CN113563573A - Block copolymer, porous material, preparation method and application thereof - Google Patents
Block copolymer, porous material, preparation method and application thereof Download PDFInfo
- Publication number
- CN113563573A CN113563573A CN202110868276.1A CN202110868276A CN113563573A CN 113563573 A CN113563573 A CN 113563573A CN 202110868276 A CN202110868276 A CN 202110868276A CN 113563573 A CN113563573 A CN 113563573A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- porous material
- polyoxyethylene
- preparation
- solvent
- 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.)
- Granted
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 68
- 239000011148 porous material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 57
- 125000002887 hydroxy group Chemical group [H]O* 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 33
- -1 polyoxyethylene, bromoisobutyryl bromide Polymers 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 27
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052794 bromium Inorganic materials 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 125000001246 bromo group Chemical group Br* 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 229920000359 diblock copolymer Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 29
- 239000004626 polylactic acid Substances 0.000 abstract description 29
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6822—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from hydroxy carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention discloses a block copolymer, a porous material, a preparation method and application thereof, wherein the block copolymer comprises the following preparation raw materials: polyoxyethylene, bromoisobutyryl bromide, styrene, D, L-lactide and a catalyst; the end groups of the polyethylene oxide are all hydroxyl groups. The porous material of the invention is formed by etching polylactic acid from the block copolymer in alkali liquor on the basis of the self-assembly structure of the polystyrene-polyoxyethylene-polylactic acid block copolymer, thereby forming an ordered porous structure. Meanwhile, block polyethylene oxide is introduced, so that polyethylene oxide is covalently grafted on the pore wall, and modification of the pore wall is realized.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a block copolymer, a porous material, and a preparation method and application thereof.
Background
The porous material has important application in the fields of catalysis, adsorption, energy sources and the like. Obtaining mesoporous materials with controllable size and structure and realizing the functionalization thereof are always research hotspots in the field.
Polyethylene oxide is used as a high molecular polymer, has good water solubility and high viscosity, and also has the properties of flocculation, thickening, slow release, antibiosis, lubrication, dispersion, retention, water retention and the like, and is non-toxic and non-irritant. Therefore, the method has wide application in industries such as papermaking, coating, printing ink, textile printing and dyeing, daily chemical industry and the like.
The block copolymer is formed by connecting two or more than two homopolymers through covalent bonds. Due to thermodynamic incompatibility between segments, block copolymers can self-assemble to form periodic ordered structures through microphase separation processes. In the related technology, the polymer mesoporous material is further obtained by a pore-forming method on the basis of a block copolymer self-assembly structure. However, since the porous material is a single composition, the porous material has single property and small specific surface area, and is greatly limited in application.
Therefore, it is required to develop a block copolymer with which a porous material having a large specific surface area can be obtained.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a block copolymer, and a porous material prepared by using the block copolymer has large specific surface area.
The invention also provides a preparation method of the block copolymer.
The invention also provides a porous material which is prepared from the block copolymer.
The invention also provides a preparation method of the porous material.
The invention also provides application of the porous material.
In a first aspect, the present invention provides a block copolymer having the formula:
wherein p is 69-173; n is 45 to 228; m is 173 to 365.
According to some embodiments of the invention, p is 124-142.
According to some embodiments of the invention, n is 105.
According to some embodiments of the invention, m is 295-336.
The length of the PS (polystyrene) block and PLA (polylactic acid) block mainly determines the shape and diameter of the pores. When the lengths of PS and PLA are similar, a laminated structure is formed, and the etched holes are not channel-shaped holes.
According to some embodiments of the invention, the block copolymer comprises the following starting materials: polyoxyethylene, bromoisobutyryl bromide, styrene, D, L-lactide and a catalyst;
the end groups of the polyethylene oxide are all hydroxyl groups.
According to some embodiments of the invention, the polyethylene oxide has a molecular weight of 1000 to 4600.
Too large a molecular weight of polyethylene oxide PEO has an effect on subsequent formation of ordered pores, and if too large a molecular weight of PEO, the degree of pore formation becomes worse.
According to some embodiments of the invention, the mass ratio of the polyethylene oxide to the bromoisobutyryl bromide is 100: 15 to 35.
According to some embodiments of the invention, the mass ratio of the polyethylene oxide to the styrene is 1:80 to 200.
