CN116948220A - Preparation method of adjustable heterostructure low surface energy microsphere and preparation method of textile - Google Patents
Preparation method of adjustable heterostructure low surface energy microsphere and preparation method of textile Download PDFInfo
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- CN116948220A CN116948220A CN202310853629.XA CN202310853629A CN116948220A CN 116948220 A CN116948220 A CN 116948220A CN 202310853629 A CN202310853629 A CN 202310853629A CN 116948220 A CN116948220 A CN 116948220A
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- Prior art keywords
- coupling agent
- microsphere
- organosilane coupling
- surface energy
- low surface
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- 239000004005 microsphere Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004753 textile Substances 0.000 title claims abstract description 14
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 92
- 239000007822 coupling agent Substances 0.000 claims abstract description 82
- 239000004793 Polystyrene Substances 0.000 claims abstract description 64
- 229920002223 polystyrene Polymers 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- -1 mercapto isopropyl trimethoxy silane Chemical compound 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 229920002050 silicone resin Polymers 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- PUDCZUQFOPHIGU-UHFFFAOYSA-N [2-methyl-4-[(2-methylphenyl)diazenyl]phenyl]azanium;chloride Chemical compound Cl.C1=C(N)C(C)=CC(N=NC=2C(=CC=CC=2)C)=C1 PUDCZUQFOPHIGU-UHFFFAOYSA-N 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- QQBPIHBUCMDKFG-GEEYTBSJSA-N phenazopyridine hydrochloride Chemical compound Cl.Nc1ccc(\N=N\c2ccccc2)c(N)n1 QQBPIHBUCMDKFG-GEEYTBSJSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002245 particle Substances 0.000 description 26
- 238000001000 micrograph Methods 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 20
- 229920000742 Cotton Polymers 0.000 description 12
- 239000011258 core-shell material Substances 0.000 description 12
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241000220223 Fragaria Species 0.000 description 3
- 235000016623 Fragaria vesca Nutrition 0.000 description 3
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- PQSQBXGSIRXRFL-UHFFFAOYSA-N 2-methylpropanamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=O PQSQBXGSIRXRFL-UHFFFAOYSA-N 0.000 description 2
- BPAZNZINLQSFMN-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole;dihydrochloride Chemical compound Cl.Cl.CC(C)C1=NCCN1 BPAZNZINLQSFMN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention provides a preparation method of an adjustable heterostructure low surface energy microsphere and a preparation method of a textile, and relates to the technical field of super-hydrophobic coating materials. According to the invention, a pre-hydrolysis process is introduced into the first organosilane coupling agent and the second organosilane coupling agent, the hydrolyzed oligomer has negative charges, and can be attracted with the polystyrene microsphere with positive charges, and then the hydrolyzed oligomer is deposited on the polystyrene microsphere through hydrolysis-condensation reaction to form an asymmetric structure, a petal-shaped structure and a strawberry-shaped structure with an adjustable heterostructure, and the first organosilane coupling agent and the second organosilane coupling agent act together due to the use of the second organosilane coupling agent with fluorine-free or fluorine-containing waterproof performance with low surface energy, so that the prepared microsphere with the adjustable heterostructure has excellent waterproof performance.
Description
Technical Field
The invention relates to the technical field of superhydrophobic coating materials, in particular to a preparation method of an adjustable heterostructure low-surface-energy microsphere and a preparation method of a textile.
Background
Currently, water-repellent finishes have wide applications in various fields, such as outdoor apparel coatings, aerospace coatings, and anti-icing coatings, etc., and these excellent properties depend on the morphology and structure of the water-repellent finish as well as the combination of low surface energy chemical components.
The heterostructure composite microsphere is a composite microsphere with a layered structure, such as an asymmetric structure, a petal-shaped structure, a strawberry-shaped structure and the like, and can integrate functional properties of different component materials into a whole, and by means of the adjustability of the composite structure, superposition or enhancement of each function is realized, so that the heterostructure composite microsphere is beneficial to people to explore new performances, and develops application of the heterostructure composite microsphere in functional coating, energy, catalysis, biomedicine and self-assembly, and is widely focused by people. In particular in the field of functional coatings, the unique structure and composition are just indispensable for constructing the super-hydrophobic coating, but grafting modification by low-surface energy substances is generally needed, and the preparation method is complicated.
The conventional low-surface-energy substances mainly comprise a fluorine-containing waterproof finishing agent and a fluorine-free waterproof finishing agent, but the fluorine-containing waterproof finishing agent has the problems of difficult degradation, environmental persistence, biological accumulation and the like, and the substances are forbidden to use, so that research on alternative finishing agents or alternative finishing methods is attracting attention.
The current common fluorine-free waterproof finishing agent mainly comprises the following two components: firstly, long-chain alkanes such as paraffin, pyridine and the like; and secondly, organic silicon. Compared with fluorine-containing finishing agents, the fluorine-free finishing agents are easy to degrade, are not easy to deposit in organisms and are harmless to human bodies, so that development of fluorine-free waterproof finishing agents has become a research hot spot at present.
