CN115558423A - Degradable self-repairing coating for digital printing substrate and preparation method thereof - Google Patents
Degradable self-repairing coating for digital printing substrate and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
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- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical group C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 claims description 8
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- 150000002513 isocyanates Chemical class 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
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- 239000006185 dispersion Substances 0.000 claims description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
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- HBCBCEPGGSBSMF-UHFFFAOYSA-N 4-(4-sulfanylanilino)benzenethiol Chemical compound Sc1ccc(Nc2ccc(S)cc2)cc1 HBCBCEPGGSBSMF-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
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Images
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention belongs to the technical field of degradable self-repairing coatings, in particular to a degradable self-repairing coating for a digital printing substrate and a preparation method thereof, which comprises the steps of firstly introducing dynamic ionic bonds and dynamic disulfide bonds into acrylate, and further regulating and controlling the mobility of polyacrylate molecular chains by changing the proportion of comonomers to realize the self-repairing function of acrylate glue; then grafting gelatin and starch degradable group biomacromolecules to prepare modified acrylic resin with degradable self-repairing performance; by adding the color fixing agent, the product is ensured to keep high color resolution and color saturation; by adding the wax emulsion, the scratch resistance effect after printing is improved; the coating prepared by the method has self-repairing capability of crease marks and scratches, high strength and low viscosity, is degradable, improves the printing display effect, prolongs the service life of the product, and reduces the pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of degradable self-repairing coatings, and particularly relates to a degradable self-repairing coating for a digital printing substrate and a preparation method thereof.
Background
The digital printing material is widely used for large indoor or outdoor advertising in markets, subways, office buildings and the like, and has extremely high requirements on the attractiveness of products. In the printing industry, surface coatings are directly applied to the surface of a substrate, and the surface coatings directly affect the quality of printed products.
The coating applied to the digital printing substrate consists of an adhesive, a pigment and other additives. The adhesive plays a vital role, so that the coating has good surface strength and printing performance, and a colloid protective film is formed between the dye and the color developing agent to isolate the dye and the color developing agent to prevent premature reaction. Currently, the commonly used adhesives include polyvinyl alcohol (PVA), methyl cellulose, hydroxyethyl cellulose, CMC, modified starch, polyvinylpyrrolidone, polyacrylamide, alkyd resin, polyester resin, acrylate, multi-component copolymers centered on acrylamide, PVA graft polymers, and the like. The adhesive is mainly used, which has no influence on color development, high bonding strength and proper viscosity range. Wherein the starch has poor cohesive force and film forming property.
The styrene-butadiene latex and the polyvinyl acetate latex have adverse effects on the color development of the coating, so that the faxed color is gray. Some adhesives are not degradable, so that the adhesives have serious pollution problems in the production and processing processes and in the aspect of garbage disposal, and cause serious harm to the environment and human bodies. On the other hand, the digital printing material is very easy to generate scratches, creases and other damages in the processes of transportation, construction, use and the like, and the display effect is seriously influenced, wherein the digital printing coating made of the sizing material with low glass-transition temperature has a certain self-repairing effect, but is soft, sticky on the surface, easy to deform in the using process, and capable of adsorbing a large amount of dust, so that the digital printing material cannot be practically applied.
Therefore, the research and development of the degradable self-repairing coating for the digital printing substrate improves the quality of the digital printing material, prolongs the service life of the product, reduces the product waste, and reduces the environmental pollution, which becomes the future development direction and is imperative.
