摘要
随着对粉煤灰本质认识的不断深化，在粉煤灰高层次的开发研究上已取得一定进展，特别是在高分子材料中的应用研究为粉煤灰综合利用开辟了新的领域。粉煤灰微珠作为有机高分子复合材料的添加剂应经过活化改性，以解决微珠与高分子材料的相容性，本文通过合成和优选偶联剂，确定了微珠在PVC、天然橡胶及不饱和聚酯树脂不同体系中的偶联剂及改性工艺条件，为微珠及其它无机填料的偶联改性提供技术支持。
本文采用废铝为原料合成铝酸酯偶联剂。铝酸酯的合成分为中间体异丙醇铝的合成和铝酸酯的合成。异丙醇铝的合成最佳条件为：反应温度82℃，反应时间5小时，异丙醇铝用量为理论量的5倍，收率大于90％。降粘实验研究表明，经偶联剂处理后，微珠表面极性得到改变，使活化微珠在液体石蜡中的亲和性和分散性得以提高，铝酸酯偶联剂和硅烷偶联剂APS降粘效果显著，偶联剂改性微珠后其表面变为亲油性，活性微珠聚集态颗粒减少，分散程度得以提高。
通过XRD分析，粉煤灰中的主要晶相为莫来石和磁铁矿、赤铁矿以及硅线石和磁赤铁矿。添加碱后焙烧对粉煤灰晶相有显著的影响，表现为粉煤灰主要晶相莫来石与硅线石在反应中消失，生成了具有霞石结构的高形态NaAlSiO_4晶相。由SEM分析看出，在1000℃下焙烧0.5小时后，粉煤灰微珠已经与碱发生了反应，形成部分的晶相重组，部分的微珠被包围在破坏了的晶相内部。反应进行2小时后，反应基本完毕，SEM照片表现为致密均匀的集合体。
在微珠／PVC复合体系加工过程中，最高转矩随微珠填充量增加而下降，与未加微珠的PVC体系相比，填加微珠后的PVC体系最高转矩和平衡转矩都有所降低，加工中热稳定时间大于30分钟。在活性微珠、活性碳酸钙填充PVC管材体系中，拉伸强度随填料份数增加而减小，在同等填加量时，活性微珠／PVC复合材料拉伸强度高于活性碳酸钙／PVC复合材料，材料拉断伸长率随填料填加份数增加而减少。SEM分析表明，未活化微珠与树脂是明显分离的，微珠界面清晰，而活化微珠在PVC树脂中没有清晰的界面，微珠被树脂缠绕、覆盖，明显看到偶联剂在微珠与树脂间的交联现象。经耐腐蚀实验发现，用铝酯偶联酸剂活化的微珠填充的PVC，无论在酸性还是在碱性条件下，都具有良好的稳定性，明显优于用铝酸酯偶联剂活化的碳酸钙填充的PVC材料。
在微珠/橡胶复合体系中，未活化微珠填充橡胶制品的硬度和拉伸强度与CaCO_3填充制品性能相当，在伸长率和永久变形上优于CaCO_3填充NR，微珠可完全代替CaCO_3作为橡胶的新型填料。铝酸酯活化微珠填充NR制品在伸长率和永久变形性
重庆大学博士学位论文
能上优于半补强炭黑填充NR和超细活性钙填充NR制品，但在硬度和拉伸强度上
有所降低。硅烷偶联剂活化微珠填充NR的力学性能优于铝酸活化微珠填充NR制
品性能。硅烷偶联剂活化微珠填充SRf加R体系的硫化加工过程中焦烧时间比半补
强炭黑填充SB凡NR体系有所延长。采用si一l和si一3协同处理微珠，其填充制品性
能优于单一硅烷偶联剂处理微珠效果。复合硅烷偶联剂协同活化微珠可部分(50%)
代替SRF填充SB凡NR，其加工工艺性良好。
不饱和聚酷树脂凝胶化时间随固化温度的升高而缩短，微珠的加入使树脂凝胶
化时间缩短。水法处理微珠使硅烷在微珠表面形成一连续的偶联剂层，增强了微珠
与树脂间的亲和力，使微珠/不饱和聚醋树脂复合材料拉伸强度和弯曲强度提高。铝
酸酷活化微珠与硅烷偶联剂和钦酸酷活化微珠相比，其填充UP制品的力学性能不
如后两种偶联剂。在介质中的腐蚀结果表明，未经偶联剂处理的微珠/不饱和聚酷
体系耐 NaCI腐蚀性好，但耐沸水、酸、碱和丙酮有机溶剂腐蚀性差，用硅烷偶联
剂处理后，改进了界面之间的粘结，能耐沸水和饱和NaCI，耐盐酸腐蚀性有所改善，
但仍不耐碱和有机溶剂。
用气相色谱分析表明，硅烷偶联剂与微珠表面的硅经基发生缩合反应，产生乙
醇新峰。经FT-IR光谱分析，硅烷与微珠表面作用出现515一O一siL键，证明了硅烷与
微珠表面硅轻基的化学作用。在非水体系中，硅烷的烷氧基与微珠的si一O一反应而
不发生自聚，硅烷分子是以单分子形态存在。在水体系中，硅烷偶联剂发生部分水
解、自聚，与微珠作用后在微珠表面形成二、三聚体形式。经差示IR光谱研究，
证明铝酸酷与微珠表面有新的51一(卜勺叼键的生成，证实了偶联机理的化学键理论，
并提出了铝酸酷在微珠表面的分子层模型，根据该模型计算所得铝酸醋最佳用量与
实验所得结果吻合较好。经偶联剂活化微珠与高分子基材界面粘接良好，润湿性提
高，断裂后微珠表面有残余树脂，说明偶联剂在微珠与树脂界面间有强烈的化学作
用，结合微珠份VC复合材料力学性能分析，除了化学键作用外，微脚高分子界面
间还具有较强的物理吸附作用。
The application in the polymer material opens up a new field for the complex application of flyash. As a kind of ploymer compound additive, flyash microspheres must be activized and modified. In this paper, the coupling agent and the technological conditions used in the PVC, nature rubber and unsaturated polyester resin are defined, it provides the technical support for the coupling and modification of microspheres and other inorganic fillers.
The synthesis of aluminate ester coupling agent consists of the synthesis of isopropanolaluminium and aluminate ester. The best synthesis conditions of isopropanolaluminium is as follows: reaction temperature is 80 , reaction time is 5 hours, the actual amount of isopropanolaluminium is 5 times of the theroetical amount, the collecting ratio is more than 90%. The experiment results show that the surface polarity of microspheres is changed through the treatment of coupling agent, its affinity and the dispersion properties in the liquid wax are improved. The modification effect of microspheres is good through the using of ester aluminate coupling agent and silane coupling agent. The experiment results show that the surface becomes oilphilic after the modification, the particle number of gathering state is decreased, the dispersion degree is improved.
