CN117603573A - Anti-falling protective sleeve for tablet personal computer based on hot press forming and preparation method thereof - Google Patents
Anti-falling protective sleeve for tablet personal computer based on hot press forming and preparation method thereof Download PDFInfo
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- CN117603573A CN117603573A CN202311568136.8A CN202311568136A CN117603573A CN 117603573 A CN117603573 A CN 117603573A CN 202311568136 A CN202311568136 A CN 202311568136A CN 117603573 A CN117603573 A CN 117603573A
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- 230000001681 protective effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 229920002635 polyurethane Polymers 0.000 claims description 34
- 239000004814 polyurethane Substances 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000010985 leather Substances 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 7
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims description 7
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 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 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 241000894006 Bacteria Species 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000009395 breeding Methods 0.000 abstract description 2
- 230000001488 breeding effect Effects 0.000 abstract description 2
- 230000009993 protective function Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 230000001580 bacterial effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DHZIIRMIXLYCRQ-UHFFFAOYSA-N benzene-1,4-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=C(C(=O)N=C=O)C=C1 DHZIIRMIXLYCRQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of anti-falling protection of tablet computers, in particular to an anti-falling protection sleeve of a tablet computer based on hot press molding and a preparation method thereof, which are used for solving the problem that the anti-falling performance and the antibacterial performance of the existing tablet computer protection sleeve are poor; according to the preparation method, the anti-falling protective sleeve is formed on the outer surface of the tablet personal computer through a hot press forming process, so that the anti-slip performance of the tablet personal computer can be improved, the tablet personal computer is prevented from falling, meanwhile, the anti-falling protective sleeve can give the tablet personal computer enough buffer after the tablet personal computer falls, an excellent protection effect is achieved, the anti-falling effect is good, the anti-falling protective sleeve has good antibacterial and antibacterial properties, bacteria breeding is avoided, the wear resistance of the anti-falling protective sleeve is good, the tablet personal computer can not be damaged easily or even scratched, and the tablet personal computer can be protected for a long time while the attractive appearance is maintained; the anti-falling protective sleeve of the tablet personal computer has an anti-falling protective function, can effectively inhibit and kill bacteria, and improves the sanitation and safety of a user using the tablet personal computer.
Description
Technical Field
The invention relates to the technical field of anti-falling protection of tablet computers, in particular to an anti-falling protection sleeve of a tablet computer based on hot press molding and a preparation method thereof.
Background
With the continuous development of technology, tablet computers have become indispensable electronic devices in daily life, study and work. However, tablet computers are easily damaged due to improper use or accidental dropping. Therefore, the tablet personal computer protective sleeve is used for protecting the tablet personal computer, so that the anti-falling performance of the tablet personal computer can be improved, the protection effect is good, however, various bacteria can be contacted in the use process, and potential threat is formed to the health of a user. Therefore, developing an anti-falling protective sleeve with antibacterial performance for a tablet personal computer has become a current urgent problem to be solved.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a hot-press molding-based anti-falling protective sleeve for a tablet personal computer and a preparation method thereof: adding high-performance polyurethane emulsion, modified graphene, sodium dodecyl benzene sulfonate, polyvinyl alcohol, silicone oil and carboxymethyl cellulose into a stirring tank, stirring and mixing to obtain an anti-falling protective material, scraping the anti-falling protective material onto release paper, then semi-curing to form semi-cured skin, attaching the semi-cured skin to the outer surface of a tablet personal computer, then placing the tablet personal computer in a hot-press mold for hot-press molding, removing redundant parts of edges, tearing off the release paper to form a leather sheath, and obtaining the anti-falling protective sleeve for the tablet personal computer based on hot-press molding.
