固定化载体材料壳聚糖基水凝胶的研究
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摘要
壳聚糖是自然界中惟一存在的阳离子聚合物，壳聚糖及其分解产物无毒，易于改性，具有良好生物相容性及生物降解性，因而倍受世人关注。壳聚糖经戊二醛交联可形成水凝胶，该水凝胶对环境pH／离子有良好的刺激响应性，但其溶胀性能、力学性能及热稳定性能等欠佳，限制了壳聚糖水凝胶的推广应用。
本论文应用聚合物结构设计理论，以壳聚糖、聚醚、聚乙烯醇、丙烯酸、甲基丙烯酸羟乙酯为主要原料，采用溶液法以戊二醛为交联剂制备了壳聚糖水凝胶、壳聚糖-聚醚水凝胶、壳聚糖-聚乙烯醇水凝胶、壳聚糖-丙烯酸水凝胶、壳聚糖-丙烯酸-甲基丙烯酸羟乙酯水凝胶，优化了制备壳聚糖基水凝胶的工艺条件，研究了影响水凝胶溶胀性能、力学性能及敏感性能的各种因素和相关理论，探讨了壳聚糖基水凝胶结构与性能的关系、加工成型及作为固定化载体材料在啤酒酿造中的应用等。本文的主要内容如下：
(1)对壳聚糖的质量进行分析，其水份为15.205％，脱乙酰度为92.671％，重均分子量为195900，黏均分子量为194100，分解温度为298℃，壳聚糖的红外光谱表明，壳聚糖—NH_2的特征吸收峰为1601cm~(-1)，β-糖苷键的特征吸收峰为986cm~(-1)，壳聚糖的X-衍射图表明壳聚糖原料的脱乙酰度和结晶度均较大。
当壳聚糖浓度为2.0％(w／v)，戊二醛浓度为0.213mol／L，凝胶温度为45℃，制备的壳聚糖水凝胶的溶胀度最好；当壳聚糖浓度为3.0％、戊二醛浓度为0.426mol／L、凝胶温度为55℃，其硬度最高。合成工艺条件对凝胶溶胀度和硬度有着显著影响，其中戊二醛、壳聚糖浓度是壳聚糖水凝胶溶胀度和硬度最重要的影响因素，干燥的壳聚糖水凝胶不能再吸水溶胀。壳聚糖水凝胶具有典型的pH／离子敏感性，其敏感性与壳聚糖分子链上氨基有着密切关系。
(2)正交实验的结果表明，当凝胶温度为45℃、聚醚与壳聚糖质量比为0.4、戊二醛浓度为0.213mol／L，壳聚糖-聚醚水凝胶的溶胀度最好；当凝胶温度为45℃、聚醚与壳聚糖质量比为0.6、戊二醛浓度为0.426mol／L时，水凝胶的硬度最高。壳聚糖分子量、聚醚和交联剂的种类和浓度是溶胀度和硬度的重要影响因素，其中戊二醛的浓度不仅影响水凝胶的结构、性能，而且影响其溶胀动力学类型。壳聚糖-聚醚水凝胶具有pH和离子敏感性，其敏感性与壳聚糖分子链上氨基密切相关，而与聚醚无关。聚醚是亲水性的柔性高分子聚合物，与壳聚糖形成半互穿网络水凝胶，干燥后水凝胶溶胀性能良好。
(3)制备高溶胀度壳聚糖-聚乙烯醇水凝胶的最佳条件为聚乙烯醇与壳聚糖质量比2、醋酸体积100mL、戊二醛浓度0.213mol／L、甲醛浓度1.086mol／L；而制备高硬度水凝胶的最佳条件为聚乙烯醇与壳聚糖质量比6、醋酸体积80mL、戊二醛浓度0.426mol／L、甲醛浓度1.086mol／L。
聚乙烯醇具有优良的机械性能，与壳聚糖共混形成半互穿网络水凝胶，可增强凝胶强度；甲醛是预交联剂，可改善壳聚糖-聚乙烯醇水凝胶的交联效果；循环冷冻-解冻使聚乙烯醇分子产生物理交联，交联密度增大，因而均可显著改善凝胶硬度。因为壳聚糖的氨基，壳聚糖-聚乙烯醇水凝胶对环境pH／离子浓度具有很好的刺激响应性，该性能与聚乙烯醇无关。
(4)硝酸铈铵是引发壳聚糖开环接枝的最常用的引发剂。当加入3mmol／L引发剂硝酸铈铵3mL、5.080mol／L丙烯酸浓度、60℃时接枝2.5h，其接枝率最高，接枝率对壳聚糖-丙烯酸水凝胶的结构和性能影响重大。
当丙烯酸浓度为5.805mol／L、硝酸铈铵体积4.0mE、戊二醛浓度0.213mol／L、50℃凝胶，壳聚糖-丙烯酸水凝胶溶胀度最高，当丙烯酸浓度为3.628mol／L、硝酸铈铵2.0mL、戊二醛浓度为0.426mol／L、45℃凝胶，其硬度最好。合成条件是影响壳聚糖-丙烯酸水凝胶溶胀度和硬度的重要因素。壳聚糖的氨基，聚丙烯酸的羧基，使得壳聚糖-丙烯酸水凝胶具有pH和离子敏感性。
(5)正交实验的结果表明，丙烯酸浓度为5.805mol／L、戊二醛浓度为0.213mol／L，加入硝酸铈铵3.0mL和甲基丙烯酸羟乙酯20.0mL，制得的水凝胶溶胀度最好；当丙烯酸浓度为2.903mol／L、戊二醛浓度为0.426mol／L，加入硝酸铈铵2.0mL和甲基丙烯酸羟乙酯40.0mL，其硬度最高，戊二醛与丙烯酸浓度、甲基丙烯酸羟乙酯添加量等对凝胶溶胀度和硬度影口向显著。凝胶结构在放置过程中发生变化，变得致密而有序，宏观上表现为凝胶透明而有光泽，其硬度大幅度增加。该水凝胶在高浓度氢氧化钠溶液中凝胶体积急剧膨胀，凝胶中的水可分为非冻结水(即束缚水)和可冻结水(即自由水和中间水)，热分析结果证明水凝胶中存在不同状态的水，即可冻结水和非冻结水。
(6)通过质构仪、傅里叶红外光谱(FTIR)、X-射线衍射(XRD)、扫描电子显微镜(SEM)、差示扫描量热(DSC)、热重分析(DSC-TGA)等对壳聚糖基水凝胶的结构和性能进行表征，结果表明壳聚糖基水凝胶的结构决定其性能。
