CN117126356A - Preparation method of amino resin and amino resin - Google Patents
Preparation method of amino resin and amino resin Download PDFInfo
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- CN117126356A CN117126356A CN202311401181.4A CN202311401181A CN117126356A CN 117126356 A CN117126356 A CN 117126356A CN 202311401181 A CN202311401181 A CN 202311401181A CN 117126356 A CN117126356 A CN 117126356A
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- 229920003180 amino resin Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004321 preservation Methods 0.000 claims abstract description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 6
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application discloses a preparation method of amino resin and the amino resin, wherein the method comprises the following steps: adding sodium hydroxide solution into formaldehyde solution and stirring; when the pH value threshold range is reached, preserving heat in a preset first temperature threshold range; after the heat preservation is finished, adding melamine; adding benzoguanamine and stirring; adding formaldehyde solution again and stirring, and controlling the temperature within a second temperature threshold range; stirring and heating to a third temperature threshold range to obtain clarified amino resin; when the clear amino resin viscosity reaches a preset viscosity value, the reaction is complete. Greatly prolongs the storage time of the amino resin.
Description
Technical Field
The application relates to the technical field of amino resins, in particular to a preparation method of an amino resin and the amino resin.
Background
The amino resin is a thermosetting resin obtained by polycondensation of an amino group-containing compound with formaldehyde or the like. The varnish has light color, high luster, high hardness and good electrical insulation property; the color paint has plump appearance, bright color, excellent adhesive force, good aging resistance and good resistance; meanwhile, the method has short drying time and convenient construction, and is favorable for continuous operation of painting. At present, the method is widely applied to vehicles, household appliances, light industrial products, machine tools and the like.
Aiming at the existing amino resin, the synthetic components of the amino resin generally comprise formaldehyde solution, melamine and alkali liquor, and then the amino resin is synthesized by modification treatment such as etherification, etc., and the amino resin has the problems of short storage period, for example, melamine formaldehyde resin is in a clear state during generation, but the storage period generally becomes turbid and is solidified about half a day, and continuous use in alternate days cannot be ensured, so that the production and use of the amino resin are difficult to independently operate. That is, the temporary manufacturing is needed when the use is needed, and the use amount is only enough, so that the manufacturing amount is basically wasted if the use amount is more.
How to solve the problem of short storage period of the existing amino resin has become a technical problem to be solved in the industry.
Disclosure of Invention
In order to at least solve the technical problems, the application aims to provide a preparation method of amino resin, which greatly prolongs the storage time of the amino resin.
In order to achieve the above object, the preparation method of the amino resin provided by the application comprises the following steps:
adding sodium hydroxide solution into formaldehyde solution and stirring;
when the pH value threshold is reached, preserving heat in a preset first temperature threshold range;
after the heat preservation is finished, adding melamine;
adding benzoguanamine and stirring;
adding formaldehyde solution again and stirring, and controlling the temperature within a second temperature threshold range;
stirring and heating to a third temperature threshold range to obtain clarified amino resin;
when the clear amino resin viscosity reaches a preset viscosity value, the reaction is complete.
Further, the formaldehyde solution is 36% by mass of an aqueous formaldehyde solution.
Further, in the step of adding a sodium hydroxide solution to the formaldehyde solution and stirring, the molar mass of the formaldehyde solution is 96 to 120mol.
Further, the molar concentration of the sodium hydroxide solution was 1mol/L.
Further, the pH threshold is 9-9.5.
Further, the first temperature threshold is in the range of 20-25 ℃.
Further, the melamine has a molar mass of 40-48mol.
Further, the benzomelamine has a molar mass of 16-20mol.
Further, the formaldehyde solution is added again and stirred, and in the step of controlling the temperature within the second temperature threshold range, the molar mass of the formaldehyde solution is 44-52mol.
Further, the second temperature threshold is in the range of 30-40 ℃.
Further, in the step of stirring and heating to within the third temperature threshold range to obtain a clarified amino resin, the heating rate is 0.4 to 1 ℃/min.
Further, the third temperature threshold range is 70-75 ℃.
Further, the preset viscosity value is not lower than 260 centipoise.
Further, after the step of completing the reaction when the clarified amino resin viscosity reaches a preset viscosity value, it further comprises:
triethanolamine was added.
In order to achieve the above purpose, the embodiment of the application also provides an amino resin, which is prepared by adopting the preparation method of the amino resin.
