CN111333759A - Preparation method of zwitterionic polymer pattern on surface of solid substrate - Google Patents
Preparation method of zwitterionic polymer pattern on surface of solid substrate Download PDFInfo
- Publication number
- CN111333759A CN111333759A CN202010120613.4A CN202010120613A CN111333759A CN 111333759 A CN111333759 A CN 111333759A CN 202010120613 A CN202010120613 A CN 202010120613A CN 111333759 A CN111333759 A CN 111333759A
- Authority
- CN
- China
- Prior art keywords
- solid
- zwitterionic polymer
- initiator
- substrate
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 239000000758 substrate Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- -1 silicon wafer Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 229910052755 nonmetal Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 5
- 229960003237 betaine Drugs 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000000813 microcontact printing Methods 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229940117986 sulfobetaine Drugs 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical group CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- MTIWEMKOWPIQCA-UHFFFAOYSA-N azanium 2-methylbutane-2-sulfonate Chemical compound CCC(C)(C)S(=O)(=O)[O-].[NH4+] MTIWEMKOWPIQCA-UHFFFAOYSA-N 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- GJLLFUKNBLVYSV-UHFFFAOYSA-N 1-sulfanylundecan-2-yl 2-bromo-2-methylpropanoate Chemical compound BrC(C(=O)OC(CS)CCCCCCCCC)(C)C GJLLFUKNBLVYSV-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000002343 gold Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- KFGDVAGWRMWGOK-UHFFFAOYSA-N 2-bromo-2-methyl-n-(3-triethoxysilylpropyl)propanamide Chemical compound CCO[Si](OCC)(OCC)CCCNC(=O)C(C)(C)Br KFGDVAGWRMWGOK-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- KQNBBQSOHFVNDL-UHFFFAOYSA-N 2-bromopropan-2-ol Chemical compound CC(C)(O)Br KQNBBQSOHFVNDL-UHFFFAOYSA-N 0.000 description 1
- LKMXQNGHQPUEDY-UHFFFAOYSA-N 4-(4-nitrophenyl)benzenethiol Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=CC=C(S)C=C1 LKMXQNGHQPUEDY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- BLFQUIPKPPBXIQ-UHFFFAOYSA-N azane 2,2-dimethyl-4-(2-methylprop-2-enoyloxy)butanoic acid Chemical compound N.CC(=C)C(=O)OCCC(C)(C)C(O)=O BLFQUIPKPPBXIQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The invention provides a preparation method of a zwitterionic polymer pattern on the surface of a solid substrate, which mainly comprises the following steps: substrate cleaning, substrate grafting initiator, and grafting the zwitterionic polymer to the surface of the substrate through atom transfer radical polymerization to obtain a solid surface with the zwitterionic polymer micro-nano pattern. The zwitterionic polymer layer obtained by the method is a zwitterionic polymer modified solid surface prepared by adopting the atom transfer radical polymerization principle, has the advantage of good uniformity of the zwitterionic polymer layer, has organic pollution resistance and biological pollution resistance, and can be used for preventing biological pollution and resisting biological corrosion on the surface of a material.
Description
Technical Field
The invention relates to the technical field of material surface chemistry, in particular to a preparation method of a zwitterionic polymer pattern on the surface of a solid substrate.
Background
Zwitterionic polymers are a very important class of macromolecular materials, ranging from naturally occurring biopolymers such as proteins, nucleotides to synthetic tackifiers and soaps. Zwitterionic polymers can be broadly classified into the following two classes, betaines: namely, the same monomer unit is provided with both anionic groups and cationic groups, such as sulfobetaine, carboxylic betaine and phosphobetaine; secondly, polyampholytes, also known as alternating block copolymers, i.e. with 1: 1, positive and negative charges; the chemical structures of the two compounds respectively contain the same number of negative charges and positive charges, so that the whole compound is electrically neutral, and due to the combination of electrostatic interaction and hydrogen bonds, a super-hydrophilic layer with super-hydrophilicity and strong resistance to non-specific proteins can be formed on the surface of the zwitterionic polymer.