According to some embodiments of the invention, the mass ratio of the D, L-lactide to the catalyst is 30-40: 1-2.
According to some embodiments of the invention, the mass ratio of styrene to D, L-lactide is 1:1 to 4.
According to some embodiments of the invention, the catalyst is an organotin catalyst.
According to some embodiments of the invention, the organotin catalyst comprises stannous isooctanoate, a Sn (ii) alkoxide, a Sn (iv) alkoxide.
According to some embodiments of the invention, the block copolymer further comprises the following starting materials: a copper catalyst and a ligand.
According to some embodiments of the invention, the copper catalyst comprises cuprous halide.
According to some embodiments of the invention, the cuprous halide comprises at least one of cuprous chloride, cuprous bromide, and cuprous iodide.
According to some embodiments of the invention, the ligand comprises an organic amine.
According to some embodiments of the invention, the organic amine comprises at least one of tetramethylethylenediamine, N', N "-pentamethyldiethylenetriamine, and 1,1,4,7,10, 10-hexamethyltriethylenetetramine.
According to some embodiments of the invention, the mass ratio of the copper catalyst to the ligand is 5-10: 5-50.
According to some embodiments of the invention, the mass ratio of the ligand to styrene is 1:80 to 200.
The second aspect of the present invention provides a method for producing the above block copolymer, comprising the steps of:
preparation of S1, terminal bromine and terminal hydroxyl polyethylene oxide:
reacting the polyoxyethylene with the bromoisobutyryl bromide, adding a precipitator I, carrying out solid-liquid separation, and collecting a solid phase to obtain the terminal bromine and the terminal hydroxyl polyoxyethylene;
s2, preparation of diblock copolymer:
reacting the end group bromine and the end group hydroxyl polyoxyethylene in the step S1 with the styrene at the temperature of 80-100 ℃ for 6-10 h, concentrating, carrying out solid-liquid separation, and collecting a solid phase to obtain the diblock copolymer;
s3, preparation of a block copolymer:
and (3) adding the diblock copolymer, the D, L-lactide and the catalyst in the step (S2) into toluene, reacting at 80-100 ℃ under a vacuum condition, adding a precipitator II, carrying out solid-liquid separation, and collecting a solid phase to obtain the block copolymer.
The structures of the terminal bromine and terminal hydroxyl polyethylene oxides according to some embodiments of the present invention are shown below:
wherein n is 45-228.
According to some embodiments of the present invention, the precipitant i in step S1 includes at least one of n-hexane, diethyl ether, and petroleum ether.
N-hexane, diethyl ether and petroleum ether are poor solvents for PEO).
According to some embodiments of the invention, the precipitant ii in step S3 includes at least one of methanol and n-hexane.
Methanol and n-hexane are poor solvents for PS.
According to some embodiments of the present invention, the reaction in step S1 also requires the addition of the copper catalyst and the ligand.
According to some embodiments of the invention, the temperature of the reaction in step S1 is between 80 ℃ and 120 ℃.
According to some embodiments of the invention, the reaction time in step S1 is 6h to 12 h.
According to some embodiments of the present invention, the reaction of step S1 is followed by the removal of copper ions using alumina or silica.
According to some embodiments of the invention, the vacuum in step S3 is 10-1Pa～10-5Pa。
According to some embodiments of the invention, the reaction time in step S3 is 3h to 4 h.
In a third aspect, the invention provides a porous material, which comprises the following preparation raw materials: the block copolymer, a solvent and an alkali liquor.
According to some embodiments of the invention, the mass ratio of the block copolymer to the solvent is 90 to 98:2 to 10.
According to some embodiments of the invention, the lye comprises an inorganic base, an alcoholic solvent and water.
According to some embodiments of the invention, the inorganic base comprises at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.
According to some embodiments of the invention, the alcoholic solvent comprises at least one of ethanol and propanol.
According to some embodiments of the invention, the mass ratio of the inorganic base, the alcohol solvent and the water is 50-100: 50-100.
According to some embodiments of the invention, the porous material has a specific surface area of 15m2/g～188m2/g。
According to some embodiments of the invention, the porosity of the porous material is between 0.15mL/g and 0.62 mL/g.
According to some embodiments of the invention, the pore size of the porous material is between 2.1nm and 31 nm.