The aim of the invention can be achieved by the following technical scheme:
a tablet personal computer anti-falling protective sleeve based on hot press forming comprises the following components in parts by weight:
90-100 parts of high-performance polyurethane emulsion, 20-40 parts of modified graphene, 2-4 parts of sodium dodecyl benzene sulfonate, 5-9 parts of polyvinyl alcohol, 1.5-3.5 parts of silicone oil and 0.8-1.6 parts of carboxymethyl cellulose;
the high-performance polyurethane emulsion is prepared by the following steps:
step A1: adding dimethylamine solution, sodium hydroxide and 3-chloro-1, 2-propanediol into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 15-20min under the conditions of 5-10 ℃ and stirring speed of 400-500r/min, heating to 50-55 ℃ and continuously stirring and reacting for 4-5h, cooling the reaction product to room temperature after the reaction is finished, distilling and collecting fraction with the temperature of 130 ℃ to obtain an intermediate 1;
the reaction process involves the following reaction formula:
step A2: adding pentafluorobenzoic acid, 2-bromoethanol and methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 30-50min under the conditions that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, then adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, continuously stirring and reacting for 20-25h, vacuum filtering a reaction product after the reaction is finished, and rotationally evaporating a filtrate to remove a solvent to obtain an intermediate 2;
the reaction process involves the following reaction formula:
step A3: adding terephthalyl diisocyanate, an intermediate 1 and dibutyltin dilaurate into a three-neck flask provided with a stirrer, a thermometer and a nitrogen gas guide pipe, introducing nitrogen for protection, stirring and reacting for 2-3 hours under the conditions of the temperature of 85-90 ℃ and the stirring speed of 400-500r/min, cooling to 50-60 ℃, adding 1, 4-butanediol, continuously stirring and reacting for 1-1.5 hours to generate an intermediate 3, adding the intermediate 2, heating to 95-100 ℃, continuously stirring and reacting for 4-6 hours, cooling a reaction product to room temperature after the reaction is finished, adding distilled water, emulsifying for 15-20 minutes under the conditions of the shearing speed of 2000-2500r/min, and controlling the solid content to 25-30%, thus obtaining the high-performance polyurethane emulsion.
The reaction process involves the following reaction formula:
as a further scheme of the invention: the dosage ratio of the dimethylamine solution, sodium hydroxide and 3-chloro-1, 2-propanediol in the step A1 is 25-30g:0.1mol:0.1mol, wherein the mass fraction of the dimethylamine solution is 35-40%.
As a further scheme of the invention: the dosage ratio of the pentafluorobenzoic acid, the 2-bromoethanol, the methylene dichloride, the dicyclohexylcarbodiimide and the 4-dimethylaminopyridine in the step A2 is 10mmol:13-15mmol:80-100mL:10-12mmol:0.1-0.5g.
As a further scheme of the invention: the dosage ratio of the p-phenylene diisocyanate, the intermediate 1, the dibutyl tin dilaurate, the 1, 4-butanediol and the intermediate 2 in the step A3 is 18-20mmol:13-15mmol:0.1-0.5g:3-5mmol:10-15mmol.
As a further scheme of the invention: the modified graphene is prepared by the following steps:
step B1: adding concentrated sulfuric acid into a three-neck flask with a stirrer and a thermometer, adding graphite powder and sodium nitrate at the temperature of 0-5 ℃ and the stirring speed of 400-500r/min for stirring reaction for 20-25min, adding potassium permanganate for continuous stirring reaction for 2-2.5h, heating to 35-40 ℃ for continuous stirring reaction for 2-3h, adding deionized water and heating to 90-95 ℃ for continuous stirring reaction for 2-3h, cooling the reaction product to room temperature after the reaction, dropwise adding hydrogen peroxide until no bubbles are generated, adding ascorbic acid and heating to 90-95 ℃ for continuous stirring reaction for 2-3h, cooling the reaction product to room temperature after the reaction, vacuum suction filtering, washing a filter cake with absolute ethyl alcohol and distilled water for 3-5 times sequentially, placing in a vacuum drying box, and drying for 8-10h at the temperature of 70-75 ℃ to obtain graphene;
step B2: adding graphene and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, regulating the pH to 8-9 by ammonia water, performing ultrasonic treatment for 1-1.5h under the condition of ultrasonic power of 250-300W, stirring at the temperature of 60-65 ℃ and the stirring rate of 400-500r/min for reacting for 20-30min, adding the modified solution dropwise while stirring, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reacting for 6-8h after the dropping, centrifuging a reaction product after the reaction is finished, placing a precipitate in a vacuum drying box, and drying for 2-3h under the temperature of 40-45 ℃ to obtain the modified graphene.
