CN114262485B - Modified high polymer material and preparation method and application thereof - Google Patents
Modified high polymer material and preparation method and application thereof Download PDFInfo
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- CN114262485B CN114262485B CN202210200039.2A CN202210200039A CN114262485B CN 114262485 B CN114262485 B CN 114262485B CN 202210200039 A CN202210200039 A CN 202210200039A CN 114262485 B CN114262485 B CN 114262485B
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- 239000002861 polymer material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 88
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 69
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011737 fluorine Substances 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 polypropylene Polymers 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 150000001343 alkyl silanes Chemical class 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 4
- UIQCRIFSBWGDTQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F UIQCRIFSBWGDTQ-UHFFFAOYSA-N 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical compound FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229960001631 carbomer Drugs 0.000 claims description 2
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 2
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 abstract description 7
- 240000002853 Nelumbo nucifera Species 0.000 abstract description 5
- 235000006508 Nelumbo nucifera Nutrition 0.000 abstract description 5
- 235000006510 Nelumbo pentapetala Nutrition 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 18
- 230000006872 improvement Effects 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 239000002077 nanosphere Substances 0.000 description 8
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- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920000891 common polymer Polymers 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
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- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YDWFEBCFKZDCTM-UHFFFAOYSA-N hexadecyl(silyloxysilyloxysilyloxysilyloxysilyloxysilyloxy)silane Chemical compound C(CCCCCCCCCCCCCCC)[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH3] YDWFEBCFKZDCTM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a modified high polymer material and a preparation method and application thereof, belonging to the technical field of high polymer materials. The method comprises the following steps: s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing nano microspheres; s2. modified SiO2Preparing nano microspheres; and S3, preparing the modified high polymer material. The modified high polymer material prepared by the invention has a lotus leaf-like structure, the surface of the high polymer material has a micro-nano secondary coarse structure which is a small bulge caused by modified silicon dioxide microspheres, and meanwhile, the upper surface of the layer of micro-nano structure is also provided with a layer of fluorine-containing group with low surface energy (comprising copolymerized fluorine-containing polyacrylate on a polypropylene molecular chain and the fluorine-containing group on the surface of the modified silicon dioxide microspheres), so that an ultra-hydrophobic structure is formed, and the ultra-hydrophobic structure is applied to a pipette tip and has extremely low liquid adsorbability, so that the accuracy of the pipette is further improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified high polymer material and a preparation method and application thereof.
Background
Materials with very low surface free energy can exhibit a number of excellent properties such as outstanding stain resistance, weatherability, high heat resistance, and high acid and alkali resistance. Can be widely applied to the fields of water-proof oil-proof antifouling treatment and the like in industrial production. Fluoropolymers and silicones are representative materials of two classes of materials with extremely low surface energy. Among them, fluorine in the fluoropolymer has the highest electronegativity among all elements, and the radius of van der waals atom is the smallest except hydrogen, the polarizability of fluorine atom is the lowest, the bond energy of the single bond formed by fluorine atom and carbon atom is the highest compared with the bond energy of the single bond formed by carbon atom and other atoms, and the bond length is short, and fluorine atom and carbon atom can form a very strong covalent bond. And the other low surface free energy substance siloxane is also called organosilicon material, is a special high molecular material with a semi-organic semi-inorganic structure and has unique excellent performance. Because of the characteristics of the organosilicon material, the organosilicon component in the organosilicon additive is compatible and different with the C-C chain of the plastic substrate, so that the organosilicon additive can be mixed with the plastic substrate to play a specific role, can not be completely submerged and assimilated by the polymer substrate to lose effectiveness, and can achieve an obvious improvement effect by adding a small amount of organosilicon additive.
Although the fluoropolymer has many excellent properties, the processing is difficult, and the price is higher than that of the common polymer, so how to exert the advantages of both the fluoropolymer and the common polymer and overcome the disadvantages of both the fluoropolymers and the common polymer is a hot spot and a difficult point of current research.
While the application of silicone materials in the plastics processing industry started in the early 20 th 70 s, silicone oil was originally used as an internal lubricant and a release agent for polyolefin injection molding, and due to incompatibility between silicone oil and polyolefin, liquid silicone with low molar mass migrates to the surface of plastic parts and spreads out, which greatly hinders the application of such silicone oil to plastics. Therefore, the development of a novel organosilicon material and the application of the organosilicon material as a plastic processing aid are a research hotspot of the plastic processing aid industry at present.
