WO2023072242A1 - 制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用 - Google Patents

制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用 Download PDF

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WO2023072242A1
WO2023072242A1 PCT/CN2022/128226 CN2022128226W WO2023072242A1 WO 2023072242 A1 WO2023072242 A1 WO 2023072242A1 CN 2022128226 W CN2022128226 W CN 2022128226W WO 2023072242 A1 WO2023072242 A1 WO 2023072242A1
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polycaprolactone
polyrotaxane
shape memory
group
memory material
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French (fr)
Inventor
贾凤
陈琛
史乐萌
高若梅
吴钊
姚卫舟
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Priority to EP22886117.5A priority Critical patent/EP4410863A4/en
Priority to JP2024525419A priority patent/JP2024540110A/ja
Priority to US18/704,364 priority patent/US20250320333A1/en
Publication of WO2023072242A1 publication Critical patent/WO2023072242A1/zh
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Definitions

  • the invention relates to the field of polycaprolactone shape memory materials, in particular to a composition for preparing polycaprolactone shape memory materials, polycaprolactone shape memory materials and their preparation methods and applications.
  • Shape memory materials can be endowed with a certain shape (initial state) under certain conditions.
  • external conditions change, for example, after certain heat, light, electricity, chemical treatment and other stimuli are applied, it can change its shape accordingly and It is fixed (temporary shape), and if the external environment changes again in a specific way and regularity, it will reversibly return to the original state of a class of materials.
  • Shape memory polymers (SMPs) as one of the shape memory materials, have good shape change (up to 1000% recoverable deformation), low density, low The advantages of cost, structural designability, and controllability of deformation recovery behavior have a wide range of applications in biomedicine, aerospace industry, automotive, and robotics industries.
  • shape memory material Once the shape memory material is formed, its permanent shape cannot be changed, and it cannot be processed again, which limits its application range in various fields.
  • Polycaprolactone shape memory materials are often used as biomedical materials due to their excellent biodegradability and biocompatibility, but due to their inhomogeneous cross-linked network and lack of reprocessability, the shape recovery rate of the material is limited. Slow, low error tolerance when used for disposable medical supplies.
  • the purpose of the present invention is to provide a composition and polymer for preparing polycaprolactone shape memory materials in order to overcome the existing problems of polycaprolactone shape memory materials in toughness, complex shape design and solid state remodelability. Caprolactone shape memory material and its preparation method and application.
  • the first aspect of the present invention provides a polycaprolactone shape memory material, wherein the material comprises: a plurality of modified polyrotaxane macromolecular chains, and a plurality of modified polyrotaxane macromolecular chains with different connections Composite macromolecular chains of alkane macromolecular chains; wherein, each of the composite macromolecular chains comprises at least two polycaprolactone macromolecular chains, reversible linking groups between different polycaprolactone macromolecular chains , and a linking modifying group that connects the polycaprolactone macromolecular chain with the cyclodextrin ring structure contained in the modified polyrotaxane macromolecular chain, wherein the reversible linking group is photoreversible linking group or thermoreversible linking group.
  • the second aspect of the present invention provides a composition for preparing the polycaprolactone shape memory material of the present invention, wherein the composition comprises: a polyrotaxane initiator, an end group modifier, ⁇ -caprolactone, Catalyst and cross-linking agent; Wherein, the end group modifier is selected from nitrocinnamic acid compounds and/or 4-((4-methyl-2-oxo-2H-chromen-7-yl) oxygen base) butyric acid.
  • the third aspect of the present invention provides a method for preparing a polycaprolactone shape memory material, wherein the method includes:
  • the fourth aspect of the present invention provides a polycaprolactone shape memory material prepared by the method of the present invention.
  • the fifth aspect of the present invention provides an application of the polycaprolactone shape memory material of the present invention in a medical recoverable fixation material.
  • the present invention prepares polycaprolactone macromolecular chain (PCL) with slidability by ring-opening polymerization by modifying polyrotaxane as an initiator; then, the terminal group part of PCL is modified as The photoreversible groups are then cross-linked to form a cross-linked structure, and the polycaprolactone shape memory material of the present application is obtained.
  • PCL polycaprolactone macromolecular chain
  • the topological defect of the polymer network is adjusted to improve the toughness of the shape memory material.
  • the introduced dynamic covalent bond can realize complex shape designability and solid-state remodelability of shape memory materials.
  • Fig. 1 is polyethylene glycol diamine and ⁇ -cyclodextrin in embodiment 1, and the NMR contrast figure of the prepared polyrotaxane;
  • Fig. 1 (a) is the structural representation of ⁇ -cyclodextrin and 1 H-NMR spectrogram
  • Fig. 1 (b) is the structural representation and 1 H-NMR spectrogram of polyethylene glycol diamine
  • Fig. 1 (c) is the structural representation and 1 H of the polyrotaxane prepared in Example 1 - NMR spectrum;
  • Fig. 2 is the GPC comparison diagram of polyethylene glycol diamine and ⁇ -cyclodextrin and the prepared polyrotaxane in Example 1;
  • Fig. 3 is the 1 H-NMR chart of the hydroxypropylated polyrotaxane prepared in Example 1;
  • Fig. 4 is the infrared comparison diagram of polyrotaxane, hydroxypropylated polyrotaxane and polycaprolactone grafted polyrotaxane copolymer prepared in Example 1;
  • Fig. 5 is the 1 H-NMR figure of the polycaprolactone grafted polyrotaxane copolymer prepared in embodiment 1;
  • FIG. 6 is a schematic diagram of a cross-linked structure network of a polycaprolactone shape memory material
  • Fig. 7 is a demonstration diagram of the shape remodeling process of the polycaprolactone shape memory material provided by the present invention.
  • the first aspect of the present invention provides a polycaprolactone shape memory material, wherein the material comprises: a plurality of modified polyrotaxane macromolecular chains, and a plurality of modified polyrotaxane macromolecular chains connected to different Composite macromolecular chains; wherein, each of the composite macromolecular chains comprises at least two polycaprolactone macromolecular chains, reversible linking groups between different polycaprolactone macromolecular chains, and connecting the
  • the polycaprolactone macromolecular chain and the modified polyrotaxane macromolecular chain contain a linking modification group from the ring structure of cyclodextrin, wherein the reversible linking group is a photoreversible linking group or a thermal Reversible linking group.
  • the polycaprolactone shape memory material provided by the present invention has a structure as shown in FIG. 6 .
  • the photoreversible linking group comes from a compound with a photoreversible group, and preferably the compound is selected from nitrocinnamic acid compounds and/or 4-((4-methyl -2-oxo-2H-chromen-7-yl)oxy)butanoic acid.
  • the nitrocinnamic acid compound can be a compound shown in the following formula: Among them, R' is a substituent substituting at least one of the positions marked with numbers 1-5 on the benzene ring, and R' is the structure shown in the following formula Among them, R"" and R"' are each independently selected from H or C 1 -C 6 straight or branched chain alkyl, * indicates the point of connection with the benzene ring; R" is a substituent with a number on the benzene ring A substituent at at least one position in 1-5 except the R' substitution position, R" is H or a C 1 -C 6 linear or branched chain alkyl group, preferably, the nitrocinnamic acid compound is Compound shown in the following formula: Among them, R 1# , R 2# and R 3# are each independently selected from H or C 1 -C 6 linear or branched chain alkyl, and the substitution position of R1# is marked with the number 1'-4 on the
  • the formed photoreversible linking group can have the following schematic structure:
  • the photoreversible process can be shown as follows:
  • R 1 and R 2 represent different polycaprolactone macromolecular chains connected with different modified polyrotaxanes.
  • the thermally reversible linking group is derived from a diisocyanate, preferably the diisocyanate is selected from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, lysine at least one of diisocyanates.
  • the formed reversible linking group can have the following schematic structure: Taking hexamethylene diisocyanate as an example, the thermally reversible process can be shown as follows:
  • R 1 , R 2 , R 3 and R 4 represent different polycaprolactone macromolecular chains connected with different modified polyrotaxanes, R represents the main group of diisocyanate (except two isocyanate groups Structure).
  • the link modification group is from a compound used for hydroxypropylation.
  • it can be a polycaprolactone macromolecule formed by the ring-opening polymerization of the modified group formed after the cyclodextrin ring structure contained in the polyrotaxane macromolecular chain reacts with propylene oxide to initiate ring-opening polymerization. chain structure. It is preferably a group represented by the structural formula -CH 2 -CH(CH 3 )-O-.
  • the total amount of the polycaprolactone macromolecular chains is 80-100wt%, preferably 95-99.9wt% .
  • the polycaprolactone macromolecular chain has a weight average molecular weight of 5000-100000 kDa, preferably 10000-80000 kDa.
  • the weight average molecular weight of the modified polyrotaxane macromolecular chain is 10kDa-100kDa, preferably 30kDa-90kDa.
  • the polycaprolactone shape memory material has improved toughness, large tensile deformation, good recovery performance, and can reshape the shape.
  • the polycaprolactone shape memory material has an elongation at break of more than 900%
  • the gel content of the polycaprolactone shape memory material is 37-78wt%
  • the polycaprolactone shape memory material The time to return to the original shape under 100% strain is not more than 5s.
  • the above-mentioned structure of the polycaprolactone shape memory material can be analyzed by combining Raman spectroscopy, gel content measurement, GPC, Fourier transform infrared spectroscopy and 1 H NMR, or by combining the synthetic methods.
  • the reaction and feeding of the material preparation process are determined, and the reversible change process of the reversible linking group can be determined.
  • the above physical and chemical properties of the polycaprolactone shape memory material can be determined by measuring the elongation at break, the gel content by Soxhlet extraction, and the shape recovery rate and shape recovery rate by heating and stretching the plate.
  • the second aspect of the present invention provides a composition for preparing the polycaprolactone shape memory material of the present invention, wherein the composition comprises: a polyrotaxane initiator, an end group modifier, ⁇ -caprolactone, Catalyst and cross-linking agent; Wherein, the end group modifier is selected from nitrocinnamic acid compounds and/or 4-((4-methyl-2-oxo-2H-chromen-7-yl) oxygen base) butyric acid.
  • the present invention provides the above composition, which contains polyrotaxane as an initiator to initiate ring-opening polymerization of ⁇ -caprolactone to have slidable polycaprolactone molecular chains.
  • the end group modifier can be used to modify part of the end groups of polycaprolactone into photoreversible groups, providing a method of changing the crosslinking method to reversible bonding, and overcoming the existing toughness, Problems of designability and reshapeability.
  • the polyrotaxane initiator has a weight average molecular weight of 10 kDa-100 kDa, preferably 30 kDa-90 kDa. It can be commercially purchased or homemade. Just meet the above requirements.