At present, only few reports exist on the method for preparing polymer layers on the surfaces of metal and inorganic non-metal solids. For example, there is a report in the literature that a pattern is engraved by an electron beam on a gold substrate modified by 4-nitrobiphenyl-4' -thiol, nitro is reduced to amino and then reacts with bromoisobutyryl bromide to connect an initiating group for atom transfer radical polymerization, and then N-isopropylacrylamide is initiated to polymerize to obtain a micro-nano pattern of the heat-sensitive poly (N-isopropylacrylamide) polymer brush; in addition, a long-chain alkyl disulfide at the tail end of bromo-isopropanolate is combined with the surface of the gold nanoparticle, and then atom transfer radical polymerization is initiated, so that the polymer-wrapped gold nanoparticle core-shell structure of which the surface of the gold nanoparticle is grafted with poly (4-vinylpyridine) is prepared. In addition, a zwitterionic polymer molecular brush consisting of methacrylic acid and dimethylaminoethyl methacrylate is prepared on a glass substrate by RAFT technology, and the molecular layer of the zwitterionic polymer is proved to improve the antifouling property of the glass substrate; as another example, a pre-synthesized random copolymer of [2- (methacryloyloxy) ethyl ] -dimethyl-acetic acid-ammonium and p-trimethoxysilylstyrene (9: 1) was attached to the surface of a glass or silicon wafer by alkoxy hydrolysis to form a thin layer of a zwitterionic polymer having a thickness of about 2nm, which was effective in inhibiting nonspecific adsorption and adhesion of proteins and cells.
Although the atom transfer radical polymerization has been applied to the production of polymers and is used for the modification and modification of micro-nano surfaces, no report of preparing zwitterionic polymer micro-nano patterns on the surface of a metal or inorganic non-metal solid substrate by in-situ polymerization reaction by adopting an atom transfer radical polymerization method is found at present, and the patent has novelty.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a zwitterionic polymer pattern on the surface of a solid substrate based on a surface-initiated atom transfer radical polymerization technology, the zwitterionic polymer layer obtained by the method is a zwitterionic polymer modified solid surface prepared by adopting an atom transfer radical polymerization principle, has the advantage of good uniformity of the zwitterionic polymer layer, has organic pollution resistance and biological pollution resistance, and can be used for preventing biological pollution and resisting biological corrosion on the surface of a material.
The technical scheme of the invention is as follows:
a method for preparing a zwitterionic polymer pattern on the surface of a solid substrate mainly comprises the following steps: substrate cleaning, substrate grafting initiator, and grafting the zwitterionic polymer to the surface of the substrate through atom transfer radical polymerization to obtain a solid surface with the zwitterionic polymer micro-nano pattern.
The preparation method of the zwitterionic polymer pattern on the surface of the solid substrate comprises the following steps:
(1) pretreatment of the surface of the solid substrate: cleaning the surface of the substrate to remove impurities on the surface;
(2) introducing a pattern of initiator to the substrate surface by microcontact printing: firstly, carrying a solution of an initiator with a specific structure and an end of which is an atom transfer radical polymerization initiation group on an organic silicon seal with a pattern, volatilizing a solvent, transferring the pattern of the initiator to the surface of a substrate at a certain pressure, and forming an initiator layer on the surface by combining a relatively stable chemical adsorption bond or a covalent bond;
(3) polymerization of zwitterionic polymer monomer on the surface of a metal substrate: placing the solid substrate printed with the initiator in a polymerization reaction system containing a zwitterionic polymer monomer, a sacrificial initiator, a catalyst, a cocatalyst and a solvent, and carrying out polymerization reaction under certain conditions;
(4) surface cleaning of solid substrates carrying patterns: after the reaction is finished, the surface of the solid substrate is repeatedly cleaned by deionized water, the solvent, the catalyst, the cocatalyst and the like are removed, and the polymer layer is reserved.
