CN109134795A - A kind of preparation method of the melamine resin of ultra-low formaldehyde content - Google Patents
A kind of preparation method of the melamine resin of ultra-low formaldehyde content Download PDFInfo
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- CN109134795A CN109134795A CN201810704956.8A CN201810704956A CN109134795A CN 109134795 A CN109134795 A CN 109134795A CN 201810704956 A CN201810704956 A CN 201810704956A CN 109134795 A CN109134795 A CN 109134795A
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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
- C08G12/42—Chemically modified polycondensates by etherifying
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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 preparation methods of the melamine resin of ultra-low formaldehyde content, wherein the ultra-low formaldehyde content is that free formaldehyde content is lower than 0.05wt% in resin, it is preferred that 0.01wt%, it the described method comprises the following steps: polyhydroxymethyl melamine and methanol are put into reactor, add inorganic acid catalysed etherification to react, terminates etherification reaction with inorganic base；Oxidant is added after terminating etherification reaction, and adds lye in time and maintains pH value between 8.0~10.0.The content of free aldehyde of amino resins can be reduced to no more than 0.05wt%, even as low as 0.01wt% by method of the invention, and other quality index all meet the requirements.
Description
Technical field
The invention belongs to amino resins fields, are related to a kind of preparation side of the melamine resin of ultra-low formaldehyde content
Method.
Background technique
The synthetic method of melamine resin is roughly divided into two kinds, and one is one-step method, i.e., raw material are disposable
It puts into reaction kettle, obtains product by adjusting technique；Another kind is two-step method, i.e., first by melamine and formaldehyde in alkaline item
Polyhydroxymethyl melamine is generated under part, and etherification reaction occurs after dry in acid condition with monohydric alcohol again, it is final to obtain product.
When using one-step method, a large amount of formalin or solid formaldehyde will use, therefore the content of formaldehyde in product is higher.
Phase after the reaction, whether formalin method or solid formaldehyde method, require that formaldehyde catching agent is added to reduce content of formaldehyde.
Common formaldehyde catching agent has: urea, melamine, borax, carbonate, oxidant (hydrogen peroxide, sodium hypochlorite) etc..It looks forward to part
Industry can select two-step process and optimize, i.e. commercially mature intermediate products --- polyhydroxy methyl melamine
Amine not only shortens process flow in this way, improves production efficiency, but also the content of formaldehyde of product is lower than one-step method.
Melamine resin whether methyl-etherified, butyl ether or mixed etherification product, or use one-step method or two steps
Method technique, the content of formaldehyde in product exist always, and professional standard is no more than 1% at present.Current research conditions and report
It is as follows:
(modern chemical industry, 2006,26 (S2): 247-248) such as luck inscriptions report free aldehyde in a kind of removal Lauxite
Method, propose to be reacted with free formaldehyde with inorganic ammonium salt, inorganic sodium, inorganic calcium salt and sodium salt containing chlorine, but many experiments table
Content of free aldehyde in resin can only be reduced to 0.3%~0.5% by this bright method.
In 101817914 A of Chinese patent application CN, using the mixture of urea and borax as formaldehyde catching agent, matter
Amount portion rate is resin liquid: urea: borax=1000:35~45:5~10.Final content of formaldehyde is 0.4~0.7%.
In 103739804 A of Chinese patent application CN, using ammonium acetate 3%~12%, urea 3%~12%, potassium carbonate
12%~24%, free formaldehyde content, can finally be reduced to by ammonium sulfate 1%~8%, the formaldehyde scavenger of deionized water composition
0.2%.
103554044 A of Chinese patent application CN describes one kind and continuously prepares hexamethoxymethyl melamine resin
Method: carrying out hydroxymethylation with organic base, be etherified with organic acid catalysis, terminates etherification reaction using oxidant.It is final to produce
The content of free aldehyde of product is 0.18%~0.2%.
As the strict demand and people of national environmental protection regulation are to the pay attention to day by day of environmental protection cause, in naval stores
Content of formaldehyde requirement will be lower and lower.Therefore, there is still a need for new can further decrease free formaldehyde in urea-formaldehyde resin content
Method.
Summary of the invention
The present invention in view of the above-mentioned problems, propose a kind of preparation method of the melamine resin of ultra-low formaldehyde content,
Wherein the ultra-low formaldehyde content is that free formaldehyde content is lower than 0.05wt%, preferably 0.01wt%, the method packet in resin
Include following steps:
Polyhydroxymethyl melamine and methanol are put into reactor, add inorganic acid catalysed etherification to react, with nothing by step S100
Machine alkali terminates etherification reaction；
Oxidant is added after terminating etherification reaction in step S200, and adds lye in time and maintain pH value 8.0~10.0
Between.