In patent CN105860120A, isotactic polypropylene-b-polyethylene glycol diblock copolymer is used as a surface modifier, and a micro-nano composite structure is constructed on the surface of a polypropylene film, so that the material has a super-hydrophobic characteristic; however, the method aims at polypropylene film materials, and has the disadvantages of high technical difficulty, high cost and difficulty in meeting the requirements of industrial production.
In patent CN107163389A, a fluorine-containing aid and silicone masterbatch are added to polypropylene to obtain a material with high hydrophobic property, and although the obtained material has high hydrophobic property, the requirements of odor, flame retardancy, etc. are not considered, so the application of the material in the industry is limited.
Disclosure of Invention
The invention aims to provide a modified high polymer material and a preparation method and application thereof, wherein the modified high polymer material has a lotus leaf-like structure, a micro-nano secondary coarse structure exists on the surface of the high polymer material and is a small bulge caused by modified silicon dioxide microspheres, meanwhile, a layer of fluorine-containing group with low surface energy (comprising copolymerized fluorine-containing polyacrylate on a polypropylene molecular chain and the fluorine-containing group on the surface of the modified silicon dioxide microspheres) is also arranged on the upper surface of the micro-nano structure, so that a super-hydrophobic structure is formed, the water contact angle of the modified high polymer material is more than 160 degrees, the n-hexadecane contact angle is more than 85 degrees, and the modified high polymer material has extremely low liquid adsorption when being applied to a pipette tip, so that the precision of the pipette is further improved.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a modified high polymer material, which comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving aminosilane, fluorine-containing silane and long-chain alkyl silane in a first solvent, and uniformly mixing to obtain an oil phase; dripping aqueous solution containing surfactant into the oil phase, emulsifying, stirring for reaction, centrifugally washing and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: SiO prepared in the step S1 and having the surface containing fluorine and long-chain alkyl chain2Adding the nano-microspheres into an ethanol aqueous solution of a silane coupling agent containing double bonds, and heating for reaction to obtain modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: dissolving fluorine-containing acrylate and an initiator in a second solvent, and adding the modified SiO prepared in the step S22And (3) uniformly dispersing the nano microspheres, and performing melt reaction with polypropylene to extrude and granulate to obtain the modified high polymer material.
As a further improvement of the invention, the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane; the fluorine-containing silane is selected from at least one of 1H,1H,2H, 2H-perfluorodecyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, 3,3, 3-trifluoropropylmethyldimethoxysilane, 3, 3-trifluoropropyltrimethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane or 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane; the long-chain alkyl silane is selected from at least one of octadecyl siloxane, hexadecyl heptasiloxane, dodecyl trimethoxy silane and hexadecyl trimethyl siloxane; the first solvent is at least one selected from toluene, xylene, petroleum ether, ethyl acetate, methyl acetate, dichloromethane, trichloromethane and chloroform; the surfactant is at least one selected from tween-80, span-80, carbomer, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate and sodium octadecyl benzene sulfonate.
As a further improvement of the invention, the mass ratio of the aminosilane, the fluorine-containing silane and the long-chain alkyl silane in the step S1 is 10: (2-5): (1-3); the content of the surfactant in the aqueous solution containing the surfactant is 2-5 wt%; the emulsification condition is emulsification for 3-7min at the rotating speed of 10000-15000r/min, and the stirring reaction condition is reaction for 5-7h at the rotating speed of 500-1000 r/min.
In a further improvement of the present invention, the double bond-containing silane coupling agent is at least one selected from the group consisting of KH570, a171, a172, and a 151.
As a further improvement of the invention, the content of the double bond-containing silane coupling agent in the ethanol aqueous solution of the double bond-containing silane coupling agent in step S2 is 3-5wt%, the content of ethanol is 40-60wt%, and the balance is water; the SiO with the surface containing fluorine and long-chain alkyl chain2The mass-volume ratio of the nano-microspheres to the double-bond-containing silane coupling agent ethanol solution is 1: (2-5) g/mL; the heating reaction condition is that the reaction is carried out for 3 to 5 hours at the temperature of between 70 and 90 ℃.
As a further improvement of the present invention, the fluorine-containing acrylate is at least one selected from trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate and heptadecafluorodecyl methacrylate; the initiator is selected from at least one of benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and cyclohexanone peroxide; the second solvent is at least one selected from acetone, acetonitrile, tetrahydrofuran, diethyl ether, ethyl acetate, methyl acetate, petroleum ether and ethanol.
