CN115819696B - Low free formaldehyde melamine formaldehyde resin with antibacterial property and preparation method thereof - Google Patents
Low free formaldehyde melamine formaldehyde resin with antibacterial property and preparation method thereof Download PDFInfo
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- CN115819696B CN115819696B CN202211315168.2A CN202211315168A CN115819696B CN 115819696 B CN115819696 B CN 115819696B CN 202211315168 A CN202211315168 A CN 202211315168A CN 115819696 B CN115819696 B CN 115819696B
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 103
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 35
- GBVVPXXNNHWBPE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.O=C.NC1=NC(N)=NC(N)=N1 GBVVPXXNNHWBPE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 78
- 235000018417 cysteine Nutrition 0.000 claims abstract description 27
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 27
- NMJSDWZNGZVCGN-UHFFFAOYSA-N guanidine;phosphoric acid;urea Chemical compound NC(N)=N.NC(N)=O.OP(O)(O)=O NMJSDWZNGZVCGN-UHFFFAOYSA-N 0.000 claims abstract description 24
- DDYDBBBQYLFRJE-UHFFFAOYSA-N (diaminomethylideneamino)urea Chemical compound NC(=N)NNC(N)=O DDYDBBBQYLFRJE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 22
- 239000010452 phosphate Substances 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 19
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 239000004202 carbamide Substances 0.000 claims description 25
- 239000001509 sodium citrate Substances 0.000 claims description 24
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 24
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 22
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 65
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 46
- 239000011787 zinc oxide Substances 0.000 abstract description 22
- 239000004005 microsphere Substances 0.000 abstract description 7
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000411 inducer Substances 0.000 abstract description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 239000004246 zinc acetate Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005234 chemical deposition Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- FNBBXJWAHDKFDW-UHFFFAOYSA-J O[Zn](O)(O)O Chemical compound O[Zn](O)(O)O FNBBXJWAHDKFDW-UHFFFAOYSA-J 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- WPJBCSPUJZOJIJ-UHFFFAOYSA-N (diaminomethylideneamino)urea;phosphoric acid Chemical compound OP(O)(O)=O.NC(=O)NN=C(N)N WPJBCSPUJZOJIJ-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical group C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229950003143 basic zinc acetate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JCPDISNOORFYFA-UHFFFAOYSA-H tetrazinc;oxygen(2-);hexaacetate Chemical compound [O-2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JCPDISNOORFYFA-UHFFFAOYSA-H 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a low free formaldehyde melamine formaldehyde resin with antibacterial property and a preparation method thereof. And (3) selecting paraformaldehyde and melamine as raw materials to obtain melamine formaldehyde resin prepolymer solution, and regulating the pH value by utilizing guanidine phosphate urea solution to obtain novel melamine formaldehyde resin powder. And then adding cysteine to reduce the content of free formaldehyde in the obtained powder. Zinc acetate is used as a zinc source by a hydrothermal method and a chemical deposition method, a structure inducer is added, and a layer of zinc oxide is coated on the outer wall of melamine formaldehyde powder. The invention creatively proposes to utilize the guanidyl urea phosphate solution to adjust the pH value of the melamine formaldehyde resin prepolymer solution, and simultaneously, the guanidyl urea phosphate can be grafted with the melamine formaldehyde resin, so that the impact resistance of the powder is improved. By a hydrothermal method, a layer of nano zinc oxide grows on the outer wall of the melamine formaldehyde microsphere, so that the antibacterial performance of the powder is integrally improved.
Description
Technical Field
The invention relates to a low free formaldehyde melamine formaldehyde resin with antibacterial property and a preparation method thereof.
Background
Melamine formaldehyde resin (MF) is an amino resin formed by polycondensation of formaldehyde and melamine, and the reaction process can be roughly divided into two stages. The first stage is to obtain melamine resin prepolymer liquid by methylolation reaction of melamine and formaldehyde, and the obtained mixture is a polymethyl melamine prepolymer. The second stage of methylolmelamine undergoes further polycondensation to form a series of different oligomers. There are generally two types of bridging that occur, namely methylene bridging and methylene ether bridging. Under acidic conditions, the methylolated oligomer crosslinks to form an insoluble material. The melamine formaldehyde resin can be degraded in an acid solution with low pH value, and can pass through small holes in the cavity wall of the core-shell microsphere to form melamine formaldehyde resin microspheres. In general, in the hydroxylation process, in order to make the reaction rate mild and controllable, hydroxylation is performed under an alkaline condition, and meanwhile, in order to meet the requirement of the subsequent powder preparation on the molecular weight of the MF prepolymer, after the methylolation reaction is performed for a period of time, the pH value of the system is adjusted to be slightly acidic. The melamine-formaldehyde resin microsphere is a novel polymer material, the raw materials are simple and easy to obtain, the cost is low, the specific surface area is large, and the structure is regular and ordered.
