CN115010887A - High-strength self-repairing protective film for mobile phone and preparation method thereof - Google Patents
High-strength self-repairing protective film for mobile phone and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, in particular to a high-strength self-repairing protective film for a mobile phone and a preparation method thereof, wherein the high-strength self-repairing protective film comprises the following raw materials in parts by weight: 40-60 parts of polyether polyol, 30-35 parts of diisocyanate, 3-5 parts of alkylphenol disulfide, 1-1.5 parts of silane end-capping agent, 2-4 parts of aromatic diamine chain extender, 0.1-0.2 part of organic tin catalyst, 5-10 parts of hydrophobic modified graphene quantum dots and 60-80 parts of solvent.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength self-repairing protective film for a mobile phone and a preparation method thereof.
Background
The mobile phone protection film is a cold mounting film which can be used for mounting the surface of a mobile phone body, a screen and other tangible objects, has various types, and can be divided into the following parts according to the purposes: a mobile phone screen protective film and a mobile phone body protective film; the functions from the original simple scratch-resistant protective film to the push-out functional protective film series can be divided into: peep-proof membrane, mirror membrane, AR membrane, frosting membrane, high-clarity membrane, scratch-proof protection film, 3D membrane, cell-phone fuselage scratch-proof protection film, diamond membrane, tempering membrane etc..
The existing mobile phone protective film does not have a self-repairing function, is often replaced after scratches appear, and is not too high in film strength and easy to crack under the action of external force, so that the use experience is influenced.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems, the invention provides a high-strength self-repairing protective film for a mobile phone and a preparation method thereof.
The adopted technical scheme is as follows:
a high-strength self-repairing protective film for a mobile phone comprises the following raw materials in parts by weight:
40-60 parts of polyether polyol, 30-35 parts of diisocyanate, 3-5 parts of alkylphenol disulfide, 1-1.5 parts of silane blocking agent, 2-4 parts of aromatic diamine chain extender, 0.1-0.2 part of organic tin catalyst, 5-10 parts of hydrophobic modified graphene quantum dots and 60-80 parts of solvent.
Further, the polyether polyol is any one or more of PPG-400, PPG-425, PPG-1000, PPG-2000, PPG-3000 and PPG-4000.
Further, the diisocyanate is any one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate.
Further, the diisocyanate is toluene diisocyanate and dimer acid diisocyanate, and the mass ratio of the toluene diisocyanate to the dimer acid diisocyanate is 2-5: 1.
further, the silane end-capping agent is any one or more of KH-550, KH-560 and KH-570.
Further, the aromatic diamine chain extender is any one or more of diamino isobutyl p-chlorobenzoate, dimethyl sulfur toluene diamine and diethyl toluene diamine.
Further, the preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 1,3, 6-trinitropyrene, sodium hydroxide and mercapto long-chain alkanoic acid into water, ultrasonically oscillating and dispersing, transferring to a hydrothermal reaction kettle, heating to 180 ℃ and 200 ℃, reacting for 10-15h, recovering the obtained reaction liquid to room temperature, dialyzing, microfiltering and drying.
Furthermore, the carbon atom number of the mercapto long-chain alkanoic acid is more than or equal to 10.
The invention provides a preparation method of a high-strength self-repairing protective film for a mobile phone, which comprises the following steps:
s1: adding diisocyanate into a solvent, heating to 50-60 ℃, uniformly stirring, adding polyether polyol and an organic tin catalyst, heating to 70-80 ℃, and stirring to react to generate a first prepolymer;
s2: cooling to 0-5 ℃, adding alkylphenol disulfide and a silane end-capping agent, uniformly stirring, heating to 70-80 ℃, and reacting to generate a second prepolymer;
s3: adding an aromatic diamine chain extender and the hydrophobically modified graphene quantum dots, uniformly stirring, then carrying out tape casting to form a film, and heating and curing.
Furthermore, the temperature is 80-90 ℃ and the time is 12-24h when heating and curing.
The organic tin catalyst in the invention is a metal organic compound formed by directly combining tin and carbon elements, and includes, but is not limited to, dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate.
The solvent in the invention is a common solvent for polyurethane synthesis, and includes but is not limited to pure benzene, butyl acetate, xylene, cyclohexanone, DMF, DMSO, THF and the like.
