CN105780468A - 超疏水织物及其制备方法 - Google Patents
超疏水织物及其制备方法 Download PDFInfo
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- CN105780468A CN105780468A CN201610183381.0A CN201610183381A CN105780468A CN 105780468 A CN105780468 A CN 105780468A CN 201610183381 A CN201610183381 A CN 201610183381A CN 105780468 A CN105780468 A CN 105780468A
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- coupling agent
- fabric
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- hydrophobic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000007822 coupling agent Substances 0.000 claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- -1 titanate ester Chemical class 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 36
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229920004934 Dacron® Polymers 0.000 claims description 12
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- 239000003999 initiator Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical group CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 2
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 claims description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 2
- RTYRHAFIKFDTFQ-UHFFFAOYSA-N 1-dodecyl-2-propan-2-ylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(C)C RTYRHAFIKFDTFQ-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
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- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- QRPMCZNLJXJVSG-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl QRPMCZNLJXJVSG-UHFFFAOYSA-N 0.000 claims description 2
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
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- 240000002853 Nelumbo nucifera Species 0.000 description 2
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- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
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- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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Abstract
本发明公开了一种超疏水织物及其制备方法,属于超疏水技术领域。所述超疏水织物包括织物本体,所述织物本体的表面粘结有偶联剂耐磨层,所述偶联剂耐磨层的表面粘结有超疏水层,其中,所述偶联剂耐磨层含有偶联剂A,所述超疏水层为偶联剂B改性的纳米粒子层。本发明的所述超疏水织物含有偶联剂耐磨层和超疏水层,偶联剂耐磨层可以增加超疏水层的耐磨强度,使超疏水织物能够长效保持超疏水效果。
Description
技术领域
本发明涉及超疏水领域,特别是指一种适用于多种织物表面的超疏水织物及其制备方法。
背景技术
超疏水表面起源于自然界中的“荷叶效应”。对荷叶表面的研究发现,微纳米粗糙结构和低表面能物质的存在是超疏水表面的两个必要条件。目前,一般利用各类溶胶在织物表面形成微纳结构。例如中国专利申请CN101397754A通过将织物浸入二氧化硅溶胶,再进行烘干处理,最后通过低表面能物质修饰,从而制备超疏水棉织物;中国专利申请CN104594028A通过制备改性二氧化硅复合溶胶处理多元羧酸改性过的纤维素织物,从而直接在纤维素织物表面获得超疏水性。
另一种在织物表面获得微纳结构的方法是直接使用纳米颗粒在表面自堆积。然而,当利用这种方法处理织物时,纳米粒子仅仅通过颗粒堆积固着在织物表面,与织物的结合牢度差,经过多次水洗后,会脱离表面,从而导致织物丧失超疏水性能。因此,如何提高纳米粒子与织物间的结合牢度,制备出具有一定耐洗牢度的超疏水纺织品,是这一技术应用的关键。
目前,有几种思路解决这一问题。例如,中国专利申请CN104790202A通过在改性纳米粒子溶液中加入异氰酸酯,利用异氰酸根与织物表面羟基间的化学反应,增强结合牢度;但是,目前提出的这些方法都只能在特定类型的织物表面使用。例如上述的专利申请CN104790202A及CN104594028A只针对棉织物有效。
因此,寻找一种能够增强耐磨强度并适用于多种织物表面疏水处理的制备超疏水织物的方法。
发明内容
本发明要解决的技术问题是提供一种超疏水织物及其制备方法,该制备方法能够增强耐磨强度并适用于多种织物表面疏水处理。
为解决上述技术问题,本发明提供技术方案如下:
一方面,提供一种超疏水织物,包括织物本体,所述织物本体的表面粘结有偶联剂耐磨层,所述偶联剂耐磨层的表面粘结有超疏水层,其中,所述偶联剂耐磨层含有偶联剂A,所述超疏水层为偶联剂B改性的纳米粒子层。
本发明的所述超疏水织物含有偶联剂耐磨层和超疏水层,偶联剂耐磨层可以增加超疏水层的耐磨强度,使超疏水织物能够长效保持超疏水效果。
进一步地,所述偶联剂A为硅烷偶联剂或钛酸酯类的偶联剂中的一种或两种;所述偶联剂B为硅烷偶联剂或钛酸酯类的偶联剂中的一种或两种;
所述偶联剂A或偶联剂B中的硅烷偶联剂为环氧基系列的硅氧烷偶联剂、氨基系列的硅烷偶联剂、乙烯基系列硅烷偶联剂、烷基系列的硅烷偶联剂、氟硅烷系列的偶联剂所组成的组中的至少一种或几种。
所述偶联剂A或偶联剂B可以相同,也可以不同。
所述偶联剂A对织物有一定的选择性,优选地,所述偶联剂A为硅烷偶联剂,所述硅烷偶联剂为环氧基系列的硅氧烷偶联剂、氨基系列的硅烷偶联剂、乙烯基系列硅烷偶联剂所组成的组中的至少一种或几种。
进一步地,所述的环氧基系列的硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三乙氧基硅烷一种或多种;
所述的氨基系列的硅烷偶联剂选自γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、双[3-(三乙氧硅丙基)]胺、γ-氨丙基甲基二甲氧基硅烷或N-甲基-γ-氨丙基三甲氧基硅烷中的至少一种;
所述的乙烯基系列的硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三乙氧基硅烷中的至少一种;
所述的烷基系列偶联剂选自甲基三甲氧基硅烷、甲基三乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅氧烷、辛基三乙氧基硅氧烷、十二烷基三甲氧基硅氧烷、十二烷基三乙氧基硅氧烷、十六烷基三甲氧基硅氧烷、十六烷基三乙氧基硅氧烷、十八烷基三甲氧基硅氧烷、十八烷基三乙氧基硅氧烷、十二烷基三氯硅烷或十八烷基三氯硅烷中的至少一种;
所述的钛酸酯类的偶联剂选自异丙基三异酞酰钛酸酯、异丙基十二烷基苯磺酰钛酸酯、异丙基三(二辛基焦磷酸酯)钛酸酯、四异丙基双(二辛基亚磷酸酯)钛酸酯、四辛基双[二(十二烷)亚磷酸酯]钛酸酯、四(2,2-二烯丙氧甲基-1-丁基)双[二(十三烷基)亚磷酸酯]钛酸酯、双(二辛基焦磷酸酯)氧乙酸酯钛酸酯或双(二辛基焦磷酸酯)乙撑钛酸酯中的至少一种;