  • the catalyst is at least one selected from stannous octoate, lithium diisopropylamide, scandium trifluoromethanesulfonate, and phosphazene base (BEMP).
  • the crosslinking agent is selected from diisocyanate, preferably at least one selected from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and lysine diisocyanate kind.
  • diisocyanate preferably at least one selected from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and lysine diisocyanate kind.
  • Different polycaprolactone macromolecular chains formed by ring-opening polymerization of ⁇ -caprolactone can be provided to connect.
  • the photoreversible group may be a cinnamic acid group or a coumarin group
  • a nitrocinnamic acid compound may be a compound having the aforementioned structure, which will not be repeated here, and a cinnamic acid group may be provided 4-((4-methyl-2-oxo-2H-chromen-7-yl)oxy)butanoic acid can donate a coumarin group.
  • the structural formula of 4-((4-methyl-2-oxo-2H-chromen-7-yl)oxy)butanoic acid is shown below:
  • the photoreversible group can modify one end of the polycaprolactone macromolecular chain formed by ring-opening polymerization of ⁇ -caprolactone, and then the photoreversible group in different polycaprolactone macromolecular chains
  • the formed structure can be reversibly broken or bonded under different wavelengths of ultraviolet light, and the obtained polycaprolactone shape memory material has designability and solid-state remodelability.
  • the composition preferably, based on the total weight of the composition, contains 0.01-0.1 wt% of the polyrotaxyl initiator, 99.99-99 wt% of ⁇ -caprolactone, 0.5-2wt% of the catalyst, 0.02-0.05wt% of the terminal modifier and 0.1-1wt% of the crosslinking agent.
  • the third aspect of the present invention provides a method for preparing a polycaprolactone shape memory material, wherein the method includes:
  • the hydroxypropylation process includes: dissolving the polyrotaxane in an alkaline solution, and reacting with a hydroxylating agent, and the obtained product is Purifying wash.
  • the hydroxylating agent may be propylene oxide.
  • the catalyst is at least one selected from stannous octoate, lithium diisopropylamide, scandium trifluoromethanesulfonate, and phosphazene base.
  • the catalyst is used in an amount of 0.5-2 wt%, preferably 0.8-1.2 wt%, of the total mass of the hydroxypropylated polyrotaxane and ⁇ -caprolactone.
  • the molar ratio of the hydroxypropylated polyrotaxane to ⁇ -caprolactone is 1:50- 600, preferably 1:50-1:200.
  • the number of active hydroxyl groups is determined by the ratio of the integral area at the chemical shift of 1.1 ppm on the H NMR spectrum to the integral area of cyclodextrin.
  • the ring-opening polymerization temperature is 100-140°C, preferably 110-130°C, and the ring-opening polymerization time is 40-50h, preferably 45-50h.
  • the process of the ring-opening polymerization comprises: polymerizing the mixture of the hydroxypropylated polyrotaxane, ⁇ -caprolactone and the catalyst under the protection of nitrogen; The initial product is dissolved in tetrahydrofuran, and then precipitated in n-hexane several times, and the obtained solid phase precipitate is dried to obtain the polycaprolactone grafted polyrotaxane copolymer.
  • the molar ratio of the terminal modifier to the polycaprolactone-grafted polyrotaxane copolymer is 100-400:1.
  • the terminal group modifier has a compound with a photoreversible group, preferably selected from nitrocinnamic acid compounds and/or 4-((4-methyl-2-oxo -2H-chromen-7-yl)oxy)butanoic acid. Specific compounds are as described above.
  • the temperature of the end group modification reaction is 40-60° C., and the time of the end group modification reaction is 15-25 h.
  • the process of the terminal modification reaction includes: preparing the terminal modification agent and the polycaprolactone-grafted polyrotaxane copolymer in a first organic solvent respectively The resulting solution is mixed, and the obtained mixed solution is added to the water absorbing agent-I and the esterification catalyst to carry out the terminal group modification reaction; the obtained initial product is subjected to multiple precipitation, and the obtained solid precipitate is dried to obtain the polymer Network precursor.
  • the first organic solvent is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, dichloromethane, and dioxane;
  • the water-absorbing agent-I is selected from At least one of N,N-diisopropylcarbodiimide, dicyclohexylcarbodiimide, and concentrated sulfuric acid;
  • the esterification catalyst is selected from 4-dimethylaminopyridine, p-toluenesulfonic acid , at least one of thionyl chloride.
  • the amount of the first organic solvent is such that the concentration of the mixed solution is 1-10 g/mL, preferably 2-8 g/mL. That is, the total content of the terminal modifier and the polycaprolactone-grafted polyrotaxane copolymer contained in the mixed solution.
  • the amount of the water absorbing agent-I is 1-5 wt% of the total amount of the terminal modifier and the polycaprolactone-grafted polyrotaxane copolymer, preferably 1.5-4.5 wt%.
  • the molar ratio of the esterification catalyst to the polycaprolactone-grafted polyrotaxane copolymer is 1:1.5-3.5, preferably 1:2-3.
  • the photoreversible group comes from a terminal modifier, which can be a cinnamic acid group or a coumarin group.
  • the polymer network precursor has a plurality of slidable polycaprolactone molecular chains, and the chain ends of some of the polycaprolactone molecular chains contain photoreversible groups from the end group modifier .
  • part of the chain ends of the polycaprolactone molecular chains contain hydroxyl groups and cinnamic acid groups.
  • the crosslinking agent is selected from diisocyanate, preferably selected from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, lysine at least one of diisocyanates.
  • the modification reaction described in step (3) may not be complete, and not all end groups of the polycaprolactone macromolecular chains in the polycaprolactone grafted polyrotaxane copolymer are all modified into photoreversible groups group, that is, the polymer network precursor may also contain unmodified hydroxyl end groups of the polycaprolactone macromolecular chain, so the diisocyanate provided by the crosslinking agent can be used to achieve thermally reversible connection. macromolecular chain of polycaprolactone. At the same time, reconnection can be achieved through transesterification, which is equivalent to the exchange connection of the same polycaprolactone macromolecular chain with different polycaprolactone macromolecular chains.
  • the crosslinking agent is used in an amount of 0.1-1 wt% of the polymer network precursor.
  • the heating temperature is 70-90° C., and the heating time is 45-60 h.
  • the wavelength of the ultraviolet light is 250-380 nm.
  • the crosslinking process includes: dissolving the polymer network precursor in a second organic solvent, and then adding the butyl acetate solution of the crosslinking agent and crosslinking catalyst , to obtain a liquid mixture; heat and dry the liquid mixture, and then irradiate it under the ultraviolet light to obtain the polycaprolactone shape memory material.
  • the second organic solvent is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, dichloromethane, and dioxane;
  • the crosslinking catalyst is selected from At least one of dibutyltin dilaurate, organic bismuth catalyst, and N,N-dimethylcyclohexylamine.
  • the amount of the second organic solvent is such that the concentration of the liquid mixture is 1-10 g/mL, preferably 2-8 g/mL. That is, the total content of the polymer network precursor, the crosslinking agent and the crosslinking catalyst in the liquid mixture.
  • the amount of the cross-linking catalyst is 1-5 wt%, preferably 2-4 wt%, of the polymer network precursor.
  • the polyrotaxane can be self-made.
  • the polyrotaxane is prepared by the following method: reacting ⁇ -cyclodextrin and polyethylene glycol diamine in the presence of a large steric hindrance compound.
  • the large steric hindrance compound is selected from N-benzyloxycarbonyl-L-tyrosine, 1-adamantaneacetic acid, fluorescein isothiocyanate, L-phenylalanine at least one of the
  • the polyethylene glycol diamine has a weight average molecular weight of 5 kDa-40 kDa, preferably 10 kDa-35 kDa.
  • the molar ratio of ⁇ -cyclodextrin to the polyethylene glycol diamine is 50-100:1, preferably 80-90:1.
  • the molar ratio of the bulky hindered compound to the polyethylene glycol diamine is 2-10:1, preferably 5-8:1.
  • the process of the reaction includes:
  • the amidation catalyst is selected from at least one of Carter's condensation reagent, zinc chloride, and ferric chloride hexahydrate;
  • the water-absorbing agent-II is selected from N,N-di At least one of isopropylethylamine, 1-hydroxybenzotriazole, and dicyclohexylcarbodiimide;
  • the third organic solvent is selected from N,N-dimethylformamide, tetrahydrofuran, dichloromethane at least one of the
  • the amount of the amidation catalyst is 1-5wt%, preferably 2-4wt%, of the total amount of polyethylene glycol diamine and ⁇ -cyclodextrin;
  • the amount of agent-II is 1-5wt% of the total amount of polyethylene glycol diamine and ⁇ -cyclodextrin, preferably 2-4wt%;
  • the amount of the third organic solvent is such that the concentration of the solution is 1-10g/mL, preferably 2-8g/mL. That is, in the solution, the total content of the bulky hindered compound, amidation catalyst, and water-absorbing agent-II.
  • the polyrotaxane has a weight average molecular weight of 10-100 kDa, preferably 30-90 kDa.
  • the fourth aspect of the present invention provides a polycaprolactone shape memory material prepared by the method of the present invention.
  • the polycaprolactone shape memory material has a polycaprolactone molecular chain that can slide on the polyethylene glycol molecular chain, and can return to more than 95% of its original shape within 5s.
  • Shape It has a cross-linked structure, and the node part of the cross-linked structure has a photoreversible dynamic covalent bond, which can break the covalent bond under the irradiation of 256nm ultraviolet light, so that the material has the ability to reshape the original shape in the solid state.
  • the demonstration of the shape remodeling process of the polycaprolactone shape memory material is shown in FIG. 7 .
  • the polycaprolactone shape memory material has an elongation at break of more than 900%, the gel content of the polycaprolactone shape memory material is 37-78wt%, and the polycaprolactone shape memory material is 100%
  • the time to return to the original shape under the strain is not more than 5s.
  • the fifth aspect of the present invention provides an application of the polycaprolactone shape memory material of the present invention in a medical recoverable fixation material.
  • applications may include shape memory medical splints.
  • the present invention will be described in detail below by way of examples.
  • the 1 H-NMR spectra were measured by Bruker ARX-500 from Bruker, Switzerland, with a resolution of ⁇ 0.2 Hz and a sensitivity of >100.
  • the GPC spectrum was measured by a three-detection size-exclusion chromatography (TD-SEC) of Waters Corporation in the United States.
  • TD-SEC three-detection size-exclusion chromatography
  • PDI molecular weight and molecular weight distribution
  • the Fourier transform infrared spectrum was measured by Avatar 370 from Nicolet Company of the United States.