壳聚糖基水凝胶可作为啤酒酵母的固定化载体应用于啤酒酿造，其中壳聚糖-聚乙烯醇水凝胶是极具应用价值的固定化载体材料，而壳聚糖-丙烯酸-甲基丙烯酸羟乙酯水凝胶在结构和性能方面与其他壳聚糖基水凝胶相比，具有无可比拟的优势。
Chitosan is the only cation polymer existent in nature. It-and its decompositionproducts are non-poisonus. Besides, theproperties of chitosan are easy to be modified,and it possesses good biocompatibility and biodegradation, thus attracting scientists'much attention. Chitosan hydrogel can be synthesized in acetic acid solution withchitosan using glutaraldehyde as crosslinker. The hydrogel are well sensitive to pHand ion, but its swelling properties, mechanical properties and thermal stability are notgood, which restricts the wide application of chitosan hydrogel.
This dissertation discusses ways to synthesize chitosan hydrogel,chitosan-polyether hydrogel, chitosan-polyvinyl alcohol hydrogel, chitosan-acrylicacid hydrogel and chitosan-acrylic acid-hydroxyethyl methacrylate hydrogel by usingchitosan, polyether, polyvinyl alcohol, acrylic acid and hydroxyethyl methacrylate asthe chief materials and glutaraldehyde as the crosslinker through the aqueous way,based on the design theory of polymer molecule. In this study, the process conditionsto produce chitosan-based hydrogels were optimized, and the optimized processvariables was determined by orthogonal experiments. The relevant theories andvarious factors affecting the swelling properties, mechanical properties and stability ofchitosan hydrogel were investigated. Moreover, the relationship between the structureand performances of chitosan-basecl hydrogels, its shaping and processing, itsapplication in beer brewing as the carrier materials for immobilization and so on. Themain contents of this dissertation are as follows:
(1) The quality analytiedal results of chitosan are as follows: water for 15.205%;degree of deacetylation 92.671%; the weight average relative molecular weight ofchitosan 195900; the viscosity average relative molecular weight of chitosan 194100;and the decomposing temperature 298℃. The infrared ray IR spectra of chitosanshows that the feature-absorbing band of chitosan amido was 1601cm~(-1), that ofβ-indican bond was 986cm~(-1). The results of the X-ray diffraction of chitosan indicatesthat its degree of deacetylation and degree of crystal are both big.