The fourth aspect of the present invention provides a method for preparing the above porous material, comprising the steps of:
adding the block copolymer to a solvent to prepare a polymer solution; and after the solvent of the polymer solution is volatilized, adding the polymer solution into the alkali liquor for etching to obtain the porous material.
According to the preparation method of the porous material, the polystyrene-polyoxyethylene-polylactic acid block copolymer is dissolved in dichloromethane by means of the phase separation characteristic of the polystyrene-polyoxyethylene-polylactic acid block copolymer, and an ordered self-assembly structure is formed after the solvent is volatilized; and then the polylactic acid is etched by alkali liquor to prepare a porous polystyrene block, and simultaneously, the exposed polyoxyethylene is enriched on the hole wall, so that the modification of the hole wall is realized.
According to some embodiments of the invention, the solvent comprises dichloromethane.
According to some embodiments of the invention, the polymer solution has a mass fraction of block copolymer of 2% to 10%.
According to some embodiments of the invention, the time of said volatilizing is between 3.5h and 4.5 h.
According to some embodiments of the invention, the drying is performed after the evaporation.
According to some embodiments of the invention, the drying time is between 0h and 24 h.
According to some embodiments of the invention, the etching time is 0.5h to 1.5 h.
The fifth aspect of the invention provides the use of the above porous material in the preparation of a catalyst and/or adsorbent.
The invention has the beneficial effects that:
the porous material of the invention is formed by etching polylactic acid from the block copolymer in alkali liquor on the basis of the self-assembly structure of the polystyrene-polyoxyethylene-polylactic acid block copolymer, thereby forming an ordered porous structure. Meanwhile, block polyethylene oxide is introduced, so that polyethylene oxide is covalently grafted on the pore wall, and modification of the pore wall is realized.
Drawings
FIG. 1 is a schematic diagram of the synthesis steps of a block copolymer in an embodiment of the present invention;
FIG. 2 is a graph showing the difference in the contents of polystyrene, polyethylene oxide and polylactic acid in the polymer blocks obtained in example 4 of the present invention and comparative example 1;
FIG. 3 is an SEM photograph of a porous material obtained in example 2 of the present invention;
FIG. 4 shows the contact angle test results of the porous material prepared in example 4 of the present invention;
FIG. 5 shows the contact angle test results of the polymer block obtained in comparative example 2 of the present invention;
FIG. 6 is an SEM photograph of a porous material obtained in comparative example 4 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
A method for preparing a block copolymer according to an embodiment of the present invention includes the steps shown in FIG. 1:
s1, preparation of hydroxyl polyethylene oxide with terminal bromine and terminal hydroxyl groups at two ends respectively:
carrying out esterification reaction on polyethylene oxide with hydroxyl at both ends and bromoisobutyryl bromide, precipitating a reactant in n-hexane, washing with n-hexane for multiple times, and drying;
s2, preparation of copolymer:
and (2) taking polyoxyethylene with the end group bromine and the end group hydroxyl at two ends prepared in the step (S1) as macroinitiators, adding a styrene monomer, reacting for 8 +/-2 h at the temperature of 100 +/-20 ℃, cooling with water after the reaction is finished, adding tetrahydrofuran for dilution, removing copper ions by using silica gel or alumina, precipitating a product in methanol after concentration, and drying in vacuum to obtain the diblock copolymer.
S3, preparation of a block copolymer:
the diblock block described in step S2The copolymer, the D, L-lactide and the catalyst were added to toluene and the vacuum (10)-1Pa～10-5Pa), reacting at 80-100 ℃, adding a precipitator II, carrying out solid-liquid separation, and collecting a solid phase to obtain the block copolymer.
Wherein, the molar ratio of polyoxyethylene to bromoisobutyryl bromide in the step S1 is 1: 1;
in step S2, the two ends respectively have terminal bromine and terminal hydroxyl polyoxyethylene as macroinitiators, polymerized styrene adopts atom transfer radical mode, cuprous bromide as catalyst, N', N "-pentamethyldiethylenetriamine as ligand, the two ends respectively have terminal bromine and terminal hydroxyl polyoxyethylene with the mass ratio of styrene being 1: 10 to 18.
Specific examples of the present invention are described in detail below.
