CN106432657B - A kind of preparation method for the melamine resin that free formaldehyde content is ultralow - Google Patents
A kind of preparation method for the melamine resin that free formaldehyde content is ultralow Download PDFInfo
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- CN106432657B CN106432657B CN201610853929.8A CN201610853929A CN106432657B CN 106432657 B CN106432657 B CN 106432657B CN 201610853929 A CN201610853929 A CN 201610853929A CN 106432657 B CN106432657 B CN 106432657B
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- necked flask
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- melamine
- free formaldehyde
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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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
Abstract
The present invention discloses a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, includes the following steps：Deionized water is added into three-necked flask, then instills lye, stirs, when temperature reaches 60 DEG C, the mixture of melamine and paraformaldehyde is added into three-necked flask, continues to heat up, solution temperature in three-necked flask is made to reach slightly boiling；Auxiliary material solution is added in three-necked flask, slight boiling condition 30min is kept；Urea and triethylamine is taken to be added in beaker respectively, stirring heating makes it dissolve, and stops heating, cooling after being warming up to 230 DEG C, a small amount of deionized water stirring is added, is transferred in three-necked flask, keeps slightly boiling 10min, stop heating and stirring later, be transferred in ice-water bath, be cooled to room temperature to get.In melamine resin in the present invention content of free formaldehyde 0.2% hereinafter, the removal rate of free formaldehyde reaches 98.9%.
Description
Technical field
The present invention relates to production of resins technical field, more particularly to a kind of melamino-formaldehyde that free formaldehyde content is ultralow
The preparation method of resin.
Background technology
Melamine resin, also known as melamine resin (melamine-formaldehyde resin), melamine formaldehyde (MF) tree
Fat is that melamine reacts obtained polymer with formaldehyde.Reaction is crosslinked when machine-shaping, product is insoluble thermosetting
Property resin, it and Lauxite are often traditionally referred to as amino resins.
Melamine resin foam sponge refers to can be made into melamino-formaldehyde foam using melamine resin by foamable reaction, this
Foam is nonflammable, water-fast, heat-resisting, ageing-resistant, resistance to electric arc, it is resistant to chemical etching, have good insulation performance, glossiness and machinery strong
Degree, while also there is good sound-absorbing effect.Therefore, it is widely used in the sound-absorbing of building, automobile even aircraft carrier, submarine etc.
It is fire-retardant.
Content of formaldehyde is higher in existing melamine resin, generally 10% or more.Utilize existing melamine
The melamine resin foam sponge of amine-formaldehyde resins production is put, and residual formaldehyde is easily occurred and is increased even exceeded phenomenon.
Invention content
The present invention provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, solves existing
The higher problem of content of formaldehyde in melamine resin.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method for the melamine resin that free formaldehyde content is ultralow, includes the following steps：
(1) deionized water is added into three-necked flask, then instills lye, stirs, speed 80r/min, temperature is worked as in heating
When degree reaches 60 DEG C, the mixture of melamine and paraformaldehyde is added into three-necked flask, raising mixing speed is 120r/
Min continues to heat up, and so that solution temperature in three-necked flask is reached slightly boiling, and solution is transparent；
(2) auxiliary material is taken to be added in deionized water, heating water bath makes auxiliary material be completely dissolved to 48 DEG C, it is made a concentration of 20~
Auxiliary material solution, is then added in the three-necked flask of step (1) by 45% auxiliary material solution, keeps slight boiling condition 30min；
(3) urea and triethylamine is taken to be added in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve, then slowly heating
Stop heating after to 230 DEG C, be cooled to room temperature, adds a small amount of deionized water stirring and be warming up to 100 DEG C, it then will be in beaker
Solution is transferred in the three-necked flask of step (2), is continued to keep 105 DEG C of slightly boiling 10min, is stopped heating and stirring later, by three
Transparency liquid in mouth flask is transferred in ice-water bath, is cooled to room temperature to get the melamine first of ultralow free formaldehyde content
Urea formaldehyde.
Wherein it is preferred in the step (1) lye be a concentration of 15~25% organic base or inorganic base it is water-soluble
Liquid.
Wherein it is preferred to which the weight ratio of melamine and paraformaldehyde is 5 in the step (1):(2~4).
Wherein it is preferred to which deionized water and the weight ratio of lye are (80~100) in the step (1)：1, the lye
Weight ratio with the melamine is 1:(150~200).
Wherein it is preferred to which auxiliary material is sodium hydrogensulfite, sodium sulfite, sodium pyrosulfite, sodium sulphate in the step (2)
Or sodium carbonate.