Further, in the step s 100, polyhydroxymethyl melamine is hexamethylolmelamine (HMM), and HMM's contains
Water is less than 15wt%, and the molar ratio of methanol purity 99wt%, HMM and methanol is 1:15 to 1:20；Etherification reaction temperature are as follows:
40 DEG C to 50 DEG C；The pH inorganic acid of etherification reaction, preferably hydrochloric acid, more preferable concentration are more than or equal to the hydrochloric acid of 30wt%, control
To 2.0~4.0；The control of etherification time is, after reaction mixture becomes colorless transparent (dissolution of six hydroxyls) by white opacity
The reaction was continued 2.0h to 4.0h；Etherification reaction terminates as, addition inorganic base, preferably sodium hydroxide, and more preferable concentration is greater than etc.
In the sodium hydrate aqueous solution of 20wt%, pH is controlled 8.0~10.0.
Further, in step s 200, oxidant is hydrogen peroxide or sodium peroxide, and preferred concentration is more than or equal to 25wt%
The hydrogen peroxide solution of (such as 30wt% or 35wt%), in hexamethylolmelamine content of formaldehyde calculate, oxidant with
The molar ratio of formaldehyde is 1.0:1 to 1.5:1.
Further, in step s 200, the lye added is sodium hydroxide solution, the sodium hydroxide water of preferably 30wt%
Solution；Preferably, the volume ratio of 30wt% sodium hydrate aqueous solution and 35wt% hydrogen peroxide is 1.5:1 to 1.8:1.
Further, in step s 200, after hydrogen peroxide is added, formaldehyde is oxidized to formic acid, leads to reaction system
PH value decline mends alkali in time to maintain pH stable in 8.0-10.0, preferably from about 9.0；Preferably, entirely mending alkali process time is
20~30min.
Further, the preparation method of the melamine resin of the ultra-low formaldehyde content, further includes:
Step S300, the product at reduced pressure dealcoholysis that step S200 is obtained are dehydrated, and diatomite is added, then filters.
Further, in step S300, to vacuum, the material temperature at -0.09Mpa is 90 DEG C for decompression dealcoholysis dehydration progress, it
After keep the temperature 1h.
The present invention utilize inorganic acid reaction advantage, sour dosage is few, reaction temperature is low, the time is short, after termination of the reaction plus
The oxidant entered is only reacted with formaldehyde, and dosage is less.The content of free aldehyde of amino resins can be reduced to not by method of the invention
More than 0.05wt%, even as low as 0.01wt%, and other quality index all meet the requirements.
Specific embodiment
The following are non-limiting examples of the invention, these embodiments are only given for illustrative purposes, not
It can be interpreted as limitation of the invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise indicated, real below
Applying reagent, instrument and equipment used in example all is commercially available conventional products.
1, the raw material in embodiment and requirement:
Hexamethylolmelamine: water content be 10% (admittedly contain method, it is desirable that < 15%)；Content of free aldehyde is 0.6% (sub-
Sodium sulphate titration, it is desirable that < 1%)；Methylol group content is 52% (iodimetric titration, it is desirable that > 50%)；Alcohol-soluble is good, and insoluble matter
Less than 5 ‰.
Methanol: industrial refined methanol, concentration 99%.
Inorganic acid: experiment uses 31% hydrochloric acid, and theoretically concentrated hydrochloric acid (36%) is more preferable.
Inorganic base: experiment uses sodium hydroxide, is prepared when experiment with piece alkali, concentration 30%.
Oxidant: experiment uses hydrogen peroxide, and concentration 35%, theoretically the higher the better for concentration.
2, in embodiment product analysis method:
Appearance: range estimation tests the product just obtained and needs to stand.
Content of free aldehyde: sodium sulfite titration (acid-base titration).
Viscosity: rotational viscometer method；Test condition is (25 ± 1) DEG C.
Non-volatile content: solid content analytic approach；Test condition is 105 DEG C × 60min.
