CN113355948A - Super-hydrophobic paper and preparation method thereof - Google Patents
Super-hydrophobic paper and preparation method thereof Download PDFInfo
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- CN113355948A CN113355948A CN202110704750.7A CN202110704750A CN113355948A CN 113355948 A CN113355948 A CN 113355948A CN 202110704750 A CN202110704750 A CN 202110704750A CN 113355948 A CN113355948 A CN 113355948A
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
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- 239000011259 mixed solution Substances 0.000 claims abstract description 23
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- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 81
- 239000002244 precipitate Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 34
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- MCBSQDOGJSTPJG-UHFFFAOYSA-N [2-(bromomethyl)phenyl]-phenylmethanone Chemical compound BrCC1=CC=CC=C1C(=O)C1=CC=CC=C1 MCBSQDOGJSTPJG-UHFFFAOYSA-N 0.000 claims description 11
- 238000012698 light-induced step-growth polymerization Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000123 paper Substances 0.000 description 70
- 238000004806 packaging method and process Methods 0.000 description 13
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
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- 238000001020 plasma etching Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PVDVNJLRYCFOOT-UHFFFAOYSA-N N12CCCCCC2=NCCC1.CC1=CC=CC=C1 Chemical compound N12CCCCCC2=NCCC1.CC1=CC=CC=C1 PVDVNJLRYCFOOT-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
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- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Paper (AREA)
Abstract
A preparation method of super-hydrophobic paper comprises the following steps: (1) preparing 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in the form of white solid powder; (2) preparing 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state; (3) preparing an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics, and mixing the acetone solution with ultraviolet curing resin to obtain a mixed solution; (4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper. The invention also provides the super-hydrophobic paper prepared by the preparation method of the super-hydrophobic paper. The preparation process of the super-hydrophobic paper does not use fluorine-containing reagents, is simple, has low energy consumption and low price of used raw materials, and is beneficial to reducing the production cost.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to super-hydrophobic paper and a preparation method thereof.
Background
The packaging material is used for manufacturing packaging containers, packaging decoration, packaging printing, packaging transportation and the like, meets the requirements of product packaging, and comprises main packaging materials such as metal, plastic, glass, ceramics, paper, bamboo, wild mushrooms, natural fibers, chemical fibers, composite materials and the like, and auxiliary materials such as strapping, decoration, printing materials and the like. With the national requirements of plastic restriction, environmental protection and the like, the packaging material can be developed towards a degradable material later. As a degradable material, the paper has the characteristics of low cost, recycling and the like, and meets the requirement. However, the conventional paper has the characteristics of easy moisture absorption and greatly reduced strength after water absorption, so that the development of the water-resistant and moisture-resistant paper is urgently needed in the field of packaging.
Photopolymerization refers to a method of polymerizing monomers by photochemical reaction. The monomer can be directly excited by light to cause polymerization, or the photosensitizer and the photoinitiator can be excited by light to cause polymerization, and the latter is also called photopolymerization. The method has the characteristics of low polymerization temperature, high reaction selectivity, easy control and the like, can generate reaction which can not be carried out by common molecules, and expands means for obtaining high molecules. The production of macromolecules by photopolymerization has the following advantages: the activation energy is low, and low-temperature polymerization is easy to realize; in the experiment, pure macromolecules without initiator residues can be obtained; the quantum efficiency is high, and a large amount of monomer molecules are polymerized into macromolecules due to the absorption of one photon.
The Chinese patent application with publication number CN 107653744A discloses super-hydrophobic paper and a preparation method thereof, wherein the preparation method of the super-hydrophobic paper comprises the following steps: (1) carrying out hydroxylation modification on paper; (2) etching the paper by adopting a plasma etching method; (3) carrying out plasma pretreatment on the paper by taking Ar as a gas source; (4) and depositing the super-hydrophobic film on the surface of the paper by adopting a plasma chemical vapor deposition method. According to the invention, the paper is etched by adopting a plasma etching method, a microstructure can be prepared on the surface of the paper, the specific surface area of the paper is increased, the roughness of the paper is increased, the surface of the paper is difficult to be soaked by water, and the contact angle is favorably improved; the paper is modified by fluorine, and the fluorine-containing super-hydrophobic film is deposited on the surface of the paper by a plasma chemical vapor deposition method, so that the paper has the advantages of high strength and scratch resistance, and the hydrophobic property of the paper is longer-lasting and longer-lasting. However, the fluorine-containing reagent used in the invention has adverse effects on human bodies and environment, and the application of the prepared super-hydrophobic paper in the field of packaging is limited by performing hydrophobic modification on the paper by adopting the fluorine-containing reagent.
