CN116694143B - Coating composition with self-repairing characteristic for printing plate and preparation method thereof - Google Patents
Coating composition with self-repairing characteristic for printing plate and preparation method thereof Download PDFInfo
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- CN116694143B CN116694143B CN202310825314.4A CN202310825314A CN116694143B CN 116694143 B CN116694143 B CN 116694143B CN 202310825314 A CN202310825314 A CN 202310825314A CN 116694143 B CN116694143 B CN 116694143B
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- 238000007639 printing Methods 0.000 title claims abstract description 41
- 239000008199 coating composition Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 229920001353 Dextrin Polymers 0.000 claims abstract description 14
- 239000004375 Dextrin Substances 0.000 claims abstract description 14
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 14
- 235000019425 dextrin Nutrition 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000008107 starch Substances 0.000 claims abstract description 14
- 235000019698 starch Nutrition 0.000 claims abstract description 14
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 11
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- FTJWOSANAYUMMU-UHFFFAOYSA-N 4-bromobutane-1,2-diol Chemical compound OCC(O)CCBr FTJWOSANAYUMMU-UHFFFAOYSA-N 0.000 claims description 9
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- -1 acyl chlorinated graphene Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- 238000001035 drying Methods 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 11
- 239000010954 inorganic particle Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MQUNPMBEKMVOHA-UHFFFAOYSA-N (sodiodiselanyl)sodium Chemical compound [Na][Se][Se][Na] MQUNPMBEKMVOHA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000341 volatile oil 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
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C09D5/08—Anti-corrosive 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
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a coating composition with self-repairing characteristic for printing plates and a preparation method thereof, belonging to the technical field of coating compositions, and comprising the following raw materials in parts by weight: 5-10 parts of starch dextrin, 2-5 parts of polyvinyl alcohol, 2-4 parts of nano cellulose, 1-2 parts of sodium metasilicate, 10-15 parts of modified graphene oxide, 2-3 parts of surfactant and 110-130 parts of deionized water; the coating composition for the printing plate with the self-repairing characteristic can be obtained by uniformly mixing the raw materials, has good film forming property, is simple in preparation method, has the hygroscopicity of an organic coating and the roughness of an inorganic coating, improves the barrier property of the coating due to a network structure of the organic coating and flaky inorganic particles, has the characteristics of easy coating and easy drying when being applied to the printing plate, and can prevent the printing plate from being corroded by gas and infected by stains.
Description
Technical Field
The invention belongs to the technical field of coating compositions, and particularly relates to a coating composition for a printing plate with self-repairing characteristics and a preparation method thereof.
Background
The printed image-text part of the printing plate has the characteristics of oleophilic and water-repellent, and on the contrary, the non-image-text part is hydrophilic and oil-repellent, so that the quality of the printing plate directly influences the quality of offset printing products, for example, the blank part of the positive PS plate is metal oxide Al 2 O 3 And its crystal water, belonging to the high energy surface (0.7J/m) 2 ) Can be well wetted by fountain solution during printing, is easy to react with oxygen, nitrogen, carbon dioxide and the like in the air at ordinary times, is easy to generate oxidation points, reduces the surface energy, worsens the wettability, adsorbs impurities, greasy dirt and the like, is difficult to clean and causes dirtying during printing, therefore, the empty white department needs to be protected, the layout is isolated from the air by utilizing the low-energy surface of a high molecular compound, and the surface scratch of the plate is prevented, and the special PS/CTP plate protective adhesive is disclosed in Chinese patent CN103804998A, and is prepared from the following component raw materials in parts by weight: 3-4 parts of Arabic gum, 2-3 parts of peach gum, 1-2 parts of pineapple pectin, 3-4 parts of hydroxyethyl fiber, 0.1-0.2 part of peppermint essential oil, 1-1.5 parts of polyvinyl alcohol, 1-2 parts of compound auxiliary agent and 75-85 parts of deionized water, although the following components can be usedThe coating composition for printing plates has a low barrier property and a high oxygen transmission rate, does not have self-repairing properties when the coating is scratched, and further, the printing plates are corroded by gases such as oxygen and stains, so that it is necessary to provide a coating composition for printing plates having a high barrier property and self-repairing properties.
