新型单宁泡沫材料的制备与应用基础研究

A novel biomass tannin foam will be prepared using local, abundant tannin resource in Yunnan province, the effect of tannin forms, structure and reactivity on the foaming process will be studied. In view of the intense polymerization between the furfuryl alcohol and acid was too dangerous to achieve the mass production in previous studies, the whipping method process on tannin resin (namely Whipping method) will be used to obtain the physical and mechanical foaming in this study. The effect of additive on the foaming process and the construction method of the three-dimensional (3D) networking structure will be studied, the uniform performance and the effect parameter as well as the control method also will be studied. The chemical variation of the foam formed and resin curing process is going to be analyzed by means of MALDI-TOF, mechanical strength of foam will be determined by an universal mechanical testing machine, and insulation characteristic and flame resistance will be measured by thermal conductivity meter and cone calorimeter, respectively, The surface morphology of foam is going to be analyzed by SEM, all of these will be provided theoretical guidance to the foam synthesis process and formula. Thereafter, the preparation method of sandwich composite with tannin foam core will be effective selected, the performances of this sandwich composite will be fully characterized..The purpose of this study was to exploit a fully bio-foam with low cost, good insulation and rival flame resistance using a green、whipping foaming method. The preparation of tannin foam and its basic and applied research to provide the theoretical and technical support for high efficient utilization of biomass resources in Yunnan province.

以云南丰富的单宁资源为原料，制备新型全生物质单宁泡沫，研究单宁原料形态、结构及活性对发泡工艺的影响。针对前期研究中大量强酸的存在易使糠醇发生爆聚反应难以实现规模化生产的问题，本项目采用“搅打”工艺实现单宁树脂物理、机械发泡；研究发泡过程中助剂的影响及泡沫三维网状结构的构建方法，探索泡沫的均匀性、影响因素及控制方法；用MALDI-TOF研究泡沫形成及树脂固化过程的机理及化学变化，采用万能力学试验机测定泡沫的力学性能，使用热传导仪和锥形量热仪分别对泡沫的保温性和阻燃性进行测定，用SEM分析泡沫的界面形貌，为合成工艺和配方提供理论指导。研究还对泡沫夹芯复合材料的制备方法进行有效选择，系统评价单宁泡沫夹芯复合材料的各项物理力学性能。.本研究通过单宁泡沫材料制备及应用基础研究，利用“搅打”的绿色发泡技术研发一种低成本、保温性和阻燃性更好的全生物质泡沫材料，为云南省生物质高效利用提供理论与技术支撑。

作为地区基金，以区域丰富的生物质资源为研究对象，选取杨梅和黑荆树单宁及糠醇作为主要原料，开展单宁树脂泡沫材料的研究。利用现代仪器分析手段研究了原料结构特性，为泡沫材料制备的配方和工艺技术路线设计提供理论依据。重点开展了甲醛基单宁树脂泡沫材料、无甲醛基单宁树脂泡沫材料、新型“机械搅打”单宁树脂泡沫材料以及单宁树脂基多层复合材料的研究。研究内容包括：单宁树脂的定向合成制备、发泡工艺技术路线优化和泡沫材料性能表征，完成泡沫三维网状结构的构建。.研究结果包括：.1）完成了杨梅单宁结构的表征和确定，为发泡配方设计和工艺技术路线优化提供理论支撑；.2）实现了单宁泡沫材料从利用甲醛到甲醛被取代，从利用发泡剂到发泡剂被“机械搅打”取代的绿色发泡工艺技术，实现了发泡工艺的绿色化和产品的环保化；.3）获得了具有优异保温、阻燃和力学性能的单宁树脂基发泡材料，最佳工艺制备的单宁泡沫材料或多层复合材料的泡沫层厚度控制在4 mm以上，材料的热传导系数可低至0.0239 W/(m·K)，保温性好，极限氧指数最高可达50%，阻燃性极佳，点火实验时无滴落物和烟气产生，泡孔分布均匀，实现了单宁泡沫开、闭孔的精准调控；.4）新型材料的设计和制备，彻底解决了单宁树脂泡沫材料脆性大、易掉渣的问题，粉化率从17.97%降低至2.64%。因此，该研究制备的泡沫材料在建筑物保温、阻燃领域具有极大的应用潜力，进一步拓宽云南丰富生物质资源的应用领域。.通过该项目的执行，已发表论文10篇，其中，SCI一区TOP期刊论文6篇（ESI 1%高被引1篇）；申请国家/国际发明专利4项，已获授权1项；出版英文论著1部；项目团队成员均晋升高一级职称和入选省部级人才支持计划、并获得国家自然科学基金支持；指导博士和硕士5人；项目负责人获第九届云南省青年科技奖、云南省政府特殊津贴等奖励。项目执行成效显著。