CN117247550B - Modified POSS molecule, segmented copolymer, preparation method and application thereof - Google Patents
Modified POSS molecule, segmented copolymer, preparation method and application thereof Download PDFInfo
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- CN117247550B CN117247550B CN202311541607.6A CN202311541607A CN117247550B CN 117247550 B CN117247550 B CN 117247550B CN 202311541607 A CN202311541607 A CN 202311541607A CN 117247550 B CN117247550 B CN 117247550B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920001577 copolymer Polymers 0.000 title description 4
- 229920001400 block copolymer Polymers 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000007783 nanoporous material Substances 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims description 76
- 150000001875 compounds Chemical class 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007810 chemical reaction solvent Substances 0.000 claims description 20
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 10
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- UKIUSKWWNRYHOO-UHFFFAOYSA-N pent-1-yn-1-ol Chemical compound CCCC#CO UKIUSKWWNRYHOO-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UGUBQKZSNQWWEV-UHFFFAOYSA-N 4-oxo-4-phenylmethoxybutanoic acid Chemical compound OC(=O)CCC(=O)OCC1=CC=CC=C1 UGUBQKZSNQWWEV-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 150000001540 azides Chemical group 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 238000000059 patterning Methods 0.000 abstract description 9
- 238000005530 etching Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005329 nanolithography Methods 0.000 abstract description 4
- 239000004793 Polystyrene Substances 0.000 description 46
- 238000003786 synthesis reaction Methods 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 18
- 229940125904 compound 1 Drugs 0.000 description 14
- 238000001338 self-assembly Methods 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- GTOFKXZQQDSVFH-UHFFFAOYSA-N 2-benzylsuccinic acid Chemical group OC(=O)CC(C(O)=O)CC1=CC=CC=C1 GTOFKXZQQDSVFH-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000000235 small-angle X-ray scattering Methods 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- -1 Polydimethylsiloxane Polymers 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical group Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 241001024099 Olla Species 0.000 description 1
- 229910000555 a15 phase Inorganic materials 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the technical field of materials, and provides a modified POSS molecule, a block copolymer, a preparation method and application thereof. The modified POSS molecule has a structure of formula I:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R in formula I representsN is an integer of 2 to 9. The modified POSS molecule provided by the invention has the advantages of accurate chemical structure, good stability, high silicon content, high etching contrast, capability of forming a series of micro-nano structures smaller than 10nm and the like, and can be applied to the fields of nano patterning, nano porous materials, nano lithography and the like.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a modified POSS molecule, a block copolymer, a preparation method and application thereof.
Background
Polydimethylsiloxane (PDMS) has very important application in the fields of nano patterning, nano porous materials, nano lithography and the like. Since PDMS is difficult to synthesize and is not an exact molecule, it is difficult to ensure that the molecular weight (Mn) and molecular weight distribution (PDI) of the polymer prepared per batch are consistent, which presents a great challenge in studying the relationship between the structure and the properties of the material. In addition, the microphase ordered structure obtained by the self-assembly process of the block copolymer composed of PDMS also tends to have a larger size, and it is difficult to form the ordered structure smaller than 10nm.
Although cage-type silsesquioxane (POSS) molecules have precise chemical structures and rigid cage-like structures, a series of microphase ordered structures smaller than 10nm can be formed, but the traditional POSS molecules have lower silicon content, and have poorer structural stability and etching contrast in the etching process, thereby limiting the application of the POSS molecules in the fields of nano patterning and the like.
Therefore, research and development of the novel POSS molecules with precise chemical structure, good stability and higher silicon content can form a series of micro-nano structures smaller than 10nm at the same time, so that the application value of the POSS in the fields of nano patterning and the like is improved, and the novel POSS molecules have important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide novel POSS molecules which have accurate chemical structure, good stability and higher silicon content, and can form a series of micro-nano structures smaller than 10nm at the same time, so as to improve the application value of POSS in the fields of nano patterning and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, embodiments of the present invention provide a compound having the structure of formula i:
；
wherein R in formula I representsN is an integer of 2 to 9.