  • the test was prepared by KBr pellets, in transmission mode, and the scanning range was 500-4000cm -1 with a resolution of 2cm -1 .
  • the gel content was determined by Soxhlet extraction method, extracted with chloroform for 24 hours and obtained by weighing the samples before and after.
  • the shape recovery rate and shape recovery rate are measured by the method of heating and stretching the sheet, using the Q800 universal testing machine of TA Instrument in the United States.
  • the prepared PCL sample was prepared into a dumbbell-shaped sample with a standard 4 ⁇ 25 cutting knife, and the mechanical properties were tested using an electronic universal testing machine at a tensile rate of 20 mm/min and a preload of 0.5 N, and then calculated by the following formula elongation at break and tensile strength of the samples. Before the test, take two centimeters in the middle of the sample and draw a line with a marker, then use a standard vernier caliper to measure the thickness of the film three times equidistantly at the marked line, then calculate the average value, and record the average thickness of the sample.
  • L 1 is the length of the sample when it breaks
  • L 0 is the initial length of the sample
  • F max is the maximum tensile force during the stretching process
  • A is the initial cross-sectional area of the sample.
  • Step 1 Weigh 5.3 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 10 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • N-benzyloxycarbonyl-L-tyrosine ZL-Tyr
  • BOP Carter condensation reagent
  • HOBt 1-hydroxybenzotriazole
  • DIEA N,N-di Dissolve isopropylethylamine
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 50° C. for 20 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried in vacuum at 80°C overnight, and finally placed in a UV box at 365nm with four powers of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 12 hours.
  • Figure 1 is a comparison of the 1 H-NMR spectra of the prepared PR and PEG (polyethylene glycol) and ⁇ -CD: (a) the peak at the chemical shift of 3.28ppm is the proton peak on the carbon marked 2 ; the peak at chemical shift 3.5-3.7ppm corresponds to the proton peak on the carbons labeled 4, 5 and 6; the peak at chemical shift 3.76ppm corresponds to the proton peak on the carbon labeled 3; the chemical shift is 4.51ppm
  • the peak at the position is the proton peak of the hydroxyl group on the carbon marked 6; the peak at the chemical shift of 4.80ppm is the proton peak at the carbon marked 1; the peak at the chemical shift at 5.45 ppm is the proton peak of the hydroxyl group at the carbon marked 3
  • the peak at the chemical shift of 5.54ppm is the proton peak of the hydroxyl group on the carbon of label 2.
  • the peak at 2.04ppm in chemical shift is the proton peak on the amine groups at both ends of PEG-NH 2 ; the peak at 3.58ppm in chemical shift (mark i) is PEG-NH 2 methylene proton peak on the .
  • the peak at the chemical shift of 3.51ppm is the proton peak of methylene on PEG; the peak at the chemical shift of 4.4-5.7ppm is the proton peak of ⁇ -CD.
  • Figure 2 is the GPC comparison chart of the prepared PR and PEG-NH 2 and ⁇ -CD. From the respective retention times, it can be seen that the molecular weight of PR is significantly larger than that of PEG-NH 2 , and there is no small molecule component; combined with Figure 1 The NMR data showed that the ⁇ -CD found in the NMR image was successfully worn on the PEG molecular chain, and PR was successfully synthesized.
  • Figure 3 is the prepared HP-PR NMR spectrum after hydroxypropyl modification, which is almost the same as the NMR of PR at a position above 2.0ppm, while the chemical shift of HP-PR is 1.0ppm (marked k) is obvious There is an extra methyl proton peak, indicating that the ⁇ -CD on PR has been successfully modified by hydroxypropyl.
  • the peaks at 4.2-6.0ppm and 1.0ppm were integrated, and the hydroxypropyl modification rate DS of PR was calculated to be 6 based on the area integration ratio of the peaks at 4.2-6.0ppm and 1.0ppm.
  • Figure 4 is the infrared comparison chart of the prepared PR, HP-PR and PCL-g-PR, the absorption peak at 3436cm -1 in the figure and the absorption peak at 3400cm -1 in PR and HP-PR are attributed to -OH Stretching vibration of -NH on -OH and -NH-; the absorption peak at 2946 cm -1 in PCL-g-PR and the absorption peak at 2923 cm -1 in PR and HP-PR are attributed to -CH 2 -on
  • the asymmetric stretching vibration of -CH, and the absorption peak at 2866cm -1 in PCL-g-PR is attributed to the symmetric stretching vibration of -CH on -CH 2 -; the absorption peak at 1725cm -1 in PCL-g-PR
  • Figure 5 is the NMR spectrum of the prepared PCL-g-PR, the chemical shift is that the peak at 1.32ppm (marked d) corresponds to the proton peak on the middlemost methylene group on the caprolactone segment; the chemical shift is 1.58
  • the peak at ppm (marked c) corresponds to the proton peak on the methylene adjacent to the middle carbon atom in the caprolactone segment; the peak at chemical shift 2.24 ppm (marked b) corresponds to the caprolactone segment
  • the proton peak on the ortho-carbon of the carbonyl group; the peak at the chemical shift of 3.99ppm (marked a) corresponds to the proton peak on the ortho-carbon of the oxygen atom in the caprolactone chain segment; there is a suspected PEG subgroup at the chemical shift of 3.58ppm
  • the very weak characteristic peak of the methyl group may be due to the shielding of the methylene proton peak signal on the PEG chain due to the growth of the PCL segment of the PCL-g-
  • FIG. 6 takes the polycaprolactone shape memory material obtained in Example 1 as an example, illustrating the cross-linked network structure of the material.
  • the polyethylene glycol macromolecular chain has a large steric hindrance group (from N-benzyloxycarbonyl-L-tyrosine) that is shown as a dot, passing through the polycaprolactone macromolecular chain.
  • ⁇ -cyclodextrin shown as a ring, forms a cross-linked network structure of polyethylene glycol macromolecular chains and polycaprolactone macromolecular chains, and, through the ring structure provided by ⁇ -cyclodextrin, polycaprolactone Macromolecular chains can slide on polyethylene glycol macromolecular chains.
  • polycaprolactone there are also reversible linking groups that provide reversible covalent bonds as squares, formed by photoreversible groups provided by end group modifiers or thermally reversible groups provided by crosslinking agents, It can introduce dynamic covalent bonds into polycaprolactone shape memory materials, realize reversible bonding, and realize complex shape designability and solid-state remodelability of shape memory materials.
  • Step 1 Weigh 6.4 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 15 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). Stirring at 30°C for 30 hours resulted in a white precipitate, which was then freeze-dried in a lyophilizer for 48 hours to obtain the clathrate.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 40min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 55°C for 22h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated in ether for 3 times, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried in vacuo at 80°C overnight, and finally placed in a UV box with four 370nm lamps with a power of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 14 hours.
  • Step 1 Weigh 8.0 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 20 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with HP-PR active hydroxyl number, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 45° C. for 15 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried under vacuum at 80°C overnight, and finally placed in a UV box with four 380nm beams with a power of 5W
  • the polycaprolactone shape memory material was obtained by irradiating for 10 h under an ultraviolet lamp.
  • Step 1 Weigh 5.3 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 20 kDa, and add it to a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 60° C. for 15 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by a silicone rubber gasket, placed in an oven at 80°C for 48h, then dried in vacuum at 80°C overnight, and finally placed in a UV box at 375nm with 4 powers of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 13 hours.
  • Step 1 Weigh 5.7 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 20 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at 30°C for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 50 hours to obtain the clathrate.
  • ⁇ -cyclodextrin 7.25 g/50 mL, double distilled H 2 O
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 40° C. for 25 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated in ether for 3 times, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes .
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried in vacuum at 80°C overnight, and finally placed in a UV box at 365nm with four powers of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 15 hours.
  • Step 1 Weigh 7.4 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 30 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • N-benzyloxycarbonyl-L-tyrosine (ZL-Tyr), Carter condensation reagent (BOP), 1-hydroxybenzotriazole (HOBt) and N,N-di Isopropylethylamine (DIEA) was dissolved in a small amount of N,N-dimethylformamide (DMF), and then the clathrate was added to the solution, and the suspension was reacted at 25°C for 24h.
  • the suspension was placed in excess diethyl ether to precipitate the initial product, and the precipitate was collected by centrifugation at 1800 rpm for 30 min at room temperature. Then, the precipitate was continuously stirred three times in a large amount of acetone, methanol and water to wash the precipitate, and then freeze-dried to obtain polyrotaxane.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 40min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 60° C. for 20 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 10 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried under vacuum at 80°C overnight, and finally placed in a UV box with four 380nm beams with a power of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 12 hours.
  • Step 1 Weigh 5.3 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 35 kDa, and add it into a saturated aqueous solution of ⁇ -CD (7.25 g/50 mL, double distilled H 2 O). After stirring at 30°C for 26 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • N-benzyloxycarbonyl-L-tyrosine (ZL-Tyr), Carter condensation reagent (BOP), 1-hydroxybenzotriazole (HOBt) and N,N-di Isopropylethylamine (DIEA) was dissolved in a small amount of N,N-dimethylformamide (DMF), and then the clathrate was added to the solution, and the suspension was amidated at 25°C for 24h.
  • the suspension was placed in excess diethyl ether to precipitate the primary product, and the precipitate was collected by centrifugation at 2000 rpm for 20 min at room temperature. Then, the precipitate was continuously stirred three times in a large amount of acetone, methanol and water to wash the precipitate, and then freeze-dried to obtain polyrotaxane.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with HP-PR active hydroxyl number, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 50° C. for 20 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 5 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried in vacuo at 80°C overnight, and finally placed in a UV box with four 370nm lamps with a power of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 15 hours.
  • Step 1 Weigh 6.9 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 35 kDa, and add it into a saturated aqueous solution of ⁇ -CD (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • N-benzyloxycarbonyl-L-tyrosine (ZL-Tyr), Carter condensation reagent (BOP), 1-hydroxybenzotriazole (HOBt) and N,N-di Isopropylethylamine (DIEA) was dissolved in a small amount of N,N-dimethylformamide (DMF), and then the clathrate was added to the solution, and the suspension was amidated at 25°C for 26h.
  • the suspension was placed in excess diethyl ether to precipitate the primary product, and the precipitate was collected by centrifugation at 1800 rpm for 30 min at room temperature. Then, the precipitate was continuously stirred three times in a large amount of acetone, methanol and water to wash the precipitate, and then freeze-dried to obtain polyrotaxane.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 60° C. for 20 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 10 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried in vacuum at 80°C overnight, and finally placed in a UV box at 365nm with four powers of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 15 hours.
