65 |
| Embodiment 4 | 3.535 | 0.276 | 0.60 | 1.68 |
| Embodiment 5 | 3.356 | 0.283 | 0.70 | 1.67 |
| Comparative Examples 1 | 3.958 | 0.265 | 0.64 | 1.63 |
| Comparative Examples 2 | 3.431 | 0.201 | 0.58 | 1.59 |
| Comparative Examples 3 | 3.396 | 0.259 | 0.57 | 1.69 |
| Comparative Examples 4 | 3.558 | 0.279 | 0.62 | 1.66 |
| Comparative Examples 5 | 3.375 | 0.277 | 0.59 | 1.62 |
Embodiment 6
Raw material form:
Formaldehyde 250Kg (25 parts), urea 100Kg(10 part), furfuryl alcohol 550Kg(55 part) and, wood sugar 350Kg(35 part).
Substitute furfuryl alcohol production casting with the method for self-hardening furan resin with the pentose compounds described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 25 parts in 37% formaldehyde, and 8 parts of urea stir, and after the urea dissolving, regulates pH 9.0-9.2 with sodium hydroxide solution and reacts 1h;
(2) add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 2.5-3.5 take 10% sulfuric acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take sodium carbonate liquor, control answers temperature 70-75 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently 35 parts of wood sugars and 35 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 1100Kg.
Embodiment 7
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 500 Kg(50 parts) and, mixture 300 Kg(30 parts of arabinose and xylitol).
Substitute furfuryl alcohol production casting with the method for self-hardening furan resin with the pentose compounds described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, and 8 parts of urea stir, and after the urea dissolving, regulates pH 9.2-9.6 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.5 take 20% hydrochloric acid solution, 95-100 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.0-8.2 take the sodium carbonate weak solution, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently mixture and 35 parts of furfuryl alcohols of 30 portions of arabinoses and xylitol, stirs, and blowing namely gets about required product 1050Kg.
Embodiment 8
Raw material form:
Polyformaldehyde solution (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 550Kg(55 part) and, xylitol 200 Kg(20 parts).
Substitute furfuryl alcohol production casting with the method for self-hardening furan resin with the pentose compounds described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 20 parts of 37% polyformaldehyde solution, and 6 parts of urea stir, and after the urea dissolving, regulates pH 9.6-10.0 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 4.8-5.0 take 25% oxalic acid solution, 85-90 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-8.5 take the sodium carbonate weak solution, 80-85 ℃ of reaction of control reaction temperature be after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently 20 parts of xylitols and 40 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 960Kg.
Embodiment 9
Raw material form:
Formaldehyde (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 600Kg(60 part) and, mixture 50 Kg(5 parts of lyxose and wood sugar).
Substitute furfuryl alcohol production casting with the method for self-hardening furan resin with the pentose compounds described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 22 parts in 37% formaldehyde, and 5 parts of urea stir, and after the urea dissolving, regulates pH 8.0-8.5 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 3.5-4.0 take 5% sulfonic acid solutions, 80-85 ℃ of reaction of control reaction temperature 1.5h;
(3) add 1 part of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.5-9.0 take dilute solution of sodium bicarbonate, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently mixture and 40 parts of furfuryl alcohols of 5 portions of lyxoses and wood sugar, stirs, and blowing namely gets about required product 900Kg.
Embodiment 10
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 560Kg(56 part) and, ribose 100Kg(10 part).
Substitute furfuryl alcohol production casting with the method for self-hardening furan resin with pentose described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 17 parts in 37% formaldehyde, and 6 parts of urea stir, and after the urea dissolving, regulates pH 8.5-9.0 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 18 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.2 take 25% oxalic acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take the sodium carbonate weak solution, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently 10 parts of ribose and 38 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 1000Kg.
Comparative Examples 6
Raw material form:
Formaldehyde (concentration 37%) 250Kg(25 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Produce casting with the method for self-hardening furan resin with art methods described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 25 parts in 37% formaldehyde, and 8 parts of urea stir, and after the urea dissolving, regulates pH 9.0-9.2 with sodium hydroxide solution and reacts 1h;
(2) add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 2.5-3.5 take 10% sulfuric acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take sodium carbonate liquor, control answers temperature 70-75 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently remaining 70 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 1100Kg.
Comparative Examples 7
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 800Kg(80 part).
Produce casting with the method for self-hardening furan resin with art methods described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, and 8 parts of urea stir, and after the urea dissolving, regulates pH 9.2-9.6 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.5 take 20% hydrochloric acid solution, 95-100 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.0-8.2 take the sodium carbonate weak solution, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently remaining 65 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 1050Kg.
