CN113444214A - Preparation method of urea-formaldehyde resin microcapsule serving as coating repairing agent - Google Patents
Preparation method of urea-formaldehyde resin microcapsule serving as coating repairing agent Download PDFInfo
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- CN113444214A CN113444214A CN202010223553.9A CN202010223553A CN113444214A CN 113444214 A CN113444214 A CN 113444214A CN 202010223553 A CN202010223553 A CN 202010223553A CN 113444214 A CN113444214 A CN 113444214A
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 94
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 77
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 35
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000002383 tung oil Substances 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- KOJYENXGDXRGDK-ZUGARUELSA-N 9(Z),11(E),13(E)-Octadecatrienoic Acid methyl ester Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(=O)OC KOJYENXGDXRGDK-ZUGARUELSA-N 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 239000011162 core material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000006748 scratching Methods 0.000 description 5
- 230000002393 scratching effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 244000153888 Tung Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 244000036975 Ambrosia artemisiifolia Species 0.000 description 2
- 235000003129 Ambrosia artemisiifolia var elatior Nutrition 0.000 description 2
- CSPPKDPQLUUTND-NBVRZTHBSA-N Sethoxydim Chemical compound CCO\N=C(/CCC)C1=C(O)CC(CC(C)SCC)CC1=O CSPPKDPQLUUTND-NBVRZTHBSA-N 0.000 description 2
- 235000003484 annual ragweed Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000006263 bur ragweed Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000003488 common ragweed Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 235000009736 ragweed Nutrition 0.000 description 2
- 239000011150 reinforced concrete Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A preparation method of a urea-formaldehyde resin microcapsule as a coating repairing agent comprises the following steps: (1) adding water and an emulsifier into a reactor, and stirring; (2) adding urea, ammonium chloride, a water-resistant auxiliary agent and a defoaming agent into a reactor; (3) adjusting the pH value to 3-4 by using acid, and starting stirring; (4) dropwise adding a repairing agent into the reactor, and continuously stirring after dropwise adding is finished; (5) dripping methanol into the reactor, and heating for reaction; (6) cooling the reactor to room temperature, pouring the mixture in the reactor into a separating funnel, standing and layering; (7) taking the layered upper layer of the separating funnel, washing with deionized water and an organic solvent respectively, and performing suction filtration; (8) and (5) drying to obtain the finished product. The urea-formaldehyde resin microcapsule is prepared by adopting an in-situ polymerization method and a one-step method, and the preparation process is simple; the obtained urea-formaldehyde resin microcapsule has large grain diameter, uniform grain diameter sealing, good dispersibility, no blocking and rough surface, can release a repairing agent to repair coating cracks, and has wide application range.
Description
Technical Field
The invention relates to a preparation method of urea-formaldehyde resin microcapsules, in particular to a preparation method of urea-formaldehyde resin microcapsules for coating repair.
Background
In the last decade, the field of self-repairing polymer materials has made great progress in automatic defect repair, and the most important one is self-healing coating. Microcapsules are added to the coating matrix to trigger the microcapsules when cracks in the coating propagate and release the encapsulated healing agent in a controlled manner to heal the cracked coating. In particular, the use of vegetable oils as remediation agents has received considerable attention due to their ecological safety profile.
China has rich varieties and resources of the tung trees, the planting region range is wider, and a plurality of hilly poor areas are also planted. However, the utilization technology level of the tung oil is low, and the application of the traditional tung oil mainly focuses on directly using the tung oil as fuel oil, ink additive and mold release oil; or prepared into clear oil which is used as a thick paint thinner when wooden products such as furniture and the like are coated; preparing putty for treating cracks and recesses of wood, steel and the like; or the tung oil is decocted into gloss oil, flood oil and elegant oil which are used as waterproof and antirust paint for rain gear tarpaulin, ship bottom plates and waterproof and anticorrosive paint for wood products; the moisture-proof coating is prepared and is commonly used in the building construction industry; the ointment is prepared and mainly used for reinforced concrete assembly or structural joints, so that the reinforced concrete assembly or structural joints are airtight and watertight; or made into silicon steel sheet paint for insulating and the like. However, the application of the tung oil has low economic benefit and is not beneficial to the development of the tung tree planting industry.
