CN109400827B - Preparation method of polymer molecular brush with ultrahigh grafting density - Google Patents
Preparation method of polymer molecular brush with ultrahigh grafting density Download PDFInfo
- Publication number
- CN109400827B CN109400827B CN201811307198.2A CN201811307198A CN109400827B CN 109400827 B CN109400827 B CN 109400827B CN 201811307198 A CN201811307198 A CN 201811307198A CN 109400827 B CN109400827 B CN 109400827B
- Authority
- CN
- China
- Prior art keywords
- solution
- initiator
- substrate
- sio
- bromo
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 80
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000758 substrate Substances 0.000 claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 22
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 17
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical group Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 23
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- -1 1-bromo-undecene tetrahydrofuran Chemical compound 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- YYTZARBMHCHZEE-UHFFFAOYSA-N docos-21-enyl 2-bromo-2-phenylacetate Chemical compound C(CCCCCCCCCCCCCCCCCCCC=C)OC(C(C1=CC=CC=C1)Br)=O YYTZARBMHCHZEE-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000861 blow drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- WAKFRZBXTKUFIW-UHFFFAOYSA-N 2-bromo-2-phenylacetic acid Chemical compound OC(=O)C(Br)C1=CC=CC=C1 WAKFRZBXTKUFIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005052 trichlorosilane Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000013545 self-assembled monolayer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002094 self assembled monolayer Substances 0.000 description 8
- CZZZWEDUOMBCQE-UHFFFAOYSA-N 1-bromoundec-1-ene Chemical compound CCCCCCCCCC=CBr CZZZWEDUOMBCQE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000001845 vibrational spectrum Methods 0.000 description 3
- XFGANBYCJWQYBI-UHFFFAOYSA-N 11-bromoundecan-1-ol Chemical compound OCCCCCCCCCCCBr XFGANBYCJWQYBI-UHFFFAOYSA-N 0.000 description 2
- GGXRSUUOWQBVFB-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanoyl bromide Chemical group BrCC(Br)(C)C(Br)=O GGXRSUUOWQBVFB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IITMQIDQEDAKOL-UHFFFAOYSA-M lithium 11-bromoundecanoate Chemical compound BrCCCCCCCCCCC(=O)[O-].[Li+] IITMQIDQEDAKOL-UHFFFAOYSA-M 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002460 vibrational spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of polymer synthesis. The invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, which comprises the following steps: firstly, preparing SiO from monocrystalline silicon wafer2On a substrate of/Si, then on SiO2A monomolecular layer of a self-assembly initiator on the surface of the Si substrate; the initiator is 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate; and finally, reacting with cuprous bromide, styrene, pentamethyl diethyl triamine and toluene under the protection of nitrogen to prepare the ultrahigh-grafting-density polymer molecular brush. The example results show that the thickness of the polymer molecular brush provided by the invention is 55-65 nm, and the grafting density is 1.21-1.23 chains/nm2。
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a preparation method of a polymer molecular brush with ultrahigh grafting density.
Background
The polymer molecular brush is a special polymer assembly system, one end of a molecular chain of the polymer molecular brush is fixed on the solid surface through a covalent bond, the physical and chemical properties of the solid surface can be effectively adjusted, and the polymer molecular brush has wide application in the fields of colloid stabilizers, biological materials, marine antifouling, lubrication, microelectronic industry and the like. For example, in the field of biomaterials, non-specific interactions between a solid surface and proteins, such as deposition of biological cells, bacteria, etc., on the surface or interface, can be attenuated by preparing a hydrophilic polymer molecular brush on the solid surface.
The grafting density of the polymer molecular brush determines the conformation of the molecular chain and the physical properties of the molecular brush. The conformation of molecular chains in the low grafting density molecular brush is in a random coil structure; the molecular chain can be gradually stretched by increasing the grafting density of the molecular brush; when the graft density is sufficiently high, the polymer chains exhibit a "hairbrush" like structure, exhibiting an increased glass transition temperature and increased thermal stabilityThe physical properties of the polymer are obviously better than those of the conventional polymer, such as high strength, increased elastic modulus, reduced surface friction coefficient and the like. For example, for polystyrene molecular brushes, the grafting density is from 0.1nm-2Increased to 0.6nm-2When the glass transition temperature is raised by 60 ℃, the glass transition temperature shows ultrahigh thermal stability. In the prior art, Yamamoto and the like think that the saturated grafting density of a dibromo isobutyryl bromide Atom Transfer Radical Polymerization (ATRP) molecular brush utilizing a common initiator is 0.6chains/nm aiming at a polystyrene system2. Therefore, the improvement of the grafting density of the polymer molecular brush is the key for improving the physical properties of the polymer molecular brush, and is an important method for optimizing the related properties of the molecular brush material. However, the preparation of polymer molecular brushes with ultra-high grafting density is still a big problem due to the effects of steric hindrance, volume exclusion and the like between the molecular brush chains.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, and the method provided by the invention can be used for preparing a polymer molecular brush with grafting density of 1.22nm-2The polymer molecular brush greatly improves the grafting density of the polymer molecular brush.
The invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, which comprises the following steps:
(1) immersing the monocrystalline silicon piece into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution, heating, and then washing and blow-drying the heated monocrystalline silicon piece in sequence to obtain SiO2a/Si substrate;
(2) SiO obtained in the step (1)2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate; the initiator is 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate;
(3) under the protection of nitrogen, the initiator obtained in the step (2) is functionalized SiO2And mixing the/Si substrate, cuprous bromide, styrene, pentamethyl diethyl triamine and toluene, and then heating to obtain the ultrahigh-grafting-density polymer molecular brush.
Preferably, SiO in the step (1)2A silicon dioxide layer in the/Si substrate covers the surface of the silicon substrate; the thickness of the silicon dioxide layer is 1.5-2.5 nm.
Preferably, the mass concentration of the aqueous hydrogen peroxide solution in the step (1) is 25-35%, and the volume ratio of the concentrated sulfuric acid to the aqueous hydrogen peroxide solution is 2.5-3.5: 1.
Preferably, the temperature of the heating treatment in the step (1) is 80-100 ℃; the heating treatment time is 50-70 min.
Preferably, the solvent of the initiator solution in the step (2) is toluene; the concentration of the initiator solution is 0.5-1.5 mmol/L.
Preferably, the environmental humidity of the standing treatment in the step (2) is less than 30%; the standing treatment time is 24-25 h.
