【作者】 程志强；

【导师】 李俊锋；

【作者基本信息】 吉林大学 ， 应用化学， 2013， 博士

【摘要】 农用高吸水树脂材料被称为继化肥、农药、地膜之后能够被农民接受的第四大类农用化学制品。但目前的保水剂成本高，保水和释水的功能单一，而且吸水后凝胶强度低，一直没有得到广泛使用。本论文以食用菌菌糠（食用菌糠是由玉米芯和木屑等物质组成的，培育食用菌后，得到菌糠。）为原料，采用溶液聚合法，通过微波辐射及紫外光引发与高分子单体混合共聚合成了多种菌糠基复合高吸水树脂，并对其制备最合成条件及性能进行了研究。主要工作如下:1、在一定中和度下，以微波辐射加热引发成功合成了黑木耳菌糠/聚（丙烯酸-co-丙烯酰胺）新型高吸水树脂共聚物。系统的研究了最佳合成条件，即黑木耳菌糠、丙烯酰胺单体、引发剂和交联剂相对丙烯酸的比率以及丙烯酸中和度对高吸水树脂性能的影响。实验发现所制备的复合高吸水树脂在蒸馏水中最大的吸水倍率达1548g.g^-1，在0.9wt%NaCl溶液中吸水倍率为72g.g^-1。傅里叶变换红外光谱测定了复合高吸水的分子结构特征，并通过扫描电子显微镜证实复合高吸水树脂为结构致密的多孔材料，透射电子显微镜进一步证实黑木耳菌糠与高分子聚合物形成互穿网络结构。热重分析表明复合高吸水树脂材料具有较高的热稳定性能。此外，树脂溶胀吸水过程符合一级动力学方程，并用复合高吸水树脂在各种肥料中的吸水倍率和吸附性也被研究，揭示出复合高吸水树脂吸水倍率及肥料吸附性与肥料浓度之间的关系。2、用KOH中和丙烯酸，一定功率的微波辐射引发合成了富含植营养元素K的白灵菇菌糠复/聚丙烯酸钾复合高吸水树脂。复合高吸水树脂在蒸馏水中最大的吸水倍率为974g.g^-1，在0.9wt%NaCl溶液中吸水倍率大为59g.g^-1。通过傅里叶变换红外光谱，热重和扫描电子显微镜表征复合高吸水材料的分子结构特征，分析了复合高吸水树脂的热稳定性能，并通过扫描电子显微镜证实复合高吸水树脂表面粗糙多孔，此外，在离心机转速为6000rpm下，50min复合高水树脂的失水率为6.2%。3、与2相同方式合成了平菇菌糠/丙烯酸钾复合高吸水树脂。复合高吸水树脂在蒸馏水中最大的吸水倍率为827g.g^-1，在0.9%NaCl溶液中吸水倍率大为87g.g^-1。在离心机转速为6000rpm下，50min复合高水树脂的失水率仅为4.3%。4、以安息香双甲醚和过硫酸铵为复合引发剂，紫外光照射引发共聚合成滑子菇菌糠/聚丙烯酸钠复合高吸水树脂，通过傅里叶变换红外光谱，扫描电子显微镜和热重对复合高吸水树脂材料的分子结构，表面形态及热稳定性能进行了分析。实验发现所制备的复合高吸水树脂在蒸馏水中最大的吸水倍率为1701g.g^-1，在0.9wt%NaCl溶液中吸水倍率388g.g^-1。并且这种复合材料在蒸馏水和NaCl溶液中吸水溶胀行为符合伪二阶溶胀动力学模型。此外，复合高吸水树脂材料在0.1wt%尿素溶液中的吸水倍率是1011g.g^-1，并且有80%尿素扩散到复合材料水凝胶中，扩散机制遵循Fickian扩散机制。复合高吸水树脂材料热和耐压保水性被测定，即恒温60°C下，保持15小时，保水率可达到65%，在高速离心机转速为6000rpm（10954KPa）下，离心60分钟，其水的保持率为75%。更多还原

