CN117417657A - High-barrier polyacrylate/graphene coating material - Google Patents
High-barrier polyacrylate/graphene coating material Download PDFInfo
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- CN117417657A CN117417657A CN202311568914.3A CN202311568914A CN117417657A CN 117417657 A CN117417657 A CN 117417657A CN 202311568914 A CN202311568914 A CN 202311568914A CN 117417657 A CN117417657 A CN 117417657A
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- graphene
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- polyacrylate
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 238000000576 coating method Methods 0.000 title claims abstract description 116
- 239000011248 coating agent Substances 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 53
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 36
- 230000004888 barrier function Effects 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 acrylic ester Chemical class 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920006290 polyethylene naphthalate film Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 238000007754 air knife coating Methods 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000007606 doctor blade method Methods 0.000 claims description 3
- 238000007765 extrusion coating Methods 0.000 claims description 3
- 238000007756 gravure coating Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high-barrier polyacrylate/graphene coating material, and belongs to the technical field of high-barrier coating synthesis. The high-barrier polyacrylate/graphene coating material comprises the following raw materials in parts by mass: 20-30 parts of acrylic ester, 5-10 parts of styrene, 5 parts of acrylic acid and 1-20 parts of modified waterborne graphene. The high-barrier polyacrylate/graphene coating material has excellent barrier performance on oxygen and water vapor, can inhibit aggregation of graphene, solves the problem of poor dispersibility, and simultaneously utilizes cross-linking bonding among polymers to fully play a synergistic effect with the graphene while improving the compactness of the coating, thereby greatly improving the barrier performance on gas.
Description
Technical Field
The invention relates to the technical field of high-barrier coating synthesis, in particular to a high-barrier polyacrylate/graphene coating material.
Background
The coating is a thin layer material which is attached to a certain base material and has a certain special function and a certain bonding strength with the base material, and has a good protection function on the base.
Graphene is the hardest and thinnest nanometer new material known by human at present, and is a hexagonal honeycomb lattice formed by carbon atoms in sp2 hybridization orbits, and a two-dimensional nanometer material with a single-layer lamellar structure is formed, so that the graphene has the advantages of large specific surface area, high orientation in a forming process and the like, and becomes a high-efficiency barrier filler. Graphene oxide is a graphene derivative formed by substituting part of double bonds on a graphene lamellar structure with hydroxyl groups, carboxyl groups and epoxy groups, and the size and the structure are similar to those of graphene. Due to the presence of oxygen-containing groups, graphene oxide can be stably dispersed in water or other solvents for a long time in the form of a single layer, and conditions are provided for preparing the graphene/polymer composite material with single layer dispersion. Theory proves that the graphene sheet layer has impermeability, and the addition of a small amount of graphene or graphene oxide can obviously improve the barrier property of the composite material. It follows that graphene (or graphene oxide) is a highly desirable high barrier nanoplatelet filler.
In order to obtain sufficient gas barrier properties and water resistance, inorganic fillers such as inorganic nanoparticles or layered compounds may be dispersed in a barrier resin composition, and among them, a composite film is most widely used in which graphene is added to a resin composition as a barrier filler.