Preferably, the dosage ratio of the cuprous bromide, the styrene, the pentamethyldiethyltriamine and the toluene in the step (3) is 0.04-0.05 g/4-6 mL/0.2-0.3 mL/8-12 mL.
Preferably, the temperature of the heating treatment in the step (3) is 80-100 ℃.
Preferably, the preparation method of the initiator comprises the following steps:
(a) dripping 1, 2-dibromoethane into tetrahydrofuran dispersion liquid of magnesium chips, and then dripping 1-bromo-undecene tetrahydrofuran solution to obtain a mixed solution; the dropping speed of the 1-bromo-undecene tetrahydrofuran solution is 0.01-0.02 mL/s;
(b) heating the mixed solution obtained in the step (a), performing low-temperature treatment, adding CuI, heating to 0 ℃, immediately cooling, adding 11-bromine-1-lithium undecanoate solution, and stirring to obtain 21-eicosadien-1-ol;
(c) mixing the 21-eicosadien-1-ol obtained in step (b), alpha-bromophenylacetic acid, 4-dimethylaminopyridine and dichloromethane to obtain a solution A; in an ice bath, dropwise adding a dichloromethane solution of N, N' -dicyclohexylcarbodiimide into the solution A, and stirring at room temperature to obtain 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester;
(d) stirring the 2-bromo-2-phenylacetic acid-21-docosene-1-yl ester obtained in the step (c) and trichlorosilane in the presence of a Karstedt catalyst, and then sequentially filtering and removing a solvent from the filtrate to obtain an initiator.
Preferably, the temperature of the low-temperature treatment in the step (b) is-75 to-80 ℃.
The invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, which comprises the following steps: immersing the monocrystalline silicon piece into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution, heating, and then washing and blow-drying the heated monocrystalline silicon piece in sequence to obtain SiO2a/Si substrate; mixing SiO2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate; the initiator is 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate; SiO with initiator functionalized under nitrogen protection2And mixing the/Si substrate, cuprous bromide, styrene, pentamethyl diethyl triamine and toluene, and then heating to obtain the ultrahigh-grafting-density polymer molecular brush.
The invention takes the initiator self-assembled monolayer as an initiating group to carry out surface initiation, and transfers the initiator in the solution to the surface of the self-assembled monolayer through initiator free radical polymerization to prepare the ultrahigh grafting density polystyrene molecular brush. Because the density of the initiator on the surface of the substrate is extremely high, and the benzyl bromide in the initiator is introduced to improve the activity of the initiator, the benzyl bromide and the initiator act together to improve the grafting density of the molecular brush. The example results show that the thickness of the polymer molecular brush provided by the invention is 55-65 nm, and the grafting density is 1.21-1.23 chains/nm2。
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of 21-eicosadien-1-ol prepared in example 1 of the present invention;
FIG. 2 is a hydrogen nuclear magnetic spectrum of an initiator 22- (trichlorosilyl) docosyl-2-bromo-2-phenylacetate prepared in example 1 of the present invention;
FIG. 3 is a schematic view of the preparation process of the ultra-high graft density polymer molecular brush of the present invention;
FIG. 4 is SiO with functionalized initiator of example 1 of the invention2Atomic force microscope spectrogram and sum frequency vibration spectrum of the self-assembled monolayer on the surface of the Si substrate;
FIG. 5 shows the principle of ellipsometry;
FIG. 6 is a graph comparing the thickness of a molecular brush made according to an example of the present invention with the thickness of a molecular brush made according to a comparative example;
FIG. 7 is a schematic view of the determination of the molecular weight of the polymer molecular brush of the present invention;
FIG. 8 is a graph showing the molecular weight of a polymer molecular brush prepared in example 1 of the present invention;
FIG. 9 is a molecular weight diagram of a polymer molecular brush prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, which comprises the following steps:
(1) immersing the monocrystalline silicon piece into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution, heating, and then washing and blow-drying the heated monocrystalline silicon piece in sequence to obtain SiO2a/Si substrate;
(2) SiO obtained in the step (1)2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate; the initiator is 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate;
(3) under the protection of nitrogen, the initiator obtained in the step (2) is functionalized SiO2And mixing the/Si substrate, cuprous bromide, styrene, pentamethyl diethyl triamine and toluene, and then heating to obtain the ultrahigh-grafting-density polymer molecular brush.
The method comprises the steps of immersing a monocrystalline silicon wafer into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide, heating, taking out the heated monocrystalline silicon wafer, and sequentially washing and blow-drying to obtain SiO2a/Si substrate.
In the invention, the crystal plane orientation of the monocrystalline silicon piece is preferably (100), and the thickness of the monocrystalline silicon piece is preferably 400-600 μm, and more preferably 500 μm. In the present invention, the single crystal silicon wafer is preferably purchased from Jinxiyuan technologies, Inc., Zhejiang. The present invention does not particularly require the source of the chemical agent to be used hereinafter, and commercially available products may be used.
In the present invention, the mass concentration of the aqueous hydrogen peroxide solution is preferably 25% to 35%, and more preferably 30%; the volume ratio of the concentrated sulfuric acid to the aqueous hydrogen peroxide solution is preferably 2.5-3.5: 1, and more preferably 3.0: 1.
The volume of the mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution of the present invention is not particularly limited as long as the single crystal silicon wafer can be immersed.
In the invention, the temperature of the heating treatment is preferably 80-100 ℃, more preferably 85-95 ℃, and more preferably 90 ℃; the time is preferably 50 to 70min, more preferably 55 to 65min, and still more preferably 60 min.
According to the invention, the monocrystalline silicon wafer is immersed in the mixed solution of concentrated sulfuric acid and hydrogen peroxide water solution and is subjected to heating treatment, so that organic pollutants on the surface of the monocrystalline silicon wafer can be effectively removed.
After the heating treatment is finished, the invention sequentially washes and dries the heated monocrystalline silicon wafer to obtain SiO2a/Si substrate.
The silicon on the surface of the monocrystalline silicon wafer provided by the invention is inevitably oxidized by air in the air, and silicon dioxide is generated on the surface of the monocrystalline silicon wafer.
In the present invention, the washing preferably includes water washing and anhydrous ethanol washing in this order; the water-washed detergent is preferably secondary deionized water. The present invention is not particularly limited to the specific embodiments of the water washing and the absolute ethanol washing, and may be performed in a manner well known to those skilled in the art.