【Abstract】 Superabsorbent polymers in agricultural are known as the fourth kind ofagricultural chemicals after fertilizers, pesticides and plastic films that can beaccepted by farmers. However, they are not widely used in many applications due tothe high cost, the single function of water retention and release, and that the gelstrength is low after swelling. In this paper, using waste edible fungus substrate（WEFS, the substrates of cultivate edible fungus, which consist of corn cobs andsawdust. After growth the edible fungus we can get the waste substrate） as the rawmaterial, mixing the modified WEFS with polymer monomer, a varietyof WMFS-based composite superabsorbent were synthesized by solutionpolymerization using microwave radiation and UV irradiation. And the preparation ofits most synthesis conditions and properties were studied. The major work of thisthesis was showed as follows:1. A novel superabsorbent polymer composite was successfully synthesized fromwaste material cultured Auricularia auricula （WMCAA） and poly （acrylicacid-co-acrylamide）（P（AA-co-AM）） using microwave irradiation at a certainneutralization degree of AA. Optimal synthesis conditions were determined byinvestigating the water absorbency of the superabsorbent composite, The effectsassociated with weight ratios of WMCAA, AM, initiators, cross-linkers to AA as wellas the degree of neutralization of AA were examined. The maximum waterabsorbencies were found to be1548g.g^-1（distilled water） and72g.g^-1g/g （0.9wt%NaCl solution）. The molecular structure characteristics of the superabsorbentcomposite were analyzed by Fourier transform infrared spectroscopy （FTIR）, andscanning electron microscopy （SEM） was used to demonstrate the characteristiccompact and porous structure of the material. Further studies conducted viatransmission electron microscopy （TEM） revealed the formation of a novelinterpenetrating polymer network structure. Thermogravimetry/differential thermal （TG/DTG） analysis demonstrated improved thermal stability in the compositematerial compared to WMCAA. Additionally, high water absorption rates observed inthe polymer during the swelling process indicated first-order kinetics. The waterabsorption and adsorption of the superabsorbent composite were studied in a varietyof fertilizer solutions, revealing an indirect relationship between water absorbingability and fertilizer concentration. Conversely, a direct relationship was observedbetween absorbed fertilizer and fertilizer concentration.2. The waste material cultured pleurotus nebrodensis （WMCPN）/Potassiumpolyacrylate（PAA-K）composite superabsorbent rich in plant nutrient elements K,neutralizing acrylic acid with potassium hydroxide, was synthesized via a certainpower of microwave radiation. The maximum water absorbency of the synthesizedcomposite superabsorbent under the optimal conditions of synthesis was974g.g^-1indistilled water and59g.g^-1in0.9wt%NaCl solution, respectively. The molecularstructure characteristics of the superabsorbent composite were measured by FTIR.The thermal stability of the composite was also analyzed by TG/DTG. SEM was usedto demonstrate the characteristic coarse and porous surface of the material. In addition,the water loss rate was6.2%with centrifuging at6000rpm for60minutes.3. The waste material cultured pleurotus ostreatus （WMCPO）/PAA-K compositesuperabsorbent was synthesized by the same way with two. The maximum waterabsorbencies of the superabsorbent was827g.g^-1in distilled water and87g.g^-1in0.9%NaCl solution, respectively.The water loss rate was only4.3%with centrifugingat6000rpm for60minutes.4. The composite superabsorbent was synthesized by copolymerization of TheWaste material cultured nameko （WMCN）and Sodium polyacrylate（PAA-Na）under UV irradiation, in the presence of dimethoxy-2-phenylacetophenone（BDK） andAPS as initiator. The structure, morphology and thermal stability of the compositesuperabsorbent were analyzed by FTIR, SEM and TG/DTG. The experiment showedthat the maximum water absorbency of the synthesized superabsorbent was1701g.g^-1in distilled water and388g.g^-1in0.9wt%NaCl solution, respectively. Moreover,the swelling process of the composite in distilled water and0.9wt%NaCl solution follows the pseudo-second-order swelling kinetic model. In addition, The waterabsorbency in0.1wt%urea solution was1011g/g, and80%amount of urea diffusedinto the gels. The urea diffusion mechanism follows Fickian diffusion mechanism.The Retention capability of superabsorbent under pressure and heating was alsodetermined, Water retention capability of composite superabsorbent is65%atconstant temperature of60°C for15hours and75%with centrifuging at6000rpm（10954KPa） for60minutes.更多还原