基于碱性溶剂体系制备壳聚糖新材料的研究
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摘要
壳聚糖是一种天然多糖,是由甲壳素脱乙酰制备而成,甲壳素在自然界的含量十分丰富,仅次于纤维素。壳聚糖具有良好的生物相容性、生物可降解性、生物活性及无毒等优点,在生物材料方面具有很高的研究意义和应用价值。壳聚糖分子中含有大量的氨基,通常采用稀酸溶液溶解,但壳聚糖在酸体系中会快速降解,对产品造成了很多缺陷。本课题采用冷冻爆破法在碱性体系中将壳聚糖溶解,研究壳聚糖在碱性体系中溶解机理和溶液性质,并通过该体系制备了壳聚糖水凝胶和纤维材料。
1.通过动态光散射对壳聚糖稀溶液研究发现,壳聚糖在碱性溶液中存在纳米级粒子,且纳米粒子的粒径与壳聚糖的浓度成线性关系。
2.系统研究了壳聚糖浓度、LiOH浓度、尿素浓度、脱乙酰度对壳聚糖浓溶液的流变行为的影响。对于酸和碱两种溶剂体系的壳聚糖溶液,其流动指数(n)都小于1,均属假塑性流体；在碱溶剂体系壳聚糖溶液中,LiOH是起到主要与壳聚糖大分子形成包合络合物结构,破坏大分子间的氢键的作用。随着LiOH浓度的增加,形成包合络合物越多,对壳聚糖大分子间的氢键破坏作用更加强烈,使得溶液的溶解就更加充分,因而整个溶液体系的粘度都在减小；同时随着亲水性基团-NH2的减少,壳聚糖浓溶液中的氢键在减少,凝胶点温度增加。因此,随着LiOH浓度、尿素浓度的增加,浓溶液的凝胶点温度会提高；随着壳聚糖脱乙酰度的增加,溶液溶胶-凝胶相变点温度逐步下降。
3.制备了具有超高强度的壳聚糖水凝胶。采用酸和碱两种溶剂体系制备了壳聚糖水凝胶,碱溶剂体系制备的水凝胶具有超高的压缩性能和拉伸性能,在含水率为95.6%时,压缩强度可达1.77MPa,压缩应变为74.1%,拉伸强度为2.30MPa,断裂伸长率为226%。碱溶剂体系制备的水凝胶压缩强度是酸溶剂体系水凝胶的47倍多,压缩应变也是其两倍多。
4.通过SEM研究了两种壳聚糖水凝胶的结构揭示了两种凝胶性能差异的根本原因。两种壳聚糖水凝胶均具有多孔状结构,但是两者结构的差别也是非常明显的。(1)高强度壳聚糖水凝胶具有类似蜂窝状的结构,而且孔径相对均匀,其范围在5μm～10μm,孔与孔之间连接紧密,孔壁薄且光滑；随着壳聚糖浓度的增加,孔径逐步减小。(2)低强度壳聚糖水凝胶具有条带状的三维有序多孔结构,孔大,其范围在230μm以上,形状不规则,孔与孔之间连接松散,孔壁厚约有10μm；随着壳聚糖浓度的增加,孔径变小,分布范围减小。(3)说明高强度壳聚糖水凝胶的物理交联点要多,形成的交联网络更多,且分布相对均匀,估算出高强度壳聚糖水凝胶的物理交联点是低强度壳聚糖水凝胶的30-40倍。这也正是两种壳聚糖凝胶强度差别的根本原因。
5.证明了采用碱溶酸凝固制备壳聚糖纤维以提高纤维的湿态力学性能的设想是正确的。通过酸溶碱凝固和碱溶酸凝固采用湿法纺丝工艺分别制备了壳聚糖纤维。研究结果表明：与酸溶碱凝固制备的壳聚糖纤维相比,由碱溶酸凝固制备的纤维湿态拉伸强度提高了125%,干态拉伸强度提高了22.6%。
Chitosan (CS) is one of polysaccharide, is prepared by N-deacetylation of chitin, which is the main structural component of cr.ab and shrimp shells. As it has many favorable properties such as biodegradability, biocompatibility, bioactivity and non-toxicity, CS has been extensively studied as a promising biomaterial. CS can only dissolve in some specific organic acids and a few inorganic solvents, but it is unstable in aqueous acid. Its hydrolysis is accompanied with the cleavage of glycosidic-bonds, which brings about the poor properties of CS products. The study includes that the mechanism of CS solution dissolved in alkali aqueous solution by freezing-blasting and preparation of CS hydrogel and fibers by this alkali solution system. Therefore, the studies are as followed:
(1) Exploration on the state of CS macromolecules in alkaline solvent and acid solvent was carried out by Dynamic Light Scattering particle size analysis, proving the existence of nanoparticles. The nanoparticle size was linear with CS concentration.
