CN115725113B - Hydrophobic surface, preparation method and application thereof - Google Patents
Hydrophobic surface, preparation method and application thereof Download PDFInfo
- Publication number
- CN115725113B CN115725113B CN202110984315.4A CN202110984315A CN115725113B CN 115725113 B CN115725113 B CN 115725113B CN 202110984315 A CN202110984315 A CN 202110984315A CN 115725113 B CN115725113 B CN 115725113B
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- CN
- China
- Prior art keywords
- side group
- monomer
- hydrophobic surface
- absorbing medium
- lipophilic side
- Prior art date
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- 230000005661 hydrophobic surface Effects 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 98
- 239000002086 nanomaterial Substances 0.000 claims abstract description 36
- -1 polypropylene Polymers 0.000 claims description 80
- 239000004743 Polypropylene Substances 0.000 claims description 72
- 239000000178 monomer Substances 0.000 claims description 72
- 229920001155 polypropylene Polymers 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 41
- 229920002545 silicone oil Polymers 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 238000005187 foaming Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 13
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- 230000002209 hydrophobic effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000003075 superhydrophobic effect Effects 0.000 description 11
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229920005604 random copolymer Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000011363 dried mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a hydrophobic surface and a preparation method and application thereof. The hydrophobic surface is a polyolefin surface with a micro-nano structure, wherein the micro-nano structure is grafted with a lipophilic side group, and the micro-nano structure exists in the form of burrs and/or holes; wherein the surface grafting rate of the lipophilic side group is 20-60wt%. According to the hydrophobic surface provided by the invention, the polyolefin surface is modified, so that the hydrophobicity of the hydrophobic surface is effectively improved and the performance is stable on the premise of ensuring that the mechanical property of the hydrophobic surface is not influenced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a hydrophobic surface and a preparation method and application thereof.
Background
Surface wetting is one of the important features of solid surfaces and is also the most common type of interfacial phenomenon. Wettability can be measured by the contact angle of water on a surface, and solid surfaces at contact angles < 90 ° are generally referred to as hydrophilic surfaces, > 90 ° as hydrophobic surfaces. Studies have shown that this particular wettability is mainly caused by the combination of surface chemistry and surface microstructure, which is particularly important for improving the hydrophobic properties. The hydrophobic surface has important application prospect in the aspects of self-cleaning, oil stain prevention, oil-water separation, oil drop manipulation of water environment and the like. Therefore, the research on the underwater oleophobic/superoleophobic direction of the functional surface is particularly important.
CN102277741a discloses a superhydrophobic fabric or nonwoven fabric and a method for preparing the same, the method comprising: mixing the fabric containing the C-H bond with an alcohol solution of a fluorine-containing monomer, and carrying out irradiation medium reaction under an anaerobic condition to obtain the superhydrophobic fabric, wherein the grafting rate of the fluorine-containing monomer in the superhydrophobic fabric is more than 12%.
CN107857893a discloses a method for preparing a superhydrophobic oil absorbing material, which prepares a low-density bacterial cellulose aerogel by self-assembly, and then composites the aerogel with silica gel prepared by taking siloxane with methyl as a precursor to prepare the superhydrophobic oil absorbing material with a multistage pore structure.
CN112759729a discloses a colored super-hydrophobic polyethylene material and a preparation method thereof, the method takes single-end hydroxyl polyethylene as a raw material, and the polyethylene material reacts with a small molecular chain transfer agent to obtain a polyethylene macromolecular chain transfer agent, and the polyethylene macromolecular chain transfer agent sequentially initiates a silane coupling agent and a coloring agent to undergo free radical polymerization to obtain the colored super-hydrophobic polyethylene material.
The method has the defects of complex preparation process, long treatment period, specific equipment, harsh process conditions or expensive low-surface-energy substances, high energy consumption, incapability of large-area production and the like. Thus, there is a need for a new hydrophobic surface and a method for preparing the same.
Disclosure of Invention
The invention aims to solve the problems of complex preparation process, long treatment period, strict process conditions, high energy consumption and the like in the preparation of the hydrophobic surface in the prior art, and provides the hydrophobic surface, the preparation method and the application thereof, wherein the hydrophobic surface has hydrophobicity, even superhydrophobicity and is durable and stable; meanwhile, the method is simple, easy to operate, low in cost and easy to industrialize.
In order to achieve the above object, a first aspect of the present invention provides a hydrophobic surface, which is a polyolefin surface having a micro-nano structure, wherein the micro-nano structure is grafted with a lipophilic side group, and the micro-nano structure exists in the form of burrs and/or holes;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%.
In a second aspect, the present invention provides a method of preparing a hydrophobic surface, the method comprising the steps of:
(1) The polyolefin surface is contacted with an etchant and subjected to first drying, so that burrs and/or holes with micro-nano structures are formed on the polyolefin surface, and a modified polyolefin surface is obtained;
(2) Mixing the modified polyolefin surface, a monomer of a lipophilic side group and an inorganic microwave absorption medium, and carrying out microwave irradiation on the obtained mixture to graft the lipophilic side group on the micro-nano structure of the modified polyolefin surface so as to obtain a hydrophobic surface;
Wherein the surface grafting rate of the lipophilic side group is 20-60wt%.
In a third aspect the present invention provides the use of a hydrophobic surface as provided in the first aspect or a hydrophobic surface obtainable by a method as provided in the second aspect for anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, drag reduction, microfluidic control.
Compared with the prior art, the invention has the following technical effects:
(1) According to the hydrophobic surface provided by the invention, the burrs and/or holes with the micro-nano structure are formed on the polyolefin surface, and the lipophilic side group is grafted on the micro-nano structure, so that the hydrophobicity of the hydrophobic surface is effectively improved and the performance is stable on the premise of ensuring that the mechanical property of the hydrophobic surface is not influenced by modifying the polyolefin surface;
(2) According to the method provided by the invention, physical modification (etching) and chemical modification (grafting) are combined, so that the hydrophobicity and even superhydrophobicity of the hydrophobic surface can be effectively improved, specifically, firstly, the polyolefin surface and an etching agent are etched, and then, the modified polyolefin surface, a monomer of a lipophilic side group and an inorganic microwave absorption medium are subjected to microwave irradiation under the condition that a grafting initiator is not added, so that the monomer of the lipophilic side group is grafted on the modified polyolefin surface; meanwhile, the method has simple process and easy operation, and is convenient for industrialized mass production.