CN101396018 discloses a urea formaldehyde resin microcapsule of herbicide sethoxydim and a preparation method thereof. The method takes sethoxydim as a core material, and urea-formaldehyde resin generated by polymerization reaction of urea and formaldehyde as a wall material, and the slow-release microcapsule is a monodisperse flowable solid microcapsule or microcapsule water suspension agent with the grain diameter of 0.1-10 microns.
CN106577647A discloses a preparation method of a ragweed extract urea-formaldehyde resin microcapsule: dissolving urea and formaldehyde in a solvent under the condition that the pH value is 8-9 to obtain a urea-formaldehyde resin prepolymer, pouring the urea-formaldehyde resin prepolymer into the ragweed extract suspension, adjusting the pH value of the system to be below 2, and continuously stirring for a period of time to carry out an emulsion reaction; adding deionized water, continuing the reaction, adding a curing agent, and adjusting the pH value of the system to 8-9; and (5) preparing the microcapsule.
The two methods firstly prepare the prepolymer under the alkaline condition, then condense the prepolymer into the prepolymer of the urea-formaldehyde resin under the acidic condition, and then solidify the prepolymer, so the operation is complex, and the prepared microcapsule is easy to agglomerate.
Yangyi et al prepared urea-formaldehyde resin microcapsules with organic solvent as internal phase by direct in situ polymerization in the research of 'one-step method for preparing urea-formaldehyde resin microcapsules' (journal of chemical engineering of colleges and universities, 6.2005, volume 19, 3 rd). The influence of conditions such as a system modifier, a pH value, reaction time and the like on the microencapsulation process and the microcapsule morphology is examined. By adopting the method in the article and taking PVA (polyvinyl alcohol) as a system modifier, the synthesized microcapsule has lower strength and is easy to break when being stirred; the pH value of the system is adjusted to be too low, so that the demulsification phenomenon is easy to occur, and microcapsules are not easy to generate. The process of this article adds less water, the emulsifier solution, and associated reagents, are very soluble, and the microcapsules formed tend to clump together.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a urea-formaldehyde resin microcapsule as a coating repairing agent, which has the advantages of simple process, good dispersibility of the obtained urea-formaldehyde resin microcapsule and wide application range.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a urea-formaldehyde resin microcapsule as a coating repairing agent comprises the following steps:
(1) adding water and an emulsifier into a reactor, and stirring;
(2) adding urea, ammonium chloride, a water-resistant auxiliary agent and a defoaming agent into a reactor;
(3) adjusting the pH value to 3-4 by using acid, and starting stirring;
(4) dropwise adding a repairing agent into the reactor, and continuously stirring after dropwise adding is finished;
(5) dripping methanol into the reactor, and heating for reaction;
(6) cooling the reactor to room temperature, pouring the mixture in the reactor into a separating funnel, standing and layering;
(7) taking the layered upper layer of the separating funnel, washing with deionized water and an organic solvent respectively, and performing suction filtration;
(8) and (5) drying to obtain the finished product.
Preferably, in the step (1), the emulsifier is one or two or more of OP-10, sodium dodecyl benzene sulfonate, polyvinyl alcohol (PVA), arabinogelatin and oleic acid, and a combination of the sodium dodecyl sulfonate and the polyvinyl alcohol in a mass ratio of 0.8-1.2: 1 is more preferred.
Preferably, in the step (1), the mass ratio of the water to the emulsifier is 0.3-8.0: 1000, and more preferably 0.7-6.0: 1000.
Preferably, in the step (1), the stirring temperature is 70-80 ℃, and the stirring is finished and then the mixture is cooled to room temperature; the rotating speed of the stirring is 300-400 r/min; the stirring time is 3-4h, and under the condition, the emulsifier and water can form a uniform system to completely form an emulsifying solvent, so that the dispersibility of the microcapsule can be improved, and the coating rate of the microcapsule coating core material can be improved. The room temperature is 20-25 ℃.
Preferably, in the step (2), the mass ratio of the urea to the water is 1.2-2.0: 100.
Preferably, in the step (2), the mass ratio of the ammonium chloride to the urea is 8-20: 100, and the ammonium chloride is used as a curing agent.
Preferably, in the step (2), the mass ratio of the water-resistant auxiliary agent to the urea is 2.5-5.0: 100.
Preferably, in the step (2), the using amount ratio of the defoaming agent to the water is 2-7 drops: 1000 g.