In the application, an initiator is adopted to fix the solid surface, then the solid surface is placed in a solution containing a zwitterionic monomer, and a polymer layer is formed on the surface in an in-situ growth mode by adopting an atom transfer radical polymerization technology; a product obtained by using a principle transfer radical polymerization technology to carry out the zwitterionic compound according to the principle of atom transfer radical polymerization has the characteristic of good molecular weight uniformity, and an obtained polymerization layer is more uniform.
Preferably, in the step (1), the surface of the solid substrate is cleaned by using a cleaning agent to remove impurities, organic pollutants and the like on the surface; the solid comprises a metallic solid or an inorganic non-metallic solid.
Preferably, the metal solid refers to gold, silver, copper, iron, zinc, lead and the like which can form a relatively stable metal sulfur bond with thiol; the inorganic nonmetal refers to solid with or carrying hydroxyl on the surface or inorganic nonmetal solid with hydroxyl on the surface after acid and alkali treatment.
Preferably, the metal solid comprises a metal hydroxide, a mixed metal hydroxide or a metal oxide; the inorganic non-metallic solid comprises a metal hydroxide, a mixed metal hydroxide or a metal oxide, such as silicon wafer, silica, glass, a metal solid oxide or a solid oxysalt.
Preferably, the silica is crystalline quartz and/or amorphous silica solid; the metal solid oxide is ferric oxide or aluminum oxide; the solid oxysalt is silicate, carbonate or phosphate, etc.
Preferably, in the step (2), the initiator refers to an initiator having a specific structure with an atom transfer radical polymerization initiating group at the end and a group attached to the solid surface; wherein, the atom transfer free radical polymerization initiating group is bromo-isobutanoylamino or bromo-isobutanoyloxy, etc.; the group connected with the surface of the metal substrate is sulfydryl and can react with the metal substrate to generate a metal-sulfur bond to realize connection; the group connected with the surface of the inorganic non-metallic solid is alkoxy silane, and S i-OH formed by alkoxy hydrolysis can be condensed with hydroxyl on the surface of the solid, so that the initiator and the surface of the inorganic non-metallic solid substrate form covalent bond connection; the two functional groups are connected by alkyl chains of different lengths, the number of carbon atoms in the alkyl chain varying from 2 to 18.
Preferably, the alkoxysilane comprises trimethoxysilane or triethoxysilane.
Preferably, in step (2), the shape and size of the pattern are determined by the pattern style of the silicone stamp, including strip, square, circle, etc., and also including full coverage; the optimized condition of the imprinting initiator pattern is that the concentration of the initiator is 0.1-2.5mmol/L, the applied pressure is 0.1-1kPa, and the imprinting time is 0.5-10 h.
Preferably, in step (3), the zwitterionic polymer monomer comprises a part containing double bonds in the structure, such as acrylate, methacrylate or acrylamide, and the like, and the zwitterionic part in the structure is betaine, such as sulfobetaine, carboxybetaine, phosphobetaine, and the like.
Preferably, in step (3), the polymerization conditions: the solvent is a mixture of water and alcohol with the volume ratio of 0.05-0.5, the monomer concentration is 1-3mol/L, the reaction temperature is 10-50 ℃, and the reaction time is 5-24 h; wherein, the concentration of the sacrificial initiator is 0.08-0.15mol/L, the concentration of the catalyst is 0.08-0.12mol/L, and the concentration of the cocatalyst is 0.3-0.9 mol/L; the sacrificial initiator is ethyl 2-bromo-2-methylpropionate, the catalyst is CuBr, the cocatalyst is pentamethyldiethylenetriamine, and the alcohol in the mixed solvent is methanol, ethanol or isopropanol.