Chinese patent CN101812194A proposes a graphene-based barrier composite material and a preparation method thereof, specifically, a coupling agent is used to perform functionalization treatment on graphene oxide, the functionalized graphene oxide is reduced, then the modified reduced graphene oxide is uniformly dispersed in a polyolefin solution by means of a solvent, and an initiator is added to promote cross-linking bonding between graphene and polyolefin to prepare the nanocomposite material. However, graphene prepared by a chemical oxidation-re-reduction method of graphene has a certain structural defect, which is unfavorable for the graphene to exert natural water-oxygen barrier property, and meanwhile, a large amount of graphene is easy to bring about waste liquid pollution, so that the industrial production of the graphene is limited. Chinese patent CN106221179A proposes a method for preparing a polyurethane-based nanocomposite by using a graphene-silicon dioxide hybrid material, specifically, using a functional 3-aminopropyl triethoxysilane monomer as an intermediate bridge linking silicon dioxide and graphene oxide to prepare the graphene-silicon dioxide hybrid material, using the hybrid material as a filler, using polypropylene resin as a matrix, and preparing the polyurethane-based nanocomposite by melt blending. According to the method, the dispersibility of graphene is improved by exerting the mutual blocking effect of graphene and silicon dioxide, but the added silicon dioxide powder is easy to agglomerate, so that the effect of inhibiting graphene agglomeration cannot be achieved, and the blocking performance of matrix resin is affected. Chinese patent CN201910607589.4 discloses a water-based high-barrier coating liquid and a preparation method thereof, wherein the water-based high-barrier coating liquid comprises 0.5 to 15 parts of water-soluble polymer containing hydroxyl, 0.1 to 15 parts of nano oxide, 0.01 to 10 parts of graphene, 0.01 to 5 parts of organosiloxane coupling agent, 0.1 to 30 parts of 0.1mol/L dilute hydrochloric acid and 30 to 95 parts of solvent. According to the preparation method, nano oxide particles prepared by a sol-gel method are used as small-size polymerization inhibitors, and are loaded on the surface of graphene in a physical adsorption mode, so that agglomeration among the graphene can be inhibited, and the problem of poor dispersibility of the graphene is solved; the crosslinking effect of the nano oxide and the water-soluble polymer is utilized, and the barrier effect of the graphene/polymer on the gas synergistic enhancement is fully exerted. However, if the thickness of the deposited layer is less than 10nm, it is insufficient to completely cover the irregularities possibly present on the surface of the base film; if the thickness of the deposited layer is more than 100nm, the situation that the film layer is cracked and the flexibility is reduced is easy to occur.
Disclosure of Invention
The invention aims to provide a high-barrier polyacrylate/graphene coating material so as to solve the problems in the prior art. The high-barrier polyacrylate/graphene coating material prepared by the invention has excellent barrier property to oxygen and water vapor, can inhibit aggregation of graphene, solves the problem of poor dispersibility, and simultaneously utilizes cross-linking bonding among polymers to fully play the synergistic effect with the graphene and greatly improve the barrier property to gas while improving the compactness of the coating.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows: the high-barrier polyacrylate/graphene coating material comprises the following raw materials in parts by mass: 20-30 parts of acrylate compound, 5-10 parts of styrene, 5 parts of acrylic acid and 1-20 parts of modified waterborne graphene.
Further, the acrylate compound comprises the following raw materials in parts by weight: 5-10 parts of methyl acrylate, 5-10 parts of methyl methacrylate and 10-15 parts of butyl acrylate.
The polymer polyacrylate formed by the acrylic ester has good coating property, film forming property, softness, light transmittance and weather resistance.
Further, the preparation method of the modified waterborne graphene comprises the following steps:
and uniformly mixing the reduced graphene, the monomer, the initiator and the water, stirring, heating and refluxing, and obtaining the modified waterborne graphene through in-situ graft polymerization.
Further, the monomers are acrylic acid and acrylamide in a mass ratio of 1:1, and the initiator is ammonium persulfate.
Further, the mass ratio of the reduced graphene to the monomer is 0.2:10; the temperature of stirring, heating and refluxing is 90 ℃ and the time is 3-8 h.
The second technical scheme of the invention is as follows: the preparation method of the high-barrier polyacrylate/graphene coating material comprises the following steps:
uniformly mixing raw materials and water according to parts by weight, and then adding ammonium persulfate for reaction to obtain a coating liquid;
coating a coating liquid on a substrate, drying to form a high-barrier coating, and covering a release protection film on the high-barrier coating to obtain the high-barrier polyacrylate/graphene coating material.
Further, the thickness of the high barrier coating is more than or equal to 0.1 mu m.
Further, the temperature of the reaction is 90 ℃ and the time is 3-8 hours; the substrate is selected from any one of a polyethylene terephthalate film (PET), an ethylene-tetrafluoroethylene copolymer film (ETFE), a polyethylene naphthalate film (PEN), a polypropylene film (PP), a polyamide film (PA), and a polyethylene film (PE).
Further, the coating method is selected from any one of roll coating, gravure coating, doctor blade coating, slit coating, extrusion coating, air knife coating, dip coating and spray coating.