Example 1
This example is a method for preparing a block copolymer, comprising the steps of:
s1, preparation of hydroxyl polyethylene oxide with terminal bromine and terminal hydroxyl groups at two ends respectively:
slowly dripping 3.45g of bromoisobutyryl bromide (0.85mL/min +/-0.15 mL/min) into 10g of double-end hydroxyl polyoxyethylene (molecular weight 2000g/mol) (Innochem, A35872, CAS number: 25322-68-3), wherein an ice water bath (0 ℃ +/-5 ℃) is adopted in the dripping process, and reacting overnight (12 hours) at room temperature (25 ℃ +/-5 ℃) after finishing dripping to obtain a reaction solution; adding n-hexane to the reaction solution to precipitate a product; after the precipitation is finished, carrying out solid-liquid separation, collecting a solid phase, washing and drying the solid phase to obtain polyoxyethylene with the end groups of bromine and hydroxyl at the two ends respectively;
s2, preparation of diblock copolymer:
adding 11g of styrene, 0.07g of cuprous bromide and 0.1g of 0.1g N, N, N' -pentamethyldiethylenetriamine to 1.2g of polyoxyethylene with terminal bromine and terminal hydroxy respectively at two ends prepared in the step S1, reacting for 8 hours at 100 ℃, cooling with water after the reaction is finished, and adding 100mL of tetrahydrofuran for dilution; removing copper ions by using silica gel or alumina, concentrating to 40mL, precipitating in methanol to obtain a product, and drying in vacuum to obtain the polystyrene-polyoxyethylene diblock copolymer with hydroxyl at the tail end;
s3, preparation of a block copolymer:
0.5g of a polystyrene-polyethylene oxide diblock copolymer having hydroxyl groups at the ends as macroinitiator, 0.37g D, L-lactide (Innochem, A43742, CAS number: 95-96-5), 0.012g of stannous isooctanoate and 5g of toluene were added, and vacuum (10 g)-1Pa～10-5Pa), reacting for 3.5h at 100 +/-20 ℃, cooling by using water after the reaction is finished, adding dichloromethane for dilution, precipitating a product in methanol, and drying in vacuum to obtain the polystyrene-polyoxyethylene-polylactic acid block copolymer.
The structure of the polystyrene-polyoxyethylene-polylactic acid block copolymer prepared in this example is as follows:
where p is 142, n is 104, and m is 336.
Example 2
The embodiment is a preparation method of a porous material, which comprises the following steps:
dissolving 25mg of the block copolymer prepared in example 1 in 1.3mL of dichloromethane solvent, completely dissolving the block copolymer, placing the container in the air with an opening, volatilizing the solvent for 4 hours, then placing the container in a vacuum oven for drying for 12 hours, taking out the solid, soaking the solid in alkali liquor (the mass ratio of sodium hydroxide to ethanol to water is 1:1:1), stirring for 0.5 hour, taking out and drying to obtain a porous material, wherein the specific surface area of the porous material is 95m2The porosity data is 0.33mL/g, and the pore size is 12 nm.
Example 3
This example is a method for preparing a block copolymer, comprising the steps of:
s1, preparation of hydroxyl polyethylene oxide with terminal bromine and terminal hydroxyl groups at two ends respectively:
slowly dripping 1.5G of bromoisobutyryl bromide (0.85mL/min +/-0.15 mL/min) into 10G of double-ended hydroxyl polyoxyethylene (molecular weight of 4600G/mol) (Sigma-aldrich, 373001-250G, CAS number of 25322-68-3), wherein an ice water bath (0 ℃ +/-5 ℃) is adopted in the dripping process, and reacting overnight (12 hours) at room temperature (25 ℃ +/-5 ℃) after finishing dripping to obtain a reaction solution; adding n-hexane to the reaction solution to precipitate a product; after the precipitation is finished, carrying out solid-liquid separation, collecting a solid phase, washing and drying the solid phase to obtain polyoxyethylene with the end groups of bromine and hydroxyl at the two ends respectively;
s2, preparation of diblock copolymer:
adding 11g of styrene, 0.07g of cuprous bromide and 0.1g of 0.1g N, N, N' -pentamethyldiethylenetriamine to 1.2g of polyoxyethylene with terminal bromine and terminal hydroxy respectively at two ends prepared in the step S1, reacting for 8 hours at 100 ℃, cooling with water after the reaction is finished, and adding 100mL of tetrahydrofuran for dilution; removing copper ions by using alumina, concentrating to 40mL, precipitating a product in methanol, and drying in vacuum to obtain the polystyrene-polyoxyethylene diblock copolymer with hydroxyl at the tail end;
s3, preparation of a block copolymer:
0.5g of a polystyrene-polyethylene oxide diblock copolymer with hydroxyl groups at the ends as macroinitiator, 0.37g D, L-lactide, 0.012g of stannous isooctanoate and 5g of toluene were added and the mixture was evacuated (10)-1Pa～10-5Pa), reacting for 3.5h at 100 +/-20 ℃, cooling by using water after the reaction is finished, adding dichloromethane for dilution, precipitating a product in methanol, and drying in vacuum to obtain the polystyrene-polyoxyethylene-polylactic acid block copolymer.