When the concentration of chitosan is 2.0%(g/mL), concentration of glutaraldehydeis 0.213mol/L, and gelatin temperature is 45℃, the swelling ratio of chitosan hydrogelis the biggest; When the concentration ofchitosan is 3.0%(g/mL), concentration ofglutaraldehyde is 0.426mol/L, and gelatin temperature is 55℃, its hardness is thehighest. The synthesis conditions have great impact on its swelling ratio and hardness.Among them, concentration of glutaraldehyde and chitosan is the main factoraffecting the swelling ratio and hardness of chitosan hydrogel. Dry chitosan hydrogel can no longer absorb water to swell. It is typically pH-sensitive and ion-sensitive, andits sensitivity is closely related to the amido on the molecular chain of chitosan.
(2) The results of orthogonal experiments showed that when the gelatin temperaturewas 45℃, the mass ratio of polyether and chitosan was 0.4, the concentration ofglutaraldehyde was 0.213mol/L, the swelling ratio of chitosan-polyether hydrogel isthe biggest. When the gelatin temperature was 45℃, the mass ratio of polyether andchitosan was 0.6, the concentration of glutaraldehyde was 0.426mol/L, its hardness isthe highest. The relative molecular weight of chitosan, polyether, and the type andconcentration of crosslinker are the main factors affecting the swelling ratio andhardness of chitosan hydrogel. Among them concentration of glutaraldehyde not onlyaffects the structure and property of chitosan hydrogel, but also affects its kinds ofswelling kinetics. Chitosan hydrogel is pH-sensitive and ion-sensitive, and itssensitivity is closely related to the amido on the molecular chain of chitosan, but it isirrelevant to polyether, which is hydrophilic yielding macromolecule polymer.Polyether and chitosan form hydrogel of semi-interpenetrating polymernetworks(semi-IPN), and the swelling properties of dry hydrogel are excellent.
(3) The best conditions for making high swelling ratio chitosan-polyvinyl alcoholhydrogel are as follows: the mass ratio of polyvinyl alcohol and chitosan 2; volume ofacetic acid 100.0mL; concentration of glutaraldehyde 0.213mol/L and concentrationof formaldehyde 1.086mol/L. However, the best conditions for making hard hydrogelare as follows: the mass ratio of polyvinyl alcohol and chitosan 6; the volume ofacetic acid 80.0mL; the concentration of glutaraldehyde 0.426mol/L andconcentration of formaldehyde 1.086mol/L.
Polyvinyl alcohol possesses excellent mechanical properties. If it formssemi-interpenetrating polymer networks hydrogel with chitosan, the hydrogel will bestronger. As a fore-crosslinker, formaldehyde can improve the crosslinking effect ofchitosan-polyvinyl alcohol hydrogel. The freeze-thaw cycle made the molecule ofpolyvinyl alcohol to formed physical crosslink, resulting in increase in hardness of thehydrogel due to increase in crosslink density. Because of amido of chitosan chitosan-polyvinyl alcohol hydrogel is well sensitive to pH and the concentration ion. However,the above fact is irrelevant to polyvinyl alcohol.
(4) Cerium ammouium nitrate is the initiator which makes chitosan ring openingand grafting. When 3.0mL 3.0mmol/L cerium ammouium nitrate was added, theconcentration of acrylic acid was 5.080mol/L, and grafting condition was 2.5h at60℃, its grafting yield was the highest. The grafting yield had great effect on thestructure and properties of chitosan-acrylic acid hydrogel.
When the concentration of acrylic acid was 5.805mol/L, the volume of ceriumammouium nitrate was 4.0mL, the concentration of glutaraldehyde was 0.213mol/L,the temperature of gelation was 50℃, the swelling ratio of chitosan-acrylic acidhydrogel was the highest. When the concentration of acrylic acid was 3.628mol/L, thevolume of cerium ammouium nitrate was 2.0mL, the concentration of glutaraldehydewas 0.426mol/L, gelation at 45℃, the hardness of chitosan-acrylic acid hydrogelwas the highest. The synthesis conditions are the main factors affecting the swellingratio and hardness of Chitosan-acrylic acid hydrogel. The amido of Chitosan and thecarboxyl of acrylic acid made Chitosan-acrylic acid hydrogel pH-sensitive andion-sensitive.
(5) The results of orthogonal experiments showed that when the concentration ofacrylic acid was 5.805mol/L, the concentration of glutaraldehyde was 0.213mol/L,3.0mL of cerium ammouium nitrate and 20.0mL of hydroxyethyl methacrylate wereadded, the swelling ratio of the hydrogel was the best. When the concentration ofacrylic acid was 2.903mol/L, the concentration of glutaraldehyde was 0.426mol/L,2.0mL of cerium ammouium nitrate and 40.0mL of hydroxyethyl methacrylate wereadded, the hardness of the hydrogel was the highest. The concentration of acrylic acidand glutaraldehyde and the amount of cerium ammouium nitrate and hydroxyethylmethacrylate added had great effect on the swelling ratio and hardness of the hydrogel.The structure of the hydrogel will change with time and it will become compact andordered. In other words, it will become transparent, lustrous and much harder. Thehydrogel will swell rapidly in the solution of sodium hydroxide, and the water in it isnon-freezing water (bond water) and freezing water (free water and intermediatewater). The results of thermal analysis showed that the water exists in different states-freezing and non-freezing.
(6) Studies on the structures and properties of chitosan-based hydrogels performedwith the help of such devices as Texture Aualyser, FTIR, XRD, SEM, DSC,DSC-TGA showed that the properties of chitosan-based hydrogels were determinedby its structures.
As the carrier for immobilization of beer yeast, chitosan-based hydrogels can beused in beer brewing. Among these chitosan-based hydrogels, chitosan-polyvinylalcohol hydrogel is regarded as valuable carrier material for immobilization, and thechitosan-acrylic acid-hydroxyethyl methacrylate hydrogel has some incomparableadvantages over other hydrogels in structure and properties.
