CN115558087A - Optically active spiral polycarbobin, preparation method thereof and post-polymerization modification method - Google Patents
Optically active spiral polycarbobin, preparation method thereof and post-polymerization modification method Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 39
- 238000002715 modification method Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000003153 chemical reaction reagent Substances 0.000 claims description 49
- 239000012074 organic phase Substances 0.000 claims description 42
- 238000004440 column chromatography Methods 0.000 claims description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 31
- 239000012043 crude product Substances 0.000 claims description 29
- 238000012986 modification Methods 0.000 claims description 23
- 230000004048 modification Effects 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 13
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- -1 methyl salicylate diazoacetate Chemical compound 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 229960001047 methyl salicylate Drugs 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001142 circular dichroism spectrum Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical group OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/148—Side-chains having aromatic units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3326—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkane-based
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
Abstract
The invention discloses an optically active spiral polycarbocarbene, a preparation method thereof and a post-polymerization modification method, wherein the method specifically comprises the following steps: the solution of Pi-allylPdCl in tetrahydrofuran is treated with chiral diphosphine ligand, and the prepared catalyst/ligand mixed solution is stirred at room temperature and can be directly used as an initiator for the polymerization of methyl salicylate diazoacetate monomer without further purification. Adding the prepared catalyst/ligand mixed solution into a tetrahydrofuran solution of methyl salicylate diazoacetate monomer, adding the catalyst/ligand mixed solution after stirring, releasing a large amount of bubbles, continuing stirring, adding n-hexane to terminate the reaction, washing the obtained product with n-hexane, and drying in vacuum until the quality is unchanged to obtain the optically active helical polycarbocarbene. The preparation method of the optically active spiral polycarbocarbene has the advantages of simple operation and simple synthesis, and the prepared raw material methyl salicylate is a natural, green and renewable biomass material.
Description
Technical Field
The invention relates to the field of chiral initiation systems and activity-controllable polymerization reactions, in particular to an optically active spiral polycarbocarbene and a preparation method and a post-polymerization modification method thereof.
Background
Chiral and helical structures play an important role in nature and in organisms. In the field of polymer material research, chiral and helical structures are attractive in the field of polymer materials because of their unique functions. In recent years, the research on chiral helical polymers has been greatly advanced, the basic characteristics of chiral helical polymers are more and more known, the variety and synthesis methods of chiral helical polymers are more and more diversified, and the potential applications of the chiral helical polymers are also being developed.
C-C main chain polymer materials, such as polyethylene, polypropylene, polyvinyl chloride and the like, play a very important role in our daily life. C1 polymerization has led to extensive research as a unique strategy to obtain polymers with all-carbon backbones, compared to C2 polymerization. In particular, the polymerization of diazo monomers has gained considerable attention as a representative example of C1 polymerization, and many people have great interest in the preparation of polycarbocarbenes from diazo monomers.
Post-polymerization modification, also known as polymer-analogous reaction, is a general synthetic method to obtain functional materials. The general concept is to chemically convert reactive polymer precursors into new functional polymers, thereby enabling the introduction of functional groups, even those that are incompatible with common polymerization conditions or inhibit precise characterization. In recent years, the occurrence of click-type coupling reactions such as azide-alkyne, thiol-ene, and thiol-alkyne addition, and the occurrence of substitution reactions based on activated esters, have laid the foundation for mass post-polymerization modification reactions. Activated ester polymers of pentafluorophenyl (PFP) ester are powerful tools for the synthesis of functional polymer materials, but the utility of these PFP ester derived polymers in the biological field is still controversial due to the toxicity of the pentafluorophenol groups released in the post-modification step and the possibility of residual PFP ester groups in the polymer. Diazo polymer post-modification currently uses a precursor of a fluorine-containing phenyl ester polymer, and has high toxicity and complex synthesis.
Disclosure of Invention
The invention aims to provide an optically active helical polycarbocarbene, a preparation method thereof and a modification method after polymerization, which have the advantages of simple synthesis, low requirements on experimental conditions and easy reaction.
In one aspect of the invention, the invention features an optically active helical polycarbocarbene. According to the embodiment of the invention, the structural general formula of the optically active helical polycarbobin is as follows:
wherein the polymerization degree m =30-200.