The invention has the beneficial effects that:
the invention provides a high-strength self-repairing protective film for mobile phones, wherein benzene rings in toluene diisocyanate bring enough rigidity to a film body, dimer acid diisocyanate is macromolecular aliphatic diisocyanate with a unique structure, the dimer acid diisocyanate has a dimer fatty acid main chain with 36 carbon atoms, a cyclohexane group is also arranged in a molecular structure, the main chain structure endows the dimer acid diisocyanate with excellent flexibility and can improve the toughness and tear resistance of the film body, a disulfide bond in alkylphenol disulfide is used as a dynamic weak covalent bond and has lower thermal effect response conditions than other reversible covalent bonds, based on the instability of the disulfide bond, the disulfide bond is easy to break to form sulfur anions/sulfur free radicals, the self-repairing can be realized through the recombination process between different sulfur anions/sulfur free radicals or the reversible reaction between the disulfide bond and a mercapto group, and the hydrophobic modified graphene quantum dots can enhance various performances of the film body, after hydrophobic modification, the high-strength self-repairing protective film has the advantages of improved stability and dispersibility, uniform dispersion in a film body, and improved compatibility with organic polymers, and the high-strength self-repairing protective film prepared by the method has excellent mechanical property, the tensile strength is more than or equal to 9MPa, the elongation at break is more than or equal to 350%, the hardness is 4H, the water contact angle is more than or equal to 118 degrees, and the hydrophobicity and the self-repairing performance are good.
Drawings
FIG. 1 is a graph showing the transmittance of a high-strength self-repairing protective film prepared in example 1 of the present invention;
FIG. 2-A shows the surface topography of the high-strength self-repairing protective film prepared in example 1 of the present invention before self-repairing;
fig. 2-B is a surface morphology of the high-strength self-healing protective film prepared in embodiment 1 of the present invention after self-healing.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The main raw materials are as follows:
polypropylene glycol PPG-2000, chemically pure, available from southbound blue & ltp new materials, inc;
toluene diisocyanate, chemically pure, available from chemical technologies ltd of jinan dahui;
dimer acid diisocyanate with CAS number of 68239-06-5, chemical purity, available from Jinan Dahui chemical technology Limited;
alkylphenol disulfide, CAS No. 60303-68-6, chemically pure, available from new materials, inc;
the silane end-capping agent KH-550 is chemically pure and is purchased from Jinan Dahui chemical technology Limited;
dimercapto toluene diamine, chemically pure, available from Wuhans McBiotech, Inc.;
stannous octoate, chemically pure, purchased from chemical technologies ltd of shorea of south china;
DMF, chemically pure, was purchased from Ji nan Dai Hui chemical science and technology Ltd.
Example 1:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the following raw materials in proportion: polypropylene glycol PPG-200060 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane end-capping agent KH-5501.2 parts, dimethyl thio toluene diamine 3 parts, stannous octoate 0.1 part, hydrophobic modified graphene quantum dots 8 parts, and DMF80 parts.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid into 10L of water, transferring the mixture into a hydrothermal reaction kettle after ultrasonic oscillation and dispersion, heating the mixture to 185 ℃ for reaction for 15h, recovering the obtained reaction solution to room temperature, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 500Da, filtering the reaction solution by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying the reaction solution for 15h at 80 ℃.
The preparation method of the high-strength self-repairing protective film for the mobile phone comprises the following steps:
adding toluene diisocyanate and dimer acid diisocyanate into DMF, heating to 55 ℃, uniformly stirring, adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring for reaction for 20min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and silane end-capping reagent KH-550, uniformly stirring, heating to 80 ℃, reacting for 5h to generate a second prepolymer, adding dimethylthio toluene diamine and hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing at 85 ℃ for 18 h.
Testing the light transmittance of the prepared protective film in the range of 400-900nm by using an ultraviolet spectrophotometer (Thermo Fisher Evo-luminescence 220 type), wherein the light transmittance curve is shown in figure 1;
a cut is scribed on the surface of the sample, the sample is placed in an oven at 80 ℃ for 5min, and then the healing state of the cut is observed, wherein a graph 2-A shows the surface appearance of the sample before self-repairing, and a graph 2-B shows the surface appearance of the sample after self-repairing.
Example 2:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the following raw materials in proportion: polypropylene glycol PPG-200060 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane end-capping agent KH-5501.5 parts, dimethyl thio toluene diamine 4 parts, stannous octoate 0.2 part, hydrophobic modified graphene quantum dot 10 parts, and DMF80 parts.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid into 10L of water, transferring the mixture into a hydrothermal reaction kettle after ultrasonic oscillation and dispersion, heating the mixture to 200 ℃ for reaction for 15h, recovering the obtained reaction solution to room temperature, dialyzing the reaction solution by using a dialysis bag with the molecular weight cutoff of 500Da, filtering the reaction solution by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying the reaction solution for 15h at 80 ℃.
The preparation method of the high-strength self-repairing protective film for the mobile phone comprises the following steps:
adding toluene diisocyanate and dimer acid diisocyanate into DMF, heating to 60 ℃, uniformly stirring, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring for reaction for 30min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and silane end-capping reagent KH-550, uniformly stirring, heating to 80 ℃, reacting for 5h to generate a second prepolymer, adding dimethylthio toluene diamine and hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing at 90 ℃ for 24 h.