As a further scheme of the invention: the dosage ratio of the concentrated sulfuric acid, the graphite powder, the sodium nitrate, the potassium permanganate, the deionized water and the ascorbic acid in the step B1 is 25-30mL:1g:0.5-0.8g:4-4.5g:90-100mL:0.3-0.5g, wherein the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 20%.
As a further scheme of the invention: the dosage ratio of the graphene to the deionized water to the modifying solution in the step B2 is 1g:200-250mL:30-40mL of the modified solution is silane coupling agent KH-550 according to 0.5g:10-15mL of the solution formed by dissolving the ammonia water in absolute ethyl alcohol, wherein the mass fraction of the ammonia water is 15-20%.
As a further scheme of the invention: a preparation method of a tablet personal computer anti-falling protective sleeve based on hot press molding comprises the following steps:
step one: weighing 90-100 parts of high-performance polyurethane emulsion, 20-40 parts of modified graphene, 2-4 parts of sodium dodecyl benzene sulfonate, 5-9 parts of polyvinyl alcohol, 1.5-3.5 parts of silicone oil and 0.8-1.6 parts of carboxymethyl cellulose according to parts by weight for later use;
step two: adding the high-performance polyurethane emulsion, the modified graphene, the sodium dodecyl benzene sulfonate, the polyvinyl alcohol, the silicone oil and the carboxymethyl cellulose into a stirring tank, and stirring and mixing for 1-1.5h under the conditions that the temperature is 40-45 ℃ and the stirring speed is 800-1000r/min to obtain an anti-falling protection material;
step three: and (3) scraping the anti-falling protective material onto release paper, then semi-curing to form semi-cured leather, attaching the semi-cured leather to the outer surface of the tablet personal computer, then placing the tablet personal computer in a hot-press die for hot-press molding, removing redundant parts of the edge, tearing off the release paper, and forming leather sleeves to obtain the anti-falling protective sleeve for the tablet personal computer based on hot-press molding.
The invention has the beneficial effects that:
according to the hot-press molding-based anti-falling protective sleeve for the tablet personal computer and the preparation method thereof, high-performance polyurethane emulsion, modified graphene, sodium dodecyl benzene sulfonate, polyvinyl alcohol, silicone oil and carboxymethyl cellulose are added into a stirring tank to be stirred and mixed, so that an anti-falling protective material is obtained, the anti-falling protective material is scraped and coated on release paper, semi-cured to form semi-cured skin, the semi-cured skin is attached to the outer surface of the tablet personal computer, the tablet personal computer is placed in a hot-press mold to be hot-press molded, and then the redundant part of the edge is removed, and the release paper is torn off, so that the leather sleeve is formed, and the hot-press molding-based anti-falling protective sleeve for the tablet personal computer is obtained; according to the preparation method, the anti-falling protective sleeve is formed on the outer surface of the tablet personal computer through a hot press forming process, so that the anti-slip performance of the tablet personal computer can be improved, the tablet personal computer is prevented from falling, meanwhile, the anti-falling protective sleeve can give the tablet personal computer enough buffer after the tablet personal computer falls, an excellent protection effect is achieved, the anti-falling effect is good, the anti-falling protective sleeve has good antibacterial and antibacterial properties, bacterial breeding is avoided, the sanitary safety is high, the wear resistance of the anti-falling protective sleeve is good, the tablet personal computer can not be damaged easily or even scratched, and meanwhile, the tablet personal computer can be protected for a long time and the attractive appearance is maintained; the anti-falling protective sleeve for the tablet personal computer provided by the invention has an anti-falling protective function, can effectively inhibit and kill bacteria, and improves the sanitation and safety of a user using the tablet personal computer.