The melamine formaldehyde resin microsphere has flame retardance, chemical corrosion resistance and the like, is widely applied, but has little antibacterial property, zinc oxide is a common inorganic antibacterial agent, under the irradiation of ultraviolet light, a nano ZnO valence band generates a hole with a point, and the hole reacts with oxygen, hydroxyl, water and the like adsorbed on the surface of a material to generate hydroxyl free radicals and active oxygen ions with reduction action, so that oxygen in air and water is excited to become active oxygen, and the active oxygen has extremely strong oxidation activity and can react with organic matters in various microorganisms such as hydroxyl and the like to destroy the proliferation capability of bacterial cells and inhibit or kill bacteria.
However, there is a clear interface between zinc oxide and melamine formaldehyde powder, and zinc oxide cannot be coated on the surface of melamine formaldehyde resin powder by simply mixing the two substances. Common methods of altering the surface of a substance are: photolithography, vapor deposition, sol-gel, hydrothermal, electrochemical, template, and the like. According to the invention, zinc oxide grows to the surface of melamine formaldehyde resin powder by a hydrothermal method and a chemical deposition method.
Disclosure of Invention
The invention aims to provide melamine formaldehyde resin powder with antibacterial property and low free formaldehyde and a preparation method thereof. The melamine formaldehyde resin powder is structurally different from the traditional melamine formaldehyde resin powder, has low free formaldehyde content and has antibacterial performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing melamine formaldehyde resin powder with antibacterial property and low free formaldehyde, which comprises the following steps:
1) 50mL of deionized water is measured, the pH is regulated to 8.5-9 by alkali, the mixture is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, after the solution is clarified, 2.6g of melamine is added, and the reaction is carried out for 1h, thus obtaining the melamine formaldehyde resin prepolymer solution.
2) The test precipitation ratio was 2:2 (i.e. sucking 2mL of reaction solution into a clean test tube, adding 2mL of ice water, turning the sample turbid, and shaking to be not clear), adding guanidine urea phosphate solution into the melamine formaldehyde resin prepolymer solution, adjusting the pH to 4-5, heating to 80 ℃, and reacting for 2h.
3) Adding a certain amount of cysteine, stirring for 1h, cooling, suction filtering and drying to obtain melamine formaldehyde resin powder.
4) Weighing melamine formaldehyde resin powder obtained in the step 3) with a certain mass, adding anhydrous zinc acetate, sodium citrate, urea and water, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, performing suction filtration, and drying to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
In step 1), substances for alkalinity adjustment are: sodium hydroxide, triethanolamine, triethylamine, ethylenediamine.
In step 1), melamine is added in portions in a ratio of 3:1:1, the time between each addition is 10min.
In step 2), a guanidyl urea phosphate solution was prepared by weighing 1g of guanidyl urea phosphate and dissolving in 120mL of deionized water.
In step 3), after addition of cysteine, the concentration is 1% to 5% by weight.
In step 4), melamine formaldehyde resin powder, anhydrous zinc acetate, sodium citrate, urea, water=5 g, 15-25g, 9g, 2g, 1l.
In the invention, sodium citrate is a structure inducer, and urea provides alkaline conditions for hydrothermal growth.
The principle of the invention is as follows: the guanidyl urea phosphate is used as a substance similar to a pH buffering agent and consists of three groups of urea, phosphoric acid and guanidyl, the pH value of an aqueous solution of the guanidyl urea phosphate is 4-5 at normal temperature, and the pH value is basically unchanged with the change of temperature, so that the weak acidic condition required by the later crosslinking of the melamine formaldehyde resin can be just satisfied. Meanwhile, the substance has amino groups, can react with melamine formaldehyde resin prepolymer, increases the distance between triazine rings, reduces the crosslinking density of molecules and improves the flexibility.
Cysteine is used as an amino acid derivative, and amino groups on molecules are easy to react with formaldehyde to generate stable and harmless compounds, so that free formaldehyde is eliminated. And the cysteine has high reactivity, and secondary pollution can not be generated in the reaction process.