Preferably, in the step (2), the water-resistant auxiliary agent is one, two or more of melamine, phenol, resorcinol, alkylamine and furfural; the urea-formaldehyde resin has poor water resistance and is easy to dissolve in water, and the water-resistant auxiliary agent can accelerate the solidification of the urea-formaldehyde resin and reduce the reaction time, thereby reducing the contact time with water.
Preferably, in the step (2), the defoaming agent is n-butanol; the n-butyl alcohol can reduce the surface tension of water, solution, suspension and the like, and prevent the formation of foam, because the suspension polymerization adopted by the reaction is added with the surfactant, the reaction system has a large amount of foam due to no defoaming, the volume of the reaction system is enlarged, the reaction device is overflowed, and the coating rate of the core material is reduced due to the large amount of foam.
Preferably, in the step (3), the acid is one or two or more of hydrochloric acid, sulfuric acid, citric acid monohydrate, acetic acid, hypochlorous acid and oxalic acid.
Preferably, in the step (4), the mass ratio of the repairing agent to the urea is 2.5-3.6: 1.
Preferably, in the step (4), the dropping rate is 1 to 2 g/min.
Preferably, in the step (4), stirring is continued for 10-15min after the dropwise addition is completed.
Preferably, in the step (4), the repairing agent is one or two or more of dicyclopentadiene, castor oil, tung oil, linseed oil, methyl eleostearate, maleic anhydride and isocyanate. The tung oil contains about 80 percent of tung oil acid triglyceride, has three conjugated double bonds in the structure, has active chemical properties and can generate oxidative polymerization reaction; methyl esterification is carried out on the eleostearic acid to generate methyl eleostearate, so that the reaction activity is increased, the viscosity is reduced, and the self-repairing microcapsule core material repairing agent is the best choice.
Preferably, in the step (3) and the step (4), the rotation speed of stirring is 600-800 r/min.
Preferably, in the step (5), the dosage ratio of the methanol to the urea is 1.8-2.6 ml:1 g.
Preferably, in the step (5), the temperature rise rate is 2-5 ℃/min.
Preferably, in the step (5), the reaction temperature is 55-60 ℃, and the reaction time is 4-5 h.
Preferably, in the step (5), the dropping and the reaction are carried out under stirring conditions, and the rotation speed of the stirring is 600-800 r/min.
Preferably, in the step (6), the standing time is 1-2 h.
Preferably, in the step (7), the organic solvent is ethanol, xylene, ethyl acetate or acetone, and the organic solvent is used for washing away the uncoated repairing agent.
Preferably, in the step (8), the drying is atmospheric drying, reduced pressure drying, spray drying or freeze drying.
Preferably, in the step (8), the drying time is 20-24 h.
The urea-formaldehyde resin microcapsule prepared by the invention has large grain diameter, uniform grain diameter sealing and rough surface, and can release the repairing agent to repair coating cracks. The prepared urea-formaldehyde resin microcapsule is added into a coating, and the coating is obtained by coating, when the coating is intact, the core material is wrapped in the wall material, and the activity can be maintained for a long time; when the coating is damaged, the microcapsule releases the core material to fill the gap, and under the action of oxygen, crosslinking polymerization is carried out, so that the coating is repaired. The method is suitable for any coating, and no catalyst is required to be added additionally.
The invention has the beneficial effects that: (1) the urea-formaldehyde resin microcapsule is prepared by adopting an in-situ polymerization method and a one-step method, and the preparation process is simple; (2) the obtained urea-formaldehyde resin microcapsule has large grain diameter, uniform grain diameter sealing, good dispersibility, no blocking and rough surface, and can release a repairing agent to repair coating cracks. (3) The coating can have self-repairing capability only by adding urea-formaldehyde resin microcapsules without adding a catalyst; (4) the application range is wide, and the coating can be added into any coating; (5) the repairing agent is preferably methyl eleostearate, so that a new way is opened for processing and application of the tung oil, the utilization additional value of the tung oil is improved, the application economic benefit of the tung oil is improved, the development of the tung tree planting industry is promoted, and poor farmers are helped to get rid of poverty and become rich.
