CN117138592A - Preparation method of modified amino resin dehumidifying film, dehumidifying film and application thereof - Google Patents
Preparation method of modified amino resin dehumidifying film, dehumidifying film and application thereof Download PDFInfo
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- CN117138592A CN117138592A CN202310790776.7A CN202310790776A CN117138592A CN 117138592 A CN117138592 A CN 117138592A CN 202310790776 A CN202310790776 A CN 202310790776A CN 117138592 A CN117138592 A CN 117138592A
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- 229920003180 amino resin Polymers 0.000 title claims abstract description 64
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000013067 intermediate product Substances 0.000 claims description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229920002675 Polyoxyl Polymers 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 20
- 238000006266 etherification reaction Methods 0.000 abstract description 8
- -1 methylol compound Chemical class 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000007791 dehumidification Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/268—Drying gases or vapours by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- 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
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
Abstract
The application provides a preparation method of a modified amino resin dehumidifying film, the dehumidifying film and application thereof, wherein the stability of a methylol compound is improved through moderate etherification, and the mechanical property of a finished product can be improved by introducing a proper amount of nonpolar groups; the potassium dichromate is added under the strong acid condition to generate oxidation reaction, so that the moisture permeability of the modified amino resin dehumidifying film can be further improved, the obtained finished product has high moisture rate, high strength, simple operation and high repeatability, and is suitable for industrial mass production.
Description
Technical Field
The application relates to the technical field of dehumidification films, in particular to a preparation method of a modified amino resin dehumidification film, the dehumidification film and application thereof.
Background
The water vapor is commonly existing in natural air, and when the water vapor content in the air exceeds a certain value, metal corrosion and wood mildew can be accelerated; in industrial production, humidity requirements are required for production links and air filled in products, so that the content of water vapor in gas is very necessary to be controlled.
In the prior art, most of the means utilize a dehumidifying film to filter air to reduce the content of water vapor, the dehumidifying film is a component used on a dehumidifier for dehumidifying gas, and the concentration difference of the water vapor between the air and other components is utilized to enable the concentration difference generated by pressure or temperature to be used as driving potential force on two sides of the dehumidifying film, so that the water vapor is fixed to pass through the dehumidifying film, and the dehumidifying film selectively passes through substances in the process of directional passing of the air to realize filtration.
Common dehumidifying films are high molecular polymer films composed of polydisiloxane and polyvinyl alcohol, but the problems of low moisture permeability and poor strength are common at present.
Therefore, a modified amino resin dehumidifying film with high moisture permeability and high strength, and a preparation method and application thereof are needed.
Disclosure of Invention
In order to solve the problems of low moisture permeability and poor strength of the existing dehumidification film, a preparation method of a modified amino resin dehumidification film with high moisture permeability and high strength, the dehumidification film and application thereof are provided, and the following technical scheme is adopted:
a method for preparing a modified amino resin dehumidifying film, comprising:
step 1: adding melamine and methylol butanol solution in a reaction kettle, regulating pH to be 4.0-6.0, adding urea and formaldehyde aqueous solution, heating to 30-35 ℃, and reacting for 2-3h to obtain an intermediate product A, wherein the intermediate product A is obtained;
the melamine and formaldehyde aqueous solution in the step 1 is introduced with hydroxyl groups in the methylol butanol under the weak acidic condition, and the hydroxyl group introduction completeness in the step is mainly limited by time, for example, the reaction time is insufficient, the number of generated hydroxyl groups is small, and the subsequent reaction is not facilitated.
Experiments show that the mixture ratio of 32 parts of melamine, 240 parts of hydroxymethyl butanol solution and 710 parts of formaldehyde aqueous solution is increased to 30 ℃ under the condition of pH=5.0, and the reaction time is 2.5 hours, so that the produced intermediate product A has the highest hydroxyl number and the highest stability of the reaction system, and the moisture permeability of the finished product is improved.
Step 2: heating to 50-90 ℃, adding aniline and potassium dichromate, adjusting the pH value to be 3-4 by strong acid, and reacting for 1-1.5h with heat preservation to obtain an intermediate product B;
urea can generate methylol urea with formaldehyde under the action of acidity, and excessive etherification can cause the finished modified amino resin to lose hydrophilic property, so that the modified amino resin is unfavorable for adsorbing water vapor in air; moderately etherifying and introducing nonpolar groups can improve the mechanical property of the finished product, improve the stability of methylol urea, increase the nonpolar groups after etherification and have high curing speed.