本论文应用聚合物结构设计理论，以壳聚糖、聚醚、聚乙烯醇、丙烯酸、甲基丙烯酸羟乙酯为主要原料，采用溶液法以戊二醛为交联剂制备了壳聚糖水凝胶、壳聚糖-聚醚水凝胶、壳聚糖-聚乙烯醇水凝胶、壳聚糖-丙烯酸水凝胶、壳聚糖-丙烯酸-甲基丙烯酸羟乙酯水凝胶，优化了制备壳聚糖基水凝胶的工艺条件，研究了影响水凝胶溶胀性能、力学性能及敏感性能的各种因素和相关理论，探讨了壳聚糖基水凝胶结构与性能的关系、加工成型及作为固定化载体材料在啤酒酿造中的应用等。本文的主要内容如下：
(1)对壳聚糖的质量进行分析，其水份为15.205％，脱乙酰度为92.671％，重均分子量为195900，黏均分子量为194100，分解温度为298℃，壳聚糖的红外光谱表明，壳聚糖—NH_2的特征吸收峰为1601cm~(-1)，β-糖苷键的特征吸收峰为986cm~(-1)，壳聚糖的X-衍射图表明壳聚糖原料的脱乙酰度和结晶度均较大。
当壳聚糖浓度为2.0％(w／v)，戊二醛浓度为0.213mol／L，凝胶温度为45℃，制备的壳聚糖水凝胶的溶胀度最好；当壳聚糖浓度为3.0％、戊二醛浓度为0.426mol／L、凝胶温度为55℃，其硬度最高。合成工艺条件对凝胶溶胀度和硬度有着显著影响，其中戊二醛、壳聚糖浓度是壳聚糖水凝胶溶胀度和硬度最重要的影响因素，干燥的壳聚糖水凝胶不能再吸水溶胀。壳聚糖水凝胶具有典型的pH／离子敏感性，其敏感性与壳聚糖分子链上氨基有着密切关系。
(2)正交实验的结果表明，当凝胶温度为45℃、聚醚与壳聚糖质量比为0.4、戊二醛浓度为0.213mol／L，壳聚糖-聚醚水凝胶的溶胀度最好；当凝胶温度为45℃、聚醚与壳聚糖质量比为0.6、戊二醛浓度为0.426mol／L时，水凝胶的硬度最高。壳聚糖分子量、聚醚和交联剂的种类和浓度是溶胀度和硬度的重要影响因素，其中戊二醛的浓度不仅影响水凝胶的结构、性能，而且影响其溶胀动力学类型。壳聚糖-聚醚水凝胶具有pH和离子敏感性，其敏感性与壳聚糖分子链上氨基密切相关，而与聚醚无关。聚醚是亲水性的柔性高分子聚合物，与壳聚糖形成半互穿网络水凝胶，干燥后水凝胶溶胀性能良好。
(3)制备高溶胀度壳聚糖-聚乙烯醇水凝胶的最佳条件为聚乙烯醇与壳聚糖质量比2、醋酸体积100mL、戊二醛浓度0.213mol／L、甲醛浓度1.086mol／L；而制备高硬度水凝胶的最佳条件为聚乙烯醇与壳聚糖质量比6、醋酸体积80mL、戊二醛浓度0.426mol／L、甲醛浓度1.086mol／L。
聚乙烯醇具有优良的机械性能，与壳聚糖共混形成半互穿网络水凝胶，可增强凝胶强度；甲醛是预交联剂，可改善壳聚糖-聚乙烯醇水凝胶的交联效果；循环冷冻-解冻使聚乙烯醇分子产生物理交联，交联密度增大，因而均可显著改善凝胶硬度。因为壳聚糖的氨基，壳聚糖-聚乙烯醇水凝胶对环境pH／离子浓度具有很好的刺激响应性，该性能与聚乙烯醇无关。
(4)硝酸铈铵是引发壳聚糖开环接枝的最常用的引发剂。当加入3mmol／L引发剂硝酸铈铵3mL、5.080mol／L丙烯酸浓度、60℃时接枝2.5h，其接枝率最高，接枝率对壳聚糖-丙烯酸水凝胶的结构和性能影响重大。
当丙烯酸浓度为5.805mol／L、硝酸铈铵体积4.0mE、戊二醛浓度0.213mol／L、50℃凝胶，壳聚糖-丙烯酸水凝胶溶胀度最高，当丙烯酸浓度为3.628mol／L、硝酸铈铵2.0mL、戊二醛浓度为0.426mol／L、45℃凝胶，其硬度最好。合成条件是影响壳聚糖-丙烯酸水凝胶溶胀度和硬度的重要因素。壳聚糖的氨基，聚丙烯酸的羧基，使得壳聚糖-丙烯酸水凝胶具有pH和离子敏感性。
(5)正交实验的结果表明，丙烯酸浓度为5.805mol／L、戊二醛浓度为0.213mol／L，加入硝酸铈铵3.0mL和甲基丙烯酸羟乙酯20.0mL，制得的水凝胶溶胀度最好；当丙烯酸浓度为2.903mol／L、戊二醛浓度为0.426mol／L，加入硝酸铈铵2.0mL和甲基丙烯酸羟乙酯40.0mL，其硬度最高，戊二醛与丙烯酸浓度、甲基丙烯酸羟乙酯添加量等对凝胶溶胀度和硬度影口向显著。凝胶结构在放置过程中发生变化，变得致密而有序，宏观上表现为凝胶透明而有光泽，其硬度大幅度增加。该水凝胶在高浓度氢氧化钠溶液中凝胶体积急剧膨胀，凝胶中的水可分为非冻结水(即束缚水)和可冻结水(即自由水和中间水)，热分析结果证明水凝胶中存在不同状态的水，即可冻结水和非冻结水。
(6)通过质构仪、傅里叶红外光谱(FTIR)、X-射线衍射(XRD)、扫描电子显微镜(SEM)、差示扫描量热(DSC)、热重分析(DSC-TGA)等对壳聚糖基水凝胶的结构和性能进行表征，结果表明壳聚糖基水凝胶的结构决定其性能。
壳聚糖基水凝胶可作为啤酒酵母的固定化载体应用于啤酒酿造，其中壳聚糖-聚乙烯醇水凝胶是极具应用价值的固定化载体材料，而壳聚糖-丙烯酸-甲基丙烯酸羟乙酯水凝胶在结构和性能方面与其他壳聚糖基水凝胶相比，具有无可比拟的优势。
Chitosan is the only cation polymer existent in nature. It-and its decompositionproducts are non-poisonus. Besides, theproperties of chitosan are easy to be modified,and it possesses good biocompatibility and biodegradation, thus attracting scientists'much attention. Chitosan hydrogel can be synthesized in acetic acid solution withchitosan using glutaraldehyde as crosslinker. The hydrogel are well sensitive to pHand ion, but its swelling properties, mechanical properties and thermal stability are notgood, which restricts the wide application of chitosan hydrogel.
