CN110194825A - A kind of modified low nitrogen furan resin and production technology - Google Patents
A kind of modified low nitrogen furan resin and production technology Download PDFInfo
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- CN110194825A CN110194825A CN201910491715.4A CN201910491715A CN110194825A CN 110194825 A CN110194825 A CN 110194825A CN 201910491715 A CN201910491715 A CN 201910491715A CN 110194825 A CN110194825 A CN 110194825A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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Abstract
The invention discloses a kind of modified low nitrogen furan resin and production technology, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560-680 parts of formaldehyde, 130-150 parts of paraformaldehyde, 289-410 parts of urea, 28-70 parts of basic catalyst, 60-120 parts of carbohydrate, 650-1500 parts of sugar alcohol substituting agent, 6-10 parts of aldehyde remover, 5-10 parts of acidic catalyst.In the present invention, compound substitution is carried out to furfuryl alcohol using ethyl alcohol and glycerine, it is expensive to solve furfuryl alcohol, lead to the higher problem of production cost, secondly the modification low nitrogen furan resin of preparation, indices are nitrogen content≤3%, content of free aldehyde≤0.1%, intensity >=2.3MPa, water content≤6% meet Foundry Production requirement.
Description
Technical field
The present invention relates to the technical fields of low nitrogen furan resin production, and in particular to a kind of modified low nitrogen furan resin and life
Production. art.
Background technique
Furane resins refer to with furan nucleus furfuryl alcohol and furfural make raw material production resinae general name, in strong acid
Insoluble and insoluble solid content is cured as under effect, type has urea-formaldehyde-modified furane resins, phenol aldehyde modified furane resins, keto-aldehyde to change
Property furane resins, the phenol aldehyde modified furane resins of ureaformaldehyde etc..Furfuryl alcohol resin is that Lauxite or phenolic aldehyde tree is added based on furfuryl alcohol
Made of rouge prepolycondensate, appearance is brown liquid, and heat resistance and water resistance are all fine, and chemical corrosion resistance is extremely strong, to acid,
Alkali, salt and organic solution have excellent resistance, are excellent preservatives.Furfuryl alcohol resin intensity is high, is timber, rubber, gold
Belong to and the excellent adhesives such as ceramics, it can also be used to produce coating.
Low nitrogen furan resin self-hardening sand, high with intensity, dimensional accuracy is high, setting rate is fast, high production efficiency, works by force
Spend low advantage, but since furfuryl alcohol in recent years is expensive, free formaldehyde content is high, has severely impacted the production of furane resins
Using.
Summary of the invention
The purpose of the present invention is to provide a kind of modified low nitrogen furan resins and production technology to solve above-mentioned background technique
The problem of middle proposition.
To achieve the above object, the invention provides the following technical scheme: a kind of modified low nitrogen furan resin and production technology,
The modified low nitrogen furan resin includes the raw material of following composition by weight: 560-680 parts of formaldehyde, 130-150 parts of paraformaldehyde, urine
289-410 parts plain, 28-70 parts of basic catalyst, 650-1500 parts of sugar alcohol substituting agent, 6-10 parts of aldehyde remover, acidic catalyst 5-
10 parts.
Preferably, the sugar alcohol sugar alcohol substituting agent is glycerine, methanol, polyalcohol A, one kind of ethyl alcohol or two kinds of combinations.
Preferably, the sodium hydroxide solution that the basic catalyst is 30%, the hydrochloric acid water that the pickling catalyst is 10%
Solution.
Preferably, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, paraformaldehyde
130 parts, 289 parts of urea, 28 parts of basic catalyst, 650 parts of glycerine, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
Preferably, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, paraformaldehyde
130 parts, 289 parts of urea, 28 parts of basic catalyst, 325 parts of glycerine, 325 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
Preferably, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, paraformaldehyde
130 parts, 289 parts of urea, 28 parts of basic catalyst, 650 parts of methanol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
Preferably, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, paraformaldehyde
130 parts, 289 parts of urea, 28 parts of basic catalyst, A650 parts of polyalcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
Preferably, the modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, paraformaldehyde
130 parts, 289 parts of urea, 28 parts of basic catalyst, 650 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst
A kind of modified low nitrogen furan resin and production technology, comprising the following steps:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half furfuryl alcohol substituting agent is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, material temperature
Degree control is reacted 50-70 minutes at 95-100 DEG C；
(4) remaining urea is added, remaining half furfuryl alcohol substituting agent is added, resin is made in stirring cooling.