The zinc oxide layer is formed by three steps of hydrolysis, nucleation and growth. The urea is heated and decomposed, and the generated ammonia gas and solvent water are mixed together to generate ammonium ions and hydroxide ions, so that an alkaline environment is provided for the reaction; zinc acetate provides zinc ions and acetate ions for the reaction; sodium citrate is a structure inducer and hydrolysis to form citrate ions helps to nucleate. Zinc ions are grafted to the outer wall of the powder under the action of a structure inducer and the hydroxyl of melamine formaldehyde resin powder, and then grow on the surface under the combined action of citrate, acetate and hydroxide. Zinc ions on the surfaces of the microspheres and hydroxyl generated by hydrolysis generate zinc hydroxide and tetrahydroxy zinc ions, and along with the progress of the reaction, the zinc hydroxide and the tetrahydroxy zinc ions are decomposed to generate zinc oxide, so that the structure of the melamine formaldehyde resin powder coated with the zinc oxide is obtained.
The invention has the beneficial effects that:
1. The traditional formaldehyde solution is replaced by the paraformaldehyde, the paraformaldehyde is solid, depolymerized in water to become small molecules, and the free formaldehyde is reduced to a certain extent.
2. The free formaldehyde content can be reduced to a certain extent by adding melamine in portions.
3. The guanidyl urea phosphate is not only a novel substance for regulating the pH, but also can regulate the acidity of a resin solution, and can react with melamine formaldehyde resin oligomer to obtain novel melamine formaldehyde resin powder with better compression resistance.
4. Cysteine can react with free formaldehyde to reduce the free formaldehyde content.
5. Zinc acetate is used as a zinc source, a layer of zinc oxide is coated on the outer wall of the melamine formaldehyde resin microsphere by a hydrothermal method, and the zinc oxide is used as a common antibacterial agent, so that the antibacterial performance of the melamine formaldehyde resin powder can be improved to a great extent.
Drawings
FIG. 1 is an SEM image of a low free formaldehyde melamine formaldehyde resin powder having antimicrobial properties of example 1;
FIG. 2 is an SEM image of low free formaldehyde melamine formaldehyde resin powder of comparative example 3;
FIG. 3 is an infrared plot of guanidyl urea phosphate and low free formaldehyde melamine formaldehyde resin powder having antimicrobial properties as in example 1;
Fig. 4 is an XRD pattern of the low free formaldehyde melamine formaldehyde resin powder with antibacterial properties of example 1.
Detailed Description
The invention is further illustrated below in connection with specific examples, but the invention is not limited to these examples only.
Example 1
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 0.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 2
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 3
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 4
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 2G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 5
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 2.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 6
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:15g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Example 7
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(5) Weighing the powder obtained in the step (4) with a certain mass, and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:25g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the low free formaldehyde melamine formaldehyde resin powder with antibacterial performance.
Comparative example 1 (compared to example 3, no cysteine was added)
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) Weighing a certain mass of powder obtained in the step (3), and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃.
Comparative example 2 (compared to example 3, the pH of the system was adjusted with dilute sulfuric acid without guanidino urea phosphate)
(1) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(2) The test precipitation ratio was 2:2, adjusting the pH value to 4 by dilute sulfuric acid, heating to 80 ℃ and reacting for 2 hours.
(3) 1.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered by suction and dried at 80 ℃.
(4) Weighing a certain mass of powder obtained in the step (3), and according to melamine formaldehyde resin powder: anhydrous zinc acetate: sodium citrate: urea: water = 5g:20g:9g:2g: adding anhydrous zinc acetate, sodium citrate, urea and water in a proportion of 1L, stirring for 1h at 40 ℃, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 8h at 95 ℃, carrying out suction filtration, and drying at 80 ℃.
Comparative example 3 (compared to example 3, uncoated zinc oxide)
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1,5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered and dried to obtain melamine formaldehyde resin powder with low free formaldehyde.
Comparative example 4 (physical method, nano zinc oxide was added by blending compared with example 3)
(1) Preparation of guanidine phosphate urea solution: 1g of guanidyl urea phosphate was weighed out and dissolved in 120mL of deionized water, and stirred at room temperature for 15min.
(2) 50ML of deionized water is measured by a measuring cylinder, the pH value is regulated to 8.5 by alkali, the deionized water is added into a three-neck flask with stirring and condensation, 3.7g of paraformaldehyde is added, the temperature is raised to 70 ℃, and after the solution is clarified, 2.6g of melamine is added for reaction for 1h.
