CN102861867B - 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 ofly take pentose compounds and partly replace furfuryl alcohol to produce the preparation technology of self-hardening furan resin for casting as material modification.
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 not molten solid content under 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 to good resistance, are good anticorrisive agents.Casting is a kind of of furfuryl alcohol resin with self-hardening furan resin, refer at room temperature and can make sand mold (core) sclerosis by acid catalysis, and in structure containing 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 by 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 by an important use of self-hardening resin, is specially adapted to large-scale, large batch of machine-building, as the production of automobile military project, internal combustion engine, diesel engine, sewing machine etc.While 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, in industries such as timber, rubber, metal, potteries, is widely used as binding agent, in mechanical industry, also play an important role.Especially add urea-modified after, can according to difference, require produce the furfuryl alcohol resin of different nitrogen contents, to meet the requirement of cast steel, cast iron and other non-ferrous metals casting techniques.
In prior art, general conventional cast with the synthesis technique of self-hardening furan resin is: in reactor, add formaldehyde (15-25 part), and start stirring a period of time, then add part urea (5-8 part) to dissolve, and regulate pH to react certain hour under alkali condition; According to the requirement of the nitrogen content of required production resin, add a part of furfuryl alcohol (15-20 part) to react again; After adding furfuryl alcohol, first regulate pH to react a period of time under alkali condition, the pH value of then adjusting again material system is reacted for acidity; Add subsequently remaining part urea (1-3 part) to reduce the free formaldehyde in 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 dehydration, and stir, obtain required casting self-hardening furan resin product.
In recent years, fast development along with China's foundry industry, a large amount of employings of self-hardening furan resin sand technique for casting, its demand is progressively increased, although its good casting property, but the price of raw material furfuryl alcohol remains on very high level in these several years always, and then cause the price of the furane resins produced also relatively high, 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 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 prior art that casting causes with a large amount of furfuryl alcohol of need of production consumption of preparing of self-hardening furan resin the problem that production cost is higher, and then provides a kind of and with pentose compounds, partly substitute furfuryl alcohol and produce and cast with self-hardening furan resin with the casting reducing production costs self-hardening furan resin preparation method.
Second technical problem to be solved by this invention is to provide a kind of raw material sources new method of preparing furane resins more widely.
For solving the problems of the technologies described above, the invention discloses a kind of pentose compounds and replace furfuryl alcohol in preparation application in self-hardening furan resin for casting.
The invention also discloses a kind of pentose compounds modification furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:,
(1) get furfuryl alcohol and regulate pH to highly acid, add subsequently pentose and control temperature 70-85 ℃ and react, to material viscosity, reach 17-40 during second (25 ℃, be coated with-No. 4 cup 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 step (1) is regulated pH to neutral, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, obtain furfuryl alcohol modified component standby;
(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 obtaining in 15-20 part step (2) to react, and adjust system pH for acid, control 80-100 ℃ of reaction of reaction temperature;
(4) again add while hot 1-3 part urea, and to adjust material system pH be alkalescent, control 70-85 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained carries out processed, and adds the furfuryl alcohol modified component obtaining in 65-80 part step (2), stirs, and obtains required product;
The above umber is parts by weight.
The method of detection material viscosity of the present invention, the viscosity data while adopting-No. 4 flow cups of painting to detect 25 ℃, when pentose compounds addition is taken off limit value, viscosity is 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 one or more the mixture in wood sugar, arabinose, xylitol, lyxose, ribose.
In described step (1), adjusting pH is 1.0-3.0.
In described step (2), adjusting pH is 6.5-7.5.
In described step (3), adjusting alkaline pH is 8.0-10.0.
In described step (3), adjustment of acidity pH is 2.5-5.5.
In described step (4), adjusting pH is 7.5-9.5.
In described step (5), described processed is carried out under vacuum condition.
In described step (5), described processed dewaters to moisture content reactant lower than 20%.
In described step (1), described formaldehyde is preferably 37% formalin.
