CN115010887B - 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 organotin catalyst, 5-10 parts of hydrophobically modified graphene quantum dot 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 protective 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, and has various kinds and can be divided into: 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 can be divided into the following series: peep-proof film, mirror film, AR film, dull polish membrane, high definition membrane, prevent scraping protection film, 3D membrane, cell-phone fuselage prevent scraping colored protection film, diamond film, tempering membrane etc..
The existing mobile phone protective film does not have a self-repairing function, the mobile phone protective film is often replaced after scratches appear, the strength of the film body is not too high, the mobile phone protective film is easy to crack under the action of external force, and the use experience is affected.
Disclosure of Invention
The invention aims to: 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 technical scheme adopted 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 end capping agent, 2-4 parts of aromatic diamine chain extender, 0.1-0.2 part of organotin catalyst, 5-10 parts of hydrophobically modified graphene quantum dot 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 thiotoluene diamine and diethyl toluene diamine.
Further, the preparation method of the hydrophobically 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 into a hydrothermal reaction kettle, heating to 180-200 ℃ for reaction for 10-15h, recovering the obtained reaction liquid to room temperature, dialyzing, micro-filtering and drying.
Further, the number of carbon atoms of the mercapto long-chain alkanoic acid is not less than 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 organotin catalyst, heating to 70-80 ℃, and stirring for reacting to generate a first prepolymer;
s2: cooling to 0-5 ℃, adding alkylphenol disulfide and 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 hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing.
Further, the temperature during heating and curing is 80-90 ℃ and the time is 12-24 hours.
Organotin catalysts of the present invention are metal-organic compounds formed by the direct combination of tin and carbon elements, including but not limited to dibutyltin dilaurate, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate.
The solvent in the invention is a common solvent for polyurethane synthesis, including but 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 protection film for a mobile phone, wherein benzene rings in toluene diisocyanate bring enough rigidity for a film body, dimer acid diisocyanate is macromolecular aliphatic diisocyanate with a unique structure, the dimer acid diisocyanate is provided with a dimer fatty acid main chain with 36 carbon atoms, a cyclohexane group is arranged in a molecular structure, the main chain structure endows the film body with excellent flexibility, the toughness and tear resistance of the film body can be improved, disulfide bonds in alkylphenol disulfide serve as dynamic weak covalent bonds, the high-strength self-repairing protection film has lower thermal effect response conditions than other reversible covalent bonds, the disulfide bonds are easily broken to form sulfide anions/sulfide free radicals based on instability of the disulfide bonds, the self-repairing can be realized through recombination processes between different sulfide anions/sulfide free radicals or reversible reactions between disulfide bonds and mercapto groups, various properties of the film body can be enhanced by hydrophobically modifying graphene quantum dots, the stability and dispersibility of the film body are improved after the hydrophobic modification, the film body can be uniformly dispersed in the film body, the high-strength self-repairing protection film can be improved, the high-strength self-repairing protection film prepared by the invention has the advantages of high-strength self-repairing protection film has the tensile strength of more than or equal to or more than 9MPa, the excellent self-repairing protection film has the tensile strength of which is equal to or more than or equal to 4 MPa, and the excellent self-repairing protection film has the excellent self-strength and water hardness of the self-repairing protection film is equal to or more than or better than or equal to or more than 4.
Drawings
FIG. 1 is a graph showing the transmittance of the high-strength self-repairing protective film prepared in example 1 of the present invention;
FIG. 2-A shows the surface morphology of the high strength self-repairing protective film prepared in example 1 of the present invention before self-repairing;
FIG. 2-B shows the surface morphology of the high-strength self-repairing protective film prepared in example 1 of the present invention after self-repairing.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The main raw materials are as follows:
polypropylene glycol PPG-2000, chemically pure, purchased from south-pass blue-zepine new materials inc;
toluene diisocyanate, chemically pure, purchased from ataxia-south dahlia chemical technology limited;
dimer acid diisocyanate, CAS number 68239-06-5, chemically pure, available from Jinan Dahui chemical technology Co., ltd;
alkylphenol disulfide, CAS number 60303-68-6, chemically pure, available from Qingdao Ruixia New Material Co., ltd;
silane end capping agent KH-550, chemically pure, purchased from Jinan Dahui chemical technology Co., ltd;
dimethylthiotoluenediamine, chemically pure, available from Wohinsm Biotechnology Co., ltd;
stannous octoate, chemically pure, purchased from ataxia-south dahlia chemical technology limited;
DMF, chemically pure, was purchased from ataxia-Nannohui chemical technology Co.
Example 1:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the raw materials according to the proportion: polypropylene glycol PPG-2000 60 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane blocking agent KH-550.2 parts, dimethyl thiotoluene diamine 3 parts, stannous octoate 0.1 parts, hydrophobically modified graphene quantum dot 8 parts and DMF80 parts.