Drawings
FIG. 1 is an SEM image of a hydrophobic surface S1 prepared in example 1;
FIG. 2 is a diagram showing the distribution of hydrophobic side groups (Si elements) on the hydrophobic surface S1 obtained in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the terms "first," "second," and "third" do not denote any order of magnitude, nor are they intended to be limiting of various materials or steps, but rather are merely used to distinguish one material or step from another, e.g., "first," "second," and "third" of "first," "second," and "third," and are merely used to distinguish one material or step from another, e.g., "first," "second," and "third," of "first," "second," and "third," and are not intended to distinguish one material or step from another; the "first" and "second" of the "first solvent" and the "second solvent" are used only to distinguish that this is not the same solvent.
The first aspect of the invention provides a hydrophobic surface, wherein the hydrophobic surface is a polyolefin surface with a micro-nano structure, the micro-nano structure is grafted with a lipophilic side group, and the micro-nano structure exists in the form of burrs and/or holes;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%.
In the present invention, without being specified in a special case, the micro-nano structure refers to burrs and/or holes having micro-or nano-scale feature sizes and arranged in a specific manner; the burrs are bulges, and the holes are grooves.
In some embodiments of the invention, preferably, the micro-nanostructures have a length of 1nm to 100 μm, e.g., any value in the range of 1nm, 10nm, 100nm, 200nm, 500nm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, and any two values, preferably 500nm to 50 μm; the depth is 1 μm to 1mm, for example, any value in the range of 1 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 700 μm, 900 μm, 1mm, and any two values, preferably 50 to 500 μm. In the invention, the micro-nano structure is beneficial to the improvement of the wettability of the surface, for example, when the flat surface is hydrophobic (more than 90 degrees), the surface with the micro-nano structure has capillary action on water, so that the water can be further infiltrated, and further a more hydrophobic or even super-hydrophobic state is shown.
In some embodiments of the present invention, preferably, the polyolefin surface is made of a thermoplastic polyolefin, and the thermoplastic polyolefin has a weight average molecular weight of 10 4 -10 6 g/mol; the melt index at 230℃under a load of 2.16kg is in the range of 0.1 to 15g/10min, for example, 0.1g/10min, 1g/10min, 2g/10min, 3g/10min, 4g/10min, 5g/10min, 6g/10min, 7g/10min, 10g/10min, 15g/10min, and any value in the range of any two values, preferably 1 to 7g/10min.
In the present invention, the melt index parameter is measured by GB/T3682.1-2018 without specific explanation.
In the present invention, the kind of the thermoplastic polyolefin has a wide selection range as long as the thermoplastic polyolefin satisfies the above-mentioned limitation. Preferably, the thermoplastic polyolefin is polypropylene, preferably at least one selected from the group consisting of homo-polypropylene, random co-polypropylene and impact co-polypropylene, more preferably random co-polypropylene.
In some embodiments of the invention, preferably, the polyolefin surface is a polypropylene surface, preferably a foamed polypropylene sheet.
In some embodiments of the invention, preferably, the foamed polypropylene sheet has a surface average pore size of 10 to 100 μm, for example, any value in the range of 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, and any two values, preferably 20 to 60 μm; the bending strength is 0.1 to 1MPa, for example, any value in the range of 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.7MPa, 0.9MPa, 1MPa, and any two values, preferably 0.1 to 0.5MPa. With the preferred conditions, burrs and/or holes with a larger length and depth are more advantageously formed on the polypropylene surface.
In one embodiment of the present invention, preferably, the foamed polypropylene sheet is produced by foaming at least one of homo-polypropylene, random copolymer polypropylene and impact copolymer polypropylene. In the invention, the foaming process has a wide selection range, and can be prepared by adopting chemical foaming or adopting physical foaming.
In the invention, the source of the foaming polypropylene sheet has a wide selection range, and the polypropylene is prepared by foaming. In the present invention, the foamed polypropylene sheet may be obtained by purchase or by preparation, and the present invention is not described herein.
In some embodiments of the invention, preferably, the polypropylene content in the foamed polypropylene sheet is greater than or equal to 50wt%, preferably 50-90wt%.
In a preferred embodiment of the present invention, the foamed polypropylene sheet is produced from a polypropylene sheet by foaming with supercritical carbon dioxide.
In some embodiments of the invention, the monomer of the lipophilic side group has a grafting ratio of 20 to 60wt%, preferably 30 to 60wt%. The preferred conditions are used to further facilitate the increase in hydrophobicity of the hydrophobic surface.
In the present invention, the surface grafting ratio parameter is measured for the content of the main element (for example, si element) of the grafting component of the hydrophobic surface by using the spectral fitting of the japanese hitachi S4800 scanning electron microscope, and the content of the graft on the hydrophobic surface is reversely deduced as the surface grafting ratio by the molecular formula of the graft.
In the present invention, the lipophilic side group has a wide selection range as long as the lipophilic side group contains a hydrophobic group. Preferably, the lipophilic side groups are selected from vinyl-containing silicone oil side groups and/or styrene-containing side groups, preferably vinyl-containing silicone oil side groups.
In some embodiments of the present invention, preferably, the monomer of the lipophilic side group is a terminal vinyl silicone oil and/or a high vinyl silicone oil, preferably at least one selected from vinyl silicone oils, methyl vinyl silicone oils, vinyl hydrogen-containing silicone oils and divinyl silicone oils.
In the present invention, the hydrophobic surface has a large hydrophobicity or even superhydrophobicity, i.e., the water contact angle of the hydrophobic surface is larger than the water contact angle of the polyolefin surface. Preferably, the water contact angle of the hydrophobic surface is not less than 120 °, more preferably 150-180 °.
In the invention, under the condition of no special condition, the water contact angle parameter adopts an EASY DROP contact angle tester of KRUSS company in Germany, the measurement range is 1-180 degrees, the resolution is +/-0.1 degrees, a dynamic contact angle measurement mode is adopted, deionized water DROPs or white oil DROPs with the fixed volume of 2 mu L each time are dripped on a hydrophobic surface, the calculated initial contact angle is a contact angle measurement value of the hydrophobic surface, the parallel measurement is carried out for 6 times, and the average value is calculated.
According to a particularly preferred embodiment of the invention, the hydrophobic surface is a polyolefin surface having micro-nanostructures grafted with lipophilic side groups, and the micro-nanostructures are present in the form of burrs and/or holes;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%;
wherein the polyolefin surface is a foaming polypropylene sheet;
wherein the average pore diameter of the surface of the foaming polypropylene sheet is 10-100 mu m; bending strength is 0.1-1MPa;
wherein the hydrophobic surface is prepared by the following method: and (3) contacting the polyolefin surface with an etchant, performing first drying to form burrs and/or holes with micro-nano structures on the polyolefin surface, mixing the obtained modified polyolefin surface with a monomer with lipophilic side groups and an inorganic microwave absorbing medium, and performing microwave irradiation to graft the lipophilic side groups on the micro-nano structures on the modified polyolefin surface.
