CN115894752A - Synthesis method of cyclic polymer - Google Patents
Synthesis method of cyclic polymer Download PDFInfo
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- CN115894752A CN115894752A CN202211468183.0A CN202211468183A CN115894752A CN 115894752 A CN115894752 A CN 115894752A CN 202211468183 A CN202211468183 A CN 202211468183A CN 115894752 A CN115894752 A CN 115894752A
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- 229920005565 cyclic polymer Polymers 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 52
- 229920002223 polystyrene Polymers 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000001540 azides Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 17
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 5
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 238000012650 click reaction Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007363 ring formation reaction Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- DUGRPDKSIFAACP-UHFFFAOYSA-N prop-1-ynyl 2-bromo-2-methylpropanoate Chemical compound C(#CC)OC(C(C)(C)Br)=O DUGRPDKSIFAACP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- -1 self-assembly Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for synthesizing a cyclic polymer. The synthesis method of the cyclic polymer comprises the following steps: (1) Synthesizing a polystyrene chain with bromine at the tail end by an Atom Transfer Radical Polymerization (ATRP) method by adopting an initiator and a styrene monomer; (2) The conversion of the tail end from a bromine group to an azide group is realized through an azide reaction; (3) In a Theta solvent, azide and alkynyl are subjected to Click (Click) reaction to synthesize the ring-shaped polystyrene. The synthesis method of the ring-shaped polymer can improve the concentration of ring-closing reaction, increase the production amount of each batch, improve the reaction speed and is beneficial to synthesizing rings with higher molecular weight.
Description
Technical Field
The invention belongs to the field of ring-shaped polymers, and particularly relates to a synthetic method of a ring-shaped polymer.
Background
Since the fifties of the last century, various kinds of circular-structured DNA, peptides, oligosaccharides, polysaccharides, and the like have been successively discovered and reported. Cyclic polymers have attracted considerable research interest to researchers. Compared with linear polymers, cyclic polymers have no terminal group, have stronger molecular chain rigidity and smaller conformational entropy, and thus have a plurality of unique physical properties, such as higher glass transition temperature, larger refractive index, smaller hydrodynamic volume, lower intrinsic viscosity and moving friction coefficient. Therefore, the cyclic polymer shows unique advantages in the fields of liquid crystal, self-assembly, drug release and the like, and is widely applied.
To date, there are two main methods for synthesizing cyclic polymers: ring expanding method and ring closing method. The ring closing method has low requirement on monomers and wide selection range of the monomers, and is the main method for synthesizing the ring-shaped polymer at present. However, in the ring-closing reaction, the cyclization reaction needs to be carried out in an extremely dilute solution to avoid intermolecular condensation, which results in very low yields of cyclic polymers. In addition, the higher the molecular weight, the larger the terminal distance, and the more difficult the formation of a ring. Therefore, the lower yield and lower molecular weight become a bottleneck in the synthesis of cyclic polymers, which has influenced the intensive research and application of cyclic polymers. How to efficiently prepare cyclic polymers is an important issue to be researched urgently in the related field.
Disclosure of Invention
In order to solve one or more of the above technical problems of the prior art, the present invention provides, in a first aspect, a method for synthesizing a cyclic polymer, the method comprising the steps of:
(1) Linear polymer chain synthesis: synthesizing a polystyrene chain with bromine at the tail end by an Atom Transfer Radical Polymerization (ATRP) method by adopting an initiator and a styrene monomer;
(2) End group conversion: converting the tail end from a bromine group to an azide group by using a polystyrene chain with bromine at the tail end through an azide reaction to obtain polystyrene with azide at the tail end;
(3) Cyclic polymer synthesis: polystyrene with azide at the tail end is dissolved in Theta solvent, and the azide and alkynyl are subjected to Click reaction to synthesize the ring-shaped polystyrene.
Preferably, the (1) linear polymer chain synthesis comprises: uniformly mixing an initiator, a styrene monomer, a ligand and a solvent, then deoxidizing (preferably deoxidizing through three times of freezing-pumping-unfreezing circulation operations), then adding a catalyst CuBr to initiate polymerization, diluting a reaction mixture with THF (tetrahydrofuran) after a certain period of time, quickly removing copper salt through a neutral alumina column, carrying out catalytic quenching reaction, removing the solvent and the monomer through rotary evaporation, precipitating a polymer solution in methanol or a mixture of methanol and water twice, and finally carrying out vacuum drying for several hours (1-10 hours, preferably 3-7 hours) to obtain the polystyrene with bromine at the tail end.