Disclosure of Invention
The invention aims to provide a coating composition for a printing plate with self-repairing property and a preparation method thereof, so as to solve the problems that the existing coating composition for the printing plate is poor in barrier property and does not have self-repairing property.
The aim of the invention can be achieved by the following technical scheme:
a coating composition for printing plates with self-repairing property comprises the following raw materials in parts by weight:
5-10 parts of starch dextrin, 2-5 parts of polyvinyl alcohol, 2-4 parts of nano cellulose, 1-2 parts of sodium metasilicate, 10-15 parts of modified graphene oxide, 2-3 parts of surfactant and 110-130 parts of deionized water;
the preparation method of the coating composition for the printing plate with the self-repairing property comprises the following steps:
mixing starch dextrin, nanocellulose and 2/3 of deionized water to obtain a mixed solution a, placing polyvinyl alcohol and 1/3 of deionized water into a reaction kettle, stirring for 2 hours at the temperature of 90-95 ℃, adding the mixed solution a, sodium metasilicate, modified graphene oxide and a surfactant, controlling the temperature of 90-95 ℃, and stirring for 2-3 hours at the temperature of heat preservation to obtain the coating composition for the printing plate.
Further, the modified graphene oxide is prepared by the following steps:
s1, adding graphene oxide into THF, performing ultrasonic dispersion for 1h to obtain a dispersion liquid, transferring the dispersion liquid into a flask, adding thionyl chloride, stirring at 65 ℃ for reaction for 12h, centrifuging, washing the precipitate with absolute ethyl alcohol, and drying to obtain the acyl chloride graphene;
s2, adding acyl chloride graphene into DMF, performing ultrasonic dispersion for 30min, transferring to a flask, adding a mixed solution a consisting of pyridine, diselenyl hyperbranched polyester and DMF into the flask, stirring at room temperature, reacting for 12h, performing suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain an intermediate product;
s3, adding an intermediate product, DMF, maleic anhydride and triethylamine into a flask, stirring and reacting for 3 hours at the temperature of 105-110 ℃, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the modified graphene oxide.
The graphene oxide is a material with excellent mechanical properties, ultra-high specific surface area and excellent barrier properties, and the surface is rich in hydroxyl, carboxyl, epoxy groups and other groups.
Further, in the step S1, the dosage ratio of graphene oxide, THF and thionyl chloride is 0.5-1g:100mL:100mL.
Further, the dosage ratio of the acyl chloride graphene, the pyridine and the diselenide hyperbranched polyester in the step S2 is 0.8-1.5g:0.5mL:6.5-8.1g.
Further, the ratio of the intermediate, DMF, maleic anhydride and triethylamine in the step S3 is 2.5-4.5g:50mL:1.5-2.0g:0.1mL.
Further, the diselenide hyperbranched polyester is prepared by the following steps:
adding 2, 2-dimethylolpropionic acid, diselenyl tetrol, dimethylbenzene and p-toluenesulfonic acid into a four-necked flask, heating to 140-150 ℃ under the protection of nitrogen, reacting for 3 hours, cutting off the nitrogen, connecting the flask to a negative pressure device, reacting for 3 hours under the negative pressure of 0.075MPa, and then distilling under reduced pressure to remove the dimethylbenzene to obtain diselenyl hyperbranched polyester;
in the reaction, the mass ratio of the 2, 2-dimethylolpropionic acid to the diselenyl tetraol is 3:14.5-16.3, wherein the dosage of p-toluenesulfonic acid is 0.5-1% of the sum of the masses of 2, 2-dimethylolpropionic acid and diselenyl tetraol, the dosage of dimethylbenzene is 6-8 times of the sum of the masses of 2, 2-dimethylolpropionic acid and diselenyl tetraol, diselenyl tetraol and 2, 2-dimethylolpropionic acid are taken as raw materials, and a one-step method is adopted to synthesize hyperbranched polyester, namely diselenyl hyperbranched polyester.