Drawings
FIG. 1 is an optical micrograph of urea-formaldehyde resin microcapsules prepared according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of 7000 times magnified dry powder of urea resin microcapsule prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a urea resin microcapsule dried powder prepared in example 1 of the present invention at a magnification of 200 times;
FIG. 4 is an optical micrograph of a coating to which urea formaldehyde resin microcapsules prepared in example 1 of the present invention were added;
FIG. 5 is a photograph showing scratches after 1 day of scratching with the tung oil coating layer to which urea resin microcapsules produced in example 1 of the present invention were added in an amount of 5% by mass;
FIG. 6 is a photograph of scratches after 2 days of scratching by a tung oil coating layer to which urea resin microcapsules prepared in example 1 of the present invention were added in an amount of 5% by mass;
FIG. 7 is a photograph of a scratch after 3 days of scratching with the tung oil coating layer to which urea resin microcapsules produced in example 1 of the present invention were added in an amount of 5% by mass;
FIG. 8 is a photograph of a scratch 4 days after scratching with a tung oil coating layer to which urea resin microcapsules produced in example 1 of the present invention were added in an amount of 5% by mass;
FIG. 9 is a photograph of a scratch after 5 days of scratching with the tung oil coating layer to which urea resin microcapsules produced in example 1 of the present invention were added in an amount of 5% by mass;
FIG. 10 is an optical diagram of a dry powder of urea resin microcapsules prepared in example 2 of the present invention;
FIG. 11 is an optical micrograph of urea formaldehyde resin microcapsules prepared according to example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
In the examples, methyl eleostearate and tung oil coatings were purchased from jabotalli chemical group.
Example 1
The following raw materials were used in this example: 400g of water, 0.15g of PVA0, 5g of urea, 11.5ml of formaldehyde, 15g of methyl eleostearate (repairing agent), 0.5g of ammonium chloride, 0.15g of resorcinol (water-resistant auxiliary agent), 0.15g of sodium dodecyl benzene sulfonate, citric acid monohydrate, n-butanol (defoaming agent), deionized water and xylene (organic solvent).
The preparation of the urea-formaldehyde resin microcapsule of this embodiment includes the following steps:
(1) 400gH is added into a three-neck flask2O, 0.15g of PVA and 0.15g of sodium dodecyl benzene sulfonate are stirred for 3 hours at the temperature of 70 ℃ and the rotating speed of 300r/min, and the mixture is cooled to the room temperature after being stirred;
(2) adding 5g of urea, 0.5g of ammonium chloride and 0.15g of m-diphenol, and then dripping 2 drops of defoaming agent;
(3) adjusting the pH value to 3 by citric acid monohydrate, setting the rotating speed to 600r/min, and starting stirring;
(4) slowly dripping 15g of methyl eleostearate at the speed of 1g/min, and continuously stirring for 15min after the dripping is finished;
(5) then 11.5ml of formaldehyde is dripped, the temperature is raised to 55 ℃ at the heating rate of 5 ℃/min, and the reaction is carried out for 4 hours;
(6) cooling to room temperature, pouring the mixture in the three-neck flask into a separating funnel, standing for 1.5h, and allowing layering to occur, wherein the upper layer is the prepared microcapsule and the lower layer is a shell (urea-formaldehyde resin without forming the microcapsule);
(7) taking the layered upper layer of the separating funnel, washing with deionized water and xylene respectively, and performing suction filtration;
(8) and (5) freeze-drying for 24h to obtain the finished product.
Fig. 1 is a picture of the urea resin microcapsule obtained in this example under an optical microscope, and it can be seen that a large amount of uniformly and stably dispersed microcapsules are successfully prepared.
Fig. 2 and 3 are SEM (scanning electron microscope) images of the urea resin microcapsule powder obtained in this example, and it can be seen from the SEM images that the urea resin microcapsule powder contains a large amount of microcapsules, the urea resin microcapsule obtained is spherical, and the surface of the urea resin microcapsule is rough.
The urea-formaldehyde resin microcapsule obtained in this example was added to the coating layer, and as can be seen from fig. 4, the urea-formaldehyde resin microcapsule in the coating layer can maintain a spherical shape and stably exist in the coating layer.
The urea-formaldehyde resin microcapsule obtained in the embodiment is added into the tung oil paint, and the urea-formaldehyde resin microcapsule accounts for 5% of the total mass. The coating is coated to obtain a coating, scratches are made on the surface of the coating, and the scratches gradually disappear after 5 days (fig. 5-9, upper left part), which shows that the coating has self-repairing capability after the urea-formaldehyde resin microcapsule obtained by the invention is added into the coating.