Compared with the prior art, the invention has the beneficial effects that:
the biological pollution resistance of the zwitterionic polymer enables the zwitterionic polymer to be widely applied to related fields such as biological medicine materials. The method prepares the micron-scale or nano-scale zwitterionic polymer pattern with specific design on the surface of the solid substrate, can change the adsorption behavior of the surface of the substrate, can adjust the surface properties of the metal substrate, such as wettability, pollution resistance, corrosion resistance, thermal stability and the like, and can be used for pollution prevention, corrosion prevention and the like. In addition, the zwitterionic polymer pattern can be used for laboratory studies of biofouling, corrosion resistance, and the like.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of the preparation process of a zwitterionic polymer pattern on the gold plate surface.
FIG. 2 is a schematic diagram of a process for preparing a zwitterionic polymer pattern on the surface of a glass sheet.
FIG. 3 is a NMR spectrum of a zwitterionic polymer (A).
FIG. 4 is an infrared spectrum (B) of a zwitterionic polymer.
FIG. 5 is an optical micrograph of an initiator (A) -modified gold plate.
FIG. 6 is an optical micrograph of the zwitterionic polymer (B) modified gold plaque.
FIG. 7 is an optical microscope photograph of a glass plate modified with initiator (A).
FIG. 8 is an optical microscope photograph of a zwitterionic polymer (B) modified glass slide.
FIG. 9 shows atomic force microscope photographs (A) and (B) of zwitterionic polymer-modified gold flakes and thickness analysis of the surface polymer pattern (C, D).
FIG. 10 is a two-dimensional (A) and three-dimensional (B) atomic force microscope photomicrograph of a zwitterionic polymer-modified glass sheet and a thickness analysis plot of the surface polymer pattern (C, D).
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
The present embodiment will be described in detail with reference to fig. 1, 3, 4, 5, 6 and 9; in the embodiment, a gold-plated silicon wafer is used as a gold wafer substrate, 2- (2-bromoisobutyryloxy) undecyl mercaptan is used as an initiator with a special structure, and a [3- (methacrylamide) propyl ] dimethyl- (3-propyl sulfonic acid) ammonium monomer is selected to prepare a poly [3- (methacrylamide) propyl ] dimethyl- (3-propyl sulfonic acid) ammonium zwitterionic polymer pattern on the surface of gold, and the pattern is characterized; a schematic of the preparation process is shown in FIG. 1.
(1) Pretreatment of metal substrates
Soaking a 10mm × 8mm gold-plated silicon wafer in a washing solution prepared from concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 3:1 for 1h, taking out the silicon wafer, washing the silicon wafer with deionized water, and drying the silicon wafer;
(2) microcontact printing of metal substrate surfaces to obtain initiator patterns
Initiator solution: the specific preparation process comprises the step of taking 353.36mg of 2- (2-bromoisobutyryloxy) undecyl mercaptan, and dissolving the 2- (2-bromoisobutyryloxy) undecyl mercaptan in 500mL of dichloromethane solution to obtain a solution with the concentration of 2 mmol/L.
