新型有机蒙脱土的制备及其在聚丙烯改性中的应用

采用十六烷基三甲基溴化铵（CTAB） 、环氧树脂（EP）、异佛尔酮二异氰酸酯(IPDI)、十八胺(ODA)对钠基蒙脱土(MMT)进行干法插层改性, 分别制备了CMMT、EMMT、IMMT和OMMT等新型有机蒙脱土,并对聚丙烯(PP)进行熔融改性制得PP/OMMT纳米复合材料。通过傅里叶变换红外光谱仪、X射线衍射仪 、透射电子显微镜、差示扫描量热仪等分析手段对新型有机蒙脱土及纳米复合材料的结构形态及性能进行了研究。结果表明,OMMT层间距由蒙脱土的1.5626 nm扩大到4.2828 nm, OMMT片层均匀分散在PP基体中;当OMMT含量为5 %（质量分数,下同）时,纳米复合材料拉伸强度、断裂伸长率及冲击强度分别比纯PP提高了25.9 %、17.1 %和127.1 %;同时,加入OMMT后,PP的结晶度先升高后降低。     

聚酰胺6/环氧树脂改性蒙脱土纳米复合材料的制备与性能

采用环氧树脂改性蒙脱土（MMT）得到有机化蒙脱土（OMMT）,再用熔融插层法制备了聚酰胺6 （PA6）/ OMMT纳米复合材料。采用X射线衍射仪、透射电子显微镜、万能材料试验机、热重分析仪等研究了PA6/OMMT复合材料的形态结构、力学性能和热稳定性。结果表明,经环氧树脂改性得到的OMMT的层间距明显增加,从未改性的1.22 nm增加到5.13 nm,并以纳米尺度分散于PA6基体中;随着OMMT含量的增加,PA6/ OMMT复合材料的强度和模量增加,热变形温度提高,其拉伸强度可达76 MPa,弯曲模量达到3.462 GPa,热变形温度为134 ℃;PA6/ OMMT复合材料失重10 %时的温度为422 ℃,比纯PA6的406 ℃提高了16 ℃,改善了PA6的热稳定性。     

有机插层剂对聚酰胺6／MMT纳米复合材料制备的影响研究

以烷基胺、季铵盐和氨基酸作为有机插层剂与蒙脱土片层进行阳离子交换，制备出层间距不同的有机蒙脱土。采用熔融插层法和原位聚合法分别制备聚酰胺（R％）／蒙脱土（MMT）纳米复合材料，并利用XRD、FT-IR、TEM对有机蒙脱土及纳米复合材料进行结构表征。研究结果表明：用烷基胺、季铵盐和氨基酸有机插层剂改性的蒙脱土层间距由原来的1．25nm分别增大到3．21nm、3．99nm和1．82m；季铵盐有机插层剂更适用于熔融插层法制备PA6／MMT纳米复合材料，而氨基酸有机插层剂更适用于原位聚合法制备PA6／MMT纳米复合材料。     

PU/OMMT纳米复合材料的制备与性能研究

采用单体插层聚合方法制备聚氨酯（PU）／有机蒙脱土（OMMT）纳米复合材料,并对其结构和性能进行分析。结果表明，经双羟乙基十二烷基三甲基氯化铵改性得到的OMMT（DK2）层间距较大；DK2质量分数为0．03时,PU／OMMT纳米复合材料中OMMT剥离程度较大，PU的插层效果较好,复合材料的物理性能和热稳定性能优良。     

聚合物/有机蒙脱土纳米复合材料分散形态的制备影响因素

选择不同种类的有机蒙脱土（OMMT）和不同聚合物种类,采用不同加工条件和工艺,利用机械混炼法或挤出法制备出了不同亚微观形态的聚合物/有机蒙脱土纳米复合材料。首先通过研究具有不同的改性层间距的OMMT,发现改性后层间距的增大有利于聚合物分子的插层及蒙脱土片层的剥离,有利于制备剥离型纳米复合材料,并用示意图简要说明了形成过程;而同一种OMMT在具有不同分子结构的聚合物中,利用实例（高密度、低密度、线型低密度聚乙烯）以及简易示意图说明了聚合物分子链结构对于制备的纳米复合材料的亚微观形态的影响机理。在加工工艺条件中,加工过程中的剪切力大小是主要影响因素,通过以挤出法和机械混炼法制备的PP/OMMT与EPDM/OMMT纳米复合材料的TEM结果对比分析,说明剪切力的增大有利于蒙脱土片层的分离,更倾向于制备出剥离型纳米复合材料。     

硅烷偶联剂复合改性蒙脱土制备NR/OMMT纳米复合材料

采用硅烷偶联剂和十六烷基三甲基溴化铵(CTAB)作为复合改性剂制备有机蒙脱土,使有机蒙脱土的结构发生了改变.其中采用硅烷偶联剂KH570与CTAB复合改性的效果较好,得到了插层效果较好的NR/OMMT纳米复合材料.     