Example 2
The following raw materials were used in this example: 400g of water, 6g of urea, 13ml of formaldehyde, 15g of methyl eleostearate (a repairing agent), 0.5g of ammonium chloride, 0.15g of resorcinol (a water-resistant auxiliary agent), 0.15g of sodium dodecyl benzene sulfonate, citric acid monohydrate, n-butanol (a defoaming agent), deionized water and xylene (an organic solvent).
The preparation of the urea-formaldehyde resin microcapsule of this embodiment includes the following steps:
(1) 400gH is added into a three-neck flask2O, 0.15g of PVA and 0.15g of sodium dodecyl benzene sulfonate, stirring for 4 hours at the temperature of 70 ℃ and the rotating speed of 300r/min, and cooling to room temperature after stirring;
(2) adding 6g of urea, 0.5g of ammonium chloride and 0.15g of m-diphenol, and then dripping 2 drops of defoaming agent;
(3) adjusting the pH value to 4 by citric acid monohydrate, setting the rotating speed to 600r/min, and starting stirring;
(4) slowly dripping 15g of methyl eleostearate at the speed of 1.5 g/min, and continuously stirring for 10min after the dripping is finished;
(5) then 13ml of formaldehyde is dripped, the temperature is raised to 60 ℃ at the heating rate of 3 ℃/min, and the reaction is carried out for 4 hours;
(6) cooling to room temperature, pouring the mixture in the three-neck flask into a separating funnel, standing for 2h, layering, and taking the upper layer as the prepared microcapsule;
(7) taking the layered upper layer of the separating funnel, washing with deionized water and xylene respectively, and performing suction filtration;
(8) and (5) freeze-drying for 24h to obtain the finished product.
Through detection, a large amount of urea resin microcapsules which are uniformly and stably dispersed are successfully prepared in the embodiment.
FIG. 10 is an optical photograph of the dry powder of urea resin microcapsules prepared in this example, showing no caking of the dry powder of urea resin microcapsules.
The urea-formaldehyde resin microcapsule powder obtained in the embodiment contains a large amount of microcapsules, the obtained urea-formaldehyde resin microcapsules are spherical, and the surfaces of the urea-formaldehyde resin microcapsules are rough.
The urea-formaldehyde resin microcapsule obtained in the embodiment is added into the coating, and the urea-formaldehyde resin microcapsule in the coating can keep a spherical shape and stably exist in the coating.
After detection, the urea-formaldehyde resin microcapsule obtained by the invention is added into the coating, and the coating has self-repairing capability.
Example 3
The following raw materials were used in this example: 350g of water, 2g of OP-10, 5g of urea, 12ml of formaldehyde, 15g of methyl eleostearate (repairing agent), 0.5g of ammonium chloride, 0.15g of resorcinol (water-resistant auxiliary agent), citric acid monohydrate, n-butanol (defoaming agent), deionized water and xylene (organic solvent).
The preparation of the urea-formaldehyde resin microcapsules of the examples included the following steps:
(1) 350gH is added into a three-neck flask2O, 2gOP-10, stirring for 3 hours at the temperature of 70 ℃ and the rotating speed of 300r/min, and cooling to room temperature after stirring;
(2) adding 5g of urea, 0.5g of ammonium chloride and 0.15g of m-diphenol, and then dripping 1 drop of defoaming agent;
(3) adjusting the pH value to 3.5 by citric acid monohydrate, setting the rotating speed to 700r/min, and starting stirring;
(4) slowly dripping 15g of methyl eleostearate at the speed of 2g/min, and continuously stirring for 10min after the dripping is finished;
(5) then 12ml of formaldehyde is dripped, the temperature is raised to 55 ℃ at the heating rate of 2 ℃/min, and the reaction is carried out for 4 hours;
(6) cooling to room temperature, pouring the mixture in the three-neck flask into a separating funnel, standing for 2h, layering, wherein the upper layer is the prepared microcapsule, and the lower layer is a shell (urea-formaldehyde resin without forming the microcapsule);
(7) taking the layered upper layer of the separating funnel, washing with deionized water and xylene respectively, and performing suction filtration;
(8) drying for 24h under normal pressure to obtain the product.