Disclosure of Invention
In order to solve the problems, the invention provides a degradable self-repairing coating for a digital printing substrate and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a degradable self-repairing coating for a digital printing substrate comprises the following components in parts by weight: 20 parts of modified acrylic resin, 8 parts of fluorane dye 2-phenylamino-6-dibutylamino-3-methylfluorane, 25 parts of color developing agent bisphenol A, 3 parts of color fixing agent cetylpyridinium chloride, 5 parts of zinc stearate, 3 parts of wax emulsion, 3 parts of organic silicon defoamer TSA-8300.01, 0.02 part of water retention agent carboxymethyl cellulose and 57 parts of water;
the modified acrylic resin is prepared by the following method: firstly, copolymerizing butyl acrylate and isocyanate ethyl acrylate to obtain a copolymer with isocyanate side groups; then reacting the prepared copolymer with the side group of isocyanic acid with disulfide to obtain a disulfide-bond crosslinked polymer; reacting acryloyl chloride with natural macromolecules to obtain reactive macromonomers; finally, copolymerizing the obtained reactive macromonomer and the disulfide bond cross-linked polymer to obtain modified acrylic resin;
the natural macromolecule is gelatin or starch.
The specific synthetic steps of the modified acrylic resin are as follows:
(1) Preparation of a copolymer with pendant isocyanate groups: adding butyl acrylate and isocyanate ethyl acrylate into an organic solvent 1, heating to 70-90 ℃, introducing argon for 0.5-1 hour, adding an initiator 1 after oxygen in the system is exhausted, continuing to react for 15-24 hours, and performing suction filtration to obtain white powder, namely the copolymer with the isocyanate side group;
the molar ratio of the butyl acrylate to the isocyanate ethyl acrylate to the initiator 1 is 1:0.5 to 3:0.05 to 0.2;
the organic solvent 1 is toluene or dioxane;
the initiator 1 is azobisisobutyronitrile, dibenzoyl peroxide or azobisisoheptonitrile;
(2) Preparation of disulfide-bonded crosslinked polymer: dissolving the copolymer with the isocyanate side group obtained in the step (1) in an organic solvent 2, adding a disulfide, stirring and dissolving at 20-30 ℃, then adding dibutyltin dilaurate, continuing to react for 2-4 hours, adding water, precipitating a white solid, filtering, and washing filter residues with an organic solvent 3 for 3-5 times to obtain a disulfide bond cross-linked polymer;
the molar ratio of disulfide to dibutyltin dilaurate is 1:1 to 1.5;
the mass ratio of the copolymer with the isocyanic acid side group to the disulfide is 1:3 to 5;
the organic solvent 2 is DMSO, DMF, toluene or dioxane;
the organic solvent 3 is tetrahydrofuran, acetone, dichloromethane or acetonitrile;
the disulfide is 4,4 '-dihydroxydiphenyl disulfide or 4,4' -dithiodiphenylamine;
(3) Synthesis of reactive macromers: dissolving acryloyl chloride in a dry organic solvent 4, adding natural macromolecules, stirring for 15 to 24 hours at the temperature of 20 to 30 ℃, carrying out suction filtration, washing filter residues for 3 to 5 times by using an organic solvent 3, and drying to obtain a reactive macromonomer;
the mass ratio of the acryloyl chloride to the natural macromolecules is 1:10 to 100;
the organic solvent 4 is dichloromethane, tetrahydrofuran, acetonitrile or acetone;
the natural macromolecules are gelatin or starch;
(4) Synthesis of modified acrylic resin: adding the reactive macromonomer obtained in the step (3) and the disulfide bond crosslinked polymer obtained in the step (2) into a dry organic solvent 1, heating to 70-90 ℃, introducing argon for 0.5-1 hour, adding an initiator 1 after oxygen in the system is exhausted, continuing to react for 15-24 hours, and performing suction filtration to obtain white powder;
the mass ratio of the reactive macromonomer to the disulfide bond cross-linked polymer to the initiator 1 is 1:0.5 to 2:0.001 to 0.005.
The synthetic route of the modified acrylic resin is as follows:
in the step (1), the molar ratio of the butyl acrylate, the isocyanate ethyl acrylate and the initiator 1 is 1:1 to 2.5:0.1 to 0.15.
The molar ratio of the disulfide to dibutyltin dilaurate in step (2) is 1:1 to 1.3, wherein the mass ratio of the copolymer with the isocyanic acid side group to the disulfide is 1:3 to 4.5.