Beneficial effect
The present invention provides a kind of modified low nitrogen furan resin and production technology, have it is following the utility model has the advantages that
The present invention is used partially replace to furfuryl alcohol using glycerine, methanol, Xylitol mother liquor, polyalcohol A, ethyl alcohol material
In generation, obtains the substitution law of each alternative materials, after the analysis to substitution law, select ethyl alcohol and glycerine to furfuryl alcohol into
The compound substitution of row carries out compound substitution to furfuryl alcohol using ethyl alcohol and glycerine to allow to prepare modified low nitrogen furan resin,
It is expensive to solve furfuryl alcohol, leads to the higher problem of production cost, secondly the modification low nitrogen furan resin of preparation, indices
For nitrogen content≤3%, content of free aldehyde≤0.1%, intensity >=2.3MPa, water content≤6% meets Foundry Production requirement.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment one:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, 650 parts of glycerine, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half glycerine is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, temperature of charge control
System is reacted 50-70 minutes at 95-100 DEG C；
(4) remaining urea is added, remaining half glycerine is added, resin is made in stirring cooling.
Embodiment two:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, 325 parts of glycerine, 325 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter 6% ethyl alcohol, basic catalyst is added, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge controls the reaction at 85 DEG C
120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) remaining 4% ethyl alcohol and glycerine is added, and acidic catalyst is added, adjusts pH value in 3.0-4.5 range
Interior, temperature of charge is controlled at 95-100 DEG C, is reacted 50-70 minutes；
(4) remaining urea is added, remaining half glycerine is added, resin is made in stirring cooling.
Embodiment three:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, 650 parts of glycerine, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half glycerine is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, temperature of charge control
System is reacted 50-70 minutes at 95-100 DEG C；
(4) remaining urea is added, remaining half glycerine is added, resin is made in stirring cooling.
Example IV:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, 650 parts of methanol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half methanol is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, temperature of charge control
At 95-100 DEG C, react 50-70 minutes；
(4) remaining urea is added, remaining half methanol is added, resin is made in stirring cooling.
Embodiment five:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, A650 parts of polyalcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half polyalcohol A is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, temperature of charge control
System is reacted 50-70 minutes at 95-100 DEG C；
(4) remaining urea is added, remaining half polyalcohol A is added, resin is made in stirring cooling.
Embodiment six:
A kind of modified low nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, urea
289 parts, 28 parts of basic catalyst, 650 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of production technology of the modified low nitrogen furan resin, the specific steps are as follows:
(1) formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, adds
Enter basic catalyst, adjusting pH value is 9.5, steam heat temperature raising, and temperature of charge is controlled at 85 DEG C, is reacted 120 minutes；
(2) aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle,
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half ethyl alcohol is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, temperature of charge control
At 95-100 DEG C, react 50-70 minutes；
(4) remaining urea is added, remaining half ethyl alcohol is added, resin is made in stirring cooling.
One, the properties for the modification low nitrogen furan resin that respectively prepared by detection embodiment 1-6, as a result as shown in table 1 below:
Table 1
| Embodiment one | Embodiment two | Embodiment three | Example IV | Embodiment five | Embodiment six | |
| Nitrogen content | 5% | 2% | 4% | 6% | 3% | 2% |
| Content of free aldehyde | 0.2% | 0.1% | 0.2% | 0.3% | 0.3% | 0.2% |
| Intensity | 1.5MPa | 2.5MPa | 2.0MPa | 1MPa | 1.5MPa | 1.5MPa |
| Water content | 6% | 4% | 5% | 7% | 6% | 6% |
As can be seen from Table I, modified low nitrogen furan resin, nitrogen content≤3% made from production technology dissociate in embodiment two
Aldehyde≤0.1%, intensity >=2.3MPa, water content≤6% meet Foundry Production requirement, have considerable economic benefit and depth
Remote social benefit.
The present invention, which is used, has carried out part to furfuryl alcohol using glycerine, methanol, Xylitol mother liquor, polyalcohol A, ethyl alcohol material
Substitution, obtains the substitution law of each alternative materials, after the analysis to substitution law, selects ethyl alcohol and glycerine to furfuryl alcohol
Compound substitution is carried out, compound replace is carried out to furfuryl alcohol using ethyl alcohol and glycerine to allow to prepare modified low nitrogen furan resin
In generation, it is expensive to solve furfuryl alcohol, leads to the higher problem of production cost, secondly the modification low nitrogen furan resin of preparation, every
Index be nitrogen content≤3%, content of free aldehyde≤0.1%, intensity >=2.3MPa, water content≤6%, meet Foundry Production requirement.