The invention also discloses another pentose compounds and substitute the method for self-hardening furan resin for furfuryl alcohol production casting, comprise the steps:
(1) in reactor, add formaldehyde 15-25 part, and 5-8 part urea stirs, and regulate pH value 8.0-10.0 to react;
(2) add 15-20 part furfuryl alcohol to react, and to adjust system pH be 2.5-5.5, control 80-100 ℃ of reaction of reaction temperature;
(3) again in the reactant obtaining in step (2), add 1-3 part urea, and to adjust material system pH be 7.5-9.5, control reaction temperature 70-85 ℃, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, and adds 5-35 part pentose compounds and 35-40 part furfuryl alcohol, stirs, and obtains required product;
Above umber is parts by weight.
Described pentose compounds comprises wood sugar, arabinose, xylitol, lyxose, ribose or its mixture.
In described step (1), described formaldehyde is preferably 37% formalin.
The invention also discloses the third pentose compounds and substitute the method for self-hardening furan resin for furfuryl alcohol production casting, comprise the steps:
(1) in reactor, add formaldehyde 15-25 part, and to regulate pH be that 8.0-10.0 reacts, add subsequently pentose compounds 5-35 part, control 80-100 ℃ of reaction of temperature;
(2) in reactor, add 5-8 part urea to stir while hot, and add 15-20 part furfuryl alcohol to react, and to adjust system pH be 2.5-5.5, control 80-100 ℃ of reaction temperature and react;
(3) again add 1-3 part urea, and to adjust material system pH value be 7.5-9.5, control 70-85 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 35-40 part furfuryl alcohol, stir, obtain required product;
The above umber is parts by weight.
In described step (1), the formalin that described formaldehyde is 37%.
Pentose compounds described in each method comprises wood sugar, arabinose, xylitol, lyxose, ribose or its mixture above.
In above procedure, adjustment of acidity pH dilute acid soln used can be the solution of the 5-25% such as sulfuric acid, hydrochloric acid, oxalic acid, sulfonic acid, take oxalic acid as best; In building-up process, regulating alkaline pH alkaline solution used can be the solution of NaOH, sodium carbonate, sodium acid carbonate etc., take NaOH as best.
The invention also discloses the casting self-hardening furan resin being prepared by above-mentioned each side method.
Technique scheme of the present invention has the following advantages compared to existing technology, 1, the technique of using self-hardening furan resin with pentose compounds replacement furfuryl alcohol production casting of the present invention, with cheap pentose compounds, partly replace expensive furfuryl alcohol, 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, by furfural hydrogenation, generate furfuryl alcohol again, finally by furfuryl alcohol, participate in the technique that reaction generates furane resins, saved production cost; 3, in technique of the present invention, utilize and in pentose compounds molecule, contain aldehyde radical and polyhydroxy structure, in preparing the process of 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 reaction system, and then unreacted formaldehyde consumes during Lauxite is synthetic, thereby reduced the content of free formaldehyde; 4, method of the present invention is directly usingd the pentose compounds that occurring in nature extensively exists and is produced casting self-hardening furan resin as raw material, is synthetic a kind of raw material sources new way more widely that provides of furane resins; 5, the prepared product of the technique of production furfuryl alcohol resin of the present invention, compares with product of the prior art, and nitrogen content and free formaldehyde content all meet national standard, are applicable in required technique.
The specific embodiment
Embodiment 1
Raw material form: formaldehyde 200Kg(20 part), and urea 100Kg(10 part).
Described in the present embodiment, pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, comprises the steps:
(1) get furfuryl alcohol and 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 ℃, be coated with-No. 4 flow cup viscosity) 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 step (1) is regulated to pH to 6.5-7.0, and under vacuum state, dewater and stop reaction to resin moisture content lower than 1.0% time, the furfuryl alcohol modified component that obtains q.s is standby;
(3) in reactor, add 20 parts, formaldehyde, and 8 parts of urea stir, and be 9.0-9.2 reaction with 15% sodium hydroxide solution adjusting pH, add subsequently the furfuryl alcohol modified component obtaining in 15 parts of steps (2) to react, and be 2.5-3.5 by 20% oxalic acid solution adjustment system pH, control 80-85 ℃ of reaction of reaction temperature;
(4) again add while hot 2 parts of urea, and with 15% sodium hydroxide solution, to adjust material system pH be 7.8-8.0, control 70-75 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add the furfuryl alcohol modified component obtaining in 75 parts of steps (2), stir, blowing obtains required product 960Kg left and right.
Embodiment 2
Raw material form: formaldehyde (concentration 37%) 250Kg(25 part), and urea 110Kg(11 part).