Further, before the coating liquid is coated, the method further comprises the step of activating the substrate; the activation treatment method comprises the following steps: the surface of the substrate is activated by corona and/or plasma treatment techniques.
The third technical scheme of the invention: the high-barrier polyacrylate/graphene coating material is applied to medical packaging, food packaging, electronic product packaging or flexible solar packaging.
The invention discloses the following technical effects:
(1) The high-barrier polyacrylate/graphene coating material has excellent barrier performance on oxygen and water vapor, can inhibit aggregation of graphene, solves the problem of poor dispersibility, and simultaneously utilizes cross-linking bonding among polymers to fully play a synergistic effect with the graphene while improving the compactness of the coating, thereby greatly improving the barrier performance on gas.
(2) According to the method for preparing the high-barrier coating by adding the modified waterborne graphene into the acrylate system, the content of the graphene in the barrier coating can be increased, so that the barrier property of the coating is improved, the good film forming property of the polyacrylate is utilized to endow the coating with good flexibility, and under a proper proportion (when the addition proportion of the modified waterborne graphene is less than 10 wt%, the light transmittance can reach 90%), the coating can be endowed with good light transmittance, so that the high-barrier coating suitable for different purposes can be obtained.
(3) According to the invention, the dispersibility of the graphene is improved by in-situ polymerization of the graft polymer on the graphene, and a compact structure is formed by utilizing the interaction between the polymers, so that the water resistance and oxygen resistance of the coating are improved, and the coating has good light transmittance, flexibility and weather resistance and can be applied to packaging and encapsulation materials. The invention has the advantages of cheap raw materials, simple process and convenient operation, reduces the cost for the industrialized production, and provides a high-efficiency preparation method.
(4) According to the invention, under the condition that the addition proportion of the modified waterborne graphene is smaller, the improvement of the barrier property can be realized, so that a large amount of reduced graphene does not need to be prepared, the microstructure of the graphene can be controlled by controlling the oxidation-reduction condition, the structural defect is reduced, and the barrier property is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a preparation flow of modified waterborne graphene in embodiment 1 of the present invention;
FIG. 2 is a schematic illustration of the preparation flow of the high barrier coating of example 1 of the present invention;
fig. 3 is a schematic structural diagram of a high-barrier polyacrylate/graphene coating material prepared in embodiment 1 of the present invention, wherein 1 is a substrate, 2 is a high-barrier coating, 3 is a release protective film, and 4 is modified waterborne graphene;
fig. 4 is a physical diagram of the high barrier polyacrylate/graphene coating material prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" described in the examples below are all "parts by weight".
The coating method of the coating liquid in the following examples of the present invention is not particularly limited. The coating method may be selected from known aqueous coating methods depending on the viscosity, coating amount, and the like of the coating liquid, and examples thereof include roll coating, gravure coating, roll coating, doctor blade coating, slit coating, extrusion coating, air knife coating, dip coating, and spray coating.
The substrates used in the following examples of the present invention are activated polyethylene terephthalate film (PET), ethylene-tetrafluoroethylene copolymer film (ETFE), polyethylene naphthalate film (PEN), polypropylene film (PP), polyamide film (PA) or polyethylene film (PE), and the choice of the substrate material has no influence on the barrier properties of the coating material; the method for activating treatment comprises the following steps: the surface of the substrate (base) is subjected to an activation treatment by a plasma treatment technique.
And (3) an activation treatment step:
(1) The PET film is prepared, the surface of the PET film is clean, dust, grease or other impurities are prevented from being generated on the surface, and the surface is kept flat.
(2) And (3) operating the plasma machine, opening the plasma machine, and putting the PET film into the plasma machine, wherein the treatment time is 10min, the power is 250W, and the airflow rate is 30sccm.
(3) The plasma machine is started, the plasma can generate plasma, the surface of the PET film is activated, and impurities such as organic matters, inorganic matters and the like on the surface are removed, so that the surface of the PET film is cleaner and smoother, and the cohesiveness and the adhesive force of the PET film are improved.