In the process of preparing the anti-falling protective sleeve of the tablet personal computer based on hot-press molding, firstly, preparing a high-performance polyurethane emulsion, firstly, reacting a secondary amino group on dimethylamine with a chlorine atom on 3-chloro-1, 2-propanediol to obtain an intermediate 1, reacting a carboxyl group on pentafluorobenzoic acid with a hydroxyl group on 2-bromoethanol to obtain an intermediate 2, then, polymerizing an isocyanate group on terephthalyl isocyanate and the hydroxyl group on the intermediate 1, and performing chain extension by using 1, 4-butanediol to form polyurethane to obtain an intermediate 3, reacting a bromine atom on the intermediate 2 with a tertiary amine group on the intermediate 3 to generate a quaternary ammonium group, and simultaneously introducing a large number of C-F bonds to obtain the high-performance polyurethane emulsion; the polymer molecular structure of the high-performance polyurethane emulsion contains a large number of quaternary ammonium groups, the quaternary ammonium groups are positively charged and can be adsorbed on negatively charged bacterial cell membranes to cause bacterial cell membrane damage and deactivate bacteria, and the C-F bond has good hydrophobic and pollution resistance, good lubricity and wear resistance; in the process of preparing the anti-falling protective sleeve of the tablet personal computer based on hot press molding, modified graphene is also prepared, graphite powder is used as a raw material, an improved Hummers method is used for synthesizing graphene oxide, then ascorbic acid is used for reducing the graphene oxide to obtain graphene, a silane coupling agent KH-550 is used for modifying the graphene, silanol is formed after the silane coupling agent KH-550 is hydrolyzed and can be dehydrated and condensed with hydroxyl groups on the graphene, and the introduced organic matters wrap the graphene to improve the dispersibility of the graphene, so that the modified graphene is obtained; the modified graphene can be uniformly dispersed in the high-performance polyurethane emulsion after being modified, a large amount of amino groups are introduced to the surface of the graphene and can react with isocyanate groups in the high-performance polyurethane emulsion, so that the modified graphene and the isocyanate groups are connected in a chemical bond mode, the binding force is high, and the modified graphene has the performances of graphene antibacterial performance, high heat conduction performance and high wear resistance;
therefore, under the action of the high-performance polyurethane emulsion and the modified graphene, the prepared anti-falling protective sleeve for the tablet personal computer has comfortable hand feeling, good antibacterial and bacteriostatic properties, excellent wear resistance and good heat conduction and heat dissipation effects, can effectively protect the tablet personal computer, can rapidly dissipate heat generated in the operation process of the tablet personal computer, and avoids adverse effects on the performance of the tablet personal computer caused by heat accumulation.
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:
the embodiment is a preparation method of high-performance polyurethane emulsion, which comprises the following steps:
step A1: 25g of dimethylamine solution with the mass fraction of 35%, 0.1mol of sodium hydroxide and 0.1mol of 3-chloro-1, 2-propanediol are added into a three-neck flask with a stirrer and a thermometer, stirred and reacted for 15min at the temperature of 5 ℃ and the stirring rate of 400r/min, then stirred and reacted for 4h under the condition of heating to 50 ℃, the reaction product is cooled to room temperature after the reaction is finished, and then distilled and fractions with the temperature of 130 ℃ are collected to obtain an intermediate 1;
step A2: 10mmol of pentafluorobenzoic acid, 13mmol of 2-bromoethanol and 80mL of dichloromethane are added into a three-neck flask provided with a stirrer and a thermometer, stirred and reacted for 30min at the temperature of 25 ℃ and the stirring speed of 400r/min, then 10mmol of dicyclohexylcarbodiimide and 0.1g of 4-dimethylaminopyridine are added for continuous stirring and reaction for 20h, after the reaction is finished, the reaction product is filtered in vacuum, and the solvent is removed by rotary evaporation of the filtrate, so as to obtain an intermediate 2;
step A3: 18mmol of terephthalyl diisocyanate, 13mmol of intermediate 1 and 0.1g of dibutyltin dilaurate are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen gas guide pipe, nitrogen gas is introduced for protection, stirring is carried out for 2 hours under the condition that the temperature is 85 ℃ and the stirring rate is 400r/min, 3mmol of 1, 4-butanediol is added after cooling to 50 ℃ for continuous stirring reaction for 1 hour, intermediate 3 is generated, 10mmol of intermediate 2 is added and stirring is carried out for 4 hours under the condition that the temperature is increased to 95 ℃, the reaction product is cooled to room temperature after the reaction is finished, distilled water is added and emulsified for 15 minutes under the condition that the shearing rate is 2000r/min, and the solid content is 25% to obtain the high-performance polyurethane emulsion.