  • Step 1 Weigh 5.8 ⁇ 10 -5 mol of polyethylene glycol diamine with a weight average molecular weight of 35 kDa, and add it into a saturated aqueous solution of ⁇ -cyclodextrin (7.25 g/50 mL, double distilled H 2 O). After stirring at room temperature for 24 hours, a white precipitate was obtained, and then freeze-dried in a lyophilizer for 48 hours to obtain an inclusion compound.
  • N-benzyloxycarbonyl-L-tyrosine (ZL-Tyr), Carter condensation reagent (BOP), 1-hydroxybenzotriazole (HOBt) and N,N-di Isopropylethylamine (DIEA) was dissolved in a small amount of N,N-dimethylformamide (DMF), and then the clathrate was added to the solution, and the suspension was amidated at 20°C for 30h.
  • the suspension was precipitated in excess diethyl ether, and the precipitate was collected by centrifugation at 2000 g for 20 min at room temperature. Then, the precipitate was continuously stirred three times in a large amount of acetone, methanol and water to wash the precipitate, and then freeze-dried to obtain polyrotaxane.
  • PCL-g-PR polycaprolactone-grafted polyrotaxane copolymer
  • Step 3 Weigh 0.5 molar equivalent of 4-nitrocinnamic acid with active hydroxyl number of HP-PR, and dissolve it in 25mL DMF at 50°C, then add the DMF solution of PCL-g-PR to 4-nitrocinnamic acid DMF solution, stirred for 30min. Then 1 molar equivalent of N,N-diisopropylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine were added, and the mixture was reacted at 40° C. for 25 h.
  • the initial product was precipitated in excess ether, the solid was collected by centrifugation, and the solid product was dissolved in a small amount of toluene, reprecipitated three times in ether, and dried under vacuum at 60°C overnight to obtain a polymer network precursor, in which the terminal group was partially modified For the cinnamic acid group.
  • Step 4 Dissolve the polymer network precursor in N,N-dimethylformamide at 80°C, then add an appropriate amount of hexamethylene diisocyanate and dibutyltin dilaurate in butyl acetate solution, and stir for 10 minutes.
  • the liquid mixture was quickly placed between two glass plates separated by silicone rubber gaskets, placed in an oven at 80°C for 48h, then dried under vacuum at 80°C overnight, and finally placed in a UV box with four 380nm beams with a power of 5W
  • the polycaprolactone shape memory material was obtained by irradiating under ultraviolet light for 12 hours.
  • a heat-crosslinked polycaprolactone shape-memory board prepared from the following components in parts by weight: 90 parts of polycaprolactone, 5 parts of crosslinking agent benzoyl peroxide, 80 parts of solvent methylene chloride, and mold release 1 dose.
  • the above-mentioned preparation method of heat-crosslinked polycaprolactone shape memory plate comprises the following preparation steps:
  • Step 1 Put polycaprolactone, crosslinking agent benzoyl peroxide and solvent methylene chloride in a round bottom flask for solution blending, after ultrasonication for 30 minutes, transfer to a mechanical stirrer and stir for 1 hour to obtain a mixture;
  • Step 2 The prepared mixture was evaporated at room temperature for 1-2 hours, and then vacuum-dried at 50-70°C for 24 hours to obtain a solid mixture of PCL/BPO;
  • Step 3 Put the solid mixture obtained in Step 2 into a custom-made iron mold, spray a release agent, and conduct thermal crosslinking treatment of peroxide-initiated polycaprolactone at 140-160°C through a flat vulcanizer , the time is 5-15min, and the maximum pressure is 10MPa to obtain a heat-crosslinked polycaprolactone shape memory plate.
  • the polycaprolactone shape memory materials in Examples 1-9 obtained by the method provided by the present invention have a faster shape recovery rate and a higher The shape recovery rate can return to more than 95% of the original shape within 5s.
  • the measurement result of elongation at break and tensile strength of the product obtained in the embodiment is compared with comparative example 1, the elongation at break is obviously improved, as in Example 9, the elongation at break has been doubled, indicating that the shape memory material can be improved toughness.

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Abstract

本发明涉及聚己内酯形状记忆材料领域，公开了制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用。该材料包含：多条改性聚轮烷大分子链，和多条连接不同的所述改性聚轮烷大分子链的复合大分子链；其中，每条所述复合大分子链包含至少两段聚己内酯大分子链、不同的所述聚己内酯大分子链之间的可逆连接基团，以及连接所述聚己内酯大分子链与所述改性聚轮烷大分子链含有的来自环糊精的环状结构的连接修饰基团，其中，所述可逆连接基团为光可逆连接基团或热可逆连接基团。本发明调节聚合物的网络拓扑缺陷以提高形状记忆材料的韧性，实现形状记忆材料的复杂形状可设计性与固态可重塑性。

Description

制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用
相关申请的交叉引用
本申请要求2021年10月28日提交的中国专利申请202111266177.2的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及聚己内酯形状记忆材料领域，具体涉及一种制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用。
背景技术
形状记忆材料是能在一定条件下被赋予一定的形状(起始态)，当外部条件发生变化时，例如施加一定热、光照、通电、化学处理等刺激后，它可相应地改变形状并将其固定(临时形状)，如果外部环境以特定的方式和规律再一次发生变化，它便可逆地回复至起始态的一类材料。形状记忆聚合物材料(SMPs)作为形状记忆材料的其中一种，与其他的形状记忆材料(合金，陶瓷)相比，具有良好的形状变化(高达1000％的可回复形变)、低密度、低成本、结构可设计性和形变恢复行为的可控性等优点，在生物医学、航空航天工业、汽车和机器人工业等领域有着广泛的应用。
通常，为了防止形状记忆循环中聚合物分子链的滑移导致的记忆性能降低，需要将其交联以固定其永久形状，但聚合物网络前体的混合、末端的连接或链增长反应的发生会一直进行到聚合物网络的形成，这是一个统计过程，使得大多数聚合物网络存在缺陷，限制了材料的性能。例如，网络结点分布不均会导致材料在应力应变循环中的应力分布不均，形状回复性能和韧性达不到预设要求。而且，常规聚合物的交联网络一般为不可逆的共价键接，形状记忆材料一旦成型，其永久形状就无法改变，不能再次加工成型，限制了其在各领域的应用范围。聚己内酯形状记忆材料由于优异的生物可降解性和生物相容性，常被用作生物医疗材料，但是由于其不均匀的交联网络和不具备再加工性，导致材料的形状回复速率慢，用于一次性医疗用品时的容错率低。
因此，需要改进的聚己内酯形状记忆材料制备方法。
发明内容