Described in the present embodiment, pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, comprises the steps:
(1) get 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-No. 4 cup viscosity) make to stop 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 step (1) is regulated to pH to 7.0-7.5, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, the furfuryl alcohol modified component that obtains q.s is standby;
(3) in reactor, add 25 parts, formaldehyde, and 8 parts of urea stir, and rare sodium bicarbonate solution adjusting pH is 9.8-10.0 reaction, adding subsequently 200Kg(20 part) the furfuryl alcohol modified component that obtains in step (2) reacts, and take 20% hydrochloric acid solution, to adjust system pH be 5.0-5.5, controls 95-100 ℃ of reaction of reaction temperature;
(4) again add while hot 3 parts of urea, and take rare sodium bicarbonate solution, to adjust material system pH be 7.5-8.0, controls 80-85 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 400Kg(40 part) the furfuryl alcohol modified component that obtains in step (2), stir, blowing obtains required product 1100Kg left and right.
Embodiment 3
Raw material form: polyformaldehyde (concentration 37%) 150Kg(15 part), and urea 80Kg(8 part).
Described in the present embodiment, pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, comprises the steps:
(1) get 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, when material viscosity reaches 20-22 second (25 ℃, be coated with-No. 4 cup viscosity), stop reaction, 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 step (1) is regulated to pH to 6.5-7.5, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, the furfuryl alcohol modified component that obtains q.s is standby;
(3) in reactor, add 15 parts of polyformaldehyde solution, and 6 parts of urea stir, and rare sodium carbonate liquor adjusting pH is 9.2-9.5 reaction, adding subsequently 150Kg(15 part) the furfuryl alcohol modified component that obtains in step (2) reacts, and take 10% formic acid solution, to adjust system pH be 4.5-5.5, controls 85-90 ℃ of reaction of reaction temperature;
(4) again add while hot 2 parts of urea, and rare sodium carbonate liquor to adjust material system pH be 8.5-9.5, control 75-80 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 600Kg(60 part) the furfuryl alcohol modified component that obtains in step (2), stir, blowing obtains required product 1100Kg left and right.
Embodiment 4
Raw material form: formaldehyde (concentration 37%) 220Kg(22 part), and urea 90Kg(9 part).
Described in the present embodiment, pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, comprises the steps:
(1) get 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-No. 4 cup viscosity) time stop 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 step (1) is regulated to pH to 6.5-6.8, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, the furfuryl alcohol modified component that obtains q.s is standby;
(3) in reactor, add 22 parts, formaldehyde, and 7 parts of urea stir, and take rare sodium hydroxide solution, to regulate pH be 9.5-10.0 reaction, adding subsequently 180Kg(18 part) the furfuryl alcohol modified component that obtains in step (2) reacts, and take 5% sulfuric acid solution, to adjust system pH be 4.5-5.5, controls 90-95 ℃ of reaction of reaction temperature;
(4) again add while hot 2 parts of urea, and take rare sodium hydroxide solution, to adjust material system pH be 8.0-8.5, controls 75-80 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 500Kg(50 part) the furfuryl alcohol modified component that obtains in step (2), stir, blowing obtains required product 1150Kg left and right.
Embodiment 5
Raw material form: formaldehyde (concentration 37%) 180Kg(18 part), and urea 60Kg(60 part).
Described in the present embodiment, pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, comprises the steps:
(1) get 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, when material viscosity reaches 30-40 second (25 ℃, be coated with-No. 4 cup viscosity), stop reaction, 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 step (1) is regulated to pH to 6.8-7.2, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, the furfuryl alcohol modified component that obtains q.s is standby;
(3) in reactor, add 18 parts, formaldehyde, and 5 parts of urea stir, and take rare sodium bicarbonate solution, to regulate pH be 9.0-9.5 reaction, adding subsequently 170Kg(17 part) the furfuryl alcohol modified component that obtains in step (2) reacts, and take 12% sulfonic acid solutions, to adjust system pH be 5.0-5.5, controls 80-85 ℃ of reaction of reaction temperature;
(4) again add while hot 1 part of urea, and take rare sodium bicarbonate solution, to adjust material system pH be 8.0-9.0, controls 72-78 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 700Kg(70 part) the furfuryl alcohol modified component that obtains in step (2), stir, blowing obtains required product 1130Kg left and right.