3, resin is prepared using the technique for being etherified polyhydroxymethyl melamine in embodiment, comprising: by polyhydroxy first
Base melamine and methanol put into reactor, add inorganic acid catalysed etherification, are terminated with inorganic base, and oxidant, side are added after termination
Stirring side adds lye and maintains pH value, and pH value is stablized after 8.0~10.0, then depressurizes dealcoholysis dehydration, finally plus diatomite, filtering
Obtain product.It is specific as follows:
Polyhydroxymethyl melamine is hexamethylolmelamine (HMM), and the molar ratio of HMM and methanol is 1:(15~20)
Etherification temperature are as follows: (40~50) DEG C
The PH: inorganic acid of etherificate uses hydrochloric acid when experiment, controls PH 2.0~4.0
Etherification time: mixed solution is become colorless by white opacity, and transparent (dissolution of six hydroxyls) the reaction was continued afterwards (2.0~4.0)
h
The PH of termination；Inorganic base uses sodium hydroxide when experiment, controls PH 8.0~10.0
The additive amount of oxidant: it is calculated with the content of formaldehyde in hexamethylolmelamine, mole of oxidant and formaldehyde
Than for (1.0~1.5): 1
Wherein, the process for adding oxidant is major control point, should include:
1. using hydrogen peroxide when experiment
2. hydrogen peroxide: the molar ratio of formaldehyde (with the conversion of six hydroxyls) is (1.0~1.5): 1
3. hydrogen peroxide is added after system is terminated reaction with inorganic base
4. adding lye in time after hydrogen peroxide is added, maintain pH value between 8.0~10.0
5. the volume ratio of the lye and hydrogen peroxide added is (1.5~1.8)~1
After hydrogen peroxide is added, formaldehyde is oxidized to formic acid, and system pH value is caused to be gradually reduced, and adds lye to maintain PH
Value is stablized, and entire alkali process of mending takes around (20~30) min.
Dehydration: by the way of decompression dehydration, taking off to vacuum the material temperature at -0.09Mpa is 90 DEG C, is kept the temperature later
1h。
Embodiment 1
The methanol of 2176g is added into the flask of 5L, starts warming-in-water, when rising to (40~50) DEG C, adds into flask
Enter the hexamethylolmelamine of 1300g, the concentrated hydrochloric acid of 30ml is then added, six hydroxyls gradually dissolve, after system is fully transparent
Start timing, maintains temperature, 45ml sodium hydroxide is added after 3.0h, the pH value of system is between 8.0~9.0 at this time.Then add
Enter 24ml hydrogen peroxide, and add 36ml sodium hydroxide, after system pH value is stablized, starts to warm up and depressurize dealcoholysis dehydration, material temperature
1h is kept the temperature after to 90 DEG C, then filters to obtain product through diatomite.
The content of free aldehyde of product in embodiment 1 is 0.01%, and for viscosity in 4500mpa.s, appearance is colorless and transparent liquid
Body, non-volatile content 98.8%.
Embodiment 2
The methanol of 1230g is added into the flask of 3L, starts warming-in-water, when rising to (40~50) DEG C, adds into flask
Enter the hexamethylolmelamine of 735g, the concentrated hydrochloric acid of 10ml is then added, six hydroxyls are gradually dissolved, opened after system is fully transparent
Beginning timing maintains temperature, 16ml sodium hydroxide is added after 3.0h, the pH value of system is between 8.0~9.0 at this time.Then it is added
16ml hydrogen peroxide, and 25ml sodium hydroxide is added, after system pH value is stablized, starts to warm up and depressurize dealcoholysis dehydration, material temperature arrives
1h is kept the temperature after 90 DEG C, then filters to obtain product through diatomite.
The content of free aldehyde of product in embodiment 2 is 0.01%, and for viscosity in 4600mpa.s, appearance is colorless and transparent liquid
Body, non-volatile content 99.1%.
Embodiment 3
The methanol of 1470g is added into the flask of 3L, starts warming-in-water, when rising to (40~50) DEG C, adds into flask
Enter the hexamethylolmelamine of 735g, the concentrated hydrochloric acid of 18ml is then added, six hydroxyls are gradually dissolved, opened after system is fully transparent
Beginning timing maintains temperature, 30ml sodium hydroxide is added after 3.0h, the pH value of system is between 9.0~10.0 at this time.Then it is added
14ml hydrogen peroxide, and 24ml sodium hydroxide is added, after system pH value is stablized, starts to warm up and depressurize dealcoholysis dehydration, material temperature arrives
1h is kept the temperature after 90 DEG C, then filters to obtain product through diatomite.
