CN114231172A - UV-resistant hydrophobic membrane material and preparation method and application thereof - Google Patents
UV-resistant hydrophobic membrane material and preparation method and application thereof Download PDFInfo
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- CN114231172A CN114231172A CN202111635466.5A CN202111635466A CN114231172A CN 114231172 A CN114231172 A CN 114231172A CN 202111635466 A CN202111635466 A CN 202111635466A CN 114231172 A CN114231172 A CN 114231172A
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000012528 membrane Substances 0.000 title claims abstract description 38
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002545 silicone oil Polymers 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 239000002250 absorbent Substances 0.000 claims abstract description 19
- 230000002745 absorbent Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000006750 UV protection Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 230000004224 protection Effects 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- -1 benzophenone compound Chemical class 0.000 claims description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012965 benzophenone Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 6
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 229960001860 salicylate Drugs 0.000 claims description 5
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 4
- NIZBFFOETCKGBI-UHFFFAOYSA-N 1-hydroxy-2,2,3,3,4-pentamethylpiperidine Chemical compound CC1CCN(O)C(C)(C)C1(C)C NIZBFFOETCKGBI-UHFFFAOYSA-N 0.000 claims description 4
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000012209 synthetic fiber Substances 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229920013822 aminosilicone Polymers 0.000 claims description 3
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 claims description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- HYSNMDQIDZNCAC-UHFFFAOYSA-N ethyl 2-(3-bromopyridin-4-yl)acetate Chemical compound CCOC(=O)CC1=CC=NC=C1Br HYSNMDQIDZNCAC-UHFFFAOYSA-N 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 229960000969 phenyl salicylate Drugs 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 19
- 239000003973 paint Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 229910008045 Si-Si Inorganic materials 0.000 description 6
- 229910006411 Si—Si Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a hydrophobic membrane material with UV resistance, a preparation method and application thereof, wherein the method comprises the following steps: dissolving an ultraviolet absorbent with hydroxyl or amino by using a solvent, adding an isocyanate silane coupling agent, reacting for 0.5-5 h at 20-60 ℃ under the protection of nitrogen, and removing the solvent by rotary evaporation after the reaction is finished to obtain an UV-Si compound, wherein the molar ratio of the isocyanate silane coupling agent to the hydroxyl or amino of the ultraviolet absorbent is 1: 1, and when the ultraviolet absorbent is the ultraviolet absorbent with hydroxyl, a catalyst with the hydroxyl molar number of 0.001-0.01 equivalent is required to be added for reaction; and uniformly mixing the UV-Si compound, the silicone oil and the solvent to obtain the UV-resistant hydrophobic membrane material. The material can form a stable film layer on the surfaces of various substrates, or can be matched with paint and ink for use, so that the UV aging resistance and the hydrophobicity of the material are enhanced.
Description
Technical Field
The invention relates to the technical field of hydrophobic membrane materials, in particular to a hydrophobic membrane material with UV resistance and a preparation method and application thereof.
Background
One of the disadvantages of many polymeric materials is their susceptibility to aging, such as in paints, plastics, inks and other polymeric materials, which can result in loss of gloss, discoloration, cracking, embrittlement, loss of strength, and the like. Three elements of material aging: light, high temperature and humidity, any of which cause aging damage to the material. Different materials have different sensitivities to light, and for durable materials, such as most paints, plastics, uv light is responsible for most polymer aging.
Organic uv absorbers are a class of organic compounds that strongly absorb uv light in the wavelength range of 290-400 nm. The organic ultraviolet absorbent can convert absorbed radiation energy into heat energy through a photophysical process or a photochemical reaction, so that the effect of protecting ultraviolet rays is achieved. The commonly used organic ultraviolet absorbent mainly comprises benzophenone, benzotriazole, salicylate and substituted triazine derivatives. Among them, benzophenone compounds are widely used by people due to advantages of wide absorption wavelength range, low price, and the like.
