WO2021063386A1 - 一种聚乳酸接枝壳聚糖纳米晶须的制备方法 - Google Patents

一种聚乳酸接枝壳聚糖纳米晶须的制备方法 Download PDF

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WO2021063386A1
WO2021063386A1 PCT/CN2020/119238 CN2020119238W WO2021063386A1 WO 2021063386 A1 WO2021063386 A1 WO 2021063386A1 CN 2020119238 W CN2020119238 W CN 2020119238W WO 2021063386 A1 WO2021063386 A1 WO 2021063386A1
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grafting
pla
chitosan
freeze
urea
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徐荷澜
罗贵清
马博谋
侯秀良
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江南大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to a preparation method of polylactic acid grafted chitosan nano whiskers, and belongs to the field of materials.
  • Organic nanomaterials refer to new types of nanomaterials based on lipids, proteins, polysaccharides and organic polymers.
  • nanomaterials have been widely used in food, biomedicine, agriculture and environmental fields.
  • the unique physical and chemical properties of nano-materials due to their nano-level size effects have brought new innovative development opportunities for food, agriculture, industry and other fields.
  • the excellent biochemical properties of polysaccharide nanowhiskers, such as good biocompatibility, good biodegradability, non-toxicity, easy modification and nano-size functionality, have caused extensive research and have been applied in different fields.
  • the application of composite materials is very extensive, and the research of nanocomposite materials based on natural polymers and polymers has been intensified.
  • PLA-g-CS For the study of the particle size of PLA-g-CS, there is a method of physical ball milling (Poly(l-lactic acid)bio -composites reinforced by oligo (d-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus. International Journal of Biological Macromolecules, 2019.131: p.495-504.), PLA-g is also produced by percolation and ultrasonic methods -CS Nanoparticle report (Preparation of biocompatible chitosan grafted poly(lactic acid) nanoparticles. International Journal of Biological Macromolecules, 2012.51(3): p.221-227.).
  • PLA-g-CS is neither soluble in acetic acid nor chloroform, which makes it difficult to make PLA-g-CS into nano-sized particles. Therefore, no scholar has studied the preparation of PLA-g-CS nano-whiskers. .
  • the above-mentioned documents prepare nano-particles, most of which are spherical, and nano-whiskers are generally small rods with a certain aspect ratio and diameter at the nanometer scale. The above-mentioned documents do not prepare nano-whiskers, and the above-mentioned In the process of preparing nanoparticles, a large amount of organic solvents are used, which causes pollution to the environment and is not environmentally friendly.
  • the present invention adopts a dry grafting method to prepare PLA-g-CS, and then disperse PLA-g-CS in lye, and obtain nano-whiskers through repeated freezing/thawing methods.
  • This method enables PLA-g-CS without a good solvent to prepare nano-whiskers, and the entire reaction is highly efficient and clean, green and environmentally friendly, and has a certain degree of generalizability.
  • the first object of the present invention is to provide a preparation method of polylactic acid grafted chitosan (PLA-g-CS) nano whiskers, the method includes the following steps:
  • PLA-g-CS Preparation of PLA-g-CS: After the lactide, catalyst and chitosan are mixed uniformly, polymerization and grafting are carried out to prepare PLA-g-CS, and there is no solvent during the polymerization and grafting process;
  • PLA-g-CS nano whiskers Disperse the PLA-g-CS prepared in step (1) in a mixed solution of NaOH:urea:H 2 O or LiOH:KOH:urea:H 2 O, After freezing/thawing, sonication, centrifugation, and dialysis, PLA-g-CS nano whiskers were obtained.
  • the mass ratio of lactide to chitosan in step (1) is (2-10):1
  • the catalyst is stannous octoate
  • the added amount is 0.1 to 0.1 of the mass percentage of lactide. 1 ⁇ .
  • the polymerization grafting conditions in step (1) are: nitrogen atmosphere; grafting temperature: 120-180°C; grafting time: 3-5h.
  • the addition amount of PLA-g-CS is 0.25% to 1%.
  • NaOH:urea:H 2 O (8-15):(4-8):(80-85).