本发明的目的是为了克服现有聚己内酯形状记忆材料在韧性、复杂形状可设计性和固态可重塑性存在的问题，提供一种制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用。
为了实现上述目的，本发明第一方面提供一种聚己内酯形状记忆材料，其中，该材料包含：多条改性聚轮烷大分子链，和多条连接不同的所述改性聚轮烷大分子链的复合大分子链；其中，每条所述复合大分子链包含至少两段聚己内酯大分子链、不同的所述聚己内酯大分子链之间的可逆连接基团，以及连接所述聚己内酯大分子链与所述改性聚轮烷大分子链含有的来自环糊精的环状结构的连接修饰基团，其中，所述可逆连接基团为光可逆连接基团或热可逆连接基团。
本发明第二方面提供一种制备本发明的聚己内酯形状记忆材料的组合物，其中，所述组合物包含：聚轮烷基引发剂、端基改性剂、ε-己内酯、催化剂和交联剂；其中，所述端基改 性剂选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸。
本发明第三方面提供一种聚己内酯形状记忆材料的制备方法，其中，该方法包括：
(1)将所述聚轮烷进行羟丙基化，得到羟丙基化聚轮烷；
(2)在催化剂存在下，将所述羟丙基化聚轮烷和ε-己内酯进行开环聚合，得到聚己内酯接枝聚轮烷共聚物；
(3)将所述聚己内酯接枝聚轮烷共聚物与端基改性剂具有的光可逆基团进行改性反应，得到聚合物网络前体，其中，所述聚合物网络前体的端基部分改性为光可逆基团；
(4)在交联剂存在下，以及加热和紫外光作用下，促使所述光可逆基团反应使所述聚合物网络前体进行交联，得到聚己内酯形状记忆材料。
本发明第四方面提供一种本发明的方法制得的聚己内酯形状记忆材料。
本发明第五方面提供一种本发明的聚己内酯形状记忆材料在医用可回复固定材料中的应用。
通过上述技术方案，本发明通过将聚轮烷改性作为引发剂，通过开环聚合制备具有可滑动的聚己内酯大分子链(PCL)；然后，将PCL的末端基团部分改性为光可逆基团后进行交联形成交联结构，得到本申请的聚己内酯形状记忆材料。通过将该聚己内酯形状记忆材料具有的交联网络设计为可滑动的结构，调节该聚合物网络拓扑缺陷以提高形状记忆材料的韧性。将交联方式改为可逆键接，引入的动态共价键可以实现形状记忆材料的复杂形状可设计性与固态可重塑性。
附图说明
图1为实施例1中聚乙二醇二胺和α-环糊精，以及所制备的聚轮烷的核磁对比图；其中，图1(a)为α-环糊精的结构示意图和 1H-NMR谱图，图1(b)为聚乙二醇二胺的结构示意图和 1H-NMR谱图，图1(c)为实施例1所制备的聚轮烷的结构示意图和 1H-NMR谱图；
图2为实施例1中聚乙二醇二胺和α-环糊精，以及所制备的聚轮烷的GPC对比图；
图3为实施例1所制备的羟丙基化聚轮烷的 1H-NMR图；
图4为实施例1所制备的聚轮烷、羟丙基化聚轮烷和聚己内酯接枝聚轮烷共聚物的红外对比图；
图5为实施例1所制备的聚己内酯接枝聚轮烷共聚物的 1H-NMR图；
图6为聚己内酯形状记忆材料的交联结构网络示意图；
图7为本发明提供的聚己内酯形状记忆材料形状重塑的过程演示图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种聚己内酯形状记忆材料，其中，该材料包含：多条改性聚轮烷大分子链，和多条连接不同的所述改性聚轮烷大分子链的复合大分子链；其中，每条所述复合大分子链包含至少两段聚己内酯大分子链、不同的所述聚己内酯大分子链之间的可逆连接 基团，以及连接所述聚己内酯大分子链与所述改性聚轮烷大分子链含有的来自环糊精的环状结构的连接修饰基团，其中，所述可逆连接基团为光可逆连接基团或热可逆连接基团。
本发明提供的聚己内酯形状记忆材料具有的结构可以如图6所示意。
本发明一些实施方式中，优选地，所述光可逆连接基团来自于具有光可逆基团的化合物，优选所述化合物选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸。所述硝基肉桂酸类化合物可以为下式所示的化合物：
Figure PCTCN2022128226-appb-000001
其中，R′为取代在苯环上标有数字1-5中至少一个位置的取代基，R′为下式所示结构
Figure PCTCN2022128226-appb-000002
其中，R″″和R″′各自独立地选自H或C 1-C 6的直链或支链烷基，*表示与苯环的连接点；R″为取代在苯环上标有数字1-5中除R′取代位置之外的至少一个位置的取代基，R″为H或C 1-C 6的直链或支链烷基，优选地，所述硝基肉桂酸类化合物为下式所示化合物：
Figure PCTCN2022128226-appb-000003
其中，R 1#、R 2#和R 3#各自独立地选自H或C 1-C 6的直链或支链烷基，R1#的取代位置为苯环上标有数字1′-4′中的至少一个，最优选为4-硝基肉桂酸(R 1#、R 2#和R 3#为H)。
以4-硝基肉桂酸为例，形成的光可逆连接基团可以具有如下的示意结构：
Figure PCTCN2022128226-appb-000004
形成光可逆过程可以示意如下：
Figure PCTCN2022128226-appb-000005
其中，R 1和R 2表示与不同的改性聚轮烷连接的不同的聚己内酯大分子链。
本发明一些实施方式中，优选地，所述热可逆连接基团基来自于二异氰酸酯，优选所述二异氰酸酯选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。形成的可逆连接基团可以具有如下的示意结构：
Figure PCTCN2022128226-appb-000006
以六亚甲基二异氰酸酯为例，形成热可逆过程可以示意如下：
Figure PCTCN2022128226-appb-000007
Figure PCTCN2022128226-appb-000008
其中，R 1、R 2、R 3和R 4表示与不同的改性聚轮烷连接的不同的聚己内酯大分子链，R表示二异氰酸酯的主基团(除两个异氰酸酯基团外的结构)。
本发明一些实施方式中，优选地，所述连接修饰基团来自用于羟丙基化的化合物。例如可以是聚轮烷大分子链含有的来自环糊精的环状结构与环氧丙烷进行羟丙基化反应后形成的改性基团再引发开环聚合而形成的聚己内酯大分子链结构。优选为结构式-CH 2-CH(CH 3)-O-所示基团。
本发明一些实施方式中，优选地，基于所述改性聚轮烷大分子链的总量，所述聚己内酯大分子链的总量为80-100wt％，优选为95-99.9wt％。
本发明一些实施方式中，优选地，所述聚己内酯大分子链的重均分子量大小为5000-100000kDa，优选为10000-80000kDa。
本发明一些实施方式中，优选地，所述改性聚轮烷大分子链的重均分子量为10kDa-100kDa，优选为30kDa-90kDa。
本发明一些实施方式中，所述聚己内酯形状记忆材料具有改进的韧性，拉伸变形大，且回复性能好，并能可重塑形态。优选地，所述聚己内酯形状记忆材料具有超过900％的断裂伸长率，所述聚己内酯形状记忆材料的凝胶含量为37-78wt％，所述聚己内酯形状记忆材料在100％的应变下回复至初始形状的时间不大于5s。
本发明中，所述聚己内酯形状记忆材料具有的上述结构可以通过拉曼光谱、凝胶含量测量、GPC、傅里叶变换红外光谱和 1H NMR相结合的分析手段，或结合合成该材料的制备过程的反应和投料来确定，并可以确定可逆连接基团的可逆变化过程。所述聚己内酯形状记忆 材料具有的上述物化性能可以通过力学性能测试测定断裂伸长率、索氏抽提法测定凝胶含量和板材加热拉伸的方法测定形状回复速率和形状回复率。
本发明第二方面提供一种制备本发明的聚己内酯形状记忆材料的组合物，其中，所述组合物包含：聚轮烷基引发剂、端基改性剂、ε-己内酯、催化剂和交联剂；其中，所述端基改性剂选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸。
本发明提供上述组合物，含有聚轮烷作为引发剂引发ε-己内酯开环聚合为具有可滑动的聚己内酯分子链。端基改性剂能够用于改性聚己内酯的部分末端基团为光可逆基团，提供将交联方式改为可逆键接，克服现有聚己内酯形状记忆材料存在的韧性、可设计性和可重塑性的问题。
本发明一些实施方式中，优选地，所述聚轮烷基引发剂的重均分子量为10kDa-100kDa，优选为30kDa-90kDa。可以是商购，也可以是自制。满足上述要求即可。
本发明一些实施方式中，优选地，所述催化剂选自辛酸亚锡、二异丙基氨基锂、三氟甲磺酸钪、磷腈碱(BEMP)中的至少一种。
本发明一些实施方式中，优选地，所述交联剂选自二异氰酸酯，优选选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。可以提供将ε-己内酯开环聚合而形成的不同的聚己内酯大分子链相连接。
本发明中，所述光可逆基团可以是肉桂酸基团或香豆素基团，例如硝基肉桂酸类化合物可以为具有前述结构的化合物，在此不再赘述，可以提供肉桂酸基团；4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸可以提供香豆素基团。4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸的结构式如下所示：
Figure PCTCN2022128226-appb-000009
所述光可逆基团可以改性由ε-己内酯经开环聚合而形成的聚己内酯大分子链的一端，然后在不同的聚己内酯大分子链具有的所述光可逆基团之间进行键合，形成的结构可以在不同波长的紫外光照下可逆地进行断键或键合，可以实现获得的聚己内酯形状记忆材料具有可设计性与固态可重塑性。
本发明一些实施方式中，优选地，基于所述组合物的总重，所述组合物含有0.01-0.1wt％的所述聚轮烷基引发剂、99.99-99wt％的ε-己内酯、0.5-2wt％的所述催化剂、0.02-0.05wt％的所述端基改性剂和0.1-1wt％的所述交联剂。
本发明第三方面提供一种聚己内酯形状记忆材料的制备方法，其中，该方法包括：
(1)将聚轮烷进行羟丙基化，得到羟丙基化聚轮烷；
(2)在催化剂存在下，将所述羟丙基化聚轮烷和ε-己内酯进行开环聚合，得到聚己内酯接枝聚轮烷共聚物；
(3)将所述聚己内酯接枝聚轮烷共聚物与端基改性剂具有的光可逆基团进行改性反应，得到聚合物网络前体，其中，所述聚合物网络前体的端基部分改性为光可逆基团；
(4)在交联剂存在下，以及加热和紫外光作用下，促使所述光可逆基团反应使所述聚合物网络前体进行交联，得到聚己内酯形状记忆材料。
本发明一些实施方式中，优选地，步骤(1)中，所述羟丙基化的过程包括：将所述聚 轮烷溶于碱溶液中，并与羟基化试剂进行反应，得到的产物进行净化洗涤。羟基化试剂可以是环氧丙烷。
本发明一些实施方式中，优选地，步骤(2)中，所述催化剂选自辛酸亚锡、二异丙基氨基锂、三氟甲磺酸钪、磷腈碱中的至少一种。
本发明一些实施方式中，优选地，所述催化剂的用量为所述羟丙基化聚轮烷与ε-己内酯的总质量的0.5-2wt％，优选为0.8-1.2wt％。
本发明一些实施方式中，优选地，所述羟丙基化聚轮烷以具有的活性羟基数计，所述羟丙基化聚轮烷与ε-己内酯的摩尔比为1:50-600，优选为1:50-1:200。活性羟基数通过核磁氢谱上化学位移为1.1ppm处的积分面积与环糊精的积分面积比值确定。
本发明一些实施方式中，优选地，开环聚合温度为100-140℃，优选为110-130℃，开环聚合时间为40-50h，优选为45-50h。
本发明一些实施方式中，优选地，所述开环聚合的过程包括：将所述羟丙基化聚轮烷、ε-己内酯和所述催化剂的混合物在氮气保护下进行聚合反应；得到的初产物用四氢呋喃溶解，再在正己烷中进行多次沉淀，得到的固相沉淀物干燥后，得到所述聚己内酯接枝聚轮烷共聚物。
本发明一些实施方式中，优选地，步骤(3)中，所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物的摩尔比为100-400:1。
本发明一些实施方式中，优选地，所述端基改性剂具有光可逆基团的化合物，优选选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸。具体化合物如前所述。
本发明一些实施方式中，优选地，所述端基改性反应的温度为40-60℃，所述端基改性反应的时间为15-25h。
本发明一些实施方式中，优选地，所述端基改性反应的过程包括：将所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物分别以第一有机溶剂配制成的溶液进行混合，得到的混合溶液加入吸水剂-I和酯化催化剂后进行所述端基改性反应；得到的初产物进行多次沉淀，所得固体沉淀物进行干燥，得到所述聚合物网络前体。