The preparation method of the amino resin provided by the embodiment of the application comprises the following steps: adding sodium hydroxide solution into formaldehyde solution and stirring; when the pH value threshold is reached, preserving heat in a preset first temperature threshold range; after the heat preservation is finished, adding melamine; adding benzoguanamine and stirring; adding formaldehyde solution again and stirring, and controlling the temperature within a second temperature threshold range; stirring and heating to a third temperature threshold range to obtain clarified amino resin; when the clear amino resin viscosity reaches a preset viscosity value, the reaction is complete. The storage time of the amino resin is greatly prolonged to 15 days, and the use convenience of the amino resin is greatly improved; the waste phenomenon is avoided; the advantages of the methylol melamine and the methylol benzoguanamine are achieved, namely the strength and the toughness are achieved.
Detailed Description
It should be understood that the various steps recited in the method embodiments of the present application may be performed in a different order and/or performed in parallel. Furthermore, method embodiments may include additional steps and/or omit performing the illustrated steps. The scope of the application is not limited in this respect.
The term "including" and variations thereof as used herein are intended to be open-ended, i.e., including, but not limited to. The term "based on" is based at least in part on. The term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one additional embodiment"; the term "some embodiments" means "at least some embodiments. Related definitions of other terms will be given in the description below.
It should be noted that references to "one", "a plurality" and "a plurality" in this disclosure are intended to be illustrative rather than limiting, and those skilled in the art will appreciate that "one or more" is intended to be construed as "one or more" unless the context clearly indicates otherwise. "plurality" is understood to mean two or more.
The embodiment of the application provides a preparation method of amino resin, which comprises the following steps:
adding sodium hydroxide solution into formaldehyde solution and stirring;
when the pH value reaches a threshold range, preserving heat in a preset first temperature threshold range;
after the heat preservation is finished, adding melamine;
adding benzoguanamine and stirring;
adding formaldehyde solution again and stirring, and controlling the temperature within a second temperature threshold range;
stirring and heating to a third temperature threshold range to obtain clarified amino resin;
when the clear amino resin viscosity reaches a preset viscosity value, the reaction is complete.
Example 1
The preparation method of the amino resin comprises the following steps:
to a 20L reaction vessel, a formaldehyde solution having a molar mass of 96 to 120mol, wherein the formaldehyde solution is a 36% by mass aqueous formaldehyde solution, for example, a 36% by mass aqueous formaldehyde solution having a molar mass of 115mol, for example, 9.6kg of a 36% by mass aqueous formaldehyde solution, is added, and stirring is started.
Dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the reaction kettle, wherein the temperature in the reaction kettle is controlled to be 20-25 ℃ in the dropwise adding process, and the dropwise adding time is more than 3 hours.
When the pH value reaches 9.0-9.5, the dropwise addition of sodium hydroxide solution is stopped, for example, the temperature is constantly controlled at 25 ℃ so that the reaction is continued, for example, the reaction is continued for 30-40 minutes.
To the reaction vessel, a melamine white powder having a molar mass of 40 to 48mol, for example a melamine white powder having a molar mass of 44.4mol, for example 5.6kg of melamine white powder, is added in batches and stirred well, and the reaction is continued at this temperature for 50 to 70 minutes.
To the reaction vessel, a benzoguanamine powder having a molar mass of 16 to 20mol, for example 18.8mol, is added, for example correspondingly 3.5kg, and stirred for 30 to 40 minutes.
Then, an aqueous 36% formaldehyde solution, for example, 48mol of an aqueous 36% formaldehyde solution, for example, 4.0kg of an aqueous 36% formaldehyde solution, is added to the reaction vessel, and the mixture is stirred for a further 30 to 40 minutes.
The reaction vessel is heated such that the temperature in the reaction vessel is raised to 30-40 ℃, for example by 25 minutes of heating, such that the temperature in the reaction vessel reaches 30 ℃, and stirring is carried out for an additional 30-40 minutes at 30 ℃.
Slowly heating the reaction kettle, for example, the heating speed is 0.4-1 ℃/min; for example, after 100 minutes of heating, the temperature in the reaction vessel is stabilized at 70-75 ℃. For example, the temperature is controlled to be about 72 ℃, and the reaction is carried out for 40 minutes at 72 ℃ to obtain clear and transparent amino resin.
Wherein, formaldehyde aqueous solution reacts with melamine to obtain methylolmelamine, namely substitution reaction, and the reaction chemical formula is as follows:
;
the formaldehyde solution and the melamine can obtain good reaction in the heating process, and substitution reaction is carried out on the formaldehyde solution and the melamine to generate the methylolmelamine.