The preparation method of the hydrophobically modified graphene quantum dot comprises the following steps:
40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid are added into 10L of water, the mixture is transferred into a hydrothermal reaction kettle after ultrasonic oscillation dispersion, the temperature is raised to 185 ℃ for reaction for 15 hours, the obtained reaction liquid is recovered to room temperature, and is dialyzed by a dialysis bag with the molecular weight cutoff of 500Da, filtered by a microfiltration membrane with the aperture of 0.45 mu m and dried 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 55 ℃, stirring uniformly, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring and reacting for 20min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and a silane end capping agent KH-550, stirring uniformly, heating to 80 ℃, reacting for 5h to generate a second prepolymer, adding dimethyl thiotoluene diamine and hydrophobically modified graphene quantum dots, stirring uniformly, casting to form a film, and heating and curing at 85 ℃ for 18 h.
The transmittance of the prepared protective film in the range of 400-900nm was tested by using an ultraviolet spectrophotometer (Thermo Fisher Evo-solution 220 type), and the transmittance curve is shown in fig. 1;
the surface of the sample is scratched with a knife edge, the healing state of the knife edge is observed after the sample is put into an oven at 80 ℃ for 5min, the surface morphology of the sample before self-repairing is shown in fig. 2-A, the surface morphology of the sample after self-repairing is shown in fig. 2-B, and the protective film has good self-repairing performance by comparison.
Example 2:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the raw materials according to the proportion: polypropylene glycol PPG-2000 60 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane end capping agent KH-550.5 parts, dimethyl thiotoluene diamine 4 parts, stannous octoate 0.2 parts, hydrophobically modified graphene quantum dot 10 parts and DMF80 parts.
The preparation method of the hydrophobically modified graphene quantum dot comprises the following steps:
40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid are added into 10L of water, the mixture is transferred into a hydrothermal reaction kettle after ultrasonic oscillation dispersion, the temperature is raised to 200 ℃ for reaction for 15 hours, the obtained reaction liquid is recovered to room temperature, and is dialyzed by a dialysis bag with the molecular weight cutoff of 500Da, filtered by a microfiltration membrane with the aperture of 0.45 mu m and dried 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 ℃, stirring uniformly, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring and reacting for 30min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and silane end capping agent KH-550, stirring uniformly, heating to 80 ℃, reacting for 5h to generate a second prepolymer, adding dimethyl thiotoluene diamine and hydrophobically modified graphene quantum dots, stirring uniformly, casting to form a film, and heating and curing at 90 ℃ for 24h.
Example 3:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the raw materials according to the proportion: polypropylene glycol PPG-2000 60 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 3 parts, silane blocking agent KH-550 parts, dimethyl thiotoluene diamine 2 parts, stannous octoate 0.1 parts, hydrophobically modified graphene quantum dot 5 parts and DMF60 parts.
The preparation method of the hydrophobically modified graphene quantum dot comprises the following steps:
40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid are added into 10L of water, the mixture is transferred into a hydrothermal reaction kettle after ultrasonic oscillation dispersion, the temperature is raised to 180 ℃ for reaction for 10 hours, the obtained reaction liquid is recovered to room temperature, and is dialyzed by a dialysis bag with the molecular weight cutoff of 500Da, filtered by a microfiltration membrane with the aperture of 0.45 mu m and dried 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 50 ℃, stirring uniformly, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 70 ℃, stirring and reacting for 15min to generate a first prepolymer, cooling to 0 ℃, adding alkylphenol disulfide and a silane end capping agent KH-550, stirring uniformly, heating to 70 ℃, reacting for 3h to generate a second prepolymer, adding dimethyl thiotoluene diamine and hydrophobically modified graphene quantum dots, stirring uniformly, 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 raw materials according to the proportion: polypropylene glycol PPG-2000 60 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 4 parts, silane blocking agent KH-550.5 parts, dimethyl thiotoluene diamine 2 parts, stannous octoate 0.2 parts, hydrophobically modified graphene quantum dot 5 parts and DMF80 parts.
The preparation method of the hydrophobically modified graphene quantum dot comprises the following steps:
40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid are added into 10L of water, the mixture is transferred into a hydrothermal reaction kettle after ultrasonic oscillation dispersion, the temperature is raised to 180 ℃ for reaction for 15 hours, the obtained reaction liquid is recovered to room temperature, and is dialyzed by a dialysis bag with the molecular weight cutoff of 500Da, filtered by a microfiltration membrane with the aperture of 0.45 mu m and dried 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 50 ℃, stirring uniformly, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 80 ℃, stirring and reacting for 15min to generate a first prepolymer, cooling to 5 ℃, adding alkylphenol disulfide and silane end capping agent KH-550, stirring uniformly, heating to 70 ℃, reacting for 5h to generate a second prepolymer, adding dimethyl thiotoluene diamine and hydrophobically modified graphene quantum dots, stirring uniformly, casting to form a film, and heating and curing at 80 ℃ for 24h.
Example 5:
a preparation method of a high-strength self-repairing protective film for a mobile phone comprises the following steps:
weighing the raw materials according to the proportion: polypropylene glycol PPG-2000 60 parts, toluene diisocyanate 25 parts, dimer acid diisocyanate 5 parts, alkylphenol disulfide 5 parts, silane blocking agent KH-550 parts, dimethyl thiotoluene diamine 4 parts, stannous octoate 0.1 parts, hydrophobically modified graphene quantum dot 10 parts and DMF60 parts.