Preferably, the (2) terminal group conversion comprises: mixing polystyrene and NaN with bromine 3 And N, N' -Dimethylformamide (DMF) are stirred for a certain time at room temperature, dichloromethane is added, then the mixture is precipitated in methanol or a mixture of methanol and water, the precipitate is dissolved by using a proper amount of THF, precipitation purification is carried out again, and then vacuum drying is carried out for a plurality of hours (1 to 10 hours, preferably 3 to 7 hours) to obtain the polystyrene with the azide at the tail end.
Preferably, the (3) cyclic polymer synthesis comprises: adding CuBr, ligand Pentamethyldiethylenetriamine (PMDETA) and a Theta solvent into a reaction bottle, introducing nitrogen to remove oxygen, then placing the reaction bottle in an oil bath pot (preferably a 100 ℃ oil bath pot), dissolving the azide-containing polystyrene in the Theta solvent, and dropwise adding the azide-containing polystyrene Theta solution into the reaction system at a slow speed after removing oxygen (preferably, placing the azide-containing polystyrene Theta solution in a syringe, and then dropwise adding the azide-containing polystyrene solution in the syringe into the reaction system at a slow speed by using a peristaltic pump). After the dropwise addition is finished, reacting for several hours, then distilling off the Theta solvent, passing the residual crude product solution through a neutral alumina column to remove copper salt, precipitating in methanol or a mixture of methanol and water after concentration, and drying in vacuum to obtain the product, namely the ring-shaped polystyrene.
In a second aspect, the present invention provides a cyclic polymer synthesized by the above method, wherein the producible amount of the cyclic polymer per batch can be increased by 2-4 times, the purity is 96-99%, and the molecular weight can be up to 8 × 10 4 g/mol。
Compared with the prior art, the invention at least has the following beneficial effects:
the synthesis method adopts a Theta solvent of the polymer as a reaction solvent for the ring closing reaction. In the end-to-end ring closure reaction, a formula of the efficiency of the ring formation reaction is followed:
in the formula, P r For cyclization efficiency, upsilon e For efficiency of ring closure reaction, R n Is the distance between reactive functional groups. From this formula, it can be seen that there are two ways to improve the efficiency of the cyclization reaction: increasing efficiency of a ring closure reaction e (ii) a Reducing the distance R between functional groups n . In order to improve the efficiency of the ring closing reaction, the method selects the high-efficiency Click reaction. In order to reduce the distance between functional groups, the method uses a Theta solvent of the polymer as a reaction solvent for the ring-closing reaction. The polymer chain exists in a state of undisturbed coil in Theta solvent, is in an expanded state in good solvent, and has root mean square radius of gyration R of linear polystyrene chain in the good solvent and the Theta solvent g The scale relationship with molecular weight is:
R g,θ ＝0.02675×M 0.5040
R g, good ＝0.01234×M 0.5936
Wherein R is g,θ Represents the root mean square radius of gyration, R, of a linear polystyrene chain in a Theta solvent g, good The root mean square radius of gyration of a linear polystyrene chain in a good solvent is shown. As can be seen from the above formula, the Theta solvent is more R than the good solvent g Is small. Therefore, compared with good solvent used in the previous synthesis method, the Theta solvent can improve the concentration of the ring-closing reaction, thereby improving the production of each batchIn addition, the terminal distance of the polymer chain becomes closer in Theta solvent, which not only increases the reaction speed but also facilitates the synthesis of higher molecular weight rings. In summary, the reaction speed of the present invention is faster, the molecular weight that can be produced is higher, the purity of the product is higher, and the amount of production per batch can be increased compared to the prior art.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a cyclic polymer of the present invention.
FIG. 2 is a GPC (gel permeation chromatography) chart of the linear chain and the cyclic chain in example 1, wherein the abscissa represents the leaching time and the ordinate represents the response signal of the differential refractometer detector.
FIG. 3 is a GPC chart of linear chains and cyclic chains in example 2.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings.