In daily application, some plastic products and coatings need to be exposed to the sun and rain frequently, so that the plastic products and the coatings not only need to have waterproof performance, but also need to have certain UV (ultraviolet) aging resistance, otherwise, phenomena such as fading, falling and the like easily occur, and the UV resistance needs to be increased along with the improvement of the performance requirements of the materials. The ultraviolet absorbent is generally added in the processing process of high polymer materials, is not suitable for being used alone in the field of surface treatment, and the UV aging resistance of some coatings and inks needs to be enhanced.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects in the prior art, the invention provides a hydrophobic membrane material with UV resistance, a preparation method and application thereof, wherein the material can form a stable membrane layer on the surfaces of various substrates, or can be matched with paint and ink for use to enhance the UV aging resistance and the hydrophobicity.
The technical scheme is as follows: a preparation method of a hydrophobic membrane material with UV resistance comprises the following steps:
(1) preparation of UV-Si compound: dissolving an ultraviolet absorbent with hydroxyl or amino by using a solvent, adding an isocyanate silane coupling agent, reacting for 0.5-5 h at 20-60 ℃ under the protection of nitrogen, and removing the solvent by rotary evaporation after the reaction is finished to obtain an UV-Si compound, wherein the molar ratio of the isocyanate silane coupling agent to the hydroxyl or amino of the ultraviolet absorbent is 1: 1, and when the ultraviolet absorbent is the ultraviolet absorbent with hydroxyl, a catalyst with the hydroxyl molar number of 0.001-0.01 equivalent is required to be added for reaction;
(2) preparation of UV-resistant hydrophobic membrane material: uniformly mixing the UV-Si compound prepared in the step (1) with silicone oil and a solvent to obtain a UV-resistant hydrophobic membrane material, wherein the weight ratio of the UV-Si compound to the silicone oil to the solvent is (0.5-5): (0.5-5): (90-99).
The ultraviolet absorbent with hydroxyl in the step (1) is monohydroxy substituted benzophenone compound, dihydroxy substituted benzophenone compound, salicylate compound, piperidinol compound or benzotriazole compound; the ultraviolet absorbent with amino is a monoamino-substituted benzophenone compound or a diamino-substituted benzophenone compound.
The monohydroxy substituted benzophenone compound is 2-hydroxybenzophenone, 4-hydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone; the dihydroxy-substituted benzophenone compound is 2, 4-dihydroxy benzophenone or 4, 4-dihydroxy benzophenone; the salicylate compound is phenyl salicylate; the piperidinol compound is pentamethylpiperidinol; the benzotriazole compound is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; the monoamino substituted benzophenone compound is 2-aminobenzophenone or 4-aminobenzophenone or; the diamino substituted benzophenone compound is 2, 4-diaminobenzophenone or 4, 4-diaminobenzophenone.
The isocyanate silane coupling agent in the step (1) is 3-isocyanate propyl trimethoxy silane or 3-isocyanate propyl triethoxy silane; the catalyst is dibutyltin dilaurate; the solvent is tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, acetone or methyl ethyl ketone.
The silicone oil in the step (2) is methyl silicone oil, ethyl silicone oil, phenyl silicone oil or modified silicone oil, and the modified silicone oil is hydroxyl silicone oil, amino silicone oil or epoxy silicone oil.
The solvent in the step (2) is one or more of ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol dimethyl ether, ethyl acetate, butyl acetate, acetone and methyl ethyl ketone.
The reaction equation in which the UV-Si compound is synthesized is exemplified as follows:
the method comprises the following steps: heating 4-hydroxybenzophenone and 3-isocyanate propyl triethoxysilane with equal molar equivalent weight in a certain solvent in the presence of a catalyst to react to obtain the target UV-Si compound.
The second formula: 4, 4-dihydroxy benzophenone and 2 times of molar equivalent of 3-isocyanate propyl triethoxysilane are heated and reacted in a certain solvent in the presence of a catalyst to obtain the target UV-Si compound.
