CN103214641A - Production method of melamine-formaldehyde resin - Google Patents
Production method of melamine-formaldehyde resin Download PDFInfo
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- CN103214641A CN103214641A CN2013101674948A CN201310167494A CN103214641A CN 103214641 A CN103214641 A CN 103214641A CN 2013101674948 A CN2013101674948 A CN 2013101674948A CN 201310167494 A CN201310167494 A CN 201310167494A CN 103214641 A CN103214641 A CN 103214641A
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Abstract
The invention discloses a production method of melamine-formaldehyde resin. The production method comprises the following steps of: adding wastewater and methanol into a reaction kettle, using alkali liquor to regulate pH to 9.5-10, then adding paraformaldehyde, and stirring for 5-10min; adding melamine, heating to increase the temperature of the material to 90-100 DEG C, and keeping the constant temperature; and sampling a test cloud point, adding triethanolamine when the could point is reached, stirring for 10-15min, and discharging. According to the production method disclosed by the invention, the treatment problem of phenolic resin wastewater and melamine-formaldehyde resin production wastewater is effectively solved, free phenol and formaldehyde in the phenolic resin wastewater are recycled, and the melamine-formaldehyde resin with specific solid content is produced by controlling the adding amount of the wastewater, thus the production cost is reduced and the production efficiency is improved; and simultaneously, the produced resin is colorless, transparent and good in glossiness, and has good mobility and flexibility, as well as excellent comprehensive performance.
Description
Technical field
The invention belongs to chemical production technical field, be specifically related to a kind of production method of terpolycyantoamino-formaldehyde resin.
Background technology
Terpolycyantoamino-formaldehyde resin is numerous in variety, is widely used in the aspects such as sizing agent, foam materials and filamentary material of phenolaldehyde moulding compound, fabric finishing agent, coating and timber etc.It mainly is that the solid content major part is lower than 60% by trimeric cyanamide and 37% left and right sides formalin prepared in reaction.For prescription and trimeric cyanamide and the formaldehyde mole ratio determined, prepared resin solid content determines that the terpolycyantoamino-formaldehyde resin that will prepare higher solids content then need dewater to polycondensation product in post-synthesis phase and realize.Simultaneously, this method will produce a certain amount of waste water, must can discharge after treatment.
In the resol production process,, need it is handled and just can discharge after up to standard because the waste water (hereinafter to be referred as phenolic resin wastewater) that later stage resin dehydration produces contains toxic substances such as more phenol and formaldehyde.At present, the treatment process of this type of phenolic resin wastewater mainly contains three major types such as physico-chemical process, chemical method, biochemical process.Defectives such as the same with the processing of terpolycyantoamino-formaldehyde resin waste water, the processing ubiquity investment cost of this type of phenolic resin wastewater is big, running cost height, intractability is big, is difficult to reach emission standard.
Summary of the invention
The object of the present invention is to provide a kind of production method of terpolycyantoamino-formaldehyde resin, effectively solve phenolic resin wastewater and terpolycyantoamino-formaldehyde resin production wastewater treatment problem, recycle free-phenol and formaldehyde in the phenolic resin wastewater, can produce the terpolycyantoamino-formaldehyde resin of specific solid content by control waste water add-on, not only reduce production costs, enhance productivity, simultaneously, the resin water white transparency of being produced, glossiness is good, have good flowability and snappiness, high comprehensive performance.
For achieving the above object, the present invention adopts following technical scheme:
Reaction raw materials and weight percent are in a kind of production method of terpolycyantoamino-formaldehyde resin: trimeric cyanamide 30-60%, and Paraformaldehyde 96 20-35%, waste water 10-35%, methyl alcohol 1-10%, trolamine 1-10%, surplus is an alkali lye; Described waste water is that resol is produced the waste water that later stage resin dehydration produces;
Waste water is both as reaction solvent, again as reaction raw materials in the present invention.Paraformaldehyde 96 and trimeric cyanamide are solid, reaction difficulty each other under normal condition, and the adding of waste water not only provides the medium of reaction, for successful reaction has been created condition.Simultaneously owing to contain a large amount of free-phenols and formaldehyde in the phenolic resin wastewater, adopt waste water as reaction raw materials, the free-phenol that has made full use of in giving up has carried out modification to resin, in the resin segment, introduce phenolic groups, this has material impact to improving aspects such as resin thermotolerance, snappiness, stability in storage, has recycled formaldehyde in addition.And how much the waste water add-on be the principal element that influences resin solid content, and wastewater flow rate can't provide enough required media of reaction very little, and then resin solid content is on the low side too much for wastewater flow rate, and the add-on that the present invention chooses waste water is 10-35%, more preferably 15-33%.Another major influence factors of the solid content of resin is the mol ratio of Paraformaldehyde 96 and trimeric cyanamide, and the consumption that the present invention chooses trimeric cyanamide is 30-60%, 35-55% more preferably, and the consumption of Paraformaldehyde 96 is 20-35%.