The methylolmelamines of different degrees of substitution react with each other, i.e. polymerize.
The methylol melamine is polymerized to form a netlike polymer, which has high strength, high hardness and high brittleness.
The benzoguanamine and formaldehyde solution undergo substitution reaction according to the same mechanism to generate methylol benzoguanamine, and the reaction chemical formula is as follows:
；
the methylol benzoguanamine with different degrees of substitution react with each other, namely, polymerization reaction.
The methylol benzoguanamine is polymerized to form chain polymer, so that the toughness can be improved and the bending resistance can be increased.
The chain polymer and the netlike polymer are mixed, and have the advantages of both, namely the strength and the toughness.
The benzomelamine reacts with formaldehyde solution under heating.
It is understood that after the melamine and the benzoguanamine are uniformly stirred, heating is performed, and then substitution reaction and polymerization reaction, that is, reaction of melamine and formaldehyde solution and reaction of benzoguanamine and formaldehyde solution are performed simultaneously.
The reaction is completed when the viscosity of the clear transparent amino resin reaches not less than 260 centipoise.
The triethanolamine is added, so that the pH value of the amino resin can be maintained in a better state for a long time after the triethanolamine is added, namely, the pH value is maintained at a preset pH threshold value, for example, the pH value of the amino resin is maintained at about 9; it is understood that triethanolamine is added to maintain the pH of the amino resin in a stable state for a long period of time.
After stirring uniformly, stopping heating, and taking out and storing from the reaction kettle; the whole body after cooling is colorless and transparent, and can be stored for 15 days in the state.
According to the preparation method of the amino resin, under the condition that no new substance is added, the prepared amino resin can be stored for 15 days and still be in a usable state, namely, still be in a clear liquid state after 15 days of generation.
According to the preparation method of the amino resin, the amino resin prepared on the premise of not using urea, urotropine, polyethylene glycol and the like can be kept in a clear liquid state for 15 days.
Example 2
The preparation method of the amino resin comprises the following steps:
an aqueous formaldehyde solution with a molar mass of 115mol and a mass ratio of 36% was added to the reaction vessel, and stirring was started, which was accomplished by stirring mechanisms.
Dropwise adding sodium hydroxide solution with the molar concentration of 1mol/L into formaldehyde water solution, and controlling the temperature in the reaction kettle within a first temperature threshold value, for example, controlling the temperature to be 25 ℃ when adding the sodium hydroxide solution dropwise.
When the pH reaches the threshold value, for example, when the pH reaches 9.2 after 3 hours and 20 minutes of dropwise addition, dropwise addition of the sodium hydroxide solution is stopped, and the temperature is constantly controlled within a first temperature threshold value so as to continue the reaction, for example, the reaction time is further 24 minutes.
To the reaction vessel was added in portions a melamine white powder having a molar mass of 44.4mol and the reaction was continued at this temperature for 54 minutes.
To the reaction vessel was added benzoguanamine powder having a molar mass of 18.8mol and stirred for 30 minutes.
Then, an aqueous formaldehyde solution having a molar mass of 48mol and a mass ratio of 36% was added to the reaction vessel, followed by stirring for another 30 minutes.
Heating the reaction kettle to enable the temperature in the reaction kettle to rise to 30 ℃, for example, heating for 25 minutes to enable the temperature in the reaction kettle to reach 30 ℃, and stirring for 28 minutes at 30 ℃;
slowly heating the reaction kettle, for example, the heating speed is 0.4-1 ℃/min; for example, after heating for 100 minutes, the temperature in the reaction kettle is stabilized at about 73 ℃, and the reaction is carried out for 31 minutes at 73 ℃ to obtain clear and transparent amino resin.
The reaction is completed when the viscosity of the clear transparent amino resin reaches not less than 260 centipoise.
And then adding triethanolamine, wherein the triethanolamine is an organic base, so that the pH value of the amino resin can be maintained in a better state for a long time after the triethanolamine is added, namely, the pH value is maintained within a preset pH threshold value range, and the pH threshold value is 8-10, for example, the pH value is maintained to be about 9.
After stirring uniformly, stopping heating, and taking out and storing from the reaction kettle; the whole body after cooling is colorless and transparent, and can be stored for 15 days in the state.