As a further improvement of the invention, the polypropylene, the fluorine-containing acrylate and the modified SiO in the step S32The mass ratio of the nano microspheres to the initiator is 100: (7-12): (10-20): (0.1-1).
As a further improvement of the invention, the melting reaction temperature in the step S3 is 200-220 ℃, and the reaction lasts for 2-4 h; the equipment for the melt reaction is a co-rotating twin-screw extruder.
The invention further protects the modified high polymer material prepared by the preparation method.
The invention further protects the application of the modified high polymer material in preparing the pipette tip.
The invention has the following beneficial effects:
the invention contains SiO with fluorine and long-chain alkyl chain on the surface2In the preparation process of the nano microsphere, after the amino silane, the fluorine-containing silane and the long-chain alkyl silane are dissolved in the oil phase, water containing a surfactant is added, and the mixture is dispersed into water-in-oil droplets in the emulsification and stirring process, and with the reaction, the amino part is protonated to become amphiphilic molecules, so that the silane droplets are further stabilized, as shown in figure 1. Meanwhile, the protonation of amino groups provides an alkaline environment, and the silane is catalyzed to generate sol-gel reaction to form the stable silicon dioxide nano microspheres. At this time, the hydrophobic long-chain alkyl part and the hydrophobic fluorine-containing part spontaneously face the outside of the shell due to hydrophobicity, so that the silica nanosphere with the outer surface of the long-chain alkyl group and the fluorine-containing group is prepared. Furthermore, the surface of the nanosphere is coupled with partial double-bond-containing silane coupling agent under the modification action of the double-bond-containing silane coupling agent, so that the surface of the microsphere is provided with double bondsBonding groups to obtain the modified silicon dioxide nano-microsphere; further, the fluorine-containing acrylate, the modified silica nano-microspheres and the polypropylene are subjected to copolymerization reaction under the action of an initiator, so that the fluorine-containing polyacrylate and the modified silica nano-microspheres are connected to a polypropylene chain, and long-chain alkyl chains on the surfaces of the modified silica nano-microspheres can be intertwined with the polypropylene molecular chains, so that the self-polymerization of the microspheres is further reduced, and the microspheres are uniformly dispersed in the polypropylene resin, and the prepared modified high polymer material is obtained.
The modified high polymer material prepared by the invention has a lotus leaf-like structure, the surface of the high polymer material has a micro-nano secondary coarse structure which is a small bulge caused by modified silicon dioxide microspheres, meanwhile, the upper surface of the layer of micro-nano structure is provided with a layer of fluorine-containing group with low surface energy (comprising copolymerized fluorine-containing polyacrylate on a polypropylene molecular chain and the fluorine-containing group on the surface of the modified silicon dioxide microspheres), so that an ultrahydrophobic structure is formed, the water contact angle of the modified high polymer material is more than 160 degrees, the n-hexadecane contact angle is more than 85 degrees, and the modified high polymer material has extremely low liquid adsorbability when applied to a pipette tip, so that the precision of the pipette tip is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows a modified SiO of the present invention2The preparation of the nano-microsphere and the interaction with the polypropylene are schematically shown;
FIG. 2 shows a modified SiO solid obtained in example 1 of the present invention2SEM image of nanospheres.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polypropylene is iPP, F401, powder, and is purchased from Yangzi petroleum chemical industry Co.
Example 1
The embodiment provides a preparation method of a modified polymer material, which comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g of N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, 2g of 1H,1H,2H, 2H-perfluorodecyltrimethoxysilane and 1g of dodecyltrimethoxysilane in 50mL of dichloromethane, and uniformly mixing to obtain an oil phase; dripping 30mL of aqueous solution containing 2wt% of tween-80 into the oil phase, emulsifying for 3min at the rotating speed of 10000r/min, reacting for 5h at the rotating speed of 500r/min, centrifugally washing, and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding the nano-microspheres into 20mL of ethanol aqueous solution of silane coupling agent A151 (the content of the silane coupling agent A151 is 3wt%, the content of ethanol is 40wt%, and the balance is water), and reacting for 3h at 70 ℃ to obtain modified SiO2Nano-microspheres, FIG. 2 shows modified SiO prepared in this example2The SEM image of the nano-microsphere shows that the particle size of the microsphere is between 100 nm and 400 nm;
s3, preparing a modified high polymer material: 7g of heptadecafluorodecyl methacrylate and 0.1g of lauroyl peroxide were dissolved in 50mL of methyl acetate, and 10g of the modified SiO prepared in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 200 ℃ for 2h, and carrying out extrusion granulation to obtain the modified high polymer material.