In another aspect of the invention, the invention provides a preparation method of optically active spiral polycarbocarbene. According to an embodiment of the invention, the method comprises the steps of:
(1) In N 2 Stirring a reagent A and redistilled tetrahydrofuran at 0-10 ℃ under the atmosphere, then dropwise adding triethylamine and bromoacetyl bromide, adding water after the reaction is finished, quenching the reaction, then extracting with ethyl acetate, washing, drying, vacuum concentrating, and obtaining a reagent B through column chromatography, wherein the reagent A has the following structural general formula:
(2) In N 2 Under the atmosphere, adding redistilled tetrahydrofuran and di-p-toluenesulfonyl hydrazide (TsNHNHTs) into the reagent B, cooling to 0-10 ℃, and then dropwise adding 1,8-diazabicyclo [5.4.0 ]]Continuing stirring undec-7-ene (DBU) for 30-60min, adding water after the reaction is finished, quenching the reaction, extracting with diethyl ether, washing, drying, vacuum concentrating, and performing column chromatography to obtain a reagent C;
(3) With chiral diphosphine ligands (L) at room temperature S /L R ) Processing a Pi-allylpdCl (palladium catalyst-allyl palladium chloride dimer) solution in tetrahydrofuran, and stirring for 30-60min to obtain a reagent D;
(4) Adding the reagent D into a tetrahydrofuran solution of the reagent C, stirring the reaction mixed solution at room temperature, releasing a large amount of bubbles after adding the reagent D, continuing stirring for 30-60min, adding n-hexane to terminate the reaction, washing the obtained product with n-hexane, and drying in vacuum until the quality is unchanged to obtain the optically active spiral polycarbocarbene.
The general formula of the synthetic reaction of the optically active spiral polycarbobin is as follows:
in addition, the preparation method of the optically active helical polycarbobin according to the above embodiment of the present invention may further have the following additional technical features: in the step (1), the mass ratio of the reagent A to the bromoacetyl bromide and the triethylamine is 1.0, the reaction time is 10-30min, the reaction solution is treated by adding water to quench the reaction, extracting with ethyl acetate, and extracting with saturated NaHCO 3 Washing the solution and saturated NaCl solution for several times, combining organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 6:1;
in the step (2), the reagent B reacts with the di-p-toluenesulfonyl hydrazide and the 1,8-diazabicyclo [5.4.0 ]]The ratio of the mass of undec-7-ene is 1.0, 3.0, the reaction time is 30-60min, the reaction solution is treated as follows, water is added to quench the reaction, then extraction is carried out with diethyl ether, saturated NaHCO is used for extraction, and the ratio of the mass of undec-7-ene is 1.0 3 Washing the solution and saturated NaCl solution for several times, combining organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 10:1;
in the step (3), the mass ratio of the diphosphine ligand to the substances of the pi-allylPdCl is 1.0:
in the step (4), the ratio of the amounts of the substances of the reagent D and the reagent C is 1.
In another aspect of the present invention, the present invention provides a method for post-polymerization modification of optically active helical polycarbocarbene, according to an embodiment of the present invention, the method comprising the steps of: stirring the optically active helical polycarbobin, n-butylamine and tetrahydrofuran of claim 1 at 50-60 ℃ for 24-48h under nitrogen atmosphere, adding dichloromethane and aqueous solution to the mixture, separating the organic phase, extracting the aqueous phase with diethyl ether, washing the combined organic phase with saturated aqueous solution and saturated NaCl solution, combining the organic phases using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent used in column chromatography is CHCl 3 And purifying to obtain a light brown product, namely the n-butylamine post-modified optically active helical polycarbocarbene.
In addition, the method for modifying the optically active helical polycarbocarbene after polymerization according to the above embodiment of the invention may further have the following additional technical features:
in some embodiments of the invention, the ratio of the amounts of the substance of the optically active helical polycarbocarbene to the n-butylamine is 1.0.
In another aspect of the present invention, the present invention provides a method for post-polymerization modification of optically active helical polycarbocarbene, according to an embodiment of the present invention, the method comprising the steps of: subjecting the optically active helical polycarbodiimide, methoxypolyethyleneglycolamine (PEG-NH) of claim 1 to nitrogen atmosphere 2 Molecular weight 2000), triethylamine and tetrahydrofuran, stirring for 24-48h at 50-60 ℃, concentrating in vacuum, and then dialyzing and purifying to obtain the optically active helical polycarbobin post-modified by polyethylene glycol.