This dissertation discusses ways to synthesize chitosan hydrogel,chitosan-polyether hydrogel, chitosan-polyvinyl alcohol hydrogel, chitosan-acrylicacid hydrogel and chitosan-acrylic acid-hydroxyethyl methacrylate hydrogel by usingchitosan, polyether, polyvinyl alcohol, acrylic acid and hydroxyethyl methacrylate asthe chief materials and glutaraldehyde as the crosslinker through the aqueous way,based on the design theory of polymer molecule. In this study, the process conditionsto produce chitosan-based hydrogels were optimized, and the optimized processvariables was determined by orthogonal experiments. The relevant theories andvarious factors affecting the swelling properties, mechanical properties and stability ofchitosan hydrogel were investigated. Moreover, the relationship between the structureand performances of chitosan-basecl hydrogels, its shaping and processing, itsapplication in beer brewing as the carrier materials for immobilization and so on. Themain contents of this dissertation are as follows:
(1) The quality analytiedal results of chitosan are as follows: water for 15.205%;degree of deacetylation 92.671%; the weight average relative molecular weight ofchitosan 195900; the viscosity average relative molecular weight of chitosan 194100;and the decomposing temperature 298℃. The infrared ray IR spectra of chitosanshows that the feature-absorbing band of chitosan amido was 1601cm~(-1), that ofβ-indican bond was 986cm~(-1). The results of the X-ray diffraction of chitosan indicatesthat its degree of deacetylation and degree of crystal are both big.
When the concentration of chitosan is 2.0%(g/mL), concentration of glutaraldehydeis 0.213mol/L, and gelatin temperature is 45℃, the swelling ratio of chitosan hydrogelis the biggest; When the concentration ofchitosan is 3.0%(g/mL), concentration ofglutaraldehyde is 0.426mol/L, and gelatin temperature is 55℃, its hardness is thehighest. The synthesis conditions have great impact on its swelling ratio and hardness.Among them, concentration of glutaraldehyde and chitosan is the main factoraffecting the swelling ratio and hardness of chitosan hydrogel. Dry chitosan hydrogel can no longer absorb water to swell. It is typically pH-sensitive and ion-sensitive, andits sensitivity is closely related to the amido on the molecular chain of chitosan.
(2) The results of orthogonal experiments showed that when the gelatin temperaturewas 45℃, the mass ratio of polyether and chitosan was 0.4, the concentration ofglutaraldehyde was 0.213mol/L, the swelling ratio of chitosan-polyether hydrogel isthe biggest. When the gelatin temperature was 45℃, the mass ratio of polyether andchitosan was 0.6, the concentration of glutaraldehyde was 0.426mol/L, its hardness isthe highest. The relative molecular weight of chitosan, polyether, and the type andconcentration of crosslinker are the main factors affecting the swelling ratio andhardness of chitosan hydrogel. Among them concentration of glutaraldehyde not onlyaffects the structure and property of chitosan hydrogel, but also affects its kinds ofswelling kinetics. Chitosan hydrogel is pH-sensitive and ion-sensitive, and itssensitivity is closely related to the amido on the molecular chain of chitosan, but it isirrelevant to polyether, which is hydrophilic yielding macromolecule polymer.Polyether and chitosan form hydrogel of semi-interpenetrating polymernetworks(semi-IPN), and the swelling properties of dry hydrogel are excellent.