In a second aspect, the present invention provides a method of preparing a hydrophobic surface, the method comprising the steps of:
(1) The polyolefin surface is contacted with an etchant and subjected to first drying, so that burrs and/or holes with micro-nano structures are formed on the polyolefin surface, and a modified polyolefin surface is obtained;
(2) Mixing the modified polyolefin surface, a monomer of a lipophilic side group and an inorganic microwave absorption medium, and carrying out microwave irradiation on the obtained mixture to graft the lipophilic side group on the micro-nano structure of the modified polyolefin surface so as to obtain a hydrophobic surface;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%.
The inventors of the present invention studied and found that: etching the polyolefin surface by using an etchant, particularly etching the polyolefin surface by using an etchant by using a foaming polypropylene sheet with a microporous structure, so that the polyolefin surface has more micro-nano structures and is more hydrophobic; and further carrying out grafting reaction with the monomer of the lipophilic side group and an inorganic microwave absorption medium by using microwave irradiation under the condition of no initiator addition to prepare the hydrophobic surface. The microwave absorbing medium can absorb microwaves under the condition of microwave irradiation, raise the temperature to 200 ℃ or above, and generate free radicals; meanwhile, high temperature can trigger nearby polypropylene molecular chains to generate free radicals, so that a monomer with a lipophilic side group can fully generate grafting reaction with polypropylene, and the grafted polypropylene surface is obtained. Since the monomer of the lipophilic side group (e.g., vinyl silicone oil side group monomer) has a low polarity, the temperature rise of the monomer cannot reach a very high temperature (the temperature in the microwave field is raised to be less than 200 ℃) when the monomer absorbs microwaves under the microwave irradiation, so that the polypropylene molecular chain cannot be effectively initiated to generate free radicals, and therefore, an inorganic microwave absorption medium is required to be added to assist the polypropylene to generate free radicals so as to carry out grafting reaction with the monomer of the lipophilic side group (e.g., vinyl silicone oil side group monomer). The inorganic microwave absorbing medium does not react with the surface of polypropylene and the monomer, and is used as a grafting reaction heat source, so that the surface performance of polypropylene is not affected. The addition of the inorganic microwave absorbing medium can help the monomer which does not absorb microwaves to be grafted on polypropylene; the monomer itself absorbing microwaves can help to increase its grafting efficiency.
Therefore, the invention utilizes the selective heating of the inorganic microwave absorbing medium to heat the inorganic microwave absorbing medium, the temperature which can be reached by heating under the microwave is above 200 ℃, the temperature can reach the vicinity of the melting point of polypropylene, the polypropylene is not broken chain at the temperature, but the tertiary carbon of the polypropylene can be dehydrogenated, so that the grafting reaction can occur but the chain breaking reaction can not be caused, after the monomer with the lipophilic side group (for example, vinyl silicone oil side group monomer) is grafted, the hydrophobicity of the surface of the polypropylene is further improved, and the obtained polypropylene surface has stronger hydrophobicity. Because the polypropylene surface has a micro-nano structure, capillary action can change the hydrophobic surface into super-hydrophobic effect.
In the present invention, in the step (1), the types of the polyolefin surfaces are all defined as described above, which is not described in detail herein.
In some embodiments of the present invention, preferably, in step (1), the weight ratio of the polyolefin surface to the etchant is 0.1 to 100:100, preferably 0.5-50:100, more preferably 1-30:100. the optimized weight ratio is adopted, so that the etchant uniformly covers the surface of the polyolefin surface, and is more favorable for the full contact and mixing of the etchant and the polyolefin surface, thereby being favorable for forming the micro-nano structure on the surface of the polyolefin surface.
In the present invention, the kind of the etchant has a wide selection range as long as the surface on the polyolefin surface can be etched. Preferably, the etchant is a polar organic solvent, preferably at least one selected from toluene, xylene, diphenyl ether, butyl acetate, isoamyl acetate, n-heptane, n-octane, and decalin.
In the present invention, the conditions for the contact have a wide range of choices. Preferably, the contacting conditions include: the temperature is 15-70deg.C, preferably 20-60deg.C; the time is 1-24 hours, preferably 5-15 hours.
In the present invention, the contact mode has a wide selection range, and preferably, the contact mode is soaking; namely, the polyolefin surface is soaked in the etchant, wherein the soaking temperature is 15-70 ℃ and the soaking time is 1-24h.
In the present invention, the first drying is intended to remove the etchant from the contact product. Preferably, the first drying conditions include: the temperature is 80-120deg.C, preferably 80-100deg.C; the time is 1-10 hours, preferably 1-5 hours.
In some embodiments of the invention, preferably, in step (2), the weight ratio of the monomer of the lipophilic side group to the modified polyolefin surface is from 20 to 50:100, e.g., 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, and any value in the range of any two values, preferably 30-40:100. the preferred weight ratio is used to facilitate the thorough mixing and grafting reaction of the materials, thereby increasing the grafting ratio of the monomer with lipophilic side groups in the hydrophobic surface.
In the present invention, the monomer of the lipophilic side group may be directly added to the modified polyolefin surface for mixing, or for better mixing effect, preferably, the monomer of the lipophilic side group exists in the form of a solution, that is, a solution of the monomer containing the lipophilic side group is used for mixing.
In some embodiments of the invention, preferably, the weight ratio of the lipophilic side group-containing monomer to the first solvent in the solution of the lipophilic side group-containing monomer is from 0.1 to 100:100, for example, any of the ranges of 0.1:100, 0.5:100, 1:100, 2:100, 3:100, 5:100, 10:100, 20:100, 30:100, 40:100, 50:100, 80:100, 100:100, and any two values, preferably 0.5-50:100, more preferably 1-30:100. the preferable weight ratio can ensure that the lipophilic side group monomer in the solution of the lipophilic side group monomer can completely cover the surface of the polyolefin surface, so that the lipophilic side group monomer and the polyolefin surface can be mixed thoroughly.
In the present invention, the type of the first solvent may be selected in a wide range, as long as the monomer of the lipophilic side group is dissolved in the first solvent. Preferably, the first solvent is selected from water and/or an organic solvent, preferably at least one selected from alcohols, ketones, esters and water, more preferably from acetone and/or ethanol.