The Chinese patent application with publication number CN 110939012A discloses low-basis weight super-hydrophobic packaging paper and a preparation method thereof, wherein the packaging paper comprises packaging base paper, a hydrophobic coating, a micro-structure coating and a nano-structure coating; the hydrophobic coating is composed of a low melting point wax; the microstructure coating is comprised of a high melting point wax; the nanostructured coating is comprised of modified nanosilica. The packaging base paper is obtained by coating wax emulsion and modified silicon dioxide respectively and then calendaring by a soft roller; the mixed wax is in a micron particle state, and can fully fill the gaps of the fibers on the surface of the paper sheet; meanwhile, the hydrophobic nano silicon dioxide particles are filled between the fibers and the micron wax to form a hydrophobic micro-nano structure, so that the hydrophobic property of the paper can be obviously improved, the contact angle is improved, and the rolling angle is reduced. The invention does not relate to fluorine-containing reagents, and the prepared paper has a good application scene, but the preparation process of the super-hydrophobic packaging paper needs to consume a large amount of energy, so that the large-scale preparation is not facilitated.
Disclosure of Invention
The invention aims to solve the technical problem of providing the super-hydrophobic paper and the preparation method thereof, wherein the preparation process of the super-hydrophobic paper does not use fluorine-containing reagents, is simple, has low energy consumption and low price of used raw materials, and is beneficial to reducing the production cost. The technical scheme is as follows:
a preparation method of super-hydrophobic paper is characterized by comprising the following steps:
(1) dissolving 4- (bromomethylbenzophenone) in toluene, then dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and stirring at the rotation speed of 300 ‒ 500 rpm at 20-30 ℃ for 12 ‒ 24 hours; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) obtained in the step (1) in water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution, and stirring at the temperature of 20-30 ℃ at the rotating speed of 300 ‒ 500 rpm for 2 ‒ 4 hours; then filtering to obtain precipitate, washing the precipitate for a plurality of times by using water, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt obtained in the step (2) and a peroxyorganic substance into acetone by using ultrasonic waves to obtain an acetone solution of the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganic substance; then mixing the acetone solution of 4- (methyl benzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenyl boron quaternary ammonium salt/peroxy organic substance with ultraviolet curing resin to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
Preferably, in the step (1), the parts by mass of the 4- (bromomethylbenzophenone), the 1, 8-diazabicyclo [5.4.0] undec-7-ene and the toluene are 1 ‒ 2 parts, 0.5 ‒ 1 parts and 97 ‒ 99 parts, respectively. In the step (1), the mass parts of 4- (bromomethylbenzophenone), 1, 8-diazabicyclo [5.4.0] undec-7-ene and toluene are 1.5 parts, 0.75 part and 97.75 parts, respectively. The toluene is the sum of toluene used for dissolving 4- (bromomethylbenzophenone) and toluene contained in a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene.
Preferably, in the step (1), the 1, 8-diazabicyclo [5.4.0] undec-7-ene toluene solution is dropwise added at a constant speed for 20-40 minutes.
In the step (2), the parts by mass of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene), sodium tetraphenylborate and water are preferably 0.6 ‒ 0.9.9 parts, 0.6 ‒ 0.8.8 parts and 97 to 99 parts, respectively. More preferably, in step (2), the parts by mass of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene), sodium tetraphenylborate and water are 0.75 part, 0.7 part and 98.55 parts, respectively.
Preferably, in the step (2), the tetraphenylboron sodium aqueous solution is dropwise added at a constant speed for 20-40 minutes.
Preferably, in the step (2), a magnetic stirrer is used for stirring.
Preferably, in the step (2), the precipitate is washed with water several times in the range of 2 to 5 times.
In the preferred step (3), the parts by mass of the quaternary ammonium salt of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron, the peroxyorganics, acetone and the ultraviolet-curable resin are 0.8 ‒ 1.2.2 parts, 0.3 ‒ 0.5.5 parts, 27 ‒ 29 parts and 69 ‒ 72 parts, respectively. More preferably, in the step (3), the parts by mass of the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt, the peroxyorganics, the acetone and the ultraviolet-curable resin are 1 part, 0.4 part, 28 parts and 70.6 parts, respectively.