Further, diselenyl tetrol is prepared by the steps of:
adding sodium borohydride into deionized water, stirring and dissolving, adding selenium powder, reacting for 10min in ice bath, adding selenium powder again, continuously stirring for 15min, heating to 50 ℃, stirring for 5min under the protection of nitrogen, adding a tetrahydrofuran solution of 4-bromo-1, 2-butanediol, performing heat preservation and stirring reaction for 20h, purifying the product by column chromatography, and purifying by using a mixed solution of dichloromethane and ethyl acetate with the volume ratio of 4:1 as an eluent to obtain diselenyl tetraol;
in the above reaction, the dosage ratio of sodium borohydride, deionized water, selenium powder and 4-bromo-1, 2-butanediol was 0.8g:20-30mL:1.58g:20mmol, 4-bromo-1, 2-butanediol in tetrahydrofuran solution from 4-bromo-1, 2-butanediol and tetrahydrofuran in a ratio of 1g:10mL, wherein the adding amount of the selenium powder is equal for two times, firstly, the selenium powder and sodium borohydride are used as raw materials to prepare a sodium diselenide solution, and then, the sodium diselenide and 4-bromo-1, 2-butanediol are subjected to substitution reaction to obtain diselenide tetraol.
Further, the polyvinyl alcohol has a polymerization degree of 500-2400, an alcoholysis degree of 86-97% and is one or more of PVA0588, PVA1088, PVA1788 and PVA 2488.
Further, the surfactant is sodium dodecyl ether sulfate or sodium dodecyl sulfate.
The invention has the beneficial effects that:
1. the invention provides a coating composition for a printing plate with self-repairing characteristics, which is prepared from starch dextrin, modified graphene oxide, polyvinyl alcohol and nanocellulose serving as main raw materials, belongs to an organic-inorganic hybrid hydrophilic coating, has good film forming property, is simple in preparation method, has the hygroscopicity of an organic coating and the roughness of an inorganic coating, and has the advantages that the barrier property of the coating is improved by a network structure of the organic coating and flaky inorganic particles.
2. According to the invention, modified graphene oxide is introduced into the coating composition, and is carboxyl-terminated diselenyl hyperbranched polyester modified graphene, through modification treatment, firstly, the steric hindrance between the graphene oxides is increased, the dispersibility of the graphene oxides in the composition is improved, so that the graphene oxide can effectively exert barrier and shielding properties, secondly, the carboxyl on the surface of the modified graphene oxide is crosslinked with the polyvinyl alcohol, the nanocellulose and the hydroxyl on the starch dextrin chain to form a network structure, so that the overall barrier property of the coating is improved, thirdly, a diselenide bond is introduced into the composition, and the characteristic that dynamic exchange can be performed under visible light by utilizing the diselenide bond is utilized, so that the coating has good self-repairing property, and fourthly, the strong hydrogen bond effect between the hydroxyl, carboxyl and other groups on the surface of the modified graphene oxide, the polyvinyl alcohol, the nanocellulose and the starch dextrin is utilized, so that the hydrogen bond self-repairing property is further provided when the gas barrier property of the coating is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Diselenide hyperbranched polyester is prepared by the following steps:
adding 3g of 2, 2-dimethylolpropionic acid, 14.5g of diselenyl tetraol, 105mL of dimethylbenzene and 0.088g of p-toluenesulfonic acid into a four-neck flask, heating to 140 ℃ under the protection of nitrogen gas for reaction for 3 hours, cutting off the nitrogen gas, connecting the flask to a negative pressure device for reaction for 3 hours under the negative pressure of 0.075MPa, and then distilling under reduced pressure to remove the dimethylbenzene to obtain diselenyl hyperbranched polyester;
diselenyl tetrol is prepared by the steps of:
adding 0.8g of sodium borohydride into 20mL of deionized water, stirring and dissolving, adding 0.79g of selenium powder, reacting for 10min in an ice bath, adding 0.79g of selenium powder again, continuously stirring for 15min, heating to 50 ℃, stirring for 5min under the protection of nitrogen, adding a solution consisting of 20mmol of 4-bromo-1, 2-butanediol and 33.8mL of tetrahydrofuran, carrying out heat preservation and stirring for reaction for 20h, purifying the product by using column chromatography, and purifying by using a mixed solution of dichloromethane and ethyl acetate with the volume ratio of 4:1 as an eluent to obtain diselenyl tetraol.