According to the preparation method of the amino resin, under the condition that no new substance is added, the prepared amino resin can be stored for 15 days and still be in a usable state, namely, still be in a clear liquid state after 15 days of generation.
Example 3
The preparation method of the amino resin comprises the following steps:
an aqueous formaldehyde solution having a molar mass of 100mol and a mass ratio of 36% was charged into a 20L reactor, and stirring was started.
Dropwise adding sodium hydroxide solution with the molar concentration of 1mol/L into the reaction kettle, wherein the temperature in the reaction kettle is controlled to be 25 ℃ in the dropwise adding process, and the dropwise adding time is 3 hours and 22 minutes.
When the pH value reaches 9.0, the dropwise addition of the sodium hydroxide solution is stopped, and the temperature is constantly controlled at 23 ℃ to continue the reaction, for example, the reaction time is 22 minutes again.
To the reaction vessel was added in portions a melamine white powder having a molar mass of 46mol and the reaction was continued at this temperature for 60 minutes.
To the reaction vessel was added benzoguanamine powder having a molar mass of 16mol and stirred for 30 minutes.
Then, an aqueous formaldehyde solution having a molar mass of 50mol and a mass ratio of 36% was added to the reaction vessel, followed by stirring for another 30 minutes.
The reaction vessel is heated such that the temperature in the reaction vessel is raised to 35 ℃, for example by 25 minutes of heating, such that the temperature in the reaction vessel reaches 35 ℃, and stirring is carried out for an additional 27 minutes at 35 ℃.
Slowly heating the reaction kettle, for example, the heating speed is 0.4-1 ℃/min; for example, after heating for 100 minutes, the temperature in the reaction kettle is stabilized at about 72 ℃, and the reaction is carried out for 36 minutes at 72 ℃ to obtain clear and transparent amino resin.
The reaction is completed when the viscosity of the clear transparent amino resin reaches not less than 260 centipoise.
And then adding triethanolamine, wherein the triethanolamine is an organic base, so that the pH value of the amino resin can be maintained in a better state for a long time after the triethanolamine is added, namely, the pH value is maintained within a preset pH threshold value range, and the pH threshold value is 8-10, for example, the pH value is maintained to be about 9.
After stirring uniformly, stopping heating, and taking out and storing from the reaction kettle; the whole body after cooling is colorless and transparent, and can be stored for 15 days in the state.
According to the preparation method of the amino resin, under the condition that no new substance is added, the prepared amino resin can be stored for 15 days and still be in a usable state, namely, still be in a clear liquid state after 15 days of generation.
Example 4
The preparation method of the amino resin comprises the following steps:
an aqueous formaldehyde solution having a molar mass of 110mol and a mass ratio of 36% was charged into a 20L reactor, and stirring was started.
Dropwise adding sodium hydroxide solution with the molar concentration of 1mol/L into the reaction kettle, wherein the temperature in the reaction kettle is controlled to be 25 ℃ in the dropwise adding process, and the dropwise adding time is 3 hours and 25 minutes.
When the pH value reaches 9.4, the dropwise addition of the sodium hydroxide solution is stopped, and the temperature is constantly controlled at 24 ℃ to continue the reaction, for example, the reaction time is 23 minutes again.
To the reaction vessel was added in portions a melamine white powder having a molar mass of 47mol and the reaction was continued at this temperature for 58 minutes.
To the reaction vessel was added benzoguanamine powder having a molar mass of 19mol and stirred for 30 minutes.
An aqueous 36% formaldehyde solution, for example, 4.0kg of an aqueous 36% formaldehyde solution, having a molar mass of 48mol, was added to the reaction vessel, followed by stirring for another 30 minutes.
The reaction vessel is heated such that the temperature in the reaction vessel is raised to 30 ℃, for example by 25 minutes of heating, such that the temperature in the reaction vessel reaches 30 ℃, and stirring is carried out for an additional 24 minutes at 30 ℃.
Slowly heating the reaction kettle, for example, the heating speed is 0.4-1 ℃/min; for example, after 100 minutes of heating, the temperature in the reaction kettle is stabilized at about 74 ℃, and the reaction is carried out for 27 minutes at 74 ℃ to obtain clear and transparent amino resin.
The reaction is completed when the viscosity of the clear transparent amino resin reaches not less than 260 centipoise.
And then adding triethanolamine, wherein the triethanolamine is an organic base, so that the pH value of the amino resin can be maintained in a better state for a long time after the triethanolamine is added, namely, the pH value is maintained within a preset pH threshold value range, and the pH threshold value is 8-10, for example, the pH value is maintained to be about 9.