In addition, the method for modifying the optically active helical polycarbocarbene after polymerization according to the above embodiment of the invention may further have the following additional technical features:
in some embodiments of the invention, the ratio of the amounts of the optically active helical polycarbodiimide and methoxypolyethyleneglycoamine is 1.0.
In another aspect of the present invention, the present invention provides a method for post-polymerization modification of optically active helical polycarbocarbene, according to an embodiment of the present invention, the method comprising the steps of:
(1) Stirring dansyl chloride and ethylenediamine in dichloromethane for one day at room temperature, adding water to quench the reaction after the reaction is finished, extracting with dichloromethane, washing, drying, vacuum concentrating, and performing column chromatography to obtain a reagent E;
(2) Stirring the optically active helical polycarbocarbene of claim 1, a reagent E, tetrahydrofuran and triethylamine at 50-60 ℃ for 24-48h under nitrogen atmosphere, adding dichloromethane and an aqueous solution to the mixture, separating the organic phase, extracting the aqueous phase with diethyl ether, washing the combined organic phase with a saturated aqueous solution and a saturated NaCl solution, combining the organic phases using anhydrous Na as the organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent used in column chromatography is CHCl 3 And purifying to obtain a light yellow product, namely the optical activity spiral polycarbobin after modification of dansyl chloride.
In addition, the method for modifying the optically active helical polycarbocarbene after polymerization according to the above embodiment of the invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (1), the ratio of the mass of dansyl chloride to the mass of ethylenediamine is 1.0, 2.5, and the reaction time is 24 to 48 hours, and the reaction solution is treated by adding water to quench the reaction, extracting with dichloromethane, washing with saturated aqueous solution and saturated NaCl solution for a plurality of times, and combining the organic phases, and the organic phase uses anhydrous Na 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted during column chromatography is a mixture of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 98:2.
in the step (2), the ratio of the amounts of the optically active helical polycarbocarbene to the reagent E is 1.0.
The post-polymerization modification process and the structures of the three amines are as follows:
compared with the prior art, the invention has the beneficial effects that:
(1) The natural methyl salicylate product is used as a raw material, has rich resources and low price, and provides a basis for realizing green preparation and large-scale preparation of the helical polymer.
(2) The invention uses chiral catalyst to initiate the spiral selective polymerization of non-chiral monomer, to prepare spiral polymer with optical activity, with mild experimental condition and simple operation, while the polymer has wide application prospect in the fields of chiral identification, enantiomer crystallization, circular polarization luminescence, etc.
(3) The side chain of the helical polymer prepared by the invention is salicylate, and can perform ester exchange reaction with nucleophiles such as amine and the like to realize post-modification of the polymer, so that the obtained helical polymer is functionalized, and simultaneously, the brush-shaped polymer with high grafting density can be prepared by the ester exchange reaction with amino-terminated polymer (such as methoxy polyethylene glycol amine).
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of optically active helical polycarbophenes in example 1 of the present invention;
FIG. 2 is an infrared spectrum of an optically active helical polycarbobin of example 1 of the present invention;
FIG. 3 is a chart of a circular dichroism spectrum and a UV-visible spectrum of the optically active helical polycarbocarbene in example 1 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of n-butylamine polymerization-modified optically active helical polycarbocarbene in example 2 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of PEG-modified optically active helical polycarbocarbene in example 3 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of optically active spiral polycarbobin comprises the following steps:
(1) In N 2 Stirring 5g of reagent A and redistilled tetrahydrofuran at 0 ℃ under the atmosphere, then dropwise adding 5.2mL of triethylamine and 3.9mL of bromoacetyl bromide, reacting for 10min, adding water to quench the reaction, then extracting with ethyl acetate, washing, drying, concentrating in vacuum, and obtaining reagent B through column chromatography; the reaction solution was treated by quenching the reaction with water, followed by extraction with ethyl acetate and then with saturated NaHCO 3 Washing the solution and saturated NaCl solution for several times, combining organic phases, and using anhydrous Na as the organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 6:1;
the structural general formula of the reagent A is as follows:
(2) In N 2 Under the atmosphere, 5.48g of reagent B was added with redistilled tetrahydrofuran and 10.21g of TsNHNHTs, cooled to 0 ℃ and then added dropwise with 8.96mL of 1, 8-diazabicyclo [5.4.0 ]]And (3) continuing stirring undec-7-ene (DBU) for 30min, adding water to quench the reaction after the reaction is finished, extracting with diethyl ether, washing, drying, concentrating in vacuum, and performing column chromatography to obtain a reagent C. The reaction solution was worked up by quenching the reaction with water, extracting with diethyl ether and then with saturated NaHCO 3 Multiple washes of the solution and saturated NaCl solutionWashing, mixing organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 10:1;
(3) With 5.24mg chiral bisphosphine ligand L at room temperature R Treating a commercially available pi-allylPdCl (3.32 mg) solution in tetrahydrofuran, and stirring for 30min to obtain a reagent D;
the structural general formula of the diphosphine ligand is as follows:
(4) Adding the reagent D into a tetrahydrofuran solution of 200mg of the reagent C, stirring the reaction mixed solution at room temperature, releasing a large amount of bubbles after adding the reagent D, continuing stirring for 30min, adding n-hexane to terminate the reaction, washing the obtained product with n-hexane, and drying in vacuum until the quality is unchanged to obtain the optically active spiral polycarbodiimide.
