CN116751510B - Preparation method of photo-curing coating of acrylic resin composite nanocellulose - Google Patents
Preparation method of photo-curing coating of acrylic resin composite nanocellulose Download PDFInfo
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- CN116751510B CN116751510B CN202310838545.9A CN202310838545A CN116751510B CN 116751510 B CN116751510 B CN 116751510B CN 202310838545 A CN202310838545 A CN 202310838545A CN 116751510 B CN116751510 B CN 116751510B
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 76
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 14
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 14
- -1 4- (4-vinylbenzyloxy) -4- (bromoethyl) benzophenone Chemical compound 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims description 39
- 229920002678 cellulose Polymers 0.000 claims description 36
- 239000001913 cellulose Substances 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000000835 fiber Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 23
- 238000000502 dialysis Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 239000002121 nanofiber Substances 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 108010059892 Cellulase Proteins 0.000 claims description 13
- 229940106157 cellulase Drugs 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 230000000415 inactivating effect Effects 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 7
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims description 6
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 6
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RQAVKYPVSDCFJQ-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxy)prop-2-enamide Chemical compound CC(C)CONC(=O)C(C)=C RQAVKYPVSDCFJQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000007650 screen-printing Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- 238000007385 chemical modification Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/16—Aryl or aralkyl ethers
- C08B11/18—Aryl or aralkyl ethers with substituted hydrocarbon radicals
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of a photo-curing coating of acrylic resin composite nanocellulose, which specifically comprises the following steps: step 1, preparing spherical nanocellulose; step 2, preparing 4- (4-vinylbenzyloxy) -4- (bromoethyl) benzophenone; step 3, modifying the spherical nanocellulose obtained in the step 1 by adopting the product obtained in the step 2 to obtain G-spherical nanocellulose; and 4, preparing the photo-curing coating according to the product obtained in the step 3. The spherical nanocellulose prepared by the invention is compounded in the ultraviolet light curing coating, so that the ultraviolet absorption capacity, rheological property, mechanical strength and friction resistance of the ultraviolet light curing coating can be improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a preparation method of a photo-curing coating of acrylic resin composite nanocellulose.
Background
Photo-curable coatings are widely used for surface treatment of paper, plastics, leather, metal, glass, wood, and the like. In recent years, photocurable resins have been successfully used in the high-end optoelectronic fields such as optical fibers, electronic circuits, and optoelectronic device packages. As the use of photocurable resins advances from the lower end to the higher end, higher demands are placed on their properties, such as color, absorption coefficient, rheology, film formation strength, and abrasion resistance. As a class of commodity, the color of the paint seriously affects the quality and the value of the paint; the absorption coefficient affects the time required for curing the coating; the film forming strength and the abrasion resistance determine the service life of the material; the rheology determines the film forming process of the photo-curable coating, e.g. a shear thinning coating is advantageous for screen printing film forming processes. In order to solve the problems of mechanical strength and wear resistance of the material, graphene is introduced into a coating component, and the high mechanical strength and friction resistance of the graphene are combined with the photo-curing performance of the resin; the nano silicon dioxide and the paint are hybridized, so that the mechanical strength and the abrasion resistance of the paint after film formation are improved. It is well known that graphene itself is black and is compounded in a coating, which can seriously affect the photocuring film-forming color thereof. The nano silicon dioxide is used as an inorganic material, has poor compatibility with coating components (organic monomers, organic oligomers, initiators) and the like, and is easy to deposit and delaminate. The unification of the light absorption coefficient, the rheological property, the mechanical strength and the wear resistance is realized, and the application of the material in the high-end fields such as optoelectronic devices and the like is facilitated.
Disclosure of Invention
The invention aims to provide a preparation method of a photo-curing coating of acrylic resin composite nanocellulose, and the spherical nanocellulose prepared by the method is compounded in the ultraviolet curing coating, so that the ultraviolet absorption capacity, rheological property, mechanical strength and friction resistance of the photo-curing coating can be improved.
The technical scheme adopted by the invention is that the preparation method of the photo-curing coating of the acrylic resin composite nanocellulose specifically comprises the following steps:
step 1, preparing spherical nanocellulose;
step 2, preparing 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone;
step 3, modifying the spherical nanocellulose obtained in the step 1 by adopting the product obtained in the step 2 to obtain G-spherical nanocellulose;
And 4, preparing the photo-curing coating according to the product obtained in the step 3.