Comparative Examples 8
Raw material form:
Polyformaldehyde solution (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 750Kg(75 part).
Produce casting with the method for self-hardening furan resin with art methods described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 20 parts of 37% polyformaldehyde solution, and 6 parts of urea stir, and after the urea dissolving, regulates pH9.6-10.0 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 4.8-5.0 take 20% hydrochloric acid solution, 85-90 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-8.5 take the sodium carbonate weak solution, control answers temperature 80-85 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently remaining 60 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 960Kg.
Comparative Examples 9
Raw material form:
Formaldehyde (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 650Kg(65 part).
Produce casting with the method for self-hardening furan resin with art methods described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 22 parts in 37% formaldehyde, and 5 parts of urea stir, and after the urea dissolving, regulates pH 8.0-8.5 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 3.5-4.0 take 5% sulfonic acid solutions, 80-85 ℃ of reaction of control reaction temperature 1.5h;
(3) add 1 part of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.5-9.0 take the sodium carbonate weak solution, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently remaining 45 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 900Kg.
Comparative Examples 10
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 660Kg(66 part).
Produce casting with the method for self-hardening furan resin with art methods described in the present embodiment, comprise the steps:
(1) adding concentration in the reactor is 17 parts in 37% formaldehyde, and 6 parts of urea stir, and after the urea dissolving, regulates pH 8.5-9.0 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add subsequently 18 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.2 take 20% hydrochloric acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take the sodium carbonate weak solution, control answers temperature 75-80 ℃ of reaction after 1 hour, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant that step (3) is obtained dewaters under vacuum condition to moisture content and is lower than 20%, adds subsequently remaining 48 parts of furfuryl alcohols, stirs, and blowing namely gets about required product 1000Kg.
More than the index comparing result of synthetic furane resins sees Table 2.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-2008 " casting self-hardening furan resin " and carry out.
The index determining result of table 2 embodiment 6-10 and Comparative Examples 6-10
| Project | Nitrogen content (%) | Free formaldehyde (%) | The normal temperature tension is intensity (MPa) just | The whole intensity (MPa) of normal temperature tension |
| Embodiment 6 | 3.537 | 0.268 | 0.60 | 1.71 |
| Embodiment 7 | 3.513 | 0.271 | 0.56 | 1.65 |
| Embodiment 8 | 3.690 | 0.265 | 0.64 | 1.68 |
| Embodiment 9 | 3.491 | 0.266 | 0.68 | 1.75 |
| Embodiment 10 | 3.519 | 0.285 | 0.58 | 1.72 |
| Comparative Examples 6 | 3. 592 | 0.274 | 0.56 | 1.63 |
| Comparative Examples 7 | 3.560 | 0.219 | 0.60 | 1.59 |
| Comparative Examples 8 | 3.639 | 0.261 | 0.58 | 1.65 |
| Comparative Examples 9 | 3.513 | 0.280 | 0.62 | 1.60 |
| Comparative Examples 10 | 3.586 | 0.268 | 0.56 | 1.66 |
Embodiment 11
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 560Kg(56 part) and, wood sugar 100Kg(10 part).
The described pentose compounds of present embodiment substitutes furfuryl alcohol production casting with the method for self-hardening furan resin, comprises the steps:
(1) in reactor, adds 17 parts in formaldehyde, regulate pH 9.2-9.4 with dilute solution of sodium bicarbonate and react, add subsequently 10 parts of wood sugars, 90-95 ℃ of reaction of control temperature 1h;
(2) add while hot 6 parts of urea dissolvings and stirring in the reactor, add subsequently 18 parts of furfuryl alcohols and react, and adjust system pH as 4.8-5.0 take 20% hydrochloric acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 38 parts of furfuryl alcohols, stir, blowing namely gets about required product 1100g.
Embodiment 12
Raw material form:
Formaldehyde (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 550Kg(55 part) and, mixture 200 Kg(20 parts of arabinose and xylitol).
The described pentose compounds of present embodiment substitutes furfuryl alcohol production casting with the method for self-hardening furan resin, comprises the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, regulates pH 9.2-9.4 with dilute solution of sodium hydroxide and reacts, and adds subsequently 20 parts of arabinoses, 85-90 ℃ of reaction of control temperature 1h;
(2) add while hot 6 parts of urea dissolvings and stirring in the reactor, add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 2.5-3.5 take 15% oxalic acid solution, 85-90 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.0-8.4 take the sodium carbonate weak solution, then 80-85 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 40 parts of furfuryl alcohols, stir, blowing namely gets about required product 1000g.