In the process of etherification under the strong acid condition for less than 3 hours, the etherification phenomenon of the product gradually undergoes emulsification, layering and precipitation, the etherification degree can be known by observing the product phenomenon, when the product state is in a uniform emulsification system to be layered, the etherification degree is in the optimal state, namely the system is uniformly emulsified within the time period of 1-1.5 hours, and the strength of the finished product is high at the moment and the moisture permeability of the finished product modified amino resin dehumidifying film cannot be weakened. As can be seen from comparison of the test data of example 1 and comparative example 2 in Table 1, the moisture permeability decreases as the oxidation proceeds when the incubation time in step 2 is changed to 2 hours, because delamination starts to occur when the system exceeds the emulsification point, the equilibrium system is broken, and the moisture permeability is poor.
In addition, potassium dichromate is added under the strong acid condition to promote the oxidation reaction of the system, hydrophilic groups are introduced to improve the polarity of the surface, and the moisture permeability of the modified amino resin dehumidifying film is further improved, and experiments show that when 40 parts of potassium dichromate is added under the acid condition and the system reacts for 1h, the moisture permeability of the finished modified amino resin dehumidifying film is improved by about 50sec/100cc compared with that without oxidation, and the oxidation effect is best. As can be seen from example 1 and comparative example 1 in Table 1, when the addition amount of potassium dichromate was changed to 40 parts and the reaction was carried out for 1 hour at a temperature, the moisture permeability of the finished product was improved by 54sec/100cc.
Step 3: and regulating the pH value of the intermediate product B to 7.0-8.0, adding an infiltrant, a stabilizer and a cellulose dispersion liquid to 55-90 ℃ for reacting for 60-75 min, and after the reaction is finished, decompressing and cooling to obtain the modified amino resin.
The hydrophilic composition system in the application can be enriched by introducing a proper amount of hydrophilic substance cellulose dispersion liquid, and the moisture permeability of the modified amino resin dehumidifying film can be further improved.
Further, the impregnant is a mixture prepared by mixing ethoxy cocoalkyl amine and dodecanol poly (oxy) ether phosphate according to the weight ratio of 1:1-1.5, preferably, the ethoxy cocoalkyl amine and the dodecanol polyoxyl gun ether phosphate are mixed according to the weight ratio of 1:1.3, and cesium fluoride and lithium bromide can be used according to actual conditions. The infiltrant in the application refers to a water-absorbing substance filled in the modified amino resin dehumidifying film, and can stably exist in the dehumidifying film without being eluted, and the infiltrant has high water absorption, so that the diffusion capacity of the modified amino resin dehumidifying film to water vapor is improved, and the moisture permeability is improved.
Further, the vacuum degree of decompression dehydration in the step 3 is minus 0.085MPa, and the dehydration temperature is 70-80 ℃. The temperature and vacuum degree can be adjusted according to the actual conditions, and in the present application, when the dehydration temperature is 70 ℃, the state of the modified amino resin is similar to a glass state, and the modified amino resin is suitable for stretching and film-forming.
Step 4: and (3) stretching the modified amino resin prepared in the step (3) to obtain the modified amino resin dehumidifying film.
Further, the stretching temperature in the step 4 is Tg+20-30 ℃.
The stretching process adopts a biaxial stretching machine to stretch into a film, and the modified amino resin dehumidifying film is prepared.
Further, the modified amino resin dehumidifying film is stretched to a thickness of 20-30S.
Further, the modified amino resin dehumidifying film prepared by the method is applied to a dehumidifier, and the porosity and the moisture permeability of the thickness of the dehumidifying film can be appropriately adjusted in the range of not exceeding the limit of the application according to the application to commercial and industrial situations.
Further, the film made of the modified amino resin is provided with a plurality of micropores having a pore diameter of 400 to 600 μm.
The smaller the pore diameter on the membrane, the smaller the molecular species in the air for selective passage, the diameter of the water molecules is 400 μm, and when the pore diameter is 400 μm, the water molecules can pass through, but other macromolecules and large ions cannot pass through the modified amino resin dehumidifying membrane, so that selective filtration is realized.
Further, the porosity of the film made of the modified amino resin is 75 to 95%.
When the film made of the modified amino resin has a pore diameter of 400 μm and a porosity of 75% in the application in a commercial dehumidifier, the human body feels that the humidity is most suitable.