Compared with the traditional PDMS or the traditional POSS molecules, the compound provided by the embodiment of the invention has the advantages of accurate chemical structure, good stability, higher silicon content and higher etching contrast, can form a series of micro-nano structures smaller than 10nm, can be applied to the fields of nano patterning, nano porous materials, nano lithography and the like, and has wide market application prospect.
In a second aspect, the embodiment of the invention provides a block copolymer, which is prepared by carrying out click chemistry reaction on a compound with a structure shown in a formula I in the first aspect and a macromolecule chain segment with the tail end modified by an azide group.
The segmented copolymer provided by the embodiment of the invention has the advantages of high silicon content, high etching contrast and the like, can form a series of micro-nano structures smaller than 10nm, can be applied to the fields of nano patterning, nano porous materials, nano photoetching and the like, and has wide market application prospect.
In a third aspect, an embodiment of the present invention provides a method for preparing a compound having a structure of formula i according to the first aspect, including the steps of:
s1, under the protection of nitrogen, carrying out reaction between heptavinyl cage-type silsesquioxane with one terminal position substituted by hydroxyl and benzyl succinate in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, the first reactant reacts with toluene at a second reaction temperature under the action of a second catalyst to obtain a second reactant;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist, and a compound with a structure shown in a formula I is obtained.
The sequence numbers of the steps in the embodiment of the invention do not limit the sequence of the steps in the embodiment of the invention, and the preparation method provided by the embodiment of the invention is simple, mild in condition, convenient to operate, low in requirement on equipment condition, easy to realize and suitable for industrial mass production.
In a fourth aspect, embodiments of the present invention provide a method for preparing a block copolymer according to the second aspect, comprising the steps of:
s1, under the protection of nitrogen, reacting heptavinyl cage-type silsesquioxane with terminal hydroxyl groups and benzyl succinate in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, the first reactant reacts with toluene at a second reaction temperature under the action of a second catalyst to obtain a second reactant;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist to obtain a compound with a structure shown in a formula I;
s5, under the protection of argon, reacting the compound with the structure shown in the formula I with a polymer chain segment with the tail end modified by an azide group in a third reaction solvent in the presence of a fifth catalyst to obtain the block copolymer.
In a fifth aspect, embodiments of the present invention provide the use of a compound having a structure of formula i as described in the first aspect, or a block copolymer as described in the second aspect, for the preparation of nanopatterned materials, nanoporous materials and nanolithographic materials.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a mass spectrum of compound 1 produced in example 1 of the present invention;
FIG. 2 is an oDMS prepared in example 7 of the present invention 7 Nuclear magnetic resonance hydrogen spectrogram of POSS-PS block copolymer;
FIG. 3 is a gel permeation chromatogram of a series of block copolymers prepared in example 8 of the present invention;
FIGS. 4 to 9 show the block copolymers oDMS prepared in example 8 of the present invention 7 POSS-PS 3.4k 、oDMS 7 POSS-PS 12.9k 、oDMS 7 POSS-PS 16.7k 、oDMS 7 POSS-PS 17.4k 、oDMS 7 POSS-PS 33.0k A small-angle X-ray scattering and transmission electron microscope characterization map;
FIG. 10 is a block copolymer oDMS prepared in example 8 of the present invention 7 POSS-PS 12.9k A transmission electron microscope image after the self-assembly of the film;
FIG. 11 is a block copolymer oDMS prepared in example 11 of the present invention 2 POSS-oLLA 16 、oDMS 3 POSS-oLLA 16 、oDMS 7 POSS-oLLA 16 Is a gel permeation chromatogram of (2);
FIGS. 12 to 13 show the block copolymers oDMS prepared in example 11 of the present invention 3 POSS-oLLA 8 、oDMS 3 POSS-oLLA 16 And carrying out small-angle X-ray scattering characterization graph after self-assembly of the body.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific examples described herein are for purposes of illustration only and that the embodiments of the invention are not limited thereto.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The experimental reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the dosage of the experimental reagent is the dosage of the reagent in the conventional experimental operation if no special description exists; the experimental methods are conventional methods unless otherwise specified.