In the present invention, the blow-drying treatment preferably includes a nitrogen blow-drying treatment. The nitrogen blow-drying treatment of the present invention is not particularly limited, and may be performed in a manner known to those skilled in the art.
In the present invention, SiO is obtained2A silicon dioxide layer in the/Si substrate covers the surface of the silicon substrate; the thickness of the silicon dioxide layer is preferably 1.5-2.5 nm, and more preferably 2.0 nm.
To obtain SiO2After the/Si substrate, the invention uses the SiO2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate.
In the present invention, the initiator is preferably 22- (trichlorosilyl) docosyl-2-bromo-2-phenylacetate, and the initiator preferably has the structure shown in formula I:
in the present invention, the method for preparing the initiator preferably comprises the steps of:
(a) dripping 1, 2-dibromoethane into tetrahydrofuran dispersion liquid of magnesium chips, and then dripping 1-bromo-undecene tetrahydrofuran solution to obtain a mixed solution; the dropping speed of the 1-bromo-undecene tetrahydrofuran solution is 0.01-0.02 mL/s;
(b) heating the mixed solution obtained in the step (a), cooling, adding CuI, heating to 0 ℃, immediately cooling, adding 11-bromine-1-lithium undecanoate solution, and stirring to obtain 21-eicosadien-1-ol;
(c) mixing the 21-eicosadien-1-ol obtained in step (b), alpha-bromophenylacetic acid, 4-dimethylaminopyridine and dichloromethane to obtain a solution A; in an ice bath, dropwise adding a dichloromethane solution of N, N' -dicyclohexylcarbodiimide into the solution A, and stirring at room temperature to obtain 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester;
(d) stirring the 2-bromo-2-phenylacetic acid-21-docosene-1-yl ester obtained in the step (c) and trichlorosilane in the presence of a Karstedt catalyst, and then sequentially filtering and removing a solvent from the filtrate to obtain an initiator.
The method comprises the steps of dropwise adding 1, 2-dibromoethane into tetrahydrofuran dispersion liquid of magnesium chips, and then dropwise adding 1-bromo-undecene tetrahydrofuran solution to obtain a mixed solution.
In the present invention, the ratio of the amount of magnesium chips to tetrahydrofuran in the tetrahydrofuran dispersion of magnesium chips is preferably 1.5 to 1.8g:2mL, and more preferably 1.68g:2 mL.
According to the invention, 1, 2-dibromoethane is dripped into tetrahydrofuran dispersion liquid of magnesium chips, and the volume ratio of the 1, 2-dibromoethane to the dispersion liquid is preferably 1: 10-15, and more preferably 1: 12-14. According to the invention, 1, 2-dibromoethane is added to react with magnesium chips to generate a Grignard reagent RMgX, so that the magnesium chip surface is prevented from being oxidized to generate magnesium oxide.
The invention then adds 1-bromine-undecene tetrahydrofuran solution into the reaction system to obtain mixed solution.
In the present invention, the amount ratio of 1-bromo-undecene to tetrahydrofuran in the 1-bromo-undecene tetrahydrofuran solution is preferably 11 to 12g:50mL, and more preferably 11.65g:50 mL. When the 1-bromo-undecene tetrahydrofuran solution is added dropwise, the reaction system releases heat, and a reflux phenomenon is observed. In the present invention, the dropping rate of the 1-bromo-undecene tetrahydrofuran solution is preferably 0.001 to 0.02mL/s, more preferably 0.005 to 0.015mL/s, and still more preferably 0.01 mL/s. In the present invention, it is preferable to control the reaction system in a moderate reflux state by controlling the dropping rate of the 1-bromo-undecene tetrahydrofuran solution, thereby preventing the occurrence of by-products or explosion phenomena caused by the intense heat generation of the reaction system. In the present invention, the 1-bromo-undecene reacts with magnesium turnings to form a magnesium grignard reagent.
After the mixed solution is obtained, the mixed solution is heated and then treated at low temperature, and after CuI is added, the temperature is raised to 0 ℃ to obtain the copper salt complex.
In the invention, the temperature of the heating treatment is preferably 50-55 ℃, and the time of the heating treatment is preferably 2-2.5 h. In the present invention, the temperature and time of the heat treatment are preferably controlled within the above-mentioned ranges, which facilitates the sufficient reaction between 1-bromo-undecene and magnesium chips to produce a magnesium grignard reagent.
After heating is finished, the reaction system is subjected to low-temperature treatment, wherein the temperature of the low-temperature treatment is preferably-75 to-80 ℃, and is further preferably-78 ℃; the time for the low-temperature treatment is preferably 15-25 min, and more preferably 20 min.
After the low-temperature treatment is finished, the CuI is preferably added under the protection of nitrogen and then the temperature is raised to 0 ℃ to obtain the copper salt complex.
In the present invention, the temperature at which CuI is added is preferably the same as the temperature of the low-temperature treatment; the molar ratio of CuI to 1-bromo-undecene is preferably 0.001-0.003: 0.05, more preferably 0.002:0.05, and more preferably 0.38: 1.68. After the CuI is added, the reaction system is preferably kept stand for 10-15 min so that the CuI is fully dispersed in the reaction system.
After CuI is added, the reaction system is preferably heated to 0 ℃ to obtain the copper salt complex.
In the present invention, the maximum temperature of the temperature raising treatment is 0 ℃. The invention produces dark purple color in the process of heating the reaction system to 0 ℃. In the temperature rising process, the magnesium-containing reagent reacts with CuI to generate a copper salt complex.
After the copper salt complex is obtained, the reaction system is preferably cooled immediately, and then the 11-bromo-1-lithium undecanol solution is added and stirred to obtain 21-eicosadien-1-ol.
In the present invention, the reaction system is preferably cooled to-75 to-80 ℃ and more preferably to-78 ℃.
After the reaction system is cooled, adding 11-bromine-1-lithium undecanoate solution into the reaction system.
In the present invention, the lithium 11-bromo-1-undecanol is preferably obtained by reacting 11-bromo-1-undecanol with methyllithium; the temperature of the reaction is preferably-75 to-80 ℃, and more preferably-78 ℃.
In the invention, the solvent of the 11-bromo-1-lithium undecanol solution is preferably tetrahydrofuran, and the ratio of the 11-bromo-1-lithium undecanol to the tetrahydrofuran in the 11-bromo-1-lithium undecanol solution is preferably 10-10.5 g:50mL, and more preferably 10.28g:50 mL. In the present invention, the molar ratio of the lithium 11-bromo-1-undecanoate to the 1-bromo-undecene is preferably 0.035 to 0.045:0.05, and more preferably 0.04: 0.05.
After the 11-bromine-1-undecylenic alcohol lithium solution is added, the reaction system is stirred to obtain reaction feed liquid. In the present invention, the temperature of the stirring is preferably-75 to-80 ℃, and more preferably-78 ℃; the time is preferably 15-20 h.
After reaction feed liquid is obtained, the invention preferably carries out hydrochloric acid hydrolysis on the reaction feed liquid, extracts an organic layer obtained by hydrolysis by using ether, washes the extracted organic layer by using hydrochloric acid, saturated bicarbonate aqueous solution and secondary water in turn, dries anhydrous magnesium sulfate, finally carries out vacuum rotary evaporation to remove a solvent, precipitates anhydrous acetone, and carries out suction filtration and drying to obtain the 21-eicosadiene-1-ol.
In the present invention, the synthesis process of the 21-eicosadien-1-ol is shown as formula II:
in formula II, each letter means as follows: a magnesium chips; b, cuprous iodide; c methyl lithium; d, stirring; e hydrochloric acid hydrolysis.
After 21-eicosadien-1-ol is obtained, the invention mixes 21-eicosadien-1-ol, alpha-bromophenyl acetic acid, 4-dimethylamino pyridine and dichloromethane to obtain solution A; and (3) dropwise adding a dichloromethane solution of N, N' -dicyclohexylcarbodiimide into the solution A in an ice bath, and stirring at room temperature to obtain the 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester.
In the present invention, the dichloromethane is preferably ultra-dry dichloromethane. In the invention, the molar ratio of the 21-eicosadien-1-ol to the alpha-bromophenyl acetic acid to the 4-dimethylaminopyridine is preferably 55-60: 45-50: 4-4.5, and more preferably 57:47: 4.2. In the present invention, the use amount ratio of dichloromethane to 21-eicosadien-1-ol is preferably 130 to 140mL:55 to 60mmol, and more preferably 134mL:57 mmol.
After the solution A is obtained, the dichloromethane solution of N, N' -dicyclohexylcarbodiimide is dripped into the solution A, and stirring treatment is carried out at room temperature to obtain 2-bromo-2-phenylacetic acid-21-docosacene-1-yl ester.
In the invention, the dosage ratio of N, N '-dicyclohexylcarbodiimide to dichloromethane in the dichloromethane solution of N, N' -dicyclohexylcarbodiimide is preferably 50-55 mmol:40mL, and more preferably 52mmol:40 mL; the volume ratio of the dichloromethane solution of the N, N' -dicyclohexylcarbodiimide to the solution A is preferably 1: 3-4, and more preferably 1: 3.2-3.8.
In the invention, the dripping speed of the dichloromethane solution of the N, N' -dicyclohexylcarbodiimide is preferably 1-1.5 mL/min; the stirring time is preferably 24-26 h.
According to the invention, after stirring is completed, the reaction system is preferably sequentially filtered, the filtrate is subjected to rotary evaporation to obtain a crude product, and then the crude product is purified by silica gel column chromatography to obtain 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester. In the present invention, the eluent for the chromatography is preferably a dichloromethane-petroleum ether mixture in a volume ratio of 30: 1.
After the 2-bromo-2-phenylacetic acid-21-docosacene-1-yl ester is obtained, the 2-bromo-2-phenylacetic acid-21-docosacene-1-yl ester and trichlorosilane are stirred in the presence of a Karstedt catalyst, and then filtration and solvent removal treatment are sequentially carried out on the filtrate to obtain the initiator.
In the present invention, the molar ratio of the 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester to trichlorosilane is preferably 4 to 4.5:42 to 43, and more preferably 4.23: 42.6. In the invention, the ratio of the 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester to the Karstedt catalyst is preferably 4-4.5 mmol: 4. mu.L, and more preferably 4.23mmol: 4. mu.L. In the invention, the stirring temperature is preferably room temperature, and the stirring time is preferably 12-15 h.
After stirring is finished, the reaction system is filtered and the filtrate is subjected to solvent removal treatment to obtain the initiator. In the present invention, the solvent removal treatment of the filtrate is preferably performed by rotary evaporation. The present invention is not particularly limited to the specific embodiments of the rotary evaporation method, and may be practiced in a manner well known to those skilled in the art.
In the invention, the preparation process of the initiator is shown as formula III:
in formula III, the letter means as follows: (a) alpha-bromophenyl acetic acid, N' -dicyclohexylcarbodiimide, dichloromethane, 4-dimethylaminopyridine; (b) trichlorosilane, Karstedt catalyst.
After the initiator is obtained, SiO is mixed in the invention2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate.
In the invention, the solvent of the initiator solution is preferably toluene, and the concentration of the initiator solution is preferably 8-12 mmol/L, and more preferably 10 mmol/L.
In the present invention, the ambient humidity of the standing treatment is preferably less than 30%, more preferably 10% to 30%, and still more preferably 20%; the time of the standing treatment is preferably 24-25 h; the temperature of the standing treatment is preferably 15-35 ℃, more preferably 20-30 ℃, and even more preferably 25 ℃.
In the standing treatment process, the initiator is in SiO2The surface of the/Si substrate is self-assembled to form an initiator self-assembled monolayer, so that the initiator is functionalized by the SiO2The structure of the/Si substrate sequentially comprises an initiator self-assembled monomolecular layer, a silicon dioxide layer and a silicon substrate from top to bottom.
In the invention, the immersed SiO is preferably treated after the standing treatment is finished2the/Si substrate is washed and dried. In the present invention, the washing detergent preferably comprises toluene, chloroform, isopropanol and ethanol in this order. In the present invention, the drying treatment is preferably nitrogen flow drying. The present invention is not particularly limited to the specific embodiments of washing and drying, and may be performed in a manner well known to those skilled in the art.
Obtaining SiO with functionalized initiator2After the/Si substrate, the invention is protected by nitrogenSiO functionalizing initiators2And mixing the/Si substrate, cuprous bromide, styrene, pentamethyl diethyl triamine and toluene, and then heating to obtain the ultrahigh-grafting-density polymer molecular brush.
The invention preferably stirs and mixes cuprous bromide, styrene, pentamethyl diethyl triamine and toluene to obtain a mixed solution, and then adds SiO functionalized by initiator2a/Si substrate. In the present invention, the amount ratio of cuprous bromide to styrene to pentamethyldiethyltriamine to toluene is preferably 0.04 to 0.05 g/4 to 6 mL/0.2 to 0.3 mL/8 to 12mL, and more preferably 0.0423 g/5 mL/0.23 mL/10 mL. The invention is to SiO2The relative amounts of the/Si substrate and the mixed solution are not particularly limited, but only SiO2And immersing the/Si substrate in a mixed solution of cuprous bromide, styrene, pentamethyl diethyl triamine and toluene.
After the steps are completed, the invention contains SiO2Heating the mixed solution of the/Si substrate, wherein the heating temperature is preferably 80-100 ℃, more preferably 85-95 ℃, and more preferably 90 ℃; the time of the heat treatment is preferably 1 to 3 hours, and more preferably 2 hours. The invention preferably controls the molecular weight of the finally prepared ultrahigh grafting density polymer molecular brush by controlling the time of the heating treatment. The molecular weight of the ultrahigh grafting density polymer molecular brush prepared by the method is preferably 15-40 kg/moL, more preferably 20-35 kg/moL, and even more preferably 25-30 kg/moL. In the heating process, cuprous bromide, styrene, pentamethyl diethyl triamine, toluene and SiO2Atom transfer radical polymerization reaction occurs between the/Si substrates, in SiO2And forming a polystyrene molecular brush on the functionalized surface of the/Si substrate.
After the heating is completed, the invention preferably treats the heated SiO2And washing the/Si substrate to obtain the polymer molecular brush with the ultrahigh grafting density.
According to the invention, the toluene is preferably used for leaching, and then the tetrahydrofuran is further cleaned by a Soxhlet extraction method, wherein the temperature of the tetrahydrofuran Soxhlet extraction method is preferably 70-80 ℃, and the further preferred temperature is 75 ℃; the time is preferably 12-15 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Synthesis of 21-eicosadien-1-ol: to a 250mL three-necked flask, magnesium turnings (1.68g, 70mM) and freshly distilled tetrahydrofuran (2mL) were added under nitrogen, and a few drops of 1, 2-dibromoethane were added to activate the magnesium turnings. Then, a solution of 1-bromo-undecene (11.65g, 0.05mol) in freshly distilled tetrahydrofuran (50mL) was added dropwise, after a few minutes moderate reflux was controlled and the temperature in the three-necked flask did not exceed 55 ℃. After the addition was complete, the reaction mixture was heated at 50 ℃ for 2 hours and then cooled to-78 ℃ for 20 minutes, purified CuI (0.38g, 2mM) was added under a stream of nitrogen, and the mixture was held at-78 ℃ for 10 minutes. Then, slowly warm to 0 ℃ until a dark purple color appears, cool immediately to-78 ℃ and add a protected alcohol solution (10.28g, 0.04mol in 50mL THF) (formed from 0.04mol 11-bromo-1-undecanol, 0.04mol methyllithium, 50mL freshly distilled tetrahydrofuran mixed at-78 ℃), keep the mixture at-78 ℃ and stir for 3 hours before reacting at room temperature overnight. Product post-treatment: after the reaction, the mixture was hydrolyzed, the organic layer was extracted three times with diethyl ether, and the three combined organic layers were washed successively with hydrochloric acid (1mol/L), a saturated aqueous bicarbonate solution, and two times with water. Anhydrous MgSO (MgSO)4After drying, the solvent is removed by vacuum rotary evaporation and concentration, anhydrous acetone is precipitated, and 21-eicosadiene-1-ol is obtained by suction filtration and drying, wherein the yield is 70%.
Synthesizing an initiator: 57mmol of 21-eicosadien-1-ol, 47mmol of α -bromophenylacetic acid and 4.2mmol of 4-dimethylaminopyridine were dissolved in 134mL of ultra-dry solvent dichloromethane in a round-bottomed flask. 52mmol of N, N' -dicyclohexylcarbodiimide were dissolved in 40mL of dry dichloromethane. Both solutions were cooled to 0 ℃ in an ice bath, and then the N, N' -dicyclohexylcarbodiimide solution was injected dropwise into the reaction flask over 30 minutes. After the addition was complete, the mixture was stirred at room temperature for 24 hours, filtered and the solid was washed with dichloromethane. The filtrate was concentrated by rotary evaporation to give the crude product. The crude product was purified by silica gel column chromatography using 30: 1(v/v) dichloromethane-petroleum ether mixture. After removal of the solvent, 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester was obtained.
To a dry flask was added 4.23mmol of 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester and 42.6mmol of trichlorosilane followed by 4. mu.L Karstedt's catalyst and the mixture was stirred at room temperature overnight. The solution was rapidly filtered through a plug of silica gel to remove the catalyst and excess solvent was removed under vacuum and reduced pressure to give the initiator 22- (trichlorosilyl) docosyl-2-bromo-2-phenylacetate.
The prepared 21-eicosadien-1-ol was subjected to nuclear magnetic resonance analysis, and the analysis results are shown in FIG. 1. As can be seen from FIG. 1, the synthesis of 21-eicosadien-1-ol according to the present invention was carried out.
The prepared initiator 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate was analyzed by nuclear magnetic spectrum, and the analysis result is shown in fig. 2. As can be seen from FIG. 2, the synthesis of 22- (trichlorosilyl) docosyl-2-bromo-2-phenylacetate according to the present invention was achieved.
Initiator functionalized SiO2Preparation of a/Si substrate
In the experiment, a monocrystalline silicon wafer (Zhejiang gold Western Garden science and technology Co., Ltd., crystal face orientation 100) is used as a substrate and is cut into a regular square shape of 1cm multiplied by 1 cm. Placing the mixture into a concentrated sulfuric acid/30% aqueous hydrogen peroxide mixed solution (volume ratio is 3:1), and heating the mixture for 1h at 90 ℃ to remove organic pollutants on the surface. Then, ultrasonic washing is carried out for three times by using secondary deionized water and absolute ethyl alcohol respectively, and nitrogen is blown to dry to prepare SiO with the thickness of about 2.0nm on the surface2Coated SiO2a/Si substrate. Mixing SiO2the/Si substrate was immersed in a 10mmol/L toluene solution of the above initiator, and then immersed in a solution containing SiO2The initiator solution of the/Si substrate is kept for 24 hours in an environment with the humidity of less than 30 percent and is placed in SiO2Forming an initiator self-assembled monomolecular layer on the surface of a/Si substrate, then sequentially washing with toluene, chloroform, isopropanol and ethanol, and drying through nitrogen flow to obtain the initiator functionalized SiO2a/Si substrate.