The invention is also characterized in that:
the specific steps of the step1 are as follows:
step 1.1, placing 2g-6g of cotton pulp into a beaker, and then sequentially adding 0.01g-0.03g of composite cellulase and 20mL-40mL of citric acid buffer solution to obtain suspension;
Step 1.2, diluting the mass concentration of the suspension obtained in the step 1.1 to 0.5-1.5 wt%, then placing the suspension in a constant-temperature water bath oscillator with the temperature of 35-45 ℃ for reaction for 1-3 hours, immediately inactivating the suspension by using a boiling water bath for 12-24 minutes after the reaction is finished, rapidly filtering under reduced pressure of 10 -2 Pa, washing a filter cake by using distilled water for 6-10 times, and collecting pretreated fibers;
1.3, taking 1-3g of the pretreated fiber obtained in the step 1.2, performing ultrasonic dispersion in water at 20Hz-40 Hz to prepare cellulose solution with concentration of 8-12 wt%, and passing through a homogenizer for 8-12 times under the pressure of 120MPa to obtain cellulose nanofiber CNFs;
step 1.4, sequentially adding 10-30 mL of citric acid buffer solution and 0.01-0.03 g of compound cellulase into the cellulose nanofiber CNFs obtained in step 1.3 to obtain a suspension;
Step 1.5, diluting the mass concentration of the suspension obtained in the step 1.4 to 0.5% -1.5%, then reacting for 2-6 hours at 35-45 ℃ in a water bath kettle, and immediately inactivating for 12-24min by using a boiling water bath when the reaction is terminated to obtain hydrolyzed cellulose;
and 1.6, dialyzing and removing glucose small molecules in the hydrolyzed cellulose obtained in the step 1.5 by using a 7000Da dialysis bag, and removing unhydrolyzed particle fibers by using a centrifuge under the condition of 5000-7000rpm to obtain the spherical nano-cellulose.
The specific process of the step2 is as follows:
step 2.1, synthesizing 4- (4-vinyl benzyl) -4' -hydroxy diphenyl ketone;
Step 2.2, 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone was synthesized according to the product obtained in step 2.1.
The specific process of the step 2.1 is as follows:
2g-6g of 4,4 '-dihydroxybenzophenone is taken to be dissolved in 10mL-20mL of N, N-dimethylformamide solvent, 40g-120g of sodium hydride is added to be stirred for half an hour, then 0.27 mL-0.9 mL of 4-vinylbenzyl chloride is dropwise added, the mixture is stirred for 12h-36h at 80 ℃ to 120 ℃ and 4- (4-vinylbenzyl) -4' -hydroxybenzophenone white products are obtained through silica gel column separation.
The specific process of the step 2.2 is as follows:
1g-3g of 4- (4-vinylbenzyloxy) -4 '-hydroxybenzophenone is weighed and dissolved in 5mL-15mL of N, N-dimethylformamide solution, then 0.5mL-1.5mL of bromoacetyl bromide is added, stirring is carried out for 12h-36h at 80 ℃ to 120 ℃, and 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone white product is obtained through silica gel column separation.
The specific process of the step 3 is as follows:
Dispersing 0.5G-1.5G of spherical nanocellulose prepared in the step 1 in 10mL-30mL of pyridine solution, performing ultrasonic dispersion for half an hour, adding 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone prepared in the step 2, reacting for 3-9 hours at 80-120 ℃, cooling after the reaction is finished, dialyzing for 12-36 hours by using a 7000Da dialysis bag to remove impurities, repeating the dialysis for three times, and then performing freeze drying at-40 ℃ for 12-48 hours to obtain G-spherical nanocellulose, and storing at 0-10 ℃ for standby.
The specific process of the step 4 is as follows:
And 4.1, respectively weighing the following components in percentage by mass: 20 to 40 weight percent of polyurethane acrylic ester, 10 to 30 weight percent of G-spherical nano cellulose, 20 to 31 weight percent of isooctyl acrylate, 15 to 35 weight percent of N-isobutoxy methacrylamide, 2 to 3 weight percent of 1-hydroxycyclohexyl phenyl ketone and 2 to 3 weight percent of polyether siloxane, wherein the sum of the mass percentages of the components is 100 percent;
And 4.2, uniformly mixing the coating components in the step 4.1 to obtain the photo-curing coating solution.