Further, the strong acid is a mixture of sulfuric acid and nitric acid.
The method comprises the following steps: the strong acid is prepared by mixing sulfuric acid and nitric acid according to a volume ratio of 1:2.
Further, the molar concentration of the aqueous formaldehyde solution is 37 percent.
An aqueous formaldehyde solution having a molar concentration of 50% can also be used instead, but the corresponding liquid content should be reduced and the contact between the individual components should be increased with appropriate stirring.
Further, the weight ratio is as follows: is prepared from melamine 30-35 parts, methylol butanol solution 200-300 parts, formaldehyde aqueous solution 600-800 parts, aniline 30-50 parts, urea 45-53 parts, infiltrant 40-60 parts, potassium dichromate 30-50 parts, stabilizer 30-50 parts, and cellulose dispersion 150-220 parts.
Compared with the prior art, the application has the following advantages:
1. the preparation method of the modified amino resin dehumidifying film provided by the application is simple to operate and high in repeatability, the stability of the hydroxymethyl compound is improved through moderate etherification, and the mechanical property of a finished product can be improved by introducing a proper amount of nonpolar groups; the modified amino resin dehumidifying film prepared by the method has high moisture permeability and high strength.
2. The modified amino resin dehumidifying film prepared by the formula has high moisture permeability and high strength, and is suitable for industrial mass production.
3. The prepared modified amino resin dehumidifying film is applied to a dehumidifier, the smaller the pore diameter of the applied film is, the smaller the molecular types in the selectively passing air are, the diameter of water molecules is 400 mu m, and when the pore diameter is 400 mu m, the water molecules can pass through the modified amino resin dehumidifying film while other macromolecules and large ions can not pass through the modified amino resin dehumidifying film, so that the selective filtration is realized.
Detailed Description
The following partial sources of raw materials are used in the present application:
melamine (chemically pure, brands: carbofuran);
methylol butanol solution (chemically pure, brand: carbofuran);
urea (purity: >99%, brand: ala Ding Shenghua);
aniline (chemically pure, brand: ala Ding Shenghua);
potassium dichromate (manufacturer: shanghai screening quasi-biotechnology limited);
aqueous formaldehyde (manufacturer: shanghai Hertz atlanto chemical Co., ltd.).
The following describes the specific technical scheme of the present application in connection with specific examples 1 to 4:
example 1:
step 1: adding 30 parts of melamine and 300 parts of hydroxymethyl butanol solution in a reaction kettle according to the weight ratio, adding a proper amount of glacial acetic acid to adjust the pH to be 4.0, adding 45 parts of urea and 700 parts of 37% formaldehyde aqueous solution, heating to 30 ℃, and reacting for 2 hours to obtain an intermediate product A;
step 2: heating to 55 ℃, adding 33 parts of aniline, 30 parts of potassium dichromate and using 1:2, adjusting the pH value of the sulfuric acid and nitric acid mixed solution to be=3.5, and carrying out heat preservation reaction for 1h to obtain an intermediate product B;
step 3: adjusting the pH value of the intermediate product B to 7.0, adding 40 parts of an infiltrant prepared by using ethoxy cocoalkyl amine and dodecanol poly (oxy) gun ether phosphate according to the weight ratio of 1:1, and 170 parts of cellulose dispersion liquid, reacting at 90 ℃ for 60 minutes, and dehydrating and cooling at 75 ℃ under the vacuum degree of-0.085 MPa after the reaction is finished, thereby obtaining the modified amino resin.
Step 4: and (3) stretching the modified amino resin at 70 ℃ by adopting a biaxial stretcher to prepare a film with the thickness of 20S, the porosity of 75% and the aperture of 400 mu m, thus obtaining the modified amino resin dehumidifying film.
Example 2:
step 1: adding 35 parts of melamine and 200 parts of hydroxymethyl butanol solution in a reaction kettle according to the weight ratio, adding a proper amount of glacial acetic acid to adjust the pH to be 5.0, adding 50 parts of urea and 800 parts of 37% formaldehyde aqueous solution, heating to 35 ℃, and reacting for 2.5 hours to obtain an intermediate product A;
step 2: heating to 50 ℃, adding 30 parts of aniline, 40 parts of potassium dichromate and using 1:2, adjusting the pH value to be 4 by a sulfuric acid and nitric acid mixed solution, and carrying out heat preservation reaction for 1h to obtain an intermediate product B;
step 3: adjusting the pH value of the intermediate product B to 8.0, adding 60 parts of an infiltrant prepared by using ethoxy cocoalkyl amine and dodecanol poly (oxy) gun ether phosphate according to the weight ratio of 1:1.3, 50 parts of a stabilizer and 220 parts of cellulose dispersion liquid, reacting for 75 minutes at 55 ℃, finishing the reaction, dehydrating and cooling at the vacuum degree of-0.085 MPa and the temperature of 70 ℃ to obtain the modified amino resin.