After stirring uniformly, stopping heating, and taking out and storing from the reaction kettle; the whole body after cooling is colorless and transparent, and can be stored for 15 days in the state.
According to the preparation method of the amino resin, under the condition that no new substance is added, the prepared amino resin can be stored for 15 days and still be in a usable state, namely, still be in a clear liquid state after 15 days of generation.
For example, no newly added adjuvants are required, including:
example 5
The preparation method of the amino resin comprises the following steps:
to a 20L reaction vessel was added a 36% aqueous formaldehyde solution having a molar mass of 115mol and a mass ratio of 36%, for example, 9.6kg of the 36% aqueous formaldehyde solution, and stirring was started.
Dropwise adding sodium hydroxide solution with the molar concentration of 1mol/L into the reaction kettle, wherein the temperature in the reaction kettle is controlled to be 25 ℃ in the dropwise adding process, and the dropwise adding time is 3 hours and 28 minutes.
When the pH reaches 9.5, the dropwise addition of sodium hydroxide solution is stopped, and the temperature is constantly controlled at 25℃to continue the reaction, for example, for a further reaction time of 27 minutes.
To the reaction vessel, a melamine white powder having a molar mass of 44.4mol, for example 5.6kg of melamine white powder, is added in portions and the reaction is continued at this temperature for 55 minutes.
To the reaction vessel was added a benzoguanamine powder having a molar mass of 18.8mol, for example, 3.5kg of benzoguanamine powder, and stirred for 30 minutes.
An aqueous 36% formaldehyde solution, for example, 4.0kg of an aqueous 36% formaldehyde solution, having a molar mass of 48mol, was added to the reaction vessel, followed by stirring for another 30 minutes.
The reaction vessel is heated such that the temperature in the reaction vessel is raised to 30 ℃, for example by 25 minutes of heating, such that the temperature in the reaction vessel reaches 30 ℃, and stirring is carried out for an additional 26 minutes at 30 ℃.
Slowly heating the reaction kettle, for example, the heating speed is 0.4-1 ℃/min; for example, after heating for 100 minutes, the temperature in the reaction kettle is stabilized at about 73 ℃, and the reaction is carried out at 73 ℃ for 29 minutes to obtain clear and transparent amino resin.
The reaction is completed when the viscosity of the clear transparent amino resin reaches not less than 260 centipoise.
And then adding triethanolamine, wherein the triethanolamine is an organic base, so that the pH value of the amino resin can be maintained in a better state for a long time after the triethanolamine is added, namely, the pH value is maintained within a preset pH threshold value range, and the pH threshold value is 8-10, for example, the pH value is maintained to be about 9.
After stirring uniformly, stopping heating, and taking out and storing from the reaction kettle; the whole body after cooling is colorless and transparent, and can be stored for 15 days in the state.
According to the preparation method of the amino resin, under the condition that no new substance is added, the prepared amino resin can be stored for 15 days and still be in a usable state, namely, still be in a clear liquid state after 15 days of generation.
Example 6
Example 6 is an amino resin prepared by the method of preparing an amino resin of the above examples.
The amino resin produced by adopting the conventional process has short storage time, the usable time of the amino resin is half a day to one day, and the amino resin gradually becomes turbid from clarification and finally solidifies along with the time extension; the amino resin provided by the embodiment of the application is clear liquid with certain viscosity, has the advantage of long storage and use time, still keeps clear liquid after 15 days of generation, and meets the actual industrial application.
In order to fully embody the excellent storage performance of the amino resin of the embodiment of the application, the amino resin of the embodiment of the application can be stored for use time comparison with the amino resin generated by a conventional process method:
TABLE 1
| Can preserve the service time (day) | |
| Amino resin produced by conventional process | 1 |
| Amino resin produced by the procedure of example 1 | 18 |
| Amino resin produced by the procedure of example 2 | 18 |
| Amino resin produced by the procedure of example 3 | 17 |
| Amino resin produced by the procedure of example 4 | 15 |
| Amino resin produced by the procedure of example 5 | 17 |
As can be seen from the above Table 1, the amino resins of the examples of the present application have a shelf life of 15 days or longer, which is far ahead of the amino resins produced by the prior art.
Although the embodiments of the present application are described above, the present application is not limited to the embodiments which are used for understanding the present application. Any person skilled in the art can make any modification and variation in form and detail without departing from the spirit and scope of the present disclosure, but the scope of the present disclosure is to be determined by the appended claims.