The ultraviolet light curing resin is preferably one or the combination of two of trimethylolpropane triacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate. More preferably, the ultraviolet curable resin is trimethylolpropane triacrylate.
Preferably, the peroxygen organic compound is one or a combination of two of dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate and cumene hydroperoxide. More preferably, the peroxygen organic compound is dibenzoyl peroxide.
The invention also provides the super-hydrophobic paper prepared by the preparation method of the super-hydrophobic paper.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation method of the super-hydrophobic paper, the used raw materials can be purchased in a large scale, and the raw materials are low in price, so that a foundation is laid for large-scale production of the super-hydrophobic paper;
(2) the preparation method of the super-hydrophobic paper utilizes ultraviolet light for curing, has low energy consumption and is beneficial to reducing the production cost of the super-hydrophobic packaging paper. The preparation process of the super-hydrophobic paper does not use a fluorine-containing reagent, so that the paper is more environment-friendly;
(3) the invention can solve the problems that the strength of the paper is reduced due to the fact that the wrapping paper absorbs moisture easily and absorbs water easily, prolongs the service life of the paper when the paper is used as the wrapping paper, and reduces the use cost of the wrapping paper.
Drawings
FIG. 1 is a graph of water contact angle of superhydrophobic paper in example 1 of the invention;
FIG. 2 is a water contact angle diagram of the super hydrophobic paper in example 2 of the present invention;
FIG. 3 is a graph of water contact angle of the superhydrophobic paper in example 3 of the invention;
FIG. 4 is a graph of water contact angle of the superhydrophobic paper in example 4 of the invention;
FIG. 5 is a water contact angle graph of the superhydrophobic paper in example 5 of the invention.
Detailed Description
Example 1
In this embodiment, the preparation method of the super-hydrophobic paper includes the following steps:
(1) dissolving 1 part of 4- (bromomethylbenzophenone) in 90 parts of toluene, dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.5 part of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 8.5 parts of toluene in the solution; dropwise adding at a constant speed for 30 minutes), and stirring at 25 ℃ at a rotating speed of 400 rpm for 18 hours; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 0.6 part of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in 90 parts of water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution (the sodium tetraphenylborate aqueous solution contains 0.6 part of sodium tetraphenylborate and 8.8 parts of water; dropwise adding at a constant speed for 30 minutes is completed), and stirring at 25 ℃ at a rotation speed of 400 rpm for 3 hours (stirring by using a magnetic stirrer); then filtering to obtain precipitate, washing the precipitate with water for 3 times, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing 0.8 part of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt and 0.3 part of peroxyorganics (both dibenzoyl peroxide) into 27 parts of acetone by ultrasonic waves to obtain an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics; then mixing the acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxy organic substance with 71.9 parts of ultraviolet curing resin (all trimethylolpropane triacrylate) to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
The contact angle of the super hydrophobic paper was measured and the water contact angle was 147 deg., as shown in fig. 1.
Example 2
In this embodiment, the preparation method of the super-hydrophobic paper includes the following steps:
(1) dissolving 1.5 parts of 4- (bromomethylbenzophenone) in 90 parts of toluene, dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene (the solution contains 0.75 part of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 7.75 parts of toluene), dropwise adding at a constant speed, after 40 minutes of dropwise addition, and stirring at 30 ℃ at a rotating speed of 500 revolutions per minute for 12 hours; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 0.75 part of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in 90 parts of water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution (the sodium tetraphenylborate aqueous solution contains 0.75 part of sodium tetraphenylborate and 8.5 parts of water; dropwise adding at a constant speed for 40 minutes is completed), and stirring at 30 ℃ for 4 hours at a rotation speed of 300 revolutions per minute (stirring by using a magnetic stirrer); then filtering to obtain precipitate, washing the precipitate with water for 4 times, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing 1 part of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt and 0.4 part of peroxyorganics (both dibenzoyl peroxide) into 28 parts of acetone by ultrasonic waves to obtain an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics; then mixing the acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxy organic substance with 70.6 parts of ultraviolet curing resin (all trimethylolpropane triacrylate) to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
The contact angle of the super hydrophobic paper was measured and the water contact angle was 150 deg., as shown in fig. 2.