Comparative example 1
Raw material form: formaldehyde (concentration 37%) 200Kg(20 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 20 parts, formaldehyde, and 8 parts of urea stir, and with 15% sodium hydroxide solution, to regulate pH be 9.0-9.2 reaction, adds subsequently 15 parts of furfuryl alcohol components to react, and be 2.5-3.5 by 20% oxalic acid solution adjustment system pH, control 80-85 ℃ of reaction of reaction temperature;
(2) again add while hot 2 parts of urea, and with 15% sodium hydroxide solution, to adjust material system pH be 7.8-8.0, control 70-75 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(3) reactant step (2) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 75 parts of furfuryl alcohol components, stir, blowing obtains required product 960Kg left and right.
Comparative example 2
Raw material form: formaldehyde (concentration 37%) 250Kg(25 part), urea 110Kg(11 part), furfuryl alcohol 600Kg(60 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 25 parts, formaldehyde, and 8 parts of urea stir, and rare sodium bicarbonate solution adjusting pH is 9.8-10.0 reaction, adding subsequently 200Kg(20 part) furfuryl alcohol component reacts, and take 20% hydrochloric acid solution, to adjust system pH be 5.0-5.5, controls 95-100 ℃ of reaction of reaction temperature;
(2) again add while hot 3 parts of urea, and take rare sodium bicarbonate solution, to adjust material system pH be 7.5-8.0, controls 80-85 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(3) reactant step (2) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 400Kg(40 part) furfuryl alcohol component, stir, blowing obtains about required product 1100Kg.
Comparative example 3
Raw material form: polyformaldehyde (concentration 37%) 150Kg(15 part), urea 80Kg(8 part), furfuryl alcohol 750Kg(75 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 15 parts of polyformaldehyde solution, and 6 parts of urea stir, and rare sodium carbonate liquor adjusting pH is 9.2-9.5 reaction, adding subsequently 150Kg(15 part) furfuryl alcohol component reacts, and take 10% formic acid solution, to adjust system pH be 4.5-5.5, controls 85-90 ℃ of reaction of reaction temperature;
(2) again add while hot 2 parts of urea, and rare sodium carbonate liquor to adjust material system pH be 8.5-9.5, control 75-80 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(3) reactant step (4) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 600Kg(60 part) furfuryl alcohol component, stir, blowing obtains about required product 1100Kg.
Comparative example 4
Raw material form: formaldehyde (concentration 37%) 220Kg(22 part), urea 90Kg(9 part), furfuryl alcohol 680Kg(68 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 22 parts, formaldehyde, and 7 parts of urea stir, and take rare sodium hydroxide solution, to regulate pH be 9.5-10.0 reaction, adding subsequently 180Kg(18 part) furfuryl alcohol component reacts, and take 5% sulfuric acid solution, to adjust system pH be 4.5-5.5, controls 90-95 ℃ of reaction of reaction temperature;
(2) again add while hot 2 parts of urea, and take rare sodium hydroxide solution, to adjust material system pH be 8.0-8.5, controls 75-80 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(3) reactant step (2) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 500Kg(50 part) furfuryl alcohol component, stir, blowing obtains about required product 1150Kg.
Comparative example 5
Raw material form: formaldehyde (concentration 37%) 180Kg(18 part), urea 60Kg(60 part), furfuryl alcohol 870Kg(87 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 18 parts, formaldehyde, and 5 parts of urea stir, and take rare sodium bicarbonate solution, to regulate pH be 9.0-9.5 reaction, adding subsequently 170Kg(17 part) furfuryl alcohol component reacts, and take 12% sulfonic acid solutions, to adjust system pH be 5.0-5.5, controls 80-85 ℃ of reaction of reaction temperature;
(2) again add while hot 1 part of urea, and take rare sodium bicarbonate solution, to adjust material system pH be 8.0-9.0, controls 72-78 ℃ of reaction of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(3) reactant step (2) being obtained under vacuum condition, carry out processed to moisture content lower than 20%, and add 700Kg(70 part) furfuryl alcohol component, stir, blowing obtains about required product 1130Kg.
More than the index comparing result of synthetic furane resins is in Table 1.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-2008 < < casting and carry out with self-hardening furan resin > >.