  • LiOH:KOH:urea:H 2 O (8-15):(5-9):8:(80-85) in the step (2).
  • the freezing condition in the step (2) is the temperature is -80 ⁇ -20°C, the time is 0.5-3h; the thawing condition is 5-10°C, the time is 0.1-0.5h, freezing/ Defrost cycle 2-5 times.
  • the ultrasonic frequency in the step (2) is 30-60 Hz, and the time is 10-30 min.
  • the centrifugal speed is 5000-10000 r/min, and the time is 15-30 min.
  • the second object of the present invention is to provide a PLA-g-CS nano whisker prepared by the above method.
  • the third object of the present invention is to provide an application of the PLA-g-CS nano whiskers in food packaging, medicine and composite materials.
  • polylactic acid is used to graft chitosan, which can enhance the hydrophobicity and mechanical properties of chitosan, while being environmentally friendly and degradable.
  • the currently known grafting methods of chitosan and polylactic acid all use solvents as the reaction medium, and even a large amount of solvents are needed to precipitate the grafts.
  • the grafting method used in the present invention is dry grafting. Lactide is in a molten state at 120 ⁇ 150°C, without using a solvent as the reaction medium, the ring-opening polymerization of lactide and the polymerization reaction of lactide and chitosan can occur.
  • the reaction process is environmentally friendly and simple and efficient.
  • the grafting rate can be as high as 97%, which is environmentally friendly and conforms to the development of the times; at the same time, the grafted product has potential applications in food packaging, medicine or as a reinforcement for composite materials.
  • PLA-g-CS which is almost insoluble, is prepared by repeatedly freezing and thawing in lye to prepare nanowhiskers. Because chitosan has good biodegradability, biocompatibility, antibacterial and multifunctional chemical and physical properties, polylactic acid is obtained by polymerizing lactic acid as a raw material. It is a renewable resource with sufficient raw material sources and good biological properties. Degradability, it can be completely degraded into water and carbon dioxide, and will not pollute the environment. After the grafted product is made into nano-whiskers, it has broad application prospects in food packaging, medicine or as a reinforcement for composite materials, etc., especially in The application of biomedical and reinforced composite materials has great potential.
  • Figure 1 shows the infrared spectra of polylactic acid (PDLA), chitosan (CS) and polylactic acid grafted chitosan (Oligo(D-LA)-g-CS).
  • Figure 2 is an SEM photo of the nanowhiskers of the grafted polylactic acid and chitosan prepared in Example 1 of the present invention.
  • Figure 3 is a comparison of the micro-compression properties of chitin hydrogel and polylactic acid grafted chitosan nanowhiskers reinforced chitin hydrogel.
  • Disperse 0.025g of PLA-g-CS in 9.975g of a mixed solution of NaOH: Urea: H 2 O 11:4:85, then freeze the suspension at -30°C for 3 hours, and then at 5°C Stir and thaw, freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers (see Figure 2) have an average diameter of 281.1 nm.
  • Disperse 0.05g of PLA-g-CS in 9.975g of NaOH:urea:H 2 O 11:4:85 mixed solution, then freeze the suspension at -30°C for 3h, and then at 5°C Stir and thaw, freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 502.7nm.
  • Disperse 0.1g of PLA-g-CS in 9.975g of NaOH:urea:H 2 O 11:4:85 mixed solution, then freeze the suspension at -30°C for 3h, and then at 5°C Stir and thaw, freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 893.6nm.
  • Disperse 0.025g of PLA-g-CS in a mixed solution of 9.975g of NaOH:urea:H 2 O 11:4:85, then freeze the suspension at -30°C for 2h, and then at 5°C Stir and thaw, freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 699.5nm.
  • Disperse 0.025g of PLA-g-CS in 9.975g of a mixed solution of NaOH: Urea: H 2 O 11:4:85, then freeze the suspension at -30°C for 1 hour, and then at 5°C Stir and thaw, freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 996.2nm.