Fig. 11 is a photograph of the urea resin microcapsule obtained in this example under an optical microscope, and it can be seen that a large amount of uniformly and stably dispersed microcapsules are successfully prepared.
The urea-formaldehyde resin microcapsule powder obtained in the embodiment contains a large amount of microcapsules, the obtained urea-formaldehyde resin microcapsules are spherical, and the surfaces of the urea-formaldehyde resin microcapsules are rough.
The urea-formaldehyde resin microcapsule obtained in the embodiment is added into the coating, and the urea-formaldehyde resin microcapsule in the coating can keep a spherical shape and stably exist in the coating.
After detection, the urea-formaldehyde resin microcapsule obtained by the invention is added into the coating, the coating has self-repairing capability.
Claims (10)
1. A preparation method of a urea-formaldehyde resin microcapsule as a coating repairing agent is characterized by comprising the following steps:
(1) adding water and an emulsifier into a reactor, and stirring;
(2) adding urea, ammonium chloride, a water-resistant auxiliary agent and a defoaming agent into a reactor;
(3) adjusting the pH value to 3-4 by using acid, and starting stirring;
(4) dropwise adding a repairing agent into the reactor, and continuously stirring after dropwise adding is finished;
(5) dripping methanol into the reactor, and heating for reaction;
(6) cooling the reactor to room temperature, pouring the mixture in the reactor into a separating funnel, standing and layering;
(7) taking the layered upper layer of the separating funnel, washing with deionized water and an organic solvent respectively, and performing suction filtration;
(8) and (5) drying to obtain the finished product.
2. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to claim 1, wherein in the step (1), the emulsifier is one or two or more of OP-10, sodium dodecyl benzene sulfonate, polyvinyl alcohol, arabinogelatin and oleic acid, and preferably the mass ratio of the sodium dodecyl benzene sulfonate to the polyvinyl alcohol is 0.8-1.2: 1; the mass ratio of the water to the emulsifier is preferably 0.3-8.0: 1000, and more preferably 0.7-6.0: 1000; the stirring temperature is preferably 70-80 ℃, and the mixture is cooled to room temperature after the stirring is finished; the rotating speed of the stirring is 300-400 r/min; the stirring time is 3-4 h.
3. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to claim 1 or 2, wherein in the step (2), the mass ratio of urea to water is 1.2-2.0: 100; the mass ratio of the ammonium chloride to the urea is preferably 8-20: 100; the mass optimal ratio of the water-resistant auxiliary agent to the urea is 2.5-5.0: 100; the dosage ratio of the defoaming agent to the water is preferably 2-7 drops to 1000 g; the water-resistant auxiliary agent is preferably one, two or more of melamine, phenol, resorcinol, alkylamine and furfural; the anti-foaming agent is preferably n-butanol.
4. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 3, wherein in the step (3), the acid is one, two or more of hydrochloric acid, sulfuric acid, citric acid monohydrate, acetic acid, hypochlorous acid and oxalic acid.
5. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 4, wherein in the step (4), the mass ratio of the repairing agent to urea is 2.5-3.6: 1; the dropping speed is 1-2 g/min; continuously stirring for 10-15min after the dropwise addition is finished; the repairing agent is preferably one, two or more of dicyclopentadiene, castor oil, tung oil, linseed oil, methyl eleostearate, maleic anhydride and isocyanate.
6. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 5, wherein the rotation speed of stirring in the steps (3) and (4) is 600-800 r/min.
7. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 6, wherein in the step (5), the dosage ratio of the methanol to the urea is 1.8-2.6 ml:1 g; the heating rate is 2-5 ℃/min, the reaction temperature is 55-60 ℃, and the reaction time is 4-5 h; the dropping and the reaction are carried out under the stirring condition, and the stirring rotating speed is 600-800 r/min.
8. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 7, wherein in the step (6), the standing time is 1 to 2 hours.
9. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 8, wherein in the step (7), the organic solvent is ethanol, xylene, ethyl acetate or acetone.
10. The preparation method of the urea-formaldehyde resin microcapsule as the coating repairing agent according to any one of claims 1 to 9, wherein in the step (8), the drying is normal pressure drying, reduced pressure drying, spray drying or freeze drying; the drying time is 20-24 h.
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