The index determining result of table 1 embodiment 1-5 and comparative example 1-5
| Project | Nitrogen content (%) | Free formaldehyde (%) | 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 example 1 | 3.958 | 0.265 | 0.64 | 1.63 |
| Comparative example 2 | 3.431 | 0.201 | 0.58 | 1.59 |
| Comparative example 3 | 3.396 | 0.259 | 0.57 | 1.69 |
| Comparative example 4 | 3.558 | 0.279 | 0.62 | 1.66 |
| Comparative example 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).
Described in the present embodiment, with pentose compounds, substitute furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 25 parts, 37% formaldehyde, and 8 parts of urea stir, after urea dissolves, with sodium hydroxide solution, regulate pH 9.0-9.2 to react 1h;
(2) add subsequently 20 parts of furfuryl alcohols to react, and take 10% sulfuric acid solution, to adjust system pH be 2.5-3.5, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate liquor, to adjust material system pH be 7.8-8.0, controls and answer temperature 70-75 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently 35 parts of wood sugars and 35 parts of furfuryl alcohols, stirs, and blowing obtains required product 1100Kg left and right.
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).
Described in the present embodiment, with pentose compounds, substitute furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, and 8 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.6 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.0-4.5, controls 95-100 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 8.0-8.2, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently mixture and 35 parts of furfuryl alcohols of 30 portions of arabinoses and xylitol, stirs, and blowing obtains required product 1050Kg left and right.
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).
Described in the present embodiment, with pentose compounds, substitute furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts of 37% polyformaldehyde solution, and 6 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 9.6-10.0 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols to react, and take 25% oxalic acid solution, to adjust system pH be 4.8-5.0, controls 85-90 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-8.5, controls 80-85 ℃ of reaction of reaction temperature after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently 20 parts of xylitols and 40 parts of furfuryl alcohols, stirs, and blowing obtains required product 960Kg left and right.
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).
Described in the present embodiment, with pentose compounds, substitute furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 22 parts, 37% formaldehyde, and 5 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 8.0-8.5 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 20 parts of furfuryl alcohols to react, and take 5% sulfonic acid solutions, to adjust system pH be 3.5-4.0, controls 80-85 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 1 part of urea, and take dilute solution of sodium bicarbonate, to adjust material system pH be 8.5-9.0, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently mixture and 40 parts of furfuryl alcohols of 5 portions of lyxoses and wood sugar, stirs, and blowing obtains required product 900Kg left and right.
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).
Described in the present embodiment, with pentose, substitute furfuryl alcohol and produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 17 parts, 37% formaldehyde, and 6 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 8.5-9.0 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 18 parts of furfuryl alcohols to react, and take 25% oxalic acid solution, to adjust system pH be 4.0-4.2, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.8-8.0, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently 10 parts of ribose and 38 parts of furfuryl alcohols, stirs, and blowing obtains required product 1000Kg left and right.
Comparative example 6
Raw material form:
Formaldehyde (concentration 37%) 250Kg(25 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 25 parts, 37% formaldehyde, and 8 parts of urea stir, after urea dissolves, with sodium hydroxide solution, regulate pH 9.0-9.2 to react 1h;
(2) add subsequently 20 parts of furfuryl alcohols to react, and take 10% sulfuric acid solution, to adjust system pH be 2.5-3.5, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate liquor, to adjust material system pH be 7.8-8.0, controls and answer temperature 70-75 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently remaining 70 parts of furfuryl alcohols, stirs, and blowing obtains required product 1100Kg left and right.
Comparative example 7
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 800Kg(80 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, and 8 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.6 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.0-4.5, controls 95-100 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 8.0-8.2, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently remaining 65 parts of furfuryl alcohols, stirs, and blowing obtains required product 1050Kg left and right.
Comparative example 8
Raw material form:
Polyformaldehyde solution (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 750Kg(75 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts of 37% polyformaldehyde solution, and 6 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH9.6-10.0 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 15 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.8-5.0, controls 85-90 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-8.5, controls and answer temperature 80-85 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently remaining 60 parts of furfuryl alcohols, stirs, and blowing obtains required product 960Kg left and right.