Example 3:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the following raw materials in proportion: PPG-200060 parts of polypropylene glycol, 25 parts of toluene diisocyanate, 5 parts of dimer acid diisocyanate, 3 parts of alkylphenol disulfide, KH-5501 parts of silane end capping agent, 2 parts of dimethyl sulfenyl toluene diamine, 0.1 part of stannous octoate, 5 parts of hydrophobic modified graphene quantum dots and 60 parts of DMF.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid into 10L of water, transferring the mixture into a hydrothermal reaction kettle after ultrasonic oscillation and dispersion, heating to 180 ℃ for reaction for 10h, recovering the obtained reaction solution to room temperature, dialyzing by using a dialysis bag with the molecular weight cutoff of 500Da, filtering by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying for 15h at 80 ℃.
The preparation method of the high-strength self-repairing protective film for the mobile phone comprises the following steps:
adding toluene diisocyanate and dimer acid diisocyanate into DMF, heating to 50 ℃, uniformly stirring, adding polypropylene glycol PPG-2000 and stannous octoate, heating to 70 ℃, stirring for reaction for 15min to generate a first prepolymer, cooling to 0 ℃, adding alkylphenol disulfide and a silane end-capping agent KH-550, uniformly stirring, heating to 70 ℃, reacting for 3h to generate a second prepolymer, adding dimethylthio toluene diamine and hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing at 80 ℃ for 12 h.
Example 4:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the following raw materials in proportion: polypropylene glycol PPG-200060 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 4 parts, silane end capping agent KH-5501.5 parts, dimethyl thio toluene diamine 2 parts, stannous octoate 0.2 part, hydrophobic modified graphene quantum dots 5 parts, and DMF80 parts.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid into 10L of water, transferring the mixture into a hydrothermal reaction kettle after ultrasonic oscillation and dispersion, heating to 180 ℃ for reaction for 15h, recovering the obtained reaction solution to room temperature, dialyzing by using a dialysis bag with the molecular weight cutoff of 500Da, filtering by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying for 15h at 80 ℃.
The preparation method of the high-strength self-repairing protective film for the mobile phone comprises the following steps:
adding toluene diisocyanate and dimer acid diisocyanate into DMF, heating to 50 ℃, uniformly stirring, adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring for reaction for 15min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and silane end-capping reagent KH-550, uniformly stirring, heating to 70 ℃, reacting for 5h to generate a second prepolymer, adding dimethylthio toluene diamine and hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing at 80 ℃ for 24 h.
Example 5:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the following raw materials in proportion: polypropylene glycol PPG-200060 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane end capping agent KH-5501 parts, dimethyl thio toluene diamine 4 parts, stannous octoate 0.1 part, hydrophobic modified graphene quantum dots 10 parts, and DMF60 parts.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid into 10L of water, transferring the mixture into a hydrothermal reaction kettle after ultrasonic oscillation and dispersion, heating the mixture to 200 ℃ for reaction for 10 hours, recovering the obtained reaction liquid to room temperature, dialyzing the reaction liquid by using a dialysis bag with the molecular weight cutoff of 500Da, filtering the reaction liquid by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying the reaction liquid for 15 hours at 80 ℃.
The preparation method of the high-strength self-repairing protective film for the mobile phone comprises the following steps:
adding toluene diisocyanate and dimer acid diisocyanate into DMF, heating to 60 ℃, uniformly stirring, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 70 ℃, stirring for reaction for 30min to generate a first prepolymer, cooling to 0 ℃, adding alkylphenol disulfide and silane end-capping reagent KH-550, uniformly stirring, heating to 80 ℃, reacting for 3h to generate a second prepolymer, adding dimethylthio toluene diamine and hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing at 90 ℃ for 12 h.
Comparative example 1:
substantially the same as example 1 except that the hydrophobically modified graphene quantum dots were not added.
Comparative example 2:
the method is basically the same as example 1, except that 16-mercaptohexadecanoic acid is not added in the preparation of the hydrophobic modified graphene quantum dot.
The preparation method of the hydrophobic modified graphene quantum dot comprises the following steps:
adding 40g of 1,3, 6-trinitropyrene and 100g of sodium hydroxide into 10L of water, ultrasonically oscillating and dispersing, transferring into a hydrothermal reaction kettle, heating to 185 ℃ for reaction for 15h, recovering the obtained reaction liquid to room temperature, dialyzing by using a dialysis bag with the molecular weight cutoff of 500Da, filtering by using a microfiltration membrane with the pore diameter of 0.45 mu m, and drying for 15h at 80 ℃.