In a first aspect, the present embodiment provides a compound having the structure of formula i:
；
wherein R in formula I representsN is an integer of 2 to 9.
Compared with the traditional PDMS or the traditional POSS molecules, the compound provided by the embodiment of the invention has the advantages of accurate chemical structure, good stability, higher silicon content and higher etching contrast, can form a series of micro-nano structures smaller than 10nm, can be applied to the fields of nano patterning, nano porous materials, nano lithography and the like, and has wide market application prospect.
By utilizing the addition reaction of silane and carbon-carbon double bond, oDMS with different silane units and branching degrees can be synthesized w POSS molecules, wherein the value range of w is 3-10. w represents the double bond addition reaction of oligomeric dimethylsiloxane (oDMS) with POSS molecules to obtain the compound with the structure shown in the formula I. For example, two-unit oligosiloxanes (oDMS) may be optionally employed 2 ) Tri-unit oligosiloxanes (oDMS) 3 ) Four unit oligo-dimethylsiloxane (oDMS) 4 ) Seven-unit oligosiloxane (oDMS) 7 ) And carrying out double bond addition reaction with POSS molecules to obtain the compound with the structure shown in the formula I.
The addition reaction between the silane and the POSS molecules is carried out through carbon-carbon double bonds, so that the composition difference between the POSS and the PDMS can be effectively reduced, and the obtained modified cage-type silsesquioxane has an accurate chemical structure, high rigidity and stability, higher silicon content and etching contrast and can form a series of micro-nano structures smaller than 10nm.
In some embodiments, the compound having the structure of formula IThis part of the structure may be synthesized by ester bond connection or amide bond connection.
In some embodiments, R may also representIs a isomer of (2). For example, when n=6, R in the compound of formula I is +.>Or->。
In a second aspect, the embodiment of the invention also provides a block copolymer, which is prepared by carrying out click chemistry reaction on the compound with the structure shown in the formula I in the first aspect and a macromolecule chain segment with the tail end modified by an azide group.
The segmented copolymer provided by the embodiment of the invention has the advantages of high silicon content, high etching contrast and the like, can form a series of micro-nano structures smaller than 10nm, can be applied to the fields of nano patterning, nano porous materials, nano photoetching and the like, and has wide market application prospect.
Click chemistry refers to the rapid and reliable completion of chemical synthesis of a wide variety of molecules by the splicing of small units.
Further, the polymer chain segment with the tail end modified by the azide group is、/>Or->(namely, polymethyl methacrylate with the tail end modified by an azide group), wherein the value range of m is 7-15, the value range of q is 16-320, and the value range of t is 20-150.
In a third aspect, an embodiment of the present invention provides a method for preparing a compound having a structure of formula i according to the first aspect, including the steps of:
s1, under the protection of nitrogen, carrying out reaction between heptavinyl cage-type silsesquioxane with one terminal position substituted by hydroxyl and benzyl succinate in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, the first reactant reacts with toluene at a second reaction temperature under the action of a second catalyst to obtain a second reactant;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist, and a compound with a structure shown in a formula I is obtained.
The sequence numbers of the steps in the embodiment of the invention do not limit the sequence of the steps in the embodiment of the invention, and the preparation method provided by the embodiment of the invention is simple, mild in condition, convenient to operate, low in requirement on equipment condition, easy to realize and suitable for industrial mass production.
Further, in step S1, the first coupling agent is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole; the first catalyst is at least one of 4-dimethylaminopyridine and triethylamine; the first reaction solvent is at least one of dichloromethane and tetrahydrofuran; the first reaction temperature is 25-60 ℃.
Further, in step S2, the second catalyst is Karstedt catalyst; the second reaction temperature is 80-115 ℃.
Further, in step S3, the third catalyst is palladium carbon.