The content of free aldehyde of product in embodiment 3 is 0.04%, and for viscosity in 3900mpa.s, appearance is colorless and transparent liquid
Body, non-volatile content 98.7%.
Comparative example 1
The methanol of 2176g is added into the flask of 5L, starts warming-in-water, when rising to (40~50) DEG C, adds into flask
Enter the hexamethylolmelamine of 1300g, the concentrated hydrochloric acid of 30ml is then added, six hydroxyls gradually dissolve, after system is fully transparent
Start timing, maintains temperature, 45ml sodium hydroxide is added after 3.0h, the pH value of system is between 8.0~9.0 at this time.Start to rise
Temperature simultaneously depressurizes dealcoholysis dehydration, and material temperature is to keeping the temperature 1h after 90 DEG C, then filters to obtain product through diatomite.
The content of free aldehyde of product in embodiment 1 is 0.17%, and for viscosity in 3560mpa.s, appearance is colorless and transparent liquid
Body, non-volatile content 99.3%.As it can be seen that the strong content of formaldehyde in product is higher in the case where not oxidizer.
Comparative example 2
The methanol of 2176g is added into the flask of 5L, starts warming-in-water, when rising to (40~50) DEG C, adds into flask
Enter the hexamethylolmelamine of 1300g, the concentrated hydrochloric acid of 30ml is then added, six hydroxyls gradually dissolve, after system is fully transparent
Start timing, maintains temperature, 45ml sodium hydroxide is added after 3.0h, the pH value of system is between 8.0~9.0 at this time.Then add
Enter 24ml hydrogen peroxide, started to warm up after stirring 10min and depressurizes dealcoholysis dehydration, to the dehydration later period, the viscosity of system is gradually increased,
So that rotating speed of agitator, which is adjusted to maximum, to be stirred reluctantly.Product is poured out while hot, discovery gel is serious, the failure of an experiment.
For the content of free aldehyde of product in embodiment 2 0.01%, viscosity is too big, is unable to measure, and appearance is colourless, is in fruit
Freeze shape, non-volatile content 99.5%.The too big reason of viscosity may be that hydrogen peroxide oxidizes the formaldehyde into formic acid even dioxy
System acidity is caused to increase after changing carbon, so that resin has occurred caused by further polymerization crosslinking reaction.
The present invention adds oxidizing formaldehyde formic acid after terminating reaction with optimised process synthetic resin, then mend alkali into
Row acid-base neutralization does not introduce other substances in the process, that is, combines the advantage of mineral acid catalytic reactions and oxidizing formaldehyde,
It has found out benefit alkali technique and has mended alkali number, so that the content of formaldehyde of melamine resin (is no more than down to 0.01%
0.05%), and other quality index all meet the requirements.In conclusion beneficial effects of the present invention at least that:
1. the free formaldehyde content in melamine resin of the invention has comparable in the industry down to 0.01%
Competitive advantage, and meet the environmentally friendly trend requirement of country.
2. since formaldehyde is oxidized to formic acid, and then being neutralized into salt with lye and being filtered, micro- excessive hydrogen peroxide also can be by
Pyrolytic, product noresidue.
There are block generation, easily blocking production flow line when using melamine as formaldehyde catching agent；Using urea as formaldehyde
Lauxite precipitating is had when agent for capturing to generate, and influences product quality.
3. the technique majority of other addition oxidants is organic acid catalysis (common formic acid), and formic acid is weak acid, on the one hand
Additional amount could be catalyzed reaction when larger, another aspect reaction temperature is high, the time is long.And using oxidant as terminator, oxidant
It is reacted with formic acid, while also to aoxidize formaldehyde, cause oxidizer larger.
The present invention utilize inorganic acid reaction advantage, sour dosage is few, reaction temperature is low, the time is short, after termination of the reaction plus
The oxidant entered is only reacted with formaldehyde, and dosage is less.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, it is all according to
According to technical spirit any simple modification to the above embodiments of the invention, equivalent variations, protection of the invention is each fallen within
Within the scope of.
Claims (7)
1. a kind of preparation method of the melamine resin of ultra-low formaldehyde content, wherein the ultra-low formaldehyde content is resin
Middle free formaldehyde content is lower than 0.05wt%, and preferably 0.01wt% the described method comprises the following steps:
Polyhydroxymethyl melamine and methanol are put into reactor, add inorganic acid catalysed etherification to react, use inorganic base by step S100
Terminate etherification reaction；
Step S200, terminate etherification reaction after oxidant is added, and add in time lye maintain pH value 8.0~10.0 it
Between.