所述的氟硅烷系列的偶联剂选自十三氟辛基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷或全氟癸基三氯硅烷中的一种或多种。
进一步地,所述织物包括棉织物、尼龙织物、丙纶织物、聚酯纤维织物、羊毛织物、麻织物或混纺织物等。
另一方面,提供一种超疏水织物的制备方法,包括如下步骤:
1)所述偶联剂耐磨层的制备:将待处理的所述织物本体织物洗净,烘干,之后浸入到偶联剂A溶液中浸渍5min-5h,取出织物后自然晾干或者在一定温度下干燥使所述偶联剂A在所述织物本体表面形成偶联剂耐磨层,获得预处理织物;其中,所述偶联剂A溶液的浓度为0.1-50g/L,所述偶联剂溶液中含有0~0.1g/L的引发剂,所述偶联剂溶液的溶剂为溶剂A;
2)利用偶联剂B对纳米粒子进行改性:将纳米颗粒加入到溶剂B中,超声震荡条件下,30-150℃下恒温搅拌5min-5h;然后加入偶联剂B,在3min-2h内分批加入催化剂,保持溶液pH值为7.5~14,恒温搅拌1h–30h制得超疏水反应溶液;
3)超疏水层的制备:将所述超疏水反应溶液施加到所述预处理织物上,自然晾干或者在一定温度下干燥,焙烘后形成超疏水层。
本发明的制备方法为两步整理法,即首先对织物用偶联剂A进行预处理得到预处理织物,再用偶联剂B改性的纳米粒子溶液继续处理预处理织物,从而获得具有较高耐磨强度、能够长时间保持超疏水效果的超疏水织物;本发明的制备方法可以在常温下进行,也可以在一定温度范围内进行,条件温和,工艺简单,适合进行大面积涂布;本发明的制备方法不仅适用于多种织物的超疏水处理,而且更加耐磨,从而达到长效疏水的效果。
优选地,所述步骤1)中偶联剂的浓度为3-50g/L。
更优选地,所述步骤1)中偶联剂的浓度为10-40g/L。
其中,大部分织物在所述步骤1)中的搅拌时间可以为5min~1h。
优选地,步骤3)的浸渍时间为10min~3h。
进一步地,所述步骤2)中的超疏水反应溶液的各物质按质量百分比组成如下:
进一步地,所述纳米颗粒包括纳米银、纳米氧化锌、纳米氧化铁、纳米氧化铝、纳米氧化钛、纳米二氧化硅、纳米氧化锆中的一种或几种;所述纳米颗粒的粒径为5-500nm。
进一步地,所述催化剂为氢氧化钠、氨水、碳酸钠、碳酸氢钠中的一种或几种;所述溶剂B为甲苯、二甲苯、甲醇、乙醇、丁醇、丙酮、甲乙酮、丁酮、乙酸乙酯、乙酸正丁酯、乙酸叔丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、水中的一种或几种。
进一步地,所述步骤1)的干燥温度为室温~150℃;所述步骤3)的干燥温度为室温~150℃,所述焙烘温度为130~220℃,所述焙烘时间为20min~1s;所述步骤3)中施加方法为浸渍或喷涂。
优选地,所述干燥温度为室温~80℃,所述焙烘温度为150~180℃,所述焙烘时间为20min~1min。
进一步地,所述溶剂A为甲苯、二甲苯、甲醇、乙醇、丁醇、丙酮、甲乙酮、丁酮、乙酸乙酯、乙酸正丁酯、乙酸叔丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、水中的一种或几种;所述引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化二(2,4-二氯苯甲酰)、过氧化二乙酰、过氧化二辛酰和过氧化二月桂酰、过氧化特戊酸叔丁酯、过氧化二碳酸二异丁酯中的一种或几种。
综上所述,本发明的有益效果表现为:
1)本发明的所述超疏水织物含有偶联剂耐磨层和超疏水层,偶联剂耐磨层可以增加超疏水层的耐磨强度,使超疏水织物能够长效保持超疏水效果;
2)本发明的制备方法为两步整理法,即首先对织物用偶联剂A进行预处理得到预处理织物,再用偶联剂B改性的纳米粒子溶液继续处理预处理织物,从而获得具有较高耐磨强度、能够长时间保持超疏水效果的超疏水织物;
3)本发明的制备方法可以在常温下进行,也可以在一定温度范围内进行,条件温和,工艺简单,适合进行大面积涂布;
4)本发明的制备方法不仅适用于多种织物的超疏水处理,而且更加耐磨,从而达到长效疏水的效果。
具体实施方式
为使本发明的实施例要解决的技术问题、技术方案和优点更加清楚,下面将结合具体实施例进行详细描述。但本发明绝非限于这些例子。以下所述仅为本发明较好的实施例,仅仅用以解释本发明,并不能因此而理解为本发明专利范围的限制。应当指出的是,凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。因此,本发明专利的保护范围应以所附权利要求为准。