The structure of the polystyrene-polyoxyethylene-polylactic acid block copolymer prepared in this example is as follows:
where p is 118, n is 45, and m is 336.
Example 4
The embodiment is a preparation method of a porous material, which comprises the following steps:
will 25mg of the block copolymer prepared in example 3 is dissolved in 1.3mL of dichloromethane solvent, the container is placed in the air with an opening until the block copolymer is completely dissolved, the solvent is volatilized for 4 hours, then the container is placed in a vacuum oven for drying for 12 hours, the solid is taken out and soaked in alkali liquor (the mass ratio of sodium hydroxide to ethanol to water is 1:1:1), the stirring is carried out for 0.5 hour, the solid is taken out and dried, and the porous material is obtained, wherein the specific surface area is 97m2The porosity data is 0.24mL/g, and the pore size is 18 nm.
Comparative example 1
The comparative example is a method of preparing a porous material comprising the steps of:
25mg of the block copolymer prepared in example 3 was dissolved in 1.3mL of methylene chloride solvent, placed in the air with the container open, and after the solvent evaporated for 4h, it was placed in a vacuum oven and dried for 12h to obtain a porous material.
Comparative example 2
This comparative example is a method of preparing a block copolymer comprising the steps of:
s1, preparing small molecules with terminal bromine and terminal hydroxyl at two ends respectively:
slowly dripping 4.4G of bromoisobutyryl bromide (0.85mL/min +/-0.15 mL/min) into 2.0G of 2, 2-dimethyl-1, 3-propanediol (Sigma-Aldrich, 538256-25G, CAS number: 126-30-7) and triethylamine as an acid-binding agent, wherein an ice water bath (0 ℃ +/-5 ℃) is adopted in the dripping process, and reacting overnight (12 hours) at room temperature (25 ℃ +/-5 ℃) after finishing dripping to obtain a reaction solution; filtering and concentrating the reaction solution, and separating by chromatographic column chromatography to obtain micromolecules with terminal bromine and terminal hydroxyl at two ends respectively;
s2, preparation of diblock copolymer:
adding 11g of styrene, 0.07g of cuprous bromide and 0.1g of 0.1g N, N, N' -pentamethyldiethylenetriamine to 1.2g of micromolecules with terminal bromine and terminal hydroxyl at two ends respectively prepared in the step S1, reacting for 6 hours at 100 ℃, cooling with water after the reaction is finished, and adding 100mL of tetrahydrofuran for dilution; removing copper ions by using silica gel or alumina, concentrating to 40ml, precipitating in methanol to obtain a product, and drying in vacuum to obtain polystyrene with hydroxyl at the tail end;
s3, preparation of a block copolymer:
0.5g of polystyrene with hydroxyl groups at the end as macroinitiator, 0.37g of L-lactide, 0.012g of stannous isooctanoate and 5g of toluene were added and the mixture was evacuated (10)-1Pa～10-5Pa), reacting at 100 +/-20 ℃, cooling with water, adding dichloromethane for dilution after the reaction is finished, precipitating a product in methanol, and drying in vacuum to obtain the polystyrene-polylactic acid block copolymer.
The structure of the polystyrene-polylactic acid block copolymer prepared by the comparative example is as follows:
where m is 336 and n is 208.
Performance test data: the specific surface area is 101m2The porosity data is 0.28 mL/g.