Dripping 20 μ L of the initiator solution on a stamp (the size of the stamp is 5mm × 4mm) printed with a pattern, covering the stamp on the substrate processed in the step (1) after the solvent is volatilized, loading a heavy object of about 1.5g, and stamping for 6 h;
(3) polymerization of zwitterionic monomers
Putting 57.2mg of CuBr and 1.46g of [3- (methacrylamide) propyl ] dimethyl- (3-propyl sulfonic acid) ammonium monomer into a 50mL Schlenk bottle, putting the gold-plated silicon wafer printed with the initiator pattern obtained in the step (2) into a reaction system, vacuumizing, introducing nitrogen, and repeating the operation for 4 times to remove oxygen in the reaction system;
placing 1mL of ultrapure water, 2mL of isopropanol and 0.5mL of pentamethyldiethylenetriamine in a sample bottle of about 10mL, introducing nitrogen for bubbling for 20 minutes (discharging oxygen in the solution), injecting the liquid in the sample bottle by using an injector into a reaction system in a Schlenk bottle, and dissolving a monomer under stirring; then, 60 μ L of initiator 2- (2-bromoisobutyryloxy) undecyl mercaptan and 1mL of isopropanol were added into a sample bottle, and after bubbling with nitrogen for 20 minutes, the mixture was injected into the reaction system in a Schlenk bottle by using an injector; finally, setting the reaction temperature at 50 ℃, and stirring for reaction for 24 hours;
(4) post-processing and characterization
After the reaction is finished, opening a Schlenk reaction bottle, taking out the gold flakes, and washing the gold flakes by using deionized water for later testing; the remaining reaction solution was dialyzed using dialysis bag (Mw3500) to remove solvent, catalyst, cocatalyst, etc., and the polymer obtained by polymerization initiated by the sacrificial initiator in the dialysis bag was collected for nuclear magnetic and infrared spectroscopy characterization, and the results are shown in FIGS. 3 and 4.
Example 2
This embodiment will be described in detail with reference to fig. 2, 3, 4, 7, 8 and 10; in the embodiment, a glass sheet is selected as an inorganic non-metallic solid substrate, 3- (2-bromoisobutyramido) propyl-triethoxysilane is selected as an initiator, and a [3- (methacrylamide) propyl ] dimethyl- (3-propylsulfonic acid) ammonium monomer is selected to prepare a poly [3- (methacrylamide) propyl ] dimethyl- (3-propylsulfonic acid) ammonium zwitterionic polymer pattern on the surface of the glass sheet, and the pattern is characterized; the preparation process is schematically shown in FIG. 2.
(1) Pretreatment of solid substrates
Soaking a glass sheet of 10mm × 8mm in a washing solution prepared from concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 3:1 for 1h, taking out, washing with deionized water, drying, soaking in 10mmol/L sulfuric acid for 30min for acidification, taking out, and drying;
(2) grafting of substrate surface initiators
Initiator solution: the specific preparation process is that 370.4mg of 3- (2-bromoisobutyramido) propyl-triethoxysilane is added into 500ml of absolute ethyl alcohol to obtain (2mmol/L) initiator solution.
Dripping 20 μ L of the above initiator solution on a stamp (5mm × 4mm) with pattern, covering the stamp on the treated glass sheet after the solvent is volatilized, loading a weight of about 1.5g, and stamping for 6 h;
(3) polymerization of zwitterionic monomers
Putting 57.2mg of CuBr and 1.46g of [3- (methacrylamide) propyl ] dimethyl- (3-propyl sulfonic acid) ammonium monomer into a 50ml Schlenk bottle, putting the glass sheet printed with the initiator pattern obtained in the step (2) into a reaction system, vacuumizing, and introducing nitrogen gas for 3 times to remove oxygen in the reaction system;
1mL of ultrapure water, 2mL of isopropyl alcohol, and 0.5mL of pentamethyldiethylenetriamine were placed in a 10mL sample bottle, and nitrogen was bubbled for 20 minutes (oxygen in the solution was discharged); injecting liquid in a sample bottle by using an injector into a reaction system in a Schlenk bottle, and dissolving a monomer under stirring; then, 60 μ L of 2- (2-bromoisobutyryloxy) undecylmercaptan (sacrificial initiator) and 1mL of isopropanol were added to a sample bottle, and after bubbling with nitrogen for 20 minutes, the mixture was injected into the reaction system in a Schlenk bottle by using a syringe; then setting the reaction temperature at 50 ℃, and stirring for reaction for 24 hours;
(4) post-processing and characterization
After the reaction is finished, opening a Schlenk reaction bottle, taking out the glass sheet, and washing the glass sheet with deionized water for characterization; the remaining reaction solution was dialyzed using dialysis bag (Mw3500) to remove solvent and catalyst, cocatalyst, etc., and the polymer obtained by polymerization initiated by the sacrificial initiator in the dialysis bag was collected and subjected to nuclear magnetic and infrared spectroscopy characterization, the results of which were in accordance with the data in example 1.