  • Disperse 0.025 g of PLA-g-CS in 9.975 g of a mixed solution of NaOH: Urea: H 2 O 11:4:85, then freeze the suspension at -80°C for 0.5h, and then at 5°C Stir down and thaw, and freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 332.0nm.
  • Disperse 0.025g of PLA-g-CS in 9.975g of a mixed solution of NaOH:urea:H 2 O 11:8:81, then freeze the suspension at -80°C for 0.5h, and then at 5°C Stir down and thaw, and freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 725.7 nm.
  • Disperse 0.025g of PLA-g-CS in 9.975g of LiOH:KOH:urea:H 2 O 4.5:7:8:80.5 mixed solution, then freeze the suspension at -30°C for 3h, and then Stir and thaw at 5°C, and freeze/thaw cycles 3 times.
  • the supernatant is put into a dialysis bag for 48 h, and then freeze-dried to obtain a continuous length of PLA-g- CS nano whiskers have an average diameter of 361.9nm.
  • the average diameter of nanowhiskers obtained at -80°C is basically the same as that obtained at -20°C, but the freezing time is shorter. This is because -80°C will damage the PLA-g-CS crystal region more severely, so The time is shorter.
  • the solution system of 81 is basically equivalent. Under the same conditions, unmodified CS and PLA-g-CS with a grafting rate of less than 50% cannot be dissolved under the same conditions, so nanoparticles or nanowhiskers cannot be prepared under these conditions.
  • Respectively disperse 5wt% of chitin and 5wt% of chitin added with 1% (based on the mass ratio of chitin) of PLA-g-CS nanowhiskers obtained in Example 1 in a NaOH solution (NaOH: urea: H2O 11:4:85, w/w/w), freeze at -80°C for 30 minutes, then stir and thaw at 5°C, repeat the freezing/thawing process 3 times to obtain a transparent solution, and prepare 0.5mm by the continuous flow method The liquid film is placed in a 45% v/v ethanol solution at 5°C to solidify for 3 hours to prepare a hydrogel. The micro-compression mechanical properties of the hydrogel were tested using a nanoindenter.

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Abstract

本发明公开了一种聚乳酸接枝壳聚糖纳米晶须的制备方法，属于材料技术领域。本发明是将丙交酯、催化剂和壳聚糖混合均匀后进行聚合接枝制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须，聚合接枝过程中无溶剂。该方法使得没有良好溶剂的PLA-g-CS可以制备得到纳米晶须，整个反应高效清洁，绿色环保。

Description

一种聚乳酸接枝壳聚糖纳米晶须的制备方法 技术领域
本发明涉及一种聚乳酸接枝壳聚糖纳米晶须的制备方法，属于材料领域。
背景技术