Example 3
In this embodiment, the preparation method of the super-hydrophobic paper includes the following steps:
(1) dissolving 2 parts of 4- (bromomethylbenzophenone) in 88 parts of toluene, dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene (the solution contains 1 part of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 9 parts of toluene; dropwise adding at a constant speed for 25 minutes), and stirring at 30 ℃ for 12 hours at a rotation speed of 500 revolutions per minute; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 0.9 part of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in 88.3 parts of water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution (the sodium tetraphenylborate aqueous solution contains 0.8 part of sodium tetraphenylborate and 10 parts of water; dropwise adding at a constant speed and after 40 minutes), and stirring at 30 ℃ at a rotating speed of 500 revolutions per minute for 2.5 hours (stirring by a magnetic stirrer); then filtering to obtain precipitate, washing the precipitate with water for 5 times, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing 1.2 parts of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt and 0.5 part of peroxyorganics (both dibenzoyl peroxide) into 29 parts of acetone by ultrasonic waves to obtain an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics; then mixing the acetone solution of 4- (methyl benzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenyl boron quaternary ammonium salt/peroxy organic substance with 69.3 parts of ultraviolet curing resin (all are n-butyl acrylate) to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
The contact angle of the super hydrophobic paper was measured and the water contact angle was 149 deg., as shown in fig. 3.
Example 4
In this embodiment, the preparation method of the super-hydrophobic paper includes the following steps:
(1) dissolving 2 parts of 4- (bromomethylbenzophenone) in 88 parts of toluene, dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene (the solution contains 1 part of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 9 parts of toluene; dropwise adding at a constant speed for 20 minutes), and stirring at the temperature of 20 ℃ for 20 hours at the rotating speed of 400 revolutions per minute; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 0.9 part of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in 88.3 parts of water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution (the sodium tetraphenylborate aqueous solution contains 0.8 part of sodium tetraphenylborate and 10 parts of water; dropwise adding at a constant speed for 25 minutes is completed), and stirring at 20 ℃ at a rotation speed of 400 rpm for 4 hours (stirring by using a magnetic stirrer); then filtering to obtain precipitate, washing the precipitate with water for 3 times, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing 1.2 parts of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt and 0.5 part of peroxyorganics (all dicumyl peroxide) into 29 parts of acetone by using ultrasonic waves to obtain an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics; then, mixing the acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxy organic substance with 69.3 parts of ultraviolet curing resin (all trimethylolpropane triacrylate) to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
The contact angle of the superhydrophobic paper was measured and the water contact angle was 148 deg., as shown in fig. 4.
Example 5
In this embodiment, the preparation method of the super-hydrophobic paper includes the following steps:
(1) dissolving 1.5 parts of 4- (bromomethylbenzophenone) in 90 parts of toluene, dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene (the solution contains 0.75 part of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 7.75 parts of toluene), dropwise adding at a constant speed, after 25 minutes of dropwise addition, and stirring at the rotation speed of 400 revolutions per minute for 20 hours at 25 ℃; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 0.75 part of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in 90 parts of water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution (the sodium tetraphenylborate aqueous solution contains 0.75 part of sodium tetraphenylborate and 8.5 parts of water; dropwise adding at a constant speed for 25 minutes is completed), and stirring at 25 ℃ at a rotation speed of 400 rpm for 2.5 hours (stirring by using a magnetic stirrer); then filtering to obtain precipitate, washing the precipitate with water for 3 times, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing 1 part of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt and 0.4 part of peroxyorganics (both tert-butyl peroxybenzoate) into 28 parts of acetone by using ultrasonic waves to obtain an acetone solution of 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganics; then mixing the acetone solution of 4- (methyl benzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenyl boron quaternary ammonium salt/peroxy organic substance with 70.6 parts of ultraviolet curing resin (methyl methacrylate) to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
The contact angle of the super hydrophobic paper was measured and the water contact angle was 149 deg., as shown in fig. 5.