The disulfide in the step (2) is 4,4' -dihydroxy diphenyl disulfide.
In the step (3), the mass ratio of the acryloyl chloride to the natural macromolecules is 1:20 to 80.
The mass ratio of the reactive macromonomer, the disulfide bond cross-linked polymer and the initiator 1 in the step (4) is 1:0.5 to 1.6:0.002 to 0.004.
The invention also comprises a preparation method of the degradable self-repairing coating for the digital printing substrate, which comprises the following steps: mixing 20 parts of modified acrylic resin, 8 parts of 2-phenylamino-6-dibutylamino-3-methylfluorane, 25 parts of a color developing agent bisphenol A, 3 parts of a color fixing agent cetylpyridinium chloride, 5 parts of zinc stearate, 3 parts of a wax emulsion, 0.02 part of an organic silicon defoamer TSA-8300.01, 0.02 part of a water retention agent carboxymethyl cellulose and 57 parts of water, stirring and dispersing for 30min at the speed of 800r/min, standing, filtering to obtain a dispersion liquid, uniformly coating the obtained dispersion liquid on the surface of a polylactic acid fiber PLA base material, and drying at the temperature of 80 ℃ until the thickness of the coating is 3 to 5 mu m;
the modified acrylic resin is prepared by the following method: firstly, copolymerizing butyl acrylate and isocyanate ethyl acrylate to obtain a copolymer with isocyanate side groups; then reacting the prepared copolymer with the side group of isocyanic acid with disulfide to obtain a disulfide-bond crosslinked polymer; reacting acryloyl chloride with natural macromolecules to obtain reactive macromonomers; finally copolymerizing the obtained reactive macromonomer and the disulfide bond crosslinked polymer to obtain modified acrylic resin;
the natural macromolecule is gelatin or starch.
Compared with the prior art, the invention has the following advantages:
the invention is used for the degradable self-repairing coating of the digital printing substrate, wherein the modified acrylic resin firstly introduces dynamic ionic bonds and dynamic disulfide bonds into acrylate, and the self-repairing function of the acrylate adhesive is realized by further changing the proportion of the comonomer to regulate and control the mobility of polyacrylate molecular chains; then grafting gelatin and starch degradable group biomacromolecules to prepare modified acrylic resin with degradable self-repairing performance; by adding the color fixing agent, the product is ensured to keep high color resolution and color saturation; by adding the wax emulsion, the scratch resistance effect after printing is improved; the coating prepared by the method has self-repairing capability of crease marks and scratches, high strength and low viscosity, is degradable, improves the printing display effect, prolongs the service life of the product, and reduces the pollution to the environment.
Drawings
FIG. 1 is an SEM scanning electron micrograph of a coating 1 prepared according to the present invention.
Fig. 2 is a scanning tunneling microscope image of the scratch and self-repair of the coating 1 prepared in the present invention.
FIG. 3 is a graph showing the change in molecular weight of the modified acrylic resin prepared in example 1 of the present invention after soaking in an amylase buffer.
FIG. 4 is SEM scanning electron microscope image of the coating 1 prepared by the invention after soaking in amylase buffer solution.
FIG. 5 is a graph showing the degradation times of the modified acrylic resins prepared in examples 1 to 6 of the present invention.
FIG. 6 is a self-repairing time chart of coatings 1 to 6 prepared by the invention.
Detailed Description
The invention aims to provide a degradable self-repairing coating for a digital printing substrate and a preparation method thereof, and the degradable self-repairing coating is realized by the following technical scheme:
the invention is further described with reference to specific examples.