Step 4: and (3) stretching the modified amino resin at 80 ℃ by adopting a biaxial stretcher to prepare a film with the thickness of 15S, the porosity of 95% and the aperture of 600 mu m, thus obtaining the modified amino resin dehumidifying film.
Example 3:
step 1: adding 35 parts of melamine and 250 parts of hydroxymethyl butanol solution in a reaction kettle according to the weight ratio, adding a proper amount of glacial acetic acid to adjust the pH to be 6.0, adding 53 parts of urea and 600 parts of 50% formaldehyde aqueous solution, heating to 35 ℃, and reacting for 3 hours to obtain an intermediate product A;
step 2: heating to 90 ℃, adding 50 parts of aniline, 50 parts of potassium dichromate and using 1:2, adjusting the pH value of the sulfuric acid and nitric acid mixed solution to be 3.5, and carrying out heat preservation reaction for 1.5 hours to obtain an intermediate product B;
step 3: adjusting the pH intermediate product B to 8.0, adding 60 parts of an infiltrant prepared by ethoxycocoalkyl amine and dodecanol poly (oxygen-generating ether) phosphate in a weight ratio of 1:1.5, 40 parts of a stabilizer and 150 parts of cellulose dispersion liquid, reacting at 90 ℃ for 65min, ending the reaction, dehydrating and cooling at 80 ℃ under the vacuum degree of-0.085 MPa, and obtaining the modified amino resin.
Step 4: and (3) stretching the modified amino resin at 70 ℃ by adopting a biaxial stretcher to prepare a film with the thickness of 30S, the porosity of 80% and the aperture of 500 mu m, thus obtaining the modified amino resin dehumidifying film.
Example 4:
step 1: adding 32 parts of melamine and 240 parts of hydroxymethyl butanol solution according to the weight ratio into a reaction kettle, adding a proper amount of glacial acetic acid to adjust the pH=5.0, adding 53 parts of urea and 710 parts of 37% formaldehyde aqueous solution, heating to 30 ℃, and reacting for 2.5 hours to obtain an intermediate product A;
step 2: heating to 90 ℃, adding 50 parts of aniline, 40 parts of potassium dichromate and using 1:2, adjusting the pH value of the sulfuric acid and nitric acid mixed solution to be 3.5, and carrying out heat preservation reaction for 1.5 hours to obtain an intermediate product B;
step 3: adjusting the pH intermediate product B to 8.0, adding 60 parts of an infiltrant prepared by ethoxycocoalkyl amine and dodecanol poly (oxygen-generating ether) phosphate in a weight ratio of 1:1.5, 40 parts of a stabilizer and 150 parts of cellulose dispersion liquid, reacting at 90 ℃ for 60 minutes, ending the reaction, dehydrating and cooling at 75 ℃ under the vacuum degree of-0.085 MPa, and obtaining the modified amino resin.
Step 4: and (3) stretching the modified amino resin at 80 ℃ by adopting a biaxial stretcher to prepare a film with the thickness of 30S, the porosity of 80% and the aperture of 500 mu m, thus obtaining the modified amino resin dehumidifying film.
The dehumidifying film prepared in the above examples 1-4 can also be properly dried to a water content below 50%, and then the dehumidifying film is prepared into a composite dehumidifying film with porous ceramics, wherein the porous ceramics is used as a supporting layer to enhance the strength of the dehumidifying film; the modified amino resin prepared by the application is used as a functional layer to selectively permeate molecules and is prepared into concentration difference.
The following describes the advantageous embodiments of the application in connection with specific comparative examples 1-2:
comparative example 1:
in example 1, the addition amount of potassium dichromate in the step 2 was changed to 40 parts, and the reaction was carried out under a constant temperature for 1 hour, while the other conditions were unchanged.
Comparative example 2:
in example 1, the reaction time for the incubation in step 2 was changed to 2 hours with the remaining conditions unchanged.