Further, in step S4, the second coupling agent is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole; the fourth catalyst is at least one of 4-dimethylaminopyridine and triethylamine; the second reaction solvent is at least one of dichloromethane and tetrahydrofuran.
In a fourth aspect, embodiments of the present invention provide a method for preparing a block copolymer according to the second aspect, comprising the steps of:
s1, under the protection of nitrogen, reacting heptavinyl cage-type silsesquioxane with terminal hydroxyl groups and benzyl succinate in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, the first reactant reacts with toluene at a second reaction temperature under the action of a second catalyst to obtain a second reactant;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist to obtain a compound with a structure shown in a formula I;
s5, under the protection of argon, reacting the compound with the structure shown in the formula I with a polymer chain segment with the tail end modified by an azide group in a third reaction solvent in the presence of a fifth catalyst to obtain the block copolymer.
Further, the fifth catalyst is cuprous bromide and pentamethyldiethylenetriamine. The third reaction solvent is toluene.
In a fifth aspect, embodiments of the present invention provide the use of a compound having a structure of formula i as described in the first aspect, or a block copolymer as described in the second aspect, for the preparation of nanopatterned materials, nanoporous materials and nanolithographic materials.
The invention has been tested several times in succession, and the invention will now be described in further detail with reference to a few test results, which are described in detail below in connection with specific examples.
Example 1 preparation of Compound 1
The structural formula of the compound 1 is as follows:
r in formula I represents->。
The preparation procedure for compound 1 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
1.00g of heptavinyl cage silsesquioxane (VPOSS-OH) with a hydroxyl group at one end position is weighed and placed in a reaction vessel, 0.67g of benzyl succinate with one end protected by benzyl and one end of carboxyl group exposed, 1.64g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.12g of 4-dimethylaminopyridine and 200mL of dichloromethane are added into the reaction vessel under the protection of nitrogen, and the reaction is carried out for 24 hours at the temperature of 50 ℃. After the reaction, 1.14g of the first reactant (i.e., VPOSS-COOBn) was isolated by means of silica gel column chromatography, and the yield was 95%.
S2, second reactant (oDMS) 7 POSS-COOBn):
dissolving 0.54g of VPOSS-COOBn in 50mL of toluene, adding 100 μl of Karstedt catalyst under the environment of a glove box protected by argon, reacting at 110deg.C for 6 hours, and separating by column chromatography to obtain a second reactant (i.e. oDMS) 7 POSS-COOBn) 1.45g, yield 97%.
S3, third reactant (oDMS) 7 POSS-COOH) synthesis:
oDMS (optical fiber array) 7 POSS-COOBn 1.00g is added into 100mL of ethyl acetate, palladium-carbon 0.34g is added, the mixture is reacted for 2 hours at room temperature under the hydrogen atmosphere, solid impurities are removed by filtration, and a third reactant (oDMS) is obtained by reduced pressure rotary evaporation 7 POSS-COOH) 0.91g, yield 99%.
S4, compound 1 (oDMS) 7 POSS) synthesis:
oDMS (optical fiber array) 7 POSS-COOH 0.64g, pentynol 0.89g, 1.18g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine 0.13g were added to 200mL methylene chloride, reacted under the protection of nitrogen for 6 hours, and after the reaction was completed, separated by column chromatography to obtain 0.60g of Compound 1 (i.e., oDMS) 7 POSS), yield was 83%.
Identification of Compound 1 prepared in example 1:
the nmr hydrogen spectrum data of compound 1 are: 1 H NMR（400MHz，Chloroform-d）δ:4.13 (q,J=7.0, 6.3 Hz, 4H)，2.53 (d,J=2.4 Hz, 4H),2.21 (td, J=7.0,2.6 Hz, 2H),1.88 (t, J=2.7 Hz, 1H), 1.78 (p,J=6.7 Hz. 2H), 1.06 (m, 5H), 0.48 (m, 25H)， 0.18- -0.19 (m, 315H).
the mass spectrum of compound 1 is shown in fig. 1.