为了证实本发明所述的超疏水织物的疏水效果,本发明对疏水处理后的织物表面的拒水性能进行测试来判断本发明的超疏水织物的疏水效果,拒水性能的测试包括静态接触角和喷淋测试,喷淋测试参照AATCCTestMethod22-2010《纺织品拒水性能测试:喷淋测试》;静态接触角的测试方法选用影像分析法中的悬滴法,采用OCA15Puls接触角测试仪进行测量。
另外,为了进一步证实本发明所述的超疏水织物具有优异的耐磨性能,对超疏水处理后的织物进行洗涤(洗涤方法参照GB/T8629-2001方法5A),测静态接触角和喷淋测试评分,按相同方法洗涤,分别测试洗涤3次、5次后织物表面的静态接触角,并进行喷淋测试。
本发明部分实施例如下:
实施例一
将棉织物清洗干净,漂洗烘干,浸渍到5g/L的γ-氨丙基三甲氧基硅烷的乙醇溶液中2min,80℃烘干待用;将2g粒径为120nm的纳米二氧化硅加入到93g乙醇中,超声波震荡15min,60℃恒温搅拌2h,加入4g十八烷基三甲氧基硅氧烷,继续搅拌,缓慢加入2mL氨水,搅拌20h。将处理后的棉织物加入到此溶液中,浸渍30min,80℃烘干,170℃焙烘1min,得到超疏水的棉织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表1。
表1.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法对麻织物、羊毛织物、聚酯纤维织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的棉织物的疏水性能相当。
实施例二
将尼龙织物清洗干净,漂洗烘干,浸渍到3g/L的γ-缩水甘油醚氧丙基三甲氧基硅烷的丙酮溶液中20min,80℃烘干待用;将3g粒径为50nm的纳米二氧化硅加入到90g丙酮中,超声波震荡20min,50℃恒温搅拌2h,加入6g十六烷基三乙氧基硅氧烷,继续搅拌,缓慢加入2mL氨水,搅拌20h。将处理后的尼龙织物加入到此溶液中,浸渍30min,晾干,150℃焙烘5min,得到耐久超疏水尼龙织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表2。
表2.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法棉织物、聚酯纤维织物、羊毛织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的尼龙织物的疏水性能相当。
实施例三
将聚酯纤维织物清洗干净,漂洗烘干,浸渍到3g/L的γ-氨丙基甲基二甲氧基硅烷的甲苯溶液中15min,80℃烘干待用;将10g粒径为100纳米的纳米二氧化钛加入到75g丙酮中,超声波震荡30min,50℃恒温搅拌2h,加入15g十八烷基三乙氧基硅氧烷,继续搅拌,缓慢加入0.5g碳酸钠,搅拌20h。将处理后的聚酯纤维加入到此溶液中,浸渍30min,80℃烘干,180℃焙烘30s,得到耐久超疏水聚酯纤维织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表3。
表3.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法对棉麻织物、尼龙织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的聚酯纤维织物的疏水性能相当。
实施例四
将羊毛纤维织物清洗干净,漂洗烘干,浸渍到30g/L的双[3-(三乙氧硅丙基)]胺的乙酸乙酯溶液中5min,70℃烘干待用;将5g粒径为25纳米的纳米二氧化钛加入到85g二甲苯中,超声波震荡30min,80℃恒温搅拌5h,加入10g辛基三乙氧基硅烷,继续搅拌,缓慢加入1.5mL氨水,搅拌19h。将处理后的羊毛纤维加入到此溶液中,浸渍30min,80℃烘干,165℃焙烘2min,得到耐久超疏水羊毛纤维织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表4。
表4.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法对聚酯纤维织物、尼龙织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的羊毛织物的疏水性能相当。
实施例五
将丙纶织物清洗干净,漂洗烘干,浸渍到20g/L的γ-甲基丙烯酰氧基丙基三甲氧基硅烷以及0.02g/L引发剂的甲苯溶液中,室温保持3h,80℃烘干待用;将5g粒径为50nm的纳米二氧化硅加入到89g乙醇中,超声波震荡15min,60℃恒温搅拌2h,加入6g十三氟辛基三甲氧基硅烷,继续搅拌,缓慢加入1mL氨水,搅拌20h。将处理后的丙纶织物加入到此溶液中,浸渍30min,80℃烘干,150℃焙烘10min,得到超疏水的丙纶织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表5。