Although the present invention has been described in detail by referring to the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or alterations of the embodiments of the present invention may be made by those skilled in the art without departing from the spirit and scope of the present invention, and such modifications or alterations are intended to be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a zwitterionic polymer pattern on the surface of a solid substrate is characterized by mainly comprising the following steps: substrate cleaning, substrate grafting initiator, and grafting the zwitterionic polymer to the surface of the substrate through atom transfer radical polymerization to obtain a solid surface with the zwitterionic polymer micro-nano pattern.
2. The method for preparing the zwitterionic polymer pattern on the surface of the solid substrate according to claim 1, characterized by comprising the following specific steps:
(1) pretreatment of the surface of the solid substrate: cleaning the surface of the substrate to remove impurities on the surface;
(2) introducing a pattern of initiator to the substrate surface by microcontact printing: firstly, carrying a solution of an initiator with a specific structure and an end of which is an atom transfer radical polymerization initiation group on an organic silicon seal with a pattern, volatilizing a solvent, transferring the pattern of the initiator to the surface of a substrate at a certain pressure, and forming an initiator layer on the surface by combining a relatively stable chemical adsorption bond or a covalent bond;
(3) polymerization of zwitterionic polymer monomer on the surface of a metal substrate: placing the solid substrate printed with the initiator in a polymerization reaction system containing a zwitterionic polymer monomer, a sacrificial initiator, a catalyst, a cocatalyst and a solvent, and carrying out polymerization reaction under certain conditions;
(4) surface cleaning of solid substrates carrying patterns: after the reaction is finished, the surface of the solid substrate is repeatedly cleaned by deionized water, the solvent, the catalyst, the cocatalyst and the like are removed, and the polymer layer is reserved.
3. The method for preparing the zwitterionic polymer pattern on the surface of the solid substrate according to claim 2, wherein in the step (1), the surface of the solid substrate is cleaned by a cleaning agent, and the solid comprises metal solid or inorganic non-metal solid.
4. The method for preparing the zwitterionic polymer pattern on the surface of the solid substrate according to claim 3, wherein the metal solid is gold, silver, copper, iron, zinc, lead and other solids capable of forming relatively stable metal sulfur bonds with thiol; the inorganic nonmetal refers to solid with or carrying hydroxyl on the surface or inorganic nonmetal solid with hydroxyl on the surface after acid and alkali treatment.
5. The method of preparing the zwitterionic polymer pattern according to claim 4, wherein the metal solid comprises a metal hydroxide, mixed metal hydroxide or metal oxide; the inorganic non-metallic solid comprises a metal hydroxide, a mixed metal hydroxide or a metal oxide, such as silicon wafer, silica, glass, a metal solid oxide or a solid oxysalt.
6. The method of claim 5, wherein the silica is crystalline quartz and/or amorphous silica solid; the metal solid oxide is ferric oxide or aluminum oxide; the solid oxysalt is silicate, carbonate or phosphate, etc.
7. The method for preparing zwitterionic polymer patterns on the surface of a solid substrate according to any one of claims 2-6, characterized in that in step (2), the initiator refers to an initiator having a specific structure with atom transfer radical polymerization initiating groups at the ends and groups attached to the solid surface; wherein, the atom transfer free radical polymerization initiating group is bromo-isobutanoylamino or bromo-isobutanoyloxy, etc.; the group connected with the surface of the metal substrate is sulfydryl; the group connected with the surface of the inorganic nonmetallic solid is alkoxy silane; the two functional groups are connected by alkyl chains of different lengths, the number of carbon atoms in the alkyl chain varying from 2 to 18.