Example 2:
the embodiment is a preparation method of high-performance polyurethane emulsion, which comprises the following steps:
step A1: 30g of dimethylamine solution with the mass fraction of 40%, 0.1mol of sodium hydroxide and 0.1mol of 3-chloro-1, 2-propanediol are added into a three-neck flask with a stirrer and a thermometer, stirred and reacted for 20min under the conditions of 10 ℃ and stirring speed of 500r/min, then stirred and reacted for 5h under the conditions of heating to 55 ℃, the reaction product is cooled to room temperature after the reaction is finished, and then distilled and fractions with the temperature of 130 ℃ are collected to obtain an intermediate 1;
step A2: 10mmol of pentafluorobenzoic acid, 15mmol of 2-bromoethanol and 100mL of dichloromethane are added into a three-neck flask provided with a stirrer and a thermometer, stirred and reacted for 50min at the temperature of 30 ℃ and the stirring speed of 500r/min, then 12mmol of dicyclohexylcarbodiimide and 0.5g of 4-dimethylaminopyridine are added for continuous stirring and reaction for 25h, after the reaction is finished, the reaction product is filtered in vacuum, and the solvent is removed by rotary evaporation of the filtrate, so as to obtain an intermediate 2;
step A3: 20mmol of terephthalyl diisocyanate, 15mmol of intermediate 1 and 0.5g of dibutyltin dilaurate are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen gas guide pipe, nitrogen gas is introduced for protection, stirring is carried out for 3 hours under the condition that the temperature is 90 ℃ and the stirring rate is 500r/min, 5mmol of 1, 4-butanediol is added after cooling to 60 ℃ for continuous stirring reaction for 1.5 hours, intermediate 3 is generated, 15mmol of intermediate 2 is added and stirring is carried out for 6 hours under the condition that the temperature is raised to 100 ℃, the reaction product is cooled to room temperature after the reaction is finished, distilled water is added and emulsified for 20 minutes under the condition that the shearing rate is 2500r/min, and the solid content is controlled to be 30%, so that the high-performance polyurethane emulsion is obtained.
Example 3:
the embodiment is a preparation method of modified graphene, which comprises the following steps:
step B1: adding 25mL of 98% by mass of concentrated sulfuric acid into a three-neck flask with a stirrer and a thermometer, adding 1g of graphite powder and 0.5g of sodium nitrate under the condition of the temperature of 0 ℃ and the stirring rate of 400r/min, stirring and reacting for 20min, adding 4g of potassium permanganate, continuing to stir and react for 2h, heating to 35 ℃, continuing to stir and react for 2h, adding 90mL of deionized water and heating to 90 ℃, continuing to stir and react for 2h, cooling the reaction product to room temperature after the reaction, dropwise adding hydrogen peroxide with the mass of 20% until no bubble is generated, adding 0.3g of ascorbic acid and heating to 90 ℃, continuing to stir and react for 2h, cooling the reaction product to room temperature after the reaction is finished, performing vacuum suction filtration, washing a filter cake with absolute ethyl alcohol and distilled water for 3 times in sequence, then placing in a vacuum drying box, and drying for 8h under the condition of the temperature of 70 ℃ to obtain graphene.
Step B2: 1g of graphene and 200mL of deionized water are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, then ammonia water with mass fraction of 15% is used for adjusting the pH to 8, then ultrasonic treatment is carried out for 1h under the condition of ultrasonic power of 250W, then stirring reaction is carried out for 20min under the condition of temperature of 60 ℃ and stirring speed of 400r/min, and 30mL of silane coupling agent KH-550 is added dropwise while stirring according to 0.5g: and (3) 10mL of modified solution formed by dissolving the graphene into absolute ethyl alcohol, controlling the dropping speed to be 1 drop/s, continuously stirring for reaction for 6h after the dropping is finished, centrifuging a reaction product after the reaction is finished, placing a precipitate in a vacuum drying oven, and drying for 2h at the temperature of 40 ℃ to obtain the modified graphene.
