Preparation of carbonxymethyl chitosan and its effects on medical dialysis paper
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摘要: 为了改善壳聚糖的水溶性，拓展其在造纸领域的应用，本研究以壳聚糖(CS)为主要原料，采用氯乙酸作为醚化剂，在碱性条件下进行羧甲基化反应，通过控制反应温度、时间和pH值来得到不同取代位点的羧甲基壳聚糖(CMCS)，利用红外光谱和核磁氢谱对CMCS产物进行结构表征和分析，并测定了其取代度及在水中的溶解度；最后将制备好的CMCS作为添加剂用于透析纸的制备，研究其用量对透析纸物理强度、透气度及抗菌性能的影响。结果表明：添加不同取代位点的羧甲基壳聚糖对透析纸的强度均有所改善，相对于氨基位取代的CMCS(N-CMCS)和氨基及羟基位同时取代的CMCS(N,O-CMCS)，添加羟基位取代的CMCS(O-CMCS)对透析纸的增强效果最为显著。当O-CMCS添加量为2.5% 时，纸张的干、湿抗张强度、耐破指数分别为61.6 N·m·g−1、8.61 N·m·g−1和6.19 kPa·m2·g−1，比未添加时分别提高了18.8%、113%和91.0%；纸张的透气度为7.98 µm·(Pa·s) −1，满足透析纸的高透气性要求。此外，添加O-CMCS、N-CMCS 和 N,O-CMCS的纸张均具有较好的抗菌性，对大肠杆菌的抑菌率分别达到86.7%、83.8%和83.6%。Abstract: In order to improve the water solubility of chitosan (CS) and extend its application in the field of papermaking, CS was used as the main raw material and chloroacetic acid was used as the etherification agent to prepare carboxymethyl chitosan (CMCS) under alkaline conditions. CMCS with different substitution sites were obtained by controlling the reaction temperature, time and pH value. Then, the structures of CMCS were analyzed by using infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H-NMR), and their degree of substitution and water solubility were measured. Finally, the prepared CMCS was used as additives to prepare dialysis paper, and the effects of CMCS dosage on the physical strength, permeability and antibacterial performance of dialysis paper were investigated. The results showed that the addition of CMCS with different substitution sites all improved the physical strength of dialysis paper, however, compared with the amino substituted CMCS (N-CMCS) and the amino and hydroxyl substituted CMCS (N,O-CMCS), the addition of the hydroxyl substituted CMCS (O-CMCS) had the most significant effects. When 2.5% O-CMCS was added to the papermaking pulp, the dry tensile, wet tensile and burst index of the paper were 61.6 N·m·g−1, 8.61 N·m·g−1 and 6.19 kPa·m2·g−1, which increased by 18.8%, 113%, and 91.0%, respectively. The air permeability of paper reached 7.98 µ m·(Pa·s) −1, meeting the requirements of air permeability of the dialysis paper. In addition, the paper containing O-CMCS, N-CMCS and N, O-CMCS all showed good antibacterial activity, and had antibacterial rates of 86.7%, 83.8%, and 83.6% against Escherichia coli, respectively.
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图 1 壳聚糖(CS)和氨基位取代的羧甲基壳聚糖(N-CMCS)、羟基位取代的CMCS(O-CMCS)、氨基及羟基位同时取代的CMCS(N,O-CMCS)的FT-IR图
Figure 1. FT-IR spectra of chitosan (CS) and amino substituted carboxymethyl chitosan (N-CMCS), hydroxyl substituted CMCS (O-CMCS), amino and hydroxyl substituted CMCS (N,O-CMCS)
图 2 O-CMCS(a)、N-CMCS(b)和N,O-CMCS(c) 核磁共振氢谱图
Figure 2. 1 H-NMR of O-CMCS (a), N-CMCS(b) and N,O-CMCS (c)
图 5 CMCS用量与纸张的干抗张指数(a)和湿抗张指数(b)的关系
Figure 5. The relationship between the amount of CMCS and the dry tensile index (a) and the wet tensile index (b) of paper
图 6 CMCS 用量与纸张(a)撕裂指数和(b)耐破指数的关系
Figure 6. The relationship between the amount of CMCS used and (a) the tear index and (b) the burst resistance index of the paper
图 7 CMCS 用量与纸张透气度的关系
Figure 7. The relationship between CMCS dosage and air permeability of paper
图 8 对照样和添加CMCS纸张的抗菌效果
Figure 8. Antimicrobial effect of control samples and addition of CMCS paper
表 1 不同取代位点CMCS的取代度、溶解度及黏度
Table 1. Substitution, solubility and viscosity of CMCS at different substitution sites
Samples Degree of
Substitution(DS)Water
Solubility/(g·L-1)Viscosity/
(mPa∙s)O-CMCS 0.566 12.44 23.20 N,O-CMCS 1.196 64.53 15.23 N-CMCS 1.227 80.00 10.56 
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