Example 2
Diselenide hyperbranched polyester is prepared by the following steps:
adding 3g of 2, 2-dimethylolpropionic acid, 16.3g of diselenyl tetraol, 154mL of dimethylbenzene and 0.19g of p-toluenesulfonic acid into a four-necked flask, heating to 150 ℃ under the protection of nitrogen, reacting for 3 hours, cutting off the nitrogen, connecting the flask to a negative pressure device, reacting for 3 hours under the negative pressure of 0.075MPa, and then distilling under reduced pressure to remove the dimethylbenzene to obtain diselenyl hyperbranched polyester;
diselenyl tetrol is prepared by the steps of:
adding 0.8g of sodium borohydride into 30mL of deionized water, stirring and dissolving, adding 0.79g of selenium powder, reacting for 10min in an ice bath, adding 0.79g of selenium powder again, continuously stirring for 15min, heating to 50 ℃, stirring for 5min under the protection of nitrogen, adding a solution consisting of 20mmol of 4-bromo-1, 2-butanediol and 33.8mL of tetrahydrofuran, carrying out heat preservation and stirring for reaction for 20h, purifying the product by using column chromatography, and purifying by using a mixed solution of dichloromethane and ethyl acetate with the volume ratio of 4:1 as an eluent to obtain diselenyl tetraol.
Comparative example 1
This comparative example provides a hyperbranched polyester in which the diselenyl tetrol of example 1 is replaced with pentaerythritol and the remaining materials and preparation process are the same as in example 1.
Example 3
A modified graphene oxide is prepared by the following steps:
s1, adding 0.5g of graphene oxide into 100mLTHF, performing ultrasonic dispersion for 1h to obtain a dispersion liquid, transferring the dispersion liquid into a flask, adding 100mL of thionyl chloride, stirring at 65 ℃ for reaction for 12h, centrifuging, washing the precipitate with absolute ethyl alcohol, and drying to obtain the acyl chloride graphene;
s2, adding 0.8g of acyl chloride graphene into 30mLDMF, ultrasonically dispersing for 30min, transferring to a flask, adding 0.5mL of pyridine, 6.5g of mixed solution a consisting of the diselenyl hyperbranched polyester of the embodiment 1 and 50mLDMF into the flask, stirring at room temperature for reacting for 12h, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain an intermediate product;
s3, adding 2.5g of intermediate product, 50 mM MF, 1.5g of maleic anhydride and 0.1mL of triethylamine into a flask, stirring at 105 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the modified graphene oxide.
Example 4
A modified graphene oxide is prepared by the following steps:
s1, adding 1g of graphene oxide into 100mL of THF, performing ultrasonic dispersion for 1h to obtain a dispersion liquid, transferring the dispersion liquid into a flask, adding 100mL of thionyl chloride, stirring at 65 ℃ for reaction for 12h, centrifuging, washing the precipitate with absolute ethyl alcohol, and drying to obtain the acyl chloride graphene;
s2, adding 1.5g of acyl chloride graphene into 50mL of DMF, ultrasonically dispersing for 30min, transferring to a flask, adding a mixed solution a consisting of 0.5mL of pyridine, 8.1g of diselenyl hyperbranched polyester of example 2 and 50mL of DMF into the flask, stirring at room temperature, reacting for 12h, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain an intermediate product;
s3, adding 4.5g of intermediate product, 50mL of DMF, 2.0g of maleic anhydride and 0.1mL of triethylamine into a flask, stirring at 110 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the modified graphene oxide.
Comparative example 2
This comparative example provides a modified graphene oxide, which is an intermediate product obtained in step S2 of example 4.
Comparative example 3
This comparative example provides a modified graphene oxide, in which the diselenide hyperbranched polyester of example 3 was substituted for the one of comparative example 1, compared with example 3, and the rest of the raw materials and the preparation process were the same as in example 3.