In the present invention, the inorganic microwave absorbing medium may employ various inorganic substances capable of absorbing microwaves in the prior art. Preferably, the inorganic microwave absorbing medium is selected from at least one of metal hydroxide, metal salt, metal oxide, graphite-based material, ferroelectric-based material, electrolytic stone, and chalcopyrite.
In some embodiments of the present invention, preferably, the metal hydroxide is selected from at least one of potassium hydroxide, barium hydroxide, sodium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, iron hydroxide, ferrous hydroxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, beryllium hydroxide, and rare earth hydroxide.
In some embodiments of the present invention, preferably, the metal salt is selected from at least one of nitrate, chlorate, sulfate, carbonate, phosphate, and titanate, preferably from at least one of ammonium nitrate, potassium nitrate, sodium nitrate, barium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, manganese nitrate, zinc nitrate, ferric nitrate, ferrous nitrate, copper nitrate, silver nitrate, ammonium chloride, potassium chloride, sodium chloride, barium chloride, calcium chloride, magnesium chloride, aluminum chloride, manganese chloride, zinc chloride, ferric chloride, ferrous chloride, copper chloride, ammonium sulfate, potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate, aluminum sulfate, manganese sulfate, zinc sulfate, ferric sulfate, ferrous sulfate, copper sulfate, silver sulfate, ammonium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, potassium dihydrogen phosphate, barium titanate, strontium titanate, and copper calcium titanate.
In some embodiments of the invention, preferably, the metal oxide is selected from the group consisting of ferric oxide and/or ferric oxide.
In some embodiments of the present invention, preferably, the graphite-based material is selected from at least one of carbon black, graphite powder, graphene, carbon nanotubes, and activated carbon.
In some embodiments of the invention, preferably, the weight ratio of the inorganic microwave absorbing medium to the modified polyolefin surface is from 10 to 50:100, e.g., 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, and any value in the range of any two values, preferably 20-30:100. the inorganic microwave absorbing medium can completely cover the mixture of the modified polyolefin surface by adopting the preferable weight ratio, thereby being more convenient for the full mixing and grafting reaction of the raw materials.
In the present invention, unless otherwise specified, the weight of the inorganic microwave absorbing medium means a single use amount of the inorganic microwave absorbing medium.
In the present invention, the inorganic microwave absorbing medium may be directly added to the surface of the modified polyolefin for mixing, or for better mixing effect, preferably, the inorganic microwave absorbing medium is present in the form of a solution/dispersion, that is, a solution/dispersion containing the inorganic microwave absorbing medium is used for mixing.
In some embodiments of the present invention, preferably, the weight ratio of inorganic microwave absorbing medium to second solvent in the solution/dispersion containing inorganic microwave absorbing medium is 0.1 to 100:100, for example, any of the ranges of 0.1:100, 0.5:100, 1:100, 2:100, 3:100, 5:100, 10:100, 20:100, 30:100, 40:100, 50:100, 80:100, 100:100, and any two values, preferably 0.5-50:100, more preferably 1-30:100.
in the present invention, the type of the second solvent may be selected in a wide range, as long as the inorganic microwave absorbing medium is dissolved in the second solvent or the inorganic microwave absorbing medium can be uniformly dispersed by weight to form a solution/dispersion. Preferably, the second solvent is selected from water and/or an organic solvent, preferably at least one selected from alcohols, ketones, esters and water, more preferably from alcohols and/or water.
In the present invention, in order to ensure that the inorganic microwave absorbing medium can form a dispersion-stable solution/dispersion with the second solvent, a surfactant may be added to the solution/dispersion containing the inorganic microwave absorbing medium. Preferably, the surfactant is selected from polyoxyethylene type surfactants and/or polyol type surfactants.
In some embodiments of the present invention, preferably, the solution/dispersion comprising the inorganic microwave absorbing medium further comprises a surfactant; further preferably, the solution/dispersion liquid containing the inorganic microwave absorbing medium further contains a surfactant, wherein the weight ratio of the surfactant to the inorganic microwave absorbing medium is 0.1-100:100, for example, any value in the range of 0.1:100, 0.5:100, 1:100, 5:100, 10:100, 15:100, 20:100, 30:100, 40:100, 50:100, 80:100, 100:100, and any two values, preferably 0.5-50:100, more preferably 1-20:100.
in the present invention, the mode of mixing has a wide range of choices, as long as the components in the mixture are uniformly mixed. For example, the mixing manner may be coating, dripping, impregnating and covering, etc., and the present invention is not described herein.
In the present invention, the conditions of the microwave irradiation have a wide selection range, as long as the monomer of the lipophilic side group is grafted on the surface of the modified polyolefin. Preferably, the conditions of the microwave irradiation include: the irradiation power is 1500-27000W, preferably 1500-15000W; the irradiation time is 1s-1min, preferably 1-30s.
In the present invention, the microwave irradiation is performed in various microwave reactors existing in the prior art, without being specifically described.
In the present invention, the solvent is removed from the mixture. Preferably, the mixture is subjected to a second drying prior to the microwave irradiation.
In some embodiments of the present invention, preferably, the second drying conditions include: the temperature is 80-120deg.C, preferably 80-100deg.C; the time is 1-10 hours, preferably 1-5 hours.
According to the invention, preferably, the method further comprises: washing the microwave irradiation product to remove unreacted lipophilic side group monomers and/or inorganic microwave absorption medium which does not participate in the reaction in the microwave irradiation product; or, the product of the microwave irradiation is washed after being reacted with alkali.
In some embodiments of the invention, the microwave irradiated product is immediately soaked with a cleaning solution having a volume exceeding that of the microwave irradiated product at a high temperature, and then excess moisture is removed using a filtering device; repeatedly cleaning for 2-6 times to obtain the cleaned microwave irradiation product.
In the invention, the cleaning liquid has a wide selection range. Preferably, the cleaning liquid is selected from water and/or organic solvents, preferably at least one selected from alcohols, ketones, esters and water, more preferably alcohols and/or water.
In some embodiments of the invention, preferably, the method further comprises: and carrying out third drying on the cleaned product. In the present invention, the third drying mode may be air drying or normal temperature drying, which is not described in detail herein. The preferred temperature for the third drying is not more than 160℃and avoids melting the polyolefin surface.
In a third aspect the present invention provides the use of a hydrophobic surface as provided in the first aspect or a hydrophobic surface obtainable by a method as provided in the second aspect for anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, drag reduction, microfluidic control.