8. The method of claim 7, wherein the alkoxysilane comprises trimethoxysilane or triethoxysilane.
9. The method for preparing zwitterionic polymer patterns on surface of solid substrate according to claim 8, characterized in that in step (2), said patterns, the shape and size of which are determined by the pattern style of silicone stamp, including stripes, squares, circles, etc., and also including full-face coverage; the optimized condition of the imprinting initiator pattern is that the concentration of the initiator is 0.1-2.5mmol/L, the applied pressure is 0.1-1kPa, and the imprinting time is 0.5-10 h.
10. The method for preparing the zwitterionic polymer pattern on the surface of the solid substrate according to claim 9, wherein in the step (3), the zwitterionic polymer monomer comprises a part containing double bonds in the structure, such as acrylate, methacrylate or acrylamide, and the like, and the zwitterionic part in the structure is betaine, such as sulfobetaine, carboxylic betaine, phosphoric betaine, and the like; polymerization conditions: the solvent is a mixture of water and alcohol with the volume ratio of 0.05-0.5, the monomer concentration is 1-3mol/L, the reaction temperature is 10-50 ℃, and the reaction time is 5-24 h; wherein, the concentration of the sacrificial initiator is 0.08-0.15mol/L, the concentration of the catalyst is 0.08-0.12mol/L, and the concentration of the cocatalyst is 0.3-0.9 mol/L; the sacrificial initiator is ethyl 2-bromo-2-methylpropionate, the catalyst is CuBr, the cocatalyst is pentamethyldiethylenetriamine, and the alcohol in the mixed solvent is methanol, ethanol or isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010120613.4A CN111333759A (en) | 2020-02-26 | 2020-02-26 | Preparation method of zwitterionic polymer pattern on surface of solid substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010120613.4A CN111333759A (en) | 2020-02-26 | 2020-02-26 | Preparation method of zwitterionic polymer pattern on surface of solid substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111333759A true CN111333759A (en) | 2020-06-26 |
Family
ID=71177782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010120613.4A Pending CN111333759A (en) | 2020-02-26 | 2020-02-26 | Preparation method of zwitterionic polymer pattern on surface of solid substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111333759A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022267841A1 (en) * | 2021-06-23 | 2022-12-29 | 清华大学 | Fibre product and preparation method therefor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2870143A1 (en) * | 2004-05-12 | 2005-11-18 | Commissariat Energie Atomique | SOL-GEL METHOD OF FUNCTIONALIZING A SURFACE OF A SOLID SUBSTRATE. |
| AU2005260147A1 (en) * | 2004-07-01 | 2006-01-12 | Mip Technologies Ab | Polymer films |
| US20090009852A1 (en) * | 2001-05-15 | 2009-01-08 | E Ink Corporation | Electrophoretic particles and processes for the production thereof |
| CN101959972A (en) * | 2008-01-04 | 2011-01-26 | 斯帕克西斯公司 | Surface modification of metal oxide nanoparticles |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN102675654A (en) * | 2012-04-11 | 2012-09-19 | 中国科学院长春应用化学研究所 | Preparation method of segmented polymer brush |
| CN105294887A (en) * | 2015-11-24 | 2016-02-03 | 华南理工大学 | Amphion polymer modified anti-adhesion surface with dopamine as anchor, and making method thereof |
| CN108641892A (en) * | 2018-04-17 | 2018-10-12 | 广州波奇亚标准及检测技术有限公司 | One kind being used for the patterned novel micro-contact printing system of cell |
-
2020
- 2020-02-26 CN CN202010120613.4A patent/CN111333759A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090009852A1 (en) * | 2001-05-15 | 2009-01-08 | E Ink Corporation | Electrophoretic particles and processes for the production thereof |
