新型无卤膨胀阻燃剂的制备及其阻燃材料的开发

工学硕士学位论文新型无卤膨胀阻燃剂的制备及其阻燃材料的开发*******大学****年*月国内图书分类号：***工学硕士学位论文新型无卤膨胀阻燃剂的制备及其阻燃材料的开发硕士研究生：导师：申请学位级别：学科、专业：所在单位：答辩日期：授予学位单位：Classified Index：TQ314.Dissertation for the Master Degree in Engineering STUDY ON NOVEL HALOGEN-FREE INTUMESCENT FlAME-RETARDANT AND ITS FLAME-RETARDEDMATERIALCandidate：Supervisor：Academic Degree Applied for：Specialty：Date of Oral Examination：University：新型无卤膨胀阻燃剂的制备及其阻燃材料的开发摘要可膨胀石墨(Expandable Graphite，简称EG)不但保持了石墨优异的理化性质，而且由于插入物质与石墨碳层的相互作用而呈现出独特的物理与化学特性而倍受关注。

作为典型物理膨胀型阻燃剂，其研究和应用是最近阻燃领域的热点。

本论文系统研究了EG的制备方法及其工艺过程，采用分步插层法成功的将硝酸盐和含磷化合物插入石墨层间，通过测试其膨胀体积、增重和热失重等着重研究了这两类插层物插层EG的性能，并采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、表面能谱分析(EDS)等方法系统研究了EG的结构。

通过将制得的EG与传统阻燃剂复配，得到了高阻燃性能的协同阻燃剂，并在此基础上获得了具有优良综合性能的无卤膨胀阻燃材料。

本论文的研究表明：(1)与直接插层法相比，分步插层法更有利于插层物质进入石墨层间，进而得到性能稳定、高膨胀倍率、高增重的EG。

同时分步插层法反应较为温和，大大降低了制备过程的危险性和刺激性气体的产生；(2)膨胀体积与插入石墨层间的插层剂质量和膨胀过程的热失重之间均存在线性关系，制备工艺条件也对EG的性能有很重要的影响，主要因素为：插层剂种类、氧化剂用量、反应时间、反应温度等；(3) 成功制备了高膨胀体积硝酸盐-硫酸共插层EG，其中硝酸铁-硫酸共插层EG的膨胀体积为450mL/g、硝酸钠-硫酸共插层EG为420mL/g；(4)成功制备了含磷化合物-硫酸共插层EG，其中磷酸-硫酸共插层EG膨胀体积为230mL/g，磷酸铵-硫酸共插层EG为280mL/g，聚磷酸铵(APP)-硫酸共插层EG为240mL/g，EG抗氧化性能明显提高；(5)不同插层剂制备的EG具有不同的阻燃性能，在添加量为25%时，分步插层法制备硝酸铁-硫酸、磷酸-硫酸、聚磷酸铵-硫酸、APP-硫酸共插层EG阻燃EVA的氧指数分别为21.2%、26.5%、27.8%、29.2%，可见含磷化合物-硫酸共插层EG具有较好的阻燃性能；(6)所制备的EG具有优于传统阻燃剂的阻燃性能。

并与ATH、IFR具有显著的协同阻燃作用，能大大提高无卤阻燃剂的阻燃效果，所制备的无卤膨胀阻燃材料具有良好的综合性能。

关键词可膨胀石墨；硝酸盐；含磷化合物；阻燃剂- I -STUDY ON NOVEL HALOGEN-FREEINTUMESCENT FLAME-RETARDANT AND ITSFLAME-RETARDED MATERIALAbstractIt is widely reported that Expandable Graphite (EG) not only possesses the unique characteristic properties of graphite, but also takes on the unusual chemical and physical properties because of the interactions betweeen intercalated agents and graphite layers. As a typical physical intumescent flame retardant, the study and application of EG have recently become a hot topic in flame retardant fields.In this paper, two methods, direct intercalation and two-step method were used to prepare EG and the process and reaction conditions were discussed in detail. EG intercalated wtih nitrate or phosphorous compounds were successfully prepared by two-step method. The properties of EG as prepared were investigated by expansion volume, weight increment, weight loss and the structure was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS). Moreover, the synergistic flame retardant properties of EG with aluminum trihydrate (ATH) or chemical intumescent flam retardants (IFR) were also studied. Thus, novel flame retardant compounds with high flame retardant efficiency were obtained and used to develop halogen-free flame retardant material with excellent mechanical and flame retardant properties.Following results can be obtained in the paper: (1) Products prepared by two-step method show bigger expansion volume, higher thermal stabilities and more mass increment than those by direct intercalation method, revealing that the two-step method is a better method to prepare EG. Meantime, the moderate reaction temperature of two-step method can be helpful to decrease the danger during experiments. (2) The expansion volume of EG has a linear relationship- II -with the mass increment after intercalation reaction and the weight loss after expansion. Reaction conditions, such as reation time, reaction temperature, dosage of oxidizer, play important roles on the properties of EG. (3) Nitrate as cointercalated agents, was successfully intercalated into the graphite interlayers. EG, as prepared, shows promising expansion volume. For example, the expansion volume of Fe(NO3)3-H2SO4-EG is 450mL/g and that of NaNO3-H2SO4-EG is 420mL/g. (4) EGs intercalated with phosphorous compounds are successfully prepared. As a result, the expansion volumes of H3PO4-H2SO4-EG, (NH4)3 PO4- H2SO4-EG and APP-H2SO4-EG are 230 mL/g, 280 mL/g and 240mL/g, respectively. The oxidation resistance of EG, as prepared, was obviously improved. (5) EG with different intercalated compounds shows different flame retardant properties. At 25% loading level, the LOI values of EVA flame retarded by Fe(NO3)3-H2SO4-EG, H3PO4-H2SO4-EG, (NH4)3PO4-H2SO4-EG or APP-H2SO4-EG can reach 21.2%, 26.5%, 27.8% and 29.2%, respectively. Among all EGs prepared, APP-H2SO4-EG possesses the best flame retardant property. (6) EG as prepared in the paper possesses better flame retardant properties than traditional flame retardants, such as ATH and IFR. Obvious synergistic effects of EG/ATH or EG/IFR can be found. Base on this, flame retardant materials with good properties have been developed.Keywords Expandable graphite; Nitrate; Phosphorous compounds; Flame retardant- III -目录摘要............................................................................................................................... I Abstract ....................................................................................................................... II第1章绪论 (1)1.1课题背景 (1)1.2可膨胀石墨的研究进展及趋势 (3)1.2.1可膨胀石墨的阻燃应用前景 (4)1.2.2可膨胀石墨的研究进展 (5)1.3本论文研究目的、意义及内容 (7)第2章理论分析 (8)2.1 可膨胀石墨的结构特征 (8)2.1.1 石墨的微观结构 (8)2.1.2 可膨胀石墨的微观结构 (9)2.2 可膨胀石墨的插层原理与膨胀过程 (11)2.2.1 石墨的插层原理 (11)2.2.2 可膨胀石墨的膨胀过程 (11)2.2.3 膨胀石墨的特性 (12)2.3 可膨胀石墨的制备方法 (13)2.4 本章小结 (15)第3章试验部分 (16)3.1试验用主要原料 (16)3.2 试验用主要仪器设备 (17)3.3试验方法与工艺路线 (17)3.3.1制备EG的试验方法及工艺路线 (17)3.3.2 阻燃材料的制备方法与路线 (19)3.4分析表征方法 (19)3.4.1膨胀体积的测定 (19)3.4.2反应增重、热失重测试 (19)3.4.3扫描电镜分析 (20)3.4.4 X-射线衍射分析 (20)- IV -3.4.5氧指数测试 (20)3.5本章小结 (21)第4章结果与讨论 (22)4.1 EG的制备方法及工艺研究 (22)4.1.1直接插层法制备EG的反应条件 (22)4.1.2直接插层法制备不同物质插层EG (27)4.1.3分步插层法制备硝酸盐-硫酸共插层EG (29)4.1.4分步插层法制备含磷化合物-硫酸共插层EG (33)4.2 EG的结构及其性能研究 (36)4.2.1 EG增重、热失重与膨胀体积的相互关系 (36)4.2.2 硝酸盐-硫酸共插层EG的结构与性能分析 (37)4.2.3含磷化合物-硫酸共插层EG的结构与性能分析 (43)4.2.4 直接插层法与分步插层法制备EG的插层原理比较 (50)4.3 新型无卤膨胀阻燃材料的开发 (50)4.3.1 不同插层剂插层EG阻燃EV A (50)4.3.2 新型无卤膨胀阻燃材料的性能 (51)4.4 本章小结 (52)结论 (53)参考文献 (54)攻读硕士学位期间发表的学术论文 (60)致谢 (61)第1章绪论1.1课题背景随着现代化科学技术的发展，塑料、橡胶、纤维等合成材料越来越广泛的应用于交通、运输、建筑材料、电子电器等各个领域，在国民经济建设和人民生活中发挥着巨大作用。