有机纳米材料是指基于脂质、蛋白、多糖及有机高分子聚合物的新型纳米材料。随着纳米技术的不断发展和应用，纳米材料已被广泛地应用于食品、生物医药、农业以及环境等领域。纳米材料由于其纳米级别的尺寸效应而具有的独特物理和化学性质，为食品、农业、工业等领域带来了新的创新发展机遇。多糖纳米晶须生物相容性好、生物降解性好、无毒性、易修饰性和纳米尺寸的功能性等优异的生化性能已引起广泛的研究，在不同的领域已有相应的应用，且在复合材料中的应用十分广泛，以天然高分子和聚合物为基质的纳米复合材料的研究日益深入。
近年来，壳聚糖/聚乳酸复合材料因其良好的抗菌性、生物相容性和可降解性得到了人们的广泛关注。目前已有较多将壳聚糖与聚合接枝的文献(壳聚糖-聚乳酸接枝共聚物的制备与表征,化工新型材料,2012,5,4005)和(壳聚糖与丙交酯接枝共聚物的制备与表征,材料科学与工程学报,2008,1,2601)，对于PLA-g-CS颗粒度的研究有通过物理球磨的方法达到15μm的(Poly(l-lactic acid)bio-composites reinforced by oligo(d-lactic acid)grafted chitosan for simultaneously improved ductility,strength and modulus.International Journal of Biological Macromolecules,2019.131:p.495-504.)，也有以渗滤法和超声波法制得PLA-g-CS纳米颗粒的报道(Preparation of biocompatible chitosan grafted poly(lactic acid)nanoparticles.International Journal of Biological Macromolecules,2012.51(3):p.221-227.)。
壳聚糖接上聚乳酸后，本身的氨基与聚乳酸的羧基反应生成酰胺，连接端基为羟基的聚乳酸链段，侧链的整体亲水性下降。由于PLA-g-CS既不溶于醋酸又不溶于氯仿，这使得将PLA-g-CS做到纳米尺寸的颗粒较为困难，因此还未有学者研究过PLA-g-CS的纳米晶须的制备。另外，而上述文献制备得到的是纳米颗粒，纳米颗粒多为球形，而纳米晶须一般是有一定长径比的直径在纳米尺度的小棍，上述文献制备得到的并非纳米晶须，且上述制备纳米颗粒过程中又需使用大量的有机溶剂，对环境造成污染，不够环保。
发明内容
为了解决上述问题，本发明采用干态接枝方法，制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须。该方法使得没有良好溶剂的PLA-g-CS可 以制备得到纳米晶须，整个反应高效清洁，绿色环保，具有一定的可推广性。
本发明的第一个目的是提供一种聚乳酸接枝壳聚糖(PLA-g-CS)的纳米晶须制备方法，所述方法包括以下步骤：
(1)制备PLA-g-CS：将丙交酯、催化剂和壳聚糖混合均匀后，进行聚合接枝，制备得到PLA-g-CS，聚合接枝过程中无溶剂；
(2)制备PLA-g-CS纳米晶须：将步骤(1)制备得到的PLA-g-CS分散在NaOH:尿素:H 2O或LiOH:KOH:尿素:H 2O的混合溶液中，冷冻/解冻、超声、离心、透析后得到PLA-g-CS纳米晶须。
在本发明一种实施方式中，步骤(1)中丙交酯和壳聚糖的质量比为(2～10):1，催化剂为辛酸亚锡，加入量为丙交酯质量百分数的0.1～1‰。
在本发明一种实施方式中，步骤(1)中聚合接枝条件为：氮气气氛；接枝温度：120-180℃；接枝时间：3-5h。
在本发明一种实施方式中，PLA-g-CS添加量为0.25％～1％。
在本发明一种实施方式中，所述步骤(2)中的NaOH:尿素:H 2O＝(8-15):(4-8):(80-85)。
在本发明一种实施方式中，所述步骤(2)中的LiOH:KOH:尿素:H 2O＝(8-15):(5-9):8:(80-85)。
在本发明一种实施方式中，所述步骤(2)中冷冻条件为温度为-80～-20℃，时间为0.5-3h；解冻条件为5-10℃，时间0.1-0.5h，冷冻/解冻循环2-5次。
在本发明一种实施方式中，所述步骤(2)中超声频率为30-60Hz，时间为10-30min。
在本发明一种实施方式中，所述步骤(2)中离心转速为5000-10000r/min，时间为15-30min。
本发明的第二个目的是提供一种上述方法制备得到的PLA-g-CS纳米晶须。
本发明的第三个目的是提供一种上述PLA-g-CS纳米晶须在食品包装、医药和复合材料方面的应用。
本发明的有益效果：
(1)本发明用聚乳酸接枝壳聚糖，可增强壳聚糖的疏水性和机械性能，同时又环保可降解。目前已知的壳聚糖与聚乳酸的接枝方法均是以溶剂作为反应介质，甚至还需要使用大量溶剂将接枝物析出，而本发明所使用的接枝方法，为干态接枝，在120～150℃下丙交酯处于熔融状态，无需使用溶剂作为反应介质，即可使丙交酯发生开环聚合，以及丙交酯与壳聚糖发生聚合反应，反应过程环保且简单高效，接枝率能高达97％，做到了绿色环保，顺应了时 代的发展；同时接枝产物在食品包装、医药或作为增强体用于复合材料等方面具有潜在应用。
(2)本发明将几乎无法溶解的PLA-g-CS通过在碱液中反复冷冻解冻得的方法制备得到了纳米晶须。由于壳聚糖具有良好的生物降解性、生物相容性、抗菌性及多功能化学和物理性质，聚乳酸是由乳酸为原料聚合得到的，属于可再生资源，原料来源充足且具有良好的生物降解性，可完全降解成水和二氧化碳，不会对环境造成污染，接枝产物做成纳米晶须后在食品包装、医药或作为增强体用于复合材料等方面具有广阔的应用前景，尤其在生物医疗和增强复合材料方面的应用具有极大的潜力。
附图说明
图1为聚乳酸(PDLA)、壳聚糖(CS)和聚乳酸接枝壳聚糖(Oligo(D-LA)-g-CS)的红外光谱图。