Comparative example 3
This comparative example is a method of preparing a block copolymer comprising the steps of:
s1, preparation of hydroxyl polyethylene oxide with terminal bromine and terminal hydroxyl groups at two ends respectively:
slowly dripping 3.45g of bromoisobutyryl bromide (0.85mL/min +/-0.15 mL/min) into 10g of double-end hydroxyl polyoxyethylene (molecular weight 2000g/mol) (Innochem, A35872, CAS number: 25322-68-3), wherein an ice water bath (0 ℃ +/-5 ℃) is adopted in the dripping process, and reacting overnight (12 hours) at room temperature (25 ℃ +/-5 ℃) after finishing dripping to obtain a reaction solution; adding n-hexane to the reaction solution to precipitate a product; after the precipitation is finished, carrying out solid-liquid separation, collecting a solid phase, washing and drying the solid phase to obtain polyoxyethylene with the end groups of bromine and hydroxyl at the two ends respectively;
s2, preparation of diblock copolymer:
adding 11g of styrene, 0.07g of cuprous bromide and 0.1g of 0.1g N, N, N' -pentamethyldiethylenetriamine to 1.2g of polyoxyethylene with terminal bromine and terminal hydroxy respectively at two ends prepared in the step S1, reacting for 8 hours at 100 ℃, cooling with water after the reaction is finished, and adding 100mL of tetrahydrofuran for dilution; removing copper ions by using silica gel or alumina, concentrating to 40mL, precipitating in methanol to obtain a product, and drying in vacuum to obtain the polystyrene-polyoxyethylene diblock copolymer with hydroxyl at the tail end;
s3, preparation of a block copolymer:
0.5g of a polystyrene-polyethylene oxide diblock copolymer having hydroxyl groups at the ends as macroinitiator, 0.37g D, L-lactide (Innochem, A43742, CAS number: 95-96-5), 0.012g of stannous isooctanoate and 5g of toluene were added, and vacuum (10 g)-1Pa～10-5Pa), reacting for 5h at 100 +/-20 ℃, cooling with water after the reaction is finished, adding dichloromethane for dilution, precipitating a product in methanol, and drying in vacuum to obtain the polystyrene-polyoxyethylene-polylactic acid block copolymer.
The structure of the polystyrene-polyoxyethylene-polylactic acid block copolymer prepared in this example is as follows:
where p is 208, n is 104, and m is 336.
Comparative example 4
The comparative example is a method of preparing a porous material comprising the steps of:
dissolving 25mg of the block copolymer prepared in the comparative example 3 in 1.3mL of dichloromethane solvent, placing the container in the air after the block copolymer is completely dissolved, volatilizing the solvent for 4 hours, then placing the container in a vacuum oven for drying for 12 hours, taking out the solid, soaking the solid in alkali liquor (the mass ratio of sodium hydroxide to ethanol to water is 1:1:1), stirring for 0.5 hour, taking out and drying to obtain the porous material.
The difference between the contents of polystyrene, polyethylene oxide and polylactic acid in the porous materials of example 4 (30 min in FIG. 2) and comparative example 1 (0 min in FIG. 2) according to the present invention is shown in FIG. 2, and it can be seen from FIG. 2 that: in the absence of etching treatment (comparative example 1), St (polystyrene, peak a in fig. 2) in the porous material: EO (polyethylene oxide, b peak in fig. 2): LA (polylactic acid, peak c in FIG. 2) is 100:19.5: 80.9; as is apparent from the above description, the content of polylactic acid is high before the etching treatment is not performed; whereas, after etching for 30min (example 4), St (polystyrene): EO (polyethylene oxide): LA (polylactic acid) is 100: 16.4: 0; namely, after etching for 30min, the polylactic acid in the porous material is removed.
The SEM image of the porous material prepared in example 2 of the present invention is shown in FIG. 3, and it can be seen from FIG. 3 that the porous material prepared in example 2 of the present invention is a porous material.
The contact angle test result of the porous material prepared in the example 4 of the present invention is shown in fig. 4, and it can be known from fig. 4 that the contact angle of the porous material prepared in the example 4 of the present invention is 72.73 °; the contact angle test results of the porous material prepared in comparative example 2 of the present invention are shown in fig. 5, and it can be seen from fig. 5 that the contact angle of the porous material prepared in comparative example 2 of the present invention is 79.78 °; from the comparison of the above results, it is known that: the contact angle of the porous material prepared by the method is smaller, the better the contact angle is, and the better the wetting effect is.
