CN116640276B - Synthesis method of sequence-controllable multi-block copolymer brush - Google Patents
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 60
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 59
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 58
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 44
- 229920001610 polycaprolactone Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001925 cycloalkenes Chemical group 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 3
- 241001264766 Callistemon Species 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000011664 nicotinic acid Substances 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000037048 polymerization activity Effects 0.000 abstract 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 42
- 239000004626 polylactic acid Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 16
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 13
- 238000001035 drying Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011988 third-generation catalyst Substances 0.000 description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920006030 multiblock copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
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- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Silicon Polymers (AREA)
Abstract
The invention discloses a synthesis method of a sequence controllable multi-block copolymer brush, which relates to the technical field of macromolecule synthesis, wherein monomers and catalysts are respectively prepared into solutions, the monomers are sequentially added into the catalyst solutions according to the block sequence of a target polymer, and the monomers of each block are completely converted by adjusting key reaction parameters (such as polymerization degree, concentration, time and feeding rate) in the synthesis process, so that the multi-block copolymer brush with narrow molecular weight distribution and precisely controllable sequence is prepared under the condition of keeping high polymerization activity, and the defects that other polymerization methods such as free radical polymerization are difficult to obtain the multi-block copolymer with a topological structure and the existing ring-opening metathesis polymerization method is limited to polymer brushes with simple short sequences and wide molecular weight distribution of products are overcome, thereby having important significance in bionic molecule design, complex function realization and advanced assembly structure construction.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a synthesis method of a sequence-controllable multi-block copolymer brush.
Background
The precise monomer sequence of the organism controls the storage, replication and translation of genetic information, guiding the three-dimensional structure of the protein. In recent years, polymer chemists have been working on controlling the microstructure and monomer sequence of polymers, inspired by natural principles, and a variety of multiblock copolymers have been synthesized using living/controlled polymerization methods. However, chain transfer and chain termination occurring during synthesis make the sequence structure of the product ambiguous, and the multiblock copolymers currently synthesized are only linear polymers.
The polymer brush consists of a polymer main chain and innumerable densely grafted side chains, compared with a linear polymer, the polymer brush has the advantages of less chain conformational extension and chain entanglement, the self-assembly dynamics are accelerated by the structural characteristics, the structural size of an assembly body is expanded from tens of nanometers to hundreds of nanometers, and the polymer brush has wide application prospect in various fields such as photonic crystal, detection, sensing, anti-counterfeiting and the like. In 2009, the two-block copolymer brush was first successfully prepared by controlled radical polymerization and living ring-opening metathesis polymerization, respectively, from the professor group of Rzayev, new York State university, U.S. and the professor group of Grubbs, california, inc. Later some groups (Grubbs, rzayev, wooley, lodge et al) also reported the synthesis of triblock copolymer brushes. To date, there has been little research on the synthesis of tetrablock and pentablock copolymer brushes, and the molecular weight distribution of the products obtained from these works is generally broad and the GPC curves have significant tailing and shoulder peaks, due to deactivation of the catalyst active sites during the complete conversion of the monomers, and no longer growth of part of the polymer chains, resulting in incomplete sequences of short chain impurities in the final product. In addition, macromers have a relatively slow rate of polymerization relative to small macromers, and it is difficult to complete the polymerization within a limited catalyst active center lifetime. In summary, the presently reported methods of multiblock copolymer synthesis have not produced well-defined multiblock copolymer brushes with long and complex sequences with narrow molecular weight distributions.
Disclosure of Invention
In order to solve the technical problems, the invention provides a synthesis method of a sequence-controllable multi-block copolymer brush, which is used for preparing a well-defined multi-block copolymer brush with narrow molecular weight distribution and long and complex sequences on the basis of controlling the molecular weight and the molecular weight distribution.
In order to achieve the above object, the present invention provides a method for synthesizing a sequence-controllable multi-block copolymer brush, comprising the steps of:
preparing solutions of each monomer and catalyst for preparing the multi-block copolymer brush respectively;
determining the addition sequence and the addition amount of the monomers according to the block sequence of the multi-block copolymer brush and the polymerization degree of each block;
sequentially adding the required monomers to the catalyst solution;
and after the last monomer is reacted, collecting the solution of the multi-block copolymer brush, and removing the solvent to obtain the sequence-controllable multi-block copolymer brush.