图2是按本发明实施例1所制备的聚乳酸与壳聚糖接枝物的纳米晶须SEM照片。
图3是甲壳素水凝胶和聚乳酸接枝壳聚糖纳米晶须增强后的甲壳素水凝胶的微观压缩性能比较。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
实施例1
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS(见图1)，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须(见图2)，平均直径为281.1nm。
实施例2
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.05g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液 超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为502.7nm。
实施例3
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.1g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为893.6nm。
实施例4
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻2h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为699.5nm。
实施例5
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻1h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为996.2nm。
实施例6
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将 PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为332.0nm。
实施例7
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:8:81的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为725.7nm。
实施例8
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的LiOH:KOH:尿素:H 2O＝4.5:7:8:80.5的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为361.9nm。
表1 PLA-g-CS纳米晶须的性能
Figure PCTCN2020119238-appb-000001
由表1可知，实施例1所得的PLA-g-CS纳米晶须的平均直径最小，达到281.1nm。 根据单因素变量原则，在其他条件不变的情况下，随着PLA-g-CS所占溶液的比例的增加，所得纳米晶须的平均直径也不断增大，这是因为PLA-g-CS的比例增加，一定的溶液对其晶区的破坏能力下降，所以得到的纳米晶须的平均直径便越大。在其他条件不变只改变冷冻时间的情况下，由上表可知，冷冻时间越长所得纳米晶须的粒度越小，这说明，溶液对PLA-g-CS晶区的破坏是一个缓慢的过程，因此需要足够的时间来完成这一过程。而在-80℃下所得纳米晶须的平均直径与-20℃所得基本一致，但冷冻时间较短，这是因为-80℃条件对PLA-g-CS晶区的破坏较为剧烈，因此所需的时间较短。NaOH:尿素:H 2O＝11:8:81的溶液体系所得的晶须平均直径较大，这是因为该体系不适合用于溶解PLA-g-CS，对PLA-g-CS的晶区破坏能力较弱。以LiOH:KOH:尿素:H 2O＝4.5:7:8:80.5的溶液体系所制得的PLA-g-CS纳米晶须的平均直径略小于NaOH:尿素:H 2O＝11:4:81的溶液体系，二者基本相当。在同样条件下，未改性的CS和接枝率小于50％的PLA-g-CS无法在相同条件下溶解，因此无法在此条件下制备纳米颗粒或纳米晶须。
实施例9：纳米晶须在作为复合材料增强体中的应用
分别将5wt％的甲壳素和加有1％(基于甲壳素的质量比)实施例1所得的PLA-g-CS纳米晶须的5wt％的甲壳素分散在NaOH溶液(NaOH:尿素:H2O＝11:4:85，w/w/w)中，在-80℃下冷冻30min，再于5℃下搅拌解冻，如此冷冻/解冻重复3次，得到透明的溶液，通过延流法制备0.5mm的液膜，将其放置在5℃的45％v/v乙醇溶液中凝固3h，制备水凝胶。使用纳米压痕仪对水凝胶进行微观压缩力学性能测试。
结果由图3可知，加入纳米晶须的甲壳素水凝胶的模量和硬度均有显著提高。其中，模量从加入前的0.7GPa上升到加入后的1.2GPa，提高了72％，硬度从加入前的91MPa上升到加入后的126MPa，提高了41％。结果说明，纳米晶须可以在水凝胶中发挥较好的增强效果。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (20)

  1. 一种聚乳酸接枝壳聚糖纳米晶须的制备方法，其特征在于，所述方法是将丙交酯、催化剂和壳聚糖混合均匀后进行聚合接枝制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须，聚合接枝过程中无溶剂；所述方法包括以下步骤：