Comparative example 9
Raw material form:
Formaldehyde (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 650Kg(65 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 22 parts, 37% formaldehyde, and 5 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 8.0-8.5 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 20 parts of furfuryl alcohols to react, and take 5% sulfonic acid solutions, to adjust system pH be 3.5-4.0, controls 80-85 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 1 part of urea, and take sodium carbonate weak solution, to adjust material system pH be 8.5-9.0, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently remaining 45 parts of furfuryl alcohols, stirs, and blowing obtains required product 900Kg left and right.
Comparative example 10
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 660Kg(66 part).
Described in the present embodiment, with art methods, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 17 parts, 37% formaldehyde, and 6 parts of urea stir, after urea dissolves, with dilute solution of sodium bicarbonate, regulate pH 8.5-9.0 and be warming up to 85 ℃ and react 1h;
(2) add subsequently 18 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.0-4.2, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.8-8.0, controls and answer temperature 75-80 ℃ of reaction after 1 hour, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant step (3) being obtained dewaters to moisture content lower than 20% under vacuum condition, adds subsequently remaining 48 parts of furfuryl alcohols, stirs, and blowing obtains required product 1000Kg left and right.
More than the index comparing result of synthetic furane resins is in Table 2.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-2008 < < casting and carry out with self-hardening furan resin > >.
The index determining result of table 2 embodiment 6-10 and comparative example 6-10
| Project | Nitrogen content (%) | Free formaldehyde (%) | 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 example 6 | 3. 592 | 0.274 | 0.56 | 1.63 |
| Comparative example 7 | 3.560 | 0.219 | 0.60 | 1.59 |
| Comparative example 8 | 3.639 | 0.261 | 0.58 | 1.65 |
| Comparative example 9 | 3.513 | 0.280 | 0.62 | 1.60 |
| Comparative example 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).
Described in the present embodiment, pentose compounds substitutes furfuryl alcohol and produces the method for self-hardening furan resin for casting, comprises the steps:
(1) in reactor, add 17 parts, formaldehyde, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.4 to react, add subsequently 10 parts of wood sugars, control 90-95 ℃ of reaction 1h of temperature;
(2) in reactor, add 6 parts of urea dissolve and stir while hot, add subsequently 18 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.8-5.0, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.8-8.0, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 38 parts of furfuryl alcohols, stir, blowing obtains required product 1100g left and right.
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).
Described in the present embodiment, pentose compounds substitutes furfuryl alcohol and produces the method for self-hardening furan resin for casting, comprises the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, with dilute solution of sodium hydroxide, regulate pH 9.2-9.4 to react, add subsequently 20 parts of arabinoses, control 85-90 ℃ of reaction 1h of temperature;
(2) in reactor, add 6 parts of urea dissolve and stir while hot, add subsequently 15 parts of furfuryl alcohols to react, and take 15% oxalic acid solution, to adjust system pH be 2.5-3.5, controls 85-90 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 8.0-8.4, controls 80-85 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 40 parts of furfuryl alcohols, stir, blowing obtains required product 1000g left and right.
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).
Described in the present embodiment, pentose compounds substitutes furfuryl alcohol and produces the method for self-hardening furan resin for casting, it is characterized in that, comprises the steps:
(1) to adding concentration in reactor, be 22 parts of 37% polyformaldehyde solution, with sodium carbonate weak solution, regulate pH 9.5-9.7 and be warming up to 85 ℃ and react 1h, add subsequently 5 parts of xylitols, control 80-85 ℃ of reaction 1h of temperature;
(2) in reactor, add 5 parts of urea dissolve and stir while hot, add subsequently 20 parts of furfuryl alcohols to react, and take 10% sulfuric acid solution, to adjust system pH be 4.0-4.5, controls 80-85 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 1 part of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-8.0, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 40 parts of furfuryl alcohols, stir, blowing obtains required product 1000g left and right.
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).
Described in the present embodiment, pentose compounds substitutes furfuryl alcohol and produces the method for self-hardening furan resin for casting, comprises the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.4 and be warming up to 85 ℃ and react 1h, add subsequently 30 parts of lyxoses, control 95-100 ℃ of reaction 1h of temperature;
(2) in reactor, add 8 parts of urea dissolve and stir while hot, add subsequently 15 parts of furfuryl alcohols to react, and take 5% semi-annular jade pendant acid solution, to adjust system pH be 3.5-4.0, controls 95-100 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-7.8, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 35 parts of furfuryl alcohols, stir, blowing obtains required product 1050g left and right.