Example 2 preparation of Compound 2
The structural formula of the compound 2 is as follows:
r in formula I represents->。
The preparation procedure for compound 2 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
the first reactant (VPOSS-COOBn) was synthesized with reference to step S1 of example 1.
S2, second reactant (oDMS) 3 POSS-COOBn):
synthesis of the second reactant (oDMS) with reference to step S2 of example 1 3 POSS-COOBn）。
S3, third reactant (oDMS) 3 POSS-COOH) synthesis:
synthesis of third reactant (oDMS) with reference to step S3 of example 1 3 POSS-COOH）。
S4, compound 2 (oDMS) 3 POSS) synthesis:
synthesis of Compound 2 (oDMS) with reference to step S4 of example 1 3 POSS）。
Identification of compound 2 prepared in example 2:
the nmr hydrogen spectrum data of compound 2 are: 1 H NMR（400MHz，Chloroform-d）δ:4.15-4.08(m,4H),3.31(t,J=6.7Hz,2H),2.53(s,4H),1.82（p,J=6.5Hz,2H）,1.08-1.00(m, 5H),0.47(m, 25H),0.02- -0.04(m,105H),-0.05- -0.09(m,42H).
EXAMPLE 3 preparation of Compound 3
The structural formula of the compound 3 is as follows:
r in formula I represents->。
The preparation procedure for compound 3 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
the first reactant (VPOSS-COOBn) was synthesized with reference to step S1 of example 1.
S2, second reactant (oDMS) 2 POSS-COOBn):
synthesis of the second reactant (oDMS) with reference to step S2 of example 1 2 POSS-COOBn）。
S3, third reactant (oDMS) 2 POSS-COOH) synthesis:
synthesis of third reactant (oDMS) with reference to step S3 of example 1 2 POSS-COOH）。
S4, compound 3 (oDMS) 2 POSS) synthesis:
synthesis of Compound 3 (oDMS) with reference to step S4 of example 1 2 POSS）。
EXAMPLE 4 preparation of Compound 4
The structural formula of the compound 4 is as follows:
r in formula I represents->。
The preparation procedure for compound 4 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
the first reactant (VPOSS-COOBn) was synthesized with reference to step S1 of example 1.
S2, second reactant (oDMS) 4 POSS-COOBn):
synthesis of the second reactant (oDMS) with reference to step S2 of example 1 4 POSS-COOBn）。
S3, third reactant (oDMS) 4 POSS-COOH) synthesis:
synthesis of third reactant (oDMS) with reference to step S3 of example 1 4 POSS-COOH）。
S4, compound 4 (oDMS) 4 POSS) synthesis:
synthesis of Compound 4 (oDMS) with reference to step S4 of example 1 4 POSS）。
EXAMPLE 5 preparation of Compound 5
The structural formula of the compound 5 is as follows:
r in formula I represents->。
The preparation procedure for compound 5 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
the first reactant (VPOSS-COOBn) was synthesized with reference to step S1 of example 1.
S2, second reactant (oDMS) 5 POSS-COOBn):
synthesis of the second reactant (oDMS) with reference to step S2 of example 1 5 POSS-COOBn）。
S3, third reactant (oDMS) 5 POSS-COOH) synthesis:
synthesis of third reactant (oDMS) with reference to step S3 of example 1 5 POSS-COOH）。
S4, compound 5 (oDMS) 5 POSS) synthesis:
synthesis of Compound 5 (oDMS) with reference to step S4 of example 1 5 POSS）。
Example 6 compound 6 has the structural formula:
r in formula I represents->。
The preparation procedure for compound 6 was as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
the first reactant (VPOSS-COOBn) was synthesized with reference to step S1 of example 1.
S2, second reactant (oDMS) 6 POSS-COOBn):
synthesis of the second reactant (oDMS) with reference to step S2 of example 1 6 POSS-COOBn）。
S3, third reactant (oDMS) 6 POSS-COOH) synthesis:
synthesis of third reactant (oDMS) with reference to step S3 of example 1 6 POSS-COOH）。
S4, compound 6 (oDMS) 6 POSS) synthesis:
synthesis of Compound 6 (oDMS) with reference to step S4 of example 1 6 POSS）。
EXAMPLE 7 oDMS 7 Preparation of POSS-PS Block copolymer:
oDMS 7 the structural formula of the POSS-PS block copolymer is as follows:
wherein, the value range of q is 16-320.
oDMS 7 The preparation steps of the POSS-PS block copolymer are as follows:
s1, synthesis of a first reactant (VPOSS-COOBn):
1.00g of heptavinyl cage silsesquioxane (VPOSS-OH) with a hydroxyl group at one end position is weighed and placed in a reaction vessel, 0.67g of benzyl succinate with one end protected by benzyl and one end of carboxyl group exposed, 1.64g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.12g of 4-dimethylaminopyridine and 200mL of dichloromethane are added into the reaction vessel under the protection of nitrogen, and the reaction is carried out for 24 hours at the temperature of 50 ℃. After the reaction, 1.14g of the first reactant (i.e., VPOSS-COOBn) was isolated by means of silica gel column chromatography, and the yield was 95%.
S2, second reactant (oDMS) 7 POSS-COOBn):
dissolving 0.54g of VPOSS-COOBn in 50mL of toluene, adding 100 μl of Karstedt catalyst under the environment of a glove box protected by argon, reacting at 110deg.C for 6 hours, and separating by column chromatography to obtain a second reactant (i.e. oDMS) 7 POSS-COOBn) 1.45g, yield 97%.
S3, third reactant (oDMS) 7 POSS-COOH) synthesis:
oDMS (optical fiber array) 7 POSS-COOBn 1.00g is added into 100mL of ethyl acetate, palladium-carbon 0.34g is added, the mixture is reacted for 2 hours at room temperature under the hydrogen atmosphere, solid impurities are removed by filtration, and a third reactant (oDMS) is obtained by reduced pressure rotary evaporation 7 POSS-COOH) 0.91g, yield 99%.
S4, compound 1 (oDMS) 7 POSS) synthesis:
oDMS (optical fiber array) 7 POSS-COOH 0.64g, pentynol 0.89g, 1.18g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine 0.13g were added to 200mL methylene chloride, reacted under the protection of nitrogen for 6 hours, and after the reaction was completed, separated by column chromatography to obtain 0.60g of Compound 1 (i.e., oDMS) 7 POSS), yield was 83%.
S5、oDMS 7 Synthesis of POSS-PS Block copolymer:
polystyrene (PS) molecule (100 mg) with terminal azide group and oDMS 7 POSS monomer (83 mg) (namely compound 1) is added into toluene, cuprous bromide (3 mg) and pentamethyldiethylenetriamine (100 mu L) are added into a glove box protected by argon gas, the mixture is reacted for 6 hours at room temperature, and after the reaction is completed, the mixture is subjected to silica gel column chromatography to obtain oDMS 7 POSS-PS block copolymer (169 mg, 92% yield).
For oDMS prepared in example 7 7 The POSS-PS block copolymer is identified, and the general formula and nuclear magnetic resonance hydrogen spectrogram of the POSS-PS block copolymer are shown in figure 2.
Example 8
oDMS of reference example 7 7 Preparation method of POSS-PS block copolymerA series of block copolymers oDMS were synthesized by the method using the compound 1 prepared in example 1 and Polystyrene (PS) molecules with different molecular weights and terminal ends modified by azide groups 7 POSS-PS 1.6k 、oDMS 7 POSS-PS 2.9k 、oDMS 7 POSS-PS 3.4k 、oDMS 7 POSS-PS 4.2k 、oDMS 7 POSS-PS 7.8k 、oDMS 7 POSS-PS 12.9k 、oDMS 7 POSS-PS 16.7k 、oDMS 7 POSS-PS 17.4k 、oDMS 7 POSS-PS 33.0k 。
A series of block copolymers oDMS synthesized in example 8 7 POSS-PS 1.6k 、oDMS 7 POSS-PS 2.9k 、oDMS 7 POSS-PS 3.4k 、oDMS 7 POSS-PS 4.2k 、oDMS 7 POSS-PS 7.8k 、oDMS 7 POSS-PS 12.9k 、oDMS 7 POSS-PS 16.7k 、oDMS 7 POSS-PS 17.4k 、oDMS 7 POSS-PS 33.0k Each set of test solutions was prepared at a concentration of 5 mg/mL by dissolving in tetrahydrofuran, and then tested using a Gel Permeation Chromatography (GPC) analyzer, the test results of which are shown in fig. 3.