Example 5
A coating composition for printing plates with self-repairing property comprises the following raw materials in parts by weight:
5 parts of starch dextrin, 2 parts of polyvinyl alcohol, 2 parts of nanocellulose, 1 part of sodium metasilicate, 10 parts of modified graphene oxide of example 3, 2 parts of surfactant and 110 parts of deionized water;
the preparation method of the coating composition for the printing plate with the self-repairing property comprises the following steps:
mixing starch dextrin, nanocellulose and 2/3 of deionized water to obtain a mixed solution a, placing polyvinyl alcohol and 1/3 of deionized water into a reaction kettle, stirring for 2 hours at 90 ℃, adding the mixed solution a, sodium metasilicate, modified graphene oxide and a surfactant, controlling the temperature to 90 ℃, and carrying out heat preservation and stirring for 2 hours to obtain the coating composition for the printing plate.
Wherein, the polyvinyl alcohol is PVA0588, and the surfactant is sodium dodecyl ether sulfate.
Example 6
A coating composition for printing plates with self-repairing property comprises the following raw materials in parts by weight:
8 parts of starch dextrin, 4 parts of polyvinyl alcohol, 3 parts of nanocellulose, 1.5 parts of sodium metasilicate, 12 parts of modified graphene oxide of example 4, 2.5 parts of surfactant and 120 parts of deionized water;
the preparation method of the coating composition for the printing plate with the self-repairing property comprises the following steps:
mixing starch dextrin, nanocellulose and 2/3 of deionized water to obtain a mixed solution a, placing polyvinyl alcohol and 1/3 of deionized water into a reaction kettle, stirring for 2 hours at 92 ℃, adding the mixed solution a, sodium metasilicate, modified graphene oxide and a surfactant, controlling the temperature to 92 ℃, and carrying out heat preservation and stirring for 2.5 hours to obtain the coating composition for the printing plate.
Wherein, the polyvinyl alcohol is PVA1088, and the surfactant is sodium dodecyl ether sulfate.
Example 7
A coating composition for printing plates with self-repairing property comprises the following raw materials in parts by weight:
10 parts of starch dextrin, 5 parts of polyvinyl alcohol, 4 parts of nanocellulose, 2 parts of sodium metasilicate, 15 parts of modified graphene oxide of example 4, 3 parts of surfactant and 130 parts of deionized water;
the preparation method of the coating composition for the printing plate with the self-repairing property comprises the following steps:
mixing starch dextrin, nanocellulose and 2/3 of deionized water to obtain a mixed solution a, placing polyvinyl alcohol and 1/3 of deionized water into a reaction kettle, stirring for 2 hours at the temperature of 95 ℃, adding the mixed solution a, sodium metasilicate, modified graphene oxide and a surfactant, controlling the temperature of 95 ℃, and carrying out heat preservation and stirring for 3 hours to obtain the coating composition for the printing plate.
Wherein, the polyvinyl alcohol PVA1788 and the surfactant is sodium dodecyl sulfate.
Comparative example 4
Compared with example 5, the modified graphene oxide in example 5 is replaced by the modified graphene oxide in comparative example 2, and the rest raw materials and the preparation process are unchanged.
Comparative example 5
Compared with example 5, the modified graphene oxide in example 5 is replaced by the modified graphene oxide in comparative example 3, and the rest raw materials and the preparation process are unchanged.