The invention has the beneficial effects that in the coating component, the ultraviolet light absorption capacity at 365nm is improved by utilizing the 4- (4-vinylbenzyloxy) -4- (bromoethyl) benzophenone modified spherical nano cellulose; as the spherical nano-cellulose is a crystal material, the crystallinity of the spherical nano-cellulose is as high as 85 percent, and the spherical nano-cellulose is combined by a large amount of hydrogen bonds, so that compared with pyridine amorphous acrylic resin, the friction resistance is improved. Meanwhile, the nano cellulose crystal is used as a guest (plasticizer) to improve the mechanical strength of the material.
Drawings
FIG. 1 is a haze light scattering diagram of the coatings prepared in example 1 and comparative example 1 in the preparation method of the photo-curable coating of acrylic resin composite nanocellulose according to the present invention;
FIG. 2 is a flow chart of the coating prepared in example 1 and comparative example 1 in the preparation method of the photo-curable coating of acrylic resin composite nanocellulose according to the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a preparation method of a photo-curing coating of acrylic resin composite nanocellulose, which specifically comprises the following steps:
step 1, preparation of spherical nanocellulose
2G-6g cotton pulp is placed in a beaker, composite cellulase (FPU, 0.01-0.03 g) and citric acid buffer solution (pH=4.8, 20-40 mL) are added to obtain suspension, the mass concentration of the suspension is regulated to 0.5-1.5wt%, and then the suspension is placed in a constant temperature water bath oscillator with the set temperature of 35-45 ℃ for reaction for 1-3h. Immediately inactivating the fiber in boiling water bath for 12-24min after the reaction, rapidly filtering under reduced pressure (10 -2 Pa), washing the filter cake with distilled water for 6-10 times, and collecting pretreated fiber.
1-3G of the pretreated fiber is taken, dispersed in water by ultrasonic (20-40 Hz) to prepare a medium-high concentration cellulose solution (8-12 wt%) and the cellulose solution is passed through a homogenizer for 8-12 times under 120MPa pressure to obtain Cellulose Nanofibers (CNFs) (the fiber pretreated by the compound cellulase is homogenized under high pressure to obtain cellulose nanofiber CNF). Further adding citric acid buffer solution (10-30 mL) with pH=4.8 and complex cellulase (FPU, 0.01-0.03 g) to obtain suspension, adjusting the mass concentration of the suspension to be diluted to 0.5-1.5%, and then reacting in a water bath kettle at 35-45 ℃ for 2-6 hours. Immediately after the reaction is terminated, the reaction is inactivated by a boiling water bath for 12-24min. The small glucose molecules after cellulose hydrolysis are removed by dialysis with a 7000Da dialysis bag, and unhydrolyzed large particle fibers are further removed by a centrifuge at 5000-7000 rpm.
Step 2, synthesis of 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone
2-6G of 4,4' -dihydroxybenzophenone is taken and dissolved in 10-20mL of N, N-Dimethylformamide (DMF) solvent, 40-120g of sodium hydride is stirred for half an hour, then 0.27 mL-0.9 mL of 4-vinylbenzyl chloride is dropwise added, and the mixture is stirred for 12-36 hours at 80-120 ℃. The 4- (4-vinylbenzyl) -4' -hydroxybenzophenone was isolated as a white product in 92% yield by silica gel column.
1-3G of 4- (4-vinylbenzyloxy) -4' -hydroxybenzophenone is weighed and dissolved in 5-15mL of DMF solution, then 0.5-1.5mL of bromoacetyl bromide is added, and stirring is carried out for 12-36h at 80-120 ℃. The 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone was obtained as a white product by silica gel column separation in 80% yield.
Step 3, chemical modification of spherical nanocellulose (G-spherical nanocellulose)
Dispersing 0.5-1.5g spherical nano cellulose in 10-30mL pyridine solution, ultrasonically dispersing for half an hour, adding 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone, and reacting at 80-120 ℃ for 3-9 hours. After the reaction is finished, cooling, dialyzing for 12-36 hours by using a 7000Da dialysis bag, removing the organic solvent and other newly generated small molecular compounds, and repeating the dialysis for three times. Freeze drying at-40 deg.c for 12-48 hr to obtain G-spherical nanometer cellulose, and low temperature preserving at 0-10 deg.c.