Preparing a polymer molecular brush with ultrahigh grafting density:
under the protection of nitrogen, 0.0423g of catalyst cuprous bromide, 10mL of solvent anhydrous toluene, 5mL of monomer styrene and 0.23mL of ligand Pentamethyldiethyltriamine (PMDETA) are added in sequence. The cuprous bromide was dissolved by magnetic stirring. Subsequently, adding initiator functionalized SiO under the protection of nitrogen2Sealing the Si substrate, heating to 90 ℃ by using a constant-temperature oil bath kettle, and reacting for 100min to obtain the polystyrene molecular brush. And after the preset reaction time, taking out the silicon wafer, leaching the silicon wafer with toluene for several minutes, cleaning the polystyrene molecular brush by using a Soxhlet extractor, taking out the silicon wafer after 12 hours at the temperature of 75 ℃ and drying the silicon wafer by using nitrogen for later use. In the present invention, a schematic process for preparing the ultra-high graft density polymer molecular brush is shown in fig. 3, SAMs represents initiator self-assembled monolayer.
Example 2
The experiment was carried out in the same manner as in example 1 except that, in the preparation of the polymer molecular brush, the heating time in the oil bath was adjusted to 130min to obtain a polystyrene molecular brush.
Example 3
The test was carried out in accordance with the method of example 1 of the present invention except that the heating time in the oil bath was adjusted to 20min, 30min, 65min, 120min and 200min, respectively.
Comparative example 1
Preparation of a conventional polymer molecular brush:
(1)SiO2the preparation of the/Si substrate comprises the steps of selecting a monocrystalline silicon wafer (Zhejiang gold Western Garden science and technology Co., Ltd., crystal face orientation 100) as a substrate, and cutting into a regular square with the size of 1cm multiplied by 1 cm. Placing the mixture into a concentrated sulfuric acid/30% hydrogen peroxide mixed solution (volume ratio is 3:1), and heating the mixture for 1h at 90 ℃ to remove organic pollutants on the surface. Then, ultrasonic washing is carried out for three times by using secondary deionized water and absolute ethyl alcohol respectively, and nitrogen is blown to dry to obtain SiO with the surface thickness of 2.0nm2A covered silicon substrate.
(2)SiO2Amination modification of the surface of a Si substrate: the surface hydroxylated substrate was soaked in 20mL of anhydrous toluene containing 0.02% by volume 3-Aminopropyltriethoxysilane (APTES)In solution. Reacting for 24 hours at normal temperature. The modified substrate was then washed with toluene to remove the physisorbed APTES. And finally, respectively cleaning the mixture for 2 times by using dichloromethane, acetone and absolute ethyl alcohol, and drying the mixture by using nitrogen for later use.
(3)SiO2Immobilization of the Si substrate surface ATRP initiator: the above modified substrate was placed in 40mL of a solution of 5% by volume Triethylamine (TEA) in anhydrous dichloromethane. The system was cooled to 0 ℃ with an ice-water bath, and a solution of 2-bromoisobutyryl bromide (BIBB) (TEA: BIBB ═ 1:1 by volume) was added dropwise with stirring. And removing the ice water bath after half an hour, and reacting for 12 hours at normal temperature. And then sequentially cleaning the mixture by using toluene, dichloromethane, acetone and absolute ethyl alcohol, and blow-drying the mixture by using nitrogen for later use.
Synthesis of Polymer molecular Brush: after the experimental device is built, the air tightness of the experimental device is checked, and the bottle is baked by an alcohol lamp (water vapor in the bottle is removed) in the vacuumizing process and is filled with high-purity nitrogen. After the device is naturally cooled to room temperature, the device is vacuumized and filled with nitrogen, and the operation is repeated for three times. Under nitrogen protection, 0.846g of cuprous bromide catalyst (CuBr), 20mL of anhydrous toluene solvent, 10mL of monomeric styrene, and 2.46mL of the ligand Pentamethyldiethyltriamine (PMDETA) were added in this order. The CuBr was dissolved thoroughly by magnetic stirring. And then adding an initiator functionalized substrate under the protection of nitrogen, sealing, and heating to 90 ℃ by using a constant-temperature oil bath kettle to react for 130 min. After a predetermined reaction time, the silicon wafer was removed, rinsed with toluene for several minutes, and the PS brush was cleaned using a soxhlet extractor (to better remove the surface-adsorbed polymer chains). The cleaning agent is tetrahydrofuran and the temperature is 75 ℃. And taking out the silicon wafer after 12h, and drying the silicon wafer by nitrogen to prepare the Polystyrene (PS) molecular brush synthesized by the common initiator dibromo isobutyryl bromide.
Comparative example 2
The test was carried out in accordance with the method of comparative example 1 of the present invention except that the heating time in the oil bath was adjusted to 60min, 120min, 180min, 240min and 320min, respectively.
Performance testing
For the SiO prepared in example 12Si substrate and initiator functionalized SiO2Contact angle and thickness of/Si substrateAnd (6) testing. The contact angle was measured as follows: a droplet analyzer; the thickness test method comprises the following steps: an elliptically polarized spectrum. The test results are shown in table 1:
TABLE 1 SiO2Si substrate and initiator functionalized SiO2Contact angle and thickness of/Si substrate
In Table 1, SiO2The thickness of the/Si substrate is SiO2SiO on surface of Si substrate2The thickness of the layer; initiator functionalized SiO2The thickness of the/Si substrate refers to the thickness of the initiator self-assembled monolayer. As can be seen from the test results in Table 1, the initiator is present in SiO2the/Si substrate base is successfully fixed, and a monomolecular layer is formed; the thickness of the initiator self-assembled monolayer was 3.1nm, consistent with the theoretical full extension length of the initiator.
SiO functionalized with initiators2The self-assembled monolayer on the surface of the/Si substrate was analyzed by atomic force microscopy and sum frequency vibrational spectroscopy, and the results are shown in fig. 4. FIG. 4 shows the atomic force microscope image on the left and the sum frequency vibration spectrum on the right. From the atomic force microscope image on the left side of FIG. 4, it can be seen that the plate crystals are evident, which have a thickness of about 3nm and correspond to the theoretical length of a completely straightened initiator molecule. At the same time, the sum frequency vibration spectrum from the right side of FIG. 4 can be found to increase with deposition time, 2850cm-1The symmetric stretching vibration signal from methylene gradually disappears at 3060cm-1The vibration peak from the benzene ring at the molecular chain terminal is enhanced, which shows that the molecular order degree is improved. When the deposition time is more than 24h, the methylene resonance peak on the SFG spectrum basically disappears, further indicating that the initiator molecules are orderly arranged on the surface.