表5.各洗涤次数下的织物静态接触角及喷淋测试评分
实施例六
将羊毛纤维织物清洗干净,漂洗烘干,浸渍到8g/LN-甲基-γ-氨丙基三甲氧基硅烷、5g/Lγ-缩水甘油醚氧丙基三乙氧基硅烷、10g/L乙烯基三甲氧基硅烷以及0.01g/L引发剂的丙酮溶液中,40℃保持0.5h,80℃烘干待用;将5g粒径为20nm的纳米二氧化硅加入到87g丁醇中,超声波震荡20min,70℃恒温搅拌2h,加入7g丙基三乙氧基硅烷,继续搅拌,缓慢加入1mL氨水,搅拌18h。将处理后的羊毛纤维织物加入到此溶液中,浸渍40min,80℃烘干,150℃焙烘20min,得到超疏水的羊毛纤维织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表6。
表6.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法对棉麻织物、尼龙织物、聚酯纤维织物、丙纶织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的羊毛织物的疏水性能相当。
实施例七
将聚酰胺织物清洗干净,漂洗烘干,浸渍到10g/Lγ-氨丙基三乙氧基硅烷、8g/Lγ-缩水甘油醚氧丙基三甲氧基硅烷、2g/L异丙基十二烷基苯磺酰酞酸酯的乙酸乙酯溶液中,50℃保持40min,100℃烘干待用;将5g粒径为30nm的纳米氧化铝加入到85g丁醇中,超声波震荡30min,70℃恒温搅拌20min,加入10g十六烷基三甲氧基硅烷,继续搅拌,缓慢加入0.1g氢氧化钠,搅拌12h。将处理后的聚酰胺纤维织物加入到此溶液中,浸渍1h,150℃烘干,得到超疏水的聚酰胺织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表7。
表7.各洗涤次数下的织物静态接触角及喷淋测试评分
通过本实施例的制备方法对棉麻织物、丙纶织物、羊毛织物、聚酯纤维织物、混纺织物等进行超疏水处理,获得的超疏水织物的超疏水性能及耐磨性能与上述超疏水处理的羊毛织物的疏水性能相当。
上述实施例表明,本发明的制备方法不仅适用于多种织物的超疏水处理,而且更加耐磨,从而达到长效疏水的效果。
本发明的偶联剂耐磨层中的偶联剂A也可以选用本发明未述及的其他偶联剂,耐磨效果与本发明选用的偶联剂相比,相对较低。
本发明的超疏水织物也可以选择本领域常规的浸渍方法在织物本体上粘结偶联剂耐磨层和超疏水层,最后制得的超疏水织物的耐磨强度相对较低。
对比例一
将聚酯纤维织物清洗干净,漂洗烘干;将10g粒径为100纳米的纳米二氧化钛加入到75g丙酮中,超声波震荡30min,50℃恒温搅拌2h,加入15g十八烷基三乙氧基硅氧烷,继续搅拌,缓慢加入2mL氨水,搅拌20h;将干净的聚酯纤维加入到此溶液中,浸渍30min,80℃烘干,150度焙烘5min,得到超疏水聚酯纤维织物,测量其静态接触角和喷淋测试评分,同时进行洗涤实验并测量,测量结果见表8。
表8.各洗涤次数下的织物静态接触角及喷淋测试评分
本对比例制备的超疏水织物在经过3次洗涤后,其表面的超疏水涂层就受到了破坏,不能持久疏水。
因此,本发明的所述超疏水织物含有偶联剂耐磨层和超疏水层,偶联剂耐磨层可以增加超疏水层的耐磨强度,使超疏水织物能够长效保持超疏水效果;本发明的制备方法为两步整理法,即首先对织物用偶联剂A进行预处理得到预处理织物,再用偶联剂B改性的纳米粒子溶液继续处理预处理织物,从而获得具有较高耐磨强度、能够长时间保持超疏水效果的超疏水织物;本发明的制备方法可以在常温下进行,也可以在一定温度范围内进行,条件温和,工艺简单,适合进行大面积涂布;本发明的制备方法不仅适用于多种织物的超疏水处理,而且更加耐磨,从而达到长效疏水的效果。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种超疏水织物,包括织物本体,其特征在于,所述织物本体的表面粘结有偶联剂耐磨层,所述偶联剂耐磨层的表面粘结有超疏水层,其中,所述偶联剂耐磨层含有偶联剂A,所述超疏水层为偶联剂B改性的纳米粒子层。
2.根据权利要求1所述的超疏水织物,其特征在于,所述偶联剂A为硅烷偶联剂或钛酸酯类的偶联剂中的一种或两种;所述偶联剂B为硅烷偶联剂或钛酸酯类的偶联剂中的一种或两种;
所述偶联剂A或偶联剂B中的硅烷偶联剂为环氧基系列的硅氧烷偶联剂、氨基系列的硅烷偶联剂、乙烯基系列硅烷偶联剂、烷基系列的硅烷偶联剂、氟硅烷系列的偶联剂所组成的组中的至少一种或几种。