The general formula of the synthetic reaction of the optically active spiral polycarbobin is as follows:
FIG. 1 is a nuclear magnetic hydrogen spectrum of optically active helical polycarbobin prepared in this example, and the structure of the prepared product is judged to be correct by distinguishing signal peaks.
FIG. 2 is an infrared spectrum of optically active helical polycarbobin in the embodiment of the present invention, and the structure of the prepared product is determined to be correct by the discrimination of signal peaks.
FIG. 3 is a chart of the circular dichroism spectrum and the UV-Vis spectrum of the optically active helical polycarbocarbene in accordance with the example of the present invention, illustrating that the polymer is optically active.
Example 2
An n-butylamine polymerization post-modification of optically active helical polycarbobin, comprising the following steps:
the general formula of the synthesis reaction for modifying after polymerization of n-butylamine is:
bisphosphine ligand L of example 1 under a nitrogen atmosphere R 50mg of the optically active helical polycarbobin thus obtained, 0.076mL of n-butylamine and 2mL of tetrahydrofuran were prepared, stirred at 50 ℃ for 24h, dichloromethane and an aqueous solution were added to the mixture, the organic phase was separated using a separatory funnel, and the aqueous phase was extracted with diethyl ether. Washing the combined organic phase with saturated aqueous solution and saturated NaCl solution for several times, combining the organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent used in column chromatography is CHCl 3 And purifying to generate a light brown product, thus obtaining the n-butylamine post-modified optically active spiral polycarbobin.
FIG. 4 is a nuclear magnetic hydrogen spectrum of n-butylamine polymerization modification of optically active helical polycarbobin in the embodiment of the present invention, and the structure of the prepared product is determined to be correct by distinguishing signal peaks.
Example 3
A PEG post-polymerization modification of optically active helical polycarbocarbene comprises the following steps:
the general formula of the synthesis reaction for PEG post-polymerization modification is as follows:
bisphosphine ligand L from example 1 under a nitrogen atmosphere R 50mg of optically active helical polycarbobin and 1.56g of methoxypolyethyleneglycolamine (PEG-NH) were prepared 2 Molecular weight 2000), 0.033mL triethylamine, 2mL tetrahydrofuran, stirring at 50 ℃ for 24h, vacuum concentrating, dialyzing and purifying to obtain the PEG post-modified optically active helical polycarbocarbene, wherein each atom of the main chain of the polycarbocarbene can carry PEG parent-parent modification due to the post-polymerization modification effectWater chains, thereby forming a brush polymer with a high graft density.
FIG. 5 is a nuclear magnetic hydrogen spectrum of PEG polymerization modification of optically active helical polycarbocarbene in the embodiment of the invention, and the structure of the prepared product is judged to be correct by distinguishing signal peaks.
Example 4
A dansyl chloride post-polymerization modification of an optically active helical polycarbobin, comprising the steps of:
the general formula of the synthesis reaction for modification after polymerization of dansyl chloride is as follows:
(1) Stirring 1.0g of dansyl chloride and 0.6mL of ethylenediamine in dichloromethane at room temperature for one day, adding water to quench the reaction after the reaction is finished, extracting with dichloromethane, washing, drying, concentrating in vacuum, and performing column chromatography to obtain a reagent E; in the step (1), the reaction solution is treated by adding water to quench the reaction, extracting with dichloromethane, adding saturated aqueous solution and saturated NaCl solution to wash for multiple times, combining organic phases, and using anhydrous Na as the organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted during column chromatography is a mixture of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 98:2.