Example 1
(1) Preparation of a copolymer with pendant isocyanate groups: adding 1.5g of butyl acrylate and 1.65g of isocyanate ethyl acrylate into 200ml of toluene, heating to 70 ℃, introducing argon for 0.75 hour, adding 0.19g of azobisisobutyronitrile after oxygen in the system is exhausted, continuing to react for 18 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 215000 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked polymer: dissolving 2.0g of the copolymer with the pendant isocyanate group obtained in the step (1) in 200ml of DMSO, adding 8.0g of 4,4' -dihydroxy diphenyl disulfide, stirring and dissolving at 20 ℃, then adding 28.1g of dibutyltin dilaurate, continuing to react for 2 hours, adding 300ml of water, filtering after a white solid is separated out, and washing filter residues with tetrahydrofuran for 3 times to obtain a crosslinked product, wherein the number average molecular weight of the crosslinked product is 412000 g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 300ml of dry dichloromethane, adding 25g of gelatin, stirring for 18 hours at 20 ℃, performing suction filtration, washing filter residues with tetrahydrofuran for 3 times, and drying to obtain double-bond modified gelatin;
(4) Synthesis of modified acrylic resin: and (3) adding 2.5g of the reactive macromonomer obtained in the step (3) and 2.5g of the disulfide bond cross-linked polymer obtained in the step (2) into 200ml of dry toluene, heating to 70 ℃, introducing argon for 0.5 hour, adding 0.01g of azobisisobutyronitrile after oxygen in the system is exhausted, continuing to react for 15 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the polymer is 770500g/mol.
Example 2
(1) Preparation of a copolymer with pendant isocyanate groups: adding 1.5g of butyl acrylate and 0.82g of isocyanate ethyl acrylate into 200ml of dioxane, heating to 70 ℃, introducing argon for 0.5 hour, adding 0.14g of dibenzoyl peroxide after oxygen in the system is exhausted, continuing to react for 15 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 202000 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked polymer: dissolving 2.0g of the copolymer with the pendant isocyanate group obtained in the step (1) in 300ml of DMF, adding 6.0g of 4,4' -dihydroxy diphenyl disulfide, stirring and dissolving at 30 ℃, then adding 17.4g of dibutyltin dilaurate, continuing to react for 2 hours, adding 400ml of water, filtering after a white solid is separated out, and washing filter residues with acetone for 3 times to obtain a crosslinked product, wherein the number average molecular weight of the crosslinked product is about 400000 g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 300ml of dry tetrahydrofuran, adding 5g of gelatin, stirring for 15 hours at 30 ℃, performing suction filtration, washing filter residues with acetone for 3 times, and drying to obtain double-bond modified gelatin;
(4) Synthesis of modified acrylic resin: and (3) adding 2.5g of the reactive macromonomer obtained in the step (3) and 1.25g of the disulfide bond cross-linked polymer obtained in the step (2) into 200ml of dry toluene, heating to 70 ℃, introducing argon for 0.5 hour, adding 0.0025g of dibenzoyl peroxide after oxygen in the system is exhausted, continuing to react for 15 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the polymer is 605000 g/mol.
Example 3
(1) Preparation of copolymer with pendant isocyanate group: adding 1.5g of butyl acrylate and 2.5g of isocyanate ethyl acrylate into 250ml of dioxane, heating to 75 ℃, introducing argon for 0.6 hour, adding 0.3g of azo-bis-iso-heptonitrile after oxygen in the system is exhausted, continuing to react for 18 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 250000 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked polymer: dissolving 2.0g of the copolymer with the pendant isocyanate group obtained in the step (1) in 300ml of toluene, adding 7.5g of 4,4' -dithio diphenylamine, stirring and dissolving at 24 ℃, then adding 22.88g of dibutyltin dilaurate, continuing to react for 3 hours, adding 400ml of water, filtering after white solids are separated out, and cleaning filter residues with dichloromethane for 4 times to obtain a cross-linked product, wherein the number average molecular weight of the cross-linked product is 407700 g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 250ml of dry acetonitrile, adding 10g of starch, stirring for 19 hours at 28 ℃, performing suction filtration, washing filter residues with tetrahydrofuran for 3 times, and drying to obtain double-bond modified starch;
(4) Synthesis of modified acrylic resin: and (3) adding 2.5g of the reactive macromonomer obtained in the step (3) and 2.5g of the disulfide-bond cross-linked polymer obtained in the step (2) into dry toluene, heating to 75 ℃, introducing argon for 0.6 hour, adding 0.005g of azodiisoheptonitrile after oxygen in the system is exhausted, continuing to react for 18 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the polymer is 750080 g/mol according to experiment measurement.