Step 4, preparation of G-spherical nanocellulose-based photocureable coating and film forming property research
Configuration of the photo-curable coating solution: polyurethane acrylic ester (20-40 wt%), G-spherical nano cellulose (10-30 wt%), isooctyl acrylate (20-31 wt%), N-isobutoxy methacrylamide (15-35 wt%), 1-hydroxycyclohexyl phenyl ketone (2-3 wt%), polyether siloxane (Tego 450 flatting agent, 2-3 wt%), and the mass percentages of the components are hundred percent.
After the coating components are uniformly mixed, vacuumizing is carried out under the negative pressure of 1x10 -3 Pa to remove air. Pouring the photo-curing coating solution into a screen printing mold, taking high molecular PET as a carrier, uniformly coating the photo-curing coating solution on the surface of the PET through screen printing, further curing the PET in an ultraviolet curing machine, and carrying out flash irradiation for 1-3 min at the temperature of 80-120 ℃, wherein the ultraviolet power is 80-120W, and the film thickness is 0.3-0.9 um.
Example 1
Step 1, preparation of spherical nanocellulose
5G of cotton pulp was placed in a beaker, and complex cellulase (FPU, 0.01 g) and citric acid buffer (ph=4.8, 20 mL) were added to adjust the mass concentration of the suspension to 1.5wt%, and then placed in a thermostatic water bath shaker at a set temperature of 40 ℃ to react for 2 hours. Immediately after the reaction, inactivating the fiber by using a boiling water bath for 24min, rapidly filtering under reduced pressure (10 -2 Pa), washing the filter cake by using distilled water for 6 times, and collecting the pretreated fiber. 2g of the pretreated fiber was prepared into an 8% cellulose solution, and the Cellulose Nanofiber (CNFs) was obtained by passing through a homogenizer 8 times under a pressure of 120 MPa. Further added (ph=4.8, 30 mL) of citric acid buffer and complex cellulase (FPU, 0.01 g) and the suspension mass concentration was adjusted to dilute to 1.5% and then reacted in a water bath at 45 ℃ for 6 hours. Immediately upon termination of the reaction, the reaction was inactivated with a boiling water bath for 24min. And (3) dialyzing to remove hydrolyzed glucose small molecules by using a 7000Da dialysis bag, and further removing the hydrolyzed glucose small molecules into hydrolyzed large-particle fibers by using a centrifuge under the condition of 7000rpm to obtain the G-spherical nano-cellulose.
Step 2, synthesis of 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone
2.14G of 4,4' -dihydroxybenzophenone is dissolved in 10mL of DMF solvent and 40g of sodium hydride are stirred for half an hour, then 0.9mL of 4-vinylbenzyl chloride are added dropwise and stirred for 12 hours at 80 ℃. The 4- (4-vinylbenzyl) -4' -hydroxybenzophenone was isolated as a white product in 92% yield by silica gel column.
1G of 4- (4-vinylbenzyloxy) -4' -hydroxybenzophenone was weighed out in 5mL of DMF solution, then 0.5mL of bromoacetyl bromide was added and stirred at 80℃for 12h. The 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone was obtained as a white product by silica gel column separation in 80% yield.
Step 3, chemical modification of spherical nanocellulose (G-spherical nanocellulose)
0.5G of spherical nanocellulose is taken and dispersed in 10mL of pyridine solution, ultrasonic dispersion is carried out for half an hour, 4- (4-vinylbenzyloxy) -4- (bromoethyl) benzophenone is added, and reaction is carried out for 3 hours at 80 ℃. After the reaction is finished, cooling, dialyzing for 12 hours by using a 7000Da dialysis bag, removing the organic solvent and other newly generated small molecular compounds, and repeating for three times. Freeze-drying at-40 deg.C for 24 hr to obtain G-spherical nano cellulose, and low-temperature preserving at 10 deg.C.
Step 4, preparation of spherical nanocellulose-based photo-curing coating and film forming property research
Configuration of the photo-curable coating solution: 20% by weight of polyurethane acrylate, 10% by weight of G-spherical nanocellulose, 31% by weight of isooctyl acrylate, 35% by weight of N-isobutoxymethyl acrylamide, 2% by weight of 1-hydroxycyclohexyl phenyl ketone, 2% by weight of polyether siloxane. The sum of the mass percentages of the components is hundred percent.