According to the invention, the monomer and the catalyst are respectively prepared into solutions, the monomer is sequentially added into the catalyst solution according to the block sequence of the target polymer, and the monomer of each block is completely converted by adjusting key reaction parameters (such as polymerization degree, concentration, time and feeding rate) in the synthesis process, so that the multi-block copolymer brush with narrow molecular weight distribution and precisely controllable sequence is prepared under the condition of no chain termination, the defects that other polymerization methods such as free radical polymerization are difficult to obtain the multi-block copolymer with a topological structure, the existing ring-opening metathesis polymerization method is limited to a polymer brush with a simple short sequence and the product molecular weight distribution is wide are overcome, and the method has important significance in bionic molecular design, complex function realization and advanced assembly structure construction.
Further, the monomer is cycloolefin polymerization monomer, and the molecular weight is 500-20000Da.
Further, the monomer terminal has a cycloolefin polymerization unit. The monomer of the invention is a macromer with a cycloolefin polymerization unit at the end and a molecular weight of 500-20000Da, such as a macromer with norbornene, cyclopropene, cyclobutene, cyclopentene, cyclooctene or bicyclooctene at the end.
Further, the monomer includes a macromer of polypropylene oxide (PPO) having a norbornene group at the end, polystyrene (PS), polyethylene glycol (PEO), polydimethylsiloxane (PDMS), polycaprolactone (PCL), polylactide (PLA), poly-t-butyl acrylate (PtBA), or polymethyl methacrylate (PMMA).
Further, the monomer includes a macromer having one norbornene terminal simultaneously linked to 1 to 3 polymer chains.
Further, the solvent used for preparing the solution is an organic solvent, and the organic solvent comprises dichloromethane, tetrahydrofuran, toluene, chloroform or N, N-dimethylformamide.
Furthermore, the invention does not limit the feeding sequence of the monomers, and can successfully feed the monomers, for example, the feeding mode of the monomers can adopt manual feeding and automatic feeding controlled by a computer.
The sequence-controllable multi-block copolymer brush is synthesized according to the synthesis method, and the block sequence of the sequence-controllable multi-block copolymer brush is any sequence.
Further, the topology of the sequence-controllable multi-block copolymer brush is a bottle brush type.
Further, the sequence controllable multi-block copolymer brush has a main chain polymerization degree of 10-2000, a polymerization degree of 5-200 of single blocks and a number of blocks of 6-100.
Further, the molecular weight of the side chain is 500-20000Da, and the molecular weight of the sequence-controllable multi-block copolymer brush is 5000-20000000Da.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) The synthesis method of the sequence controllable multi-block copolymer brush successfully synthesizes the multi-block copolymer brush with long, complex, arbitrary and accurate sequence in the limited service life interval of the catalyst active center, overcomes the defects that other polymerization modes are difficult to obtain products with topological structures and the existing ring-opening metathesis polymerization method is limited to short and simple sequences, the molecular weight distribution of the products is wide, GPC curves have obvious tailing or shoulder peaks, establishes a universal method for preparing the sequence controllable multi-block copolymer brush with complex structures, has the advantages of simplicity, rapidness, expandability and the like, and has important significance for bionic molecule design, complex function realization and advanced assembly structure construction.
(2) The sequence-controllable multi-block copolymer brush synthesized by the invention has long, complex, arbitrary and accurate sequence and narrow molecular weight distribution, and is expected to play an important role in the fields of high polymers, biology and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic illustration of the process of synthesizing a sequence-controllable multi-block copolymer brush of the present invention;
FIG. 2 is a schematic view of the structure of a twelve-block copolymer brush of the present invention;
FIG. 3 is a GPC curve of a twelve-block copolymer brush of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The process schematic diagram of the synthesis sequence controllable multi-block copolymer brush is shown in fig. 1, and the structure schematic diagram of the sequence controllable multi-block copolymer brush is shown in fig. 2.