The thicknesses of the polymer molecular brushes prepared in the embodiment of the invention and the comparative example are respectively tested, the invention adopts an ellipsometer to test the thickness of the molecular brush, the testing principle of the ellipsometer is shown in figure 5, and as can be seen from figure 5, the main devices of the ellipsometer comprise a polarizer, a laser, a wave plate, a photomultiplier and an analyzer on a reflection light path. In the test process, a beam of monochromatic light is emitted by a laser, the monochromatic light is changed into linearly polarized light through a polarizer, and then the linearly polarized light passes through a wave plate to generate a phase difference of 90 degrees, so that elliptically polarized light is finally formed. When polarized light irradiates the surface of the polymer film (or molecular brush), light reflection occurs, and the light path is decomposed into component waves in the S direction and the P direction, and the light reflected by the surface of the sample is linearly polarized. And obtaining the thickness and the refractive index of the film by computer fitting according to the polarization state change of the polarized light before and after reflection, including the change of amplitude and phase. The thickness of the PS molecular brush in both the functionalized substrate and the dry state was determined by means of an imaging ellipsometer model EP3SW (Accurion, Germany). The xenon lamp light source has laser wavelength of 658.0nm, variable angle range from 45 deg to 70 deg, and data collected every 5 deg to obtain the parameters of the amplitude and laser phase difference. The thickness of the substrate and the polymer brush was obtained by fitting the parameters Δ and Ψ. The results are shown in Table 2.
TABLE 2 thickness of polymer molecular brush prepared in example and comparative example
For comparison, the data in table 2 are plotted into a spectrogram, which is shown in fig. 6, and as can be seen from fig. 6, when polymer molecular brushes with the same thickness are prepared, the method provided by the invention can effectively improve the preparation efficiency of the polymer molecular brushes.
The molecular weight of the polymer molecular brush prepared in the embodiment 1-2 of the invention is tested, and the test method is schematically shown in FIG. 7. The test method specifically comprises the following steps: 25mL of a tetrahydrofuran (chromatographically pure) solution of tetrabutylammonium fluoride having a solution concentration of 0.04mol/L was placed in a glass flask, heated to 55 ℃ under magnetic stirring, a sample of the washed polymer molecular brush was added, reacted for 24 hours, the reaction solution was collected and concentrated to 1mL by a rotary evaporator, and then filtered through a 0.2 μm polytetrafluoroethylene filter, and the molecular weight and the distribution thereof were measured by Gel Permeation Chromatography (GPC). The test results of the polymer molecular brush prepared in example 1 are shown in fig. 8, and the test results of the polymer molecular brush prepared in example 2 are shown in fig. 9. As is apparent from fig. 8, the number average molecular weight of the polymer molecular brush prepared in example 1 was 28.6kg/moL, and as is apparent from fig. 9, the number average molecular weight of the polymer molecular brush prepared in example 2 was 33.2 kg/moL.
And calculating the grafting density value of the polymer molecular brush according to the molecular weight of the polymer molecular brush obtained by testing. Graft density σpCalculated from formula IV:
wherein rho (1.05 g/cm)3) Is the bulk density of polystyrene; h ispIs the molecular brush thickness as determined by an ellipsometer; mn(g/mol) is the number average molecular weight of the polymer molecular brush; n is a radical ofA(6.02×1023) Is the Avogastron constant.
The graft density of the polymer brush prepared in example 1 was calculated to be 1.21chains/nm2The polymer molecular brush prepared in example 2 had a graft density of 1.23chains/nm2The average grafting density of the polymer molecular brush prepared by the invention is 1.22nm-2(ii) a The degree of stretching of the molecular chain at the substrate surface is about 81% of the theoretical full stretching of the molecular chain at its molecular weight. This value is the highest graft density value for the polymer brush currently reported. Therefore, the invention provides a preparation method of the polymer molecular brush with the ultrahigh grafting density.
In conclusion, the invention provides a preparation method of a polymer molecular brush with ultrahigh grafting density, the thickness of the polymer molecular brush prepared by the method is 55-65 nm, and the grafting density is 1.21-1.23 chains/nm2. Therefore, the invention provides a preparation method of the polymer molecular brush with the ultrahigh grafting density.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a polymer molecular brush with ultrahigh grafting density comprises the following steps:
(1) immersing the monocrystalline silicon piece into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution, heating, and then washing and blow-drying the heated monocrystalline silicon piece in sequence to obtain SiO2a/Si substrate;
(2) SiO obtained in the step (1)2Immersing the/Si substrate in an initiator solution, and standing to obtain the initiator functionalized SiO2a/Si substrate; the initiator is 22- (trichlorosilyl) docosyl-2-bromo-2-phenyl acetate;
(3) under the protection of nitrogen, the initiator obtained in the step (2) is functionalized SiO2And mixing the/Si substrate, cuprous bromide, styrene, pentamethyl diethyl triamine and toluene, and then heating to obtain the ultrahigh-grafting-density polymer molecular brush.
2. The method according to claim 1, wherein SiO in the step (1)2A silicon dioxide layer in the/Si substrate covers the surface of the silicon substrate; the thickness of the silicon dioxide layer is 1.5-2.5 nm.
3. The preparation method according to claim 1, wherein the mass concentration of the aqueous hydrogen peroxide solution in the step (1) is 25% to 35%, and the volume ratio of the concentrated sulfuric acid to the aqueous hydrogen peroxide solution is 2.5 to 3.5: 1.
4. The method according to any one of claims 1 to 3, wherein the temperature of the heating treatment in the step (1) is 80 to 100 ℃; the heating treatment time is 50-70 min.
5. The method according to claim 1, wherein the solvent of the initiator solution in the step (2) is toluene; the concentration of the initiator solution is 0.5-1.5 mmol/L.
6. The method according to claim 1 or 5, wherein the ambient humidity of the standing treatment in the step (2) is less than 30%; the standing treatment time is 24-25 h.
7. The preparation method according to claim 1, wherein the amount ratio of cuprous bromide to styrene to pentamethyldiethyltriamine to toluene in the step (3) is 0.04-0.05 g/4-6 mL/0.2-0.3 mL/8-12 mL.