Example 1
A high barrier polyacrylate/graphene coating material:
(1) Preparation of modified waterborne graphene
1.0g of crystalline flake graphite is added into a mixture of 1.0g of potassium nitrate and 40mL of concentrated sulfuric acid (98%), ultrasonic mixing is uniform, stirring is carried out in an ice-water bath, 6.0g of potassium permanganate is slowly added, stirring is carried out at a high speed (more than 320 r/min) for fully reacting for 4 hours at a temperature of 0 ℃, then slowly heating is carried out, 100mL of distilled water is added for reacting for 4 hours at a temperature of 65 ℃, then 80mL of distilled water and 6mL of hydrogen peroxide are added for fully reacting for 1 hour, centrifugal washing is carried out by using distilled water until pH=7, ultrasonic mixing is carried out uniformly, and then drying is carried out, thus obtaining Graphene Oxide (GO).
Adding graphene oxide into distilled water to prepare a graphene oxide solution with the concentration of 20wt.%, adding sodium borohydride (the mass ratio of the graphene oxide to the sodium borohydride in the graphene oxide solution is 0.25:1) under vigorous stirring, refluxing in a water bath at 80 ℃ for 1h, cooling to room temperature, filtering, washing with absolute ethyl alcohol for multiple times, and drying to obtain pure reduced graphene (RGO, redox graphene).
Adding 5g of acrylic acid, 5g of acrylamide, 0.2g of reduced graphene and a proper amount of water into a container, uniformly mixing by ultrasonic, stirring and refluxing at a constant temperature of 90 ℃, adding 1g of ammonium persulfate, and reacting for 4.0h (65 ℃, N) 2 Under atmosphere), suction filtration, repeated washing with absolute ethyl alcohol and drying to obtain the modified waterborne graphene G-PAM-PAA (the preparation flow diagram is shown in figure 1).
(2) 20 parts of acrylate compound (5 parts of methyl acrylate, 5 parts of methyl methacrylate and 10 parts of butyl acrylate), 5 parts of styrene, 5 parts of acrylic acid, 1 part of modified waterborne graphene and 100 parts of deionized water are added into a container, and are uniformly mixed by ultrasound, and after stirring and refluxing at a constant temperature of 90 ℃,1 part of ammonium persulfate is added for reaction for 4 hours, and the mixture is left at room temperature to obtain a coating solution (coating solution 1).
(3) Coating the coating liquid 1 on a 50 μm thick A4 paper-sized polyethylene terephthalate film (PET), and curing at a high temperature of 85 ℃ to obtain a high-barrier coating (the thickness is 1.0 μm, the high-barrier coating 1), wherein the preparation flow diagram is shown in figure 2.
And (3) covering a release protective film on the high-barrier coating to obtain the high-barrier polyacrylate/graphene coating material (the structural schematic diagram is shown in fig. 3, and the physical diagram is shown in fig. 4), wherein the protective film is only required to be torn off when the high-barrier coating is used.
In fig. 3, 1 is a substrate, 2 is a high barrier coating, 3 is a release protective film, and 4 is modified waterborne graphene.
Example 2
A high barrier polyacrylate/graphene coating material:
(1) The preparation of the modified waterborne graphene is the same as in example 1.
(2) 30 parts of acrylate compound (5 parts of methyl acrylate, 10 parts of methyl methacrylate and 15 parts of butyl acrylate), 10 parts of styrene, 5 parts of acrylic acid, 5 parts of modified waterborne graphene and 100 parts of deionized water are added into a container, ultrasonic mixing is uniform, stirring and refluxing are carried out at a constant temperature of 90 ℃,1 part of ammonium persulfate is added for reaction for 6 hours, and standing is carried out at room temperature, so that coating liquid 2 is obtained.
(3) Coating the coating liquid 2 on an A4 paper-sized ethylene terephthalate film (PET) with the thickness of 50 mu m, and curing at a high temperature of 85 ℃ to obtain a high-barrier coating (the thickness is 1.5 mu m, and the high-barrier coating 2).
And covering a release protective film on the high-barrier coating 2 to obtain the high-barrier polyacrylate/graphene coating material.
Example 3
A high barrier polyacrylate/graphene coating material:
(1) The preparation of the modified waterborne graphene is the same as in example 1.