Example 1
Six-block copolymer brush PLA 10 -b-PDMS 10 -b-PLA 10 -b-PDMS 10 -b-PLA 10 -b-PDMS 10 The synthesis method of (2) comprises the following steps:
(1) NB-PLA (norbornene-terminated polylactic acid) macromer (molecular weight 5200Da, molecular weight distribution index 1.15), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromer (molecular weight 4670Da, molecular weight distribution index 1.20) and Grubbs third generation catalyst (relative molecular weight 884.53 Da) were formulated as ultra-dry dichloromethane solutions of 50mmol/L, 50mmol/L and 0.25mmol/L, respectively.
(2) Adding 2mL of catalyst solution into a reaction bottle filled with nitrogen and stirring, and sequentially adding NB-PLA, NB-PDMS, NB-PLA and NB-PDMS, wherein the interval time of each monomer addition is 5min, and the addition amount of each monomer is 0.1mL, 0.091mL, 0.081mL, 0.077mL, 0.073mL and 0.069mL respectively; the sampled amounts before the addition of the next monomer were 0.2mL, 0.1mL, respectively, and the withdrawn samples were immediately immersed in a methylene chloride solution of vinyl ether to analyze the conversion per block and the molecular weight.
(3) After the last monomer is added for continuous reaction for 5min, vinyl ethyl ether is added to terminate the reaction, the solvent is removed from the collected polymer solution, and the PLA is obtained after drying 10 -b-PDMS 10 -b-PLA 10 -b-PDMS 10 -b-PLA 10 -b-PDMS 10 Six-block copolymer brush, the monomer of each block is completely converted, the polymerization degree of each block is 10, and the molecular weight of the copolymer brush is 2.8X10 5 Da, molecular weight distribution index 1.19.
Example 2
Seven-block copolymer brush PLA 10 -b-PDMS 10 -b-PCL 10 -b-PPO 10 -b-PS 10 -PMMA 10 -b-PEO 10 The synthesis method of (2) comprises the following steps:
(1) NB-PLA (norbornene-terminated polylactic acid) macromonomer (molecular weight 5200Da, molecular weight distribution index 1.15), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromonomer (molecular weight 4670Da, molecular weight distribution index 1.20), NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight 3000Da, molecular weight distribution index 1.15), NB-PPO (norbornene-terminated polypropylene oxide) macromonomer (molecular weight 3000Da, molecular weight distribution index 1.09), NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight 2500Da, molecular weight distribution index 1.13), NB-PMMA (norbornene-terminated polymethyl methacrylate) macromonomer (molecular weight 2400Da, molecular weight distribution index 1.11), NB-PEO (norbornene-terminated polyethylene glycol) macromonomer (molecular weight 2000, molecular weight distribution index 1.08), grubthird generation catalyst (relative molecular weight 884.53 Da) 50mmol/L, 25mmol/L, respectively, and a dry solution of methylene chloride was prepared.
(2) Adding 2mL of catalyst solution into a reaction bottle filled with nitrogen and stirring, and sequentially adding NB-PLA, NB-PDMS, NB-PCL, NB-PPO, NB-PS, NB-PMMA and NB-PEO macromolecular monomers, wherein the interval time of each monomer addition is 5min, and the addition amount of each monomer is 0.1mL, 0.091mL, 0.081mL, 0.077mL, 0.073mL, 0.069mL and 0.065mL respectively; the sampled amounts before the addition of the next monomer were 0.2mL, 0.1mL, and 0.1mL, respectively, and the withdrawn samples were immediately immersed in a methylene chloride solution of vinyl ether to analyze the conversion rate and molecular weight per block.
(3) After the last monomer is added for continuous reaction for 5min, vinyl ethyl ether is added to terminate the reaction, the solvent is removed from the collected polymer solution, and the PLA is obtained after drying 10 -b-PDMS 10 -b-PCL 10 -b-PPO 10 -b-PS 10 -PMMA 10 -b-PEO 10 Seven-block copolymer brushes, the monomers of each block being completely converted, the degree of polymerization of each block being 10, the molecular weight of the copolymer brush being 3.4X10 5 Da, molecular weight distribution index 1.15.
Example 3
Six-block copolymer brush PLA 50 -b-PDMS 50 -b-PLA 50 -b-PDMS 50 -b-PLA 50 -b-PDMS 50 The synthesis method of (2) comprises the following steps:
(1) NB-PLA (norbornene-terminated polylactic acid) macromer (molecular weight 5200Da, molecular weight distribution index 1.15), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromer (molecular weight 4670Da, molecular weight distribution index 1.20) and Grubbs third generation catalyst (relative molecular weight 884.53 Da) were formulated as ultra-dry dichloromethane solutions of 50mmol/L, 50mmol/L and 0.25mmol/L, respectively.
(2) Adding 2mL of catalyst solution into a reaction bottle filled with nitrogen and stirring, and sequentially adding NB-PLA, NB-PDMS, NB-PLA and NB-PDMS, wherein the interval time of each monomer addition is 10min, and the addition amount of each monomer is 0.50mL, 0.48mL, 0.46mL, 0.45mL, 0.44mL and 0.43mL respectively; the sampling amounts before the addition of the next monomer were 0.1mL, and 0.1mL, respectively, the withdrawn sample was immediately immersed in a methylene chloride solution of vinyl ether to analyze the conversion per block and the molecular weight.
(3) Adding vinyl ethyl ether to terminate the reaction after the last monomer is added for 10min, removing the solvent from the collected polymer solution, and drying to obtain PLA 50 -b-PDMS 50 -b-PLA 50 -b-PDMS 50 -b-PLA 50 -b-PDMS 50 Six-block copolymer brush, the monomers of each block are completely converted, the polymerization degree of each block is 50, and the molecular weight of the copolymer brush is 1.1X10 6 Da, molecular weight distribution index 1.20.
Example 4
Six-block copolymer brush PLA 150 -b-PDMS 150 -b-PLA 150 -b-PDMS 150 -b-PLA 150 -b-PDMS 150 The synthesis method of (2) comprises the following steps:
(1) An ultra-dry methylene chloride solution of 100mmol/L, 100mmol/L and 1mmol/L was prepared from NB-PLA (norbornene-terminated polylactic acid) macromonomer (molecular weight: 1500Da, molecular weight distribution index: 1.12), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromonomer (molecular weight: 1900Da, molecular weight distribution index: 1.14) and Grubbs third generation catalyst (relative molecular weight: 884.53 Da), respectively.
(2) Adding 2mL of catalyst solution into a reaction bottle filled with nitrogen and stirring, and sequentially adding NB-PLA, NB-PDMS, NB-PLA and NB-PDMS, wherein the interval time of each monomer addition is 15min, and the addition amount of each monomer is 3mL, 3mL and 3mL respectively; the sampling amounts before the addition of the next monomer were 0.1mL, and 0.1mL, respectively, the withdrawn sample was immediately immersed in a methylene chloride solution of vinyl ether to analyze the conversion per block and the molecular weight.
(3) Adding vinyl ethyl ether to terminate the reaction after the last monomer is added for 15min, removing the solvent from the collected polymer solution, and drying to obtain PLA 150 -b-PDMS 150 -b-PLA 150 -b-PDMS 150 -b-PLA 150 -b-PDMS 150 Six-block copolymer brush, the monomers of each block are completely converted, the polymerization degree of each block is 150, and the molecular weight of the copolymer brush is 2.0X10 6 Da, molecular weight distribution index 1.20.
Example 5
Six-block copolymer brush PLA 6 -b-3PDMS 6 -b-PLA 6 -b-3PDMS 6 -b-PLA 6 -b-3PDMS 6 The synthesis method of (2) comprises the following steps:
(1) NB-PLA (norbornene-terminated polylactic acid) macromer (molecular weight 18000Da, molecular weight distribution index 1.25), NB-3PDMS (one norbornene end group linked to three polydimethylsiloxanes) macromer (molecular weight 6300Da, molecular weight distribution index 1.20) and Grubbs third generation catalyst (relative molecular weight 884.53 Da) were formulated as ultra-dry dichloromethane solutions of 20mmol/L, 20mmol/L and 1mmol/L, respectively.