8. The preparation method according to claim 1 or 7, wherein the temperature of the heat treatment in the step (3) is 80 to 100 ℃, and the time of the heat treatment is 1 to 3 hours.
9. The method of claim 1, wherein the initiator is prepared by a method comprising the steps of:
(a) dripping 1, 2-dibromoethane into tetrahydrofuran dispersion liquid of magnesium chips, and then dripping 1-bromo-undecene tetrahydrofuran solution to obtain a mixed solution; the dropping speed of the 1-bromo-undecene tetrahydrofuran solution is 0.01-0.02 mL/s;
(b) heating the mixed solution obtained in the step (a), performing low-temperature treatment, adding CuI, heating to 0 ℃, immediately cooling, adding 11-bromine-1-lithium undecanoate solution, and stirring to obtain 21-eicosadien-1-ol; the temperature of the low-temperature treatment is-75 to-80 ℃;
(c) mixing the 21-eicosadien-1-ol obtained in step (b), alpha-bromophenylacetic acid, 4-dimethylaminopyridine and dichloromethane to obtain a solution A; in an ice bath, dropwise adding a dichloromethane solution of N, N' -dicyclohexylcarbodiimide into the solution A, and stirring at room temperature to obtain 2-bromo-2-phenylacetic acid-21-docosen-1-yl ester;
(d) stirring the 2-bromo-2-phenylacetic acid-21-docosene-1-yl ester obtained in the step (c) and trichlorosilane in the presence of a Karstedt catalyst, and then sequentially filtering and removing a solvent from the filtrate to obtain an initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811307198.2A CN109400827B (en) | 2018-11-05 | 2018-11-05 | Preparation method of polymer molecular brush with ultrahigh grafting density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811307198.2A CN109400827B (en) | 2018-11-05 | 2018-11-05 | Preparation method of polymer molecular brush with ultrahigh grafting density |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109400827A CN109400827A (en) | 2019-03-01 |
| CN109400827B true CN109400827B (en) | 2020-10-30 |
Family
ID=65471306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811307198.2A Active CN109400827B (en) | 2018-11-05 | 2018-11-05 | Preparation method of polymer molecular brush with ultrahigh grafting density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109400827B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808247B (en) * | 2020-05-23 | 2022-10-21 | 浙江理工大学 | Preparation and application of TEMPO nano reactor based on molecular brush |
| CN113036087B (en) * | 2021-02-26 | 2022-04-26 | 中山大学 | Ultrahigh-sulfur-content two-dimensional molecular brush and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010024263A (en) * | 2008-07-15 | 2010-02-04 | Toyota Central R&D Labs Inc | Polymerization initiator, method for producing polymeric modified material using the same, and molded body containing polymeric modified material |
| CN102936321A (en) * | 2012-11-06 | 2013-02-20 | 上海交通大学 | Living polymerization preparation method for polyacrylic acid ball brush and application of polyacrylic acid ball brush |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1754731A1 (en) * | 2005-08-16 | 2007-02-21 | Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO | Method of modifying materials surfaces |
| JP6453590B2 (en) * | 2014-09-08 | 2019-01-16 | Jsr株式会社 | Solid phase carrier, ligand-bound solid phase carrier, target substance detection or separation method, and method for producing the solid phase carrier |
-
2018
- 2018-11-05 CN CN201811307198.2A patent/CN109400827B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010024263A (en) * | 2008-07-15 | 2010-02-04 | Toyota Central R&D Labs Inc | Polymerization initiator, method for producing polymeric modified material using the same, and molded body containing polymeric modified material |
| CN102936321A (en) * | 2012-11-06 | 2013-02-20 | 上海交通大学 | Living polymerization preparation method for polyacrylic acid ball brush and application of polyacrylic acid ball brush |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109400827A (en) | 2019-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Advincula et al. | Polymer brushes by living anionic surface initiated polymerization on flat silicon (sio x) and gold surfaces: Homopolymers and block copolymers | |
| CN109400827B (en) | Preparation method of polymer molecular brush with ultrahigh grafting density | |
| Gurbuz et al. | Synthesis of cationic N‐[3‐(dimethylamino) propyl] methacrylamide brushes on silicon wafer via surface‐initiated RAFT polymerization | |
| Fleischmann et al. | Modification of polymer surfaces by click chemistry | |
| CN102875195B (en) | Method for preparing polymer brush films with multiple stimulation responses | |
| Münch et al. | Tuning of smart multifunctional polymer coatings made by zwitterionic phosphorylcholines | |
| KR102426440B1 (en) | Method and composition for selective modification of substrate surface | |
| Chang et al. | Roughness-enhanced thermal-responsive surfaces by surface-initiated polymerization of polymer on ordered ZnO pore-array films | |
| CN108586681B (en) | Block copolymer aqueous hyperdispersant and preparation method thereof | |
| Chekurov et al. | Synthesis and repellent properties of fluorinated diblock-copolymers | |
| Cimen et al. | Synthesis of dual‐functional poly (6‐azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups | |
| Lee et al. | On‐Surface RAFT Polymerization using Oxygen to form Triblock Copolymer Brushes | |
| Li et al. | Synthesis and properties of UV-curable polysiloxane methacrylate obtained by one-step method | |
| Mandal et al. | In situ monitoring of SI-ATRP throughout multiple reinitiations under flow by means of a quartz crystal microbalance | |
| JP2510345B2 (en) | Alkoxysilyl group-containing azo compound and method for producing the same | |
| Huang et al. | Synthesis and comparison of two poly (methyl methacrylate-b-3-(trimethoxysilyl) propyl methacrylate)/SiO2 hybrids by “grafting-to” approach | |
| CN110372836B (en) | Vinyl sulfone surface initiated aqueous phase anion polymerization method | |
| WO2019196041A1 (en) | Chiral main-chain-type azobenzene polymer aggregate and preparation method therefor | |
| Kursun et al. | Glycopolymer brushes with specific protein recognition property | |
| JP2000319530A (en) | Composition for semiconductor element | |
| JP7136182B2 (en) | Method for modifying substrate surface, composition and polymer | |
| US11578230B2 (en) | Composition, polymer, and method of producing substrate | |
| JP3719982B2 (en) | Method for forming a molecular layer having a high density of primary amine groups on a solid support | |
| Zhou et al. | Preparation of silane‐terminated polystyrene and polymethylmethacrylate self‐assembled films on silicon wafer | |
| CN112870763B (en) | Solid phase micro-extraction probe and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |