CN110527044A - Second etherified amino resins and its production method - Google Patents
Second etherified amino resins and its production method Download PDFInfo
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- CN110527044A CN110527044A CN201810499495.5A CN201810499495A CN110527044A CN 110527044 A CN110527044 A CN 110527044A CN 201810499495 A CN201810499495 A CN 201810499495A CN 110527044 A CN110527044 A CN 110527044A
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- formaldehyde
- melamine
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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
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
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- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Second etherified amino resins and its production method, comprising: utilize the low melamine methylol of high-concentration formaldehyde continuous production；The above-mentioned low melamine methylol of etherization simultaneously controls pH value by acetic acid and ammonium acetate；Acetylacetone,2,4-pentanedione is added to eliminate extra formaldehyde；Dealcoholysis dehydration is to obtain amino resins.Amino resins produced according to the present invention, it is no matter very excellent in terms of content of formaldehyde, antistatic property or autohemagglutination, suitable for a variety of conventional coating, good water solubility and at low cost.
Description
Technical field
The present invention relates to the industrialization environmental protection of amino resins productions.
Background technique
Etherified amino resins are synthesized using melamine such as hexamethylolmelamine or low melamine methylol etc.,
It may refer to the patent or patent application CN 103739563B, CN 103739803B, CN103709111B, CN before applicant
105968283A, CN105968281A, CN105968282A and CN106008870A are also complete to introduce it in a manner of herein
Portion's content.In addition, CN103102466A and CN105585684A etc. also discloses the synthesis of high imino group etherified amino resins
Method.But the above method that there are content of formaldehyde is higher, etherificate and condensation reaction poor selectivity, imino content are not high enough, at
The problems such as this height, waste discharge.
Summary of the invention
The object of the present invention is to provide a kind of production methods of amino resins, can at least overcome the above-mentioned prior art to mention
And certain defect.
The production method of amino resins according to the present invention, comprising:
1) formaldehyde and melamine are added in hydroxylation reaction kettle, so that the molar ratio of melamine and formaldehyde is 1:3~4
Left and right；
2) adjusting reacting solution pH value in hydroxylation reaction kettle is between 7 to 8；
3) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, reacts 2~3 hours；
4) centrifuge is introduced into after reaction solution is cooling to be centrifuged, obtain low melamine methylol and mother
Liquid；
5) mother liquor is returned in hydroxylation reaction kettle；
6) high-concentration formaldehyde and melamine are added in hydroxylation reaction kettle, so that the molar ratio of melamine and formaldehyde is still
For 1:3~4 or so, and formaldehyde (in reaction kettle in reaction solution) content remains 20% or so；
7) step 2) is repeated to 6) with the low melamine methylol of continuous production；
8) the low melamine methylol of ethyl alcohol and above-mentioned production is added in etherifying reactor, so that low methylol melamine
The molar ratio of amine and ethyl alcohol is 1:(4~5) left and right；
9) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, first reacts 10~20 minutes (pH value is 7 or so)；
10) in etherifying reactor be added equimolar ratio acetic acid and ammonium acetate by reacting solution pH value be adjusted to 5~6 a left side
It is right；
It 11) is 50 DEG C or so by the control of reaction solution temperature, the reaction was continued 0.5~1 hour；
12) acetylacetone,2,4-pentanedione is added in etherifying reactor again, wherein the molar ratio of acetylacetone,2,4-pentanedione and the ethyl alcohol of above-mentioned addition
In 1:500 hereinafter, 55 DEG C of reaction temperature or so of control, the reaction was continued 10~30 minutes；
13) pH value of solution is adjusted in etherifying reactor to 8~9；
14) at 75~95 DEG C of temperature and vacuum condition to solution dealcoholysis 0.5~3h of dehydration in etherifying reactor, from
And obtain amino resins.
In accordance with the present production process, above-mentioned steps 1) used in formaldehyde can be 40% or less (quality hundred of concentration
Point ratio) formalin；High-concentration formaldehyde used in step 6) is preferably prepared in situ and the formaldehyde of 60% or more concentration
Aqueous solution.
In accordance with the present production process, the molar ratio of acetylacetone,2,4-pentanedione and the ethyl alcohol of above-mentioned addition is preferably in 1:800 to 1:
Between 1000.
The present invention is using the low melamine methylol of solid-state as intermediate raw material come synthetic amino resin, it is ensured that product matter
Amount, while reducing waste water and waste liquid yield.
The present invention recycles mother liquor using high-concentration formaldehyde by controlling the molar ratio range of melamine and formaldehyde
Realize low cost, zero-emission, the low melamine methylol of industrialized production.
The present invention passes through the catalyst combination of acetic acid and ammonium acetate, accurately selects and control pH value range, promotes etherificate anti-
Condensation reaction is inhibited while answering to the maximum extent, to realize the industrialized production for the amino resins haveing excellent performance.
The present invention utilizes the ammonium acetate of above-mentioned addition by the way that a small amount of acetylacetone,2,4-pentanedione is finally added in etherifying reactor
Extra formaldehyde is converted pentanedione substance by catalytic action, to essentially eliminate the free formaldehyde in resin.
Present invention amino resins produced to have antistatic effect, presses down simultaneously due to containing ammonium salt (ammonium acetate)
Amino resins autohemagglutination effect is made, product stability also significantly improves.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, it will be understood by those skilled in the art that being described below
Embodiment be intended merely to more fully understand and implement the present invention, not be used to any restrictions are made to the present invention.
The production of low melamine methylol intermediate raw material
Formaldehyde and melamine are added first in hydroxylation reaction kettle, so that the molar ratio of melamine and formaldehyde is 1:3
~4 or so；
It adds alkali such as sodium hydroxide reacting solution pH value in reaction kettle is adjusted between 7 to 8；
Controlling reactor temperature is 50 DEG C~70 DEG C, is reacted 2~3 hours；
Centrifuge is introduced into after reaction solution is cooling to be centrifuged, obtain low melamine methylol wet feed and
Mother liquor；
Mother liquor is returned again in reaction kettle；
High-concentration formaldehyde and melamine is added in a kettle again, so that the molar ratio of melamine and formaldehyde is still kept
For 1:3~4 or so, and mass content of the formaldehyde in reaction kettle in reaction solution remains 20% or so；
It is wet among the low melamine methylol to repeat the above steps with continuous production based on trimethylol melamine
Material.
The formaldehyde started with can be the formalin of 40% or less concentration (mass percent)；Then use
High-concentration formaldehyde can be to be prepared in situ and the formalin of 60% or more concentration.Can also all it make in certain whole process
Use high-concentration formaldehyde.
Etherification procedure
Ethyl alcohol and above-mentioned low melamine methylol is added in etherifying reactor, so that low melamine methylol and ethyl alcohol
Molar ratio be 1:(4~5) left and right；
It is 50 DEG C~70 DEG C by the control of reaction solution temperature, preferably 60 DEG C or so, first reacts that (pH value is 10~20 minutes
7 or so)；
Again in etherifying reactor be added equimolar ratio acetic acid and ammonium acetate by reacting solution pH value be adjusted to 5~6 a left side
It is right；
It is 50 DEG C or so by the control of reaction solution temperature, the reaction was continued 0.5~1 hour.
Resin modified process
A small amount of acetylacetone,2,4-pentanedione is finally added in etherifying reactor, (the molar ratio of acetylacetone,2,4-pentanedione and the ethyl alcohol of above-mentioned addition
In 1:500 or less), 55 DEG C of reaction temperature or so are controlled, the reaction was continued 10~30 minutes.
Last handling process
PH value of solution is adjusted in etherifying reactor to 8~9；
To solution dealcoholysis 0.5~3h of dehydration in etherifying reactor at 75~95 DEG C of temperature and vacuum condition, thus
Obtain amino resins.
Amino resins produced according to the present invention, no matter content of formaldehyde (detection level be less than 3mg/100g), resist it is quiet
It is very excellent in terms of electrical property (surface resistivity is between 10E6-10E10 ohm-sq) or autohemagglutination, it is suitable for
A variety of routine coating, good water solubility and at low cost.
Claims (4)
1. a kind of production method of amino resins, comprising:
1) formaldehyde and melamine are added in hydroxylation reaction kettle, so that the molar ratio of melamine and formaldehyde is 1:3~4 left
It is right；
2) adjusting reacting solution pH value in hydroxylation reaction kettle is between 7 to 8；
3) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, reacts 2~3 hours；
4) centrifuge is introduced into after reaction solution is cooling to be centrifuged, obtain low melamine methylol and mother liquor；
5) mother liquor is returned in hydroxylation reaction kettle；
6) high-concentration formaldehyde and melamine are added in hydroxylation reaction kettle, so that the molar ratio of melamine and formaldehyde is still 1:
3~4 or so, and content of formaldehyde remains 20% or so；
7) step 2) is repeated to 6) with the low melamine methylol of continuous production；
8) etherifying reactor be added ethyl alcohol and above-mentioned production low melamine methylol so that low melamine methylol and
The molar ratio of ethyl alcohol is 1:(4~5) left and right；
9) it is 50 DEG C~70 DEG C by the control of reaction solution temperature, first reacts 10~20 minutes (pH value is 7 or so)；
10) acetic acid of equimolar ratio is added in etherifying reactor and reacting solution pH value is adjusted to 5~6 or so by ammonium acetate；
It 11) is 50 DEG C or so by the control of reaction solution temperature, the reaction was continued 0.5~1 hour；
12) acetylacetone,2,4-pentanedione is added in etherifying reactor again, wherein the molar ratio of acetylacetone,2,4-pentanedione and the ethyl alcohol of above-mentioned addition is 1:
500 hereinafter, 55 DEG C of reaction temperature or so of control, the reaction was continued 10~30 minutes；
13) pH value of solution is adjusted in etherifying reactor to 8~9；
14) to solution dealcoholysis 0.5~3h of dehydration in etherifying reactor at 75~95 DEG C of temperature and vacuum condition, thus
To amino resins.
2. production method according to claim 1, wherein formaldehyde used in step 1) is 40% or less (quality percentage of concentration
Than) formalin；High-concentration formaldehyde used in step 6) is to be prepared in situ and the formalin of 60% or more concentration.
3. production method according to claim 1, wherein the molar ratio of acetylacetone,2,4-pentanedione and the ethyl alcohol of above-mentioned addition is in 1:800 to 1:
Between 1000.
4. a kind of amino resins is produced according to the method for one of the claims 1-3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810499495.5A CN110527044A (en) | 2018-05-23 | 2018-05-23 | Second etherified amino resins and its production method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810499495.5A CN110527044A (en) | 2018-05-23 | 2018-05-23 | Second etherified amino resins and its production method |
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| CN110527044A true CN110527044A (en) | 2019-12-03 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774299A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Methyl etherified melamino-formaldehyde resin production technology |
| CN107325061A (en) * | 2017-08-15 | 2017-11-07 | 重庆建峰浩康化工有限公司 | The production technology of pentamethylol melamine |
| CN107353382A (en) * | 2017-09-14 | 2017-11-17 | 重庆建峰浩康化工有限公司 | High Amino resin is synthesized using trimethylol melamine |
-
2018
- 2018-05-23 CN CN201810499495.5A patent/CN110527044A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774299A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Methyl etherified melamino-formaldehyde resin production technology |
| CN107325061A (en) * | 2017-08-15 | 2017-11-07 | 重庆建峰浩康化工有限公司 | The production technology of pentamethylol melamine |
| CN107353382A (en) * | 2017-09-14 | 2017-11-17 | 重庆建峰浩康化工有限公司 | High Amino resin is synthesized using trimethylol melamine |
Non-Patent Citations (2)
| Title |
|---|
| 赵广超主编: "《环境学实验》", 31 December 2016 * |
| 邓舜扬编著: "《纺织化学品》", 31 August 2001 * |
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