The invention provides a synthetic method of a cyclic polymer, the synthetic process of the cyclic polymer is shown as figure 1, and the method comprises the following steps:
(1) Linear polymer chain synthesis: uniformly mixing an initiator, a styrene monomer, a ligand and a solvent, then deoxidizing through three times of freezing-pumping-unfreezing circulation operation, then adding a catalyst CuBr to initiate polymerization, diluting a reaction mixture with THF (tetrahydrofuran), quickly removing copper salt through a neutral alumina column, carrying out catalytic quenching reaction, removing the solvent and the monomer through rotary evaporation, precipitating a polymer solution in methanol or a mixture of methanol and water twice, and finally carrying out vacuum drying for several hours to obtain polystyrene with bromine at the tail end;
(2) End group conversion: mixing polystyrene with bromine and NaN 3 Stirring the mixture with N, N' -Dimethylformamide (DMF) at room temperature for a certain time, adding dichloromethane, precipitating in methanol or a mixture of methanol and water, dissolving the precipitate with a proper amount of THF, carrying out precipitation purification again, and then carrying out vacuum oven for several hours to obtain polystyrene with azide at the tail end;
(3) Synthesis of cyclic Polymer: adding CuBr, ligand Pentamethyldiethylenetriamine (PMDETA) and a Theta solvent into a reaction bottle, introducing nitrogen to remove oxygen, then placing the reaction bottle in an oil bath kettle at 100 ℃, dissolving the polystyrene with azide in the Theta solvent, and dropwise adding the Theta solution of the polystyrene with azide into the reaction system at a slow speed after removing the oxygen (preferably, the Theta solution of the polystyrene with azide is placed in a syringe, and then the polystyrene solution in the syringe is dropwise added into the reaction system at a slow speed by using a peristaltic pump). After the dropwise addition, reacting for several hours, then evaporating the Theta solvent, passing the residual crude product solution through a neutral alumina column to remove copper salt, precipitating in methanol or a mixture of methanol and water after concentration, and drying in vacuum to obtain the product.
In some preferred embodiments, in step (1), the initiator is represented by formula (I) in FIG. 1, i.e., propynyl bromoisobutyrate. One end of the initiator is a tertiary bromine group, the other end of the initiator is alkynyl, the tertiary bromine end is used for initiating styrene to carry out controllable free radical polymerization, then the styrene is converted into an azide group through an azide reaction, and then the azide group and the alkynyl end of the initiator carry out efficient Click reaction. The initiator can also be other substances with alkynyl at one end and bromine at the other end.
In some preferred embodiments, in step (1), the ligand is selected from tris (2-dimethylaminoethyl) amine (Me) 6 TREN), 2' -bipyridine (bpy), and PMDETA. When using Me 6 Adding stannous octoate (Sn (EH) when TREN is needed 2 )。
In some preferred embodiments, in step (1), the solvent is selected from one of toluene and anisole.
In some preferred embodiments, in step (1), the molar ratio of the initiator to the styrene monomer is 1; the molar ratio of the initiator to the ligand is 1 to 1 (e.g. 1; the molar ratio of the initiator to the CuBr is 1; the volume ratio of the styrene monomer to the solvent is 1.5 to 1 (for example, 1; of said methanol and waterThe volume ratio of methanol to water in the mixture is 1; said Me 6 TREN and Sn (EH) 2 1 is 1.
In some preferred embodiments, in step (1), the reaction temperature is from 80 to 110 ℃ (e.g., 80 ℃, 90 ℃, 100 ℃ or 110 ℃);
in some preferred embodiments, in step (1), the reaction time is from 1 to 48h (e.g., 1, 6, 12, 24, or 48 h);
in some preferred embodiments, in step (2), the polystyrene with bromine is reacted with NaN 3 A molar ratio of 1; the mass ratio of the brominated polystyrene to DMF is 1; the volume ratio of the DMF to the dichloromethane is 1.1-1 (for example, 1; the volume ratio of methanol to water in the mixture of methanol and water is 1;
in some preferred embodiments, in step (2), the reaction time is from 48 to 60 hours (e.g., 48, 50, 52, 54, 56, 58, or 60 hours);
in some preferred embodiments, in step (3), the Theta solvent is selected from one of cyclopentane and cyclohexane;
in some preferred embodiments, in step (3), the mass concentration of polystyrene in the Theta solution ranges from 3.0 to 4.0g/L (e.g., 3.0, 3.2, 3.4, 3.6, 3.8, or 4.0 g/L); the mass concentration of the PMDETA in DMF is 1.5mg/L; the mass concentration of CuBr in DMF is 80mg/L;
in some preferred embodiments, in step (3), the dropping rate is 0.5 to 1mL/h (e.g., 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 mL/h);
in some preferred embodiments, in step (3), the reaction time is 4 to 7h (e.g., 4, 5, 6, or 7 h);
in some preferred embodiments, the amount of the cyclic polymer producible per batch can be increased by a factor of 2 to 4 (e.g. 2, 3 or 4), pureThe degree is 96-99% (e.g. 96%, 97%, 98% or 99%), and the molecular weight can be up to 8X 10 4 g/mol。
In other preferred embodiments, the cyclic polymer is prepared by the synthesis method of the first aspect of the invention.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples.
Example 1
This example synthesizes a cyclic polymer, the synthesis method of which includes the following steps:
(1) Linear polymer chain synthesis: to a three-necked flask equipped with a stirring magneton were added initiator (33.4 mg, 0.173mmol), styrene (2mL, 17.3mmol), me 6 TREN(46.3μL，0.173mmol)、Sn(EH) 2 (56.1 μ L,0.173 mmol) and anisole (2 mL) followed by oxygen removal by three freeze-pump-thaw cycles, followed by addition of catalyst CuBr (2.5 mg, 0.0173mmol), placing in a 90 ℃ oil bath, after 4h reaction, diluting the reaction mixture with about 20mL of thf and removing the copper salts quickly through a neutral alumina column, quenching the reaction, removing the solvent and monomers by rotary evaporation, and precipitating the polymer solution twice in 20mL of a methanol and water mixture (methanol: water =10, temperature 0 ℃), and finally drying in vacuum for several hours (5 hours in this example) to give polystyrene (M W =3200g/mol, mass 510 mg);
(2) End group conversion: a10 mL round-bottom flask was charged with polystyrene (0.5g, 0.156mmol) with bromine and NaN 3 (51mg, 0.781mmol) and DMF (3 mL) were stirred at room temperature for 48mL, dichloromethane (0.3 mL) was added, and then the precipitate was precipitated in 33mL of a methanol and water mixture (methanol: water =10:1, temperature 0 ℃), dissolved with an appropriate amount of THF, and purified by precipitation again, followed by vacuum drying for several hours (5 hours in this example) to give a polystyrene (460 mg) with azide at the end;
(3) Cyclic polymer synthesis: 120g of cuprous bromide, 2.61mL of pentamethyldiethylenetriamine and 1.5L of cyclohexane are added into a 5L three-necked bottle, nitrogen is introduced to remove oxygen, then the three-necked bottle is placed in an oil bath kettle at 100 ℃ to dissolve the azide-containing polystyrene (450 mg) into 50mL of cyclohexane, and after the oxygen is removed, a peristaltic pump is used for dropwise adding the polystyrene solution into a reaction system at a slow speed. After the addition was completed, the reaction was carried out for 5 hours, followed by distilling off cyclohexane, and the remaining crude product solution was passed through a neutral alumina column to remove copper salts, concentrated, precipitated in a methanol and water mixture (methanol: water =10, temperature 0 ℃) and dried under vacuum to obtain a product (404 mg).
The GPC charts before and after the final ring formation reaction in this example are shown in FIG. 2.
Example 2
This example synthesizes a cyclic polymer, the synthesis method of which includes the following steps:
(1) Linear polymer chain synthesis: to a three-necked flask equipped with a stirring magneton were added initiator (33.4 mg, 0.173mmol), styrene (32mL, 277mmol), me 6 TREN(46.3μL，0.173mmol)、Sn(EH) 2 (56.1. Mu.L, 0.173 mmol) and anisole (32 mL), followed by oxygen removal by three freeze-pump-thaw cycles, after which the catalyst CuBr (2.5 mg, 0.0173mmol) was added, placed in a 90 ℃ oil bath, reacted for 4h, the reaction mixture was diluted with about 100mL THF and the copper salts were removed quickly through a neutral alumina column, catalyzed reaction, solvent and monomer are removed by rotary evaporation, the polymer solution is precipitated twice in 500mL of methanol, and finally vacuum dried for several hours (3 hours in this example) to obtain polystyrene (M) with bromine at the end W =35000g/mol, mass 6.08 g);
(2) End group conversion: a10 mL round-bottom flask was charged with polystyrene (6 g, 0.171mmol) with bromine and NaN 3 (111mg, 1.71mmol) and DMF (36 mL) were stirred at room temperature for 48mL, followed by addition of dichloromethane (4 mL), followed by precipitation in 400mL of methanol, dissolution of the precipitate with an appropriate amount of THF, and purification by precipitation again, followed by vacuum drying for several hours (3 hours in this example) to give azide-terminated polystyrene (5.2 g);
(3) Cyclic polymer synthesis: 120g of cuprous bromide, 2.61mL of pentamethyldiethylenetriamine and 1.5L of cyclohexane are added into a 5L three-necked bottle, nitrogen is introduced to remove oxygen, then the three-necked bottle is placed in an oil bath kettle at 100 ℃ to dissolve the polystyrene (400 mg) with the azide into 50mL of cyclohexane, and after the oxygen is removed, a peristaltic pump is used for dropwise adding the polystyrene solution into a reaction system at a slow speed. After the addition was complete, the reaction was carried out for 5 hours, followed by evaporation of cyclohexane, and the remaining crude product solution was passed through a neutral alumina column to remove the copper salts, concentrated, precipitated in methanol, and dried under vacuum to give the product (382 mg).
The GPC charts before and after the final ring formation reaction in this example are shown in FIG. 3.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for synthesizing a cyclic polymer, comprising the steps of:
(1) Synthesizing a polystyrene chain with bromine at the tail end by an atom transfer radical polymerization method by adopting an initiator and a styrene monomer;
(2) Converting the tail end from a bromine group to an azide group by using a polystyrene chain with bromine at the tail end through an azide reaction to obtain polystyrene with azide at the tail end;
(3) And (2) dissolving the polystyrene with azide at the tail end in a Theta solvent, and carrying out click reaction on the azide and alkynyl to synthesize the ring-shaped polystyrene.
2. The method for synthesizing a cyclic polymer according to claim 1, wherein the steps (1) to (3) specifically include:
(1) Uniformly mixing an initiator, a styrene monomer, a ligand and a solvent, then deoxidizing, adding a catalyst CuBr to initiate polymerization, diluting a reaction mixture by using THF after a certain time, quickly removing copper salt through a neutral alumina column, carrying out catalytic quenching reaction, removing the solvent and the monomer through rotary evaporation, precipitating a polymer solution twice in methanol or a mixture of methanol and water, and finally carrying out vacuum drying for several hours to obtain polystyrene with bromine at the tail end;
(2) Mixing polystyrene with bromine and NaN 3 Stirring with DMF at room temperature for a certain time, adding dichloromethane, precipitating in methanol or a mixture of methanol and water, dissolving the precipitate with a proper amount of THF, performing precipitation purification again, and then performing vacuum drying for several hours to obtain polystyrene with azide at the tail end;
(3) Adding CuBr, ligand PMDETA and Theta solvent into a reaction bottle, introducing nitrogen to remove oxygen, then placing the reaction bottle in an oil bath pot, dissolving the azide-containing polystyrene into the Theta solvent, and dropwise adding the azide-containing polystyrene Theta solution into a reaction system at a slow speed after removing the oxygen; after the dropwise addition is finished, reacting for several hours, then distilling off the Theta solvent, passing the residual crude product solution through a neutral alumina column to remove copper salt, precipitating in methanol or a mixture of methanol and water after concentration, and drying in vacuum to obtain the product, namely the ring-shaped polystyrene.
3. The process for synthesizing a cyclic polymer according to claim 1 or 2, wherein: in step (1), the ligand is selected from Me 6 TREN, 2' -bipyridine (bpy) and PMDETA. When using Me 6 Addition of Sn (EH) when TREN is required 2 (ii) a The solvent is selected from one of toluene and anisole.
4. The method for synthesizing a cyclic polymer according to claim 2, wherein: in the step (1), the molar ratio of the initiator to the styrene monomer is 1; the molar ratio of the initiator to the ligand is 1 to 1; the molar ratio of the initiator to the CuBr is 1; the volume ratio of the styrene monomer to the solvent is 1; the firstThe volume ratio of methanol to water in the mixture of alcohol and water is 1; said Me 6 TREN and Sn (EH) 2 1 is 1.
5. The process for synthesizing a cyclic polymer according to claim 1 or 2, wherein: in the step (1), the reaction temperature is 80-110 ℃, and the reaction time is 1-48 h.
6. The method for synthesizing a cyclic polymer according to claim 2, wherein: in the step (2), the polystyrene with bromine is mixed with NaN 3 1 to 10; the mass ratio of the polystyrene with bromine to DMF is 1; the volume ratio of the DMF to the dichloromethane is 1; the volume ratio of methanol to water in the mixture of methanol and water is 1; in the step (2), the reaction time is 48 to 60 hours.
7. The process for synthesizing a cyclic polymer according to claim 1 or 2, wherein: in the step (3), the Theta solvent is selected from one of cyclopentane and cyclohexane.
8. The method for synthesizing a cyclic polymer according to claim 1, wherein: in the step (3), the mass concentration range of the polystyrene in the Theta solution is 3.0-4.0 g/L; the mass concentration of the PMDETA in DMF is 1.5mg/L; the mass concentration of CuBr in DMF is 80mg/L; in the step (3), the dropping speed is 0.5-1 mL/h, and the reaction time is 4-7h.
9. The process for synthesizing a cyclic polymer according to claim 1 or 2, wherein the amount of the cyclic polymer producible per batch is increased by 2 to 4 times, the purity is 96 to 99%, and the molecular weight is up to 8 x 10 4 g/mol。
10. A cyclic polymer obtained by the synthesis method according to any one of claims 1 to 9.
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