    (1)制备PLA-g-CS：将丙交酯、催化剂和壳聚糖混合均匀后，进行聚合接枝，制备得到PLA-g-CS；丙交酯和壳聚糖的质量比为(2～10):1；聚合接枝条件为：氮气气氛；接枝温度：120-180℃；接枝时间：3-5h；
    (2)制备PLA-g-CS纳米晶须：将步骤(1)制备得到的PLA-g-CS分散在NaOH:尿素:H 2O或LiOH:KOH:尿素:H 2O的混合溶液中，冷冻/解冻、超声、离心、透析后得到PLA-g-CS纳米晶须；NaOH：尿素：H 2O＝11:4:81；LiOH：KOH：尿素：H 2O＝(8-15)：(5-9)：8：(80-85)；
    PLA-g-CS添加量为0.25％～0.5％。
  2. 一种聚乳酸接枝壳聚糖纳米晶须的制备方法，其特征在于，所述方法是将丙交酯、催化剂和壳聚糖混合均匀后进行聚合接枝制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须，聚合接枝过程中无溶剂。
  3. 根据权利要求2所述的方法，其特征在于，所述方法包括以下步骤：
    (1)制备PLA-g-CS：将丙交酯、催化剂和壳聚糖混合均匀后，进行聚合接枝，制备得到PLA-g-CS；
    (2)制备PLA-g-CS纳米晶须：将步骤(1)制备得到的PLA-g-CS分散在NaOH:尿素:H 2O或LiOH:KOH:尿素:H 2O的混合溶液中，冷冻/解冻、超声、离心、透析后得到PLA-g-CS纳米晶须。
  4. 根据权利要求1或2所述的方法，其特征在于，丙交酯和壳聚糖的质量比为(2～10):1，催化剂为辛酸亚锡，加入量为丙交酯的0.1～1‰。
  5. 根据权利要求1或2所述的方法，其特征在于，聚合接枝条件为：氮气气氛；接枝温度：120-180℃；接枝时间：3-5h。
  6. 根据权利要求1或2所述的方法，其特征在于，PLA-g-CS添加量为0.25％～1％。
  7. 根据权利要求3所述的方法，其特征在于，所述步骤(2)中的NaOH：尿素：H 2O＝(8-15):(4-8):(80-85)。
  8. 根据权利要求3所述的方法，其特征在于，所述步骤(2)中的LiOH：KOH：尿素：H 2O＝(8-15)：(5-9)：8：(80-85)。
  9. 根据权利要求3所述的方法，其特征在于，所述步骤(2)中冷冻条件为温度为-80～-20℃，时间为0.5-3h；解冻条件为5-10℃，时间0.1-0.5h，冷冻/解冻循环2-5次。
  10. 根据权利要求3所述的方法，其特征在于，所述步骤(2)中超声频率为30-60Hz， 时间为10-30min。
  11. 根据权利要求3所述的方法，其特征在于，所述步骤(2)中离心转速为5000-10000r/min，时间为15-30min。
  12. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  13. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.05g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  14. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.1g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  15. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.025g的将 PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻2h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  16. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:4:85的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  17. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H 2O＝11:8:81的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  18. 根据权利要求3所述的方法，其特征在于，所述方法包括以下步骤：
    将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌；接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％；将0.025g的将PLA-g-CS分散在9.975g的LiOH:KOH:尿素:H 2O＝4.5:7:8:80.5的混合溶液中，然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次；使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须。
  19. 权利要求1～18任一所述的方法制备得到的PLA-g-CS纳米晶须。
  20. 一种权利要求10所述的PLA-g-CS纳米晶须在食品包装、医药和复合材料方面的应用。
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