本发明一些实施方式中，优选地，所述第一有机溶剂选自四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二恶烷中的至少一种；所述吸水剂-I选自N,N-二异丙基碳二亚胺、二环己基碳二亚胺、浓硫酸中的至少一种；所述酯化催化剂选自4-二甲氨基吡啶、对甲基苯磺酸、氯化亚砜中的至少一种。
本发明一些实施方式中，优选地，所述第一有机溶剂的用量使得所述混合溶液的浓度为1-10g/mL，优选为2-8g/mL。即所述混合溶液中含有的述端基改性剂与所述聚己内酯接枝聚轮烷共聚物的总含量。
本发明一些实施方式中，优选地，所述吸水剂-I的用量为所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物总量的1-5wt％，优选为1.5-4.5wt％。
本发明一些实施方式中，优选地，所述酯化催化剂与聚己内酯接枝聚轮烷共聚物的摩尔比为1:1.5-3.5，优选为1:2-3。
本发明一些实施方式中，所述光可逆基团来自端基改性剂，可以是肉桂酸基团或香豆素 基团。优选地，所述聚合物网络前体具有多条可滑动的聚己内酯分子链，且部分所述聚己内酯分子链的链端含有来自所述端基改性剂的光可逆基团。例如部分所述聚己内酯分子链的链端含有羟基和肉桂酸基团。
本发明一些实施方式中，优选地，步骤(4)中，所述交联剂选自二异氰酸酯，优选选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。步骤(3)中所述改性反应可能不完全，并不是所有的所述聚己内酯接枝聚轮烷共聚物中的聚己内酯大分子链的端基都改性为光可逆基团，即所述聚合物网络前体中还有可能含有未改性的所述聚己内酯大分子链的羟端基，因此可以通过所述交联剂提供的二异氰酸酯实现热可逆连接不同的聚己内酯大分子链。同时，可以通过酯交换实现再次连接，相当于同一条聚己内酯大分子链交换连接不同的聚己内酯大分子链。
本发明一些实施方式中，优选地，所述交联剂的用量为所述聚合物网络前体的0.1-1wt％。
本发明一些实施方式中，优选地，所述加热的温度为70-90℃，所述加热的时间为45-60h。
本发明一些实施方式中，优选地，所述紫外光的波长为250-380nm。
本发明一些实施方式中，优选地，所述交联的过程包括：将所述聚合物网络前体溶于第二有机溶剂中，再加入所述交联剂和交联催化剂的醋酸丁酯溶液，得到液体混合物；将所述液体混合物进行加热干燥，再在所述紫外光下照射，得到所述聚己内酯形状记忆材料。
本发明一些实施方式中，优选地，所述第二有机溶剂选自四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二恶烷中的至少一种；所述交联催化剂选自二月桂酸二丁基锡、有机铋催化剂、N,N-二甲基环己胺中的至少一种。
本发明一些实施方式中，优选地，所述第二有机溶剂的用量使得所述液体混合物的浓度为1-10g/mL，优选为2-8g/mL。即所述液体混合物中，所述聚合物网络前体、所述交联剂和交联催化剂的总含量。所述交联催化剂的用量为所述聚合物网络前体的1-5wt％，优选为2-4wt％。
本发明一些实施方式中，所述聚轮烷能够使自制。优选地，所述聚轮烷通过以下方法制得：在大位阻化合物存在下，将α-环糊精、聚乙二醇二胺进行反应。
本发明一些实施方式中，优选地，所述大位阻化合物选自N-苄氧羰基-L-酪氨酸、1-金刚烷乙酸、异硫氰酸荧光素酯、L-苯丙氨酸中的至少一种。
本发明一些实施方式中，优选地，聚乙二醇二胺的重均分子量为5kDa-40kDa，优选为10kDa-35kDa。
本发明一些实施方式中，优选地，α-环糊精与所述聚乙二醇二胺的摩尔比50-100:1，优选为80-90:1。
本发明一些实施方式中，优选地，所述大位阻化合物与所述聚乙二醇二胺的摩尔比为2-10:1，优选为5-8:1。
本发明一些实施方式中，优选地，所述反应的过程包括：
(i)将所述聚乙二醇二胺加入α-环糊精的饱和水溶液中，在20-35℃下搅拌20-40h，得到的白色沉淀经干燥得到包合物；
(ii)将所述大位阻化合物、酰胺化催化剂、吸水剂-II溶于第三有机溶剂中配制成溶液， 再将所述包合物加入所述溶液，得到的悬浮液进行酰胺化反应后进行沉淀，将得到的固相沉淀物进行洗涤、干燥，得到所述聚轮烷。
本发明一些实施方式中，优选地，所述酰胺化催化剂选自自卡特缩合试剂、氯化锌、六水氯化铁中的至少一种；所述吸水剂-II选自N,N-二异丙基乙胺、1-羟基苯并三唑、二环己基碳二亚胺中的至少一种；所述第三有机溶剂选自N,N-二甲基甲酰胺、四氢呋喃、二氯甲烷中的至少一种。
本发明一些实施方式中，优选地，所述酰胺化催化剂的用量为所述聚乙二醇二胺和α-环糊精总量的1-5wt％，优选为2-4wt％；所述吸水剂-II的用量为所述聚乙二醇二胺和α-环糊精总量的1-5wt％，优选为2-4wt％；所述第三有机溶剂的用量使得所述溶液的浓度为1-10g/mL，优选为2-8g/mL。即所述溶液中，所述所述大位阻化合物、酰胺化催化剂、吸水剂-II的总含量。
本发明一些实施方式中，优选地，所述聚轮烷的重均分子量为10-100kDa，优选为30-90kDa。
本发明第四方面提供一种本发明的方法制得的聚己内酯形状记忆材料。
本发明一些实施方式中，优选地，所述聚己内酯形状记忆材料具有能够在聚乙二醇分子链上滑移的聚己内酯分子链，能在5s内回复至95％以上的原始形状；具有交联结构，在交联结构的节点部分具有光可逆的动态共价键，能在256nm的紫外光照射下断开共价键，使材料在固态下具备重塑原始形状的能力。所述聚己内酯形状记忆材料形状重塑的过程演示如图7所示。所述聚己内酯形状记忆材料具有超过900％的断裂伸长率，所述聚己内酯形状记忆材料的凝胶含量为37-78wt％，所述聚己内酯形状记忆材料在100％的应变下回复至初始形状的时间不大于5s。
本发明第五方面提供一种本发明的聚己内酯形状记忆材料在医用可回复固定材料中的应用。
优选地，应用可以包括形状记忆医用固定夹板。
以下将通过实施例对本发明进行详细描述。以下实施例中， 1H-NMR谱图通过瑞士布鲁克公司的Bruker ARX-500测得，分辨率<0.2Hz，灵敏度>100。采用核磁共振氢谱分析，以氘代氯仿或氘代二甲基亚砜作溶剂，500MHz的工作频率，7.05T的磁场强度，在常温下测试；
GPC谱图通过美国Waters公司的三检测体积排阻色谱仪(TD-SEC)测得，在35℃下对聚合物的分子量及分子量分布(PDI)进行表征，聚苯乙烯为标样，THF为流动相，测试流速为1.0mL/min；
傅里叶变换红外谱图通过美国Nicolet公司的Avatar 370测得，测试采用KBr压片制样，透射模式，扫描范围500-4000cm -1分辨率为2cm -1。
凝胶含量测定通过索氏抽提法，用氯仿抽提24小时后通过称重前后样品质量得到。
形状回复速率和形状回复率通过板材加热拉伸的方法，使用美国TA Instrument的Q800万能试验机测定。
将制备的PCL样品用标准4×25裁刀制备成哑铃状样条，使用电子万能试验机以20 mm/min的拉伸速率和0.5N预加载荷进行力学性能测试，然后通过如下公式计算每个样品的断裂伸长率和拉伸强度。测试前，在样条中间取两厘米用记号笔划线，再使用标准游标卡尺于划线处等距测量三次膜的厚度，然后算出其平均值，记录样品的平均厚度。
Figure PCTCN2022128226-appb-000010
Figure PCTCN2022128226-appb-000011
其中，L 1为样品断裂时的长度，L 0为样品的初始长度，F max为拉伸过程中的最大拉力，A为样品的初始截面积。
实施例1
制备聚己内酯可重塑形状记忆材料步骤如下：
步骤1：称量重均分子量为10kDa的聚乙二醇二胺5.3×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将2.6×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应24h后，将悬浮液置于过量乙醚中沉淀初产物，并在室温下以1800rpm离心20min收集沉淀物，然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷(PR)。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯(ε-CL)按摩尔比(HP-PR上活性羟基数:ε-CL＝1:200)加入干燥、硅烷化的圆底烧瓶中，加入总质量(HP-PR和ε-己内酯的总重，下同)1wt％的辛酸亚锡，通高纯氮气置换，混合物在120℃下反应48h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀物在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于50℃反应20h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在 紫外箱中于4根功率为5W的365nm紫外灯下照射12h，得到聚己内酯形状记忆材料。
图1为制备的PR与PEG(聚乙二醇)和α-CD的 1H-NMR谱图的对比图：(a)中化学位移为3.28ppm处的峰为标记2的碳上的质子峰；化学位移为3.5-3.7ppm处的峰对应于标记4、5和6的碳上的质子峰；化学位移为3.76ppm处的峰对应于标记3的碳上的质子峰；化学位移为4.51ppm处的峰为标记6的碳上羟基的质子峰；化学位移为4.80ppm处的峰为标记1的碳上的质子峰；化学位移为5.45ppm处的峰为标记3的碳上羟基的质子峰；化学位移为5.54ppm处的峰为标记2的碳上羟基的质子峰。(b)中化学位移为2.04ppm处的峰(标记j)为PEG-NH 2两端胺基上的质子峰；化学位移为3.58ppm处的峰(标记i)为PEG-NH 2亚甲基上的质子峰。(c)化学位移为3.51ppm处的峰为PEG上亚甲基的质子峰；化学位移为4.4-5.7ppm处的峰为α-CD上的质子峰。从核磁图中可以看出合成的PR核磁图上既有PEG 3.5ppm处的亚甲基特征峰，又有α-CD上4.8ppm处的标记1的碳上的特征峰，表明PR分子上含有PEG和α-CD结构单元。对4.8ppm和3.5ppm处的特征峰进行积分，发现∫4.8：∫3.5＝1：4，平均约六个PEG结构单元上有一个α-CD分子。
图2为制备的PR与PEG-NH 2和α-CD的GPC对比图，从各自的保留时间可以看出PR的分子量明显比PEG-NH 2更大，且没有小分子成分；结合图1中的核磁数据，表明在核磁图中发现的α-CD成功地穿在了PEG分子链上，PR成功合成。
图3为制备的羟丙基改性后的HP-PR核磁谱图，与PR的核磁谱图在2.0ppm以上的位置几乎一样，而HP-PR在化学位移为1.0ppm处(标记k)明显多了一处甲基的质子峰，表明PR上的α-CD被成功地羟丙基改性。对4.2-6.0ppm和1.0ppm处的峰进行积分，由4.2-6.0ppm处和1.0ppm处峰的面积积分比计算得PR的羟丙基改性率DS为6。
图4为制备的PR、HP-PR和PCL-g-PR的红外对比图，图中3436cm -1处的吸收峰和PR与HP-PR中3400cm -1处的吸收峰归因于-OH上的-O-H和-NH-上的-N-H的伸缩振动；PCL-g-PR中2946cm -1处的吸收峰和PR与HP-PR中2923cm -1处的吸收峰归因于-CH 2-上的-C-H的不对称伸缩振动，而PCL-g-PR中2866cm -1处的吸收峰则归因于-CH 2-上-C-H的对称伸缩振动；PCL-g-PR中1725cm -1处的吸收峰则归因于聚己内酯侧链上羰基的伸缩振动(C＝O)，而PR和HP-PR中1640cm -1(C＝O)处的吸收峰是因为酰胺键上羰基的伸缩振动；PR、HP-PR和PCL-g-PR中1300-1500cm -1则归因于C-H面内弯曲振动，1000-1300cm -1处的吸收峰是因为C-C骨架振动和C-C骨架振动造成的，650-1000cm -1处的吸收峰则归因于C-H面外弯曲振动。在PR和HP-PR中发现的羰基峰归因于酰胺键，而PCL-g-PR中发现的羰基峰明显频率更高，对应为酯键，说明了以HP-PR为引发剂成功的引发了ε-己内酯的开环聚合，形成了大分子酯键。PR和HP-PR的红外特征峰几乎一样，只是HP-PR的特征峰强度更高，可能是由于PR上α-环糊精被羟丙基化后，α-环糊精之间的氢键被削弱，原子间的振动频率更大。