The composition compositions obtained in examples 5 to 7 and comparative examples 4 to 5 were tested as follows:
(1) Barrier properties: coating each group of compositions to be tested on PET films by using a 6 μm coating side, wherein the coating thickness is 6 μm, drying for 30min at room temperature, and then placing into a 105 ℃ oven for drying for 2h, wherein the PET films have 46 μm thickness and 102.8cm oxygen permeability 3 /(m 2 D) with reference to the oxygen permeability (ORT) value of the differential pressure composite membrane in standard GB/T1038-2000, usingThe 2/21 tester is tested at a temperature of 23 ℃ and a relative humidity of 0%;
(2) Self-repairing performance: coating each group of compositions to be tested on a glass plate respectively, wherein the coating thickness is 6 mu m, drying for 30min at room temperature, putting into a 105 ℃ oven for drying for 2h, scratching with a blade for 2mm deep, irradiating for 16h under visible light, and observing whether the scratch is closed or not for repair;
the test results are shown in table 1:
TABLE 1
As can be seen from table 1, the coating compositions prepared in examples 5, 6 and 7 have not only good barrier properties but also excellent self-repairing properties, compared to comparative examples 4 and 5, and can effectively prevent contamination of printing and ensure the quality of subsequent printing when applied to the surface protection of printing plates.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The coating composition for the printing plate with the self-repairing property is characterized by comprising the following raw materials in parts by weight:
5-10 parts of starch dextrin, 2-5 parts of polyvinyl alcohol, 2-4 parts of nano cellulose, 1-2 parts of sodium metasilicate, 10-15 parts of modified graphene oxide, 2-3 parts of surfactant and 110-130 parts of deionized water;
wherein the modified graphene oxide is prepared by the following steps:
adding acyl chloride graphene into DMF, ultrasonically dispersing, transferring to a flask, adding a mixed solution a consisting of pyridine, diselenyl hyperbranched polyester and DMF, and stirring at room temperature for reacting for 12 hours to obtain an intermediate product;
adding the intermediate product, DMF, maleic anhydride and triethylamine into a flask, and stirring at 105-110 ℃ for reaction for 3h to obtain modified graphene oxide;
the diselenide hyperbranched polyester is prepared by the following steps:
adding 2, 2-dimethylolpropionic acid, diselenyl tetrol, dimethylbenzene and p-toluenesulfonic acid into a four-necked flask, heating to 140-150 ℃ under the protection of nitrogen, reacting for 3 hours, cutting off the nitrogen, connecting the flask to a negative pressure device, reacting for 3 hours under the negative pressure of 0.075MPa, and then distilling under reduced pressure to remove the dimethylbenzene to obtain diselenyl hyperbranched polyester;
diselenyl tetrol is prepared by the steps of:
adding sodium borohydride into deionized water, stirring and dissolving, adding selenium powder, reacting for 10min in ice bath, adding selenium powder again, continuously stirring for 15min, heating to 50 ℃, stirring for 5min under the protection of nitrogen, adding a tetrahydrofuran solution of 4-bromo-1, 2-butanediol, keeping the temperature and stirring for reacting for 20h, and purifying the product by column chromatography to obtain diselenyl tetrol.
2. The coating composition for printing plates with self-repairing property according to claim 1, wherein the dosage ratio of the acyl chlorinated graphene, the pyridine and the diselenyl hyperbranched polyester is 0.8-1.5g:0.5mL:6.5-8.1g.
3. A coating composition for printing plates with self-healing properties according to claim 1, wherein the ratio of the amount of intermediate product, DMF, maleic anhydride and triethylamine is 2.5-4.5g:50mL:1.5-2.0g:0.1mL.
4. The coating composition for printing plates having self-healing properties according to claim 1, wherein the acid chlorinated graphene is prepared by the steps of:
adding graphene oxide into THF, performing ultrasonic dispersion for 1h to obtain a dispersion liquid, transferring the dispersion liquid into a flask, adding thionyl chloride, and stirring at 65 ℃ for reaction for 12h to obtain the acyl chloride graphene.
5. The coating composition for printing plates having self-healing properties according to claim 4, wherein the ratio of graphene oxide, THF and thionyl chloride is 0.5 to 1g:100mL:100mL.
6. A coating composition for printing plates having self-healing properties according to claim 1, wherein the mass ratio of 2, 2-dimethylolpropionic acid to diselenyl tetrol is 3:14.5-16.3, and the dosage of the p-toluenesulfonic acid is 0.5-1 percent of the sum of the mass of the 2, 2-dimethylolpropionic acid and the diselenyl tetraol.
7. The coating composition for printing plates having self-healing properties according to claim 1, wherein the dosage ratio of sodium borohydride, deionized water, selenium powder and 4-bromo-1, 2-butanediol is 0.8g:20-30mL:1.58g:20mmol.
8. A method of preparing a coating composition for printing plates having self-healing properties according to claim 1, comprising the steps of:
mixing starch dextrin, nanocellulose and 2/3 of deionized water to obtain a mixed solution a, placing polyvinyl alcohol and 1/3 of deionized water into a reaction kettle, stirring for 2 hours at the temperature of 90-95 ℃, adding the mixed solution a, sodium metasilicate, modified graphene oxide and a surfactant, controlling the temperature of 90-95 ℃, and stirring for 2-3 hours at the temperature of heat preservation to obtain the coating composition for the printing plate.
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