Example 4
(1) Preparation of a copolymer with pendant isocyanate groups: adding 1.5g of butyl acrylate and 3.5g of isocyanate ethyl acrylate into 250ml of dioxane, heating to 80 ℃, introducing argon for 0.7 hour, adding 0.25g of azobisisobutyronitrile after oxygen in the system is exhausted, continuing to react for 20 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 310500 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked Polymer: dissolving 2.0g of the copolymer with the isocyanate side group obtained in the step (1) in 300ml of toluene, adding 9.0g of 4,4' -dithio diphenylamine, stirring and dissolving at 26 ℃, then adding 29.75g of dibutyltin dilaurate, continuing to react for 4 hours, adding 400ml of water, filtering after white solids are separated out, and cleaning filter residues with acetonitrile for 4 times to obtain a cross-linked product, wherein the number average molecular weight of the cross-linked product is 407900 g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 250ml of dry acetone, adding 20g of starch, stirring for 20 hours at 26 ℃, performing suction filtration, washing filter residues with tetrahydrofuran for 3 times, and drying to obtain double-bond modified starch;
(4) Synthesis of modified acrylic resin: adding 2.5g of reactive macromonomer obtained in the step (3) and 3.75g of disulfide bond cross-linked polymer obtained in the step (2) into dry toluene, heating to 80 ℃, introducing argon for 0.8 hour, adding 0.01g of azobisisoheptonitrile after oxygen in the system is exhausted, continuing to react for 20 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the polymer is about 790000 g/mol as measured by experiments.
Example 5
(1) Preparation of copolymer with pendant isocyanate group: adding 1.5g of butyl acrylate and 3.75g of isocyanate ethyl acrylate into 300ml of dioxane, heating to 80 ℃, introducing argon for 0.8 hour, adding 0.4g of dibenzoyl peroxide after oxygen in the system is exhausted, continuing to react for 22 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 390800 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked Polymer: dissolving 2.0g of the copolymer with the pendant isocyanate group obtained in the step (1) in 300ml of toluene, adding 7.0g of 4,4' -dihydroxy diphenyl disulfide, stirring and dissolving at 25 ℃, then adding 24.9g of dibutyltin dilaurate, continuing to react for 4 hours, adding 400ml of water, filtering after a white solid is precipitated, and washing filter residues with tetrahydrofuran for 4 times to obtain a crosslinked product, wherein the number-average molecular weight of the crosslinked product is about 408200g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 250ml of dry acetone, adding 30g of gelatin, stirring for 22 hours at 28 ℃, performing suction filtration, washing filter residues with tetrahydrofuran for 3 times, and drying to obtain double-bond modified gelatin;
(4) Synthesis of modified acrylic resin: and (3) adding 2.5g of the reactive macromonomer obtained in the step (3) and 4.5g of the disulfide-bond cross-linked polymer obtained in the step (2) into dry toluene, heating to 80 ℃, introducing argon for 0.8 hour, adding 0.0075g of azodiisoheptonitrile after oxygen in the system is exhausted, continuing to react for 22 hours, and performing suction filtration to obtain white powder, wherein the number-average molecular weight of the polymer is 768000 g/mol as measured by experiments.