(2) Bisphosphine ligand L of example 1 under a nitrogen atmosphere R 50mg of the optically active helical polycarbocarbene obtained, 0.23g of reagent E, 2mL of tetrahydrofuran, 0.033mL of triethylamine are prepared, stirred at 50 ℃ for 24h, dichloromethane and aqueous solution are added to the mixture, the organic phase is separated using a separating funnel, and the aqueous phase is extracted with diethyl ether. Washing the combined organic phase with saturated aqueous solution and saturated NaCl solution for several times, combining the organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent used in column chromatography is CHCl 3 Purification gives a pale yellow product, i.e.Obtaining the optical activity spiral polycarbobin modified by dansyl chloride.
Example 5
The preparation method of the optically active spiral polycarbocarbene comprises the following steps of preparing a reagent C in the first three steps, wherein the reagent C is the same as that in the embodiment 1:
(4) With 5.24mg of chiral bisphosphine ligand L at room temperature S Treating a commercially available pi-allylPdCl (3.32 mg) solution in tetrahydrofuran, and stirring for 30min to obtain a reagent E;
the structural general formula of the diphosphine ligand is as follows:
(5) Adding the reagent E into a tetrahydrofuran solution of 200mg of the reagent C, stirring the reaction mixed solution at room temperature, adding the reagent D, releasing a large amount of bubbles, continuing stirring for 30min, adding n-hexane to terminate the reaction, washing the obtained product with n-hexane, and drying in vacuum until the quality of the product is unchanged to obtain the optically active spiral polycarbocarbene.
The foregoing is merely illustrative and explanatory of the present invention and various modifications, additions or substitutions may be made to the specific embodiments described by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (9)
1. An optically active helical polycarbocarbene, characterized in that the structural general formula is as follows:
wherein the polymerization degree m =30-200.
2. A method of preparing an optically active helical polycarbodiimide according to claim 1, wherein the method comprises the steps of:
(1) In N 2 Stirring a reagent A and redistilled tetrahydrofuran at 0-10 ℃ under the atmosphere, then dropwise adding triethylamine and bromoacetyl bromide, adding water after the reaction is finished, quenching the reaction, then extracting with ethyl acetate, washing, drying, vacuum concentrating, and obtaining a reagent B through column chromatography, wherein the reagent A has the following structural general formula:
(2) In N 2 Under the atmosphere, adding redistilled tetrahydrofuran and di-p-toluenesulfonyl hydrazide into the reagent B, cooling to 0-10 ℃, and then dropwise adding 1,8-diazabicyclo [5.4.0 ]]Continuing stirring the undecyl-7-ene for 30-60min, adding water to quench the reaction after the reaction is finished, extracting with diethyl ether, washing, drying, concentrating in vacuum, and performing column chromatography to obtain a reagent C;
(3) Treating a palladium catalyst-allyl palladium chloride dimer solution in tetrahydrofuran by using a chiral diphosphine ligand at room temperature, and stirring for 30-60min to obtain a reagent D;
(4) Adding the reagent D into a tetrahydrofuran solution of the reagent C, stirring the reaction mixed solution at room temperature, releasing a large amount of bubbles after adding the reagent D, continuing stirring for 30-60min, adding n-hexane to terminate the reaction, washing the obtained product with n-hexane, and drying in vacuum until the quality is unchanged to obtain the optically active spiral polycarbocarbene.