图5为制备的PCL-g-PR的核磁谱图，化学位移为1.32ppm处(标记d)的峰对应于己内酯链段上最中间的亚甲基上的质子峰；化学位移为1.58ppm处(标记c)的峰对应于己内酯链段中与中间碳原子相邻的亚甲基上的质子峰；化学位移为2.24ppm处(标记b)的峰对应于己内酯链段羰基邻位碳上的质子峰；化学位移为3.99ppm处(标记a)的峰对应于己内酯链段氧原子邻位碳上的质子峰；在化学位移为3.58ppm处有一处疑似PEG亚甲基很微弱 的特征峰，可能是由于PCL-g-PR侧链PCL链段的增长导致PEG链上的亚甲基质子峰信号被屏蔽。
图6是以实施例1获得的聚己内酯形状记忆材料为例，示例说明该材料具有的交联网络结构。图中聚乙二醇大分子链带有示意为圆点的大位阻基团(来自于N-苄氧羰基-L-酪氨酸)，穿过聚己内酯大分子链上带有的示意为圆环的α-环糊精，形成聚乙二醇大分子链与聚己内酯大分子链的交联网络结构，并且，通过α-环糊精提供的环形结构，聚己内酯大分子链能够在聚乙二醇大分子链上滑动。在聚己内酯大分子链上还有示意为方块的提供可逆共价键的可逆连接基团，由端基改性剂提供的光可逆基团或交联剂提供的热可逆基团形成，能够为聚己内酯形状记忆材料引入动态共价键，实现可逆键接，实现形状记忆材料的复杂形状可设计性与固态可重塑性。
实施例2
制备聚己内酯可重塑形状记忆材料步骤如下：
步骤1：称量重均分子量为15kDa的聚乙二醇二胺6.4×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。30℃温度下搅拌30h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将3.4×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应26h后，将悬浮液置于过量乙醚中沉淀初产物，并在室温下以1800rpm离心25min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于55℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:400)加入干燥、硅烷化的圆底烧瓶中，加入总质量(HP-PR和ε-己内酯的总重)1wt％的辛酸亚锡，通高纯氮气置换，混合物在130℃下反应50h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌40min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于55℃反应22h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5min。将液体混合物快速置于两个用 硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的370nm紫外灯下照射14h，得到聚己内酯形状记忆材料。
实施例3
制备聚己内酯可重塑形状记忆材料步骤如下：
步骤1：称量重均分子量为20kDa的聚乙二醇二胺8.0×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将4.2×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于30℃下酰胺化反应25h后，将悬浮液置于过量乙醚中沉淀初产物，并在室温下以2000rpm离心15min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，之后冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:600)加入干燥、硅烷化的圆底烧瓶中，加入总质量(HP-PR和ε-己内酯的总重)1wt％的辛酸亚锡，通高纯氮气置换，混合物在130℃下反应55h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，之后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于45℃反应15h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的380nm紫外灯下照射10h，得到聚己内酯形状记忆材料。
实施例4
制备聚己内酯形状记忆材料步骤如下：
步骤1：称量重均分子量为20kDa的聚乙二醇二胺5.3×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将2.6×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1- 羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应30h后，将悬浮液置于过量乙醚中沉淀初产物，并在室温下以2000rpm离心25min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:200)加入干燥、硅烷化的圆底烧瓶中，加入总质量(HP-PR和ε-己内酯的总重)1wt％的辛酸亚锡，通高纯氮气置换，混合物在120℃下反应48h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于60℃反应15h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的375nm紫外灯下照射13h，得到聚己内酯形状记忆材料。
实施例5
制备聚己内酯形状记忆材料步骤如下：
步骤1：称量重均分子量为20kDa的聚乙二醇二胺5.7×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。30℃下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥50h，获得包合物。
按顺序将2.7×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应28h后，将悬浮液置于过量乙醚中沉淀初产物，并在室温下以1800rpm离心30min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得 羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:400)加入干燥、硅烷化的圆底烧瓶中，加入总质量1wt％的辛酸亚锡，通高纯氮气置换，混合物在125℃下反应50h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于40℃反应25h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5分钟。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的365nm紫外灯下照射15h，得到聚己内酯形状记忆材料。
实施例6
制备聚己内酯可重塑形状记忆材料步骤如下：
步骤1：称量重均分子量为30kDa的聚乙二醇二胺7.4×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL，双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将3.5×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下反应24h。将悬浮液置于过量乙醚中沉淀初产物，并在室温下以1800rpm离心30min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:600)加入干燥、硅烷化的圆底烧瓶中，加入总质量1wt％的辛酸亚锡，通高纯氮气置换，混合物在110℃下反应50h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌40min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于60℃ 反应20h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌10min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的380nm紫外灯下照射12h，得到聚己内酯形状记忆材料。
实施例7
制备聚己内酯形状记忆材料步骤如下：
步骤1：称量重均分子量为35kDa的聚乙二醇二胺5.3×10 -5mol，并加入到α-CD的饱和水溶液(7.25g/50mL，双蒸H 2O)中。30℃温度下搅拌26h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将2.6×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应24h。将悬浮液置于过量乙醚中沉淀初产物，并通过在室温下以2000rpm离心20min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:200)加入干燥、硅烷化的圆底烧瓶中，加入总质量1wt％的辛酸亚锡，通高纯氮气置换，混合物在130℃下反应45h。之后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，之后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于50℃反应20h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌5min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的370nm紫外灯下照射15h，得到聚己内酯形状记忆材料。
实施例8
制备聚己内酯形状记忆材料步骤如下：
步骤1：称量重均分子量为35kDa的聚乙二醇二胺6.9×10 -5mol，并加入到α-CD的饱和水溶液(7.25g/50mL，双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将3.5×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于25℃下酰胺化反应26h。将悬浮液置于过量乙醚中沉淀初产物，并通过在室温下以1800rpm离心30min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:400)加入干燥、硅烷化的圆底烧瓶中，加入总质量1wt％的辛酸亚锡，通高纯氮气置换，混合物在110℃下反应50h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于60℃反应20h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌10min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的365nm紫外灯下照射15h，得到聚己内酯形状记忆材料。
实施例9
制备聚己内酯形状记忆材料步骤如下：
步骤1：称量重均分子量为35kDa的聚乙二醇二胺5.8×10 -5mol，并加入到α-环糊精的饱和水溶液(7.25g/50mL,双蒸H 2O)中。室温下搅拌24h，得白色沉淀，然后于冻干机中冷冻干燥48h，获得包合物。
按顺序将2.7×10 -3mol的N-苄氧羰基-L-酪氨酸(Z-L-Tyr)、卡特缩合试剂(BOP)、1-羟基苯并三唑(HOBt)和N,N-二异丙基乙胺(DIEA)溶于少量N,N-二甲基甲酰胺(DMF)中，再将包合物添加到溶液中，悬浮液于20℃下酰胺化反应30h。将悬浮液于过量乙醚中沉淀初产物，并在室温下以2000g离心20min收集沉淀物。然后在大量丙酮、甲醇和水中连续搅拌 沉淀三次来洗涤沉淀，再冷冻干燥得聚轮烷。
称量适量聚轮烷溶于50mL的1mol/L的NaOH溶液，在冰浴条件下逐滴添加适量环氧丙烷，并将混合物搅拌过夜。随着溶液中冰的融化，反应温度逐渐升至室温。用去离子水透析纯化样品一周，并冷冻干燥。将冻干样品倒入100mL二氯甲烷中搅拌过夜以滤出羟丙基化过程中分解产生的游离聚乙二醇，然后用大量丙酮洗涤，离心收集沉淀并于60℃真空干燥得羟丙基化的聚轮烷(HP-PR)。
步骤2：将HP-PR和纯化后的ε-己内酯按摩尔比(HP-PR上活性羟基数:ε-CL＝1:600)加入干燥、硅烷化的圆底烧瓶中,加入总质量1wt％的辛酸亚锡，通高纯氮气置换，混合物在130℃下反应48h。然后，初产物用少量四氢呋喃溶解，于过量正己烷中沉淀三次，沉淀在60℃下真空干燥48h，得到聚己内酯接枝聚轮烷共聚物(PCL-g-PR)。