Example 4:
the embodiment is a preparation method of modified graphene, which comprises the following steps:
step B1: adding 30mL of 98% by mass of concentrated sulfuric acid into a three-neck flask with a stirrer and a thermometer, adding 1g of graphite powder and 0.8g of sodium nitrate under the condition of the temperature of 5 ℃ and the stirring rate of 500r/min, stirring and reacting for 25min, adding 4.5g of potassium permanganate, continuing stirring and reacting for 2.5h, heating to 40 ℃ and continuing stirring and reacting for 3h, adding 100mL of deionized water and heating to 95 ℃ and continuing stirring and reacting for 3h, cooling the reaction product to room temperature after the reaction, dropwise adding hydrogen peroxide with the mass of 20% until no bubble is generated, adding 0.5g of ascorbic acid and continuing stirring and reacting for 3h under the condition of the temperature of 95 ℃, cooling the reaction product to room temperature after the reaction, vacuum suction filtering, washing a filter cake with absolute ethyl alcohol and distilled water for 5 times sequentially, placing in a vacuum drying box, and drying for 10h under the condition of the temperature of 75 ℃ to obtain graphene.
Step B2: 1g of graphene and 250mL of deionized water are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, then ammonia water with the mass fraction of 20% is used for adjusting the pH to 9, then ultrasonic treatment is carried out for 1.5h under the condition of ultrasonic power of 300W, then stirring reaction is carried out for 30min under the condition of temperature of 65 ℃ and stirring speed of 500r/min, and then 40mL of silane coupling agent KH-550 is added dropwise while stirring according to 0.5g:15mL of modified solution formed by dissolving the graphene oxide into absolute ethyl alcohol, controlling the dropping speed to be 2 drops/s, continuously stirring for reaction for 8 hours after the dropping, centrifuging a reaction product after the reaction is finished, placing a precipitate in a vacuum drying oven, and drying for 3 hours at the temperature of 45 ℃ to obtain the modified graphene.
Example 5:
the embodiment relates to a preparation method of a tablet personal computer anti-falling protective sleeve based on hot press molding, which comprises the following steps:
step one: 90 parts of high-performance polyurethane emulsion from example 1, 20 parts of modified graphene from example 3, 2 parts of sodium dodecyl benzene sulfonate, 5 parts of polyvinyl alcohol, 1.5 parts of silicone oil and 0.8 part of carboxymethyl cellulose are weighed according to parts by weight for standby;
step two: adding the high-performance polyurethane emulsion, the modified graphene, the sodium dodecyl benzene sulfonate, the polyvinyl alcohol, the silicone oil and the carboxymethyl cellulose into a stirring tank, and stirring and mixing for 1h under the conditions that the temperature is 40 ℃ and the stirring speed is 800r/min to obtain an anti-falling protective material;
step three: and (3) scraping the anti-falling protective material onto release paper, then semi-curing to form semi-cured leather, attaching the semi-cured leather to the outer surface of the tablet personal computer, then placing the tablet personal computer in a hot-press die for hot-press molding, removing redundant parts of the edge, tearing off the release paper, and forming leather sleeves to obtain the anti-falling protective sleeve for the tablet personal computer based on hot-press molding.
Example 6:
the embodiment relates to a preparation method of a tablet personal computer anti-falling protective sleeve based on hot press molding, which comprises the following steps:
step one: 100 parts of high-performance polyurethane emulsion from example 2, 40 parts of modified graphene from example 4, 4 parts of sodium dodecyl benzene sulfonate, 9 parts of polyvinyl alcohol, 3.5 parts of silicone oil and 1.6 parts of carboxymethyl cellulose are weighed according to parts by weight for standby;
step two: adding the high-performance polyurethane emulsion, the modified graphene, the sodium dodecyl benzene sulfonate, the polyvinyl alcohol, the silicone oil and the carboxymethyl cellulose into a stirring tank, and stirring and mixing for 1.5 hours under the conditions that the temperature is 45 ℃ and the stirring speed is 1000r/min to obtain an anti-falling protection material;
step three: and (3) scraping the anti-falling protective material onto release paper, then semi-curing to form semi-cured leather, attaching the semi-cured leather to the outer surface of the tablet personal computer, then placing the tablet personal computer in a hot-press die for hot-press molding, removing redundant parts of the edge, tearing off the release paper, and forming leather sleeves to obtain the anti-falling protective sleeve for the tablet personal computer based on hot-press molding.
Example 7:
the embodiment is a preparation method of polyurethane emulsion, comprising the following steps:
dissolving PU-894 aqueous polyurethane resin in distilled water, and then emulsifying for 20min under the condition of the shearing rate of 2500r/min, and controlling the solid content to be 30%, thus obtaining polyurethane emulsion.
