CN104558270B - Cyclopoly(N-vinylcaprolactam) as well as preparation method and application thereof - Google Patents

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

Annular is poly-（N- caprolactam）And its preparation method and application

Technical field

The invention belongs to functional high polymer material field is and in particular to a kind of annular is poly-（N- caprolactam）With one Plant the annular with hydroxyl on ring to gather（N- caprolactam）, the ring with hydroxyl on their preparation method and ring Shape is gathered（N- caprolactam）Poly- containing annular in synthesis（N- caprolactam）Annular and Linear block copolymerization Thing（Tadpole-shaped block copolymer）Application in synthesis.

Background technology

Annular polymeric is the special topological structure polymer that a class does not have end group, and the unit on its strand has equivalent Property, compared with corresponding line polymer precursor, annular polymeric has higher density, lower inherent viscosity, less Coefficient of friction, higher glass transition temperature and bigger refraction coefficient, have less hydrodynamics in the solution Radius, and annular high molecular crystallization rate is much larger than the crystallization rate of linear molecule.Line polymer is permissible in vivo Pass through the nanometer micropore of glomerulus by way of " snakelike ", and annular polymeric is difficult to by this side due to its unique structure Formula is passed through, and therefore molecular weight can stop the longer time in blood more than the annular polymeric of renal excretion threshold value, and this is just big Improve greatly its bioavilability, can more effectively be enriched with tumor locus.Due to these distinctive properties, annular polymeric As a kind of new function polymeric material, there is important answering in fields such as biological medicine, material modification and nanosecond science and technology Use prospect.The preparation of annular polymeric mainly has " ring expansion polymerization " and " the intramolecular cyclization of line polymer " two methods, uses " ring expansion polymerization " method prepares annular polymeric, will not form linear accessory substance, but generated time is longer, needs special monomer Or catalyst.It is another master preparing annular polymeric that the intramolecular " from beginning to end " of the line polymer of two ends functionalization connects cyclization Want method, the key of synthesis annular polymeric is so that annulation is efficiently carried out, due to two ends functionalization in this way Line polymer terminal functionality reactivity relatively low, and there is coupling between polymer chain is line polymer Side reaction, therefore reaction must be carried out to reduce the coupling between polymer chain in extremely dilute solution, gathered by this method preparation ring-type Often yield is extremely low for compound, and post-processes and need to remove substantial amounts of solvent, relatively complicated.

Poly-（N- caprolactam）（PNVCL）It is that one kind has amphipathic, non-toxic, biocompatibility, nonionic Characteristic and the polymer of temperature-responsive, its lower critical solution temperature（LCST）In physiological temp（32 DEG C～40 DEG C）In the range of, Different from most polyacrylamide, the hydrolysis of PNVCL does not produce poisonous small molecule amine, and therefore it is in biomedicine field Have broad application prospects；Temperature-responsive polymer -- NIPA with current most study (PNIPAM) single phase ratio, the monomer N-vinyl caprolactam of PNVCL（NVCL）Price is relatively inexpensive.Poly- based on NVCL Compound has larger actual application value, but at present with regard to being focused mostly in line polymer side based on the research of NVCL polymer Face, it is poly- that literature search there are no pass annular（N- caprolactam）（PNVCL）Research report.

Content of the invention

It is an object of the invention to provide annular is poly-（N- caprolactam）, described annular poly-（Acyl in N- vinyl is own Amine）Poly- for annular（N- caprolactam）C-PNVCL, and the annular with a hydroxyl is poly-（Acyl in N- vinyl is own Amine）(c-PNVCL)-OH；The present invention also provides above two annular poly-（N- caprolactam）Preparation method, Yi Jiti Gather for the annular with a hydroxyl（N- caprolactam）Application.

Two kinds of annulars provided by the present invention are gathered（N- caprolactam）, a kind of poly- for annular（Oneself is interior for N- vinyl Acid amides）C-PNVCL, another kind is that the annular with a hydroxyl is gathered（N- caprolactam）(c-PNVCL)-OH, its point Minor 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：

1st, preparation end carries the atom transfer radical polymerization initiator of alkynyl（alkynyl-Cl）：

Propilolic alcohol and triethylamine are dissolved in dichloromethane, the volume ratio of propilolic alcohol, triethylamine and dichloromethane is 1:2.5 ~3.0:5~8；Under 0 ~ 5 DEG C and stirring, the dichloromethane solution of dropping 2- chlorpromazine chloride, the dichloro of added 2- chlorpromazine chloride Dichloromethane is 1 with the volume ratio of propilolic alcohol and triethylamine solution:2 ~ 2.5, the wherein volume ratio of propilolic alcohol and 2- chlorpromazine chloride For 1:1.5~2.0；Drip and finish, in 0 ~ 5 DEG C of stirring reaction 30 ~ 60min, reaction 10 ~ 16 h, the reaction of handy drying are stirred at room temperature Container carries out above-mentioned reaction.Filter, filtrate uses saturation NaHCO₃Solution washs filtrate in three times, and is had with anhydrous magnesium sulfate drying Machine phase, filters, and steams solvent, separates crude product and atom transfer radical polymerization initiator that end carry alkynyl is obtained （alkynyl-Cl）.The most handy silica gel column chromatography of crude product separates（Petroleum ether:Ethyl acetate=50:1）.Alkynyl-Cl's Molecular structure is as follows：

2nd, the atom transfer radical polymerization initiator with hydroxyl in alkynyl, molecule for the preparation end（alkynyl (- OH)-Cl）：

A. press prior art（For example can refer to document Ozcan A, Gurkan H, Umit T.J. Polym. Sci., Part A: Polym. Chem., 2006, 44(19): 5699-5707）, with triethylamine and DMAP for catalysis Agent, with propilolic alcohol and succinic anhydride reaction, prepares 4- oxo -4- (propyl- 2- alkynyloxy group) butyric acid；

B. press prior art（For example can refer to document Zhang Y F, Li C H, Liu S Y. J. Polym. Sci., Part A: Polym. Chem., 2009, 47(12): 3066-3077）, with p-methyl benzenesulfonic acid as catalyst, use 1,1,1- tri-（Methylol）Ethane and 2,2-dimethoxypropane reaction, prepare 2,2- dimethyl -5- ethyl -5- hydroxyl first Base -1,3- dioxane；

C. press prior art（For example can refer to document Zhang Y F, Li C H, Liu S Y. J. Polym. Sci., Part A: Polym. Chem., 2009, 47(12): 3066-3077）, with dicyclohexylcarbodiimide and 4- bis- Methylamino pyridine is catalyst, with 4- oxo -4- (propyl- 2- alkynyloxy group) and 2,2- dimethyl -5- ethyl -5- methylol -1, 3- dioxane reacts, and preparation end carries the ketal compound of alkynyl, then with toluenesulfonic acid as catalyst, end is carried alkynes After the ketal group of the ketal compound of base is hydrolyzed to hydroxyl, then react preparation end with alkynyl, molecule with 2- chlorpromazine chloride The atom transfer radical polymerization initiator of hydroxyl（alkynyl (-OH)-Cl）.The molecular structure of alkynyl (- OH)-Cl As follows：

3rd, preparation end carries the poly- of alkynyl（N- caprolactam）（Alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl）：

A. 5,5,7,12,12,14- vegolysen, 4,8,11- tetraazacyclododecane tetradecane hydrate are prepared （Me₆Cyclam）：Me₆The preparation method of Cyclam is prior art, for example, can refer to document（Hu Minqi, Shao Lidong, Chen Lin Deng. Yunnan chemical, 2009,36 (6): 4-7）, in the presence of hydrobromic acid, with acetone, ethylenediamine as raw material, it is obtained four first Nitrogen heterocyclic ring schiff base compounds, then use NaBH₄Reduction preparation 5,5,7,12,12,14- vegolysen, 4,8, 11- tetraazacyclododecane tetradecane hydrate（Me₆Cyclam）；

B. prepare end and carry the poly- of alkynyl（N- caprolactam）：

Add N- caprolactam in reaction vessel, after vacuum nitrogen gas are multiple, add under nitrogen protection CuCl、CuCl₂, the Me that obtains of step 3a₆Acyl in the mixed solvent of Cyclam, dioxane and isopropanol, wherein N- vinyl are own Amine, CuCl, CuCl₂And Me₆The mass ratio of Cyclam is 1000 ~ 1030:6~8:1:20 ~ 23, every ml dioxane and isopropanol Dissolved with 1 ~ 4g N- caprolactam, the volume ratio of dioxane and isopropanol is 1 to mixed solvent: 10~12；Vacuumize and fill Nitrogen 30 ~ 60 min, adds initiator alkynyl-Cl or alkynyl (- the OH)-Cl that step 1 or step 2 obtain, its Middle initiator is 1 with the mass ratio of N- caprolactam:1000 ~ 1030,30 ~ 35 DEG C of reaction 1 ~ 3 h, product distills Water dissolves, filter, and filtrate is put in the bag filter that molecular cut off is 3500 and dialysed 5 ~ 8 days, after decompression steams water, vacuum drying Obtain the PNVCL that end carries alkynyl（Alkynyl-PNVCL-Cl or alkynyl (- OH)-PNVCL-Cl）.alkynyl- The molecular structure of 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；

4th, preparation two ends respectively carry the poly- of alkynyl and azido（N- caprolactam）（alkynyl-PNVCL-N₃ Or alkynyl (- OH)-PNVCL-N₃）：

The end that sodium azide addition step 3 is obtained carries the PNVCL of alkynyl（Alkynyl-PNVCL-Cl or alkynyl (-OH)-PNVCL-Cl）Dimethyl formamide solution, every ml dimethylformamide is dissolved with 0.2 ~ 0.5 g end band The mass ratio that the PNVCL of alkynyl, sodium azide and end carry the PNVCL of alkynyl is had to be 1:25 ~ 30,40 ~ 45 DEG C of stirring reactions 45 ~ 50h, decompression steams dimethylformamide, after residue is dissolved with oxolane, oxidized aluminium column chromatography（Dichloromethane is Eluant, eluent）Remove the sodium azide of residual, after distillation and concentration, vacuum drying is obtained two ends and respectively carries alkynyl and azido PNVCL（alkynyl-PNVCL-N₃Or alkynyl (- OH)-PNVCL-N₃）.alkynyl-PNVCL-N₃With alkynyl (- OH)-PNVCL-N₃Molecular structure as follows：

alkynyl-PNVCL-N₃alkynyl (-OH)-PNVCL-N₃

Formula alkynyl-PNVCL-N₃With alkynyl (- OH)-PNVCL-N₃Middle n=20 ~ 200；

5th, prepare annular poly-（N- caprolactam）（C-PNVCL and (c-PNVCL)-OH）：

Two ends that step 4 is obtained respectively carry the PNVCL of alkynyl and azido（alkynyl-PNVCL-N₃Or alkynyl (-OH)-PNVCL-N₃）It is dissolved in distilled water, described every ml distilled water carries dissolved with 0.01 ~ 0.05g two end Alkynyl and the PNVCL of azido, under 28 ~ 32 DEG C of stirrings, add sodium ascorbate and CuSO₄·5H₂O, added ascorbic acid Sodium, CuSO₄·5H₂Respectively the mass ratio with alkynyl and the PNVCL of azido is 0.1 ~ 0.3 for O and two ends:0.05~0.08:1, 28 ~ 33 DEG C of stirring reaction 20 ~ 28h, decompression steams solvent, after residue is dissolved with oxolane, oxidized aluminium column chromatography（Dichloro Methane is eluant, eluent）Remove copper salt catalyst, after distillation and concentration, it is poly- that vacuum drying is obtained annular（N- caprolactam） （C-PNVCL or (c-PNVCL)-OH）.

The annular of present invention preparation is gathered（N- caprolactam）Application it is simply that the annular with a hydroxyl is gathered （N- caprolactam）As initiator, cause the ring-opening polymerisation of lactide and caprolactone, synthesis is poly- containing annular（N- ethene Base caprolactam）Annular and shape block copolymer（Tadpole-shaped block copolymer）.

Add lactide or lactone and stannous octoate, described lactide and lactone to be glycolide in reaction vessel, D- lactide, Any one in L- lactide, DL- lactide and 6-caprolactone, the amount of the material of lactide or lactone and stannous octoate is than for 15 ~20:1；Vacuum nitrogen gas 15 ~ 20 min, is heated with stirring to 100 ~ 150 DEG C, and after lactide or lactone melt completely, nitrogen is protected (c-PNVCL)-OH is rapidly joined, (c-PNVCL)-OH is 2 ~ 8 with the mass ratio of lactide or lactone under shield:1；90 ~ 150 DEG C are gathered After closing 5 ~ 16h, dissolve product with a small amount of dichloromethane, filter, filtrate is co-precipitated 3 ~ 5 times through petroleum ether, collect precipitation, very Empty dry 24 ~ 48h, obtains poly- containing annular（N- caprolactam）Annular and shape block copolymer（Tadpole-shaped block Copolymer）.The molecular structure of tadpole-shaped block 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, vacuum distillation, column chromatography, the same routine techniques of operation such as vacuum drying.

In the present invention, prepared annular is gathered（N- caprolactam）（C-PNVCL and (c-PNVCL)-OH）Structure Clearly, all there is narrower molecular weight distribution（PDI<1.2）, can pass through¹HNMR, GPC and MALDI-TOF MS is carried out in detail Thin sign.

Beneficial effects of the present invention：Generally, in order to avoid the generation of intermolecular coupling reaction, respectively carry alkynyl with two ends When cyclization being closed into by intramolecular click-reaction with the line polymer of azido and circularizing polymer, need pole dilute concentration （c≤10^-6mg/mL）Line polymer solution slow（10μL/min）It is added drop-wise in copper catalyst solution, process is loaded down with trivial details, instead Long between seasonable, post processing is difficult, low yield.The present invention is using poly-（N- caprolactam）Have amphipathic, in selectivity In solvent can feature with self assembly as micella, in conjunction with ATRP（ATRP）, click-reaction and supermolecule from Assembling, is successfully realized in higher concentration（10 mg/mL）Under carry out the Intra-molecular condensation of linear precursor polymer, simultaneously Coupling reaction between suppression precursor molecule, not only shortens the reaction time, and can disposably prepare substantial amounts of annular polymerization Thing is it is achieved that annular is poly-（N- caprolactam）The preparation of efficient high yield.The present invention develop with a hydroxyl Annular is poly-（N- caprolactam）(c-PNVCL)-OH can cause the ring-opening polymerisation of lactide and lactone compound, synthesis Annular is poly-（N- caprolactam）Block copolymer with linear polyglycolic acid, PLA or polycaprolactone（Tadpole-shaped Block copolymer）, the Linear block of these tadpole-shaped block copolymers is biodegradable macromolecule, and annular is poly-（N- Caprolactam）Block then has temperature response performance, and therefore these tadpole-shaped block copolymers are in biomedicine field There is potential using value.

Brief description

Fig. 1 is embodiment three and example IV gained alkynyl-PNVCL-N₃Infrared spectrum with c-PNVCL.

Fig. 2 is embodiment three and example IV gained alkynyl-PNVCL-N₃GPC curve with c-PNVCL.

Fig. 3 is embodiment nine and embodiment ten gained alkynyl (- OH)-PNVCL-N₃(c-PNVCL)-OH's is infrared Spectrum.

Fig. 4 is embodiment nine and embodiment ten gained alkynyl (- OH)-PNVCL-N₃(c-PNVCL) GPC of-OH Curve.

Specific embodiment

It is described in further detail the present invention with embodiment below, but present disclosure is not limited thereto.

Embodiment one：

10 mL dichloromethane, propilolic alcohol is sequentially added in the round-bottomed flask of 50 mL（2.0 mL, 33.7 mmol）, three Ethamine（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 be slowly dropped in above-mentioned solution, 0 DEG C stir 30 min, be warmed to room temperature, continue stirring reaction 12 H, filters, and filtrate is washed with saturated sodium bicarbonate solution 3 times, and anhydrous magnesium sulfate is dried, and filters, evaporates solvent, obtain faint yellow Prescribed liquid, separates through silica gel column chromatography（Petroleum ether:Ethyl acetate=50: 1）Obtain the atom transfer with alkynyl for the end freely Base is polymerized（ATRP）Initiator（alkynyl-Cl）, yield 60.3%.

Embodiment two：

NVCL is added in the polymerization pipe of 10 mL（0.6103 g, 4.38 mmol）, after vacuum nitrogen gas are multiple, Nitrogen protection is lower to add CuCl（0.0039 g, 0.040 mmol）、CuCl₂（0.0006 g, 0.004 mmol）、Me₆Cyclam （0.0125 g, 0.044 mmol）With the mixed solvent of 0.2 mL dioxane/isopropanol, continue vacuum nitrogen gas 30 Min, adds alkynyl initiator alkynyl-Cl（0.0006 g, 0.0044 mmol）, 30 DEG C of reaction 2 h, product distilled water Dissolving, is filtered to remove insoluble matter, and filtrate is put into dialysis in the bag filter that molecular cut off is 3500 and concentrated after 6 days, vacuum drying 24 h, obtain the PNVCL that end carries alkynyl（alkynyl-PNVCL-Cl）.

Embodiment three：

8.5 g ends are added to carry the PNVCL of alkynyl in the round-bottomed flask of 100 mL（alkynyl-PNVCL-Cl）, 30 ML DMF, after thing dissolving to be polymerized, adds 0.33g NaN₃, reactant mixture stirs 48 h at 45 DEG C, and decompression boils off DMF, Product is dissolved in THF, oxidized aluminium column chromatography for separation（Dichloromethane is eluant, eluent）, after distillation and concentration, it is vacuum dried 24 h, obtains Two ends respectively carry the poly- of alkynyl and azido（N- caprolactam）（alkynyl-PNVCL-N₃）, yield 93%.

Example IV：

0.4 g two end is added respectively to carry the poly- of alkynyl and azido in the round-bottomed flask of 100 mL（N- vinyl is own Lactams）（alkynyl-PNVCL-N₃）, 40 mL distilled water, be stirred at room temperature and be completely dissolved to PNVCL, be heated to 30 DEG C, then Add 0.05 g sodium ascorbate successively, 0.025 g CuSO₄·5H₂O, after reactant mixture stirs 24 h at 30 DEG C, decompression Distillation, product is dissolved in THF, oxidized aluminium post separation（Dichloromethane is eluant, eluent）, after distillation and concentration, it is vacuum dried 24 h, Obtain annular poly-（N- caprolactam）（c-PNVCL）, yield is 85%.

Embodiment five：

1,4- dioxane, the propilolic alcohol that 100 mL are dried is sequentially added in the round-bottomed flask of 250 mL（4.75 g, 84.7 mmol）, succinic anhydride（10.58 g, 105.7 mmol）, triethylamine（10.7 g, 105.7 mmol）, 4- dimethylamine Yl pyridines（12.9 g, 105.8 mmol）.Reactant mixture reacts 24 h at room temperature, vacuum distillation remove most of Isosorbide-5-Nitrae- Dioxane, uses dichloromethane dissolution residual substance, adds the HCl solution of 1 M to wash 3 times, anhydrous MgSO₄It is dried, filter, evaporate Solvent, obtains 4- oxo -4- through recrystallization after separating（Propyl- 2- alkynyloxy group）Butyric acid, yield is 59%.

Embodiment six：

50 mL acetone, 1,1,1- tri- is sequentially added in the round-bottomed flask of 100 mL（Methylol）Ethane（5 g, 41.6 mmol）, p-methyl benzenesulfonic acid hydrate（0.3 g, 1.6 mmol）, 2,2- dimethoxy propane（8.7 g, 83.2 mmol）.Instead Answer mixture to react 12 h at room temperature, acetone is distilled off, residue is dissolved in ethyl acetate, uses saturation NaHCO₃Solution Washing 3 times, anhydrous MgSO₄It is dried, filter, evaporate solvent, obtain 2,2- dimethyl -5- ethyl -5- methylol -1,3- dioxy six Ring, yield is 67.6%.

Embodiment seven：

The round-bottomed flask of 250 mL sequentially adds 100 mL be dried dichloromethane, 2,2- dimethyl -5- ethyl - 5- methylol -1,3- dioxane（7.8 g, 48.8 mmol）, 4- oxo -4-（Propyl- 2- alkynyloxy group）Butyric acid（7.6 g, 48.7 mmol）, reactant mixture ice bath is cooled to 0 DEG C, is alternately slowly added to dicyclohexylcarbodiimide（10.3 g, 50 mmol）, DMAP（0.6 g, 5 mmol）, stir 1 h at 0 DEG C, be warmed to room temperature, continue stirring reaction 12 h, mistake Filter, evaporates solvent, separates through silica gel column chromatography（Petroleum ether: ethyl acetate=1:2）Obtain 2,2- dimethyl -5- ethyl -5- hydroxyl first Base -1, the acetylenic acid ester of 3- dioxane, yield is 79.8%.

Embodiment eight：

In the round-bottomed flask of 250 mL, add 2,2- dimethyl -5- ethyl -5- methylol -1,3- dioxane Acetylenic acid ester（7g, 22.4 mmol）With 50 ml methyl alcohol, after stirring and dissolving, add 50 mL hydrochloric acid（1 mol/L）, stirring reaction 2 After h, with 2 mol/L sodium hydroxide solutions, pH value is transferred to 7.0, steams methyl alcohol, surplus solution is extracted with ethyl acetate.Organic layer Use anhydrous MgSO₄It is dried, steam ethyl acetate, the crude on silica gel column chromatography for separation obtaining（Petroleum ether: ethyl acetate=1: 1）Obtain the acetylenic acid ester of 2,2- dimethyl -5- ethyl -5- methylol -1,3- glycol（alkynyl (-OH)₂）.Then 250 Alkynyl (- OH) is sequentially added in mL round-bottomed flask₂（3 g, 10.9 mmol）, triethylamine（1.12 g, 11 mmol）With The oxolane that 100 mL are dried, stirring in ice-water bath is cooled to 0 DEG C, 2- chlorpromazine chloride（1.2 mL, 11.3 mmol）'s Dichloromethane solution is slowly dropped in above-mentioned solution, stirs 30 min at 0 DEG C, is warmed to room temperature, and continues stirring reaction 24 h, mistake Filter, filtrate is washed with saturated sodium bicarbonate solution 3 times, and anhydrous magnesium sulfate is dried, and filters, evaporates solvent, divide through silica gel column chromatography From（Petroleum ether: ethyl acetate=2:1）Obtain the ATRP initiator with hydroxyl in alkynyl, molecule for the end（alkynyl (- OH)-Cl）, yield is 65.4%.

Embodiment nine：

Basic with embodiment two, be a difference in that initiator is that end carries alkynyl, the ATRP of hydroxyl causes in molecule Agent alkynyl (- OH)-Cl：8.5 g alkynyl (- OH)-Cl, 30 mL DMF are added in the round-bottomed flask of 100 mL, After thing dissolving to be polymerized, add 0.33g NaN₃, reactant mixture stirs 48 h at 45 DEG C, and decompression boils off DMF, and product is dissolved in In THF, oxidized aluminium column chromatography for separation（Dichloromethane is eluant, eluent）, after distillation and concentration, it is vacuum dried 24 h, obtains two ends each With in alkynyl and azido, molecule hydroxyl poly-（N- caprolactam）（alkynyl-(OH)-PNVCL-N₃）, produce Rate 92%.

Embodiment ten：

Substantially with embodiment three, it is a difference in that reactant is that two ends respectively carry in alkynyl and azido, molecule containing hydroxyl Base poly-（N- caprolactam）（alkynyl-(OH)-PNVCL-N₃）：0.5 g is added in the round-bottomed flask of 100 mL alkynyl-(OH)-PNVCL-N₃, 40 mL distilled water, be stirred at room temperature and be completely dissolved to PNVCL, be heated to 30 DEG C, be subsequently adding 0.06 g sodium ascorbate successively, 0.03 g CuSO₄·5H₂O, after reactant mixture stirs 24 h at 30 DEG C, vacuum distillation, Product is dissolved in THF, oxidized aluminium post separation（Dichloromethane is eluant, eluent）, after distillation and concentration, it is vacuum dried 24 h, must carry The annular of one hydroxyl is gathered（N- caprolactam）（(c-PNVCL)-OH）, yield is 80%.

Embodiment 11：

Sequentially add 0.2 g in 50 mL polymerization bottles（1.4 mmol）D, L- lactide, stannous octoate 22.7 uL （0.07 mmol）, vacuum nitrogen gas 15 min, it is heated with stirring to 130 DEG C, treats D, after L- lactide melts completely, nitrogen is protected (c-PNVCL)-OH is rapidly joined under shield（0.4 g）, after 130 DEG C of polymerisation 5 h, produced with the dissolving reaction of a small amount of dichloromethane Thing, filters off insoluble matter, and filtrate is co-precipitated 3 times through petroleum ether, is vacuum dried 24 h, obtains linear-Cyclic block copolymer (c- PNVCL)-b- PDLLA, yield is 65%.The structural formula of target product：

¹H NMR (CDCl₃) δ_H(ppm)：1.13～2.05 (CH₃, CH₂), 2.20～2.61 (CH₂C=O), 3.29 (NCH₂), 3.51(OCH₂), 4.42 (OCH, OCH₂), 5.03 (OCH₂C=), 5.33 (NCHN), 8.05 (NCH=).

Embodiment 12：

Substantially with embodiment 11, it is a difference in that and replaces D with 6-caprolactone, L- lactide；In 50 mL polymerization bottles Sequentially add 0.2 mL（0.21 g, 1.8 mmol）6-caprolactone, stannous octoate（32.4 uL, 0.1 mmol）, vacuumize and fill Nitrogen 15 min, is heated with stirring to 110 DEG C, treats D, after L- lactide melts completely, rapidly joins (c- under nitrogen protection PNVCL)-OH（0.5 g）, after 100 DEG C of polymerisation 14 h, dissolve product with a small amount of dichloromethane, filter off insoluble matter, filter Liquid through petroleum ether be co-precipitated 3 times, be vacuum dried 24 h, obtain linear-Cyclic block copolymer (c-PNVCL)-b- PCL, yield is 62%.The structural formula of target product：

¹H NMR (CDCl₃) δ_H(ppm)：1.08～2.01 (CH₃, CH₂), 2.19～2.64 (CH₂C=O), 3.26 (NCH₂), 3.49(OCH₂), 4.16 (OCH₂), 5.07 (OCH₂C=), 5.38 (NCHN), 8.12 (NCH=).

Claims (4)

1. annular poly- (N- caprolactam) it is characterised in that：A kind of is annular poly- (N- caprolactam) c- PNVCL, another kind is annular poly- (N- caprolactam) (the c-PNVCL)-OH with a hydroxyl, and its molecular structure is such as Under：

N=20～200 in formula c-PNVCL and (c-PNVCL)-OH.

2. poly- (N- caprolactam) c-PNVCL of annular as claimed in claim 1 and the annular with a hydroxyl are gathered The preparation method of (N- caprolactam) (c-PNVCL)-OH is it is characterised in that as follows：

A. propilolic alcohol and triethylamine are dissolved in dichloromethane, the volume ratio of propilolic alcohol, triethylamine and dichloromethane is 1:2.5～ 3.0:5～8；Under 0～5 DEG C and stirring, the dichloromethane solution of dropping 2- chlorpromazine chloride, the dichloro of added 2- chlorpromazine chloride Dichloromethane is 1 with the volume ratio of propilolic alcohol and triethylamine solution:2～2.5, the wherein volume ratio of propilolic alcohol and 2- chlorpromazine chloride For 1:1.5～2.0；Drip and finish, in 0～5 DEG C of stirring reaction 30～60min, reaction 10～16h is stirred at room temperature, filter, filtrate is with satisfying And NaHCO₃Solution washs filtrate in three times, and organic phase is dried with anhydrous magnesium sulfate, filters, and steams solvent, separates crude product Prepared end carries the atom transfer radical polymerization initiator alkynyl-Cl of alkynyl；

B. end atom transfer radical polymerization initiator alkynyl (- OH)-Cl with alkynyl, molecule hydroxyl is obtained；

C. 5,5,7,12,12,14- vegolysen, 4,8,11- tetraazacyclododecane tetradecane hydrate Me are obtained₆Cyclam；

D. add N- caprolactam in reaction vessel, after vacuum nitrogen gas are multiple, add under nitrogen protection CuCl、CuCl₂、Me₆The mixed solvent of Cyclam, dioxane and isopropanol, wherein N- caprolactam, CuCl, CuCl₂And Me₆The mass ratio of Cyclam is 1000～1030:6～8:1:20～23, the mixing of every ml dioxane and isopropanol Dissolved with 1～4g N- caprolactam, the volume ratio of dioxane and isopropanol is 1 to solvent:10～12；Vacuum nitrogen filling Gas 30～60min, adds initiator alkynyl-Cl or alkynyl (- OH)-Cl, and wherein initiator is own with N- vinyl interior The mass ratio of acid amides is 1:1000～1030,30～35 DEG C of reaction 1～3h, product distillation water dissolves, filter, filtrate is put into and cut Stay in the bag filter that molecular weight is 3500 and dialyse 5～8 days, after decompression steams water, vacuum drying is obtained end and carries the poly- of alkynyl (N- caprolactam) alkynyl-PNVCL-Cl or alkynyl (- OH)-PNVCL-Cl；

E. sodium azide is added the dimethylformamide of alkynyl-PNVCL-Cl or alkynyl (- OH)-PNVCL-Cl molten Liquid, every ml dimethylformamide, dissolved with 0.2～0.5g alkynyl-PNVCL-Cl or alkynyl (- OH)-PNVCL-Cl, is folded The mass ratio of sodium nitride and alkynyl-PNVCL-Cl or alkynyl (- OH)-PNVCL-Cl is 1:25～30,40～45 DEG C, Stirring reaction 45～50h, decompression steams dimethylformamide, residue with after oxolane dissolving, oxidized aluminium column chromatography, two Chloromethanes is eluant, eluent, removes the sodium azide remaining, and after distillation and concentration, vacuum drying is obtained two ends and respectively carries alkynyl and fold Poly- (N- caprolactam) alkynyl-PNVCL-N of nitrogen base₃Or alkynyl (- OH)-PNVCL-N₃；

F. by alkynyl-PNVCL-N₃Or alkynyl (- OH)-PNVCL-N₃Be dissolved in distilled water, every ml distilled water dissolved with 0.01～0.05g alkynyl-PNVCL-N₃Or alkynyl (- OH)-PNVCL-N₃, under 28～32 DEG C of stirrings, add anti- Bad hematic acid sodium and CuSO₄·5H₂O, added sodium ascorbate, CuSO₄·5H₂O and alkynyl-PNVCL-N₃Or alkynyl (- OH)-PNVCL-N₃Mass ratio be 0.1～0.3:0.05～0.08:1,28～33 DEG C of stirring reaction 20～28h, decompression steams Solvent, residue is with, after oxolane dissolving, oxidized aluminium column chromatography, dichloromethane are eluant, eluent, remove copper salt catalyst, steam After evaporating concentration, vacuum drying is obtained poly- (N- caprolactam) c-PNVCL or (c-PNVCL)-OH of annular.

3. preparation method as claimed in claim 2 it is characterised in that in step a gained end carry alkynyl atom transfer Radical polymerization initiator alkynyl-Cl crude product purified by silica gel column chromatography for separation, petroleum ether:Ethyl acetate=50:1.

4. the application of the annular containing a hydroxyl poly- (N- caprolactam) (c-PNVCL)-OH is it is characterised in that be used for Cause the ring-opening polymerisation of any one in glycolide, D- lactide, L- lactide, DL- lactide and 6-caprolactone, synthesis contains There is the tadpole-shaped block copolymer of annular poly- (N- caprolactam).