And (3) formula III: 4, 4-diaminobenzophenone and 2 times of molar equivalent of 3-isocyanate propyl triethoxysilane react in a certain solvent to obtain the target UV-Si compound.
And IV, formula IV: reacting pentamethylpiperidinol with 3-isocyanate propyl triethoxysilane with equal molar equivalent in a certain solvent to obtain the target UV-Si compound.
The silicone oil has good chemical stability, electrical insulation, weather resistance and hydrophobic property. The silicone oil suitable for the invention can be selected from methyl silicone oil, ethyl silicone oil, phenyl silicone oil or modified silicone oil such as hydroxyl silicone oil, amino silicone oil and epoxy silicone oil. The modified silicone oil has better adsorbability and compatibility, for example, hydroxyl at the tail end of the main chain of the hydroxyl silicone oil molecule is crosslinked by heat energy, and can form a more stable film layer with a UV-Si compound. The molecular weight of the silicone oil is also an important consideration, and the silicone oil should have a kinematic viscosity of 100-5000cSt, and more preferably of 200-1000cSt, based on solubility and film-forming properties.
The solvent is prepared by dissolving synthesized UV-Si compound and silicone oil into a certain concentration for dip coating, roll coating or spray coating to form a film layer with a certain thickness. The solvent may be one or more selected from ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol dimethyl ether, ethyl acetate, butyl acetate, acetone, and methyl ethyl ketone. The solvent is further selected to account for 90 to 99 percent of the whole component.
The UV-resistant hydrophobic membrane material prepared by the preparation method is provided.
The UV-resistant hydrophobic membrane material prepared by the preparation method is applied to the surface of a base material to form a membrane.
The film forming process is as follows: the UV-resistant hydrophobic membrane material is uniformly applied to the surface of a base material by adopting a dip coating, roll coating or spraying method, and then is heated and cured into a membrane at 50-150 ℃, wherein the curing time is 10-120 min.
The base material is a synthetic plastic material, a synthetic fiber material, natural wood or an inorganic material; the synthetic plastic material is PE, PP, PC or PMMA; the synthetic fiber material is PET or PA; the inorganic material is glass.
The UV-resistant hydrophobic membrane material disclosed by the invention is formed on the surface of a base material, the heating and curing temperature and time are selected according to the temperature which the base material can bear, the high polymer material is generally selected at the temperature of not higher than 80 ℃ for not less than 1h, and the high-temperature resistant base material can be selected at the temperature of 100 ℃ and 150 ℃ for 0.5-1 h.
The UV-resistant hydrophobic membrane material can also be cured into a membrane together with some coatings and printing ink. However, the strength of the bond, the durability of the effect will vary from substrate to substrate.
Has the advantages that: the UV-resistant hydrophobic membrane material, the preparation method and the application thereof provided by the invention have the following beneficial effects: the UV-resistant hydrophobic membrane material has the functions of absorbing UV groups and hydrophobicity, has a water contact angle of 100-110 degrees after being applied to the surface of a base material and cured to form a membrane, can improve the UV aging resistance of the base material, and has lasting hydrophobicity when being exposed to an ultraviolet environment.
Drawings
FIG. 1 is a HNMR map of UV-Si compound 1 prepared in Synthesis example 1.
FIG. 2 is an IR spectrum of UV-Si compound 1 prepared in Synthesis example 1.
FIG. 3 is a HNMR map of UV-Si compound 2 prepared in Synthesis example 2.
FIG. 4 is an IR spectrum of UV-Si compound 2 prepared in Synthesis example 2.
FIG. 5 is a HNMR map of the Si-Si compound prepared in comparative Synthesis example 1.