Comparative example 1:
comparative example 1 differs from example 6 in that the polyurethane emulsion in example 7 was used instead of the high-performance polyurethane emulsion.
Comparative example 2:
comparative example 2 is different from example 6 in that modified graphene is not added.
Comparative example 3:
comparative example 3 is different from example 6 in that the polyurethane emulsion in example 7 was used instead of the high-performance polyurethane emulsion, and modified graphene was not added.
The performance of the anti-falling protective sleeves of the tablet personal computers based on hot press molding of examples 5-6 and comparative examples 1-3 was tested, wherein the abrasion resistance was measured according to QB/T2726-2005 abrasion resistance test of leather physical and mechanical test, and the antibacterial test bacteria were E.coli and candida albicans, and the test results are shown below:
| project | Coliform bacteria inhibition rate, percent | Antibacterial rate of candida albicans, percent | Wear resistance grade, grade |
| Example 5 | 99.1 | 99.3 | 4 |
| Example 6 | 99.8 | 99.9 | 4 |
| Comparative example 1 | 73.7 | 75.0 | 3 |
| Comparative example 2 | 85.6 | 87.1 | 3 |
| Comparative example 3 | 41.5 | 42.9 | 2 |
Referring to the above table data, according to the comparison of examples 5-6 and comparative examples 1-3, it can be known that the use of the high-performance polyurethane emulsion and the addition of the modified graphene can provide the anti-falling protective sleeve of the tablet computer based on hot press molding with good antibacterial performance, and can also provide the anti-falling protective sleeve of the tablet computer based on hot press molding with good wear resistance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. Anti-falling protective sleeve for tablet personal computer based on hot press forming is characterized by comprising the following components in parts by weight:
90-100 parts of high-performance polyurethane emulsion, 20-40 parts of modified graphene, 2-4 parts of sodium dodecyl benzene sulfonate, 5-9 parts of polyvinyl alcohol, 1.5-3.5 parts of silicone oil and 0.8-1.6 parts of carboxymethyl cellulose;
the high-performance polyurethane emulsion is prepared by the following steps:
step A1: adding dimethylamine solution, sodium hydroxide and 3-chloro-1, 2-propanediol into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 15-20min under the conditions of 5-10 ℃ and stirring speed of 400-500r/min, heating to 50-55 ℃ and continuously stirring and reacting for 4-5h, cooling the reaction product to room temperature after the reaction is finished, distilling and collecting fraction with the temperature of 130 ℃ to obtain an intermediate 1;
step A2: adding pentafluorobenzoic acid, 2-bromoethanol and methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 30-50min under the conditions that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, then adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, continuously stirring and reacting for 20-25h, vacuum filtering a reaction product after the reaction is finished, and rotationally evaporating a filtrate to remove a solvent to obtain an intermediate 2;
step A3: adding terephthalyl diisocyanate, an intermediate 1 and dibutyltin dilaurate into a three-neck flask provided with a stirrer, a thermometer and a nitrogen gas guide pipe, introducing nitrogen for protection, stirring and reacting for 2-3 hours under the conditions of the temperature of 85-90 ℃ and the stirring speed of 400-500r/min, cooling to 50-60 ℃, adding 1, 4-butanediol, continuously stirring and reacting for 1-1.5 hours to generate an intermediate 3, adding the intermediate 2, heating to 95-100 ℃, continuously stirring and reacting for 4-6 hours, cooling a reaction product to room temperature after the reaction is finished, adding distilled water, emulsifying for 15-20 minutes under the conditions of the shearing speed of 2000-2500r/min, and controlling the solid content to 25-30%, thus obtaining the high-performance polyurethane emulsion.
2. The hot press molding-based anti-falling protective sleeve for a tablet personal computer according to claim 1, wherein the dosage ratio of the dimethylamine solution, sodium hydroxide and 3-chloro-1, 2-propanediol in the step A1 is 25-30g:0.1mol:0.1mol, wherein the mass fraction of the dimethylamine solution is 35-40%.
3. The hot press molding-based anti-falling protective sleeve for a tablet personal computer according to claim 1, wherein the dosage ratio of the pentafluorobenzoic acid, the 2-bromoethanol, the methylene dichloride, the dicyclohexylcarbodiimide and the 4-dimethylaminopyridine in the step A2 is 10mmol:13-15mmol:80-100mL:10-12mmol:0.1-0.5g.