As can be seen from FIG. 3, a series of block copolymers of different molecular weights can be synthesized using the preparation method provided in example 8.
Example 9
For the block copolymer oDMS synthesized in example 8 7 POSS-PS 3.4k 、oDMS 7 POSS-PS 12.9k 、oDMS 7 POSS-PS 16.7k 、oDMS 7 POSS-PS 17.4k 、oDMS 7 POSS-PS 33.0k And (3) performing self-assembly of the body to obtain a complete phase diagram, wherein the small-angle X-ray scattering and transmission electron microscope characterization diagrams of the block copolymers are shown in fig. 4-9. As can be seen from FIGS. 4-9, the block copolymers are all less than 10nm in size. Wherein FIG. 4 is a block copolymer oDMS 7 POSS-PS 3.4k A small angle X-ray scattering and transmission electron microscope characterization plot measured at 60 ℃; FIG. 5 is a block copolymer oDMS 7 POSS-PS 3.4k Low angle X-ray scatter and transmission electron microscopy characterization images measured at room temperature.
Example 10
Samples with lamellar phase in terms of self-assembly behavior to the bulk (Block copolymer oDMS prepared in example 8) 7 POSS-PS 12.9k ) Thin film self-assembly studies were performed. Block copolymer oDMS 7 POSS-PS 12.9k The transmission electron microscope image after the self-assembly of the film is shown in fig. 10.
As can be seen from FIG. 10, the block copolymer oDMS 7 POSS-PS 12.9k The transmission electron microscope image of the (B) can clearly observe the lines of the lamellar phase, and proves that the lines are perpendicular to the silicon wafer substrate. This shows that the series of samples can be given lamellar phase behaviour perpendicular to the substrate by a simple thermal annealing process, i.e. the block polymers can be given different phase separation behaviour by a simple thermal annealing process.
EXAMPLE 11 oDMS w Preparation of POSS-oLLA Block copolymer:
oDMS w the structural formula of the POSS-oLLA block copolymer is as follows:
wherein "Bn" represents a benzyl group.
oDMS of reference example 7 7 Preparation procedure of POSS-PS Block copolymer A series of Block copolymer oDMS was synthesized using Compound 1 prepared in example 1 and Olla molecules with terminal ends modified with azido groups of different molecular weights 2 POSS-oLLA 16 、oDMS 3 POSS-oLLA 16 、oDMS 7 POSS-oLLA 16 、oDMS 3 POSS-oLLA 8 。
Block copolymer oDMS synthesized in example 11 by Gel Permeation Chromatography (GPC) 2 POSS-oLLA 16 、oDMS 3 POSS-oLLA 16 、oDMS 7 POSS-oLLA 16 The test was performed and the test results are shown in fig. 11. As can be seen from FIG. 11, a series of oDMS having different molecular weights can be synthesized by the preparation method provided in the examples of the present application w POSS-oLLA block copolymers.