Because the bonding force between the organosilane with low surface energy and the polystyrene microsphere is poor and even the organosilane with low surface energy cannot be quantitatively bonded, the organosilane with low surface energy is difficult to nucleate out of phase on the polystyrene microsphere, so that certain difficulty exists in preparing the microsphere with adjustable heterostructure and low surface energy.
Disclosure of Invention
The invention aims at providing a preparation method of an adjustable heterostructure low surface energy microsphere with good waterproof performance.
An object of a second aspect of the present invention is to provide a method for preparing a textile.
According to the object of the first aspect of the present invention, the present invention provides a method for preparing an adjustable heterostructure low surface energy microsphere, comprising the steps of:
preparing a dispersion of positively charged polystyrene microspheres;
adding a mixed solution of water and ethanol and an alkaline catalyst in a preset volume ratio into the dispersion liquid of the polystyrene microspheres with positive charges at a preset temperature to obtain a first reaction liquid;
adding a mixed solution of a first organosilane coupling agent and a second organosilane coupling agent into an acidic solution for hydrolysis to obtain a second reaction solution, wherein the first organosilane coupling agent has reactivity, and the second organosilane coupling agent has low surface energy;
and mixing and reacting the first reaction liquid and the second reaction liquid, and centrifuging, washing and drying to obtain the adjustable heterostructure low surface energy microsphere.
Optionally, the preset volume ratio of water to ethanol is 7-21:9 to 23.
Optionally, the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent is any one of 1.5-6:1.
Optionally, the first organosilane coupling agent is one or two of vinyl triethoxysilane or mercaptoisopropyl trimethoxysilane;
the second organosilane coupling agent is one or two of fluorine-free octavinyl silsesquioxane, octadecyltrimethoxy silane, fluorine-containing 1H, 2H-perfluoro decyl triethoxysilane and 1H, 2H-nonafluorohexyl triethoxysilane.
Alternatively, the dispersion of positively charged polystyrene microspheres is prepared as follows:
synthesizing a positively charged dispersant-stabilized polystyrene microsphere from a positively charged additive, a polymeric dispersant and a styrene monomer;
centrifugally washing the polystyrene microspheres by using ethanol and water;
and stirring and dispersing the polystyrene microspheres in an ethanol solution to obtain a dispersion liquid of the polystyrene microspheres with positive charges.
Optionally, the positive charge additive is one or more of 2, 2-azobis (2-methylpropionamide) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 3-phenylazo-2, 6-diaminopyridine monohydrochloride, or 2-aminoazotoluene hydrochloride;
optionally, the mass ratio of the polymer dispersant to the styrene monomer is 0.2-2: 5.
optionally, the acidic solution is a mixed solution of ethanol and acetic acid, and the volume ratio of the ethanol to the acetic acid is 5-1: any one of values 0-4.
Optionally, the alkaline catalyst is one or more of triethanolamine, triethylamine, ammonia water or sodium hydroxide;
optionally, the volume ratio of the dispersion of positively charged polystyrene microspheres to the basic catalyst is 1.08: any value of 0.03 to 0.1;
optionally, the preset temperature is any one of 20 ℃ to 60 ℃.
According to an object of the second aspect of the present invention, the present invention also provides a method for preparing a textile, comprising the steps of:
dissolving a first organic silicon resin matrix in an organic solvent, and mixing and stirring the organic solvent with a second organic silicon resin matrix containing a catalyst to obtain a mixed solution;
adding the adjustable heterostructure low surface energy microsphere prepared by the preparation method into the mixed solution to obtain a third reaction solution;
and immersing the fabric in the third reaction liquid, and drying at 80-120 ℃ for 1-2h to obtain the textile.
Optionally, the first organic silicon resin matrix is one of hydrogen-containing silicone oil and vinyl silicone oil, and the second organic silicon resin matrix is catalyst-containing silicone oil, wherein at least three hydrogen atoms in the hydrogen-containing silicone oil are directly connected with silicon atoms, and the content of the hydrogen atoms is 0.5-1%;
the organic solvent is any one of vinyl organosilane coupling agent, cyclohexane and n-hexane;
optionally, the volume ratio of the first silicone resin matrix to the tunable heterostructure low surface energy microsphere is any one of 5-50:1;
alternatively, the catalyst is a platinum-containing catalyst, and the content of platinum in the catalyst is 100 to 500000ppm.
According to the invention, the first organosilane coupling agent and the second organosilane coupling agent are introduced into a pre-hydrolysis process, the hydrolyzed oligomer has negative charges, and can be attracted with the polystyrene microsphere with positive charges, and then deposited on the polystyrene microsphere through hydrolysis-condensation reaction to form an asymmetric structure, a petal-shaped structure and a strawberry-shaped structure with an adjustable heterostructure. However, because the co-hydrolytic condensation degree of the first organosilane coupling agent and the second organosilane coupling agent is low, the particles which are finally prepared by directly adding the first organosilane coupling agent and the second organosilane coupling agent into the prepared first reaction solution are core-shell, in order to improve the co-hydrolytic condensation degree of the first organosilane coupling agent and the second organosilane coupling agent, the first organosilane coupling agent and the second organosilane coupling agent are hydrolyzed in an acid solution in advance to obtain a second reaction solution, and then the second reaction solution is added into the first reaction solution, so that the adjustable heterostructure low-surface energy microsphere with good waterproof performance can be prepared.
The above, as well as additional objectives, advantages, and features of the present invention will become apparent to those skilled in the art from the following detailed description of a specific embodiment of the present invention when read in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter by way of example and not by way of limitation with reference to the accompanying drawings. The same reference numbers will be used throughout the drawings to refer to the same or like parts or portions. It will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the accompanying drawings:
FIG. 1 is a schematic flow chart of a method of preparing a tunable heterostructure low surface energy microsphere according to one embodiment of the present invention;
fig. 2 is a schematic flow chart of a method of preparing a textile according to one embodiment of the invention;
FIG. 3 is a transmission electron microscope image of PS microspheres with positive charges prepared according to example 1 of the present invention;
FIG. 4a is a transmission electron microscope image of the strawberry-shaped low surface energy microsphere prepared in example 1 of the present invention;
FIG. 4b is an enlarged view of a portion of FIG. 4 a;
FIG. 4c is an elemental distribution diagram of the high power transmission electron microscope corresponding to FIG. 4 a;
FIG. 5a is a scanning electron microscope image of the fabric of example 1 of the present invention;
FIG. 5b is an enlarged view of a portion of FIG. 5 a;
FIG. 5c is a scanning electron microscope image of the coated fabric of the present invention prepared from the strawberry-shaped low surface energy microspheres of example 1;
FIG. 5d is an enlarged view of a portion of FIG. 5 c;
FIG. 6 is a graph of water contact angle for the preparation of the coated fabric of FIG. 1 from strawberry-like low surface energy microspheres according to the present invention;
FIG. 7a is a transmission electron microscope image of petal-shaped low surface energy microspheres prepared in example 2 of the present invention;
FIG. 7b is an enlarged view of a portion of FIG. 7 a;
FIG. 8a is a transmission electron microscope image of an asymmetric low surface energy microsphere prepared in example 3 of the present invention;
FIG. 8b is an enlarged view of a portion of FIG. 8 a;
FIG. 9a is a transmission electron microscope image of the asymmetric low surface energy microsphere prepared in example 4 of the present invention;
FIG. 9b is an enlarged view of a portion of FIG. 9 a;
FIG. 10a is a transmission electron microscope image of an asymmetric low surface energy microsphere prepared in example 5 of the present invention;
FIG. 10b is an enlarged view of a portion of FIG. 10 a;
FIG. 11a is a transmission electron microscope image of the strawberry-shaped microspheres prepared in comparative example 1 of the present invention;
FIG. 11b is an enlarged view of a portion of FIG. 11 a;
FIG. 12 is a Fourier infrared spectrum of microspheres obtained without addition of a second organosilane coupling agent and low surface energy microspheres prepared with addition of a second organosilane coupling agent;
FIG. 13a is a transmission electron microscope image of core-shell microspheres prepared in comparative example 2 of the present invention;
FIG. 13b is an enlarged view of a portion of FIG. 13 a;
FIG. 14a is a transmission electron microscope image of core-shell microspheres prepared in comparative example 3 of the present invention;
FIG. 14b is an enlarged view of a portion of FIG. 14 a;
FIG. 15 is a transmission electron micrograph of microspheres prepared according to comparative example 4 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
FIG. 1 is a schematic flow chart of a method of preparing a tunable heterostructure low surface energy microsphere according to one embodiment of the present invention. As shown in fig. 1, the preparation method of the adjustable heterostructure low surface energy microsphere comprises the following steps:
step S100, preparing a dispersion liquid of polystyrene microspheres with positive charges;
step S200, adding a mixed solution of water and ethanol with a preset volume ratio and an alkaline catalyst into a dispersion liquid of polystyrene microspheres with positive charges at a preset temperature to obtain a first reaction liquid;
step S300, adding the mixed solution of the first organosilane coupling agent and the second organosilane coupling agent into an acid solution for hydrolysis to obtain a second reaction solution, wherein the first organosilane coupling agent has reactivity, and the second organosilane coupling agent has low surface energy;
step S400, mixing and reacting the first reaction liquid and the second reaction liquid, and obtaining the adjustable heterostructure low surface energy microsphere after centrifugation, washing and drying.
In the embodiment, the first organosilane coupling agent and the second organosilane coupling agent are introduced into a pre-hydrolysis process, the hydrolyzed oligomer is negatively charged and can be attracted with the polystyrene microsphere with positive charge, the polystyrene microsphere is deposited to form an asymmetric structure, a petal-shaped structure and a strawberry-shaped structure with an adjustable heterostructure through hydrolysis-condensation reaction, and the first organosilane coupling agent and the second organosilane coupling agent are combined to act together, so that the prepared microsphere with the adjustable heterostructure and the low surface energy has excellent waterproof performance. However, because the co-hydrolytic condensation degree of the first organosilane coupling agent and the second organosilane coupling agent is low, the particles which are finally prepared by directly adding the first organosilane coupling agent and the second organosilane coupling agent into the prepared first reaction solution are core-shell, in order to improve the co-hydrolytic condensation degree of the first organosilane coupling agent and the second organosilane coupling agent, the first organosilane coupling agent and the second organosilane coupling agent are hydrolyzed in an acid solution in advance to obtain a second reaction solution, and then the second reaction solution is added into the first reaction solution, so that the adjustable heterostructure low-surface energy microsphere with good waterproof performance can be prepared.