(2) 25 parts of acrylate compound (10 parts of methyl acrylate, 5 parts of methyl methacrylate and 10 parts of butyl acrylate), 5 parts of styrene, 5 parts of acrylic acid, 10 parts of modified waterborne graphene and 100 parts of deionized water are added into a container, ultrasonic mixing is uniform, stirring and refluxing are carried out at a constant temperature of 90 ℃,1 part of ammonium persulfate is added for reaction for 8 hours, and standing is carried out at room temperature, so that coating liquid 3 is obtained.
(3) Coating the coating liquid 3 on a 50 μm thick A4 paper-sized polyethylene terephthalate film (PET), and curing at a high temperature of 85 ℃ to obtain a high-barrier coating (thickness of 1.8 μm, high-barrier coating 3).
And covering a release protective film on the high-barrier coating 3 to obtain the high-barrier polyacrylate/graphene coating material.
Example 4
A high barrier polyacrylate/graphene coating material:
(1) The preparation of the modified waterborne graphene is the same as in example 1.
(2) 25 parts of acrylate compound (10 parts of methyl acrylate, 5 parts of methyl methacrylate and 10 parts of butyl acrylate), 5 parts of styrene, 5 parts of acrylic acid, 20 parts of modified waterborne graphene and 100 parts of deionized water are added into a container, ultrasonic mixing is uniform, stirring and refluxing are carried out at a constant temperature of 90 ℃,1 part of ammonium persulfate is added for reaction for 8 hours, and standing is carried out at room temperature, so that coating liquid 4 is obtained.
(3) Coating the coating liquid 4 on a 50 μm thick A4 paper-sized polyethylene terephthalate film (PET), and curing at a high temperature of 85 ℃ to obtain a high-barrier coating (the thickness is 2.0 μm, the high-barrier coating 4).
And covering a release protective film on the high-barrier coating 4 to obtain the high-barrier polyacrylate/graphene coating material.
Comparative example 1
The difference from example 1 is only that the modified aqueous graphene in step (2) was replaced with acrylic acid, acrylamide and reduced graphene in a mass ratio of 5:5:0.2.
In the comparative example, the reduced graphene is not subjected to modification treatment, so that the reduced graphene is unevenly dispersed in the coating liquid, and the barrier property of the prepared coating material is reduced.
Comparative example 2
The only difference from example 1 is that step (1) is specifically:
(1) Preparation of modified waterborne graphene
1.0g of crystalline flake graphite is added into a mixture of 1.0g of potassium nitrate and 40mL of concentrated sulfuric acid (98%), ultrasonic mixing is uniform, stirring is carried out in an ice-water bath, 6.0g of potassium permanganate is slowly added, stirring is carried out at a high speed (more than 320 r/min) at a temperature of 0 ℃ for fully reacting for 4 hours, then heating is carried out slowly, 100mL of distilled water is added for reacting for 4 hours at a temperature of 65 ℃, then 80mL of distilled water and 6mL of hydrogen peroxide are added for fully reacting for 1 hour, centrifugal washing is carried out by using distilled water until pH=7, ultrasonic mixing is carried out uniformly, and then drying is carried out, thus obtaining Graphene Oxide (GO).
Adding 5g of acrylic acid, 5g of acrylamide, 0.2g of graphene oxide and a proper amount of water into a container, uniformly mixing by ultrasonic, stirring and refluxing at a constant temperature of 90 ℃, adding 1g of ammonium persulfate, and reacting for 4.0h (65 ℃, N) 2 Under atmosphere), suction filtration, repeated washing with absolute ethyl alcohol and drying to obtain the modified waterborne graphene.
In the comparative example, the graphene oxide is not subjected to reduction treatment, so that the prepared coating material is rugged.
Comparative example 3
The difference from example 1 was only that the amount of the modified aqueous graphene used in step (2) was 30 parts.
The light transmittance of the coating material prepared by the embodiment is only about 25%, and the coating material cannot have excellent barrier property and excellent light transmittance.
Comparative example 4
The same as in example 1 was conducted except that 5g of acrylic acid and 5g of acrylamide in step (1) were replaced with 10g of acrylic acid.
Comparative example 5
The same as in example 1 was repeated except that 10 parts of methyl acrylate, 5 parts of methyl methacrylate, and 10 parts of butyl acrylate in step (2) were replaced with 25 parts of methyl acrylate.
Effect example 1
The stability, water blocking (water permeability) and oxygen blocking (oxygen permeability) properties of the high barrier polyacrylate/graphene coating materials prepared in the examples were measured, and the results are shown in table 1.
The water permeability is measured according to the national standard GB/T21529-2008 method for measuring the water vapor permeability of plastic films and sheets; the oxygen permeability is measured according to the national standard GB/T21529-2008 "method for measuring Water vapor permeability of Plastic films and sheets" electrolytic sensor method ".
TABLE 1
As can be seen from Table 1, the high barrier polyacrylate/graphene coating materials prepared in examples 1 to 4 have low oxygen permeability and water permeability, and can achieve less than 0.01cc/m, respectively 2 D, the coating has good flexibility and is not easy to be peeled off.
After the high-barrier polyacrylate/graphene coating material is used for a long time, cracking and air layer falling phenomena are not found.
From the industrial practicability point of view, the high-barrier coating containing the uniformly dispersed graphene has excellent water-oxygen barrier property, and can be widely applied to medical, food, electronic product packaging, flexible solar packaging and other purposes.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The high-barrier polyacrylate/graphene coating material is characterized by comprising the following raw materials in parts by weight: 20-30 parts of acrylate compound, 5-10 parts of styrene, 5 parts of acrylic acid and 1-20 parts of modified waterborne graphene.
2. The high barrier polyacrylate/graphene coating material of claim 1, wherein the acrylate composite comprises the following raw materials in parts by mass: 5-10 parts of methyl acrylate, 5-10 parts of methyl methacrylate and 10-15 parts of butyl acrylate.
3. The high barrier polyacrylate/graphene coating material of claim 1, wherein the preparation method of the modified waterborne graphene comprises the following steps:
and uniformly mixing the reduced graphene, the monomer, the initiator and the water, stirring, heating and refluxing, and obtaining the modified waterborne graphene through in-situ graft polymerization.
4. The high barrier polyacrylate/graphene coating material according to claim 3, wherein the monomers are acrylic acid and acrylamide in a mass ratio of 1:1, and the initiator is ammonium persulfate.
5. The high barrier polyacrylate/graphene coating material according to claim 3, wherein the mass ratio of reduced graphene to monomer is 0.2:10; the temperature of stirring, heating and refluxing is 90 ℃ and the time is 3-8 h.
6. A method for preparing the high barrier polyacrylate/graphene coating material according to any one of claims 1 to 5, comprising the following steps:
uniformly mixing raw materials and water according to parts by weight, and then adding ammonium persulfate for reaction to obtain a coating liquid;
coating a coating liquid on a substrate, drying to form a high-barrier coating, and covering a release protection film on the high-barrier coating to obtain the high-barrier polyacrylate/graphene coating material.
7. The method according to claim 6, wherein the high barrier coating has a thickness of 0.1 μm or more.
8. The method according to claim 6, wherein the reaction temperature is 90 ℃ for 3 to 8 hours; the substrate is selected from any one of a polyethylene terephthalate film, an ethylene-tetrafluoroethylene copolymer film, a polyethylene naphthalate film, a polypropylene film, a polyamide film, and a polyethylene film.
9. The method according to claim 6, wherein the coating method is selected from any one of roll coating, gravure coating, doctor blade coating, slit coating, extrusion coating, air knife coating, dip coating, and spray coating.
10. Use of the high barrier polyacrylate/graphene coating material of any one of claims 1 to 5 in medical packaging, food packaging, electronic product packaging or flexible solar packaging.
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| CN117867855A (en) * | 2024-02-20 | 2024-04-12 | 广东康尔医疗科技有限公司 | High-barrier-property breathable composite cloth, preparation method thereof and surgical kit |
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| CN117867855A (en) * | 2024-02-20 | 2024-04-12 | 广东康尔医疗科技有限公司 | High-barrier-property breathable composite cloth, preparation method thereof and surgical kit |
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