Detailed Description
Synthesis example 1
The synthesis method of the UV-Si compound 1 comprises the following steps: a50 mL round bottom flask was taken, 2.14g of 4, 4-dihydroxybenzophenone was dissolved in 20mL of dry tetrahydrofuran, 4.94g of isocyanatopropyltriethoxysilane and 50uL of dibutyltin dilaurate were added, the reaction was stirred at 50 ℃ for 2h under nitrogen protection, and the completion of the reaction was judged by TLC dot plate. The tetrahydrofuran solvent was removed by rotary evaporation to obtain 7.10g of a yellowish solid, which was UV-Si compound 1, and the structure was confirmed by HNMR and IR tests. The HNMR and IR spectra of UV-Si compound 1 are shown in FIGS. 1 and 2.
The reaction equation is as follows:
synthesis example 2
The synthesis method of the UV-Si compound 2 comprises the following steps: a50 mL round bottom flask was taken, 1.71g pentamethylpiperidinol was dissolved in 20mL dry tetrahydrofuran, 2.47g isocyanatopropyltriethoxysilane and 50uL dibutyltin dilaurate were added, the reaction was stirred at 50 ℃ for 2 hours under nitrogen protection, and the reaction was judged complete by TLC spotting. The tetrahydrofuran solvent was removed by rotary evaporation to obtain 4.19g of a colorless transparent liquid, which was the UV-Si compound 2, and the structure was confirmed by HNMR and IR tests. The HNMR and IR spectra of UV-Si compound 2 are shown in fig. 3 and 4.
The reaction equation is as follows:
comparative Synthesis example 1
Si-Si Compound: a50 mL round-bottomed flask was charged with 2.47g of isocyanatopropyltriethoxysilane, followed by dropwise addition of 2.25g of 3-aminopropyltrimethoxysilane, and the reaction was stirred at 50 ℃ for 2 hours to give 4.72g of a colorless transparent liquid as a Si-Si compound. The HNMR map of the Si-Si compound is shown in FIG. 5.
The reaction equation is as follows:
examples 1 to 8 and comparative examples 1 to 4
The UV-resistant hydrophobic film material was prepared according to the composition in table 1 below. The silicone oil used was Dow Corning company brand PMX-200 dimethicone, with a kinematic viscosity of 500 cSt. Two substrates (100 x 50mm in size) of chemically strengthened glass and Polycarbonate (PC) membranes were selected, cleaned by ultrasonic cleaning with absolute ethanol and then treated with plasma to increase their surface active groups (hydroxyl groups). The prepared UV-resistant hydrophobic membrane material is uniformly sprayed on the chemical glass and the PC membrane respectively by adopting a spraying mode, and each piece of base material is sprayed with about 0.5g of surface treating agent. And finally, placing the glass sheet in a drying oven at 120 ℃ for heating for 30min, placing the PC membrane in a drying oven at 80 ℃ for heating for 2h, and curing to form a film, wherein the thickness of the formed film is about 0.5-1 um.
TABLE 1
| Compounds used, proportions | Proportion of silicone oil | Ratio of isopropyl alcohol solvent | Base material | |
| Example 1 | UV- |
3％ | 95％ | Glass |
| Example 2 | UV-Si Compound 1, 4% | 6％ | 90％ | Glass |
| Example 3 | 2, 2% of UV-Si compound | 3％ | 95％ | Glass |
| Example 4 | UV- |
6％ | 90％ | Glass |
| Example 5 | UV- |
3％ | 95％ | PC |
| Example 6 | UV-Si Compound 1, 4% | 6％ | 90％ | PC |
| Example 7 | 2, 2% of UV-Si compound | 3％ | 95％ | PC |
| Example 8 | UV- |
6％ | 90％ | PC |
| Comparative example 1 | Si-Si Compound, 4% | 6％ | 90％ | Glass |
| Comparative example 2 | Si-Si Compound, 4% | 6％ | 90％ | PC |
| Comparative example 3 | / | / | / | Blank glass |
| Comparative example 4 | / | / | / | Blank PC |
The film layers obtained in examples 1 to 8 and comparative examples 1 to 4 were tested as follows:
1. water contact Angle measurement
The water contact angles of the treated substrate surfaces obtained in examples 1 to 8 and comparative examples 1 to 6 were measured. The test was performed using a contact angle tester (manufactured by Beijing Harke Co., Ltd.) with 2uL of water at 20 ℃ under an environment of 50% humidity.
2. Water drop landing Angle test
The drop angle of the water droplets on the surface of the treated substrates obtained in examples 1 to 8 and comparative examples 1 to 6 was measured. 100uL of water drop is placed at one end of the substrate, and the end is slowly lifted to make the water drop slide down, and the inclination angle of the substrate and the plane is tested.
UV aging test
Using a Q-Lab UV tester, UV aging test parameters: UV irradiation for 4 hours (UV-A, 340nm 0.63W/m 225 deg.C), and storing for 4 hr under heating and humidityAt that time (temperature 50 ℃ C., humidity close to 100%).
The entire test procedure contained 15 cycles (120 hours). And taking out the sample after the test is finished, and carrying out performance test.
4. Friction durability test
And respectively carrying out friction durability test on the surface treatment base material before the UV aging test and the surface treatment base material after the UV aging test by using wool felts. Specifically, the surface-treated substrate was horizontally placed and fixed on a linear abrasion tester, and a felt (3 mm × 10mm in size) was used as a friction medium, and a load of 1000g was applied thereto, and the substrate was reciprocated at a frequency of 60 times/min for a distance of 4 cm. The water contact angle was tested after each 500 reciprocations until the contact angle was less than 90 °.
The test results and evaluations were as follows:
the water contact angle and the slip angle before and after the UV aging test are shown in table 2:
TABLE 2
The abrasion durability before and after the UV aging test is shown in table 3:
TABLE 3
| Number of wear-resistance times before UV aging test | Number of wear-resistance times after UV aging test | |
| Example 1 | 6000 | 5500 |
| Example 2 | 7000 | 6000 |
| Example 3 | 4500 | 4000 |
| Example 4 | 5000 | 4000 |
| Example 5 | 1000 | 1000 |
| Example 6 | 1000 | 1000 |
| Example 7 | 1500 | 1500 |
| Example 8 | 2000 | 2000 |
| Comparative example 1 | 6000 | 2000 |
| Comparative example 2 | 2000 | 500 |
As can be seen from Table 2, the substrate using the surface treatment agent containing the UV-Si compound has good hydrophobicity, and the water contact angle and the water drop sliding angle before and after the UV aging test do not change much; it is understood from Table 3 that the surface-treated layers formed in examples 1 to 8 have the same wear resistance durability before and after the UV aging test, while the wear resistance of comparative examples 1 and 2 is significantly reduced.
Therefore, the UV-resistant hydrophobic membrane material is suitable for the waterproof requirements of various base materials, and particularly requires UV aging-resistant materials, such as building exterior wall glass, photovoltaic panels, sun protection clothes, sun umbrellas and the like.
While the embodiments of the present invention have been described in detail, those skilled in the art will recognize that the embodiments of the present invention can be practiced without departing from the spirit and scope of the claims.
Claims (10)
1. A preparation method of a hydrophobic membrane material with UV resistance is characterized by comprising the following steps:
(1) preparation of UV-Si compound: dissolving an ultraviolet absorbent with hydroxyl or amino by using a solvent, adding an isocyanate silane coupling agent, reacting for 0.5-5 h at 20-60 ℃ under the protection of nitrogen, and removing the solvent by rotary evaporation after the reaction is finished to obtain an UV-Si compound, wherein the molar ratio of the isocyanate silane coupling agent to the hydroxyl or amino of the ultraviolet absorbent is 1: 1, and when the ultraviolet absorbent is the ultraviolet absorbent with hydroxyl, a catalyst with the hydroxyl molar number of 0.001-0.01 equivalent is required to be added for reaction;
(2) preparation of UV-resistant hydrophobic membrane material: uniformly mixing the UV-Si compound prepared in the step (1) with silicone oil and a solvent to obtain a UV-resistant hydrophobic membrane material, wherein the weight ratio of the UV-Si compound to the silicone oil to the solvent is (0.5-5): (0.5-5): (90-99).
2. The method of claim 1, wherein the hydrophobic UV-resistant membrane material is prepared by: the ultraviolet absorbent with hydroxyl in the step (1) is monohydroxy substituted benzophenone compound, dihydroxy substituted benzophenone compound, salicylate compound, piperidinol compound or benzotriazole compound; the ultraviolet absorbent with amino is a monoamino-substituted benzophenone compound or a diamino-substituted benzophenone compound.
3. The method of claim 2, wherein the hydrophobic UV-resistant membrane material is prepared by: the monohydroxy substituted benzophenone compound is 2-hydroxybenzophenone, 4-hydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone; the dihydroxy-substituted benzophenone compound is 2, 4-dihydroxy benzophenone or 4, 4-dihydroxy benzophenone; the salicylate compound is phenyl salicylate; the piperidinol compound is pentamethylpiperidinol; the benzotriazole compound is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; the monoamino substituted benzophenone compound is 2-aminobenzophenone or 4-aminobenzophenone or; the diamino substituted benzophenone compound is 2, 4-diaminobenzophenone or 4, 4-diaminobenzophenone.
4. The method of claim 1, wherein the hydrophobic UV-resistant membrane material is prepared by: the isocyanate silane coupling agent in the step (1) is 3-isocyanate propyl trimethoxy silane or 3-isocyanate propyl triethoxy silane; the catalyst is dibutyltin dilaurate; the solvent is tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, acetone or methyl ethyl ketone.
5. The method of claim 1, wherein the hydrophobic UV-resistant membrane material is prepared by: the silicone oil in the step (2) is methyl silicone oil, ethyl silicone oil, phenyl silicone oil or modified silicone oil, and the modified silicone oil is hydroxyl silicone oil, amino silicone oil or epoxy silicone oil.
6. The method of claim 1, wherein the hydrophobic UV-resistant membrane material is prepared by: the solvent in the step (2) is one or more of ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol dimethyl ether, ethyl acetate, butyl acetate, acetone and methyl ethyl ketone.
7. A UV-resistant hydrophobic membrane material prepared by the preparation method of any one of claims 1 to 6.
8. Use of the UV-resistant hydrophobic film material prepared by the preparation method of any one of claims 1-6 to form a film on the surface of a substrate.
9. The use of the UV-resistant hydrophobic film material according to claim 8 for forming a film on a substrate surface, characterized in that the film forming step is as follows: the UV-resistant hydrophobic membrane material is uniformly applied to the surface of a base material by adopting a dip coating, roll coating or spraying method, and then is heated and cured into a membrane at 50-150 ℃, wherein the curing time is 10-120 min.
10. Use of the UV-resistant hydrophobic film material according to claim 9 for forming a film on a substrate surface, characterized in that: the base material is a synthetic plastic material, a synthetic fiber material, natural wood or an inorganic material; the synthetic plastic material is PE, PP, PC or PMMA; the synthetic fiber material is PET or PA; the inorganic material is glass.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672055A (en) * | 2022-04-25 | 2022-06-28 | 江南大学 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
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| US20160347956A1 (en) * | 2015-05-27 | 2016-12-01 | Gaco Western, LLC | Dirt pick-up resistant silicone compositions |
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| GB1241236A (en) * | 1969-05-01 | 1971-08-04 | Owens Illinois Inc | Process of coating plastics with organopolysiloxanes and articles made thereby |
| JP2005343969A (en) * | 2004-06-01 | 2005-12-15 | Showa Techno Coat Kk | Ultraviolet light-shading coating |
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| US20160347956A1 (en) * | 2015-05-27 | 2016-12-01 | Gaco Western, LLC | Dirt pick-up resistant silicone compositions |
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