| FR2870143A1 (en) * | 2004-05-12 | 2005-11-18 | Commissariat Energie Atomique | SOL-GEL METHOD OF FUNCTIONALIZING A SURFACE OF A SOLID SUBSTRATE. |
| AU2005260147A1 (en) * | 2004-07-01 | 2006-01-12 | Mip Technologies Ab | Polymer films |
| CN101959972A (en) * | 2008-01-04 | 2011-01-26 | 斯帕克西斯公司 | Surface modification of metal oxide nanoparticles |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN102675654A (en) * | 2012-04-11 | 2012-09-19 | 中国科学院长春应用化学研究所 | Preparation method of segmented polymer brush |
| CN105294887A (en) * | 2015-11-24 | 2016-02-03 | 华南理工大学 | Amphion polymer modified anti-adhesion surface with dopamine as anchor, and making method thereof |
| CN108641892A (en) * | 2018-04-17 | 2018-10-12 | 广州波奇亚标准及检测技术有限公司 | One kind being used for the patterned novel micro-contact printing system of cell |
Non-Patent Citations (3)
| Title |
|---|
| DAVID N ET AL.: ""Microcontact Printing: Limitations and Achievements"", 《ADVANCED MATERIALS》 * |
| 慈吉良 等: ""两性离子聚合物的抗蛋白质吸附机理及其应用"", 《化学进展》 * |
| 王怀新: ""基于两性离子聚合物抗吸附阵列芯片的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022267841A1 (en) * | 2021-06-23 | 2022-12-29 | 清华大学 | Fibre product and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Thermosensitive nanostructures comprising gold nanoparticles grafted with block copolymers | |
| KR101832025B1 (en) | Monomer and block copolymer | |
| Zhang et al. | Surface-initiated Cu (0) mediated controlled radical polymerization (SI-CuCRP) using a copper plate | |
| JP6496318B2 (en) | Block copolymer | |
| US10240035B2 (en) | Block copolymer | |
| JP6483694B2 (en) | Monomers and block copolymers | |
| Li et al. | Air‐tolerantly surface‐initiated AGET ATRP mediated by iron catalyst from silica nanoparticles | |
| Liu et al. | A novel and universal route to SiO2-supported organic/inorganic hybrid noble metal nanomaterials via surface RAFT polymerization | |
| JP2016539239A (en) | Block copolymer | |
| WO2002028914A2 (en) | A catalyst system for controlled polymerization | |
| Wei et al. | Stratified polymer brushes from microcontact printing of polydopamine initiator on polymer brush surfaces | |
| CN109224863A (en) | A kind of preparation method of amphipathic modified antipollution polyamide nanofiltration membrane | |
| CN111542550B (en) | Base for forming polymer brush, method for producing the base, and precursor liquid used in the method | |
| JP6645324B2 (en) | Surface modified film | |
| Xiong et al. | A facile approach to modify poly (dimethylsiloxane) surfaces via visible light-induced grafting polymerization | |
| Sangermano et al. | Light induced grafting-from strategies as powerful tool for surface modification | |
| CN111333759A (en) | Preparation method of zwitterionic polymer pattern on surface of solid substrate | |
| JP5545694B2 (en) | Carbon-containing metal oxide hollow particles and method for producing the same | |
| Chang et al. | Roughness-enhanced thermal-responsive surfaces by surface-initiated polymerization of polymer on ordered ZnO pore-array films | |
| Chen et al. | Polymeric vesicles with well-defined poly (methyl methacrylate)(PMMA) brushes via surface-initiated photopolymerization (SIPP) | |
| Yang et al. | Immobilization of RAFT agents on silica nanoparticles utilizing an alternative functional group and subsequent surface‐initiated RAFT polymerization | |
| Nguyen et al. | Facile and efficient Cu (0)-mediated radical polymerisation of pentafluorophenyl methacrylate grafting from poly (ethylene terephthalate) film | |
| Yang et al. | Synthesis, characterization, and tunable wettability of poly (ionic liquid) brushes via nitroxide-mediated radical polymerization (NMP) | |
| Raghuraman et al. | Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature | |
| Li et al. | Surface and particle modification via the RAFT process: approach and properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |