CN104558270A - Cyclopoly(N-vinylcaprolactam) as well as preparation method and application thereof - Google Patents
Cyclopoly(N-vinylcaprolactam) as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses cyclopoly(N-vinylcaprolactam) as well as a preparation method and application thereof, and belongs to the field of functional polymer materials. Two types of cyclopoly(N-vinylcaprolactam) including c-PNVCL and (c-PNVCL)-OH are obtained for the first time. The preparation method comprises the steps of combining with atom transfer radical polymerization, supermolecular self-assembly and click chemistry, and performing a ring closing reaction of a linear precursor at a high concentration, so as to obtain the high-efficiency and high-yield cyclopoly(N-vinylcaprolactam). (C-PNVCL)-OH prepared according to the invention can be used for triggering the ring opening polymerization of any one of glycolide, D-lactide, L-lactide, DL-lactide and epsilon-caprolactone, so as to synthesize and obtain a tadpole-shaped segmented copolymer containing cyclopoly(N-vinylcaprolactam), wherein the tadpole-shaped segmented copolymer has a potential application value in the field of biological medicine. The molecular structures of c-PNVCL and (c-PNVCL)-OH are as shown in the specifications, wherein in the formulae of c-PNVCL and (c-PNVCL)-OH, n is equal to 20-200.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related on a kind of annular poly-(N-caprolactam) and a kind of ring with on the annular poly-(N-caprolactam) of hydroxyl, their preparation method and ring with the application in synthesis to gather the annular of (N-caprolactam) containing annular and shape block copolymer (tadpole-shaped segmented copolymer) synthesizes of the annular poly-(N-caprolactam) of hydroxyl.
Background technology
Annular polymeric is the special topological framework polymkeric substance that a class does not have end group, unit on its molecular chain has identity property, with corresponding line polymer precursor phase ratio, annular polymeric has higher density, lower limiting viscosity, less frictional coefficient, higher second-order transition temperature and larger specific refraction, there is less hydrodynamic radius in the solution, and annular high molecular crystallization velocity is much larger than the crystallization velocity of linear molecule.Line polymer in vivo can by the nanometer micropore of the mode of " snakelike " through renal glomerulus, and annular polymeric is difficult to pass through in such a way due to the structure of its uniqueness, therefore the annular polymeric that molecular weight is greater than renal excretion threshold value can stop the longer time in blood, this just substantially increases its bioavailability, can more effectively in tumor locus enrichment.Due to these distinctive character, annular polymeric, as a kind of new function polymer materials, has important application prospect in fields such as biological medicine, material modification and nanosecond science and technology.The preparation of annular polymeric mainly contains " ring expansion polymerization " and " in the molecule of line polymer Cheng Huan " two kinds of methods, annular polymeric is prepared by " ring expansion polymerization " method, can not form linear by product, but generated time is longer, needs special monomer or catalyzer.In the molecule of the line polymer of two ends functionalization, " from beginning to end " connects into another main method that ring is preparation annular polymeric, the key of synthesizing annular polymeric in this way how to make annulation efficiently carry out, because the reactive behavior of the line polymer terminal functionality of two ends functionalization is lower, and to there is coupling between polymer chain be the side reaction of line polymer, therefore the coupling must carrying out reducing between polymer chain in extremely dilute solution is reacted, method is prepared cyclic polymer often productive rate is extremely low thus, and aftertreatment needs to remove a large amount of solvents, comparatively loaded down with trivial details.
Poly-(N-caprolactam) (PNVCL) a kind ofly has amphipathic, nontoxicity, biocompatibility, nonionic characteristic and temperature-responsive polymkeric substance, its lower critical solution temperature (LCST) is in physiological temp (32 DEG C ~ 40 DEG C) scope, be different from most polyacrylamide, the hydrolysis of PNVCL does not produce poisonous small molecule amine, and therefore it has broad application prospects at biomedicine field; With the temperature-responsive polymkeric substance of current most study--compared with the monomer of NIPA (PNIPAM), monomer N-vinyl hexanolactam (NVCL) price of PNVCL is more cheap.Polymkeric substance based on NVCL has larger actual application value, but focuses mostly in line polymer about the research based on NVCL polymkeric substance at present, and literature search has no the research report of respective annular poly-(N-caprolactam) (PNVCL).
Summary of the invention
The object of this invention is to provide annular poly-(N-caprolactam), said annular poly-(N-caprolactam) is poly-(N-caprolactam) c-PNVCL of annular, and gathers (N-caprolactam) (c-PNVCL)-OH with the annular of a hydroxyl; The present invention also provides the preparation method of above-mentioned two kinds of annulars poly-(N-caprolactam), and provides the application of the annular poly-(N-caprolactam) with a hydroxyl.
Two kinds of annulars provided by the present invention gather (N-caprolactam), one is poly-(N-caprolactam) c-PNVCL of annular, another kind is poly-(N-caprolactam) (the c-PNVCL)-OH of annular with a hydroxyl, and its molecular structure is as follows respectively:
c-PNVCL (c-PNVCL)-OH
N=20 ~ 200 in formula c-PNVCL and (c-PNVCL)-OH.
Preparation method of the present invention is as follows:
1, the atom transfer radical polymerization initiator (alkynyl-Cl) of end with alkynyl is prepared:
Be dissolved in methylene dichloride by propiolic alcohol and triethylamine, the volume ratio of propiolic alcohol, triethylamine and methylene dichloride is 1:2.5 ~ 3.0:5 ~ 8; At 0 ~ 5 DEG C with under stirring, drip the dichloromethane solution of 2-chlorpromazine chloride, add the dichloromethane solution of 2-chlorpromazine chloride and the volume ratio of propiolic alcohol and triethylamine solution is 1:2 ~ 2.5, wherein the volume ratio of propiolic alcohol and 2-chlorpromazine chloride is 1:1.5 ~ 2.0; Drip and finish, at 0 ~ 5 DEG C of stirring reaction 30 ~ 60min, stirring at room temperature reaction 10 ~ 16 h, the reaction vessel of the most handy drying carries out above-mentioned reaction.Filter, filtrate uses saturated NaHCO
3solution divides three wash filtrates, and uses anhydrous magnesium sulfate drying organic phase, filters, steams solvent, is separated crude product and obtains the atom transfer radical polymerization initiator (alkynyl-Cl) of end with alkynyl.The most handy silica gel column chromatography of crude product is separated (sherwood oil: ethyl acetate=50:1).The molecular structure of alkynyl-Cl is as follows:
2, the atom transfer radical polymerization initiator (alkynyl (-OH)-Cl) of end with hydroxyl in alkynyl, molecule is prepared:
A. (such as can refer to document Ozcan A by prior art, Gurkan H, Umit T. J. Polym. Sci., Part A:Polym. Chem., 2006,44 (19): 5699-5707), with triethylamine and DMAP for catalyzer, with propiolic alcohol and Succinic anhydried reaction, preparation 4-oxo-4-(the third-2-alkynyloxy group) butyric acid;
B. (such as can refer to document Zhang Y F, Li C H, Liu S Y. J. Polym. Sci. by prior art, Part A:Polym. Chem., 2009,47 (12): 3066-3077), take tosic acid as catalyzer, with 1,1,1-tri-(methylol) ethane and 2,2-Propanal dimethyl acetal reacts, preparation 2,2-dimethyl-5-ethyl-5-methylol-1,3-dioxane;
C. (such as can refer to document Zhang Y F by prior art, Li C H, Liu S Y. J. Polym. Sci., Part A:Polym. Chem., 2009, 47 (12): 3066-3077), with dicyclohexylcarbodiimide and DMAP for catalyzer, with 4-oxo-4-(the third-2-alkynyloxy group) and 2, 2-dimethyl-5-ethyl-5-methylol-1, 3-dioxane reacts, prepare the ketal compound of end with alkynyl, be catalyzer again with toluenesulphonic acids, after end is hydrolyzed to hydroxyl with the ketal group of the ketal compound of alkynyl, react with 2-chlorpromazine chloride again and prepare end with alkynyl, the atom transfer radical polymerization initiator (alkynyl (-OH)-Cl) of hydroxyl in molecule.The molecular structure of alkynyl (-OH)-Cl is as follows:
3, end poly-(N-caprolactam) (alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl) with alkynyl is prepared:
A. 5,5,7,12,12,14-vegolysen is prepared, 4,8,11-tetraazacyclododecane tetradecane hydrate (Me
6cyclam): Me
6the preparation method of Cyclam is prior art, such as can refer to document (Hu Minqi, Shao Lidong, Chen Lin etc. Yunnan chemical, 2009,36 (6): 4-7), under Hydrogen bromide exists, with acetone, quadrol for raw material, first obtained four major esters schiff base compounds, then use NaBH
4reduction preparation 5,5,7,12,12,14-vegolysen, 4,8,11-tetraazacyclododecane tetradecane hydrate (Me
6cyclam);
B. poly-(the N-caprolactam) of end with alkynyl is prepared:
In reaction vessel, add N-caprolactam, vacuum nitrogen filling gas repeatedly after, add CuCl, CuCl under nitrogen protection
2, the Me that obtains of step 3a
6the mixed solvent of Cyclam, dioxane and Virahol, wherein N-caprolactam, CuCl, CuCl
2and Me
6the mass ratio of Cyclam is 1000 ~ 1030:6 ~ 8:1:20 ~ 23, and the mixed solvent of every ml dioxane and Virahol is dissolved with 1 ~ 4g N-caprolactam, and the volume ratio of dioxane and Virahol is 1:10 ~ 12; Vacuum nitrogen filling gas 30 ~ 60 min, add initiator alkynyl-Cl or alkynyl (-the OH)-Cl that step 1 or step 2 obtain, wherein the mass ratio of initiator and N-caprolactam is 1:1000 ~ 1030,30 ~ 35 DEG C of reaction 1 ~ 3 h, product distilled water dissolves, filter, filtrate put into molecular weight cut-off be 3500 dialysis tubing dialysis 5 ~ 8 days, after decompression steams water, vacuum-drying obtains PNVCL(alkynyl-PNVCL-Cl or alkynyl (-the OH)-PNVCL-Cl of end with alkynyl).The molecular structure of alkynyl-PNVCL-Cl and alkynyl (-OH)-PNVCL-Cl is as follows:
alkynyl-PNVCL-Cl alkynyl (-OH)-PNVCL-Cl
N=20 ~ 200 in formula alkynyl-PNVCL-Cl and alkynyl (-OH)-PNVCL-Cl;
4, two ends are prepared respectively with poly-(N-caprolactam) (alkynyl-PNVCL-N of alkynyl and azido-
3or alkynyl (-OH)-PNVCL-N
3):
Sodiumazide is added end that step 3 obtains PNVCL(alkynyl-PNVCL-Cl or alkynyl (-the OH)-PNVCL-Cl with alkynyl) dimethyl formamide solution, every ml dimethyl formamide is dissolved with the PNVCL of 0.2 ~ 0.5 g end with alkynyl, sodiumazide and end are 1:25 ~ 30 with the mass ratio of the PNVCL of alkynyl, 40 ~ 45 DEG C of stirring reaction 45 ~ 50h, decompression steams dimethyl formamide, after residuum dissolves with tetrahydrofuran (THF), through the sodiumazide that alumina column chromatography (methylene dichloride is eluent) removing is residual, after distillation and concentration, vacuum-drying obtains two ends respectively with the PNVCL(alkynyl-PNVCL-N of alkynyl and azido-
3or alkynyl (-OH)-PNVCL-N
3).Alkynyl-PNVCL-N
3with alkynyl (-OH)-PNVCL-N
3molecular structure as follows:
alkynyl-PNVCL-N
3
alkynyl (-OH)-PNVCL-N
3
Formula alkynyl-PNVCL-N
3with alkynyl (-OH)-PNVCL-N
3middle n=20 ~ 200;
5, preparation annular poly-(N-caprolactam) (c-PNVCL and (c-PNVCL)-OH):
Two ends step 4 obtained are respectively with the PNVCL (alkynyl-PNVCL-N of alkynyl and azido-
3or alkynyl (-OH)-PNVCL-N
3) be dissolved in distilled water, described every ml distilled water is dissolved with 0.01 ~ 0.05g two end respectively with the PNVCL of alkynyl and azido-, under stirring, adds sodium ascorbate and CuSO at 28 ~ 32 DEG C
45H
2o, added sodium ascorbate, CuSO
45H
2o and two ends are respectively 0.1 ~ 0.3:0.05 ~ 0.08:1 with the mass ratio of the PNVCL of alkynyl and azido-, 28 ~ 33 DEG C of stirring reaction 20 ~ 28h, decompression steams solvent, after residuum dissolves with tetrahydrofuran (THF), copper salt catalyst is removed through alumina column chromatography (methylene dichloride is eluent), after distillation and concentration, poly-(N-caprolactam) (c-PNVCL or (the c-PNVCL)-OH) of the obtained annular of vacuum-drying.
The application of annular prepared by the present invention poly-(N-caprolactam), be exactly as initiator using the annular poly-(N-caprolactam) with a hydroxyl, cause the ring-opening polymerization of lactide and caprolactone, synthesis gathers annular and the shape block copolymer (tadpole-shaped segmented copolymer) of (N-caprolactam) containing annular.
In reaction vessel, add lactide or lactone and stannous octoate, said lactide and lactone are any one in glycollide, D-rac-Lactide, L-rac-Lactide, DL-rac-Lactide and 6-caprolactone, and the amount of substance ratio of lactide or lactone and stannous octoate is 15 ~ 20:1; Vacuum nitrogen filling gas 15 ~ 20 min, is heated with stirring to 100 ~ 150 DEG C, after lactide or the complete melting of lactone, adds (c-PNVCL)-OH under nitrogen protection fast, and (c-PNVCL)-OH is 2 ~ 8:1 with the mass ratio of lactide or lactone; After 90 ~ 150 DEG C of polymerization 5 ~ 16h, with a small amount of methylene dichloride solubilizing reaction product, filter, filtrate is through sherwood oil co-precipitation 3 ~ 5 times, collecting precipitation, vacuum-drying 24 ~ 48h, must gather annular and the shape block copolymer (tadpole-shaped segmented copolymer) of (N-caprolactam) containing annular.The molecular structure of tadpole-shaped segmented copolymer is as follows:
N=20 ~ 200 in formula;
Wherein M represents one of following line polymer:
M=20 ~ 500 in formula.
Filtration in above-mentioned steps, underpressure distillation, column chromatography, the same routine techniques of the operations such as vacuum-drying.
In the present invention, prepared annular is gathered (N-caprolactam) (c-PNVCL and (c-PNVCL)-OH) structure and clearly, is all had narrower molecular weight distribution (PDI<1.2), can pass through
1hNMR, GPC and MALDI-TOF MS carries out detailed characterizations.
Beneficial effect of the present invention: usually, in order to avoid the generation of intermolecular coupled reaction, with two ends respectively with alkynyl and azido-line polymer by click-reaction in molecule be closed into cyclization circularize polymkeric substance time, need dilute concentration (c≤10, pole
-6mg/mL) line polymer solution slowly (10 μ L/min) is added drop-wise in copper catalyst solution, and process is loaded down with trivial details, long reaction time, and not easily, productive rate is low in aftertreatment.The present invention utilize poly-(N-caprolactam) have amphipathic, can self-assembly be the feature of micella in selective solvent, in conjunction with atom transfer radical polymerization (ATRP), click-reaction and Supramolecular self assembly, successfully achieve the Intra-molecular condensation carrying out linear precursor polymer under higher concentration (10 mg/mL), suppress the coupled reaction between precursor molecule simultaneously, not only shorten the reaction times, and can a large amount of annular polymeric of one time to produce, achieve the efficient high yield preparation of annular poly-(N-caprolactam).Poly-(N-caprolactam) (c-PNVCL)-OH of the annular with a hydroxyl of the present invention's development can cause the ring-opening polymerization of lactide and lactone compound, synthesis annular poly-(N-caprolactam) and linear polyglycolic acid, the segmented copolymer (tadpole-shaped segmented copolymer) of poly(lactic acid) or polycaprolactone, the Linear block of these tadpole-shaped segmented copolymers is biodegradable polymer, poly-(N-caprolactam) block of annular then has temperature response performance, therefore these tadpole-shaped segmented copolymers have potential using value at biomedicine field.
Accompanying drawing explanation
Fig. 1 is embodiment three and embodiment four gained alkynyl-PNVCL-N
3with the infrared spectra of c-PNVCL.
Fig. 2 is embodiment three and embodiment four gained alkynyl-PNVCL-N
3with the GPC curve of c-PNVCL.
Fig. 3 is embodiment nine and embodiment ten gained alkynyl (-OH)-PNVCL-N
3(c-PNVCL) infrared spectra of-OH.
Fig. 4 is embodiment nine and embodiment ten gained alkynyl (-OH)-PNVCL-N
3(c-PNVCL) the GPC curve of-OH.
Embodiment
Be described in further detail the present invention by embodiment below, but content of the present invention is not limited thereto.
Embodiment one:
10 mL methylene dichloride are added successively in the round-bottomed flask of 50 mL, propiolic alcohol (2.0 mL, 33.7 mmol), triethylamine (TEA, 5.6 mL, 37.1 mmol), stir in ice-water bath and be cooled to 0 DEG C, 2-chlorpromazine chloride (3.4 mL, 33.8 mL) dichloromethane solution slowly instill in above-mentioned solution, 30 min are stirred at 0 DEG C, rise to room temperature, continue stirring reaction 12 h, filter, filtrate washs 3 times with saturated sodium bicarbonate solution, anhydrous magnesium sulfate drying, filter, evaporate solvent, obtain light yellow transparent liquid, (sherwood oil: ethyl acetate=50: 1) obtain atom transfer radical polymerization (ATRP) initiator (alkynyl-Cl) of end with alkynyl is separated through silica gel column chromatography, productive rate 60.3%.
Embodiment two:
In the polymerizing pipe of 10 mL, add NVCL(0.6103 g, 4.38 mmol), vacuum nitrogen filling gas repeatedly after, add CuCl(0.0039 g under nitrogen protection, 0.040 mmol), CuCl
2(0.0006 g, 0.004 mmol), Me
6cyclam(0.0125 g, 0.044 mmol) and the mixed solvent of 0.2 mL dioxane/Virahol, continue vacuum nitrogen filling gas 30 min, add alkynyl initiator alkynyl-Cl(0.0006 g, 0.0044 mmol), 30 DEG C of reaction 2 h, product distilled water dissolves, cross filter insolubles, filtrate put into molecular weight cut-off be 3500 dialysis tubing dialysis 6 days after concentrate, vacuum-drying 24 h, obtains the PNVCL(alkynyl-PNVCL-Cl of end with alkynyl).
Embodiment three:
The PNVCL(alkynyl-PNVCL-Cl of 8.5 g ends with alkynyl is added in the round-bottomed flask of 100 mL), 30 mL DMF, thing to be polymerized adds 0.33g NaN after dissolving
3reaction mixture stirs 48 h at 45 DEG C, pressure reducing and steaming DMF, product is dissolved in THF, (methylene dichloride is eluent) is separated through alumina column chromatography, after distillation and concentration, vacuum-drying 24 h, obtains two ends respectively with poly-(N-caprolactam) (alkynyl-PNVCL-N of alkynyl and azido-
3), productive rate 93%.
Embodiment four:
0.4 g two end is added respectively with poly-(N-caprolactam) (alkynyl-PNVCL-N of alkynyl and azido-in the round-bottomed flask of 100 mL
3), 40 mL distilled water, stirring at room temperature is dissolved completely to PNVCL, is heated to 30 DEG C, then adds 0.05 g sodium ascorbate successively, 0.025 g CuSO
45H
2o, after reaction mixture stirs 24 h at 30 DEG C, underpressure distillation, product is dissolved in THF, is separated (methylene dichloride is eluent), after distillation and concentration through alumina column, vacuum-drying 24 h, obtain annular poly-(N-caprolactam) (c-PNVCL), productive rate is 85%.
Embodiment five:
1 of 100 mL dryings are added successively in the round-bottomed flask of 250 mL, 4-dioxane, propiolic alcohol (4.75 g, 84.7 mmol), Succinic anhydried (10.58 g, 105.7 mmol), triethylamine (10.7 g, 105.7 mmol), 4-dimethylamino pyridine (12.9 g, 105.8 mmol).Reaction mixture at room temperature reacts 24 h, and underpressure distillation removes most of Isosorbide-5-Nitrae-dioxane, uses methylene dichloride dissolution residual substance, adds the HCl solution washing 3 times of 1 M, anhydrous MgSO
4drying, filters, evaporates solvent, after recrystallization is separated, obtain 4-oxo-4-(third-2-alkynyloxy group) butyric acid, productive rate is 59%.
Embodiment six:
50 mL acetone, 1,1,1-tri-(methylol) ethane (5 g, 41.6 mmol), tosic acid hydrate (0.3 g, 1.6 mmol), 2,2-dimethoxypropane (8.7 g, 83.2 mmol) is added successively in the round-bottomed flask of 100 mL.Reaction mixture at room temperature reacts 12 h, and distillation removing acetone, residue is dissolved in ethyl acetate, uses saturated NaHCO
3solution washing 3 times, anhydrous MgSO
4drying, filter, evaporate solvent, obtain 2,2-dimethyl-5-ethyl-5-methylol-1,3-dioxane, productive rate is 67.6%.
Embodiment seven:
The methylene dichloride of 100 mL dryings is added successively in the round-bottomed flask of 250 mL, 2, 2-dimethyl-5-ethyl-5-methylol-1, 3-dioxane (7.8 g, 48.8 mmol), 4-oxo-4-(third-2-alkynyloxy group) butyric acid (7.6 g, 48.7 mmol), reaction mixture ice bath is cooled to 0 DEG C, alternately slowly add dicyclohexylcarbodiimide (10.3 g, 50 mmol), DMAP (0.6 g, 5 mmol), 1 h is stirred at 0 DEG C, rise to room temperature, continue stirring reaction 12 h, filter, evaporate solvent, be separated (sherwood oil: ethyl acetate=1:2) through silica gel column chromatography and obtain 2, 2-dimethyl-5-ethyl-5-methylol-1, the acetylenic acid ester of 3-dioxane, productive rate is 79.8%.
Embodiment eight:
In the round-bottomed flask of 250 mL, add 2, the acetylenic acid ester (7g, 22.4 mmol) of 2-dimethyl-5-ethyl-5-methylol-1,3-dioxane and 50 ml methyl alcohol, after stirring and dissolving, add 50 mL hydrochloric acid (1 mol/L), after stirring reaction 2 h, with 2 mol/L sodium hydroxide solutions, pH value is transferred to 7.0, steam methyl alcohol, surplus solution is extracted with ethyl acetate.Organic over anhydrous MgSO
4drying, steams ethyl acetate, and the crude on silica gel column chromatography for separation (sherwood oil: ethyl acetate=1:1) obtained obtains the acetylenic acid ester (alkynyl (-OH) of 2,2-dimethyl-5-ethyl-5-methylol-1,3-glycol
2).Then in 250 mL round-bottomed flasks, alkynyl (-OH) is added successively
2(3 g, 10.9 mmol), triethylamine (1.12 g, 11 mmol) and the tetrahydrofuran (THF) of 100 mL dryings, stir in ice-water bath and be cooled to 0 DEG C, 2-chlorpromazine chloride (1.2 mL, 11.3 mmol) dichloromethane solution slowly instill in above-mentioned solution, 30 min are stirred at 0 DEG C, rise to room temperature, continue stirring reaction 24 h, filter, filtrate washs 3 times with saturated sodium bicarbonate solution, anhydrous magnesium sulfate drying, filter, evaporate solvent, be separated (sherwood oil: ethyl acetate=2:1) through silica gel column chromatography and obtain end with alkynyl, the ATRP initiator (alkynyl (-OH)-Cl) of hydroxyl in molecule, productive rate is 65.4%.
Embodiment nine:
Basic with embodiment two, difference is initiator is ATRP initiator alkynyl (-the OH)-Cl of end with hydroxyl in alkynyl, molecule: in the round-bottomed flask of 100 mL, add 8.5 g alkynyl (-OH)-Cl, 30 mL DMF, thing to be polymerized adds 0.33g NaN after dissolving
3reaction mixture stirs 48 h at 45 DEG C, pressure reducing and steaming DMF, product is dissolved in THF, (methylene dichloride is eluent) is separated through alumina column chromatography, after distillation and concentration, vacuum-drying 24 h, obtains two ends respectively with poly-(N-caprolactam) (alkynyl-(OH)-PNVCL-N of hydroxyl in alkynyl and azido-, molecule
3), productive rate 92%.
Embodiment ten:
Basic with embodiment three, difference to be reactant be two ends are respectively with poly-(N-caprolactam) (alkynyl-(OH)-PNVCL-N of hydroxyl in alkynyl and azido-, molecule
3): in the round-bottomed flask of 100 mL, add 0.5 g alkynyl-(OH)-PNVCL-N
3, 40 mL distilled water, stirring at room temperature is dissolved completely to PNVCL, is heated to 30 DEG C, then adds 0.06 g sodium ascorbate successively, 0.03 g CuSO
45H
2o, after reaction mixture stirs 24 h at 30 DEG C, underpressure distillation, product is dissolved in THF, (methylene dichloride is eluent) is separated through alumina column, after distillation and concentration, vacuum-drying 24 h, must with poly-(N-caprolactam) ((the c-PNVCL)-OH) of the annular of a hydroxyl, productive rate is 80%.
Embodiment 11:
0.2 g(1.4 mmol is added successively in 50 mL polymerization bottles) D; L-rac-Lactide, stannous octoate 22.7 uL(0.07 mmol); vacuum nitrogen filling gas 15 min; be heated with stirring to 130 DEG C; treat D; after the complete melting of L-rac-Lactide;-OH(0.4 g) to add (c-PNVCL) under nitrogen protection fast; after 130 DEG C of polyreaction 5 h; with a small amount of methylene dichloride solubilizing reaction product, elimination insolubles, filtrate is through sherwood oil co-precipitation 3 times; vacuum-drying 24 h, obtain linear-Cyclic block copolymer (c-PNVCL)-
b-PDLLA, productive rate is 65%.The structural formula of target product:
1H NMR (CDCl
3) δ
H(ppm)：1.13～2.05 (CH
3, CH
2), 2.20～2.61 (CH
2C=O), 3.29 (NCH
2), 3.51(OCH
2), 4.42 (OCH, OCH
2), 5.03 (OCH
2C=), 5.33 (NCHN), 8.05 (NCH=)。
Embodiment 12:
Basic with embodiment 11, difference replaces D with 6-caprolactone, L-rac-Lactide; 0.2 mL(0.21 g is added successively in 50 mL polymerization bottles; 1.8 mmol) 6-caprolactone, stannous octoate (32.4 uL; 0.1 mmol); vacuum nitrogen filling gas 15 min; be heated with stirring to 110 DEG C; treat D; after the complete melting of L-rac-Lactide; (c-PNVCL)-OH(0.5 is added fast g), after 100 DEG C of polyreaction 14 h, with a small amount of methylene dichloride solubilizing reaction product under nitrogen protection; elimination insolubles; filtrate through sherwood oil co-precipitation 3 times, vacuum-drying 24 h, obtain linear-Cyclic block copolymer (c-PNVCL)-
b-PCL, productive rate is 62%.The structural formula of target product:
1H NMR (CDCl
3) δ
H(ppm)：1.08～2.01 (CH
3, CH
2), 2.19～2.64 (CH
2C=O), 3.26 (NCH
2), 3.49(OCH
2), 4.16 (OCH
2), 5.07 (OCH
2C=), 5.38 (NCHN), 8.12 (NCH=)。
Claims (4)
1. annular poly-(N-caprolactam), it is characterized in that: a kind of is poly-(N-caprolactam) c-PNVCL of annular, another kind is poly-(N-caprolactam) (the c-PNVCL)-OH of annular with a hydroxyl, and its molecular structure is as follows:
N=20 ~ 200 in formula c-PNVCL and (c-PNVCL)-OH.
2. annular gathers the preparation method of (N-caprolactam) c-PNVCL and poly-(N-caprolactam) (the c-PNVCL)-OH of annular with a hydroxyl as claimed in claim 1, it is characterized in that as follows:
A. be dissolved in methylene dichloride by propiolic alcohol and triethylamine, the volume ratio of propiolic alcohol, triethylamine and methylene dichloride is 1:2.5 ~ 3.0:5 ~ 8; At 0 ~ 5 DEG C with under stirring, drip the dichloromethane solution of 2-chlorpromazine chloride, add the dichloromethane solution of 2-chlorpromazine chloride and the volume ratio of propiolic alcohol and triethylamine solution is 1:2 ~ 2.5, wherein the volume ratio of propiolic alcohol and 2-chlorpromazine chloride is 1:1.5 ~ 2.0; Drip and finish, at 0 ~ 5 DEG C of stirring reaction 30 ~ 60min, stirring at room temperature reaction 10 ~ 16h, filter, filtrate uses saturated NaHCO
3solution divides three wash filtrates, and uses anhydrous magnesium sulfate drying organic phase, filters, steams solvent, is separated crude product and obtains the atom transfer radical polymerization initiator alkynyl-Cl of end with alkynyl;
B. obtained end is with atom transfer radical polymerization initiator alkynyl (-the OH)-Cl of hydroxyl in alkynyl, molecule;
C. obtained 5,5,7,12,12,14-vegolysen, 4,8,11-tetraazacyclododecane tetradecane hydrate Me
6cyclam;
D. in reaction vessel, add N-caprolactam, vacuum nitrogen filling gas repeatedly after, add CuCl, CuCl under nitrogen protection
2, Me
6the mixed solvent of Cyclam, dioxane and Virahol, wherein N-caprolactam, CuCl, CuCl
2and Me
6the mass ratio of Cyclam is 1000 ~ 1030:6 ~ 8:1:20 ~ 23, and the mixed solvent of every ml dioxane and Virahol is dissolved with 1 ~ 4g N-caprolactam, and the volume ratio of dioxane and Virahol is 1:10 ~ 12; Vacuum nitrogen filling gas 30 ~ 60min, add initiator alkynyl-Cl or alkynyl (-OH)-Cl, wherein the mass ratio of initiator and N-caprolactam is 1:1000 ~ 1030,30 ~ 35 DEG C of reaction 1 ~ 3h, product distilled water dissolves, filter, filtrate put into molecular weight cut-off be 3500 dialysis tubing dialysis 5 ~ 8 days, after decompression steams water, vacuum-drying obtains end poly-(N-caprolactam) alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl with alkynyl;
E. sodiumazide is added alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl) dimethyl formamide solution, every ml dimethyl formamide is dissolved with 0.2 ~ 0.5g alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl, sodiumazide and alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl) mass ratio be 1:25 ~ 30, 40 ~ 45 DEG C, stirring reaction 45 ~ 50h, decompression steams dimethyl formamide, after residuum dissolves with tetrahydrofuran (THF), through alumina column chromatography, methylene dichloride is eluent, the sodiumazide that removing is residual, after distillation and concentration, vacuum-drying obtains two ends respectively with poly-(N-caprolactam) alkynyl-PNVCL-N of alkynyl and azido-
3or alkynyl (-OH)-PNVCL-N
3,
F. by alkynyl-PNVCL-N
3or alkynyl (-OH)-PNVCL-N
3be dissolved in distilled water, every ml distilled water is dissolved with 0.01 ~ 0.05g alkynyl-PNVCL-N
3or alkynyl (-OH)-PNVCL-N
3, under stirring at 28 ~ 32 DEG C, add sodium ascorbate and CuSO
45H
2o, added sodium ascorbate, CuSO
45H
2o and alkynyl-PNVCL-N
3or alkynyl (-OH)-PNVCL-N
3mass ratio be 0.1 ~ 0.3:0.05 ~ 0.08:1,28 ~ 33 DEG C of stirring reaction 20 ~ 28h, decompression steams solvent, after residuum dissolves with tetrahydrofuran (THF), be eluent through alumina column chromatography, methylene dichloride, removing copper salt catalyst, after distillation and concentration, poly-(N-caprolactam) c-PNVCL or (c-PNVCL)-OH of the obtained annular of vacuum-drying.
3. preparation method as claimed in claim 2, is characterized in that the atom transfer radical polymerization initiator alkynyl-Cl crude product purified by silica gel column chromatography for separation of the end of gained in step a with alkynyl, sherwood oil: ethyl acetate=50:1.
4. the application of poly-(N-caprolactam) (the c-PNVCL)-OH of the annular containing a hydroxyl, it is characterized in that any one the ring-opening polymerization for causing in glycollide, D-rac-Lactide, L-rac-Lactide, DL-rac-Lactide and 6-caprolactone, the tadpole-shaped segmented copolymer of synthesis containing annular poly-(N-caprolactam).
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|---|---|---|---|---|
| CN102358748A (en) * | 2011-07-15 | 2012-02-22 | 云南师范大学 | Star chain transferring agent using cyclotriphosphazene as nucleus, and preparation method and application thereof |
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| CN102358748A (en) * | 2011-07-15 | 2012-02-22 | 云南师范大学 | Star chain transferring agent using cyclotriphosphazene as nucleus, and preparation method and application thereof |
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| LIDONG SHAO等: ""RAFT polymerization of N-vinylcaprolactam and effects of the end group on the thermal response of poly(N-vinylcaprolactam)"", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
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| CN106750334A (en) * | 2016-12-08 | 2017-05-31 | 云南师范大学 | Amphipathic tadpole-shaped block copolymer and preparation method thereof |
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