Embodiment 13
Raw material form:
Polyformaldehyde solution (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 600Kg(60 part) and, xylitol 50 Kg(5 parts).
The described pentose compounds of present embodiment substitutes furfuryl alcohol production casting with the method for self-hardening furan resin, it is characterized in that, comprises the steps:
(1) adding concentration in the reactor is 22 parts of 37% polyformaldehyde solution, regulates pH 9.5-9.7 and is warming up to 85 ℃ with the sodium carbonate weak solution and react 1h, adds subsequently 5 parts of xylitols, 80-85 ℃ of reaction of control temperature 1h;
(2) add while hot 5 parts of urea dissolvings and stirring in the reactor, add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.5 take 10% sulfuric acid solution, 80-85 ℃ of reaction of control reaction temperature 1.5h;
(3) add 1 part of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-8.0 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 40 parts of furfuryl alcohols, stir, blowing namely gets about required product 1000g.
Embodiment 14
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 500 Kg(50 parts) and, mixture 300 Kg(30 parts of lyxose and wood sugar).
The described pentose compounds of present embodiment substitutes furfuryl alcohol production casting with the method for self-hardening furan resin, comprises the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, regulates pH 9.2-9.4 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h, adds subsequently 30 parts of lyxoses, 95-100 ℃ of reaction of control temperature 1h;
(2) add while hot 8 parts of urea dissolvings and stirring in the reactor, add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 3.5-4.0 take 5% semi-annular jade pendant acid solution, 95-100 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-7.8 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 35 parts of furfuryl alcohols, stir, blowing namely gets about required product 1050g.
Embodiment 15
Raw material form:
Formaldehyde (concentration 37%) 250Kg (25 parts), urea 100Kg(10 part), furfuryl alcohol 550Kg(55 part) and, ribose 350Kg(35 part).
The described pentose compounds of present embodiment substitutes furfuryl alcohol production casting with the method for self-hardening furan resin, comprises the steps:
(1) adding concentration in the reactor is 25 parts in 37% formaldehyde, regulates pH 9.0-9.2 with dilute solution of sodium hydroxide and reacts 1h, adds subsequently 35 parts of wood sugars, 90-95 ℃ of reaction of control temperature 1h;
(2) add while hot 8 parts of urea dissolvings and stirring in the reactor, add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 5.0-5.5 take 15% oxalic acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 9.0-9.5 take the sodium carbonate weak solution, then 70-75 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 35 parts of furfuryl alcohols, stir, blowing namely gets about required product 1100g.
Comparative Examples 11
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 660Kg(66 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with prior art, comprises the steps:
(1) in reactor, adds 17 parts in formaldehyde, regulate pH 9.2-9.4 and control temperature 90-95 ℃ of reaction 1h with dilute solution of sodium bicarbonate;
(2) add while hot 6 parts of urea dissolvings and stirring in the reactor, add subsequently 18 parts of furfuryl alcohols and react, and adjust system pH as 4.8-5.0 take 20% hydrochloric acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 48 parts of furfuryl alcohols, stir, blowing namely gets about required product 1100g.
Comparative Examples 12
Raw material form:
Formaldehyde (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 750Kg(75 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with prior art, comprises the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, regulates pH 9.2-9.4 and controls temperature 85-90 ℃ of reaction 1h with dilute solution of sodium hydroxide;
(2) add while hot 6 parts of urea dissolvings and stirring in the reactor, add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 2.5-3.5 take 15% oxalic acid solution, 85-90 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 8.0-8.4 take the sodium carbonate weak solution, then 80-85 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 60 parts of furfuryl alcohols, stir, blowing namely gets about required product 1000g.
Comparative Examples 13
Raw material form:
Polyformaldehyde solution (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 650Kg(65 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with prior art, comprises the steps:
(1) adding concentration in the reactor is 22 parts of 37% polyformaldehyde solution, regulates pH 9.5-9.7 and is warming up to 85 ℃ with the sodium carbonate weak solution and react 1h;
(2) add while hot 5 parts of urea dissolvings and stirring in the reactor, add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 4.0-4.5 take 10% sulfuric acid solution, 80-85 ℃ of reaction of control reaction temperature 1.5h;
(3) add 1 part of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-8.0 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 45 parts of furfuryl alcohols, stir, blowing namely gets about required product 1000g.