Comparative example 3:
essentially the same as example 1, except that no alkylphenol disulfide was added.
Comparative example 4:
essentially the same as in example 1, except that 1, 3-propanediol was used in place of dimethylthiotoluenediamine.
And (3) performance testing:
the high-strength self-repairing protective films prepared in the examples 1 to 5 and the comparative examples 1 to 4 are used as samples;
the tensile property of the sample is tested by a universal tensile machine (Instron5943 type) at room temperature and at the tensile speed of 15 mm/min;
according to the GB/T6739-2006 standard, the hardness of the sample is measured by a manual coating hardness pencil method.
The contact angles of the respective samples were measured by a contact angle measuring instrument (Dropshape Analyzer-DSA25 type), and the test liquid was ultrapure water.
Table 1:
as can be seen from the above table 1, the high-strength self-repairing protective film prepared by the invention has excellent mechanical properties, the tensile strength is more than or equal to 9MPa, the elongation at break is more than or equal to 350%, the hardness is 4H, the water contact angle is more than or equal to 118 degrees, and the hydrophobicity is good.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The high-strength self-repairing protective film for the mobile phone is characterized by comprising the following raw materials in parts by weight:
40-60 parts of polyether polyol, 30-35 parts of diisocyanate, 3-5 parts of alkylphenol disulfide, 1-1.5 parts of silane blocking agent, 2-4 parts of aromatic diamine chain extender, 0.1-0.2 part of organic tin catalyst, 5-10 parts of hydrophobic modified graphene quantum dots and 60-80 parts of solvent.
2. The high-strength self-repairing protective film for the mobile phone of claim 1, wherein the polyether polyol is one or more of PPG-400, PPG-425, PPG-1000, PPG-2000, PPG-3000 and PPG-4000.
3. The protective film of claim 1, wherein the diisocyanate is any one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate.
4. The high-strength self-repairing protective film for the mobile phone as claimed in claim 3, wherein the diisocyanate is toluene diisocyanate and dimer acid diisocyanate, and the mass ratio of the toluene diisocyanate to the dimer acid diisocyanate is 2-5: 1.
5. the high-strength self-repairing protective film for the mobile phone as claimed in claim 1, wherein the silane end capping agent is any one or more of KH-550, KH-560 and KH-570.
6. The protective film of claim 1, wherein the aromatic diamine chain extender is one or more of isobutyl diamido p-chlorobenzoate, dimethylthiotoluenediamine and diethyltoluenediamine.
7. The high-strength self-repairing protective film for the mobile phone of claim 1, wherein the preparation method of the hydrophobic modified graphene quantum dots comprises the following steps:
adding 1,3, 6-trinitropyrene, sodium hydroxide and mercapto long-chain alkanoic acid into water, ultrasonically oscillating and dispersing, transferring to a hydrothermal reaction kettle, heating to 180 ℃ and 200 ℃, reacting for 10-15h, recovering the obtained reaction liquid to room temperature, dialyzing, microfiltering and drying.
8. The high-strength self-repairing protective film for the mobile phone according to claim 7, wherein the number of carbon atoms of the mercapto long-chain alkanoic acid is not less than 10.
9. The preparation method of the high-strength self-repairing protective film for the mobile phone as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
s1: adding diisocyanate into a solvent, heating to 50-60 ℃, uniformly stirring, adding polyether polyol and an organic tin catalyst, heating to 70-80 ℃, and stirring to react to generate a first prepolymer;
s2: cooling to 0-5 ℃, adding alkylphenol disulfide and a silane end-capping agent, uniformly stirring, heating to 70-80 ℃, and reacting to generate a second prepolymer;
s3: adding an aromatic diamine chain extender and the hydrophobic modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing.
10. The method for preparing the high-strength self-repairing protective film for the mobile phone according to claim 9, wherein the temperature during heating and curing is 80-90 ℃ and the time is 12-24 h.
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| CN113088176A (en) * | 2021-04-01 | 2021-07-09 | 南阳金牛彩印集团有限公司 | Self-repairing scratch-resistant polyurethane coating and preparation method thereof |
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| US20030027923A1 (en) * | 2001-07-05 | 2003-02-06 | Industrial Technology Research Institute | High performance aqueous polyurethanes and methods of fabricating the same |
| CN111234175A (en) * | 2020-03-10 | 2020-06-05 | 科顺防水科技股份有限公司 | Preparation method of self-repairing waterproof material, self-repairing waterproof material and application of self-repairing waterproof material |
| CN113088176A (en) * | 2021-04-01 | 2021-07-09 | 南阳金牛彩印集团有限公司 | Self-repairing scratch-resistant polyurethane coating and preparation method thereof |
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