(3) The best conditions for making high swelling ratio chitosan-polyvinyl alcoholhydrogel are as follows: the mass ratio of polyvinyl alcohol and chitosan 2; volume ofacetic acid 100.0mL; concentration of glutaraldehyde 0.213mol/L and concentrationof formaldehyde 1.086mol/L. However, the best conditions for making hard hydrogelare as follows: the mass ratio of polyvinyl alcohol and chitosan 6; the volume ofacetic acid 80.0mL; the concentration of glutaraldehyde 0.426mol/L andconcentration of formaldehyde 1.086mol/L.
Polyvinyl alcohol possesses excellent mechanical properties. If it formssemi-interpenetrating polymer networks hydrogel with chitosan, the hydrogel will bestronger. As a fore-crosslinker, formaldehyde can improve the crosslinking effect ofchitosan-polyvinyl alcohol hydrogel. The freeze-thaw cycle made the molecule ofpolyvinyl alcohol to formed physical crosslink, resulting in increase in hardness of thehydrogel due to increase in crosslink density. Because of amido of chitosan chitosan-polyvinyl alcohol hydrogel is well sensitive to pH and the concentration ion. However,the above fact is irrelevant to polyvinyl alcohol.
(4) Cerium ammouium nitrate is the initiator which makes chitosan ring openingand grafting. When 3.0mL 3.0mmol/L cerium ammouium nitrate was added, theconcentration of acrylic acid was 5.080mol/L, and grafting condition was 2.5h at60℃, its grafting yield was the highest. The grafting yield had great effect on thestructure and properties of chitosan-acrylic acid hydrogel.
When the concentration of acrylic acid was 5.805mol/L, the volume of ceriumammouium nitrate was 4.0mL, the concentration of glutaraldehyde was 0.213mol/L,the temperature of gelation was 50℃, the swelling ratio of chitosan-acrylic acidhydrogel was the highest. When the concentration of acrylic acid was 3.628mol/L, thevolume of cerium ammouium nitrate was 2.0mL, the concentration of glutaraldehydewas 0.426mol/L, gelation at 45℃, the hardness of chitosan-acrylic acid hydrogelwas the highest. The synthesis conditions are the main factors affecting the swellingratio and hardness of Chitosan-acrylic acid hydrogel. The amido of Chitosan and thecarboxyl of acrylic acid made Chitosan-acrylic acid hydrogel pH-sensitive andion-sensitive.
(5) The results of orthogonal experiments showed that when the concentration ofacrylic acid was 5.805mol/L, the concentration of glutaraldehyde was 0.213mol/L,3.0mL of cerium ammouium nitrate and 20.0mL of hydroxyethyl methacrylate wereadded, the swelling ratio of the hydrogel was the best. When the concentration ofacrylic acid was 2.903mol/L, the concentration of glutaraldehyde was 0.426mol/L,2.0mL of cerium ammouium nitrate and 40.0mL of hydroxyethyl methacrylate wereadded, the hardness of the hydrogel was the highest. The concentration of acrylic acidand glutaraldehyde and the amount of cerium ammouium nitrate and hydroxyethylmethacrylate added had great effect on the swelling ratio and hardness of the hydrogel.The structure of the hydrogel will change with time and it will become compact andordered. In other words, it will become transparent, lustrous and much harder. Thehydrogel will swell rapidly in the solution of sodium hydroxide, and the water in it isnon-freezing water (bond water) and freezing water (free water and intermediatewater). The results of thermal analysis showed that the water exists in different states-freezing and non-freezing.
(6) Studies on the structures and properties of chitosan-based hydrogels performedwith the help of such devices as Texture Aualyser, FTIR, XRD, SEM, DSC,DSC-TGA showed that the properties of chitosan-based hydrogels were determinedby its structures.
As the carrier for immobilization of beer yeast, chitosan-based hydrogels can beused in beer brewing. Among these chitosan-based hydrogels, chitosan-polyvinylalcohol hydrogel is regarded as valuable carrier material for immobilization, and thechitosan-acrylic acid-hydroxyethyl methacrylate hydrogel has some incomparableadvantages over other hydrogels in structure and properties.
引文
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