In the description of the present invention, it is to be understood that, term " aperture ", "upper", "lower", " thickness ", "top", " in ",
Indicating positions or the positional relationship such as " length ", "inner", " surrounding ", are merely for convenience of description of the present invention and simplification of the description, without
It is that the component of indication or suggestion meaning or element must have a particular orientation, is constructed and operated in a specific orientation, therefore not
It can be interpreted as limitation of the present invention.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Specific features described in conjunction with this embodiment or example, structure, material live feature and are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of modified low nitrogen furan resin and production technology, which is characterized in that the modified low nitrogen furan resin includes following
The raw material of composition by weight: 560-680 parts of formaldehyde, 130-150 parts of paraformaldehyde, 289-410 parts of urea, basic catalyst 28-70
Part, 60-120 parts of carbohydrate, 650-1500 parts of sugar alcohol substituting agent, 6-10 parts of aldehyde remover, 5-10 parts of acidic catalyst.
2. a kind of modified low nitrogen furan resin according to claim 1 and production technology, it is characterised in that: the sugar alcohol sugar
Alcohol substituting agent is glycerine, methanol, polyalcohol A, one kind of ethyl alcohol or two kinds of combinations.
3. a kind of modified low nitrogen furan resin according to claim 1 and production technology, it is characterised in that: the alkalinity is urged
The sodium hydroxide solution that agent is 30%, the aqueous hydrochloric acid solution that the pickling catalyst is 10%.
4. a kind of modified low nitrogen furan resin according to claim 1 and production technology, which is characterized in that the modification is low
Nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, 289 parts of urea, basic catalyst
28 parts, 650 parts of glycerine, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
5. a kind of modified low nitrogen furan resin according to claim 1 and production technology, which is characterized in that the modification is low
Nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, 289 parts of urea, basic catalyst
28 parts, 325 parts of glycerine, 325 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
6. a kind of modified low nitrogen furan resin according to claim 1 and production technology, which is characterized in that the modification is low
Nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, 289 parts of urea, basic catalyst
28 parts, 650 parts of methanol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
7. a kind of modified low nitrogen furan resin according to claim 1 and production technology, which is characterized in that the modification is low
Nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, 289 parts of urea, basic catalyst
28 parts, A650 parts of polyalcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
8. a kind of modified low nitrogen furan resin according to claim 1 and production technology, which is characterized in that the modification is low
Nitrogen furan resin includes the raw material of following composition by weight: 560 parts of formaldehyde, 130 parts of paraformaldehyde, 289 parts of urea, basic catalyst
28 parts, 650 parts of ethyl alcohol, 6 parts of aldehyde remover, 5 parts of acidic catalyst.
A kind of modified low nitrogen furan resin and production technology described in 9., which comprises the following steps:
Formaldehyde and paraformaldehyde are added in reaction kettle, urea is added, makes formaldehyde and urea mol ratio 2.0-3.5, alkali is added
Property catalyst, adjust pH value be 9.5, steam heat temperature raising, temperature of charge control at 85 DEG C, react 120 minutes；
Aldehyde remover is added, when being cooled to 50 DEG C, adjusts the pH value of solution to 8.0~8.5, closes the return valve on reaction kettle, beat
Steam valve is opened, keeps the vacuum degree of 0.065~0.075Mpa to be dehydrated, 70 DEG C of dehydrations terminate；
(3) half furfuryl alcohol substituting agent is added, and acidic catalyst is added, adjusts pH value within the scope of 3.0-4.5, material temperature
Degree control is reacted 50-70 minutes at 95-100 DEG C；
(4) remaining urea is added, remaining half furfuryl alcohol substituting agent is added, resin is made in stirring cooling.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655628A (en) * | 2019-11-06 | 2020-01-07 | 徐州盛安化工科技有限公司 | Synthetic method of environment-friendly furan resin for cast iron |
| CN114632908A (en) * | 2021-11-29 | 2022-06-17 | 江苏丽莎环保科技有限公司 | Low-gas-evolution high-performance furan resin for casting |
-
2019
- 2019-06-06 CN CN201910491715.4A patent/CN110194825A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 胡保全等: "《先进复合材料》", 31 May 2013, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655628A (en) * | 2019-11-06 | 2020-01-07 | 徐州盛安化工科技有限公司 | Synthetic method of environment-friendly furan resin for cast iron |
| CN114632908A (en) * | 2021-11-29 | 2022-06-17 | 江苏丽莎环保科技有限公司 | Low-gas-evolution high-performance furan resin for casting |
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