Wherein it is preferred to which the addition of auxiliary material solution and the weight ratio of melamine are 10 in the step (2):(1~
2)。
Wherein it is preferred to which the addition of urea and the weight ratio of melamine are 100 in the step (3):(2~4),
The addition of triethylamine and the weight ratio of melamine are 100 in the step (3):(3~5).
Beneficial effects of the present invention：
Using the content of free formaldehyde in the melamine resin of the method for the present invention production 0.2% hereinafter, free
The removal rate of formaldehyde reaches 98.9% and is compared with existing melamine resin, greatly reduces the content of free formaldehyde.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
In following embodiments, the assay method of free formaldehyde in resin：
It weighs 5 grams or so (accurately to 0.0002 gram) samples to be placed in 250 milliliters of iodine flasks, 50 millis is diluted to distilled water
Rise or so, 5 drop thymolphthalein indicator are added, as resin liquid pH<9.3 or PH>When 10.5,0.5N sodium hydroxides can be used molten respectively
Liquid or hydrochloric acid are adjusted to atomic blue.
After 50 milliliters of 1.0M sodium sulfite solutions are added, it is from blue rapid titration to atomic blue with 0.5N hydrochloric acid immediately
Terminal.
Dosage V1 is recorded, in kind into line blank test, record dosage Vo.Three times, absolute error is or not parallel determination
More than 0.04%, its average value is taken.
Free formaldehyde percentage composition is calculated as follows：
Free formaldehyde %=[(V1-Vo) N*0.03003]/m*100
In formula:
V1 ,-sample consume hydrochloric acid standard solution ml；
Vo- blank consumes hydrochloric acid standard solution ml；
The concentration of N-hydrochloric acid standard solution；
The quality of m-resin finishing agent sample, gram；
0.03003-the grams per milliequivalent formaldehyde.
Embodiment 1
The present embodiment provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, including it is following
Step：
(1) 244g deionized waters are added into three-necked flask, then instill the sodium hydroxide that 3.0g mass concentrations are 20%
Solution stirs (rotating speed 80r/min) and heats up, and when temperature reaches 60 DEG C, 500g melamines are added into three-necked flask
With the mixture of 330g paraformaldehydes, raising mixing speed is 120r/min, continues to heat up, solution temperature in three-necked flask is made to reach
To 105 DEG C (slightly boilings) and solution it is transparent；
(2) 25g sodium pyrosulfites are taken to be added in the beaker for filling 40g deionized waters, heating water bath makes burnt Asia to 48 DEG C
Sodium sulphate is completely dissolved, and then sodium metabisulfite solution is added in the three-necked flask of the first step, keeps slight boiling condition
30min；
(3) 15g urea and 18g ethylenediamines being mixed to join in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve,
Then stop heating after being to slowly warm up to 230 DEG C, be cooled to room temperature, the stirring of 6g deionized waters is then added and is warming up to 100 DEG C, so
The solution in beaker is transferred in the three-necked flask of second step afterwards, continues to keep 105 DEG C of slightly boiling 10min, stops heating later
And stirring, the transparency liquid in three-necked flask is transferred in ice-water bath, is cooled to room temperature to get ultralow free formaldehyde content
Melamine resin.
The test result of melamine resin made from the present embodiment：
Embodiment 2
The present embodiment provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, including it is following
Step：
(1) 240g deionized waters are added into three-necked flask, then instill the sodium hydroxide that 2.5g mass concentrations are 25%
Solution stirs (rotating speed 80r/min) and heats up, and when temperature reaches 60 DEG C, 500g melamines are added into three-necked flask
With the mixture of 200g paraformaldehydes, raising mixing speed is 120r/min, continues to heat up, solution temperature in three-necked flask is made to reach
To 105 DEG C (slightly boilings) and solution it is transparent；
(2) 10g sodium hydrogensulfites are taken to be added in the beaker for filling 40g deionized waters, heating water bath makes sulfurous to 48 DEG C
Sour hydrogen sodium is completely dissolved, and then solution of sodium bisulfite is added in the three-necked flask of the first step, keeps slight boiling condition
30min；
(3) 10g urea and 25g ethylenediamines being mixed to join in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve,
Then stop heating after being to slowly warm up to 230 DEG C, be cooled to room temperature, the stirring of 6g deionized waters is then added and is warming up to 100 DEG C, so
The solution in beaker is transferred in the three-necked flask of second step afterwards, continues to keep 105 DEG C of slightly boiling 10min, stops heating later
And stirring, the transparency liquid in three-necked flask is transferred in ice-water bath, is cooled to room temperature to get ultralow free formaldehyde content
Melamine resin.