Concrete production method of the present invention may further comprise the steps:
(1) in reactor, adds waste water and methyl alcohol, regulate pH to 9.5-10, add Paraformaldehyde 96 then, stirred 5-10 minute with alkali lye;
(2) add trimeric cyanamide in the reaction solution of step (1), heating makes material be warming up to 90-100 ℃ and constant temperature;
(3) sampling and testing cloud point adds trolamine when arriving cloud point, stirred discharging 10-15 minute.
The phenol content of described waste water is 5000ppm-100000ppm, and aldehyde is 5000ppm-100000ppm, and COD is 100000-400000ppm.
Described alkali lye is that massfraction is 40% sodium hydroxide solution.
Remarkable advantage of the present invention is: adopting phenolic resin wastewater and Paraformaldehyde 96 is raw material, effectively solve phenolic resin wastewater and handle a difficult problem, reclaim free-phenol and formaldehyde in the waste water, utilize the phenol in the waste water that terpolycyantoamino-formaldehyde resin is carried out modification, have certain effect to improving aspects such as resin flexible toughness, water Combination and package stability, can obtain the terpolycyantoamino-formaldehyde resin of high comprehensive performance.In addition, by regulating the waste water add-on, can conveniently control the solid content of terpolycyantoamino-formaldehyde resin, exempt the dehydration in production of resins later stage, no waste water produces.Simultaneously, the present invention is easy and simple to handle, and equipment is not had harsh requirement, can produce smoothly under the existing equipment condition, is highly suitable for suitability for industrialized production.
Embodiment
Embodiment 1
With waste water 157kg(free phenol is 38627.20ppm, free aldehyde is 34863.22ppm, and COD is 230283.02ppm), 99.8% methyl alcohol 18kg adds in the reactor, pH is 9.56 with the adjusting of 40% aqueous sodium hydroxide solution, add 98.0% Paraformaldehyde 96 155kg, stirred 10 minutes, and added 99.9% trimeric cyanamide 250kg again, heating makes material be warming up to 97 ℃, sampling and testing cloud point after reaction for some time, when arriving cloud point, add 99.5% trolamine 31kg, stirred discharging 15 minutes.
After testing, free formaldehyde is 1.62% in the product, and free-phenol is 0.02%, and solid content is 70.25%.
Embodiment 2
With waste water 194kg(free phenol is 33324.38ppm, free aldehyde is 38667.74ppm, and COD is 211472.26ppm), 99.8% methyl alcohol 12kg adds in the reactor, pH is 9.68 with the adjusting of 40% aqueous sodium hydroxide solution, add 98.0% Paraformaldehyde 96 150kg, stirred 10 minutes, and added 99.9% trimeric cyanamide 230kg again, heating makes material be warming up to 96 ℃, sampling and testing cloud point after reaction for some time, when arriving cloud point, add 99.5% trolamine 17kg, stirred discharging 15 minutes.
After testing, free formaldehyde is 1.06% in the product, and free-phenol is 0.01%, and solid content is 66.49%.
Embodiment 3
With waste water 116kg(free phenol is 40515.14ppm, free aldehyde is 34332.62ppm, and COD is 241322.32ppm), 99.8% methyl alcohol 20kg adds in the reactor, pH is 9.71 with the adjusting of 40% aqueous sodium hydroxide solution, add 98.0% Paraformaldehyde 96 142kg, stirred 10 minutes, and added 99.9% trimeric cyanamide 260kg again, heating makes material be warming up to 95 ℃, sampling and testing cloud point after reaction for some time, when arriving cloud point, add 99.5% trolamine 36kg, stirred discharging 15 minutes.
After testing, free formaldehyde is 1.01% in the product, and free-phenol is 0.02%, and solid content is 72.66%.