Example 6
(1) Preparation of a copolymer with pendant isocyanate groups: adding 1.5g of butyl acrylate and 4.95g of isocyanate ethyl acrylate into 400ml of dioxane, heating to 90 ℃, introducing argon for 1 hour, adding 0.57g of dibenzoyl peroxide after oxygen in the system is exhausted, continuing to react for 24 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the white powder is 405000 g/mol according to experimental measurement;
(2) Preparation of disulfide-bonded crosslinked Polymer: dissolving 2.0g of the copolymer with the pendant isocyanate group obtained in the step (1) in 300ml of toluene, adding 10.0g of 4,4' -dihydroxy diphenyl disulfide, stirring and dissolving at 25 ℃, then adding 43.4g of dibutyltin dilaurate, continuing to react for 4 hours, adding 400ml of water, filtering after a white solid is precipitated, and washing filter residues with tetrahydrofuran for 5 times to obtain a crosslinked product, wherein the number-average molecular weight of the crosslinked product is about 475000 g/mol;
(3) Synthesis of reactive macromers: dissolving 0.5g of acryloyl chloride in 300ml of dry acetone, adding 50g of gelatin, stirring for 24 hours at 25 ℃, performing suction filtration, washing filter residues with acetone for 5 times, and drying to obtain double-bond modified gelatin;
(4) Synthesis of modified acrylic resin: and (3) adding 2.5g of the reactive macromonomer obtained in the step (3) and 5.0g of the disulfide bond cross-linked polymer obtained in the step (2) into dry toluene, heating to 90 ℃, introducing argon for 1 hour, adding 0.0125g of azodiisoheptanonitrile after oxygen in the system is exhausted, continuing to react for 24 hours, and performing suction filtration to obtain white powder, wherein the number average molecular weight of the polymer is 799000 g/mol as measured by experiments.
Examples of the experiments
Mixing 20 parts of modified acrylic resin prepared in examples 1 to 6, 8 parts of fluorane dye 2-phenylamino-6-dibutylamino-3-methylfluorane, 25 parts of color developing agent bisphenol A, 3 parts of color fixing agent cetylpyridinium chloride, 5 parts of zinc stearate, 3 parts of wax emulsion, 0.02 part of organic silicon defoamer TSA-8300.01 part of water retention agent carboxymethyl cellulose and 57 parts of water, stirring and dispersing at 800r/min for 30min, standing, self-repairing, obtaining dispersion liquid, uniformly coating the obtained dispersion liquid on the surface of polylactic acid fiber PLA, drying at 80 ℃, and preparing degradable coatings 1 to 6, wherein the thickness of the coating is about 4 mu m. Wherein the SEM characterization of coating 1 is shown in figure 1.
The adhesion of the coating is tested according to the national standard GB/T9286-1998, after the scribing knife is used for marking, 3M glue is used for adhering and pulling, and the area of the coating which is not pulled is estimated by visual qualitative observation. Meanwhile, the hardness of the coating is tested according to GB/T6739-2006, after the coating is cured, the sample is horizontally placed, pencils with different hardness are pushed on the surface to test the hardness of the coating, and the hardness of the pencils without scratches represents the hardness of the coating; observing the apparent condition of the prepared coating under a magnifying glass; the measured hardness, adhesion and appearance were as shown in Table 1.
TABLE 1 hardness, adhesion and appearance of the coatings 1 to 6 prepared in examples 1 to 6
| Coating numbering | Coating adhesion/% | Apparent condition of the | Hardness scale | |
| 1 | 100 | The surface of the coating is uniform and | 2H | |
| 2 | 95 | The coating surface has a small amount of | 2H | |
| 3 | 100 | The surface of the coating is uniform and | 2H | |
| 4 | 100 | The surface of the coating is uniform and | 2H | |
| 5 | 99 | The surface of the coating is uniform and | 2H | |
| 6 | 96 | The coating surface has a small amount of stripes | 2H |
Taking the coating 1 as an experimental example, the scratch is created on the surface of the coating by using a scribing knife with three forces, and the corresponding scratch area is observed under magnification by using a scanning tunneling microscope, as shown in fig. 2, the scratches with different depths can be perfectly healed within 30 minutes after the scratches are scribed on the coating.