Claims (15)
1. The preparation method of the amino resin is characterized by comprising the following steps:
adding sodium hydroxide solution into formaldehyde solution and stirring;
when the pH value threshold range is reached, preserving heat in a preset first temperature threshold range;
after the heat preservation is finished, adding melamine;
adding benzoguanamine and stirring;
adding the formaldehyde solution again and stirring, and controlling the temperature within a second temperature threshold range;
stirring and heating to a third temperature threshold range to obtain clarified amino resin;
when the clear amino resin viscosity reaches a preset viscosity value, the reaction is complete.
2. The method for producing an amino resin according to claim 1, wherein the formaldehyde solution is an aqueous formaldehyde solution having a mass ratio of 36%.
3. The method for producing an amino resin according to claim 1, wherein in the step of adding a sodium hydroxide solution to a formaldehyde solution and stirring, the molar mass of the formaldehyde solution is 96 to 120mol.
4. The method for producing an amino resin according to claim 1, wherein the molar concentration of the sodium hydroxide solution is 1mol/L.
5. The method for producing an amino resin according to claim 1, wherein the pH threshold value is 9 to 9.5.
6. The method of producing an amino resin according to claim 1, wherein the first temperature threshold value is in the range of 20 to 25 ℃.
7. The method for producing an amino resin according to claim 1, wherein the melamine has a molar mass of 40 to 48mol.
8. The method for producing an amino resin according to claim 1, wherein the benzomelamine has a molar mass of 16 to 20mol.
9. The method for producing an amino resin according to claim 1, wherein in the step of adding the formaldehyde solution again and stirring while controlling the temperature within the second temperature threshold range, the molar mass of the formaldehyde solution is 44 to 52mol.
10. The method for producing an amino resin according to claim 1, wherein the second temperature threshold value is in the range of 30 to 40 ℃.
11. The method according to claim 1, wherein in the step of stirring and heating to a temperature within a third temperature threshold range to obtain a clarified amino resin, the heating rate is 0.4 to 1 ℃/min.
12. The method for producing an amino resin according to claim 1, wherein the third temperature threshold value is in the range of 70 to 75 ℃.
13. The method for producing an amino resin according to claim 1, wherein the preset viscosity value is not less than 260 cps.
14. The method for preparing an amino resin according to claim 1, wherein after the step of completing the reaction when the clarified amino resin viscosity reaches a preset viscosity value, further comprising:
triethanolamine was added.
15. An amino resin comprising a preparation method of the amino resin according to any one of claims 1 to 14.
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Citations (6)
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| 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 |
| CN104233510A (en) * | 2014-10-16 | 2014-12-24 | 恒天海龙股份有限公司 | Amino resin reinforced cellulosic fiber and preparation method thereof |
| CN105906772A (en) * | 2016-06-16 | 2016-08-31 | 浙江农林大学 | Melamino-formaldehyde resin adhesive and preparation process thereof with internally forming method |
| CN110894272A (en) * | 2019-11-04 | 2020-03-20 | 圣象实业（江苏）有限公司 | Synthesis process of melamine resin for long-storage-period impregnation |
| CN110894273A (en) * | 2019-12-05 | 2020-03-20 | 江苏长顺高分子材料研究院有限公司 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
| CN115926085A (en) * | 2022-12-26 | 2023-04-07 | 佛山市华立龙科技有限公司 | Water-based phenylamine resin and preparation method and application thereof |
-
2023
- 2023-10-26 CN CN202311401181.4A patent/CN117126356A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104233510A (en) * | 2014-10-16 | 2014-12-24 | 恒天海龙股份有限公司 | Amino resin reinforced cellulosic fiber and preparation method thereof |
| CN105906772A (en) * | 2016-06-16 | 2016-08-31 | 浙江农林大学 | Melamino-formaldehyde resin adhesive and preparation process thereof with internally forming method |
| CN110894272A (en) * | 2019-11-04 | 2020-03-20 | 圣象实业（江苏）有限公司 | Synthesis process of melamine resin for long-storage-period impregnation |
| CN110894273A (en) * | 2019-12-05 | 2020-03-20 | 江苏长顺高分子材料研究院有限公司 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
| CN115926085A (en) * | 2022-12-26 | 2023-04-07 | 佛山市华立龙科技有限公司 | Water-based phenylamine resin and preparation method and application thereof |
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