Example 2
The embodiment provides a preparation method of a modified polymer material, which comprises the following steps:
s1. surface containsFluorine and long alkyl chain SiO2Preparing the nano microspheres: dissolving 10g of gamma-aminopropyltrimethoxysilane, 5g of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane and 3g of hexadecyl trimethylsiloxane in 50mL of petroleum ether, and uniformly mixing to obtain an oil phase; dripping 30mL of aqueous solution containing 5wt% of sodium hexadecyl sulfate into the oil phase, emulsifying for 7min at the rotating speed of 15000r/min, reacting for 7h at the rotating speed of 1000r/min, centrifugally washing, and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding 50mL of ethanol aqueous solution of silane coupling agent KH570 (the content of the silane coupling agent KH570 is 5wt%, the content of ethanol is 60wt%, and the balance is water) into the nano-microspheres, and reacting for 5h at 90 ℃ to obtain modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: 12g of dodecafluoroheptyl methacrylate and 1g of t-butyl benzoylperoxide were dissolved in 50mL of tetrahydrofuran, and 20g of the modified SiO prepared in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 220 ℃ for 4h, and carrying out extrusion granulation to obtain the modified high polymer material.
Example 3
The embodiment provides a preparation method of a modified polymer material, which comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3.5g of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane and 2g of octadecylsiloxane in 50mL of ethyl acetate, and uniformly mixing to obtain an oil phase; dropwise adding 30mL of aqueous solution containing 3.5wt% of sodium octadecyl sulfonate into the oil phase, emulsifying for 5min at the rotating speed of 12500r/min, reacting for 6h at the rotating speed of 700r/min, centrifugally washing, and drying to obtain SiO containing fluorine and long-chain alkyl chain on the surface2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding 35mL of silane coupling agent A17 into the nano microspheres1 (the content of the silane coupling agent A171 is 4wt percent, the content of the ethanol is 50wt percent, and the balance is water) in an ethanol aqueous solution, and the reaction is carried out for 4 hours at the temperature of 80 ℃ to obtain the modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: 10g of trifluoroethyl methacrylate and 0.5g of t-butyl hydroperoxide were dissolved in 50mL of acetone, and 15g of the modified SiO obtained in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 210 ℃ for 3h, and carrying out extrusion granulation to obtain the modified high polymer material.
Comparative example 1
Compared with the example 3, 1H,2H, 2H-perfluorooctyltrimethoxysilane is not added, and other conditions are not changed.
The method comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 5.5g of octadecylsiloxane in 50mL of ethyl acetate, and uniformly mixing to obtain an oil phase; dripping 30mL of aqueous solution containing 3.5wt% of sodium octadecyl sulfonate into the oil phase, emulsifying for 5min at the rotating speed of 12500r/min, reacting for 6h at the rotating speed of 700r/min, centrifuging, washing and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding 35mL of ethanol aqueous solution of silane coupling agent A171 (the content of silane coupling agent A171 is 4wt%, the content of ethanol is 50wt%, and the balance is water) into the nano-microspheres, and reacting for 4h at 80 ℃ to obtain modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: 10g of trifluoroethyl methacrylate and 0.5g of t-butyl hydroperoxide were dissolved in 50mL of acetone, and 15g of the modified SiO obtained in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 210 ℃ for 3h, and carrying out extrusion granulation to obtain the modified high polymer material.
Comparative example 2
In comparison with example 3, no octadecylsiloxane was added, and the other conditions were unchanged.
The method comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 5.5g of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane in 50mL of ethyl acetate, and uniformly mixing to obtain an oil phase; dripping 30mL of aqueous solution containing 3.5wt% of sodium octadecyl sulfonate into the oil phase, emulsifying for 5min at the rotating speed of 12500r/min, reacting for 6h at the rotating speed of 700r/min, centrifuging, washing and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding 35mL of ethanol aqueous solution of silane coupling agent A171 (the content of silane coupling agent A171 is 4wt%, the content of ethanol is 50wt%, and the balance is water) into the nano-microspheres, and reacting for 4h at 80 ℃ to obtain modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: 10g of trifluoroethyl methacrylate and 0.5g of t-butyl hydroperoxide were dissolved in 50mL of acetone, and 15g of the modified SiO obtained in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 210 ℃ for 3h, and carrying out extrusion granulation to obtain the modified high polymer material.
Comparative example 3
Step S2 was not performed, and other conditions were not changed, as compared with example 3.