The main crystal phase of flyash includes mullite, magnetite, hematiite, sillimante and maghemite through the XRD analysis. The crystal phase is changed after roast with alkali, the main crystal phase, mullite and sillimante, disappears during the reaction process, and produces high form crystal phase NaAlSiO4. Through the SEM analysis, it shows that, after roast for 0.5 hour hi 1000, the reaction between flyash microspheres and aickle occured, the crystal phase was recombinated, part of the microspheres was surrounded by the destructive crystal phase. After 2 hours, the reaction finished, SEM photo shows that it has become compact uniform aggregate.
The highest moment will decreased with the increasing filling amount of microspheres. Comparing with the PVC without microspheres, The highest moment and balance moment of microspheres/PVC system decreases, the thermal stable time is more than 30 minutes during the processing course, hi the active microspheres/PVC systems and active CaCO3/PVC systems tensile strength decreases with the increasing amount of fillers. The tensile strength of active microspheres/ PVC system is stronger than that of active CaCO3/PVC system. The SEM analysis shows that unactive
microspheres are separated from the rosin clearly, the interface of microspheres is distinct, but the active microspheres have not distinct interface in the rosin system, the coupling agent links the microspheres and rosin. Through the against corrosion experiment, it proves that the anti-corrosion property of active microspheres/ PVC is better than that of active CaC03/PVC.
Under the same preparing conditions, the hardness and tensile strength of unactivized microspheres/rubber composite as the same as CaCO3/rubber composite. So flyash microspheres can substitute CaCO3 as new filler in rubber. If the flyash microspheres are activized by aluminate ester and doped in NR, the extend ration and permanent set of NR is better than the NR doped with SRF and superfine CaCO3, but the hardness and tensile strength is worse than the last one. If the microspheres are activized by silane coupling agent and aluminate ester coupling agent, the mechanic properties of the first one are better than the second one.. If the microspheres are activized by silane coupling agent and doped in SBR/NR, the coal carbonization time is longer than the SBR/NR doped with SRF. The micropheres activized by composite silane coupling agent can partly subsitute SRF and be doped in SBR/NR.
The gel time of unsaturated polyester resin shortens with the increasing of solidifying temperature. Check the microspheres activized by aluminate ester coupling agent against the microspheres activized by silane coupling agent and ester titanate coupling agent, we can get the ef
引文
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