Embodiment 4
With waste water 92kg(free phenol is 43219.26ppm, free aldehyde is 41451.37ppm, and COD is 221361.54ppm), 99.8% methyl alcohol 30kg adds in the reactor, pH is 9.64 with the adjusting of 40% aqueous sodium hydroxide solution, add 98.0% Paraformaldehyde 96 171kg, stirred 10 minutes, and added 99.9% trimeric cyanamide 240kg again, heating makes material be warming up to 97 ℃, sampling and testing cloud point after reaction for some time, when arriving cloud point, add 99.5% trolamine 23kg, stirred discharging 15 minutes.
After testing, free formaldehyde is 1.53% in the product, and free-phenol is 0.01%, and solid content is 81.48%.
Embodiment 5
With waste water 101kg(free phenol is 36345.24ppm, free aldehyde is 38637.91ppm, and COD is 200142.49ppm), 99.8% methyl alcohol 15kg adds in the reactor, pH is 9.59 with the adjusting of 40% aqueous sodium hydroxide solution, add 98.0% Paraformaldehyde 96 155kg, stirred 10 minutes, and added 99.9% trimeric cyanamide 250kg again, heating makes material be warming up to 95 ℃, sampling and testing cloud point after reaction for some time, when arriving cloud point, add 99.5% trolamine 25kg, stirred discharging 15 minutes.
After testing, free formaldehyde is 1.64% in the product, and free-phenol is 0.01%, and solid content is 77.18%.
The above only is preferred embodiment of the present invention, and all equalizations of being done according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. the production method of a terpolycyantoamino-formaldehyde resin, it is characterized in that: reaction raw materials and weight percent are: trimeric cyanamide 30-60%, Paraformaldehyde 96 20-35%, waste water 10-35%, methyl alcohol 1-10%, trolamine 1-10%, surplus is an alkali lye; Described waste water is that resol is produced the waste water that later stage resin dehydration produces;
Production method may further comprise the steps:
(1) in reactor, adds waste water and methyl alcohol, regulate pH to 9.5-10, add Paraformaldehyde 96 then, stirred 5-10 minute with alkali lye;
(2) add trimeric cyanamide in the reaction solution of step (1), heating makes material be warming up to 90-100 ℃ and constant temperature;
(3) sampling and testing cloud point adds trolamine when arriving cloud point, stirred discharging 10-15 minute.
2. the production method of terpolycyantoamino-formaldehyde resin according to claim 1, it is characterized in that: the phenol content of described waste water is 5000ppm-100000ppm, and aldehyde is 5000ppm-100000ppm, and COD is 100000-400000ppm.
3. the production method of terpolycyantoamino-formaldehyde resin according to claim 1, it is characterized in that: described alkali lye is that massfraction is 40% sodium hydroxide solution.
4. the production method of terpolycyantoamino-formaldehyde resin according to claim 1, it is characterized in that: the weight percent of described trimeric cyanamide is preferably 35-55%.
5. the production method of terpolycyantoamino-formaldehyde resin according to claim 1, it is characterized in that: the weight percent of described waste water is preferably 15-33%.
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| CN201310167494.8A CN103214641B (en) | 2013-05-09 | 2013-05-09 | Production method of melamine-formaldehyde resin |
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| CN201310167494.8A CN103214641B (en) | 2013-05-09 | 2013-05-09 | Production method of melamine-formaldehyde resin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106758A (en) * | 1986-10-20 | 1987-04-22 | 沈阳化工学院 | A kind of synthetic method of resol |
| CN102241802A (en) * | 2011-04-28 | 2011-11-16 | 北京化工大学 | Comprehensive utilization of phenol-containing wastewater |
| CN102604325A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Tripolycyanamide formaldehyde moulding compound and preparation method thereof |
| CN102898778A (en) * | 2012-09-07 | 2013-01-30 | 南通紫鑫实业有限公司 | Preparation method for melamine formaldehyde resin closed-cell foam |
-
2013
- 2013-05-09 CN CN201310167494.8A patent/CN103214641B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106758A (en) * | 1986-10-20 | 1987-04-22 | 沈阳化工学院 | A kind of synthetic method of resol |
| CN102241802A (en) * | 2011-04-28 | 2011-11-16 | 北京化工大学 | Comprehensive utilization of phenol-containing wastewater |
| CN102604325A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Tripolycyanamide formaldehyde moulding compound and preparation method thereof |
| CN102898778A (en) * | 2012-09-07 | 2013-01-30 | 南通紫鑫实业有限公司 | Preparation method for melamine formaldehyde resin closed-cell foam |
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