The modified acrylic resin prepared in example 1 and the degradable self-repairing coating prepared therefrom were immersed in an amylase buffer solution (phosphate buffer solution with pH of 5.6) for degradation experiments. For the degradation of the polymer, the degradability of the polymer is characterized by testing the molecular weight of the polymer at different times, and the change result of the molecular weight of the polymer at different times is shown in figure 3, and the polymer can be completely degraded in about 120 hours under the condition. For the degradation of the coating, we operated under the same conditions, after soaking the coating material in an amylase buffer solution (pH 5.6 phosphate buffer) for 120 hours, using SEM characterization results are shown in fig. 4, with a significant change in SEM image of the coating after degradation compared to the SEM image before soaking.
Degradation and self-repair tests are carried out on the modified acrylic resins prepared in examples 1 to 6 and coating samples 1 to 6 prepared from the modified acrylic resins, and the results are shown in fig. 5 and 6, wherein the self-repair time and the degradation time of the modified acrylic resins are also changed remarkably due to different polymer molecular weights. The increase of the molecular weight of the polymer simultaneously increases the number and the density of self-repairing functional groups, namely disulfide bonds, which undoubtedly enhances the self-repairing performance of the material and shortens the self-repairing time; meanwhile, the increase of the molecular weight of the polymer also increases the degradation difficulty of the polymer and prolongs the degradation time of the polymer.
Claims (8)
1. A degradable self-repairing coating for a digital printing substrate is characterized in that: the composition comprises the following components in parts by weight: 20 parts of modified acrylic resin, 8 parts of fluorane dye 2-phenylamino-6-dibutylamino-3-methylfluorane, 25 parts of color developing agent bisphenol A, 3 parts of color fixing agent cetylpyridinium chloride, 5 parts of zinc stearate, 3 parts of wax emulsion, 0.01 part of organic silicon defoamer TSA-830, 0.02 part of water retention agent carboxymethyl cellulose and 57 parts of water;
the modified acrylic resin is prepared by the following method: firstly, copolymerizing butyl acrylate and isocyanate ethyl acrylate to obtain a copolymer with a pendant isocyanate group; then reacting the prepared copolymer with the side group of isocyanic acid with disulfide to obtain a disulfide-bond crosslinked polymer; reacting acryloyl chloride with natural macromolecules to obtain reactive macromonomers; finally copolymerizing the obtained reactive macromonomer and the disulfide bond crosslinked polymer to obtain modified acrylic resin;
the natural macromolecule is gelatin or starch.
2. The degradable self-healing coating for a digital printing substrate of claim 1, wherein: the specific synthetic steps of the modified acrylic resin are as follows:
(1) Preparation of copolymer with pendant isocyanate group: adding butyl acrylate and isocyanate ethyl acrylate into an organic solvent 1, heating to 70-90 ℃, introducing argon for 0.5-1 hour, adding an initiator 1 after oxygen in the system is exhausted, continuing to react for 15-24 hours, and performing suction filtration to obtain white powder, namely the copolymer with the isocyanate side group;
the mol ratio of the butyl acrylate to the isocyanate ethyl acrylate to the initiator 1 is 1:0.5 to 3:0.05 to 0.2;
the organic solvent 1 is toluene or dioxane;
the initiator 1 is azobisisobutyronitrile, dibenzoyl peroxide or azobisisoheptonitrile;
(2) Preparation of disulfide-bonded crosslinked polymer: dissolving the copolymer with the isocyanate side group obtained in the step (1) in an organic solvent 2, adding a disulfide, stirring and dissolving at 20-30 ℃, then adding dibutyltin dilaurate, continuing to react for 2-4 hours, adding water, precipitating a white solid, filtering, and washing filter residues with an organic solvent 3 for 3-5 times to obtain a disulfide bond cross-linked polymer;