(2) A systematic study of effects on rheological behavior of chitosan aqueous solution by CS concentration, LiOH, urea, degree of deacetylation of Chitosan. In the case of chitosan solution prepared by acid and alkali solvent system, the flow indexes (n) were less than1, which were pseudoplastic fluid; In CS alkali solution, LiOH played a vital role in forming inclusion complexes structure with CS macromolecules and destroying hydrogen bonds between CS macromolecules. With the increase of LiOH concentration, the solution formed more inclusion complexes, and hydrogen bonds between CS macromolecules were destroyed more strongly, therefore CS were dissolved sufficiently. So the viscosity of entire solution system were reduced. At the same time, along with the decrease of the free hydrophilic groups (-NH2), hydrogen bonds between chitosan macromolecules were reduced, and the temperature of gel point increased. In short, with the increase of LiOH and urea, the temperature of gel point of CS solution increased. With the increase of the degree of deacetylation. the temperature of gel point of CS solution decreased.
(3) The high strength pure chitosan (CS) hydrogel was prepared. CS hydrogels were prepared by two kinds of solvent systems (alkaline solvent and acid solvent). The results from universal testing machine indicated that the high strength CS hydrogel prepared by alkaline solvent sustains a compressive stress of1.77MPa. which was47times more than that sustained by the low strength CS hydrogel by acid solvent. The fracture compressive strain (ε) of the high strength CS hydrogel was74.1%, which is much higher than that of the low strength CS hydrogel (ε=32.3%). In addition, the tensile stress and strain of CS hydrogel prepared by alkaline solvent were2.30MPa and226%.
(4) SEM of two hydrogels showed the network structure, which appeared to be highly porous with the interconnected macrodomains. The morphology comprised the CS and pores as features not only of these samples but also of all of the samples that were produced. It is obvious that the structures of two CS hydrogels are different. For the High strength CS (H-CS) hydrogels, these pores possessed honeycomb-like shapes. The pore size and morphology of the various hydrogels were quite similar. The inner surface of pore was smooth, and the pores had a mean diameter of<10μm. The sizes of pore walls were1μm at most. For the low strength CS (L-CS) hydrogels. F it was a ribbon structure. The pores between ribbons had a mean diameter in a range of200to600μm, which were more than30times that H-CS hydrogels. The sizes of pore walls were almost10μm, which were more10times than the size of pore walls of the H-CS hydrogels. The H-CS hydrogels had well-distributed pores. And above all, the results showed that the physical cross-linking points of H-CS hydrogels were more regularly distributed and20times than L-CS hydrogels. The increase of cross-linking points enhanced the cross-linked network of hydrogel, and therefore, the mechanical properties of H-CS hydrogels were improved greatly.
(5) Improving wet mechanical properties of chitosan fibers by a new approach was correct. The results from Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and universal testing machine indicated that the new approach did not change the chemical structure of chitosan. The approach performed better in forming dense structure in the cross section of chitosan fiber and improved thermal stability and mechanical properties of CS65fibers. The wet and dry tensile strength of the novel CS65fibers reached0.8cN/dtex, which were increased by125%, compared with that of CS65fibers prepared by conventional approach.
1.通过动态光散射对壳聚糖稀溶液研究发现,壳聚糖在碱性溶液中存在纳米级粒子,且纳米粒子的粒径与壳聚糖的浓度成线性关系。
2.系统研究了壳聚糖浓度、LiOH浓度、尿素浓度、脱乙酰度对壳聚糖浓溶液的流变行为的影响。对于酸和碱两种溶剂体系的壳聚糖溶液,其流动指数(n)都小于1,均属假塑性流体；在碱溶剂体系壳聚糖溶液中,LiOH是起到主要与壳聚糖大分子形成包合络合物结构,破坏大分子间的氢键的作用。随着LiOH浓度的增加,形成包合络合物越多,对壳聚糖大分子间的氢键破坏作用更加强烈,使得溶液的溶解就更加充分,因而整个溶液体系的粘度都在减小；同时随着亲水性基团-NH2的减少,壳聚糖浓溶液中的氢键在减少,凝胶点温度增加。因此,随着LiOH浓度、尿素浓度的增加,浓溶液的凝胶点温度会提高；随着壳聚糖脱乙酰度的增加,溶液溶胶-凝胶相变点温度逐步下降。
3.制备了具有超高强度的壳聚糖水凝胶。采用酸和碱两种溶剂体系制备了壳聚糖水凝胶,碱溶剂体系制备的水凝胶具有超高的压缩性能和拉伸性能,在含水率为95.6%时,压缩强度可达1.77MPa,压缩应变为74.1%,拉伸强度为2.30MPa,断裂伸长率为226%。碱溶剂体系制备的水凝胶压缩强度是酸溶剂体系水凝胶的47倍多,压缩应变也是其两倍多。
4.通过SEM研究了两种壳聚糖水凝胶的结构揭示了两种凝胶性能差异的根本原因。两种壳聚糖水凝胶均具有多孔状结构,但是两者结构的差别也是非常明显的。(1)高强度壳聚糖水凝胶具有类似蜂窝状的结构,而且孔径相对均匀,其范围在5μm～10μm,孔与孔之间连接紧密,孔壁薄且光滑；随着壳聚糖浓度的增加,孔径逐步减小。(2)低强度壳聚糖水凝胶具有条带状的三维有序多孔结构,孔大,其范围在230μm以上,形状不规则,孔与孔之间连接松散,孔壁厚约有10μm；随着壳聚糖浓度的增加,孔径变小,分布范围减小。(3)说明高强度壳聚糖水凝胶的物理交联点要多,形成的交联网络更多,且分布相对均匀,估算出高强度壳聚糖水凝胶的物理交联点是低强度壳聚糖水凝胶的30-40倍。这也正是两种壳聚糖凝胶强度差别的根本原因。
5.证明了采用碱溶酸凝固制备壳聚糖纤维以提高纤维的湿态力学性能的设想是正确的。通过酸溶碱凝固和碱溶酸凝固采用湿法纺丝工艺分别制备了壳聚糖纤维。研究结果表明：与酸溶碱凝固制备的壳聚糖纤维相比,由碱溶酸凝固制备的纤维湿态拉伸强度提高了125%,干态拉伸强度提高了22.6%。