2. the preparation method of the melamine resin of the ultra-low formaldehyde content according to claim 1, wherein in step
In S100, polyhydroxymethyl melamine is hexamethylolmelamine (HMM), and the water content of HMM is less than 15wt%, methanol purity
For 99wt%, the molar ratio of HMM and methanol is 1:15 to 1:20；Etherification reaction temperature are as follows: 40 DEG C to 50 DEG C；The pH of etherification reaction
With inorganic acid, preferably hydrochloric acid, more preferable concentration is more than or equal to the hydrochloric acid of 30wt%, control to 2.0~4.0；The control of etherification time
It is made as, is become colorless transparent (dissolution of six hydroxyls) the reaction was continued afterwards 2.0h to 4.0h in reaction mixture by white opacity；Etherificate
Reaction terminates as, and inorganic base, preferably sodium hydroxide is added, and more preferable concentration is water-soluble more than or equal to the sodium hydroxide of 20wt%
Liquid controls pH 8.0~10.0.
3. the preparation method of the melamine resin of ultra-low formaldehyde content according to claim 1 or 2, wherein
In step S200, oxidant be hydrogen peroxide or sodium peroxide, preferred concentration be more than or equal to 25wt% (such as 30wt% or
Hydrogen peroxide solution 35wt%) is calculated with the content of formaldehyde in hexamethylolmelamine, and the molar ratio of oxidant and formaldehyde is
1.0:1 to 1.5:1.
4. the preparation method of the melamine resin of the ultra-low formaldehyde content according to claim 3, wherein in step
In S200, the lye added is sodium hydroxide solution, the preferably sodium hydrate aqueous solution of 30wt%；Preferably, 30wt% hydrogen-oxygen
The volume ratio for changing sodium water solution and 35wt% hydrogen peroxide is 1.5:1 to 1.8:1.
5. according to the preparation method of the melamine resin of the ultra-low formaldehyde content of claim 3 or 4, wherein
In step S200, after hydrogen peroxide is added, formaldehyde is oxidized to formic acid, and the pH value of reaction system is caused to decline, in time mend alkali with
Maintain pH stable in 8.0-10.0, preferably from about 9.0；Preferably, entirely mending alkali process time is 20~30min.
6. the preparation method of the melamine resin of the ultra-low formaldehyde content as claimed in one of claims 1-6,
Further include:
Step S300, the product at reduced pressure dealcoholysis that step S200 is obtained are dehydrated, and diatomite is added, then filters.
7. the preparation method of the melamine resin of the ultra-low formaldehyde content according to claim 6, wherein in step
In S300, to vacuum, the material temperature at -0.09Mpa is 90 DEG C for decompression dealcoholysis dehydration progress, keeps the temperature 1h later.
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| CN201810704956.8A CN109134795B (en) | 2018-07-02 | 2018-07-02 | Preparation method of melamine formaldehyde resin with ultralow formaldehyde content |
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| CN201810704956.8A CN109134795B (en) | 2018-07-02 | 2018-07-02 | Preparation method of melamine formaldehyde resin with ultralow formaldehyde content |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109778552A (en) * | 2019-01-30 | 2019-05-21 | 山东科技大学 | A kind of organic furfuryl alcohol modified aminoresin-inorganic sol composite coating, preparation method and application for net filter used for casting |
| CN113956415A (en) * | 2021-11-09 | 2022-01-21 | 山东阳谷华泰化工股份有限公司 | Preparation method of aqueous imino methylated melamine formaldehyde resin |
| CN114059382A (en) * | 2021-11-02 | 2022-02-18 | 胡子和 | Stiffness modifier for paper cone and sample testing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778552A (en) * | 2019-01-30 | 2019-05-21 | 山东科技大学 | A kind of organic furfuryl alcohol modified aminoresin-inorganic sol composite coating, preparation method and application for net filter used for casting |
| CN109778552B (en) * | 2019-01-30 | 2021-09-03 | 山东科技大学 | Organic furfuryl alcohol modified amino resin-inorganic sol composite coating for casting filter screen, preparation method and application |
| CN114059382A (en) * | 2021-11-02 | 2022-02-18 | 胡子和 | Stiffness modifier for paper cone and sample testing method thereof |
| CN113956415A (en) * | 2021-11-09 | 2022-01-21 | 山东阳谷华泰化工股份有限公司 | Preparation method of aqueous imino methylated melamine formaldehyde resin |
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