(3) The test precipitation ratio was 2:2, adding guanidine phosphate urea solution, adjusting the pH to 4, heating to 80 ℃ and reacting for 2h.
(4) 1.5G of cysteine is added, stirred for 1h, cooled to room temperature, filtered and dried.
(5) Weighing a certain amount of the novel melamine formaldehyde resin powder obtained in the step (4), and uniformly mixing the novel melamine formaldehyde resin powder with a certain amount of nano zinc oxide at room temperature, wherein the melamine formaldehyde resin powder is prepared by the steps of: nano zinc oxide = 5g:8.85g.
To determine the free formaldehyde content of the melamine formaldehyde powders prepared in the examples and comparative examples, spectrophotometry was used. The method comprises the following steps: 150mg of modified or unmodified powder was weighed, 100mL of distilled water was added thereto, and stirred at 40℃for 1 hour, followed by filtration to obtain a formaldehyde extraction solution. A solution of 37.5g of anhydrous ammonium acetate, 0.75mL of acetic acid and 0.5mL of acetylacetone was weighed, and the volume was determined by a 250mL volumetric flask to obtain an acetylacetone solution. Taking 5mL of extract, 5mL of acetylacetone solution, developing at 40 ℃ for 30min in a cuvette, testing at 410nm by using an ultraviolet spectrophotometer to obtain absorbance, and calculating the content of free formaldehyde in the powder according to a standard curve of formaldehyde content.
Table 1 shows the free formaldehyde content of melamine formaldehyde resin powders prepared at different concentrations of cysteine. Examples 1-5 correspond to cysteine concentrations of 1% -5%, respectively, and comparative example 1 does not add cysteine.
TABLE 1 results of free formaldehyde content test
As can be seen from Table 1, the resulting materials were tested for free formaldehyde content using an ultraviolet spectrophotometer. The result shows that the addition of the cysteine can obviously reduce the content of free formaldehyde in the powder, the addition of the cysteine with different concentrations has different formaldehyde elimination effects, and in the concentration range of the invention, when the concentration is 3%, the content of the free formaldehyde is the lowest, but the concentration is continuously increased, the effect is found to be reduced, because when the concentration of the cysteine is too high, the cysteine and the melamine formaldehyde resin can generate a coupling negative effect, so that the structure of the melamine formaldehyde resin is unstable, the melamine formaldehyde resin is decomposed into small molecules again, and meanwhile, the concentration of the cysteine is not suitable for being too high from the aspect of economy.
Examples 3, 6, 7 and comparative examples 3, 4 were tested for antibacterial properties using E.coli. And (3) taking a nutrient agar culture of the third generation to the eighth generation of the escherichia coli, and diluting the strain concentration to about 10 5 cfu/mL by using a 0.03mol/L phosphate buffer solution to obtain a pre-prepared strain suspension. 0.5g of powder to be measured is weighed, placed into a three-necked flask, 95mL of PBS containing 0.1% Tween 80 is added, and after uniform mixing, 5mL of the pre-bacterial suspension is added. The three-neck flask is fixed on a constant temperature shaking table, the three-neck flask is oscillated at the speed of 150r/min at the temperature of 37 ℃, the luminescence value of the liquid is measured at intervals, and the antibacterial rate is calculated.
Table 2 shows the antibacterial property test of the powders obtained in some examples and comparative examples
As can be seen from Table 2, after the zinc oxide coating is applied, the antibacterial performance of each example is improved, the antibacterial performance of example 7 is best, the antibacterial performance is obtained by culturing in a culture medium for 10min, the antibacterial performance is 86.18%, and after 50min, the antibacterial rate reaches 99.97%, and meanwhile, the antibacterial performance is gradually improved along with the increase of the addition amount of zinc oxide. Comparative example 4 simply physically mixes the nano zinc oxide powder and the melamine formaldehyde resin powder, and from the results, although the antibacterial performance is improved, it is not as good as the coating effect by the hydrothermal method, because only the bacteria contacting the nano zinc oxide powder can be inactivated when the antibacterial performance test is performed by physically mixing the obtained powder, but the bacteria contacting the melamine formaldehyde resin powder is not rapidly inactivated, and the melamine formaldehyde resin powder coated with the nano zinc oxide has been modified on its outer wall, so that the contact area with the bacteria is improved, and the antibacterial performance is remarkably improved.