According to the embodiment, the adjustable heterostructure low-surface-energy microsphere with a coarse structure and good waterproof performance is synthesized in one step by introducing a prehydrolysis method, and subsequent modification is not needed, so that the preparation method is simpler.
In this embodiment, the tunable heterostructure low surface energy microsphere includes an asymmetric structure, a petal-like structure, and a strawberry-like structure, and does not include a core-shell structure. This example requires the preparation of tunable heterostructure low surface energy microspheres with good water resistance.
In this embodiment, the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent is any one of 1.5-6:1. For example, it may be 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1. When the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent is less than 1.5:1, free small particles appear in the solution, and composite microspheres are not formed; when the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent is greater than 6:1, the overall content of the second organosilane coupling agent with low surface energy is reduced, and the superhydrophobic effect is not achieved.
The short service life of non-wetted surfaces limits practical applications due to poor or even no quantitative bonding between low surface energy materials and multi-stage surface textures. This example employs a multi-stage strawberry-like colloidal particle with chemically bonded low surface energy material and reactive c=c double bonds, a strategy that results in a highly durable liquid repellent non-wetting surface. This example designs and prepares these colloidal particles by interfacial engineering of a mixture of reactive vinyl groups and low surface energy organosilanes on positively charged and polymer stabilized polystyrene seeds by introducing a prehydrolysis process to the organosilane mixture, controlling the polarity of the solvent and the amount of organosilane. The non-wetting surface can be built on a variety of substrates and repels a variety of simple liquids, has good self-cleaning properties, and has an enhanced duration of up to 1000 rubs.
In this embodiment, the first organosilane coupling agent is one or both of vinyltriethoxysilane or mercaptoisopropyltrimethoxysilane. The second organosilane coupling agent is one or two of fluorine-free octavinyl silsesquioxane, octadecyltrimethoxy silane, fluorine-containing 1H, 2H-perfluoro decyl triethoxysilane and 1H, 2H-nonafluorohexyl triethoxysilane.
In this example, a dispersion of positively charged polystyrene microspheres was prepared as follows:
step one: synthesizing a positively charged dispersant-stabilized polystyrene microsphere from a positively charged additive, a polymeric dispersant and a styrene monomer;
step two: centrifugally washing the polystyrene microspheres by using ethanol and water;
step three: and stirring and dispersing the polystyrene microspheres in an ethanol solution to obtain a dispersion liquid of the polystyrene microspheres with positive charges.
In step one, the positive charge additive is one or more of 2, 2-azobis (2-methylpropionamide) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 3-phenylazo-2, 6-diaminopyridine monohydrochloride or 2-aminoazotoluene hydrochloride. The positive charge additive mainly has the effect of making the surface of the prepared polystyrene microsphere positively charged, so that the subsequent organosilane coupling agent can be attracted to the surface of the polystyrene microsphere to react. The polystyrene microspheres, i.e., PS microspheres, in this example were prepared by a dispersion polymerization method.
In this example, the polymer dispersant mainly affects the particle size and particle distribution of the prepared polystyrene microsphere, and the particle size of the prepared polystyrene microsphere is more uniform after the dispersant is added.
In this example, the mass ratio of the polymeric dispersant to the styrene monomer is 0.2 to 2:5. when the mass ratio of the polymer dispersant to the styrene monomer is less than 0.2:5, the monodispersity of the obtained polystyrene microsphere is poor; when the mass ratio of the polymer dispersant to the styrene monomer is greater than 2: and 5, the subsequent organosilicon cannot grow on the surface of the polystyrene microsphere, and the adjustable heterostructure low surface energy microsphere cannot be obtained.
In step S200, the preset volume ratio of water to ethanol is any one of 7-21:9-23, and may be, for example, 13:17, 7:9, 8:9, 10:20, 17:13, 19:11, 21:23, 7:10, 8:10, 9:10, 11:10, 20:20, 15:16, 14:17, 18:17, 21:10, 20:15, 18:23, 12:23, 12:21, 16:9, 16:13, 17:15, or the like. In the embodiment, the volume ratio of the water to the ethanol can influence the appearance of the polystyrene microsphere, the volume ratio of the water to the ethanol is gradually increased, the appearance of the polystyrene microsphere is gradually changed from a core-shell shape to a strawberry shape, and finally the polystyrene microsphere is changed into an asymmetric shape, and the surface roughness of the polystyrene microsphere in the strawberry shape is larger than that of the polystyrene microsphere in the core-shell shape and the asymmetric shape, so that the polystyrene microsphere has better waterproof performance.