步骤3：称量0.5摩尔当量HP-PR活性羟基数的4-硝基肉桂酸，并于50℃下溶于25mL DMF，然后将PCL-g-PR的DMF溶液加入到4-硝基肉桂酸的DMF溶液中，搅拌30min。随后加入1摩尔当量的N,N-二异丙基碳二亚胺和0.5摩尔当量的4-二甲氨基吡啶，混合物于40℃反应25h。初产物于过量乙醚中沉淀，离心收集固体，并将固体产物溶于少量甲苯，于乙醚中再沉淀3次，在60℃下真空干燥过夜，得到聚合物网络前体，其中端基部分改性为肉桂酸基团。
步骤4：将聚合物网络前体溶于80℃的N,N-二甲基甲酰胺中，然后加入适量的六亚甲基二异氰酸酯与二月桂酸二丁基锡的醋酸丁酯溶液，搅拌10min。将液体混合物快速置于两个用硅橡胶垫片隔开的玻璃板间，于80℃烘箱中放置48h，随后在80℃下真空干燥过夜，最后在紫外箱中于4根功率为5W的380nm紫外灯下照射12h，得到聚己内酯形状记忆材料。
对比例1
一种热交联聚己内酯形状记忆板材，由以下重量份数的组分制备：聚己内酯90份，交联剂过氧化苯甲酰5份，溶剂二氯甲烷80份，脱模剂1份。
上述的热交联聚己内酯形状记忆板材的制备方法，包括以下制备步骤：
步骤1：将聚己内酯，交联剂过氧化苯甲酰和溶剂二氯甲烷，置于圆底烧瓶中进行溶液共混，超声30min后，转移到机械搅拌器中搅拌1h，得到混合物；
步骤2：将制得的混合物在室温下使溶剂挥发1-2h，然后于50-70℃下真空干燥24h，得到PCL/BPO固态混合物；
步骤3：将步骤2得到的固态混合物，置于定制的铁质模具中，喷上脱模剂，通过平板硫化机于140-160℃下使过氧化物引发聚己内酯进行热交联处理，时间5-15min，最高压力为10MPa，得到热交联聚己内酯形状记忆板材。
将实施例1-9和对比例1获得的产品进行凝胶含量、形状回复速率、形状回复率、断裂伸长率和拉伸强度的测定，结果见表1。
表1实施例与对比例性能参数对比
Figure PCTCN2022128226-appb-000012
Figure PCTCN2022128226-appb-000013
通过表1的结果可以看出，采用本发明提供的方法获得的实施例1-9中的聚己内酯形状记忆材料，具有比对比例制得的产物更快的形状回复速率以及更高的形状回复率，能够在5s以内回复至95％以上的原始形状。并且实施例获得产品的断裂伸长率和拉伸强度的测定结果相比于对比例1，断裂伸长率明显提高，如实施例9断裂伸长率提升了一倍，说明能够改进形状记忆材料的韧性。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (15)

  1. 一种聚己内酯形状记忆材料，其特征在于，该材料包含：多条改性聚轮烷大分子链，和多条连接不同的所述改性聚轮烷大分子链的复合大分子链；其中，每条所述复合大分子链包含至少两段聚己内酯大分子链、不同的所述聚己内酯大分子链之间的可逆连接基团，以及连接所述聚己内酯大分子链与所述改性聚轮烷大分子链含有的来自环糊精的环状结构的连接修饰基团，其中，所述可逆连接基团为光可逆连接基团或热可逆连接基团。
  2. 根据权利要求1所述的聚己内酯形状记忆材料，其中，所述光可逆连接基团来自于具有光可逆基团的化合物，优选所述化合物选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸；
    优选地，所述热可逆连接基团来自于二异氰酸酯，优选所述二异氰酸酯选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。
  3. 根据权利要求1或2所述的聚己内酯形状记忆材料，其中，所述连接修饰基团来自用于羟丙基化的化合物，优选为结构式-CH 2-CH(CH 3)-O-所示基团。
  4. 根据权利要求1-3中任意一项所述的聚己内酯形状记忆材料，其中，基于所述改性聚轮烷大分子链的总量，所述聚己内酯大分子链的总量为80-100wt％，优选为95-99.9wt％；
    优选地，所述聚己内酯大分子链的重均分子量为5000-100000kDa，优选为10000-80000kDa；
    优选地，所述改性聚轮烷大分子链的重均分子量为10kDa-100kDa，优选为30kDa-90kDa。
  5. 根据权利要求1-4中任意一项所述的聚己内酯形状记忆材料，其中，所述聚己内酯形状记忆材料具有超过900％的断裂伸长率，所述聚己内酯形状记忆材料的凝胶含量为37-78wt％，所述聚己内酯形状记忆材料在100％应变下回复至初始形状的时间不大于5s。
  6. 一种制备权利要求1-5中任意一项所述的聚己内酯形状记忆材料的组合物，其特征在于，所述组合物包含：聚轮烷基引发剂、端基改性剂、ε-己内酯、催化剂和交联剂；其中，所述端基改性剂选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸。
  7. 根据权利要求6所述的组合物，其中，所述聚轮烷基引发剂的重均分子量为10kDa-100kDa，优选为30kDa-90kDa；
    优选地，所述催化剂选自辛酸亚锡、二异丙基氨基锂、三氟甲磺酸钪、磷腈碱中的至少一种；
    优选地，所述交联剂选自二异氰酸酯，优选选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。
  8. 根据权利要求6或7所述的组合物，其中，基于所述组合物的总重，所述组合物含有0.01-0.1wt％的所述聚轮烷基引发剂、99.99-99wt％的ε-己内酯、0.5-2wt％的所述催化剂、0.02-0.05wt％的所述端基改性剂和0.1-1wt％的所述交联剂。
  9. 一种聚己内酯形状记忆材料的制备方法，其特征在于，该方法包括：
    (1)将聚轮烷进行羟丙基化，得到羟丙基化聚轮烷；
    (2)在催化剂存在下，将所述羟丙基化聚轮烷和ε-己内酯进行开环聚合，得到聚己内酯接枝聚轮烷共聚物；
    (3)将所述聚己内酯接枝聚轮烷共聚物与端基改性剂具有的光可逆基团进行改性反应，得到聚合物网络前体，其中，所述聚合物网络前体的端基部分改性为光可逆基团；
    (4)在交联剂存在下，以及加热和紫外光作用下，促使所述光可逆基团反应使所述聚合物网络前体进行交联，得到聚己内酯形状记忆材料。
  10. 根据权利要求9所述的方法，其中，步骤(2)中，所述催化剂选自辛酸亚锡、二异丙基氨基锂、三氟甲磺酸钪、磷腈碱中的至少一种；
    优选地，所述催化剂的用量为所述羟丙基化聚轮烷与ε-己内酯的总质量的0.5-2wt％，优选为0.8-1.2wt％；
    优选地，所述羟丙基化聚轮烷以具有的活性羟基数计，所述羟丙基化聚轮烷与ε-己内酯的摩尔比为1:50-600，优选为1：50-1:200；
    优选地，开环聚合温度为100-140℃，优选为110-130℃，开环聚合时间为40-50h，优选为45-50h；
    优选地，所述开环聚合的过程包括：将所述羟丙基化聚轮烷、ε-己内酯和所述催化剂的混合物在氮气保护下进行聚合反应；得到的初产物用四氢呋喃溶解，再在正己烷中进行多次沉淀，得到的固相沉淀物干燥后，得到所述聚己内酯接枝聚轮烷共聚物。
  11. 根据权利要求9或10所述的方法，其中，步骤(3)中，所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物的摩尔比为100-400:1；
    优选地，所述端基改性剂选自具有光可逆基团的化合物，优选选自硝基肉桂酸类化合物和/或4-((4-甲基-2-氧代-2H-色烯-7-基)氧基)丁酸；
    优选地，所述端基改性反应的温度为40-60℃，所述端基改性反应的时间为15-25h；
    优选地，所述端基改性反应的过程包括：将所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物分别以第一有机溶剂配制成的溶液进行混合，得到的混合溶液加入吸水剂-I和酯化催化剂后进行所述端基改性反应；得到的初产物进行多次沉淀，所得的固体沉淀物进行干燥，得到所述聚合物网络前体；
    优选地，所述第一有机溶剂选自四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二恶烷中的至少一种；所述吸水剂-I选自N,N-二异丙基碳二亚胺、二环己基碳二亚胺、浓硫酸中的至少一种；所述酯化催化剂选自4-二甲氨基吡啶、对甲基苯磺酸、氯化亚砜中的至少一种；
    优选地，所述第一有机溶剂的用量使得所述混合溶液的浓度为1-10g/mL，优选为2-8g/mL；所述吸水剂-I的用量为所述端基改性剂与所述聚己内酯接枝聚轮烷共聚物总量的1-5wt％，优选为1.5-4.5wt％；所述酯化催化剂与聚己内酯接枝聚轮烷共聚物的摩尔比为1:1.5-3.5，优选为1:2-3；
    优选地，所述聚合物网络前体具有多条可滑动的聚己内酯分子链，且部分所述聚己内酯分子链的链端含有来自所述端基改性剂的光可逆基团，优选所述光可逆基团为香豆素基团或肉桂酸基团。
  12. 根据权利要求9-11中任意一项所述的方法，其中，步骤(4)中，所述交联剂选自二异氰酸酯，优选选自六亚甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯中的至少一种；
    优选地，所述交联剂的用量为所述聚合物网络前体的0.1-1wt％；
    优选地，所述加热的温度为70-90℃，所述加热的时间为45-60h；
    优选地，所述紫外光的波长为250-380nm；
    优选地，所述交联的过程包括：将所述聚合物网络前体溶于第二有机溶剂中，再加入所述交联剂和交联催化剂的醋酸丁酯溶液，得到液体混合物；将所述液体混合物进行加热干燥，再在所述紫外光下照射，得到所述聚己内酯形状记忆材料；
    优选地，所述第二有机溶剂选自四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二恶烷中的至少一种；所述交联催化剂选自二月桂酸二丁基锡、有机铋催化剂、N,N-二甲基环己胺中的至少一种；
    优选地，所述第二有机溶剂的用量使得所述液体混合物的浓度为1-10g/mL，优选为2-8g/mL；所述交联催化剂的用量为所述聚合物网络前体的1-5wt％，优选为2-4wt％。
  13. 根据权利要求9-12中任意一项所述的方法，其中，所述聚轮烷通过以下方法制得：在大位阻化合物存在下，将α-环糊精、聚乙二醇二胺进行反应；
    优选地，所述大位阻化合物选自N-苄氧羰基-L-酪氨酸、1-金刚烷乙酸、异硫氰酸荧光素酯、L-苯丙氨酸中的至少一种；
    优选地，所述聚乙二醇二胺的重均分子量为5kDa-40kDa，优选为10kDa-35kDa；
    优选地，α-环糊精与所述聚乙二醇二胺的摩尔比为50-100:1，优选为80-90:1；
    优选地，所述大位阻化合物与所述聚乙二醇二胺的摩尔比为2-10:1，优选为5-8:1；
    优选地，所述反应的过程包括：
    (i)将所述聚乙二醇二胺加入α-环糊精的饱和水溶液中，在20-35℃下搅拌20-40h，得到的白色沉淀经干燥得到包合物；
    (ii)将所述大位阻化合物、酰胺化催化剂、吸水剂-II溶于第三有机溶剂中配制成溶液，再将所述包合物加入所述溶液，得到的悬浮液进行酰胺化反应后进行沉淀，将得到的固相沉淀物进行洗涤、干燥，得到所述聚轮烷；
    优选地，所述酰胺化催化剂选自卡特缩合试剂、氯化锌、六水氯化铁中的至少一种；所述吸水剂-II选自N,N-二异丙基乙胺、1-羟基苯并三唑、二环己基碳二亚胺中的至少一种；所述第三有机溶剂选自N,N-二甲基甲酰胺、四氢呋喃、二氯甲烷中的至少一种；
    优选地，所述酰胺化催化剂的用量为所述聚乙二醇二胺和α-环糊精总量的1-5wt％，优选为2-4wt％；所述吸水剂-II的用量为所述聚乙二醇二胺和α-环糊精总量的1-5wt％，优选为2-4wt％；所述第三有机溶剂的用量使得所述溶液的浓度为1-10g/mL，优选为2-8g/mL；
    优选地，所述聚轮烷的重均分子量为10-100kDa，优选为30-90kDa。
  14. 一种权利要求9-13中任意一项所述的方法制得的聚己内酯形状记忆材料。
  15. 一种权利要求1-5和14中任意一项所述的聚己内酯形状记忆材料在医用可回复固定材料中的应用，优选所述应用包括形状记忆医用固定夹。
PCT/CN2022/128226 2021-10-28 2022-10-28 制备聚己内酯形状记忆材料的组合物和聚己内酯形状记忆材料及其制备方法与应用 Ceased WO2023072242A1 (zh)

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