4. The hot press molding-based anti-falling protective sleeve for a tablet personal computer according to claim 1, wherein the dosage ratio of the terephthalyl diisocyanate, the intermediate 1, the dibutyltin dilaurate, the 1, 4-butanediol and the intermediate 2 in the step A3 is 18-20mmol:13-15mmol:0.1-0.5g:3-5mmol:10-15mmol.
5. The hot-press molding-based anti-falling protective sleeve for tablet personal computers according to claim 1, wherein the modified graphene is prepared by the following steps:
step B1: adding concentrated sulfuric acid into a three-neck flask with a stirrer and a thermometer, adding graphite powder and sodium nitrate at the temperature of 0-5 ℃ and the stirring speed of 400-500r/min for stirring reaction for 20-25min, adding potassium permanganate for continuous stirring reaction for 2-2.5h, heating to 35-40 ℃ for continuous stirring reaction for 2-3h, adding deionized water and heating to 90-95 ℃ for continuous stirring reaction for 2-3h, cooling the reaction product to room temperature after the reaction, dropwise adding hydrogen peroxide until no bubbles are generated, adding ascorbic acid and heating to 90-95 ℃ for continuous stirring reaction for 2-3h, cooling the reaction product to room temperature after the reaction, vacuum suction filtering, washing a filter cake with absolute ethyl alcohol and distilled water for 3-5 times sequentially, placing in a vacuum drying box, and drying for 8-10h at the temperature of 70-75 ℃ to obtain graphene;
step B2: adding graphene and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, regulating the pH to 8-9 by ammonia water, performing ultrasonic treatment for 1-1.5h under the condition of ultrasonic power of 250-300W, stirring at the temperature of 60-65 ℃ and the stirring rate of 400-500r/min for reacting for 20-30min, adding the modified solution dropwise while stirring, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reacting for 6-8h after the dropping, centrifuging a reaction product after the reaction is finished, placing a precipitate in a vacuum drying box, and drying for 2-3h under the temperature of 40-45 ℃ to obtain the modified graphene.
6. The hot press forming-based anti-falling protective sleeve for a tablet personal computer according to claim 5, wherein the dosage ratio of concentrated sulfuric acid, graphite powder, sodium nitrate, potassium permanganate, deionized water and ascorbic acid in the step B1 is 25-30mL:1g:0.5-0.8g:4-4.5g:90-100mL:0.3-0.5g, wherein the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 20%.
7. The hot press molding-based anti-falling protective sleeve for a tablet personal computer according to claim 5, wherein the dosage ratio of the graphene, deionized water and the modifying solution in the step B2 is 1g:200-250mL:30-40mL of the modified solution is silane coupling agent KH-550 according to 0.5g:10-15mL of the solution formed by dissolving the ammonia water in absolute ethyl alcohol, wherein the mass fraction of the ammonia water is 15-20%.
8. The preparation method of the anti-falling protective sleeve of the tablet personal computer based on hot press molding is characterized by comprising the following steps of:
step one: weighing 90-100 parts of high-performance polyurethane emulsion, 20-40 parts of modified graphene, 2-4 parts of sodium dodecyl benzene sulfonate, 5-9 parts of polyvinyl alcohol, 1.5-3.5 parts of silicone oil and 0.8-1.6 parts of carboxymethyl cellulose according to parts by weight for later use;
step two: adding the high-performance polyurethane emulsion, the modified graphene, the sodium dodecyl benzene sulfonate, the polyvinyl alcohol, the silicone oil and the carboxymethyl cellulose into a stirring tank, and stirring and mixing for 1-1.5h under the conditions that the temperature is 40-45 ℃ and the stirring speed is 800-1000r/min to obtain an anti-falling protection material;
step three: and (3) scraping the anti-falling protective material onto release paper, then semi-curing to form semi-cured leather, attaching the semi-cured leather to the outer surface of the tablet personal computer, then placing the tablet personal computer in a hot-press die for hot-press molding, removing redundant parts of the edge, tearing off the release paper, and forming leather sleeves to obtain the anti-falling protective sleeve for the tablet personal computer based on hot-press molding.
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