The test result of melamine resin made from the present embodiment：
Embodiment 3
The present embodiment provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, including it is following
Step：
(1) 300g deionized waters are added into three-necked flask, then instill the sodium hydroxide that 3.3g mass concentrations are 15%
Solution stirs (rotating speed 80r/min) and heats up, and when temperature reaches 60 DEG C, 500g melamines are added into three-necked flask
With the mixture of 400g paraformaldehydes, raising mixing speed is 120r/min, continues to heat up, solution temperature in three-necked flask is made to reach
To 105 DEG C (slightly boilings) and solution it is transparent；
(2) 45g sodium sulfites are taken to be added in the beaker for filling 55g deionized waters, heating water bath makes sulfurous acid to 48 DEG C
Sodium is completely dissolved, and then sodium sulfite solution is added in the three-necked flask of the first step, keeps slight boiling condition 30min；
(3) 20g urea and 15g ethylenediamines being mixed to join in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve,
Then stop heating after being to slowly warm up to 230 DEG C, be cooled to room temperature, the stirring of 6g deionized waters is then added and is warming up to 100 DEG C, so
The solution in beaker is transferred in the three-necked flask of second step afterwards, continues to keep 105 DEG C of slightly boiling 10min, stops heating later
And stirring, the transparency liquid in three-necked flask is transferred in ice-water bath, is cooled to room temperature to get ultralow free formaldehyde content
Melamine resin.
The test result of melamine resin made from the present embodiment：
Embodiment 4
The present embodiment provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, including it is following
Step：
(1) 274g deionized waters are added into three-necked flask, then instill the sodium hydroxide that 2.8g mass concentrations are 18%
Solution stirs (rotating speed 80r/min) and heats up, and when temperature reaches 60 DEG C, 500g melamines are added into three-necked flask
With the mixture of 350g paraformaldehydes, raising mixing speed is 120r/min, continues to heat up, solution temperature in three-necked flask is made to reach
To 105 DEG C (slightly boilings) and solution it is transparent；
(2) 25g sodium sulphate is taken to be added in the beaker for filling 50g deionized waters, heating water bath keeps sodium sulphate complete to 48 DEG C
Then metabisulfite solution is added in the three-necked flask of the first step by fully dissolved, keep slight boiling condition 30min；
(3) 18g urea and 20g ethylenediamines being mixed to join in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve,
Then stop heating after being to slowly warm up to 230 DEG C, be cooled to room temperature, the stirring of 6g deionized waters is then added and is warming up to 100 DEG C, so
The solution in beaker is transferred in the three-necked flask of second step afterwards, continues to keep 105 DEG C of slightly boiling 10min, stops heating later
And stirring, the transparency liquid in three-necked flask is transferred in ice-water bath, is cooled to room temperature to get ultralow free formaldehyde content
Melamine resin.
The test result of melamine resin made from the present embodiment：
Embodiment 5
The present embodiment provides a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, including it is following
Step：
(1) 266g deionized waters are added into three-necked flask, then instill the sodium hydroxide that 3.1g mass concentrations are 22%
Solution stirs (rotating speed 80r/min) and heats up, and when temperature reaches 60 DEG C, 500g melamines are added into three-necked flask
With the mixture of 280g paraformaldehydes, raising mixing speed is 120r/min, continues to heat up, solution temperature in three-necked flask is made to reach
To 105 DEG C (slightly boilings) and solution it is transparent；
(2) 25g sodium carbonate is taken to be added in the beaker for filling 45g deionized waters, heating water bath keeps sodium carbonate complete to 48 DEG C
Then sodium metabisulfite solution is added in the three-necked flask of the first step by fully dissolved, keep slight boiling condition 30min；
(3) 12g urea and 22g ethylenediamines being mixed to join in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve,
Then stop heating after being to slowly warm up to 230 DEG C, be cooled to room temperature, the stirring of 6g deionized waters is then added and is warming up to 100 DEG C, so
The solution in beaker is transferred in the three-necked flask of second step afterwards, continues to keep 105 DEG C of slightly boiling 10min, stops heating later
And stirring, the transparency liquid in three-necked flask is transferred in ice-water bath, is cooled to room temperature to get ultralow free formaldehyde content
Melamine resin.