The method comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3.5g of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane and 2g of octadecylsiloxane in 50mL of ethyl acetate, and uniformly mixing to obtain an oil phase; dropwise adding 30mL of aqueous solution containing 3.5wt% of sodium octadecyl sulfonate into the oil phase, emulsifying for 5min at the rotating speed of 12500r/min, reacting for 6h at the rotating speed of 700r/min, centrifugally washing, and drying to obtain SiO containing fluorine and long-chain alkyl chain on the surface2Nano-microspheres;
s2. modified PolymerPreparation of the material: 10g of trifluoroethyl methacrylate and 0.5g of t-butyl hydroperoxide were dissolved in 50mL of acetone, and 15g of SiO prepared in step S1 and having a surface containing fluorine and a long-chain alkyl chain was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 100g of polypropylene at 210 ℃ for 3h, and carrying out extrusion granulation to obtain the modified high polymer material.
Comparative example 4
In comparison with example 3, no trifluoroethyl methacrylate was added, and the other conditions were not changed.
The method comprises the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving 10g N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3.5g of 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane and 2g of octadecylsiloxane in 50mL of ethyl acetate, and uniformly mixing to obtain an oil phase; dropwise adding 30mL of aqueous solution containing 3.5wt% of sodium octadecyl sulfonate into the oil phase, emulsifying for 5min at the rotating speed of 12500r/min, reacting for 6h at the rotating speed of 700r/min, centrifugally washing, and drying to obtain SiO containing fluorine and long-chain alkyl chain on the surface2Nano-microspheres;
s2. modified SiO2Preparing the nano microspheres: 10g of SiO prepared in step S1 and having a surface containing fluorine and long-chain alkyl chains2Adding 35mL of ethanol aqueous solution of silane coupling agent A171 (the content of silane coupling agent A171 is 4wt%, the content of ethanol is 50wt%, and the balance is water) into the nano-microspheres, and reacting for 4h at 80 ℃ to obtain modified SiO2Nano-microspheres;
s3, preparing a modified high polymer material: 0.5g of tert-butyl hydroperoxide was dissolved in 50mL of acetone, and 15g of the modified SiO obtained in step S2 was added2And (3) carrying out ultrasonic dispersion on the nano microspheres at 1000W for 30min, carrying out melt reaction on the nano microspheres and 110g of polypropylene at 210 ℃ for 3h, and carrying out extrusion granulation to obtain the modified high polymer material.
Test example 1
The modified polymer materials obtained in examples 1 to 3 of the present invention and comparative examples 1 to 4 were subjected to a performance test, and the results are shown in Table 1.
TABLE 1
As can be seen from the above table, the modified polymer materials prepared in embodiments 1-3 of the present invention have good mechanical properties and hydrophobic and oleophobic properties.
Compared with example 3, the hydrophobic and oleophobic performance of comparative example 1 is obviously reduced without adding 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane, and the fluorine-containing surface obviously promotes the hydrophobic and oleophobic performance. The prepared modified high polymer material has a lotus leaf-like structure, the surface of the high polymer material has a micro-nano secondary coarse structure which is a small bulge caused by modified silicon dioxide microspheres, and meanwhile, the upper surface of the layer of micro-nano structure is provided with a layer of fluorine-containing group with low surface energy (including copolymerized fluorine-containing polyacrylate on a polypropylene molecular chain and the fluorine-containing group on the surface of the modified silicon dioxide microspheres), so that a super-hydrophobic structure is formed.
Compared with the embodiment 3, the modified silicon dioxide nano microsphere has the advantages that the mechanical property is obviously reduced because octadecyl siloxane is not added, the long-chain alkyl chain on the surface of the modified silicon dioxide nano microsphere can be intertwined with the polypropylene molecular chain, the self-polymerization of the microsphere is reduced, and the microsphere is uniformly dispersed in polypropylene resin, so that the prepared modified high polymer material has the advantage of improving the mechanical property of the material.
Compared with the embodiment 3, the step S2 is not carried out, the mechanical property is obviously reduced, the surface of the nanosphere is coupled with part of the double-bond-containing silane coupling agent under the modification action of the double-bond-containing silane coupling agent, so that double-bond groups are carried on the microsphere surface, the modified silica nanosphere is obtained, the modified silica nanosphere and the polypropylene have copolymerization reaction under the action of the initiator, the fluorine-containing polyacrylate and the modified silica nanosphere are connected on the polypropylene chain, the modified silica nanosphere can not agglomerate, and the mechanical property of the material is improved.