The SEM image of the porous material prepared in comparative example 4 of the present invention is shown in FIG. 6, and it can be seen from FIG. 6 that when the lengths of PS and PLA are similar, a layered structure is formed and pores which are not channel-type after etching are formed.
The invention is not the best known technology.
In summary, according to the polystyrene-polyoxyethylene-polylactic acid block copolymer provided by the invention, by means of the phase separation characteristic of the polystyrene-polyoxyethylene-polylactic acid block copolymer, the polystyrene-polyoxyethylene-polylactic acid block copolymer is dissolved in dichloromethane, and after the solvent is evaporated, an ordered self-assembly structure is formed, polylactic acid is etched away by alkali liquor, so that a porous polystyrene block is prepared, and meanwhile, the exposed polyoxyethylene is enriched on the pore wall, so that the modification of the pore wall is realized, the contact angle of the material is reduced, and the hydrophilicity of the pore wall is increased.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
While the embodiments of the present invention have been described in detail with reference to the specific embodiments, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A block copolymer characterized by: the structural formula is shown as the following formula:
wherein p is 69-173; n is 45 to 228; m is 173 to 365.
2. A block copolymer according to claim 1, wherein: the method comprises the following preparation raw materials: polyoxyethylene, bromoisobutyryl bromide, styrene, D, L-lactide and a catalyst;
the end groups of the polyethylene oxide are all hydroxyl groups.
3. A block copolymer according to claim 1, wherein: the mass ratio of the polyoxyethylene to the bromoisobutyryl bromide is 100: 15-35; preferably, the mass ratio of the polyoxyethylene to the styrene is 1: 80-200; preferably, the mass ratio of the D, L-lactide to the catalyst is 30-40: 1-2; preferably, the mass ratio of the styrene to the D, L-lactide is 1: 1-4.
4. A method for preparing the block copolymer according to claim 2 or 3, characterized in that: the method comprises the following steps:
preparation of S1, terminal bromine and terminal hydroxyl polyethylene oxide:
reacting the polyoxyethylene with the bromoisobutyryl bromide, adding a precipitator I, carrying out solid-liquid separation, and collecting a solid phase to obtain the terminal bromine and the terminal hydroxyl polyoxyethylene;
s2, preparation of diblock copolymer:
reacting the end group bromine and the end group hydroxyl polyoxyethylene in the step S1 with the styrene at the temperature of 80-100 ℃ for 6-10 h, concentrating, carrying out solid-liquid separation, and collecting a solid phase to obtain the diblock copolymer;
s3, preparation of a block copolymer:
adding the diblock copolymer, the D, L-lactide and the catalyst in the step S2 into toluene, reacting at 80-100 ℃ under a vacuum condition, adding a precipitator II, carrying out solid-liquid separation, and collecting a solid phase to obtain the block copolymer;
wherein the structure of the terminal bromine and the terminal hydroxyl polyethylene oxide is shown as the following formula:
5. the method of claim 4, wherein: in the step S1, the precipitant I comprises at least one of n-hexane, diethyl ether and petroleum ether; preferably, the precipitant ii in step S3 includes at least one of methanol and n-hexane.
6. A porous material characterized by: the method comprises the following preparation raw materials: a block copolymer as claimed in any one of claims 1 to 3, a solvent and a base solution.
7. A porous material according to claim 6, wherein: the mass ratio of the block copolymer to the solvent is 90-98: 2-10.
8. A porous material according to claim 6, wherein: the alkali liquor comprises inorganic alkali, an alcohol solvent and water; preferably, the inorganic base comprises at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide; preferably, the alcoholic solvent includes at least one of ethanol and propanol; preferably, the mass ratio of the inorganic base to the alcohol solvent to the water is 50-100: 50-100.
9. The method for producing a porous material according to any one of claims 6 to 8, characterized in that: the method comprises the following steps:
adding the block copolymer to a solvent to prepare a polymer solution; and after the solvent of the polymer solution is volatilized, adding the polymer solution into the alkali liquor for etching to obtain the porous material.