The hydrophobic surface provided by the invention is more hydrophobic than the polyolefin surface, and even achieves the super-hydrophobic performance; meanwhile, the hydrophobic surface provided by the invention does not reduce the molecular weight of the polyolefin surface, has no monomer residue of lipophilic side groups, does not introduce an initiator, is colorless and odorless, and has greatly improved hydrophobicity and lasting stability.
The present invention will be described in detail by examples.
The water contact angle parameter adopts an EASY DROP contact angle tester of KRUSS company of Germany, the measurement range is 1-180 degrees, the resolution is +/-0.1 degrees, a dynamic contact angle measurement mode is adopted, deionized water DROPs or white oil DROPs with a fixed volume of 2 mu L each time are dripped on the polypropylene surface, the calculated initial contact angle is a contact angle measurement value of the polypropylene surface, the measurement is carried out for 6 times in parallel, and the average value is calculated.
The surface grafting ratio parameter adopts the energy spectrum fitting of Japanese Hitachi S4800 scanning electron microscope to measure the content of the main element (Si element) of the grafting component of the hydrophobic surface, and the content of the grafting on the hydrophobic surface is reversely deduced through the molecular formula of the grafting to be used as the grafting ratio.
The foaming polypropylene sheet-1 is prepared by foaming injection polypropylene sheet-1 by supercritical carbon dioxide; wherein the random copolymer polypropylene content in the foamed polypropylene sheet-1 is 90wt%, the surface average pore diameter is 50 μm, and the bending strength is 0.15MPa.
The foaming polypropylene sheet-2 is prepared by foaming injection polypropylene sheet-2 by supercritical carbon dioxide; wherein the random copolymer polypropylene content in the foamed polypropylene sheet-2 is 70wt%, the surface average pore diameter is 40 μm, and the bending strength is 0.45MPa.
The foaming polypropylene sheet-3 is prepared by foaming injection polypropylene sheet-3 by supercritical carbon dioxide; wherein the random copolymer polypropylene content in the foamed polypropylene sheet-3 is 80wt%, the surface average pore diameter is 25 μm, and the flexural strength is 0.33MPa.
Injection molded polypropylene sheet-1 (a blend of 70wt% random copolymer polypropylene E02ES with 30wt% POE), purchased from New materials Inc. of Shensai, jiangsu, had a smooth and flat surface and a flexural strength of 10.5MPa.
Injection molded polypropylene sheet-2 (blend of 90wt% random copolymer polypropylene E02ES and 10wt% homo polypropylene T30S), purchased from Zhejiang Jiaxing New Hengtai New Material Co., ltd., smooth and flat surface, flexural strength 17.5MPa.
Injection molded polypropylene sheet-3 (random copolymer polypropylene E02 ES) purchased from Ningbo micro new material technology Co., ltd., smooth and flat surface, and bending strength of 15.0MPa.
Xylene (national pharmaceutical group chemical agent Co., ltd.), decalin (national pharmaceutical group chemical agent Co., ltd.), acetone (Schlemn scientific Co., ltd.), sodium chloride (national pharmaceutical group chemical agent Co., ltd.), vinyl silicone oil (Shandong Dayi chemical agent Co., ltd.), vinyl hydrogen-containing silicone oil (Tokyo chemical industry Co., ltd.), divinyl silicone oil (Shandong Dayi chemical agent Co., ltd.), sodium chloride (national pharmaceutical group chemical agent Co., ltd.), graphene Oxide (GO) aqueous solution (Nanjing Jiku Nakagaku Co., ltd.), ascorbic acid (largehead Co., ltd.), styrene (national pharmaceutical group chemical agent Co., ltd.); the other various raw materials are commercially available.
The physical properties of the hydrophobic surfaces (S1-S10 and D1-D5) obtained in examples 1-10 and comparative examples 1-5 are shown in Table 1.
Example 1
(1) 10g of polyolefin surface (foaming polypropylene sheet-1, water contact angle is 108 ℃) is soaked in 100g of etchant (dimethylbenzene), sealed and soaked for 12 hours at the temperature of 25 ℃ of an incubator, and then placed in a blast drying oven at the temperature of 90 ℃ for 2 hours, so as to obtain a modified polyolefin surface;
(2) 30 parts by weight of a monomer (vinyl silicone oil) with a lipophilic side group is dissolved in 100 parts by weight of ethanol to obtain a solution of the monomer with the lipophilic side group; dissolving 20 parts by weight of an inorganic microwave absorbing medium (sodium chloride) in 100 parts by weight of deionized water to obtain a dispersion liquid containing the inorganic microwave absorbing medium;
mixing 100 parts by weight of modified polyolefin surface, the solution of the monomer containing the lipophilic side group and the dispersion liquid containing the inorganic microwave absorbing medium, and drying the obtained mixture in a blast drying oven at 80 ℃;
irradiating the dried mixture with microwave at irradiation power of 2000W for 25s, and circulating for 2 times at intervals of 1min; and soaking the product of microwave irradiation in deionized water for 10min, replacing the deionized water for 3 times to ensure that vinyl silicone oil and sodium chloride which do not participate in the grafting reaction are removed, and then placing the cleaning product in 80 ℃ for forced air drying and drying to obtain the hydrophobic surface S1.
As shown in fig. 1, the SEM image of the hydrophobic surface S1 is shown in fig. 1, and it can be seen from fig. 1 that the hydrophobic surface S1 has a micro-nano pore structure and holes;
as shown in fig. 2, the distribution diagram of the hydrophobic side groups (Si elements) of the hydrophobic surface S1 is shown in fig. 2, and it is clear from fig. 2 that the hydrophobic side groups (Si elements) of the hydrophobic surface S1 can be uniformly distributed on the micro-nano structure.
Example 2
(1) 10g of polyolefin surface (foaming polypropylene sheet-1, water contact angle is 108 ℃) is soaked in 100g of etchant (dimethylbenzene), sealed and soaked for 12 hours at the temperature of 25 ℃ of an incubator, and then placed in a blast drying oven at the temperature of 90 ℃ for 2 hours, so as to obtain a modified polyolefin surface;
(2) Dissolving 20 parts by weight of a monomer (vinyl silicone oil) with a lipophilic side group in 100 parts by weight of ethanol to obtain a solution of the monomer with the lipophilic side group; dissolving 10 parts by weight of an inorganic microwave absorbing medium (sodium chloride) in 50 parts by weight of deionized water to obtain a dispersion liquid containing the inorganic microwave absorbing medium;
mixing 100 parts by weight of modified polyolefin surface, the solution of the monomer containing the lipophilic side group and the dispersion liquid containing the inorganic microwave absorbing medium, and drying the obtained mixture in a blast drying oven at 80 ℃;
And (3) carrying out microwave irradiation on the dried mixture for 20S at the irradiation power of 5000W for 3 times at intervals of 1min, soaking the product of microwave irradiation in deionized water for 10min, replacing the deionized water for 3 times to ensure that vinyl silicone oil and sodium chloride which do not participate in the grafting reaction are removed, and then placing the cleaning product in 80 ℃ for air blast drying and drying to obtain the hydrophobic surface S2.