the molar ratio of the disulfide to dibutyltin dilaurate is 1:1 to 1.5;
the mass ratio of the copolymer with the pendant isocyanate group to the disulfide is 1:3 to 5;
the organic solvent 2 is DMSO, DMF, toluene or dioxane;
the organic solvent 3 is tetrahydrofuran, acetone, dichloromethane or acetonitrile;
the disulfide is 4,4 '-dihydroxydiphenyl disulfide or 4,4' -dithiodiphenylamine;
(3) Synthesis of reactive macromers: dissolving acryloyl chloride in a dry organic solvent 4, adding natural macromolecules, stirring for 15 to 24 hours at the temperature of 20 to 30 ℃, carrying out suction filtration, washing filter residues for 3 to 5 times by using an organic solvent 3, and drying to obtain a reactive macromonomer;
the mass ratio of the acryloyl chloride to the natural macromolecules is 1:10 to 100;
the organic solvent 4 is dichloromethane, tetrahydrofuran, acetonitrile or acetone;
the natural macromolecules are gelatin or starch;
synthesis of modified acrylic resin: adding the reactive macromonomer obtained in the step (3) and the disulfide bond crosslinked polymer obtained in the step (2) into a dry organic solvent 1, heating to 70-90 ℃, introducing argon for 0.5-1 hour, adding an initiator 1 after oxygen in the system is exhausted, continuing to react for 15-24 hours, and performing suction filtration to obtain white powder;
the mass ratio of the reactive macromonomer, the disulfide bond cross-linked polymer and the initiator 1 is 1:0.5 to 2:0.001 to 0.005.
3. The degradable self-healing coating for a digital printing substrate of claim 2, wherein: in the step (1), the molar ratio of the butyl acrylate, the isocyanate ethyl acrylate and the initiator 1 is 1:1 to 2.5:0.1 to 0.15.
4. The degradable self-repairing coating for the digital printing substrate as recited in claim 2, wherein: the molar ratio of the disulfide to dibutyltin dilaurate in step (2) is 1:1 to 1.3, wherein the mass ratio of the copolymer with the isocyanic acid side group to the disulfide is 1:3 to 4.5.
5. The degradable self-healing coating for a digital printing substrate of claim 2, wherein: the disulfide in the step (2) is 4,4' -dihydroxy diphenyl disulfide.
6. The degradable self-repairing coating for the digital printing substrate as recited in claim 2, wherein: in the step (3), the mass ratio of the acryloyl chloride to the natural macromolecules is 1:20 to 80.
7. The degradable self-repairing coating for the digital printing substrate as recited in claim 2, wherein: the mass ratio of the reactive macromonomer to the disulfide bond crosslinked polymer to the initiator 1 in the step (4) is 1:0.5 to 1.6:0.002 to 0.004.
8. The preparation method of the degradable self-repairing coating for the digital printing substrate as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps: mixing 20 parts of modified acrylic resin, 8 parts of 2-phenylamino-6-dibutylamino-3-methylfluoran of a fluoran dye, 25 parts of a color developing agent bisphenol A, 3 parts of a color fixing agent cetylpyridinium chloride, 5 parts of zinc stearate, 3 parts of a wax emulsion, 0.02 part of an organic silicon defoamer TSA-8300.01, 0.02 part of a water retention agent carboxymethyl cellulose and 57 parts of water, stirring and dispersing at 800r/min for 30min, standing, filtering to obtain a dispersion liquid, uniformly coating the obtained dispersion liquid on the surface of a polylactic acid fiber PLA substrate, and drying at 80 ℃, wherein the thickness of the coating is 3 to 5 mu m;
the modified acrylic resin is prepared by the following method: firstly, copolymerizing butyl acrylate and isocyanate ethyl acrylate to obtain a copolymer with a pendant isocyanate group; then reacting the prepared copolymer with the side group of isocyanic acid with disulfide to obtain a disulfide-bond crosslinked polymer; reacting acryloyl chloride with natural macromolecules to obtain a reactive macromonomer; finally copolymerizing the obtained reactive macromonomer and the disulfide bond crosslinked polymer to obtain modified acrylic resin;
the natural macromolecule is gelatin or starch.
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