The test result of melamine resin made from the present embodiment：
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (4)
1. a kind of preparation method for the melamine resin that free formaldehyde content is ultralow, it is characterised in that including following step
Suddenly：
(1) deionized water is added into three-necked flask, then instills lye, stirs, speed 80r/min, heating, when temperature reaches
When to 60 DEG C, the mixture of melamine and paraformaldehyde is added into three-necked flask, raising mixing speed is 120r/min, after
Temperature of continuing rising makes solution temperature in three-necked flask reach slightly boiling, and solution is transparent；
(2) auxiliary material is taken to be added in deionized water, heating water bath makes auxiliary material be completely dissolved to 48 DEG C, is made a concentration of 20~45%
Then auxiliary material solution is added in the three-necked flask of step (1) by auxiliary material solution, keep slight boiling condition 30min；
(3) urea and triethylamine is taken to be added in beaker respectively, stirring is warming up to 100 DEG C and makes it dissolve, and is then to slowly warm up to 230
Stop heating after DEG C, be cooled to room temperature, adds a small amount of deionized water stirring and be warming up to 100 DEG C, then by the solution in beaker
It is transferred in the three-necked flask of step (2), continues to keep 105 DEG C of slightly boiling 10min, stop heating and stirring later, three mouthfuls are burnt
Transparency liquid in bottle is transferred in ice-water bath, is cooled to room temperature to get the melamino-formaldehyde tree of ultralow free formaldehyde content
Fat；
Auxiliary material is sodium hydrogensulfite, sodium sulfite, sodium pyrosulfite, sodium sulphate or sodium carbonate in the step (2)；The step
(2) addition of auxiliary material solution and the weight ratio of melamine are 10 in:(1~2)；The addition of urea in the step (3)
Weight ratio with melamine is 100:(2~4), the addition of triethylamine and the weight ratio of melamine in the step (3)
It is 100:(3~5).
2. a kind of preparation method of the ultralow melamine resin of free formaldehyde content according to claim 1,
It is characterized in that：The aqueous solution of lye is a concentration of 15~25% in the step (1) organic base or inorganic base.
3. a kind of preparation method of the ultralow melamine resin of free formaldehyde content according to claim 1,
It is characterized in that：The weight ratio of melamine and paraformaldehyde is 5 in the step (1):(2~4).
4. a kind of preparation method of the ultralow melamine resin of free formaldehyde content according to claim 1,
It is characterized in that：Deionized water and the weight ratio of lye are (80~100) in the step (1)：1, the lye and the trimerization
The weight ratio of cyanamide is 1:(150~200).
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109400943A (en) * | 2018-11-02 | 2019-03-01 | 郑州峰泰纳米材料有限公司 | A kind of aftertreatment technology that ultra-low formaldehyde melamine bubble is continuous |
| CN109400945A (en) * | 2018-11-02 | 2019-03-01 | 郑州峰泰纳米材料有限公司 | A kind of production technology that ultra-low formaldehyde melamine bubble is continuous |
| CN109880033B (en) * | 2019-03-04 | 2022-01-28 | 上海金狮化工有限公司 | Synthesis method of water-soluble melamine resin and prepared water-soluble melamine resin |
| CN112280406B (en) * | 2020-11-10 | 2022-04-05 | 三棵树(上海)新材料研究有限公司 | High-performance water-based steel structure expansion type fireproof coating and preparation method thereof |
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| US4996289A (en) * | 1988-08-25 | 1991-02-26 | Basf Aktiengesellschaft | Continuous preparation of aqueous melamine/formaldehyde precondensate solutions |
| CN102702460A (en) * | 2012-05-10 | 2012-10-03 | 戴新春 | Novel preparation and continuous production method of melamine resin |
| CN104774427A (en) * | 2015-05-07 | 2015-07-15 | 成都玉龙化工有限公司 | High-density soft melamine foam and preparing method |
| CN105731857A (en) * | 2016-02-20 | 2016-07-06 | 深圳爱易瑞科技有限公司 | Novel sulfonation melamino-formaldehyde resin and preparation method thereof |
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2016
- 2016-09-27 CN CN201610853929.8A patent/CN106432657B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996289A (en) * | 1988-08-25 | 1991-02-26 | Basf Aktiengesellschaft | Continuous preparation of aqueous melamine/formaldehyde precondensate solutions |
| CN102702460A (en) * | 2012-05-10 | 2012-10-03 | 戴新春 | Novel preparation and continuous production method of melamine resin |
| CN104774427A (en) * | 2015-05-07 | 2015-07-15 | 成都玉龙化工有限公司 | High-density soft melamine foam and preparing method |
| CN105731857A (en) * | 2016-02-20 | 2016-07-06 | 深圳爱易瑞科技有限公司 | Novel sulfonation melamino-formaldehyde resin and preparation method thereof |
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