Comparative Examples 14
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 800Kg(80 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with prior art, comprises the steps:
(1) adding concentration in the reactor is 20 parts in 37% formaldehyde, regulates pH 9.2-9.4 and is warming up to 85 ℃ with dilute solution of sodium bicarbonate and react 1h;
(2) add while hot 8 parts of urea dissolvings and stirring in the reactor, add subsequently 15 parts of furfuryl alcohols and react, and adjust system pH as 3.5-4.0 take 5% semi-annular jade pendant acid solution, 95-100 ℃ of reaction of control reaction temperature 1.5h;
(3) add 3 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.5-7.8 take the sodium carbonate weak solution, then 75-80 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 65 parts of furfuryl alcohols, stir, blowing namely gets about required product 1050g.
Comparative Examples 15
Raw material form:
Formaldehyde (concentration 37%) 250Kg(25 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Present embodiment is described produces casting with the method for self-hardening furan resin with prior art, comprises the steps:
(1) adding concentration in the reactor is 25 parts in 37% formaldehyde, regulates pH 9.0-9.2 with dilute solution of sodium hydroxide and reacts 1h;
(2) add while hot 8 parts of urea dissolvings and stirring in the reactor, add subsequently 20 parts of furfuryl alcohols and react, and adjust system pH as 5.0-5.5 take 15% oxalic acid solution, 90-95 ℃ of reaction of control reaction temperature 1.5h;
(3) add 2 parts of urea in the reactant that again obtains in the step (2), and adjust the material system pH as 7.8-8.0 take the sodium carbonate weak solution, then 70-75 ℃ of reaction of control temperature 1h is cooled to system 45-50 ℃ and stop reaction;
(4) reactant that obtains in the step (3) is dewatered under vacuum condition to moisture content and be lower than 20%, and add 70 parts of furfuryl alcohols, stir, blowing namely gets about required product 1100g.
More than the index comparing result of synthetic furane resins sees Table 3.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-1994 " casting self-hardening furan resin " and carry out.
The index determining result of table 3 embodiment 11-15 and Comparative Examples 11-15
| Project | Nitrogen content (%) | Free formaldehyde (%) | The normal temperature tension is intensity (MPa) just | The whole intensity (MPa) of normal temperature tension |
| Embodiment 11 | 3.556 | 0.252 | 0.67 | 1.68 |
| Embodiment 12 | 3.937 | 0.265 | 0.65 | 1.70 |
| Embodiment 13 | 3.603 | 0.271 | 0.72 | 1.75 |
| Embodiment 14 | 3.667 | 0.252 | 0.68 | 1.69 |
| Embodiment 15 | 3.619 | 0.278 | 0.71 | 1.72 |
| Comparative Examples 11 | 3. 586 | 0.265 | 0.64 | 1.69 |
| Comparative Examples 12 | 3.907 | 0.223 | 0.68 | 1.70 |
| Comparative Examples 13 | 3.679 | 0.257 | 0.70 | 1.67 |
| Comparative Examples 14 | 3.651 | 0.276 | 0.66 | 1.69 |
| Comparative Examples 15 | 3.565 | 0.279 | 0.69 | 1.65 |
Can find out from the above results, compare with the furane resins that prepare with prior art with the furane resins that obtain with the production of pentose compounds Partial Replacement furfuryl alcohol of the present invention, its nitrogen content performance, the first intensity of normal temperature tension and the whole intensity of normal temperature tension are all suitable with the prior art index, and the free formaldehyde content of whole handicraft product is also suitable with prior art, as seen method of the present invention goes for preparation production casting fully and uses self-hardening furan resin, and effectively reduces process costs.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (11)
1. a pentose compounds replaces furfuryl alcohol to cast with the application in the self-hardening furan resin in preparation.
2. pentose compounds modification furfuryl alcohol production casting is characterized in that with the method for self-hardening furan resin, comprise the steps:,
(1) get furfuryl alcohol and regulate pH to highly acid, add subsequently the pentose compounds and control temperature 70-85 ℃ and react, the weight part ratio of described furfuryl alcohol and described pentose compounds is 50-60:5-35;
(2) reactant that obtains in the step (1) is regulated pH to neutral, and dewatered under vacuum state stop reaction when moisture content is lower than 1.0%, it is for subsequent use to obtain the furfuryl alcohol modified component;
(3) in reactor, add formaldehyde 15-20 part, and 5-8 part urea stirs, and to regulate pH be alkaline reaction, adds subsequently the furfuryl alcohol modified component that obtains in 15-20 part step (2) and reacts, and to adjust system pH be acid, controls 80-100 ℃ of reaction of reaction temperature;
(4) again add while hot 1-3 part urea, and to adjust the material system pH be alkalescent, then 70-85 ℃ of reaction of control temperature be cooled to system 45-50 ℃ and stop reaction;
(5) reactant that step (4) is obtained carries out processed, and adds the furfuryl alcohol modified component that obtains in 40-75 part step (2), stirs, and namely gets required product;
The above umber is parts by weight.
