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煤矿复合注浆材料的研发应用&共聚物聚(3-己基噻吩)-b-聚(2-(二甲基氨基)乙基甲基丙烯酸酯)的合成及其自组装
中文摘要

近年来,煤炭企业为提高安全生产水平,不断引入新材料、新技术、新工艺,其中就包括化学注浆材料。化学注浆材料广泛应用于煤矿井下封孔、堵漏、加固等环节。由于井下环境复杂,要求所采用的注浆材料除了具有与煤体粘性好、有效固结范围大,形成的固结体有一定强度、封闭性好、质轻、化学性质稳定等特点,还要求材料具有绿色环保、安全可靠等性能。目前的化学注浆材料的性能经常难以满足井下使用和安全性能要求,因此研究开发新型注浆材料来弥补现有材料的不足势在必行。 通过调研和初步试验,本文在国际上首次提出聚氨酯/聚脲矿用复合注浆材料,注册了“固特结〓”商标,利用聚氨酯膨胀性、密封性,结合聚脲材料强度高、粘结力强、物理化学性能稳定、反应时对水分和湿气不像聚氨酯那样敏感,施工时可以达到稳定、坚固、严密、快速的特点,来解决目前煤矿注浆材料效果不稳定,达到使用要求的强度时间长和成本高的问题。根据使用目的不同,研究开发了封孔材料和加固材料两个产品系列,并在现场应用。 利用正交试验进行了配方设计,根据试验结果优选出合理的材料配方。综合考虑价格、反应速度及材料性能的影响等因素,选择多异氰酸酯、聚醚多元醇、聚醚多元胺、聚天冬氨酸酯等作为材料的主原料。封孔材料配方中,以三乙醇胺和有机锡(二月桂酸二丁基锡)质量比4:1配成复合催化剂,以HCFC-141B作为发泡剂,SD-501硅油作为匀泡剂,阻燃剂是以磷酸三(2-氯乙基)酯(TCEP)为主、阻燃聚醚为辅;确定PAPI、发泡剂、催化剂、聚醚多元胺的用量分别是94、6、6、2(质量份)。加固材料配方中,以叔胺类化合物作为催化剂,阻燃剂是以TCEP为主、阻燃聚醚为辅;确定PAPI、聚天冬氨酸酯、催化剂、聚醚胺的用量分别是105、1、0.5、3(质量份)。 为更准确掌握所研制的封孔材料和加固材料的性能,按照《煤矿充填密闭用高分子发泡材料》(AQ1090-201 1)、《煤矿加固煤岩体用高分子材料》(AQ 1089-201 1)标准,分别对封孔材料和加固材料的性能参数进行测试,各项指标均达到要求。煤矿对加固材料的性能要求中,安全性能尤为重要,在煤矿的应用过程中发现,有些高分子加固材料在进行松散煤岩体加固时,注入煤层4至24个小时后,井下注浆地点还会有很明显的材料分解的味道,注浆材料有冒烟、烧芯情况发生。因此,对加固材料的反应温度、比热容和放热量、热分解温度、氧指数等指标进行测试,对加固材料的安全性能做出了进一步评价。 材料要发挥最大性能,必须有配套的施工工艺相配合。根据封孔材料的特性,研发了两端自堵封孔囊袋,一次封孔具备带压功能,实现了可在任意封孔深度封堵钻孔漏气裂隙的目的;整合封孔材料和两端自堵封孔囊袋优势,提出的集封孔材料、封孔囊袋、注浆设备三位一体的两端自堵封孔工艺,简化了封孔工序,而且操作简便、设备器材运输便捷、劳动强度低,大幅度提升了封孔效率。在加固材料施工工艺研发时,分析了加固材料的扩散模式、加固机理和浆液扩散模式,在此基础上,对注浆加固的时机、深度、注浆孔布置、注浆压力等进行分析和确定,形成系统注浆加固施工技术。 井下现场应用试验阶段,在河南能源焦煤公司九里山矿进行了井下封孔试验,在河南能源焦煤公司赵固二矿进行了巷道煤壁加固、工作面煤壁加固试验。通过工业性试验,验证了新研发的材料和施工工艺完全符合煤矿要求。 采用原子转移活性聚合(ATRP)的方法,通过共轭聚合物P3HT和pH响应性聚合物PDMAEMA相结合合成P3HT-b-PDMAEMA共聚物,并系统的研究了它们在空气/水界面上的自组装过程和pH响应特性。P3HT链的自组装很容易通过调节在不同的pH环境下的PDMAEMA链的两亲性来控制,而且在溶液中的P3HT链的高发光效率通过从PDMAEMA“屏蔽效应”造成LB膜的形成也被成功的保存下来。另一方面,通过发光谱中的发射位移,P3HT链也被发现可以作为监测PDMAEMA链的pH响应的指标器,在pH传感器上具有广阔的应用前景。据我们所知,这是国内外首次在空气/水界面上研究共轭反应性嵌段共聚物体系,同时也是首次利用共轭聚合物的光学性质来监测聚合物膜的响应性能。如果能把这种光电嵌段共聚物引入煤矿化学注浆材料,来监测注浆材料的流动范围和与周围煤岩体的温度传递变化,将对煤矿化学注浆材料的安全性评价提供新的思路。 关键词:煤矿,复合注浆材料,聚氨酯,聚脲,固特结,天门冬氨酸酯,封孔,靶向两端自堵封孔工艺,两端自堵囊袋,加固,光致发光,聚(3-己基噻吩-b-聚(2-(二甲基氨基)乙基甲基丙烯酸酯)