Chitosan (CS) is one of polysaccharide, is prepared by N-deacetylation of chitin, which is the main structural component of cr.ab and shrimp shells. As it has many favorable properties such as biodegradability, biocompatibility, bioactivity and non-toxicity, CS has been extensively studied as a promising biomaterial. CS can only dissolve in some specific organic acids and a few inorganic solvents, but it is unstable in aqueous acid. Its hydrolysis is accompanied with the cleavage of glycosidic-bonds, which brings about the poor properties of CS products. The study includes that the mechanism of CS solution dissolved in alkali aqueous solution by freezing-blasting and preparation of CS hydrogel and fibers by this alkali solution system. Therefore, the studies are as followed:
(1) Exploration on the state of CS macromolecules in alkaline solvent and acid solvent was carried out by Dynamic Light Scattering particle size analysis, proving the existence of nanoparticles. The nanoparticle size was linear with CS concentration.
(2) A systematic study of effects on rheological behavior of chitosan aqueous solution by CS concentration, LiOH, urea, degree of deacetylation of Chitosan. In the case of chitosan solution prepared by acid and alkali solvent system, the flow indexes (n) were less than1, which were pseudoplastic fluid; In CS alkali solution, LiOH played a vital role in forming inclusion complexes structure with CS macromolecules and destroying hydrogen bonds between CS macromolecules. With the increase of LiOH concentration, the solution formed more inclusion complexes, and hydrogen bonds between CS macromolecules were destroyed more strongly, therefore CS were dissolved sufficiently. So the viscosity of entire solution system were reduced. At the same time, along with the decrease of the free hydrophilic groups (-NH2), hydrogen bonds between chitosan macromolecules were reduced, and the temperature of gel point increased. In short, with the increase of LiOH and urea, the temperature of gel point of CS solution increased. With the increase of the degree of deacetylation. the temperature of gel point of CS solution decreased.
(3) The high strength pure chitosan (CS) hydrogel was prepared. CS hydrogels were prepared by two kinds of solvent systems (alkaline solvent and acid solvent). The results from universal testing machine indicated that the high strength CS hydrogel prepared by alkaline solvent sustains a compressive stress of1.77MPa. which was47times more than that sustained by the low strength CS hydrogel by acid solvent. The fracture compressive strain (ε) of the high strength CS hydrogel was74.1%, which is much higher than that of the low strength CS hydrogel (ε=32.3%). In addition, the tensile stress and strain of CS hydrogel prepared by alkaline solvent were2.30MPa and226%.
(4) SEM of two hydrogels showed the network structure, which appeared to be highly porous with the interconnected macrodomains. The morphology comprised the CS and pores as features not only of these samples but also of all of the samples that were produced. It is obvious that the structures of two CS hydrogels are different. For the High strength CS (H-CS) hydrogels, these pores possessed honeycomb-like shapes. The pore size and morphology of the various hydrogels were quite similar. The inner surface of pore was smooth, and the pores had a mean diameter of<10μm. The sizes of pore walls were1μm at most. For the low strength CS (L-CS) hydrogels. F it was a ribbon structure. The pores between ribbons had a mean diameter in a range of200to600μm, which were more than30times that H-CS hydrogels. The sizes of pore walls were almost10μm, which were more10times than the size of pore walls of the H-CS hydrogels. The H-CS hydrogels had well-distributed pores. And above all, the results showed that the physical cross-linking points of H-CS hydrogels were more regularly distributed and20times than L-CS hydrogels. The increase of cross-linking points enhanced the cross-linked network of hydrogel, and therefore, the mechanical properties of H-CS hydrogels were improved greatly.
(5) Improving wet mechanical properties of chitosan fibers by a new approach was correct. The results from Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and universal testing machine indicated that the new approach did not change the chemical structure of chitosan. The approach performed better in forming dense structure in the cross section of chitosan fiber and improved thermal stability and mechanical properties of CS65fibers. The wet and dry tensile strength of the novel CS65fibers reached0.8cN/dtex, which were increased by125%, compared with that of CS65fibers prepared by conventional approach.
引文
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