3. the method with self-hardening furan resin is cast in pentose compounds modification furfuryl alcohol production according to claim 2, it is characterized in that:
Described pentose compounds comprises wood sugar, arabinose, xylitol, come one or more the mixture in crisp sweets, the ribose.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (1), adjusting pH is 1.0-3.0.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (2), adjusting pH is 6.5-7.5.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (3), the adjusting alkaline pH is 8.0-10.0.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (3), adjustment of acidity pH is 2.5-5.5.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (4), adjusting pH is 7.5-9.5.
According to claim 2 or 3 described pentose compounds modification furfuryl alcohol productions casting with the method for self-hardening furan resins, it is characterized in that:
In the described step (5), described processed is carried out under vacuum condition.
10. the method with self-hardening furan resin is cast in pentose compounds modification furfuryl alcohol production according to claim 9, it is characterized in that:
In the described step (5), described processed is dewatered reactant to moisture content and is lower than 20%.
11. the casting self-hardening furan resin for preparing of arbitrary described method according to claim 2-10.
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| CN201210099085.4A CN102861867B (en) | 2012-04-06 | 2012-04-06 | Method for producing self-hardened furan resin for casting by modifying furfuryl alcohol through pentose compound |
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| CN201210099085.4A Active CN102861867B (en) | 2012-04-06 | 2012-04-06 | Method for producing self-hardened furan resin for casting by modifying furfuryl alcohol through pentose compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103113548A (en) * | 2013-03-06 | 2013-05-22 | 苏州兴业材料科技股份有限公司 | Preparation method of novel modified furan resin for casting |
| CN103113547A (en) * | 2013-03-06 | 2013-05-22 | 苏州兴业材料科技股份有限公司 | Preparation method for modified foundry furan resin |
| CN105175669A (en) * | 2015-08-04 | 2015-12-23 | 宁夏共享化工有限公司 | Method for fast and integral hardening of furan resin |
| JP2021020240A (en) * | 2019-07-29 | 2021-02-18 | 花王株式会社 | Binder composition for mold forming |
| CN112512722A (en) * | 2018-08-24 | 2021-03-16 | 花王株式会社 | Binder composition for mold making |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113548A (en) * | 2013-03-06 | 2013-05-22 | 苏州兴业材料科技股份有限公司 | Preparation method of novel modified furan resin for casting |
| CN103113547A (en) * | 2013-03-06 | 2013-05-22 | 苏州兴业材料科技股份有限公司 | Preparation method for modified foundry furan resin |
| CN103113548B (en) * | 2013-03-06 | 2014-09-24 | 苏州兴业材料科技股份有限公司 | Preparation method of novel modified furan resin for casting |
| CN103113547B (en) * | 2013-03-06 | 2014-11-05 | 苏州兴业材料科技股份有限公司 | Preparation method for modified foundry furan resin |
| CN105175669A (en) * | 2015-08-04 | 2015-12-23 | 宁夏共享化工有限公司 | Method for fast and integral hardening of furan resin |
| CN112512722A (en) * | 2018-08-24 | 2021-03-16 | 花王株式会社 | Binder composition for mold making |
| CN112512722B (en) * | 2018-08-24 | 2023-02-28 | 花王株式会社 | Binder composition for mold making |
| JP2021020240A (en) * | 2019-07-29 | 2021-02-18 | 花王株式会社 | Binder composition for mold forming |
| JP7316137B2 (en) | 2019-07-29 | 2023-07-27 | 花王株式会社 | Binder composition for mold making |
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Denomination of invention: Method for producing self-hardened furan resin for casting by modifying furfuryl alcohol through pentose compound Effective date of registration: 20160302 Granted publication date: 20141001 Pledgee: Industrial Commercial Bank of China Ltd Zhangqiu branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2016990000130 |
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Date of cancellation: 20190709 Granted publication date: 20141001 Pledgee: Industrial Commercial Bank of China Ltd Zhangqiu branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2016990000130 |