Compared with the embodiment 3, the hydrophobic and oleophobic performance of the modified polymer material is obviously reduced without adding trifluoroethyl methacrylate, so that the prepared modified polymer material has a lotus leaf-like structure, the surface of the polymer material has a micro-nano secondary coarse structure and small bulges caused by modified silica microspheres, and meanwhile, the upper surface of the micro-nano structure is provided with a layer of fluorine-containing group with low surface energy (including copolymerized fluorine-containing polyacrylate on a polypropylene molecular chain and fluorine-containing group on the surface of the modified silica microspheres), thereby forming a super-hydrophobic structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The preparation method of the modified high polymer material is characterized by comprising the following steps:
s1, SiO with surface containing fluorine and long-chain alkyl chain2Preparing the nano microspheres: dissolving aminosilane, fluorine-containing silane and long-chain alkyl silane in a first solvent, and uniformly mixing to obtain an oil phase; dripping aqueous solution containing surfactant into the oil phase, emulsifying, stirring for reaction, centrifugally washing and drying to obtain SiO with the surface containing fluorine and long-chain alkyl chain2Nano-microspheres; the mass ratio of the aminosilane to the fluorine-containing silane to the long-chain alkyl silane is 10: (2-5): (1-3); the content of the surfactant in the aqueous solution containing the surfactant is 2-5 wt%; the emulsification condition is emulsification for 3-7min at the rotating speed of 10000-15000r/min, and the stirring reaction condition is reaction for 5-7h at the rotating speed of 500-1000 r/min;
s2. modified SiO2Preparing the nano microspheres: SiO prepared in the step S1 and having the surface containing fluorine and long-chain alkyl chain2Adding the nano-microspheres into an ethanol aqueous solution of a silane coupling agent containing double bonds, and heating for reaction to obtain modified SiO2Nano-microspheres; the content of the double-bond silane coupling agent in the ethanol water solution of the double-bond silane coupling agent is 3-5wt%, the content of ethanol is 40-60wt%, and the balance is water; the SiO with the surface containing fluorine and long-chain alkyl chain2The mass-volume ratio of the nano microspheres to the double-bond-containing ethanol solution of the silane coupling agent is 1: (2-5) g/mL; the heating reaction condition is reaction at 70-90 ℃ 3-5h；
S3, preparing a modified high polymer material: dissolving fluorine-containing acrylate and an initiator in a second solvent, and adding the modified SiO prepared in the step S22Dispersing the nano microspheres uniformly, and performing melt reaction with polypropylene to extrude and granulate to obtain a modified high polymer material; the polypropylene, the fluorine-containing acrylate and the modified SiO2The mass ratio of the nano microspheres to the initiator is 100: (7-12): (10-20): (0.1-1); the fluorine-containing acrylate is at least one of trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate and heptadecafluorodecyl methacrylate.
2. The method for preparing a modified polymer material according to claim 1, wherein the aminosilane is at least one selected from the group consisting of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane, and diethylenetriaminopropyltrimethoxysilane; the fluorine-containing silane is selected from at least one of 1H,1H,2H, 2H-perfluorodecyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, 3,3, 3-trifluoropropylmethyldimethoxysilane, 3, 3-trifluoropropyltrimethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane or 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane; the long-chain alkyl silane is selected from at least one of octadecyl siloxane, dodecyl trimethoxy silane and hexadecyl trimethyl siloxane; the first solvent is at least one selected from toluene, xylene, petroleum ether, ethyl acetate, methyl acetate, dichloromethane and trichloromethane; the surfactant is at least one selected from tween-80, span-80, carbomer, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate and sodium octadecyl benzene sulfonate.
3. The method according to claim 1, wherein the double bond-containing silane coupling agent is at least one selected from the group consisting of KH570, A171, A172, and A151.
4. The method for preparing a modified polymer material according to claim 1, wherein the initiator is at least one selected from the group consisting of benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and cyclohexanone peroxide; the second solvent is at least one selected from acetone, acetonitrile, tetrahydrofuran, diethyl ether, ethyl acetate, methyl acetate, petroleum ether and ethanol.
5. The method as claimed in claim 1, wherein the melting reaction temperature in step S3 is 200 ℃ to 220 ℃, and the reaction time is 2-4 h; the equipment for the melt reaction is a co-rotating twin-screw extruder.
6. A modified polymer material obtained by the production method as claimed in any one of claims 1 to 5.
7. Use of a modified polymeric material according to claim 6 in the manufacture of a pipette tip.
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