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).
Described in the present embodiment, pentose compounds substitutes furfuryl alcohol and produces the method for self-hardening furan resin for casting, comprises the steps:
(1) to adding concentration in reactor, be 25 parts, 37% formaldehyde, with dilute solution of sodium hydroxide, regulate pH 9.0-9.2 to react 1h, add subsequently 35 parts of wood sugars, control 90-95 ℃ of reaction 1h of temperature;
(2) in reactor, add 8 parts of urea dissolve and stir while hot, add subsequently 20 parts of furfuryl alcohols to react, and take 15% oxalic acid solution, to adjust system pH be 5.0-5.5, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 9.0-9.5, controls 70-75 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 35 parts of furfuryl alcohols, stir, blowing obtains required product 1100g left and right.
Comparative example 11
Raw material form:
Formaldehyde (concentration 37%) 170Kg(17 part), urea 80Kg(8 part), furfuryl alcohol 660Kg(66 part).
Described in the present embodiment, with prior art, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) in reactor, add 17 parts, formaldehyde, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.4 and control temperature 90-95 ℃ of reaction 1h;
(2) in reactor, add 6 parts of urea dissolve and stir while hot, add subsequently 18 parts of furfuryl alcohols to react, and take 20% hydrochloric acid solution, to adjust system pH be 4.8-5.0, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.8-8.0, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 48 parts of furfuryl alcohols, stir, blowing obtains required product 1100g left and right.
Comparative example 12
Raw material form:
Formaldehyde (concentration 37%) 150Kg(15 part), urea 90Kg(9 part), furfuryl alcohol 750Kg(75 part).
Described in the present embodiment, with prior art, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, with dilute solution of sodium hydroxide, regulate pH 9.2-9.4 and control temperature 85-90 ℃ of reaction 1h;
(2) in reactor, add 6 parts of urea dissolve and stir while hot, add subsequently 15 parts of furfuryl alcohols to react, and take 15% oxalic acid solution, to adjust system pH be 2.5-3.5, controls 85-90 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 8.0-8.4, controls 80-85 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 60 parts of furfuryl alcohols, stir, blowing obtains required product 1000g left and right.
Comparative example 13
Raw material form:
Polyformaldehyde solution (concentration 37%) 220Kg(22 part), urea 60Kg(6 part), furfuryl alcohol 650Kg(65 part).
Described in the present embodiment, with prior art, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 22 parts of 37% polyformaldehyde solution, with sodium carbonate weak solution, regulate pH 9.5-9.7 and be warming up to 85 ℃ and react 1h;
(2) in reactor, add 5 parts of urea dissolve and stir while hot, add subsequently 20 parts of furfuryl alcohols to react, and take 10% sulfuric acid solution, to adjust system pH be 4.0-4.5, controls 80-85 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 1 part of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-8.0, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 45 parts of furfuryl alcohols, stir, blowing obtains required product 1000g left and right.
Comparative example 14
Raw material form:
Formaldehyde (concentration 37%) 200Kg(20 part), urea 110Kg(11 part), furfuryl alcohol 800Kg(80 part).
Described in the present embodiment, with prior art, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 20 parts, 37% formaldehyde, with dilute solution of sodium bicarbonate, regulate pH 9.2-9.4 and be warming up to 85 ℃ and react 1h;
(2) in reactor, add 8 parts of urea dissolve and stir while hot, add subsequently 15 parts of furfuryl alcohols to react, and take 5% semi-annular jade pendant acid solution, to adjust system pH be 3.5-4.0, controls 95-100 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 3 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.5-7.8, controls 75-80 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 65 parts of furfuryl alcohols, stir, blowing obtains required product 1050g left and right.
Comparative example 15
Raw material form:
Formaldehyde (concentration 37%) 250Kg(25 part), urea 100Kg(10 part), furfuryl alcohol 900Kg(90 part).