Experimental test:
the modified amino resin dehumidifying films of examples 1 to 4 were subjected to conventional performance test, and the results are shown in the following table:
TABLE 1
As can be seen from examples 1-4 in the table, the modified amino resin dehumidifying film prepared by the application has an average moisture permeability of about 2200sec/100cc, an average of about 2300N/15mm and good moisture permeability; and has high strength. Example 4 is the preferred embodiment of the present application, where the moisture permeability is the highest and the strength is the highest.
The dehumidifying films prepared in examples 1 to 4 are mainly applied to a dehumidifier, and the thickness, pore diameter and porosity of the film can be modified according to actual requirements.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. A preparation method of a modified amino resin dehumidifying film is characterized by comprising the following steps:
step 1: adding melamine and methylol butanol solution into a reaction kettle, adjusting pH to be 4.0-6.0, adding urea and formaldehyde aqueous solution, heating to 30-35 ℃, and reacting for 2-3h to obtain an intermediate product A;
step 2: heating the intermediate product A to 50-90 ℃, adding aniline and potassium dichromate, adjusting the pH value to be 3-4 by strong acid, and carrying out heat preservation reaction for 1-1.5h to obtain an intermediate product B;
step 3: regulating the pH value of the intermediate product B to 7.0-8.0, adding an infiltrant, a stabilizer and a cellulose dispersion liquid, reacting for 60-75 min at 55-90 ℃, and after the reaction is finished, decompressing, dehydrating and cooling to obtain the modified amino resin.
Step 4: and (3) stretching the modified amino resin prepared in the step (3) to obtain the modified amino resin dehumidifying film.
2. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the vacuum degree of decompression dehydration in the step 3 is minus 0.085MPa, and the dehydration temperature is 70-80 ℃.
3. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the stretching temperature in the step 4 is Tg+20-30 ℃.
4. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the impregnant is a mixture prepared by mixing ethoxy cocoalkyl amine and dodecanol polyoxyl ether phosphate according to the weight ratio of 1:1-1.5.
5. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the strong acid is prepared by mixing sulfuric acid and nitric acid according to a volume ratio of 1:2.
6. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the molar concentration of the formaldehyde aqueous solution is 37% -50%.
7. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the film made of the modified amino resin is provided with a plurality of micropores with a pore diameter of 400-600 mu m.
8. The method for producing a modified amino resin dehumidifying film as claimed in claim 1, wherein: the porosity of the film made of the modified amino resin is 75-95%.
9. A modified amino resin dehumidifying film, characterized in that: the weight ratio is as follows: is prepared from melamine 30-35 parts, methylol butanol solution 200-300 parts, formaldehyde aqueous solution 600-800 parts, aniline 30-50 parts, urea 45-53 parts, infiltrant 40-60 parts, potassium dichromate 30-50 parts, stabilizer 30-50 parts, and cellulose dispersion 150-220 parts.
10. Use of the modified amino resin dehumidifying film produced by the production method according to any one of claims 1 to 6 in a dehumidifier.
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Citations (5)
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|---|---|---|---|---|
| US20080017552A1 (en) * | 2004-12-23 | 2008-01-24 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| CN109107399A (en) * | 2018-07-30 | 2019-01-01 | 绍兴百立盛新材料科技有限公司 | A kind of hydrone permeable membrane and its preparation method and application |
| CN110724484A (en) * | 2019-11-06 | 2020-01-24 | 徐州盛安化工科技有限公司 | Preparation method of melamine modified urea-formaldehyde resin adhesive |
| CN112295418A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof |
| CN115970487A (en) * | 2023-03-02 | 2023-04-18 | 安徽中环环保科技股份有限公司 | Polymer resin denitration agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080017552A1 (en) * | 2004-12-23 | 2008-01-24 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| CN109107399A (en) * | 2018-07-30 | 2019-01-01 | 绍兴百立盛新材料科技有限公司 | A kind of hydrone permeable membrane and its preparation method and application |
| CN112295418A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof |
| CN110724484A (en) * | 2019-11-06 | 2020-01-24 | 徐州盛安化工科技有限公司 | Preparation method of melamine modified urea-formaldehyde resin adhesive |
| CN115970487A (en) * | 2023-03-02 | 2023-04-18 | 安徽中环环保科技股份有限公司 | Polymer resin denitration agent and preparation method thereof |
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