In this embodiment, the acidic solution is a mixed solution of ethanol and acetic acid, and the volume ratio of ethanol to acetic acid is 5-1: any one of values 0-4. For example, it may be 5:0, 5:1, 5:2, 5:3, 5:4, 4:0, 4:1, 4:2, 4:3, 4:4, 3:0, 3:1, 3:2, 3:4, 2:0, 2:1, 2:2, 2:3, 2:4, 1:0, 1:1, 1:2, 1:3, and 1:4. The organic silane coupling agent with low surface energy is difficult to be completely dissolved in the alcohol-acetic acid water if the organic silane coupling agent is all acetic acid water, so that the polystyrene-organic silicon composite microsphere cannot be formed. Acetic acid provides an acidic environment, ethanol can be used as a cosolvent in a system, so that the solubility of two types of organosilane in water can be increased, the interfacial tension between the organosilane and seeds can be reduced, the organosilane is facilitated to be hydrolyzed to generate Si-OH groups, the cohydrolytic condensation degree of the two types of silane is improved, and heterogeneous nucleation of the organosilane on the surfaces of the seeds is facilitated. Therefore, under the condition that only acetic acid solution is used, the co-hydrolytic condensation degree of the acetic acid solution and the acetic acid solution is low, and the prepared particles are core-shell; when only ethanol is used, the co-hydrolytic condensation degree is high, the prehydrolysis liquid contains a large amount of silane oligomer, and the prepared particles are asymmetric.
In this embodiment, the alkaline catalyst is one or more of triethanolamine, triethylamine, ammonia or sodium hydroxide. The alkaline catalyst is used to regulate the pH value of polystyrene microsphere alkaline solution to 8-13.
In this example, the volume ratio of the dispersion of positively charged polystyrene microspheres to the basic catalyst was 1.08: any value of 0.03 to 0.1.
In this embodiment, the preset temperature is any one of 20℃to 60℃and may be, for example, 20℃40℃or 60 ℃.
In this example, consider first that the hydrolysis product of organosilane is negatively charged, and therefore, positively charged and polymer-stabilized PS microspheres are formed by dispersion polymerization, electrostatically acting with the hydrolysis product of organosilane negatively charged, thereby allowing heterogeneous nucleation of organosilane on PS microspheres. When the first organosilane coupling agent is vinyltriethoxysilane and the second organosilane coupling agent is 1H, 2H-perfluorodecyl triethoxysilane, only slightly coarser colloidal particles are obtained when a mixture of vinyltriethoxysilane and 1H, 2H-perfluorodecyl triethoxysilane is directly added to the basic PS microsphere solution. This is probably due to the fact that the reactivity of 1H, 2H-perfluorodecyl triethoxysilane and vinyl triethoxysilane differ greatly, and therefore the degree of cohydrolytic condensation of 1H, 2H-perfluorodecyl triethoxysilane and vinyl triethoxysilane is low, resulting in slightly rough surfaces of the colloidal particles. To increase the degree of cohydrolysis and condensation between 1H, 2H-perfluorodecyl triethoxysilane and vinyl triethoxysilane, an acid-catalyzed prehydrolysis process in an acidic water and ethanol mixture favors vinyl triethoxysilane and 1H, 2H-perfluorodecyl triethoxysilane Si-OCH 3 The radical hydrolysis introduces Si-OH groups. The introduction of the silicon hydroxyl Si-OH has hydrophilicity on one hand, and can adjust the hydrophilicity and hydrophobicity of the organosilane coupling agent so that the organosilane coupling agent can heterogeneous nucleate and grow on the hydrophilic PS microsphere; on the other hand, acidic hydrolysis facilitates the generation of silicon hydroxyl Si-OH, and the condensation reaction between Si-OH is easier, so that the cohydrolytic condensation degree of vinyl triethoxysilane and 1H, 2H-perfluoro decyl triethoxysilane is increased.
Fig. 2 is a schematic flow chart of a method of making a textile according to one embodiment of the invention. As shown in fig. 2, in one specific embodiment, the method of making a textile product comprises the steps of:
step S500, dissolving a first organic silicon resin matrix in an organic solvent, and mixing and stirring the first organic silicon resin matrix and a second organic silicon resin matrix containing a catalyst to obtain a mixed solution;
step S600, adding the adjustable heterostructure low surface energy microsphere prepared by the preparation method into the mixed solution to obtain a third reaction solution;
and step S700, immersing the fabric in the third reaction solution, and drying at 80-120 ℃ for 1-2 hours to obtain the textile.
In this embodiment, the first silicone resin matrix is one of hydrogen-containing silicone oil and vinyl silicone oil, and the second silicone resin matrix is a catalyst-containing silicone oil, where at least three hydrogen atoms in the hydrogen-containing silicone oil are directly connected to silicon atoms, and the content of hydrogen atoms is 0.5-1%.
In this embodiment, the organic solvent is any one of a vinyl organosilane coupling agent, cyclohexane, and n-hexane.
In this embodiment, the volume ratio of the first silicone resin matrix to the strawberry finish is any one of 5-50:1;
in this embodiment, the catalyst is a platinum-containing catalyst, and the content of platinum in the catalyst is 100 to 500000ppm.