3. The method for preparing optically active helical polycarbocarbene according to claim 2, wherein the method comprises the following steps: in the step (1), the mass ratio of the reagent A to the bromoacetyl bromide and the triethylamine is 1.0, the reaction time is 10-30min, the reaction solution is treated by adding water to quench the reaction, extracting with ethyl acetate, and extracting with saturated NaHCO 3 Washing the solution and saturated NaCl solution for several times, combining organic phases, and using anhydrous Na as organic phase 2 SO 4 Drying, vacuum filtering, concentrating the filtrate under reduced pressure to obtain crude product, and separating the crude product by column chromatographyCollecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 6:1;
in the step (2), the reagent B reacts with the di-p-toluenesulfonyl hydrazide and the 1,8-diazabicyclo [5.4.0 ]]The ratio of the mass of undec-7-ene is 1.0, 3.0, the reaction time is 30-60min, the reaction solution is treated as follows, water is added to quench the reaction, then extraction is carried out with diethyl ether, saturated NaHCO is used for extraction, and the ratio of the mass of undec-7-ene is 1.0 3 Washing the solution and saturated NaCl solution for several times, combining organic phases, and using anhydrous Na as the organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 10:1;
in the step (3), the mass ratio of the diphosphine ligand to the substances of the pi-allylPdCl is 1.0, and the general structural formula of the diphosphine ligand is as follows:
L R ：
or L S ：
In the step (4), the ratio of the substance amount of the reagent D to the substance amount of the reagent C is 1.
4. A polymerization post-modification method of optically active helical polycarbocarbene is characterized by comprising the following steps: stirring the optically active helical polycarbobin, n-butylamine and tetrahydrofuran of claim 1 at 50-60 ℃ for 24-48h under nitrogen atmosphere, adding dichloromethane and aqueous solution to the mixture, separating the organic phase, extracting the aqueous phase with diethyl ether, washing the combined organic phase with saturated aqueous solution and saturated NaCl solution, combining the organic phases using anhydrous Na as the organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product;the eluent used in column chromatography is CHCl 3 And purifying to obtain a light brown product, namely the n-butylamine post-modified optically active helical polycarbocarbene.
5. The method for post-polymerization modification of optically active helical polycarbocarbene according to claim 4, wherein: the ratio of the amounts of the substances of the optically active helical polycarbobin and n-butylamine is 1.0.
6. A polymerization post-modification method of optically active helical polycarbocarbene is characterized by comprising the following steps: stirring the optically active helical polycarbocarbene, methoxy polyethylene glycol amine, triethylamine and tetrahydrofuran of claim 1 at 50-60 ℃ for 24-48h under nitrogen atmosphere, concentrating in vacuum, and dialyzing and purifying to obtain the optically active helical polycarbocarbene post-modified by polyethylene glycol.
7. The method for post-polymerization modification of optically active helical polycarbocarbene according to claim 6, wherein: the ratio of the quantity of the optically active helical polycarbobin to the quantity of the methoxy polyethylene glycol amine is 1.0.
8. A polymerization post-modification method of optically active helical polycarbocarbene is characterized by comprising the following steps:
(1) Stirring dansyl chloride and ethylenediamine in dichloromethane for one day at room temperature, adding water to quench the reaction after the reaction is finished, extracting with dichloromethane, washing, drying, vacuum concentrating, and performing column chromatography to obtain a reagent E;
(2) Stirring the optically active helical polycarbocarbene of claim 1, a reagent E, tetrahydrofuran and triethylamine at 50-60 ℃ for 24-48h under nitrogen atmosphere, adding dichloromethane and an aqueous solution to the mixture, separating the organic phase, extracting the aqueous phase with diethyl ether, washing the combined organic phase with a saturated aqueous solution and a saturated NaCl solution, combining the organic phases using anhydrous Na as the organic phase 2 SO 4 Drying, vacuum filtering, concentrating the filtrate under reduced pressure to obtain crude product, and separating by column chromatographySeparating and collecting a product; the eluent used in column chromatography is CHCl 3 And purifying to obtain a light yellow product, namely the optical activity spiral polycarbobin after modification of dansyl chloride.
9. The method for post-polymerization modification of optically active helical polycarbocarbene according to claim 8, wherein:
in the step (1), the mass ratio of dansyl chloride to ethylenediamine is 1.0, the reaction time is 24-48h, the reaction solution is treated by adding water to quench the reaction, extracting with dichloromethane, adding saturated aqueous solution and saturated NaCl solution to wash for multiple times, combining organic phases, and using anhydrous Na as an organic phase 2 SO 4 Drying, performing suction filtration, concentrating the filtrate under reduced pressure to obtain a crude product, separating the crude product by using column chromatography, and collecting the product; the eluent adopted in the column chromatography is a mixture of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 98:2.
in the step (2), the ratio of the amounts of the optically active helical polycarbocarbene to the reagent E is 1.0.
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