10. Use of a porous material according to any one of claims 6 to 8 in the preparation of a catalyst and/or adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110868276.1A CN113563573B (en) | 2021-07-30 | 2021-07-30 | Block copolymer, porous material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110868276.1A CN113563573B (en) | 2021-07-30 | 2021-07-30 | Block copolymer, porous material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113563573A true CN113563573A (en) | 2021-10-29 |
| CN113563573B CN113563573B (en) | 2022-05-24 |
Family
ID=78169183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110868276.1A Active CN113563573B (en) | 2021-07-30 | 2021-07-30 | Block copolymer, porous material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113563573B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1198066B (en) * | 1962-10-25 | 1965-08-05 | Shell Int Research | Process for the preparation of copolymers |
| CN102399353A (en) * | 2011-07-29 | 2012-04-04 | 常州大学 | Preparation method of amphiphilic segmented copolymer |
| CN102863596A (en) * | 2012-10-08 | 2013-01-09 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and modified polylactic acid preparation method |
| CN103772737A (en) * | 2014-01-24 | 2014-05-07 | 同济大学 | Porous polystyrene block material with high specific area and preparation method thereof |
-
2021
- 2021-07-30 CN CN202110868276.1A patent/CN113563573B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1198066B (en) * | 1962-10-25 | 1965-08-05 | Shell Int Research | Process for the preparation of copolymers |
| CN102399353A (en) * | 2011-07-29 | 2012-04-04 | 常州大学 | Preparation method of amphiphilic segmented copolymer |
| CN102863596A (en) * | 2012-10-08 | 2013-01-09 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and modified polylactic acid preparation method |
| CN103772737A (en) * | 2014-01-24 | 2014-05-07 | 同济大学 | Porous polystyrene block material with high specific area and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIE SONG: "Functionality- and Size-Dependent Target-Differentiation of Nanoporous Carboxylated Polystyrenes in Polar Protic Solvents", 《ACS MACRO LETTERS》 * |
| 蓝荣肇: "原子转移自由基聚合法合成两亲性嵌段共聚物mPEG-PtBA", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113563573B (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI402277B (en) | Method of forming an adsorptive ion-exchange material | |
| US9234082B2 (en) | Polymer material having high capacity for hydrogen storage and preparation method thereof | |
| CN113698579B (en) | Porphyrin conjugated microporous polymer and its synthesis method and application | |
| CN103204978B (en) | Method for preparing temperature-sensitive graphene/polymer hybrid material | |
| CN111672329B (en) | Preparation method of solvent-resistant charged composite nanofiltration membrane | |
| CN104084057A (en) | Preparation method of diffusion dialysis cation exchange membrane | |
| CN113563573B (en) | Block copolymer, porous material, preparation method and application thereof | |
| CN111116912A (en) | Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin | |
| CN108899567B (en) | Hyperbranched anion exchange membrane and preparation method thereof | |
| CN111495214B (en) | Method for improving performance of porous membrane through crosslinking | |
| CN110201552B (en) | Nano porous fiber membrane with micropore/mesopore structure and preparation method thereof | |
| CN116102775B (en) | Porous polyimide film for lithium ion battery and preparation method thereof | |
| CN114471487B (en) | Super-crosslinked porous polymer material capable of being dissolved and processed and preparation method thereof | |
| CN114044863B (en) | Multi-arm [ PS-b-PMA (11C) Az ] x liquid crystal block copolymer and preparation method and application thereof | |
| JPWO2013069681A1 (en) | Vinyl chloride copolymer porous body and method for producing the same | |
| JPS5892409A (en) | Selective permeable membrane | |
| Zhu et al. | Synthesis of organo-montmorillonite/sodium alginate graft poly (acrylic acid-co-2-acrylamido-2-methyl-1-propane sulfonic acid) superabsorbent composite and its adsorption studies | |
| CN113072064B (en) | Modified graphene, graphene film, preparation method and application thereof | |
| Lin et al. | Cellulose functionalization via ATRP grafting of glycidyl methacrylate for Cr (VI) adsorption | |
| CN113717430A (en) | Preparation method and application of super-crosslinked braided super-high specific surface area PolyHIPE fluorine-containing hierarchical pore material | |
| Ran et al. | Preparation and performance for CO2 adsorption of large‐scale microporous fiber membrane based on electrostatic spinning technology | |
| CN108905641B (en) | Nanofiltration membrane and preparation method thereof | |
| CN110364370B (en) | Pyridyl porous carbon material and preparation method and application thereof | |
| CN110938180A (en) | PMMA-b-PEO-b-PMMA triblock copolymer, and preparation method and application thereof | |
| CN113717425B (en) | Porous material and preparation method and application 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 |