In the embodiment, a mixed solution is formed by polystyrene-organosilicon adjustable heterostructure low-surface energy microsphere and organosilicon resin containing Si-H groups, the mixed solution is spin-coated on various substrates, and C=C double bonds and Si-H groups undergo hydrosilylation reaction to obtain a non-wetting surface, and the appearance and the surface morphology of the surface are observed on different substrates through a scanning electron microscope. It can be seen that the surfaces on the different substrates all exhibit micro/nano three-dimensional multi-level structures, which indicates that the surfaces have a certain roughness.
The following is a detailed description of specific embodiments:
example 1
The first step: measuring 100mL of deionized water in a 500mL four-neck flask, adding 2g of polymer dispersing agent, standing for dissolution, then adding 5g of styrene, stirring for 0.5h at 250rpm, introducing nitrogen for 1h, heating to 70 ℃, adding a positive charge additive solution (0.5 g of AIBA/10mL of deionized water) prepared in advance under the protection of nitrogen and stirring, and continuing to react for 24h to obtain PS microspheres with positive charges and stable dispersing agent;
and a second step of: measuring water and ethanol with a volume ratio of 13:17 in a 50mL round bottom flask, adding 1g of the dispersion liquid of the PS microspheres into the round bottom flask, carrying out ultrasonic dispersion uniformly, putting the mixture into a water bath, continuously stirring for 1.0h at a rotation speed of 600rpm, heating to 50 ℃, stirring for 10min, adding 1.0mL of alkaline catalyst solution (1 mol/L) to obtain a first reaction liquid, quickly adding 5mL of a second reaction liquid after 5min, reacting for 3.0h, centrifuging, washing and drying to obtain the strawberry-shaped low-surface-energy microspheres. Here, the second reaction liquid may be understood as a prehydrolysis liquid.
Wherein, the preparation process of the second reaction liquid is as follows: the volume ratio is measured to be 4:1 in a 25mL round bottom flask, stirring at 600rmp and heating to 50 ℃, adding the ethanol and the diluted acetic acid with the volume ratio of 5:1 and the second organosilane coupling agent.
FIG. 3 is a transmission electron microscope image of PS microspheres with positive charges prepared according to example 1 of the present invention. As shown in fig. 3, PS microspheres prepared according to the above scheme are round particles with smooth surfaces.
Fig. 4a is a transmission electron microscope image of the strawberry-shaped low surface energy microsphere prepared in example 1 of the present invention, fig. 4b is a partial enlarged view of fig. 4a, and fig. 4c is an element distribution diagram of the high power transmission electron microscope corresponding to fig. 4 a. As shown in fig. 4a and fig. 4b, the strawberry-shaped low surface energy microsphere prepared in example 1 has a rough surface, more raised particles appear, and a typical strawberry-shaped structure is formed, and as shown in fig. 4, each element of carbon, silicon, oxygen and fluorine is uniformly distributed on the surface of the microsphere, especially fluorine element is distributed on the surface of the microsphere.
And (3) dissolving the first organic silicon resin matrix in an organic solvent, mixing and stirring the organic solvent with the second organic silicon resin matrix containing the catalyst to obtain a mixed solution, adding the strawberry-shaped low-surface-energy microspheres into the mixed solution to obtain a third reaction solution, finally immersing the fabric in the third reaction solution, and drying at 100 ℃ for 2 hours to obtain the textile.
Fig. 5a is a scanning electron microscope image of the fabric of example 1 of the present invention, fig. 5b is a partial enlarged view of fig. 5a, fig. 5c is a scanning electron microscope image of the coated fabric of the strawberry-shaped low surface energy microsphere of example 1 of the present invention, fig. 5d is a partial enlarged view of fig. 5c, and fig. 6 is a water contact angle image of the coated fabric of the strawberry-shaped low surface energy microsphere of example 1 of the present invention. Referring to fig. 6, the water contact angle of the coated fabric prepared by using the strawberry-shaped low surface energy microspheres prepared in example 1 was 151.6 °, and thus it can be confirmed that the coated fabric prepared by using the strawberry-shaped low surface energy microspheres prepared in example 1 has better waterproof performance.
Example 2:
based on example 1, the volume ratio of water to ethanol was adjusted to 17:13, with other conditions unchanged. Fig. 7a is a transmission electron microscope image of petal-shaped low surface energy microspheres prepared in example 2 of the present invention, and fig. 7b is a partial enlarged view of fig. 7 a. As shown in fig. 7a and 7b, the low surface energy microsphere prepared in example 2 has a plurality of obvious convex particles connected to the surface, and is in a typical petal-shaped structure.
Example 3:
based on example 1, the volume ratio of water to ethanol was adjusted to 21:9, with other conditions unchanged. Fig. 8a is a transmission electron microscope image of the asymmetric low surface energy microsphere prepared in example 3 of the present invention, and fig. 8b is a partial enlarged view of fig. 8 a. As shown in fig. 8a and 8b, the low surface energy microsphere prepared in example 3 has a convex particle connected to a large particle, and is in a typical asymmetric structure.
Example 4:
based on example 1, the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent was adjusted to 5:1.5 under other conditions. Fig. 9a is a transmission electron microscope image of the core-shell low surface energy microsphere prepared in example 4 of the present invention, and fig. 9b is a partial enlarged view of fig. 9 a. As shown in fig. 9a and 9b, the low surface energy microsphere prepared in example 4 has a convex particle connected to a large particle, and is in a typical asymmetric structure.
Example 5:
based on example 1, the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent was adjusted to 5 under other conditions: 2.5. fig. 10a is a transmission electron microscope image of the strawberry-shaped low surface energy microsphere prepared in example 5 of the present invention, and fig. 10b is a partial enlarged view of fig. 10 a. As shown in fig. 10a and 10b, the low surface energy microsphere prepared in example 5 has a convex particle connected to a large particle, and is in a typical asymmetric structure.
Comparative example 1:
based on example 1, the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent was adjusted to 6:0 under other conditions. Fig. 11a is a transmission electron microscope image of the nano-microsphere prepared in comparative example 1 of the present invention, and fig. 11b is a partial enlarged view of fig. 11 a. As shown in fig. 11a and 11b, the nanoparticle prepared in comparative example 1 showed more protruding particles, forming a typical strawberry-like structure.
FIG. 12 is a Fourier infrared spectrum of microspheres obtained without addition of a second organosilane coupling agent and low surface energy microspheres prepared with addition of a second organosilane coupling agent. FAS13 in FIG. 12 refers to 1H, 2H-perfluorodecyl triethoxysilane, PS@oSiO 2 Refers to polystyrene-silicone. As shown in FIG. 12, both exhibited characteristic absorption peaks of benzene rings at 3030, 2920, 1490, 1450, 758, 698cm-1, and at 1140, 1050cm -1 Stretching vibration peak of Si-O-Si bond at 1600cm -1 The c=c double bond stretching vibration peak at the position is attributed to the characteristic absorption peak of the first organosilane coupling agent, which indicates that the first organosilane coupling agent successfully grows to the surface of the PS microsphere. From the figure PS@oSiO 2 As can be seen from the infrared spectrum of the FAS13 composite microsphere, the peaks were found to be 1240cm apart from the above peaks -1 And 1190cm -1 The expansion vibration peak of the C-F bond appears, and the second organosilane coupling agent on the surface grows to PS microsphere successfully, which indicates that both organosilane coupling agents are hydrolyzed and condensed to the surface of PS microsphere particles successfully.
Comparative example 2:
on the basis of example 1, the first organosilane coupling agent and the second organosilane coupling agent were directly added to react with the first reaction solution without prehydrolysis under other conditions. Fig. 13a is a transmission electron microscope image of the nano-microsphere prepared in comparative example 2 in the present invention, and fig. 13b is a partial enlarged view of fig. 13 a. As shown in fig. 13a and 13b, the nanoparticle prepared in comparative example 2 had a smooth surface, and formed a typical core-shell structure.
Comparative example 3:
based on example 1, the volume ratio of water to ethanol was adjusted to 28:2, with other conditions unchanged. FIG. 14a is a transmission electron microscope image of the core-shell low surface energy microsphere prepared in comparative example 3 of the present invention, and FIG. 14b is a partial enlarged view of FIG. 14 a. As shown in fig. 14a and 14b, the low surface energy microsphere prepared in comparative example 3 has a smooth surface, and has a particle size larger than that of PS microsphere, which indicates that the surface has a shell layer growing up and is in a core-shell structure with a smooth surface.
Comparative example 4:
based on example 1, the volume ratio of water to ethanol was adjusted to 2:28, with other conditions unchanged. FIG. 15 is a transmission electron micrograph of microspheres prepared according to comparative example 4 of the present invention. As shown in FIG. 15, the microspheres prepared in comparative example 4 were smooth in surface, similar to PS microspheres in particle size, and small particles of silicone alone appeared next to the microspheres, indicating that the silicone failed to grow to the surface of the PS microspheres.
The adjustable heterostructure low surface energy microspheres prepared in examples 1-5 and comparative examples 1-4 are respectively mixed with organic silicon resin according to a mass ratio of 2:10, then are directly immersed or coated on the surface of cotton fabric, the coating amount is about 2mL, and the cotton fabric is placed in a baking oven at 100 ℃ for baking for 2 hours, so that the application finishing of the cotton fabric is completed. The water contact angle was measured and the results are shown in table 1.
TABLE 1
| Water contactAngle (°) | |
| Example 1 | 151.6 |
| Example 2 | 140.5 |
| Example 3 | 130.0 |
| Example 4 | 134.5 |
| Example 5 | 138.6 |
| Comparative example 1 | 105.5 |
| Comparative example 2 | 122.8 |
| Comparative example 3 | 123.0 |
| Comparative example 4 | 120.0 |
As can be seen from Table 1, in examples 1 to 5, the cotton fabric of example 1 has the maximum water contact angle of 151.6 DEG, and the micro-nano structure is formed by the arrangement of the low surface energy microsphere with the adjustable heterostructure on the fabric due to the rough surface, so that the waterproof performance is better. The water contact angle of the cotton fabric of example 2 was 140.5 °, the water contact angle of the cotton fabric of example 3 was 130.0 °, the water contact angle of the cotton fabric of example 4 was 134.5 °, and the water contact angle of the cotton fabric of example 5 was 138.6 °. In comparative examples 1 to 4, the cotton fabric of comparative example 1 had a water contact angle of 105.5 °, and thus it could be demonstrated that the absence of the second organosilane coupling agent resulted in a decrease in the water-repellent performance of the strawberry-like structure, and that it was not possible to prepare the tunable heterostructure low surface energy microspheres having better water-repellent performance. The cotton fabric of comparative example 2 had a water contact angle of 122.8 °, and thus it was found that the waterproof performance was relatively poor. The cotton fabric of comparative example 3 had a water contact angle of 123.0 °, and thus it was found that the waterproof performance was relatively poor. The cotton fabric of comparative example 4 had a water contact angle of 120.0 °, and thus it was found that the waterproof performance was relatively poor.
By now it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described herein in detail, many other variations or modifications of the invention consistent with the principles of the invention may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.
Claims (10)
1. The preparation method of the adjustable heterostructure low surface energy microsphere is characterized by comprising the following steps of:
preparing a dispersion of positively charged polystyrene microspheres;
adding a mixed solution of water and ethanol and an alkaline catalyst in a preset volume ratio into the dispersion liquid of the polystyrene microspheres with positive charges at a preset temperature to obtain a first reaction liquid;
adding a mixed solution of a first organosilane coupling agent and a second organosilane coupling agent into an acidic solution for hydrolysis to obtain a second reaction solution, wherein the first organosilane coupling agent has reactivity, and the second organosilane coupling agent has low surface energy;
and mixing and reacting the first reaction liquid and the second reaction liquid, and centrifuging, washing and drying to obtain the adjustable heterostructure low surface energy microsphere.
2. The method according to claim 1, wherein,
the preset volume ratio of water to ethanol is 7-21:9 to 23.
3. The method according to claim 1, wherein,
the volume ratio of the first organosilane coupling agent to the second organosilane coupling agent is any value of 1.5-6:1.
4. The method according to claim 2, wherein,
the first organosilane coupling agent is one or two of vinyl triethoxysilane or mercapto isopropyl trimethoxy silane;
the second organosilane coupling agent is one or two of fluorine-free octavinyl silsesquioxane, octadecyltrimethoxy silane, fluorine-containing 1H, 2H-perfluoro decyl triethoxysilane and 1H, 2H-nonafluorohexyl triethoxysilane.
5. A method according to claim 3, wherein the dispersion of positively charged polystyrene microspheres is prepared as follows:
synthesizing a positively charged dispersant-stabilized polystyrene microsphere from a positively charged additive, a polymeric dispersant and a styrene monomer;
centrifugally washing the polystyrene microspheres by using ethanol and water;
and stirring and dispersing the polystyrene microspheres in an ethanol solution to obtain a dispersion liquid of the polystyrene microspheres with positive charges.
6. The method according to claim 5, wherein,
the positive charge additive is one or more of 2, 2-azo bis (2-methylpropyl) dihydrochloride, 2' -azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 3-phenylazo-2, 6-diaminopyridine monohydrochloride or 2-aminoazotoluene hydrochloride;
optionally, the mass ratio of the polymer dispersant to the styrene monomer is 0.2-2: 5.
7. the method according to any one of claim 1 to 6, wherein,
the acidic solution is a mixed solution of ethanol and acetic acid, and the volume ratio of the ethanol to the acetic acid is 5-1: any one of values 0-4.
8. The method according to any one of claim 1 to 6, wherein,
the alkaline catalyst is one or more of triethanolamine, triethylamine, ammonia water or sodium hydroxide;
optionally, the volume ratio of the dispersion of positively charged polystyrene microspheres to the basic catalyst is 1.08: any value of 0.03 to 0.1;
optionally, the preset temperature is any one of 20 ℃ to 60 ℃.
9. A method for preparing a textile, comprising the steps of:
dissolving a first organic silicon resin matrix in an organic solvent, and mixing and stirring the organic solvent with a second organic silicon resin matrix containing a catalyst to obtain a mixed solution;
adding the adjustable heterostructure low surface energy microsphere prepared by the preparation method of any one of claims 1 to 8 into the mixed solution to obtain a third reaction solution;
and immersing the fabric in the third reaction liquid, and drying at 80-120 ℃ for 1-2h to obtain the textile.
10. The method according to claim 9, wherein,
the first organic silicon resin matrix is one of hydrogen-containing silicone oil and vinyl silicone oil, and the second organic silicon resin matrix is catalyst-containing silicone oil, wherein at least three hydrogen atoms in the hydrogen-containing silicone oil are directly connected with the silicon atoms, and the content of the hydrogen atoms is 0.5-1%;
the organic solvent is any one of vinyl organosilane coupling agent, cyclohexane and n-hexane;
optionally, the volume ratio of the first silicone resin matrix to the tunable heterostructure low surface energy microsphere is any one of 5-50:1;
alternatively, the catalyst is a platinum-containing catalyst, and the content of platinum in the catalyst is 100 to 500000ppm.
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