Table 3 shows the impact strength test of example 3 and comparative example 2. The obtained powder was pressed into 80mm x 10mm x 2mm bars by hot pressing at 200 ℃ and 5 MPa. As can be seen from Table 3, the powder prepared using guanidine phosphate urea has a stronger impact strength than the powder prepared using sulfuric acid as the pH adjustor in the conventional synthesis.
Table 3 impact strength test table
Fig. 1 is a scan of a low free formaldehyde melamine formaldehyde resin powder with antimicrobial properties of example 1, illustrating that the melamine formaldehyde resin powder is spherical in morphology, not smooth in surface, and has a layer of network material attached to it, which is zinc oxide.
FIG. 2 is a sweep of the low free formaldehyde melamine formaldehyde resin powder of comparative example 3, with partial bonding between particles observed and in the shape of full spheres.
FIG. 3 is an infrared plot of guanidyl urea phosphate and melamine formaldehyde resin powder having antimicrobial properties. In guanidyl urea phosphate, 3000 cm -1-3500cm-1 is the stretching vibration of O-H, 2500-3000 is upsilon (-CH 2-), 1639 cm -1 is upsilon (O=P-OH), 1265 cm -1 is upsilon (P=O), 1118 cm -1 is the stretching vibration of P-O. The melamine formaldehyde resin powder with antibacterial performance has an absorption peak at 1618 cm -1 as a primary amine bond telescopic vibration absorption peak, 3410 cm -1 as a secondary amine N-H telescopic vibration absorption peak, and a broad peak of 1500 cm -1 -1600cm < -1 > as a combination of a triazine ring vibration absorption peak and upsilon (O=P-OH), and three absorption peaks of 1557 cm -1,1350 cm-1,810 cm-1 as triazine ring skeleton vibration absorption peaks. 1152 At cm -1 and 992 cm -1 are the symmetrical and antisymmetric telescopic vibration absorption peaks of C-O-C, with the occurrence of v (P-O) at the position of 1004 cm -1.
FIG. 4 is an XRD pattern of zinc oxide/melamine formaldehyde resin powder, showing the characteristic absorption peaks of (001) (101) and (110) of wurtzite crystal forms of zinc oxide according to JCPDS standard Carno. 36-1451, diffraction angles of 33.8 °, 38.1 ° and 59.2 °, respectively. Diffraction peaks in a diffraction range of less than 30 ° are consistent with diffraction peaks of layered basic zinc acetate (Zn 5（OH）8Ac2·2H2 O), 7.11 °,14.14 °, and 21.36 ° correspond to (001), (002), and (003) crystal planes, respectively, while 33.07 °, 58.67 °, and 69.2 ° correspond to (100), (110), and (200) crystal planes.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. A method for preparing a low free formaldehyde melamine formaldehyde resin with antibacterial property, which is characterized by comprising the following steps:
1) Measuring 50mL of deionized water, regulating the pH to 8.5-9 with alkali, adding the deionized water into a three-neck flask with stirring and condensation, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, and reacting for 1h to obtain melamine formaldehyde resin prepolymer solution;
2) Adding guanidine urea phosphate solution into melamine formaldehyde resin prepolymer solution, regulating pH to 4-5, heating to 80 ℃ and reacting for 2h;
3) Adding a certain amount of cysteine, stirring for 1h, cooling, performing suction filtration and drying to obtain melamine formaldehyde resin powder;
4) Weighing a certain mass of the powder obtained in the step 3), adding anhydrous zinc acetate, sodium citrate, urea and water, stirring at 40 ℃ for 1h, pouring into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction at 95 ℃ for 8h, performing suction filtration, and drying to obtain the low free formaldehyde melamine formaldehyde resin with antibacterial property;
In step 4), melamine formaldehyde resin powder, anhydrous zinc acetate, sodium citrate, urea, water=5 g, 15-25g, 9g, 2g, 1l.
2. The method according to claim 1, wherein the method for preparing the guanidyl urea phosphate solution comprises: 1g of guanidyl urea phosphate was weighed and dissolved in 120mL of deionized water to prepare the product.
3. The process according to claim 1, wherein the final concentration of cysteine added in step 3) is 1% to 5% by weight.
4. A low free formaldehyde melamine formaldehyde resin with antibacterial properties prepared by the preparation method as claimed in any one of claims 1 to 3.
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| CN102120810A (en) * | 2011-01-25 | 2011-07-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high solid content expandable melamine modified urea resin |
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