For block copolymer oDMS 3 POSS-oLLA 16 And (3) identifying, wherein nuclear magnetic resonance hydrogen spectrum data are as follows:
1 H NMR（500MHz，Chloroform-d）δ: 7.39(s,1H), 7.38-7.30(m,5H), 5.17(m,18H),4.40(t,J=7.0Hz,2H),4.24-4.18(m,2H),4.11(t,J=6.0Hz,2H),3.06(t,J=7.3Hz,2H),2.81(t,J=7.3Hz,2H),2.61(s,4H),2.23(p,J=6.9Hz,2H),1.59(s,30H), 1.56-1.50(m,18H), 1.15-1.09(m,5H),0.55(s,25H),0.15- -0.03(s,147H).
furthermore, by reacting the block copolymer oDMS 3 POSS-oLLA 16 、oDMS 3 POSS-oLLA 8 Bulk self-assembly studies have found that such block copolymers can form hexagonal columnar phases as well as more complex Frank-Kasper a15 phases, and small angle X-ray scattering characterization of these block copolymers is shown in figures 12 and 13 below. As can be seen from FIGS. 12-13, the block copolymers are all less than 10nm in size.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (10)
1. A compound having the structure of formula i:
；
wherein R in formula I representsN is an integer of 2 to 9.
2. A block copolymer is characterized in that the block copolymer is prepared by click chemistry reaction of a compound with a structure shown in a formula I in claim 1 and a polymer chain segment with the tail end modified by an azide group.
3. The block copolymer according to claim 2, wherein the polymer segment having an azide group-modified end is、/>Or->Wherein, the value range of m is 7-15, the value range of q is 16-320, and the value range of t is 20-150.
4. A process for the preparation of a compound of formula i according to claim 1, comprising the steps of:
s1, under the protection of nitrogen, carrying out reaction between heptavinyl cage-type silsesquioxane with hydroxyl substituted at one terminal position and mono-benzyl succinate in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, reacting the compound with the structural formula II with toluene under the action of a second catalyst at a second reaction temperature to obtain a second reactant, wherein the structural formula of the compound with the structural formula II is as follows:n is an integer of 2 to 9;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist, and a compound with a structure shown in a formula I is obtained.
5. The method for preparing a compound having a structure according to claim 4, wherein in step S1, the first coupling agent is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole;
the first catalyst is at least one of 4-dimethylaminopyridine and triethylamine;
the first reaction solvent is at least one of dichloromethane and tetrahydrofuran;
the first reaction temperature is 25-60 ℃.
6. The method for producing a compound having the structure of formula i according to claim 4, wherein in step S2, the second catalyst is Karstedt catalyst;
the second reaction temperature is 80-115 ℃.
7. The method for preparing a compound having the structure of formula i according to claim 4, wherein in step S3, the third catalyst is palladium on carbon.
8. The method for preparing a compound having a structure of formula i according to claim 4, wherein in step S4, the second coupling agent is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole;
the fourth catalyst is at least one of 4-dimethylaminopyridine and triethylamine;
the second reaction solvent is at least one of dichloromethane and tetrahydrofuran.
9. A method of preparing a block copolymer according to claim 2 or 3, comprising the steps of:
s1, under the protection of nitrogen, reacting heptavinyl cage-type silsesquioxane with terminal hydroxyl substituted with succinic acid monobenzyl ester in a first reaction solvent in the presence of a first coupling agent and a first catalyst at a first reaction temperature to obtain a first reactant;
s2, under the protection of argon, reacting the compound with the structural formula II with toluene under the action of a second catalyst at a second reaction temperature to obtain a second reactant, wherein the structural formula of the compound with the structural formula II is as follows:n is an integer of 2 to 9;
s3, reacting the second reactant with ethyl acetate under the action of a third catalyst in a hydrogen atmosphere to obtain a third reactant;
s4, under the protection of nitrogen, the third reactant reacts with the pentynol in a second reaction solvent in which a second coupling agent and a fourth catalyst exist to obtain a compound with a structure shown in a formula I;
s5, under the protection of argon, reacting the compound with the structure shown in the formula I with a polymer chain segment with the tail end modified by an azide group in a third reaction solvent in the presence of a fifth catalyst to obtain the block copolymer.
10. The use of a compound of formula i according to claim 1 or of a block copolymer according to any one of claims 2 to 3 for the preparation of nanopatterned materials, nanoporous materials and nanolithographic materials.
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