3.根据权利要求2所述的超疏水织物,其特征在于,所述的环氧基系列的硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三乙氧基硅烷一种或多种;
所述的氨基系列的硅烷偶联剂选自γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、双[3-(三乙氧硅丙基)]胺、γ-氨丙基甲基二甲氧基硅烷或N-甲基-γ-氨丙基三甲氧基硅烷中的至少一种;
所述的乙烯基系列的硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三乙氧基硅烷中的至少一种;
所述的烷基系列偶联剂选自甲基三甲氧基硅烷、甲基三乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅氧烷、辛基三乙氧基硅氧烷、十二烷基三甲氧基硅氧烷、十二烷基三乙氧基硅氧烷、十六烷基三甲氧基硅氧烷、十六烷基三乙氧基硅氧烷、十八烷基三甲氧基硅氧烷、十八烷基三乙氧基硅氧烷、十二烷基三氯硅烷或十八烷基三氯硅烷中的至少一种;
所述的钛酸酯类的偶联剂选自异丙基三异酞酰钛酸酯、异丙基十二烷基苯磺酰钛酸酯、异丙基三(二辛基焦磷酸酯)钛酸酯、四异丙基双(二辛基亚磷酸酯)钛酸酯、四辛基双[二(十二烷)亚磷酸酯]钛酸酯、四(2,2-二烯丙氧甲基-1-丁基)双[二(十三烷基)亚磷酸酯]钛酸酯、双(二辛基焦磷酸酯)氧乙酸酯钛酸酯或双(二辛基焦磷酸酯)乙撑钛酸酯中的至少一种;
所述的氟硅烷系列的偶联剂选自十三氟辛基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷或全氟癸基三氯硅烷中的一种或多种。
4.根据权利要求1至3任一所述的超疏水织物,其特征在于,所述织物包括棉织物、尼龙织物、丙纶织物、聚酯纤维织物、羊毛织物、麻织物或混纺织物。
5.一种权利要求1至4任一所述的超疏水织物的制备方法,其特征在于,包括如下步骤:
1)所述偶联剂耐磨层的制备:将待处理的所述织物本体织物洗净,烘干,之后浸入到偶联剂A溶液中浸渍5min-5h,取出织物后自然晾干或者在一定温度下干燥使所述偶联剂A在所述织物本体表面形成偶联剂耐磨层,获得预处理织物;其中,所述偶联剂A溶液的浓度为0.1-50g/L,所述偶联剂溶液中含有0~0.1g/L的引发剂,所述偶联剂溶液的溶剂为溶剂A;
2)利用偶联剂B对纳米粒子进行改性:将纳米颗粒加入到溶剂B中,超声震荡条件下,30-150℃下恒温搅拌5min-5h;然后加入偶联剂B,在3min-2h内分批加入催化剂,保持溶液pH值为7.5~14,恒温搅拌1h–30h制得超疏水反应溶液;
3)超疏水层的制备:将所述超疏水反应溶液施加到所述预处理织物上,自然晾干或者在一定温度下干燥,焙烘后形成超疏水层。
6.根据权利要求5所述的制备方法,其特征在于,所述步骤2)中的超疏水反应溶液的各物质按质量百分比组成如下:
7.根据权利要求6所述的制备方法,其特征在于,所述纳米颗粒包括纳米银、纳米氧化锌、纳米氧化铁、纳米氧化铝、纳米氧化钛、纳米二氧化硅、纳米氧化锆中的一种或几种;所述纳米颗粒的粒径为5-500nm。
8.根据权利要求5所述的制备方法,其特征在于,所述催化剂为氢氧化钠、氨水、碳酸钠、碳酸氢钠中的一种或几种;所述溶剂B为甲苯、二甲苯、甲醇、乙醇、丁醇、丙酮、甲乙酮、丁酮、乙酸乙酯、乙酸正丁酯、乙酸叔丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、水中的一种或几种。
9.根据权利要求5所述的制备方法,其特征在于,所述步骤1)的干燥温度为室温~150℃;所述步骤3)的干燥温度为室温~150℃,所述焙烘温度为130~220℃,所述焙烘时间为30min~1s;所述步骤3)中施加方法为浸渍或喷涂。
10.根据权利要求5至9任一所述的制备方法,其特征在于,所述溶剂A为甲苯、二甲苯、甲醇、乙醇、丁醇、丙酮、甲乙酮、丁酮、乙酸乙酯、乙酸正丁酯、乙酸叔丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、水中的一种或几种;
所述引发剂为:偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化二(2,4-二氯苯甲酰)、过氧化二乙酰、过氧化二辛酰和过氧化二月桂酰、过氧化特戊酸叔丁酯、过氧化二碳酸二异丁酯等中的一种或几种。
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