CN114989426B - Polymer brush of poly (isonitrile) grafted polyoxazoline and preparation method thereof - Google Patents
Polymer brush of poly (isonitrile) grafted polyoxazoline and preparation method thereof Download PDFInfo
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- 150000002527 isonitriles Chemical class 0.000 title claims abstract description 93
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 229920000765 poly(2-oxazolines) Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 95
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 31
- 150000002367 halogens Chemical class 0.000 claims abstract description 31
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 p-toluenesulfonyl Chemical group 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- PDVSQOWBJWFAJE-UHFFFAOYSA-N N#[C-].FC1=C(C(=C(C(=C1O)F)F)F)F Chemical compound N#[C-].FC1=C(C(=C(C(=C1O)F)F)F)F PDVSQOWBJWFAJE-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 claims description 3
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 claims description 2
- CSGPUODXEMKHSY-UHFFFAOYSA-N 4-(iodomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CI)C=C1 CSGPUODXEMKHSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 239000003814 drug Substances 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 6
- 229940079593 drug Drugs 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 125000001246 bromo group Chemical group Br* 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000009304 pastoral farming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QBIONHJLZYJTSC-UHFFFAOYSA-N bromoazaniumylidynemethane Chemical compound Br[N+]#[C-] QBIONHJLZYJTSC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 description 1
- 150000000376 2-oxazolines Chemical class 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polymer brush of poly (isonitrile) grafted polyoxazoline and a preparation method thereof, wherein the polymer brush is prepared by preparing isonitrile monomer containing p-toluenesulfonyl or halogen, firstly initiating the polymerization of the isonitrile monomer to obtain a functional macromolecular initiator, and then initiating the polymerization of the oxazoline monomer to form a brush-shaped polymer; or firstly initiating oxazoline monomer polymerization to obtain long-chain isonitrile monomer, and then carrying out isonitrile polymerization to obtain brush polymer. Compared with the prior art, the invention has the following advantages: the synthesized isonitrile monomer with the oxazoline polymerization initiation active center can be polymerized into polyisonitrile by the isonitrile monomer, and then the oxazoline polymerization is initiated, and the reverse is also performed, so that the flexibility is high; the isonitrile and the oxazoline monomer are innovatively combined, and the biocompatibility or the thermal responsiveness and the self-assembly behavior of the isonitrile and the oxazoline monomer are endowed by introducing different functional groups, so that the medicine transportation is finished, and the isonitrile and oxazoline monomer has great potential application value in future biological medicines.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polymer brush of poly (isonitrile) grafted polyoxazoline and a preparation method thereof.
Background
Among the artificially synthesized helical polymers, the synthesis of optically active polyisonitriles has been the focus of research in recent years due to the unique rigidity of the main chain and the presence of chiral side groups, chiral main chains or chiral helical conformations, which enable the use of the chiral polymeric heteronitriles in chiral discrimination, enantiomer separation, asymmetric catalysis, liquid crystals, and the like. Poly (2-oxazolines) are important polymers formed from the cationic ring-opening polymerization of 2-oxazolines. There is great interest in the biomedical field due to their higher performance than conventional biomedical polymers such as polyethylene glycol. Their physicochemical properties and stealth behavior are used to produce lubricating and biocompatible brushes, circulating brushes and bulk brush polymers that exhibit superior performance compared to "gold standard" polyethylene glycols.
Brush polymers are densely grafted polymer chains attached to a surface or polymer backbone. They are most often synthesized by three different methods: "grazing through", "grazing from" or "grazing to" methods. Their structure gives brush polymers unique properties such as a stretched polymer backbone due to steric repulsion of the sides, high concentration of side chains and reduced chain entanglement steric density. Thus, brush polymers are suitable for a wide range of applications, for example, anti-fouling surfaces and bio-lubrication by surface modification and drug transport by their interesting self-assembly behaviour. However, the polymerization efficiency is often low due to too dense side chains in the polymerization process.
Disclosure of Invention
The invention aims to provide a polymer brush of poly (isonitrile) grafted polyoxazoline and a preparation method thereof, which combines isonitrile with oxazoline monomer, can be used for antifouling surfaces and biological lubrication, and has great potential application value in future biological medicine by introducing different functional groups, endowing the polymer brush with biocompatibility or thermal responsiveness and self-assembly behavior to complete medicine transportation.
In one aspect of the invention, the invention provides a polymeric brush of a polyisonitrile grafted polyoxazoline. According to an embodiment of the present invention, the general structural formula is:
in the method, in the process of the invention,
n=100 to 700, m=100 to 500, and m and n are integers.
In another aspect of the invention, the invention provides a method for preparing a polymeric brush of a polyisonitrile grafted polyoxazoline. According to an embodiment of the invention, the method comprises the following steps:
(1) Preparing an isonitrile monomer containing tosyl or halogen;
(2) Weighing the isonitrile monomer containing the p-toluenesulfonyl or halogen, the oxazoline monomer and the methoxy catalyst obtained in the step (1) for reaction, and after the reaction is finished, precipitating, filtering and vacuum drying until the quality is unchanged, thus obtaining the polymer brush of the polyisonitrile grafted polyoxazoline.
In addition, the preparation method of the polymer brush of the polyisonitrile grafted polyoxazoline according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the present invention, in the step (2), firstly weighing the isonitrile monomer containing the p-toluenesulfonyl or halogen and the oxazoline monomer obtained in the step (1), vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding the solvent A, and after the reaction is finished, precipitating with the solvent B, filtering, and vacuum drying until the quality is unchanged, thus obtaining the product a; and then weighing the product a and the methoxy catalyst, vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding the solvent C, and after the reaction is finished, precipitating with the solvent D, filtering, and vacuum drying until the quality is unchanged to obtain the polymer brush of the poly (isonitrile) grafted polyoxazoline.
In some embodiments of the invention, the molar ratio of the p-toluenesulfonyl or halogen containing isonitrile monomer to the oxazoline monomer is 1: 100-500, the reaction temperature is 80-100 ℃, and the reaction time is 6-8 h; in the step (3), the molar ratio of the product a to the methoxy catalyst is 1: 70-700 deg.c, 50-55 deg.c and 14-16 hr.
In some embodiments of the present invention, in the step (2), firstly weighing the isonitrile monomer containing p-toluenesulfonyl or halogen and the methoxy catalyst obtained in the step (1), vacuumizing and filling nitrogen under anhydrous and anaerobic conditions, adding a solvent C, and after the reaction is finished, precipitating with the solvent D, filtering, and vacuum drying until the quality is unchanged to obtain a product b; and then weighing the product B and oxazoline monomers, vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding the solvent A, and after the reaction is finished, precipitating with the solvent B, filtering, and vacuum drying until the quality is unchanged, thus obtaining the brush polymer based on the spiral polyisonitrile.
In some embodiments of the invention, the molar ratio of the p-toluenesulfonyl or halogen-containing isonitrile monomer to the methoxy catalyst is 1: 70-700, the reaction temperature is 50-55 ℃, and the reaction time is 14-16 h; the molar ratio of product b to oxazoline monomer is 1: 20-50, the reaction temperature is 80-100 ℃, and the reaction time is 4-8 h.
In some embodiments of the present invention, the solvent A is dimethyl sulfoxide or N, N-dimethylformamide, the solvent B is diethyl ether, the solvent C is chloroform, the solvent D is methanol, the methoxy catalyst has a structural formula of,
the structural general formula of the oxazoline monomer is as follows,
wherein R and the polymer brush structure general formula of the poly (isonitrile) grafted polyoxazoline 1 Or R is 2 The structural formulas of (2) are the same.
In some embodiments of the present invention, the p-toluenesulfonyl-containing isonitrile monomer has the structural formula:
the structural general formula of the isonitrile monomer containing the p-toluenesulfonyl is as follows:
wherein R is-Br or-Cl or-I or-COCl.
In some embodiments of the present invention, the method for preparing the p-toluenesulfonyl-containing isonitrile monomer comprises the steps of:
(I) Reacting 1, 4-butanediol, pentafluorophenol isonitrile and 4-dimethylaminopyridine in nitrogen atmosphere, then carrying out organic extraction, and drying to obtain a product c;
(II) under the nitrogen atmosphere, reacting p-toluenesulfonyl chloride with a product c, then carrying out organic extraction, and drying to obtain an isonitrile monomer containing sulfonyl chloride;
the preparation method of the halogen-containing isonitrile monomer comprises the following steps:
(I) Weighing 1, 4-butanediol, 4-dimethylaminopyridine, halogen-containing raw materials and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, after the reaction is finished, carrying out organic extraction, and drying to obtain a product d, wherein the halogen-containing raw materials are 4- (bromomethyl) benzoic acid or 4- (chloromethyl) benzoic acid or 4- (iodomethyl) benzoic acid or 4- (acyl chloride) benzoic acid;
and (II) weighing the product d, the pentafluorophenol isonitrile and the 4-dimethylaminopyridine under the nitrogen atmosphere, and after the reaction is finished, carrying out organic extraction and drying to obtain the halogen-containing isonitrile monomer.
In some embodiments of the present invention, in the method for preparing the p-toluenesulfonyl-containing isonitrile monomer, in the step (I), the mass ratio of the 1, 4-butanediol to the pentafluorophenol isonitrile is 3: the mass ratio of the pentafluorophenol isonitrile to the 4-dimethylaminopyridine is 1:1, the reaction temperature is 55 ℃, and the reaction time is 6 hours;
in step (II), the mass ratio of p-toluenesulfonyl chloride to product c was 1.2:1, the reaction temperature is room temperature, and the reaction time is 6 hours;
in the preparation method of the halogen-containing isonitrile monomer, in the step (I), the mass ratio of the 1, 4-butanediol to the halogen-containing raw material is 3: the mass ratio of 1, 4-dimethylaminopyridine to halogen-containing raw material was 0.8: the mass ratio of 1, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to halogen-containing raw material was 1.2:1, reacting at room temperature for 6 hours;
in step (II), the mass ratio of the product d to the pentafluorophenol isonitrile is 1.2: the mass ratio of the pentafluorophenol isonitrile to the 4-dimethylaminopyridine is 1:1, the reaction temperature is 55 ℃, and the reaction time is 6 hours;
the structural general formula of the monomer of the pentafluorophenol isonitrile is as follows:
compared with the prior art, the invention has the beneficial effects that:
1) The brush polymer based on the spiral polyisonitrile is simple to synthesize, mild in experimental condition, simple to operate, environment-friendly in raw materials and environment-friendly;
2) The synthesized isonitrile monomer containing p-toluenesulfonyl or halogen can be polymerized into polyisonitrile by firstly polymerizing the isonitrile monomer and then polymerizing oxazoline, and the method is vice versa, so that the flexibility is high;
3) The polymer material synthesized by the invention has wide raw material sources, saves the synthesis efficiency, is efficient, and has wide variety of catalytic polymerized monomers;
4) The invention combines the isonitrile and the oxazoline monomer innovatively, can be used for antifouling surfaces and biological lubrication, gives biocompatibility or thermal responsiveness to the isonitrile and the oxazoline monomer by introducing different functional groups, finishes drug transportation by self-assembly behavior, and has great potential application value in future biological medicines.
5) The isonitrile polymerization introduced by the invention is advanced active polymerization, and a mature polymerization mode exists, so that the isonitrile monomer with short chain or long chain has a corresponding polymerization method, and the problem of low polymerization efficiency caused by too dense molecular chain is successfully avoided.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of an isonitrile monomer containing a p-toluenesulfonyl group in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the bromoisonitrile monomer of example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of pentafluorophenol isonitrile monomer in example 1 or 2 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In fig. 1, four hydrogen peak positions of benzene rings on the isonitrile monomer are between 7.5 and 8.5, and the integral ratio is 2:2, so that two peaks near 7.5 and 8.5 are the four hydrogen out peak positions of the benzene ring on the isonitrile monomer, the middle two peaks represent the four hydrogen of the benzene ring on the p-toluenesulfonyl, the peak of the methyl is at the highest field, the position of 1.83, the chemical shift is 4.10 and 4.31 respectively due to the difference of the connecting groups, the middle two carbons are in consistent chemical shift, the integral ratio is in accordance with the expectation, and the successful synthesis of the isonitrile monomer containing sulfonyl chloride can be judged; in fig. 2, four hydrogen peak positions of benzene rings on the isonitrile monomer are between 7.5 and 8.5, and the integral ratio is 2:2, so that two peaks near 7.5 and 8.5 are the positions of four hydrogen out of the benzene ring on the isonitrile monomer, the middle two peaks represent four hydrogen of the benzene ring on benzyl bromide, the peaks of two hydrogen on carbon beside bromine are at the positions of 4.62, the chemical shift of four hydrogen on two carbon near oxygen is 4.42 due to the same connecting group, the middle two carbon chemical shifts are consistent, the peak is at the position of 1.95, and the integral ratio is consistent with the expectation, so that the successful synthesis of the isonitrile monomer containing the bromo can be judged.
Example 1
A polymeric brush of a polyisonitrile grafted polyoxazoline comprising the steps of:
(1) First, preparation of an isonitrile monomer containing a p-toluenesulfonyl group is carried out
a. In a 100mL two-necked flask, 1, 4-butanediol, pentafluorophenol isonitrile and 4-Dimethylaminopyridine (DMAP) were dissolved with a small amount of solvent C (tetrahydrofuran) (the smaller the solvent, the better), then a reflux apparatus was set up, and the reaction atmosphere was replaced with nitrogen gas with a water pump. The reaction vessel was placed in an oil bath at 55 ℃ for overnight reaction. And (3) carrying out organic extraction and drying to obtain a product c, wherein the structural general formula of c is as follows:
the route for synthesis c in this example is as follows:
b. after dissolving p-toluenesulfonyl chloride in 10mL of redistilled solvent E (dichloromethane), the solution was placed in a 100mL two-necked flask (slightly undissolved), and then 0.4mL of redistilled solvent F (triethylamine) was added dropwise thereto, and the solution became clear. The atmosphere in the two vials was replaced with nitrogen by a water pump and placed in an ice bath at 0 ℃. And then dissolving the product c by using a small amount of solvent E, injecting the product c into a reaction container by using a syringe, reacting overnight, performing organic extraction, and drying to obtain the isonitrile monomer containing p-toluenesulfonyl or halogen, wherein the structure general formula of the isonitrile monomer containing sulfonyl chloride is as follows:
the synthetic route for the sulfonyl chloride-containing isonitrile monomer of this example is as follows:
as can be seen from the nuclear magnetic resonance spectrum of the pentafluorophenol isonitrile monomer shown in FIG. 3, the four hydrogen peak positions of the benzene ring on the isonitrile monomer are between 7.5 and 8.5, and the integral ratio is 2:2, so two peaks around 7.5 and 8.5 in FIG. 1 are four hydrogen out peak positions of benzene ring on isonitrile monomer, the middle two peaks represent four hydrogen of benzene ring on p-toluenesulfonyl, the peak of methyl is at the highest field, 1.83 position, four hydrogen on two carbons near oxygen, chemical shift is 4.10 and 4.31 respectively due to different connecting groups, the middle two carbons are consistent in chemical shift, the integral ratio is consistent with expectations at 2.45, so that successful synthesis of isonitrile monomer containing sulfonyl chloride can be judged.
(2) 100.00mg of the isonitrile monomer containing sulfonyl chloride and 1.20mg of the methoxy catalyst are weighed and placed in a polymerization bottle, under the anhydrous and anaerobic condition, vacuum pumping and nitrogen filling are carried out, 1.0mL of solvent chloroform is added, after reaction is carried out for 15 hours at 55 ℃, the solvent methanol is used for precipitation, filtration and vacuum drying are carried out until the quality is unchanged, and 90.00mg of the isonitrile monomer polymer containing sulfonyl chloride is obtained.
The synthetic route for the sulfonyl chloride group-containing isonitrile monomer polymer of this example is as follows:
(3) 30.00mg of the sulfonyl chloride group-containing isonitrile monomer polymer and 342.00mg of 2-ethyl-2-oxazoline are weighed into a polymerization bottle, under the anhydrous and anaerobic condition, vacuum pumping and nitrogen filling are carried out, 1.0mL of solvent acetonitrile is added, after 2 hours of reaction at 100 ℃, the reaction is stopped by using a methanol solution of potassium hydroxide, and 300.00mg of brush polymer based on spiral polyisonitrile is obtained.
Example 2
A polymeric brush of a polyisonitrile grafted polyoxazoline comprising the steps of:
(1) First, preparation of a bromogroup-containing isonitrile monomer
a. Weighing raw materials 1, 4-butanediol and 4-dimethylaminopyridine, dissolving in a solvent E (dichloromethane), and stirring in an erlenmeyer flask for 20min; raw materials 4- (bromomethyl) benzoic acid and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride are weighed, dissolved in a solvent E (methylene dichloride), stirred in a two-necked flask for 20min, and then a reaction solution in a conical flask is added into the two-necked flask. After 6h of reaction, the product d is obtained by organic extraction and drying, wherein the structural general formula of d is as follows:
the route for synthesis d in this example is as follows:
b. in a 100mL two-port bottle, the product d, pentafluorophenol isonitrile and 4-dimethylaminopyridine were dissolved with a little solvent C (tetrahydrofuran) (the smaller the solvent the better), then a reflux apparatus was set up, and the reaction atmosphere was replaced with nitrogen gas with a water pump. The reaction vessel was placed in an oil bath at 55 ℃ for overnight reaction. Organic extraction and drying are carried out to obtain the bromogroup-containing isonitrile monomer, wherein the bromogroup-containing isonitrile monomer has the following structural general formula:
the synthetic route for the bromo-containing isonitrile monomer of this example is as follows:
as can be seen from the nuclear magnetic resonance spectrum of the pentafluorophenol isonitrile monomer shown in FIG. 3, the four hydrogen peak positions of the benzene ring on the isonitrile monomer are between 7.5 and 8.5, and the integral ratio is 2:2, so in FIG. 2, two peaks around 7.5 and 8.5 are the positions of four hydrogen peaks of benzene ring on isonitrile monomer, the middle two peaks represent four hydrogen peaks of benzene ring on benzyl bromide, the two peaks of two hydrogen peaks on carbon beside bromine are at the position of 4.62, the four hydrogen peaks on two carbon near oxygen are at the position of 4.42 due to the same connecting group, the chemical shift is at the position of 4.42, the two middle carbon chemical shifts are consistent, the peak is at the position of 1.95, the integral ratio is consistent with the expected, so that the successful synthesis of the isonitrile monomer containing bromo can be judged.
(2) 100.00mg of the bromogroup-containing isonitrile monomer and 1.36mg of methoxy catalyst are weighed into a polymerization bottle, under the anhydrous and anaerobic condition, vacuum pumping and nitrogen filling are carried out, 1.0mL of solvent chloroform is added, after reaction is carried out for 15 hours at 55 ℃, the solvent methanol is used for precipitation, filtration and vacuum drying until the quality is unchanged, and 90.00mg of the bromogroup-containing isonitrile monomer polymer is obtained.
The synthetic route for the bromogroup-containing isonitrile monomer polymer of this example is as follows:
(3) 30.00mg of a bromogroup-containing isonitrile monomer polymer and 307.00mg of 2-ethyl-2-oxazoline are weighed into a polymerization bottle, under the anhydrous and anaerobic condition, vacuum pumping and nitrogen filling are carried out, 1.0mL of solvent acetonitrile is added, after 2 hours of reaction at 100 ℃, the reaction is stopped by using a methanol solution of potassium hydroxide, and 300.00mg of the brush polymer based on spiral polyisonitrile is obtained.
The brush polymers prepared based on helical polyisonitriles can be used for antifouling surfaces and biological lubrication by surface modification and for drug transport by their interesting self-assembly behaviour.
Example 3
A polymeric brush of a polyisonitrile grafted polyoxazoline comprising the steps of:
(1) Firstly, initiating 2-ethyl-2-oxazoline by using an isonitrile monomer containing bromo
a. 50mg of a bromoisonitrile monomer was weighed, dissolved in 1mL of anhydrous acetonitrile, added to a 10mL Schlenk flask, and then 0.3mL of anhydrous 2-ethyl-2-oxazoline was measured by a syringe and injected into the Schlenk flask, the flask cap was closed, nitrogen was repeatedly replaced with an oil pump eight times, and the mixture was reacted in an oil bath at 80℃under a nitrogen atmosphere for 4 hours. After the reaction, the mixture is placed on a stirring table for cooling, and a small amount of saturated aqueous solution of potassium carbonate is added into the reaction solution and stirred for 1h at room temperature. After the reaction was terminated, the solvent was drained with an oil pump, and the solvent was drained after washing by ether precipitation to give 300mg of polymer a, wherein a has the following structural formula:
the route for synthesis a in this example is as follows:
(2) 100.00mg of polymer a and 1.36mg of methoxy catalyst are weighed into a polymerization bottle, under the condition of no water and no oxygen, vacuum pumping and nitrogen charging are carried out, 1.0mL of solvent chlorobenzene is added, after reaction is carried out for 24 hours at 90 ℃, the solvent diethyl ether is used for precipitation, filtration and vacuum drying until the quality is unchanged, and 90.00mg of brush polymer based on spiral poly isonitrile is obtained.
Example 4
A polymeric brush of a polyisonitrile grafted polyoxazoline comprising the steps of:
(1) Firstly, initiating 2-ethyl-2-oxazoline by using isonitrile monomer containing p-toluenesulfonyl
a. 50mg of p-toluenesulfonyl group-containing isonitrile monomer was weighed, dissolved in 1mL of anhydrous acetonitrile, added to a 10mL Schlenk flask, and then 0.34mL of anhydrous 2-ethyl-2-oxazoline was measured by syringe and injected into the Schlenk flask, the flask cap was closed, nitrogen was repeatedly replaced under an oil pump for eight times, and the reaction was carried out under nitrogen atmosphere in an oil bath at 80℃for 4 hours. After the reaction, the mixture is placed on a stirring table for cooling, and a small amount of saturated aqueous solution of potassium carbonate is added into the reaction solution and stirred for 1h at room temperature. After the reaction was terminated, the solvent was drained off by an oil pump, and the solvent was drained off after washing by diethyl ether precipitation to obtain 300mg of polymer b, wherein b has the following structural formula:
the route for synthesis b in this example is as follows:
(2) 100.00mg of polymer b and 1.36mg of methoxy catalyst are weighed into a polymerization bottle, under the condition of no water and no oxygen, vacuum pumping and nitrogen charging are carried out, 1.0mL of solvent chlorobenzene is added, after reaction is carried out for 24 hours at 90 ℃, the solvent diethyl ether is used for precipitation, filtration and vacuum drying until the quality is unchanged, and 90.00mg of brush polymer based on spiral poly isonitrile is obtained.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention, as it is intended to provide those skilled in the art with various modifications, additions and substitutions to the specific embodiments disclosed and those skilled in the art without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (10)
1. The polymer brush of the poly (isonitrile) -grafted polyoxazoline is characterized by having the following structural general formula:
in the method, in the process of the invention,
R 1 ：or- -CH 3 Or->
R 2 ：
n=100 to 700, m=100 to 500, and m and n are integers.
2. A method of preparing a polymeric brush of a polyisonitrile grafted polyoxazoline according to claim 1, comprising the steps of:
(1) Preparing an isonitrile monomer containing tosyl or halogen;
(2) Weighing the isonitrile monomer containing the p-toluenesulfonyl or halogen, the oxazoline monomer and the methoxy catalyst obtained in the step (1) for reaction, and after the reaction is finished, precipitating, filtering and vacuum drying until the quality is unchanged, thus obtaining the polymer brush of the polyisonitrile grafted polyoxazoline.
3. The method for preparing a polymer brush of poly (isonitrile) -grafted polyoxazoline according to claim 2, characterized in that: in the step (2), firstly weighing the isonitrile monomer and the oxazoline monomer which are obtained in the step (1) and contain p-toluenesulfonyl or halogen, vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding a solvent A, and after the reaction is finished, precipitating with a solvent B, filtering, and vacuum drying until the quality is unchanged to obtain a product a; and then weighing the product a and the methoxy catalyst, vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding the solvent C, and after the reaction is finished, precipitating with the solvent D, filtering, and vacuum drying until the quality is unchanged to obtain the polymer brush of the poly (isonitrile) grafted polyoxazoline.
4. A method of preparing a polymeric brush of a polyisonitrile grafted polyoxazoline according to claim 3, characterized by: the mol ratio of the isonitrile monomer containing tosyl or halogen to the oxazoline monomer is 1:100-500, the reaction temperature is 80-100 ℃, and the reaction time is 4-8 h; in the step (3), the mol ratio of the product a to the methoxy catalyst is 1:70-700, the reaction temperature is 50-55 ℃, and the reaction time is 14-16 h.
5. The method for preparing a polymer brush of poly (isonitrile) -grafted polyoxazoline according to claim 2, characterized in that: in the step (2), firstly weighing the isonitrile monomer containing the tosyl or halogen and the methoxy catalyst obtained in the step (1), vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding a solvent C, and after the reaction is finished, precipitating with the solvent D, filtering, and vacuum drying until the quality is unchanged to obtain a product b; and then weighing the product B and oxazoline monomers, vacuumizing and filling nitrogen under the anhydrous and anaerobic condition, adding the solvent A, and after the reaction is finished, precipitating with the solvent B, filtering, and vacuum drying until the quality is unchanged, thus obtaining the brush polymer based on the spiral polyisonitrile.
6. The method for preparing a polymer brush of poly (isonitrile) -grafted polyoxazoline according to claim 5, wherein: the mol ratio of the isonitrile monomer containing p-toluenesulfonyl or halogen to the methoxy catalyst is 1:70-700, the reaction temperature is 50-55 ℃, and the reaction time is 14-16 h; the mol ratio of the product b to the oxazoline monomer is 1:20-50, the reaction temperature is 80-100 ℃, and the reaction time is 4-8 h.
7. The method for preparing a polymer brush of poly (isonitrile) grafted polyoxazoline according to claim 3 or 5, characterized in that: the solvent A is dimethyl sulfoxide or N, N-dimethylformamide, the solvent B is diethyl ether, the solvent C is chloroform, the solvent D is methanol, the structural general formula of the methoxy catalyst is shown in the specification,
the structural general formula of the oxazoline monomer is as follows,
wherein R and the polymer brush structure general formula of the poly (isonitrile) grafted polyoxazoline 1 Or R is 2 The structural formulas of (2) are the same.
8. The method for preparing a polymer brush of poly (isonitrile) -grafted polyoxazoline according to claim 2, characterized in that: the structural general formula of the isonitrile monomer containing the p-toluenesulfonyl is as follows:
the structural general formula of the halogen-containing isonitrile monomer is as follows:
wherein R is-Br or-Cl or-I or-COCl.
9. The method for preparing a polymer brush of poly (isonitrile) -grafted polyoxazoline according to claim 2, wherein the method for preparing isonitrile monomer containing p-toluenesulfonyl group comprises the following steps:
(I) Reacting 1, 4-butanediol, pentafluorophenol isonitrile and 4-dimethylaminopyridine in nitrogen atmosphere, then carrying out organic extraction, and drying to obtain a product c;
(II) under the nitrogen atmosphere, reacting p-toluenesulfonyl chloride with a product c, then carrying out organic extraction, and drying to obtain an isonitrile monomer containing sulfonyl chloride;
the preparation method of the halogen-containing isonitrile monomer comprises the following steps:
(I) Weighing 1, 4-butanediol, 4-dimethylaminopyridine, halogen-containing raw materials and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, after the reaction is finished, carrying out organic extraction, and drying to obtain a product d, wherein the halogen-containing raw materials are 4- (bromomethyl) benzoic acid or 4- (chloromethyl) benzoic acid or 4- (iodomethyl) benzoic acid or 4- (acyl chloride) benzoic acid;
and (II) weighing the product d, the pentafluorophenol isonitrile and the 4-dimethylaminopyridine under the nitrogen atmosphere, and after the reaction is finished, carrying out organic extraction and drying to obtain the halogen-containing isonitrile monomer.
10. The method for preparing the polymer brush of the polyisonitrile grafted polyoxazoline according to claim 9, which is characterized in that: in the preparation method of the isonitrile monomer containing the tosyl, in the step (I), the mass ratio of the 1, 4-butanediol to the pentafluorophenol isonitrile is 3:1, the mass ratio of the pentafluorophenol isonitrile to the 4-dimethylaminopyridine is 1:1, the reaction temperature is 55 ℃, and the reaction time is 6 hours;
in the step (II), the mass ratio of the tosyl chloride to the substance of the product c is 1.2:1, the reaction temperature is room temperature, and the reaction time is 6 hours;
in the step (I), the ratio of the 1, 4-butanediol to the halogen-containing raw material is 3:1, the ratio of the 4-dimethylaminopyridine to the halogen-containing raw material is 0.8:1, the ratio of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the halogen-containing raw material is 1.2:1, and the reaction time is 6 hours at room temperature;
in the step (II), the mass ratio of the product d to the pentafluorophenol isonitrile is 1.2:1, the mass ratio of the pentafluorophenol isonitrile to the 4-dimethylaminopyridine is 1:1, the reaction temperature is 55 ℃, and the reaction time is 6 hours;
the structural general formula of the monomer of the pentafluorophenol isonitrile is as follows:
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