The preparation method of the hydrophobically modified graphene quantum dot comprises the following steps:
40g of 1,3, 6-trinitropyrene, 100g of sodium hydroxide and 200g of 16-mercaptohexadecanoic acid are added into 10L of water, the mixture is transferred into a hydrothermal reaction kettle after ultrasonic oscillation dispersion, the temperature is raised to 200 ℃ for reaction for 10 hours, the obtained reaction liquid is recovered to room temperature, and is dialyzed by a dialysis bag with the molecular weight cutoff of 500Da, filtered by a microfiltration membrane with the aperture of 0.45 mu m and dried 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 ℃, stirring uniformly, then adding polypropylene glycol PPG-2000 and stannous octoate, heating to 70 ℃, stirring and reacting for 30min to generate a first prepolymer, cooling to 0 ℃, adding alkylphenol disulfide and silane end capping agent KH-550, stirring uniformly, heating to 80 ℃, reacting for 3h to generate a second prepolymer, adding dimethyl thiotoluene diamine and hydrophobically modified graphene quantum dots, stirring uniformly, casting to form a film, and heating and curing at 90 ℃ for 12 h.
Comparative example 1:
substantially the same as in example 1, except that the hydrophobically modified graphene quantum dots were not added.
Comparative example 2:
substantially the same as in example 1, except that 16-mercaptohexadecanoic acid was not added in the preparation of the hydrophobically modified graphene quantum dots.
The preparation method of the hydrophobically 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 15 hours, 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 aperture of 0.45 mu m, and drying at 80 ℃ for 15 hours.
Comparative example 3:
substantially the same as in example 1, except that alkylphenol disulfide was not added.
Comparative example 4:
substantially the same as in example 1, except that 1, 3-propanediol was used instead of xylylenediamine.
Performance test:
the high-strength self-repairing protective films prepared in examples 1 to 5 and comparative examples 1 to 4 were used as test samples;
the test specimen is subjected to tensile property test by a universal tensile machine (Instron 5943 type) at room temperature and a tensile speed of 15 mm/min;
the hardness of the test specimens was determined according to GB/T6739-2006 standard using the manual film hardness pencil method.
The contact angle of the sample was measured by a contact angle measuring instrument (DropShape Analyzer-DSA25 type), and the test liquid was ultrapure water.
Table 1:
as shown in the table 1, the high-strength self-repairing protective film prepared by the invention has excellent mechanical properties, tensile strength of more than or equal to 9MPa, elongation at break of more than or equal to 350%, hardness of 4H, water contact angle of more than or equal to 118 degrees and good hydrophobic property.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
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 end capping agent, 2-4 parts of aromatic diamine chain extender, 0.1-0.2 part of organotin catalyst, 5-10 parts of hydrophobically modified graphene quantum dot and 60-80 parts of solvent;
the aromatic diamine chain extender is any one or more of diamino isobutyl p-chlorobenzoate, dimethyl thiotoluene diamine and diethyl toluene diamine;
the preparation method of the hydrophobically 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 into a hydrothermal reaction kettle, heating to 180-200 ℃ for reaction for 10-15h, recovering the obtained reaction liquid to room temperature, dialyzing, micro-filtering and drying.
2. The high-strength self-repairing protective film for a mobile phone according to claim 1, wherein the polyether polyol is any one or more of PPG-400, PPG-425, PPG-1000, PPG-2000, PPG-3000 and PPG-4000.
3. The high-strength self-repairing protective film for a mobile phone according to 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 mobile phones according to claim 3, wherein the diisocyanate is toluene diisocyanate and dimer acid diisocyanate, and the mass ratio of toluene diisocyanate to dimer acid diisocyanate is 2-5:1.
5. the high-strength self-repairing protective film for mobile phones according to claim 1, wherein the silane end capping agent is any one or more of KH-550, KH-560 and KH-570.
6. The high-strength self-repairing protective film for a mobile phone according to claim 1, wherein the number of carbon atoms of the mercapto long-chain alkanoic acid is not less than 10.
7. A method for preparing the high-strength self-repairing protective film for a mobile phone according to any one of claims 1 to 6, comprising the following steps:
s1: adding diisocyanate into a solvent, heating to 50-60 ℃, uniformly stirring, adding polyether polyol and an organotin catalyst, heating to 70-80 ℃, and stirring for reacting to generate a first prepolymer;
s2: cooling to 0-5 ℃, adding alkylphenol disulfide and 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 hydrophobically modified graphene quantum dots, uniformly stirring, casting to form a film, and heating and curing.
8. The method for producing a high-strength self-healing protective film for a mobile phone according to claim 7, wherein the temperature is 80-90 ℃ and the time is 12-24 hours when the protective film is cured by heating.
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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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| 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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| 王玉龙 ; 李雅琼 ; 王怡博 ; 白静静 ; 李振中 ; .一种基于动态双硫键的自修复聚氨酯弹性体的制备与性能.聚氨酯工业.2020,(第02期), * |
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