Claims (10)
1. A preparation method of super-hydrophobic paper is characterized by comprising the following steps:
(1) dissolving 4- (bromomethylbenzophenone) in toluene, then dropwise adding a toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and stirring at the rotation speed of 300 ‒ 500 rpm at 20-30 ℃ for 12 ‒ 24 hours; then filtering to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) in a white solid powder state;
(2) dissolving 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) obtained in the step (1) in water, then dropwise adding an excessive sodium tetraphenylborate aqueous solution, and stirring at the temperature of 20-30 ℃ at the rotating speed of 300 ‒ 500 rpm for 2 ‒ 4 hours; then filtering to obtain precipitate, washing the precipitate for a plurality of times by using water, and then carrying out vacuum drying on the precipitate; dissolving the precipitate in a mixed solvent of ethanol and acetone, and recrystallizing to obtain 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt in a white crystal state;
(3) preparing a resin mixed solution capable of being subjected to ultraviolet light induced polymerization: dispersing the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt obtained in the step (2) and a peroxyorganic substance into acetone by using ultrasonic waves to obtain an acetone solution of the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt/peroxyorganic substance; then mixing the acetone solution of 4- (methyl benzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenyl boron quaternary ammonium salt/peroxy organic substance with ultraviolet curing resin to obtain a mixed solution;
(4) and (4) coating the mixed solution obtained in the step (3) on the surface of paper to form a coating, and curing the coating through ultraviolet irradiation to obtain the super-hydrophobic paper.
2. The method for preparing superhydrophobic paper according to claim 1, characterized by: in the step (1), the mass parts of 4- (bromomethylbenzophenone), 1, 8-diazabicyclo [5.4.0] undec-7-ene and toluene are 1 ‒ 2 parts, 0.5 ‒ 1 parts and 97 ‒ 99 parts, respectively.
3. The method for preparing superhydrophobic paper according to claim 1, characterized by: in the step (1), the toluene solution of 1, 8-diazabicyclo [5.4.0] undec-7-ene is dropwise added at a constant speed for 20-40 minutes.
4. The method for preparing superhydrophobic paper according to claim 1, characterized by: in the step (2), the mass parts of 4- (bromomethylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene), sodium tetraphenylborate and water are 0.6-0.9 part, 0.6-0.8 part and 97-99 parts respectively.
5. The method for preparing superhydrophobic paper according to claim 1, characterized by: and (3) dropwise adding the sodium tetraphenylborate aqueous solution at a constant speed for 20-40 minutes.
6. The method for preparing superhydrophobic paper according to claim 1, characterized by: in the step (2), a magnetic stirrer is adopted for stirring; in the step (2), the precipitate is washed with water for 2 to 5 times.
7. The method for preparing superhydrophobic paper according to claim 1, characterized by: in the step (3), the mass parts of the 4- (methylbenzophenone) - (1, 8-diazabicyclo [5.4.0] undec-7-ene) tetraphenylboron quaternary ammonium salt, the peroxy organic compound, the acetone and the ultraviolet curing resin are 0.8-1.2 parts, 0.3-0.5 part, 27-29 parts and 69-72 parts respectively.
8. The method for preparing superhydrophobic paper according to claim 1, characterized by: the ultraviolet light curing resin is one or the combination of two of trimethylolpropane triacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate and n-butyl methacrylate.
9. The method for preparing superhydrophobic paper according to claim 1, characterized by: the peroxide organic matter is one or the combination of two of dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate and cumene hydroperoxide.
10. The superhydrophobic paper made by the method of making the superhydrophobic paper of any of claims 1-9.
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| WO2010095390A1 (en) * | 2009-02-18 | 2010-08-26 | サンアプロ株式会社 | Photosensitive resin composition |
| WO2012064745A2 (en) * | 2010-11-08 | 2012-05-18 | University Of Florida Research Foundation, Inc. | Articles having superhydrophobic and oleophobic surfaces |
| CN109440525A (en) * | 2018-10-31 | 2019-03-08 | 华南理工大学 | A kind of wear-resisting ultra-hydrophobic paper and preparation method thereof |
| CN112029325A (en) * | 2020-09-01 | 2020-12-04 | 淮阴工学院 | Preparation method of polyacrylate super-hydrophobic coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010095390A1 (en) * | 2009-02-18 | 2010-08-26 | サンアプロ株式会社 | Photosensitive resin composition |
| WO2012064745A2 (en) * | 2010-11-08 | 2012-05-18 | University Of Florida Research Foundation, Inc. | Articles having superhydrophobic and oleophobic surfaces |
| CN109440525A (en) * | 2018-10-31 | 2019-03-08 | 华南理工大学 | A kind of wear-resisting ultra-hydrophobic paper and preparation method thereof |
| CN112029325A (en) * | 2020-09-01 | 2020-12-04 | 淮阴工学院 | Preparation method of polyacrylate super-hydrophobic coating |
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