And (3) uniformly mixing the coating components, and vacuumizing to remove air. Pouring the photo-curing coating solution into a screen printing mold, taking high molecular PET as a carrier, uniformly coating the photo-curing coating solution on the surface of PET through screen printing, further placing the film into an ultraviolet curing machine for curing, and carrying out flash irradiation for 1 minute at 80 ℃, wherein the ultraviolet power is 80W, and the film thickness is 0.5um.
Comparative example 1
Chemical modification of cellulose nanofibers (G-nanocellulose)
0.5G of nanocellulose is taken and dispersed in 10mL of pyridine solution, ultrasonic dispersion is carried out for half an hour, 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone is added, and reaction is carried out for 3 hours at 80 ℃. After the reaction is finished, cooling, dialyzing for 12 hours by using a 7000Da dialysis bag, removing the organic solvent and other newly generated small molecular compounds, and repeating for three times. Freeze-drying at-40 deg.C for 24 hr to obtain G-nanocellulose, and storing at 10deg.C for use.
Preparation of photo-curing coating of cellulose nanofiber and film forming property research
Configuration of the photo-curable coating solution: 20% by weight of polyurethane acrylate, 10% by weight of G-nanocellulose, 31% by weight of isooctyl acrylate, 35% by weight of N-isobutoxymethyl acrylamide, 2% by weight of 1-hydroxycyclohexyl phenyl ketone, 2% by weight of polyether siloxane. The sum of the mass percentages of the components is hundred percent.
And (3) uniformly mixing the coating components, and vacuumizing to remove air. Pouring the photo-curing coating solution into a screen printing mold, taking high molecular PET as a carrier, uniformly coating the photo-curing coating solution on the surface of PET through screen printing, further placing the film into an ultraviolet curing machine for curing, and carrying out flash irradiation for 1 minute at 80 ℃, wherein the ultraviolet power is 80W, and the film thickness is 0.5um.
The test results of example 1 and comparative example 1 are shown in table 1 below:
TABLE 1
The pencil hardness test shows that the G-spherical nanocellulose photocureable coating prepared in the example 1 has higher pencil hardness (3H) after film formation under the same test conditions, mainly because the G-spherical nanocellulose has higher hardness.
And the G-nanocellulose photo-curing coating prepared in comparative example 1, the film formed has voids inside the film due to the cellulose nanofibers being prone to intertwining between fibers, resulting in an increase in haze to 9.0%. In terms of rheology, since the G-spherical nanocellulose prepared in example 1 has the same orientation in all directions, while avoiding intertwining between fibers, the resulting coating exhibits shear thinning.
In contrast, the G-nanocellulose prepared in comparative example 1 was easily entangled between fibers, and the fiber orientation tended to move in the direction of motion, eventually being shear thickened.
Fracture strength aspect: the photo-curable coatings prepared in example 1 and comparative example 1 formed films (65 MPa and 63MPa, respectively) with relatively similar strengths, because the G-spherical nanocellulose as a guest compound produced a mechanical reinforcing effect in the acrylic resin host.
Molar absorption coefficient: the nano cellulose-based light-cured coating and the cellulose nano fiber-based light-cured coating both contain strong light absorption structural elements of 4' -dihydroxybenzophenone, so that the ultraviolet light absorption capacity of the material at 365nm is greatly improved.
FIG. 1 shows the optical haze properties of G-spherical nanocellulose and G-cellulose nanofiber-based photocurable coatings after film formation by photocuring. The G-spherical nanocellulose based photocureable coating has low haze value (only 0.6%) at the wavelength of 450-750nm after film formation, and is mainly because the spherical nanocellulose has small nano-size which is far smaller than the wavelength of visible light of 450-750 and weak light scattering. In contrast, the G-cellulose nanofiber-based photo-curing coating has long fiber length, so that the fibers generate curling, bending and the like in a coating system, the fibers cannot be closely stacked, a non-uniform medium is formed after the coating is formed into a film, and the haze is increased (to 9%)
Fig. 2 is a graph of rheological measurements of G-spherical nanocellulose and G-cellulose nanofiber-based photocurable coatings. From the graph, the G-spherical nanocellulose-based photo-curing coating shows obvious shear thinning phenomenon, namely, the apparent viscosity starts to drop rapidly along with the increase of the shear rate, and the coating is stable after reaching a certain value. It is generally known that the shear thinning properties of a coating facilitate its application in the field of coatings (e.g., screen printing, coating, etc.). In contrast, the G-cellulose nanofiber-based photocurable coating material has a fiber length that is often susceptible to formation of entanglement points and entanglement and disentanglement during the shear rate change. The viscosity of the coating increases rapidly with increasing shear rate and then tends to stabilize, which is detrimental to screen printing, coating, etc.
Example 2
Step 1, preparation of spherical nanocellulose
2G of cotton pulp was placed in a beaker, and complex cellulase (FPU, 0.02 g) and citric acid buffer (ph=4.8, 40 mL) were added, the suspension mass concentration was adjusted to 0.5wt%, and then placed in a thermostatic water bath shaker at a set temperature of 35 ℃ for reaction for 1h. Immediately after the reaction, inactivating the fiber by using a boiling water bath for 12min, rapidly filtering under reduced pressure (10 -2 Pa), washing the filter cake by using distilled water for 10 times, and collecting the pretreated fiber. 1g of the pretreated fiber was prepared into a 12% cellulose solution, and the solution was passed through a homogenizer 10 times under a pressure of 120MPa to obtain Cellulose Nanofibers (CNFs). Further add ph=4.8, 10mL of citric acid buffer and complex cellulase (FPU, 0.03 g), adjust the suspension mass concentration to dilute to 0.5%, then react in a water bath at 35 ℃ for 5 hours. Immediately upon termination of the reaction, the reaction was inactivated with a boiling water bath for 20min. And (3) dialyzing to remove hydrolyzed glucose small molecules by using a 7000Da dialysis bag, and further removing the hydrolyzed glucose small molecules into hydrolyzed large-particle fibers by using a centrifuge under the condition of 5000rpm to obtain the G-spherical nano cellulose.
Step 2, synthesis of 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone
2G of 4,4' -dihydroxybenzophenone is dissolved in 20mL of DMF solvent and 120g of sodium hydride are stirred for half an hour, then 0.27mL of 4-vinylbenzyl chloride is added dropwise and stirred for 30 hours at 120 ℃. The 4- (4-vinylbenzyl) -4' -hydroxybenzophenone was isolated as a white product in 92% yield by silica gel column.
3G of 4- (4-vinylbenzyloxy) -4' -hydroxybenzophenone was weighed out in 15mL of DMF solution, 1.5mL of bromoacetyl bromide was then added and stirred at 120℃for 36h. The 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone was obtained as a white product by silica gel column separation in 80% yield.
Step 3, chemical modification of spherical nanocellulose (G-spherical nanocellulose)
1.5G of spherical nanocellulose is taken and dispersed in 30mL of pyridine solution, ultrasonic dispersion is carried out for half an hour, 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone is added, and reaction is carried out for 9 hours at 120 ℃. After the reaction is finished, cooling, dialyzing for 36 hours by using a 7000Da dialysis bag, removing the organic solvent and other newly generated small molecular compounds, and repeating for three times. Freeze-drying at-40 deg.C for 12 hr to obtain G-spherical nano cellulose, and low-temperature preserving at 0 deg.C.
Step 4, preparation of spherical nanocellulose-based photo-curing coating and film forming property research
Configuration of the photo-curable coating solution: 40wt% polyurethane acrylate, 20wt% G-spherical nanocellulose, 20wt% isooctyl acrylate, 15wt% N-isobutoxymethyl acrylamide, 2.5wt% 1-hydroxycyclohexyl phenyl ketone, 2.5wt% polyether siloxane. The sum of the mass percentages of the components is hundred percent.
And (3) uniformly mixing the coating components, and vacuumizing to remove air. Pouring the photo-curing coating solution into a screen printing mold, taking high molecular PET as a carrier, uniformly coating the photo-curing coating solution on the surface of PET through screen printing, further placing the film into an ultraviolet curing machine for curing, and carrying out flash irradiation for 3 minutes at 120 ℃, wherein the ultraviolet power is 120W, and the film thickness is 0.3um.