Wherein the SEM image of the hydrophobic surface S2 is similar to fig. 1; the hydrophobic side group (Si element) profile of the hydrophobic surface S2 is similar to that of fig. 2.
Example 3
(1) 10g of polyolefin surface (foaming polypropylene sheet-2, water contact angle is 112 ℃) is soaked in 90g of etchant (decalin), the mixture is soaked in a sealed way for 4 hours at the temperature of 50 ℃ in an incubator, and then the mixture is placed in a blast drying oven at the temperature of 90 ℃ for 2 hours, so that the modified polyolefin surface is obtained;
(2) Dissolving 40 parts by weight of a monomer with a lipophilic side group (vinyl hydrogen-containing silicone oil) in 200 parts by weight of ethanol to obtain a solution of the monomer with the lipophilic side group; dissolving 20 parts by weight of an inorganic microwave absorbing medium (sodium chloride) in 100 parts by weight of deionized water to obtain a dispersion liquid containing the inorganic microwave absorbing medium;
mixing 100 parts by weight of modified polyolefin surface, the solution of the monomer containing the lipophilic side group and the dispersion liquid containing the inorganic microwave absorbing medium, and drying the obtained mixture in a blast drying oven at 80 ℃;
Microwave irradiating the dried mixture for 3min under the irradiation power of 10000W, and circulating for 3 times at intervals of 1min each time; and soaking the product of microwave irradiation in deionized water for 10min, replacing the deionized water for 3 times to ensure that vinyl hydrogen-containing silicone oil and sodium chloride which do not participate in the grafting reaction are removed, and then placing the cleaning product in 80 ℃ for air blast drying and drying to obtain the hydrophobic surface S3.
Wherein the SEM image of the hydrophobic surface S3 is similar to fig. 1; the hydrophobic side group (Si element) profile of the hydrophobic surface S3 is similar to fig. 2.
Example 4
(1) Immersing 10g of polyolefin surface (foaming polypropylene sheet-3, water contact angle is 108 ℃) in 90g of etchant (decalin), sealing and immersing for 10 hours at the temperature of 25 ℃ in an incubator, and then placing in a blast drying oven at the temperature of 80 ℃ for 2 hours to obtain a modified polyolefin surface;
(2) Dissolving 50 parts by weight of a monomer (vinyl silicone oil) with a lipophilic side group in 200 parts by weight of ethanol to obtain a solution of the monomer with the lipophilic side group; 30 parts by weight of an inorganic microwave absorbing medium (graphene oxide) and 3 parts by weight of ascorbic acid (as a reducing agent for the graphene oxide) were dissolved in 150 parts by weight of deionized water to obtain a dispersion containing the inorganic microwave absorbing medium;
Mixing 100 parts by weight of modified polyolefin surface, the solution of the monomer containing the lipophilic side group and the dispersion liquid containing the inorganic microwave absorbing medium, and drying the obtained mixture in a blast drying oven at 80 ℃;
irradiating the dried mixture with microwave at irradiation power of 15000W for 3s, and circulating for 5 times at intervals of 1min; and soaking the product of microwave irradiation in deionized water for 10min, replacing the deionized water for 3 times to ensure that vinyl silicone oil and sodium chloride which do not participate in the grafting reaction are removed, and then placing the cleaning product in 80 ℃ for forced air drying and drying to obtain the hydrophobic surface S4.
Wherein the SEM image of the hydrophobic surface S4 is similar to fig. 1; the hydrophobic side group (Si element) profile of the hydrophobic surface S4 is similar to fig. 2.
Example 5
(1) Immersing 10g of polyolefin surface (foaming polypropylene sheet-3, water contact angle is 108 ℃) in 90g of etchant (decalin), sealing and immersing for 10 hours at the temperature of 25 ℃ in an incubator, and then placing in a blast drying oven at the temperature of 80 ℃ for 2 hours to obtain a modified polyolefin surface;
(2) Dissolving 40 parts by weight of a monomer (styrene) with a lipophilic side group in 200 parts by weight of ethanol to obtain a solution of the monomer with the lipophilic side group; dissolving 25 parts by weight of an inorganic microwave absorbing medium (graphene oxide) and 2.5 parts by weight of ascorbic acid in 150 parts by weight of deionized water to obtain a dispersion liquid containing the inorganic microwave absorbing medium;
Mixing 100 parts by weight of modified polyolefin surface, the solution of the monomer containing the lipophilic side group and the dispersion liquid containing the inorganic microwave absorbing medium, and drying the obtained mixture in a blast drying oven at 80 ℃;
irradiating the dried mixture with microwave at irradiation power of 20000W for 2s, and circulating for 4 times at intervals of 1min each time; and soaking the product of microwave irradiation in deionized water for 10min, replacing the deionized water for 3 times to ensure that vinyl silicone oil and sodium chloride which do not participate in the grafting reaction are removed, and then placing the cleaning product in 80 ℃ for forced air drying and drying to obtain the hydrophobic surface S5.
Wherein the SEM image of the hydrophobic surface S5 is similar to fig. 1; the hydrophobic side group (Si element) profile of the hydrophobic surface S5 is similar to fig. 2.
Example 6
The procedure of example 1 was followed except that in step (1), 10g of the polyolefin surface (expanded polypropylene sheet-1, water contact angle of 108 ℃) was replaced with 35g of the polyolefin surface (expanded polypropylene sheet-1, water contact angle of 108 ℃) under the same conditions to obtain a hydrophobic surface S6.
Example 7
The procedure of example 1 was followed except that in step (2), 30 parts by weight of the lipophilic side group monomer (vinyl silicone oil) was replaced with 10 parts by weight of the lipophilic side group monomer (vinyl silicone oil), and the remaining conditions were the same, to obtain a hydrophobic surface S7.
Example 8
The procedure of example 1 was followed except that in step (2), 20 parts by weight of the inorganic microwave absorbing medium (sodium chloride) was replaced with 10 parts by weight of the inorganic microwave absorbing medium (sodium chloride), and the remaining conditions were the same, to obtain a hydrophobic surface S8.