英文摘要

In recent years, in order to improve the level of safety, coal enterprises continue to introduce new materials, new technologies and new process, including chemical grouting material. Chemical grouting materials are widely used in sealing, plugging and strengthening of underground coal mines. Due to the special underground environment, the grouting material are required with good cohesion with the coal body, effective consolidation range, the formed consolidation body with certain strength, good sealing property, light quality and stable chemical properties. With the gradual improvement of environmental protection requirements, green environmental protection has become an important issue of material impact. At present, the performance of the existing chemical materials is difficult to meet the requirements. Therefore, it is imperative to study and develop new grouting materials to make up for the shortcomings of existing materials. Through the investigation and preliminary tests, we proposed and developed polyurethane / polyurea composite grouting material. Registed “Gutejie” trade mark for the product. We take advantage of the expansion and tightness of polyurethane and combine the characteristics of polyurea with good tightness, strong adhesive force, stable physical and chemical properties, not sensitive to water and humidity that unlike polyurethane, stable during the construction to solve the unstable effect of mine grouting material and high cost. According to the use of different purposes, we develop both sealing materials and reinforcing materials. We made the formula design by orthogonal design, and selected the reasonable material formula according to the experimental results. Considering the factors such as price, reaction speed and material properties, polyisocyanate, polyether polyol, polyamine and polyaspartic acid were selected as the main raw materials. The sealing material is with triethanolamine and organic tin as catalyst with a mass ratio of 4:1 , with HCFC-141B as foaming agent, SD-501 silicone oil as foam stabilizer, TCEP as the main flame retardant and flame retardant polyether as supplement. In the formula PAPI, foaming agent, catalyst, polyether amine dosages are respectively 94, 6, 6 2 (mass). Reinforcement material formula is with tertiary amine compounds as catalyst, TCEP as main flame retardant and flame retardant polyether as a supplement. In the formula PAPI, polyaspartic ester, polyether amine, catalyst dosages are 105, 1, 0.5, 3 (mass). To accurately grasp the properties of developed reinforcement and sealing materials, in accordance with the "coal mine filling and sealing with polymer foam material" (AQ1090-2011), the "coal mine coal and rock reinforcement with polymer materials" (AQ 1089-2011), we tested the performance parameters of the sealing material and the reinforcement material separately, in which all the indexes reached the requirements. Safety performance is particularly important in the performance requirements of reinforced materials. Found during application, there are obvious smells and smoke of decomposition material after the polymer material is injected into the seam 4 hours to 20 hours during reinforcement of loose coal rocks. Therefore, we tested the reaction temperature, specific heat capacity, heat release capacity, and thermal decomposition temperature and oxygen index of the reinforcing material. The safety performance of the strengthening material was evaluated. To maximize materials performance, the construction process must be matched. Based on the characteristics of the sealing material, the self-sealing bladder bag with two ends has been developed, which has the function of carrying pressure and realizes the sealing of the gas leakage fissure at any sealing depth in the hole. To integrate the advantages of both sealing material and self-sealing bladder bag at two ends, we put forward the self-sealing process which combined of sealing material, sealing hole bag and grouting equipment. The utility model simplifies the sealing procedure, in which the operation is simple, the equipment is transported conveniently, the labor intensity is reduced, and the sealing efficiency is improved.During the research and development of reinforcing material construction technology, we analyzed the diffusion model, reinforcement mechanism and slurry diffusion model. On this basis, the time and depth of grouting reinforcement, grouting hole layout and grouting pressure are analyzed and determined to form grouting reinforcement construction technology. Finally, the underground sealing experiments are finished in jiulishan mine of Henan Energy Coal Company, and the reinforced Roadway wall testes are conducted in the first zhao Gu Mine of Henan Energy Coal Company. Through these industrial tests, it is proved that the newly developed materials and construction technology meet the requirements of the coal mine, and ensure the safe production of the mine. A facile strategy to synthesize responsive conjugated rod-coil diblock copolymer P3HT-b-PDMAEMA is introduced based on GRIM and ATRP, and its self-assembly process at the air/water interface is systematically explored using the Langmuir Blodgett (LB) technique. The self-assembly of P3HT chains was readily controlled through tunning amphiphilicity of PDMAEMA chains under different PH environment, which functions effeicviely as “indicator” to show pH responsive property of resulted LB monolayer. Moreover, the high PL-efficiency state of P3HT chains originally in solution was also successfully preserved after LB monolayer formation due to the “screen effect” from PDMAEMA. To best of our knowledge, this is the first work to investigated conjugated-responsive block copolymer system at the air/water interface and also first work to utilized improved optical property of conjugated polymer into monitoring of performance of responsive polymers. Key words: coal mine, cracked coal and rockmass, Composite grouting material, PU, PUA, Gutejie, safety performance, photoluminescence, Poly(3-hexylthiophene)-block-poly(2-(dimethylamino)ethyl methacrylate)

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