Example 3
Step 1, preparation of spherical nanocellulose
6G of cotton pulp was placed in a beaker, and complex cellulase (FPU, 0.03 g) and citric acid buffer (ph=4.8, 30 mL) were added to adjust the mass concentration of the suspension to 1wt%, and then placed in a thermostatic water bath shaker at a set temperature of 45 ℃ for reaction for 3 hours. Immediately after the reaction, inactivating the fiber by using a boiling water bath for 15min, rapidly filtering under reduced pressure (10 -2 Pa), washing the filter cake by using distilled water for 8 times, and collecting the pretreated fiber. 3g of the pretreated fiber was prepared into a 10% cellulose solution, and the solution was passed through a homogenizer 12 times under a pressure of 120MPa to obtain Cellulose Nanofibers (CNFs). Further add ph=4.8, 20mL of citric acid buffer and complex cellulase (FPU, 0.02 g), adjust the suspension mass concentration to dilute to 1%, then react in a water bath at 40 ℃ for 2 hours. Immediately upon termination of the reaction, the reaction was inactivated with a boiling water bath for 12min. And (3) dialyzing to remove hydrolyzed glucose small molecules by using a 7000Da dialysis bag, and further removing the hydrolyzed glucose small molecules into hydrolyzed large-particle fibers by using a centrifuge under the condition of 6000rpm to obtain the G-spherical nano cellulose.
Step 2, synthesis of 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone
6G of 4,4' -dihydroxybenzophenone is dissolved in 15mL of DMF solvent and 80g of sodium hydride are stirred for half an hour, then 0.5mL of 4-vinylbenzyl chloride are added dropwise and stirred for 36 hours at 100 ℃. The 4- (4-vinylbenzyl) -4' -hydroxybenzophenone was isolated as a white product in 92% yield by silica gel column.
2G of 4- (4-vinylbenzyloxy) -4' -hydroxybenzophenone was weighed out in 10mL of DMF solution, 1mL of bromoacetyl bromide was then added and stirred at 100℃for 20h. The 4- (4-vinylbenzyloxy) -4- (bromoethyl) benzophenone was obtained as a white product by silica gel column separation in 80% yield.
Step 3, chemical modification of spherical nanocellulose (G-spherical nanocellulose)
1G of spherical nanocellulose is taken and dispersed in 20mL of pyridine solution, ultrasonic dispersion is carried out for half an hour, 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone is added, and reaction is carried out for 6 hours at 100 ℃. After the reaction is finished, cooling is carried out, and the organic solvent and other newly generated small molecular compounds are removed after dialysis for 24 hours by a 7000Da dialysis bag and repeated three times. Freeze-drying at-40 deg.C for 48 hr to obtain G-spherical nano cellulose, and low-temperature preserving at 5 deg.C.
Step 4, preparation of spherical nanocellulose-based photo-curing coating and film forming property research
Configuration of the photo-curable coating solution: 21wt% of polyurethane acrylate, 30wt% of G-spherical nanocellulose, 27wt% of isooctyl acrylate, 16wt% of N-isobutoxy methacrylamide, 3wt% of 1-hydroxycyclohexyl phenyl ketone, 3wt% of polyether siloxane. The sum of the mass percentages of the components is hundred percent.
And (3) uniformly mixing the coating components, and vacuumizing to remove air. Pouring the photo-curing coating solution into a screen printing mold, taking high molecular PET as a carrier, uniformly coating the photo-curing coating solution on the surface of PET through screen printing, further placing the film into an ultraviolet curing machine for curing, and carrying out flash irradiation for 2 minutes at 120 ℃, wherein the ultraviolet power is 100W, and the film thickness is 0.9um.