(2) Adding 2mL of catalyst solution into a reaction bottle filled with nitrogen and stirring, and sequentially adding NB-PLA, NB-PDMS, NB-PLA and NB-PDMS, wherein the interval time of each monomer addition is 15min, and the addition amount of each monomer is 0.6mL, 0.58mL, 0.56mL, 0.54mL, 0.53mL and 0.52mL respectively; the sampling amounts before the addition of the next monomer were 0.1mL, and 0.1mL, respectively, the withdrawn sample was immediately immersed in a methylene chloride solution of vinyl ether to analyze the conversion per block and the molecular weight.
(3) Adding vinyl ethyl ether to terminate the reaction after the last monomer is added for 15min, removing the solvent from the collected polymer solution, and drying to obtain PLA 6 -b-3PDMS 6 -b-PLA 6 -b-3PDMS 6 -b-PLA 6 -b-3PDMS 6 Six-block copolymer brush, the monomer of each block is completely converted, the polymerization degree of each block is 6, and the molecular weight of the copolymer brush is 5.2 multiplied by 10 5 Da, molecular weight distribution index 1.20.
Example 6
Dodecablock copolymer brush PLA 10 -b-[PDMS 10 -b-PLA 10 ] 5 -b-PDMS 10 The synthesis method of (2) comprises the following steps:
(1) An ultra-dry methylene chloride solution of 50mmol/L, 50mmol/L and 1mmol/L was prepared from NB-PLA (norbornene-terminated polylactic acid) macromonomer (molecular weight 5200Da, molecular weight distribution index 1.15), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromonomer (molecular weight 4670Da, molecular weight distribution index 1.20) and Grubbs third generation catalyst (relative molecular weight 884.53 Da) respectively.
(2) 2mL of the catalyst solution was added to a stirred nitrogen-filled reaction flask, followed by sequential addition of macromers, each monomer addition at 5min intervals, each monomer addition at 0.4mL, according to the sequence of the target copolymer brush.
(3) After the last monomer is added for continuous reaction for 5min, vinyl ethyl ether is added to terminate the reaction, the solvent is removed from the collected polymer solution, and the PLA is obtained after drying 10 -b-[PDMS 10 -b-PLA 10 ] 5 -b-PDMS 10 Twelve block copolymer brushes, the monomers of each block being fully converted, the degree of polymerization of each block being 10, the molecular weight of the copolymer brush being 5.8X10 5 Da, molecular weight distribution index 1.20.
Example 7
Forty-block copolymer brush PLA 10 -b-[PDMS 10 -b-PLA 10 ] 19 -b-PDMS 10 The synthesis method of (2) comprises the following steps:
(1) An ultra-dry methylene chloride solution of 100mmol/L, 100mmol/L and 1mmol/L was prepared from NB-PLA (norbornene-terminated polylactic acid) macromonomer (molecular weight 800Da, molecular weight distribution index 1.07), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromonomer (molecular weight 1000Da, molecular weight distribution index 1.09) and Grubbs third generation catalyst (relative molecular weight 884.53 Da).
(2) 2mL of the catalyst solution was added to a stirred nitrogen-filled reaction flask, followed by sequential addition of macromers, each monomer addition at 5min intervals, each monomer addition at 0.2mL, according to the sequence of the target copolymer brush.
(3) After the last monomer is added for continuous reaction for 5min, vinyl ethyl ether is added to terminate the reaction, the solvent is removed from the collected polymer solution, and the PLA is obtained after drying 10 -b-[PDMS 10 -b-PLA 10 ] 19 -b-PDMS 10 Forty-block copolymer brushes, the monomers of each block being fully converted, the degree of polymerization of each block being 10, the molecular weight of the copolymer brush being 3.0X10 5 Da, molecular weight distribution index 1.12.
Example 8
Eighty block copolymer brush PCL 10 -b-[PDMS 10 -b-PCL 10 ] 39 -b-PDMS 10 The synthesis method of (2) comprises the following steps:
(1) An ultra-dry methylene chloride solution of 200mmol/L, 200mmol/L and 1mmol/L was prepared from NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight 550Da, molecular weight distribution index 1.06), NB-PDMS (norbornene-terminated polydimethylsiloxane) macromonomer (molecular weight 600Da, molecular weight distribution index 1.08) and Grubbs third generation catalyst (relative molecular weight 884.53 Da) respectively.