Example 9
According to the method of example 1, except that 100 parts by weight of the modified polyolefin surface, 30 parts by weight of the lipophilic side group monomer (vinyl silicone oil), and 20 parts by weight of the inorganic microwave absorbing medium (sodium chloride) were directly mixed in step (2), the other conditions were the same, to obtain a hydrophobic surface S9.
Example 10
The procedure of example 1 was followed except that in step (2), the dried mixture was subjected to microwave irradiation at an irradiation power of 27000W for 1S under the same conditions to obtain a hydrophobic surface S10.
Comparative example 1
The procedure of example 1 was followed, except that step (2) was not carried out, i.e., the modified polyolefin surface obtained in step (1) was used as the hydrophobic surface D1.
Comparative example 1'
The procedure of example 1 was followed except that injection molded polypropylene sheet-1 was used, the remaining conditions being the same, to obtain a hydrophobic surface D1'.
Comparative example 2
The procedure of example 3 was followed, except that step (2) was not carried out, i.e., the modified polyolefin surface obtained in step (1) was used as the hydrophobic surface D2.
Comparative example 3
The procedure of example 4 was followed, except that step (2) was not carried out, i.e., the modified polyolefin surface obtained in step (1) was used as the hydrophobic surface D3.
Comparative example 3'
The procedure of example 3 was followed except that injection molded polypropylene sheet-2 was used, the remaining conditions being the same, to give a hydrophobic surface D3'.
Comparative example 4
The procedure of example 1 was followed except that step (1) was not carried out, namely, 100 parts by weight of the polyolefin surface, the above-mentioned solution of the monomer having a lipophilic side group, and the above-mentioned dispersion containing the inorganic microwave absorbing medium were directly mixed, and the other conditions were the same, to obtain a hydrophobic surface D4.
Comparative example 4'
The procedure of example 4 was followed except that injection molded polypropylene sheet-3 was used, the remaining conditions being the same, to give a hydrophobic surface D4'.
Comparative example 5
The procedure of example 1 was followed except that 100 parts by weight of the polyolefin surface and the above-mentioned solution of the lipophilic side group-containing monomer were mixed without adding an inorganic microwave absorbing medium, and the other conditions were the same, to obtain a hydrophobic surface D5.
TABLE 1
| Water contact angle, ° | Surface grafting rate, wt% | Flexural Strength, MPa | |
| Example 1 | 159 | 39.5 | 0.15 |
| Example 2 | 155 | 57.9 | 0.15 |
| Example 3 | 155 | 48.6 | 0.45 |
| Example 4 | 164 | 52.7 | 0.33 |
| Example 5 | 159 | 37.5 | 0.33 |
| Example 6 | 151 | 34.1 | 0.15 |
| Example 7 | 150 | 32.4 | 0.15 |
| Example 8 | 137 | 27.1 | 0.15 |
| Example 9 | 135 | 22.0 | 0.15 |
| Example 10 | 157 | 38.4 | 0.15 |
| Comparative example 1 | 115 | - | 0.16 |
| Comparative example 1' | 112 | 5.2 | 10.4 |
| Comparative example 2 | 115 | - | 0.43 |
| Comparative example 3 | 115 | - | 0.31 |
| Comparative example 3' | 115 | 3.7 | 17.4 |
| Comparative example 4 | 117 | 15.1 | 0.43 |
| Comparative example 4' | 115 | 4.1 | 14.8 |
| Comparative example 5 | 116 | 3.1 | 0.16 |
As can be seen from the results in Table 1, the hydrophobic surface provided by the invention has a larger water contact angle than the polyolefin surface, namely, compared with the pure polyolefin surface, the hydrophobic surface provided by the invention can greatly improve the hydrophobic performance of the hydrophobic surface and even reach the super-hydrophobic level on the premise of ensuring that the mechanical performance is not affected.
In comparison with example 6, example 1 further improved the hydrophobic properties of the hydrophobic surface by defining the weight ratio of polyolefin surface to etchant within the preferred protective range by increasing the water contact angle and grafting ratio of the hydrophobic surface.
In comparison with example 7, example 1 further improved the hydrophobic properties of the hydrophobic surface by increasing the water contact angle and grafting ratio of the hydrophobic surface by defining the weight ratio of the monomer of the lipophilic side group to the modified polyolefin surface within the preferred protective range.
In comparison with example 8, example 1 further improved the hydrophobic properties of the hydrophobic surface by increasing the water contact angle and grafting ratio of the hydrophobic surface by defining the weight ratio of the inorganic microwave absorbing medium to the modified polyolefin surface within the preferred protective range.
In comparison with example 9, example 1 further improved the hydrophobic properties of the hydrophobic surface by increasing the water contact angle and grafting ratio of the hydrophobic surface by mixing the monomers defining the lipophilic side groups in the form of a solution and the inorganic microwave absorbing medium in the form of a dispersion.
In comparison with example 10, example 1 further improved the hydrophobic properties of the hydrophobic surface by increasing the water contact angle and grafting ratio of the hydrophobic surface by limiting the microwave irradiation within the preferred protective range.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. The hydrophobic surface is characterized by being a polyolefin surface with a micro-nano structure, wherein the micro-nano structure is grafted with a lipophilic side group, and the micro-nano structure exists in the form of burrs and/or holes;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%;
Wherein the hydrophobic surface is prepared by the following method: (1) The polyolefin surface is contacted with an etchant and subjected to first drying, so that burrs and/or holes with micro-nano structures are formed on the polyolefin surface, and a modified polyolefin surface is obtained; (2) Mixing the modified polyolefin surface, a monomer of a lipophilic side group and an inorganic microwave absorption medium, and carrying out microwave irradiation on the obtained mixture to graft the lipophilic side group on the micro-nano structure of the modified polyolefin surface so as to obtain the hydrophobic surface; wherein the contacting conditions include: the temperature is 15-70 ℃; the time is 1-24h; the conditions of the microwave irradiation include: the irradiation power is 1500-27000 and W; the irradiation time is 1s-1min;
wherein the polyolefin surface is a foaming polypropylene sheet, and the average pore diameter of the surface of the foaming polypropylene sheet is 10-100 mu m; the bending strength is 0.1-1 MPa.
2. The hydrophobic surface of claim 1, wherein the micro-nano structure has a length of 1nm-100 μm; the depth is 1 mu m-1mm;
and/or the polyolefin surface is made of a thermoplastic polyolefin, and the thermoplastic polyolefin has a weight average molecular weight of 10 4 -10 6 g/mol; the melt index at 230 ℃ and under a load of 2.16kg is 0.1-15 g/10min;
and/or the surface average pore diameter of the foaming polypropylene sheet is 20-60 mu m; the bending strength is 0.1-0.5 MPa.