Claims (3)
1. The preparation method of the photo-curing coating of the acrylic resin composite nanocellulose is characterized by comprising the following steps of: the method specifically comprises the following steps:
step 1, preparing spherical nanocellulose;
The specific steps of the step 1 are as follows:
step 1.1, placing 2g-6g of cotton pulp into a beaker, and then sequentially adding 0.01g-0.03g of composite cellulase and 20mL-40mL of citric acid buffer solution to obtain suspension;
Step 1.2, diluting the mass concentration of the suspension obtained in the step 1.1 to 0.5-1.5 wt%, then placing the suspension in a constant-temperature water bath oscillator with the temperature of 35-45 ℃ for reaction for 1-3 hours, immediately inactivating the suspension by using a boiling water bath for 12-24 minutes after the reaction is finished, carrying out suction filtration under reduced pressure of 10 -2 Pa, washing a filter cake by using distilled water for 6-10 times, and collecting pretreated fibers;
1.3, taking 1-3g of the pretreated fiber obtained in the step 1.2, performing ultrasonic dispersion in water at 20Hz-40 Hz to prepare cellulose solution with concentration of 8-12 wt%, and passing through a homogenizer for 8-12 times under the pressure of 120MPa to obtain cellulose nanofiber CNFs;
step 1.4, sequentially adding 10-30 mL of citric acid buffer solution and 0.01-0.03 g of compound cellulase into the cellulose nanofiber CNFs obtained in step 1.3 to obtain a suspension;
Step 1.5, diluting the mass concentration of the suspension obtained in the step 1.4 to 0.5% -1.5%, then reacting for 2h-6h at the temperature of 35 ℃ -45 ℃ in a water bath kettle, and immediately inactivating for 12min-24min by using a boiling water bath when the reaction is ended to obtain hydrolyzed cellulose;
Step 1.6, dialyzing and removing glucose small molecules in the hydrolyzed cellulose obtained in step 1.5 by using a 7000Da dialysis bag, and removing unhydrolyzed particle fibers by using a centrifuge under the condition of 5000rpm-7000rpm to obtain spherical nano-cellulose;
step 2, preparing 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone;
the specific process of the step 2 is as follows:
step 2.1, synthesizing 4- (4-vinyl benzyl) -4' -hydroxy diphenyl ketone;
The specific process of the step 2.1 is as follows:
2g-6g of 4,4 '-dihydroxybenzophenone is taken to be dissolved in 10mL-20mL of N, N-dimethylformamide solvent, 40g-120g of sodium hydride is added to be stirred for half an hour, then 0.27 mL-0.9 mL of 4-vinylbenzyl chloride is dropwise added, the mixture is stirred for 12h-36h at 80 ℃ to 120 ℃, and 4- (4-vinylbenzyl) -4' -hydroxybenzophenone white product is obtained through silica gel column separation;
step 2.2, synthesizing 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone according to the product obtained in step 2.1;
The specific process of the step 2.2 is as follows:
1g-3g of 4- (4-vinylbenzyloxy) -4 '-hydroxybenzophenone is weighed and dissolved in 5mL-15mL of N, N-dimethylformamide solution, then 0.5mL-1.5mL of bromoacetyl bromide is added, stirring is carried out for 12h-36h at 80 ℃ to 120 ℃, and 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone white product is obtained through silica gel column separation;
step 3, modifying the spherical nanocellulose obtained in the step 1 by adopting the product obtained in the step 2 to obtain G-spherical nanocellulose;
And 4, preparing the photo-curing coating according to the product obtained in the step 3.
2. The method for preparing the photo-curing coating of the acrylic resin composite nanocellulose as claimed in claim 1, wherein the method comprises the following steps: the specific process of the step 3 is as follows:
Dispersing 0.5G-1.5G of spherical nanocellulose prepared in the step 1 in 10mL-30mL of pyridine solution, performing ultrasonic dispersion for half an hour, adding 4- (4-vinylbenzyloxy) -4' - (bromoethyl) benzophenone prepared in the step 2, reacting for 3-9 hours at 80-120 ℃, cooling after the reaction is finished, dialyzing for 12-36 hours by using a 7000Da dialysis bag to remove impurities, repeating the dialysis for three times, and then performing freeze drying at-40 ℃ for 12-48 hours to obtain G-spherical nanocellulose, and storing at 0-10 ℃ for standby.
3. The method for preparing the photo-curing coating of the acrylic resin composite nanocellulose as claimed in claim 1, wherein the method comprises the following steps: the specific process of the step 4 is as follows:
And 4.1, respectively weighing the following components in percentage by mass: 20 to 40 weight percent of polyurethane acrylic ester, 10 to 30 weight percent of G-spherical nano cellulose, 20 to 40 weight percent of isooctyl acrylate, 15 to 35 weight percent of N-isobutoxy methacrylamide, 2 to 3 weight percent of 1-hydroxycyclohexyl phenyl ketone and 2 to 3 weight percent of polyether siloxane, wherein the sum of the mass percentages of the components is 100 percent;
And 4.2, uniformly mixing the coating components in the step 4.1 to obtain the photo-curing coating solution.
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