Described in the present embodiment, with prior art, produce the method for self-hardening furan resin for casting, comprise the steps:
(1) to adding concentration in reactor, be 25 parts, 37% formaldehyde, with dilute solution of sodium hydroxide, regulate pH 9.0-9.2 to react 1h;
(2) in reactor, add 8 parts of urea dissolve and stir while hot, add subsequently 20 parts of furfuryl alcohols to react, and take 15% oxalic acid solution, to adjust system pH be 5.0-5.5, controls 90-95 ℃ of reaction 1.5h of reaction temperature;
(3) again in the reactant obtaining in step (2), add 2 parts of urea, and take sodium carbonate weak solution, to adjust material system pH be 7.8-8.0, controls 70-75 ℃ of reaction 1h of temperature, then system be cooled to 45-50 ℃ and stop reaction;
(4) reactant obtaining in step (3) is dewatered under vacuum condition to moisture content lower than 20%, and add 70 parts of furfuryl alcohols, stir, blowing obtains required product 1100g left and right.
More than the index comparing result of synthetic furane resins is in Table 3.
The analytical method of nitrogen content, free formaldehyde and intensity: press JB/T7526-1994 < < casting and carry out with self-hardening furan resin > >.
The index determining result of table 3 embodiment 11-15 and comparative example 11-15
| Project | Nitrogen content (%) | Free formaldehyde (%) | 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 example 11 | 3. 586 | 0.265 | 0.64 | 1.69 |
| Comparative example 12 | 3.907 | 0.223 | 0.68 | 1.70 |
| Comparative example 13 | 3.679 | 0.257 | 0.70 | 1.67 |
| Comparative example 14 | 3.651 | 0.276 | 0.66 | 1.69 |
| Comparative example 15 | 3.565 | 0.279 | 0.69 | 1.65 |
From the above results, can find out, with the furane resins that partly replace furfuryl alcohol production to obtain with pentose compounds of the present invention, compare with the furane resins that prepare with prior art, its nitrogen content performance, the first intensity of normal temperature tension and the whole intensity of normal temperature tension are all suitable with prior art index, and the free formaldehyde content of whole handicraft product is also suitable with prior art, visible method of the present invention goes for preparation completely and produces casting self-hardening furan resin, and effectively reduces process costs.
Obviously, above-described embodiment is only for example is clearly described, and the not 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 exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (10)
1. pentose compounds replaces furfuryl alcohol in preparation application in self-hardening furan resin for casting, and described pentose compounds comprises one or more the mixture in wood sugar, arabinose, lyxose, ribose.
2. pentose compounds modification furfuryl alcohol is produced the method for self-hardening furan resin for casting, it is characterized in that, comprises the steps:
(1) get furfuryl alcohol and regulate pH to highly acid, add subsequently 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 step (1) is regulated pH to neutral, and under vacuum state, dewater and stop reaction to moisture content lower than 1.0% time, obtain furfuryl alcohol modified component standby;
(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 obtaining in 15-20 part step (2) to react, and adjust system pH for acid, control 80-100 ℃ of reaction of reaction temperature;
(4) again add while hot 1-3 part urea, and to adjust material system pH be alkalescent, control 70-85 ℃ of reaction of temperature, then system is cooled to 45-50 ℃ and stop reaction;
(5) reactant step (4) being obtained carries out processed, and adds the furfuryl alcohol modified component obtaining in 40-75 part step (2), stirs, and obtains required product;
Described pentose compounds comprises one or more the mixture in wood sugar, arabinose, lyxose, ribose;
The above umber is parts by weight.
3. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (1), adjusting pH is 1.0-3.0.
4. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (2), adjusting pH is 6.5-7.5.
5. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (3), adjusting alkaline pH is 8.0-10.0.
6. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (3), adjustment of acidity pH is 2.5-5.5.
7. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (4), adjusting pH is 7.5-9.5.
8. pentose compounds modification furfuryl alcohol according to claim 2 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (5), described processed is carried out under vacuum condition.
9. pentose compounds modification furfuryl alcohol according to claim 8 is produced the method for self-hardening furan resin for casting, it is characterized in that:
In described step (5), described processed dewaters to moisture content reactant lower than 20%.
10. the casting self-hardening furan resin preparing according to the arbitrary described method of claim 2-9.
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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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| 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 |
| CN105175669B (en) * | 2015-08-04 | 2017-09-22 | 宁夏共享化工有限公司 | A kind of production method of quick overall hardening furane resins |
| JP6627012B1 (en) * | 2018-08-24 | 2019-12-25 | 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 |