3. The hydrophobic surface of claim 2, wherein the micro-nano structure has a length of 500nm-50 μm; the depth is 50-500 mu m;
and/or the thermoplastic polyolefin has a melt index of 1 to 7 g/10min at 230 ℃ under a load of 2.16 kg;
and/or the thermoplastic polyolefin is selected from at least one of homo-polypropylene, random co-polypropylene and impact co-polypropylene.
4. The hydrophobic surface of claim 1, wherein the lipophilic side group is selected from vinyl-containing silicone oil side groups and/or styrene-containing side groups;
and/or the monomer of the lipophilic side group is vinyl-terminated silicone oil and/or high vinyl silicone oil.
5. The hydrophobic surface of claim 4 wherein said lipophilic side group monomer is selected from at least one of vinyl silicone oil, vinyl hydrogen silicone oil and divinyl silicone oil.
6. The hydrophobic surface of claim 5 wherein said lipophilic side group monomer is selected from methyl vinyl silicone oils.
7. The hydrophobic surface of any one of claims 1-6, wherein the hydrophobic surface has a water contact angle of greater than or equal to 120 °.
8. The hydrophobic surface of claim 7 wherein said hydrophobic surface has a water contact angle of 150-180 °.
9. A method of preparing a hydrophobic surface, the method comprising the steps of:
(1) The polyolefin surface is contacted with an etchant and subjected to first drying, so that burrs and/or holes with micro-nano structures are formed on the polyolefin surface, and a modified polyolefin surface is obtained;
(2) Mixing the modified polyolefin surface, a monomer of a lipophilic side group and an inorganic microwave absorption medium, and carrying out microwave irradiation on the obtained mixture to graft the lipophilic side group on the micro-nano structure of the modified polyolefin surface so as to obtain a hydrophobic surface;
wherein the surface grafting rate of the lipophilic side group is 20-60wt%;
wherein the contacting conditions include: the temperature is 15-70 ℃; the time is 1-24h; the conditions of the microwave irradiation include: the irradiation power is 1500-27000 and W; the irradiation time is 1s-1min;
wherein the polyolefin surface is a foaming polypropylene sheet, and the average pore diameter of the surface of the foaming polypropylene sheet is 10-100 mu m; the bending strength is 0.1-1 MPa.
10. The method of claim 9, wherein in step (1), the weight ratio of polyolefin surface to etchant is 0.1-100:100;
And/or the etchant is a polar organic solvent;
and/or, the contacting conditions include: the temperature is 20-60 ℃; the time is 5-15h;
and/or, the contact mode is soaking;
and/or, the first drying conditions include: the temperature is 80-120 ℃; the time is 1-10h.
11. The method of claim 10, wherein the weight ratio of polyolefin surface to etchant is 0.5-50:100;
and/or the etchant is at least one selected from toluene, xylene, diphenyl ether, butyl acetate, isoamyl acetate, n-heptane, n-octane and decalin;
and/or, the first drying conditions include: the temperature is 80-100 ℃; the time is 1-5h.
12. The method of claim 11, wherein the polyolefin surface and etchant are present in a weight ratio of 1-30:100.
13. the method of claim 9, wherein in step (2), the weight ratio of the monomer of the pendant lipophilic group to the modified polyolefin surface is from 20 to 50:100;
and/or the monomer of the lipophilic side group exists in a solution form, and in the solution of the monomer containing the lipophilic side group, the weight ratio of the monomer of the lipophilic side group to the first solvent is 0.1-100:100;
And/or, in the step (2), the weight ratio of the inorganic microwave absorbing medium to the modified polyolefin surface is 10-50:100;
and/or the inorganic microwave absorbing medium exists in the form of solution/dispersion liquid, and the weight ratio of the inorganic microwave absorbing medium to the second solvent in the solution/dispersion liquid containing the inorganic microwave absorbing medium is 0.1-100:100.
14. the method of claim 13, wherein in step (2), the weight ratio of the monomer of the pendant lipophilic group to the modified polyolefin surface is from 30 to 40:100;
and/or, in the solution of the monomer containing the lipophilic side group, the weight ratio of the monomer containing the lipophilic side group to the first solvent is 0.5-50:100;
and/or the weight ratio of the inorganic microwave absorbing medium to the modified polyolefin surface is 20-30:100;
and/or, in the solution/dispersion containing the inorganic microwave absorbing medium, the weight ratio of the inorganic microwave absorbing medium to the second solvent is 0.5 to 50:100;
and/or the solution/dispersion containing the inorganic microwave absorbing medium further contains a surfactant; in the solution/dispersion liquid containing the inorganic microwave absorbing medium, the weight ratio of the surfactant to the inorganic microwave absorbing medium is 0.1-100:100.
15. The method of claim 14, wherein the weight ratio of lipophilic side group containing monomer to first solvent in the solution of lipophilic side group containing monomer is from 1 to 30:100;
and/or, in the solution/dispersion containing the inorganic microwave absorbing medium, the weight ratio of the inorganic microwave absorbing medium to the second solvent is 1-30:100;
and/or, in the solution/dispersion liquid containing the inorganic microwave absorbing medium, the weight ratio of the surfactant to the inorganic microwave absorbing medium is 0.5-50:100.
16. the method of claim 15, wherein the weight ratio of surfactant to inorganic microwave absorbing medium in the solution/dispersion comprising inorganic microwave absorbing medium is from 1 to 20:100.
17. the method according to any one of claims 9-16, wherein in step (2), the conditions of microwave irradiation include: the irradiation power is 1500-15000W; the irradiation time is 1-30 s;
and/or, subjecting the mixture to a second drying prior to the microwave irradiation; the second drying conditions include: the temperature is 80-120 ℃; the time is 1-10h.
18. The method of claim 17, wherein the second drying conditions comprise: the temperature is 80-100 ℃; the time is 1-5h.
19. The method according to any one of claims 9-16, wherein the method further comprises: washing the microwave irradiated product, or,
the product of the microwave irradiation is washed after being reacted with alkali;
wherein the washed product is subjected to a third drying.
20. Use of a hydrophobic surface according to any one of claims 1-8, or a hydrophobic surface obtainable by a method according to any one of claims 9-19, for anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, drag reduction, microfluidic control.
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| 选择性加热固相接枝法及其在聚丙烯功能化方面的应用;王崧合;中国博士学位论文全文数据库(第1期);第4.2.2.1节，第4.2.2.3节，第4.3.1节、第4.3.2节 * |
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