(2) 2mL of the catalyst solution was added to a stirred nitrogen-filled reaction flask, followed by sequential addition of macromers, each monomer addition at 3min intervals, each monomer addition at 0.1mL, according to the sequence of the target copolymer brush.
(3) After the last monomer is added for continuous reaction for 5min, vinyl ethyl ether is added to terminate the reaction, the solvent is removed from the collected polymer solution, and the PCL is obtained after drying 10 -b-[PDMS 10 -b-PCL 10 ] 39 -b-PDMS 10 Eighty block copolymer brushes, the monomers of each block being fully converted, the degree of polymerization of each block being 10, the molecular weight of the copolymer brush being 5.0X10 5 Da, molecular weight distribution index 1.14.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (7)
1. A method for synthesizing a sequence-controllable multi-block copolymer brush, which is characterized by comprising the following steps:
preparing solutions of each monomer and catalyst for preparing the multi-block copolymer brush respectively;
determining the addition sequence and the addition amount of the monomers according to the block sequence of the multi-block copolymer brush and the polymerization degree of each block; sequentially adding the required monomers to the catalyst solution;
collecting the solution of the multi-block copolymer brush after the last monomer is reacted, and removing the solvent to obtain the sequence-controllable multi-block copolymer brush, wherein the number of blocks is 6-80, and the sequence of the blocks is any sequence;
the monomer is cycloolefin polymerization monomer, and the molecular weight is 500-20000Da;
the tail end of the monomer is provided with a cycloolefin polymerization unit;
the monomer comprises polypropylene oxide, polystyrene, polyethylene glycol, polydimethylsiloxane, polycaprolactone, polylactide, poly-tert-butyl acrylate or polymethyl methacrylate with norbornene groups at the end.
2. The method for synthesizing a sequence-controllable multi-block copolymer brush according to claim 1, wherein one norbornene end is simultaneously linked to 1 to 3 polymer chains.
3. The method of synthesizing a sequence-controllable multi-block copolymer brush according to claim 1, wherein the solvent used for preparing the solution is an organic solvent, and the organic solvent comprises dichloromethane, tetrahydrofuran, toluene, chloroform or N, N-dimethylformamide.
4. A sequence controllable multi-block copolymer brush, characterized in that the block sequence of the sequence controllable multi-block copolymer brush is any sequence, synthesized according to the synthesis method of any one of claims 1-3.
5. The sequential controllable multi-block copolymer brush of claim 4, wherein the sequential controllable multi-block copolymer brush topology is a bottle brush.
6. The sequence controllable multi-block copolymer brush of claim 4, wherein the backbone polymerization degree of the sequence controllable multi-block copolymer brush is 10-2000, the polymerization degree of individual blocks is 5-200, and the number of blocks is 6-80.
7. The sequence controllable multi-block copolymer brush of claim 4, wherein the side chain molecular weight range is 500-20000Da and the sequence controllable multi-block copolymer brush molecular weight range is 5000-20000000Da.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101309943A (en) * | 2005-09-15 | 2008-11-19 | 陶氏环球技术公司 | Catalytic olefin block copolymers with controlled block sequence distribution |
| CN109467660A (en) * | 2018-10-06 | 2019-03-15 | 天津大学 | Poly- (ethylene-r- norbornene/ethylene) segmented copolymer is synthesized using chain shuttle method |
| WO2020207088A1 (en) * | 2019-04-10 | 2020-10-15 | 浙江大学 | Multi-block copolymer with narrow molecular weight distribution and preparation method therefor |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309943A (en) * | 2005-09-15 | 2008-11-19 | 陶氏环球技术公司 | Catalytic olefin block copolymers with controlled block sequence distribution |
| CN109467660A (en) * | 2018-10-06 | 2019-03-15 | 天津大学 | Poly- (ethylene-r- norbornene/ethylene) segmented copolymer is synthesized using chain shuttle method |
| WO2020207088A1 (en) * | 2019-04-10 | 2020-10-15 | 浙江大学 | Multi-block copolymer with narrow molecular weight distribution and preparation method therefor |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
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| Synthesis and Direct Visualization of Dumbbell-Shaped Molecular Brushes;Ang Li等;《ACS Macro Letters》;第1卷(第1期);补充信息第S5页倒数第1段-第S6页第1段，表1，方案1 * |
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