硅烷偶联剂对OMMT/NR纳米复合材料结构与性能的影响

采用混炼插层法制备有机蒙脱土(OMMT)/NR纳米复合材料,研究硅烷偶联剂对其结构和性能的影响.结果表明,与NR相比,OMMT/NR纳米复合材料的物理性能,热稳定性和动态力学性能均有所提高;采用硅烷偶联剂KH-560改性的OMMT制备的纳米复合材料各项性能均优于采用硅烷偶联剂KH-550改性的OMMT制备的纳米复合材料.     

乳液插层法制备丁苯橡胶/有机蒙脱土纳米复合材料

对蒙脱土(MMT)进行了有机化改性,采用乳液插层法制备了丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,用透射电子显微镜、X射线衍射法对OMMT及复合材料进行了表征,研究了复合材料的物理机械性能及动态力学性能.结果表明,MMT的层间距为1.47 nm,OMMT的层间距增大到2.94 nm;OMMT片层均匀分散在SBR基体中,具有良好的界面相容性;随着OMMT用量的增加,SBR/OMMT纳米复合材料的物理机械性能明显改善,且具有低填充量高增强效果的特点;SBR/OMMT纳米复合材料具有与SBR/炭黑N 330复合材料相当的抗湿滑性能,同时具有更小的滚动阻力.     

乳液插层法制备丁苯橡胶/蒙脱土纳米复合材料的结构与性能

选用一种能够在水中分散良好的有机改性蒙脱土（OMMT），采用乳液插层法制备了SBR／OMMT纳米复合材料，X射线衍射和透射电镜观察显示制得了半剥离型与插层型共存的纳米复合材料。研究了复合材料的力学性能和耐溶剂性能。测试结果表明，随着蒙脱土用量的增加，复合材料的定伸应力、拉伸强度和撕裂强度均大幅度提高。复合材料具有优异的耐溶剂性能。     

聚吡咯/有机蒙脱土纳米复合材料的制备及其导电性

以三氯化铁(FeCl3)为氧化剂,对甲苯磺酸钠(TSANa)为掺杂剂,使进入经有机插层剂改性的有机蒙脱土(OMMT)层间的吡咯(Py)发生氧化聚合反应,制备了具有良好导电性的聚吡咯/有机蒙脱土(PPy/OMMT)纳米复合材料。结果表明,采用插层剂为十八烷基三甲基氯化铵(OTAC)改性的有机蒙脱土OMMT-O,FeCl3与Py的摩尔比为2 14,Py与OMMT-O的质量比为0 24,TSANa的浓度为0 023g·ml-1,在20℃反应6h,得到的PPy/OMMT-O纳米复合材料的电导率达到3 07S·cm-1。XRD测试表明,在形成复合材料过程中PPy已经插层进入到蒙脱土的片层中。     

PBA/OMMT制备及其对PA6力学性能的影响

用十二烷基磺酸钠(SDS)将Na基蒙脱土(MMT)改性成有机蒙脱土(OMMT),采用原位聚合法制备了聚丙烯酸丁酯(PBA)/OMMT,并将其按适当比例添加到尼龙6(PA6)中。通过红外光谱仪、差示扫描量热仪等表征了OMMT、PBA/OMMT的结构,并检测了PA6/PBA/OMMT复合材料的力学性能。结果表明:添加5%的PBA/OMMT后,PA6/PBA/OMMT复合材料的拉伸强度提高了23.1%,缺口冲击强度的降低幅度有所减缓。     

HDPE/PA 6/有机蒙脱土复合体系的结构及性能

采用熔融共混法制备高密度聚乙烯(HDPE)/聚酰胺(PA)6/有机蒙脱土(OMMT)多元复合材料,借助X射线衍射仪、扫描电子显微镜、透射电子显微镜等分析了OMMT对HDPE/PA 6体系结构、性能的影响及作用机理。加入的少量OMMT以剥离形态分散在基体中,能起到较好的增容作用,并且改善了材料的冲击性能。但OMMT的加入使材料的熔体流动速率降低,剪切黏度增大。     

Influence of the clay modification and compatibilizer on the structure and mechanical properties of ethylene–propylene–diene rubber/montmorillonite composites

Ethylene–propylene–diene rubber (EPDM)/montmorillonite (MMT) composites were prepared through a melt process, and three kinds of surfactants with different ammonium cations were used to modify MMT and affect the morphology of the composites. The morphology of the composites depended on the alkyl ammonium salt length, that is, the hydrophobicity of the organic surfactants. Organophilic montmorillonite (OMMT), modified by octadecyltrimethyl ammonium salt and distearyldimethyl ammonium salt, was intercalated and partially exfoliated in the EPDM matrix, whereas OMMT modified by hexadecyltrimethyl ammonium chloride exhibited a morphology in which OMMT existed as a common filler. Ethylene–propylene–diene rubber grafted with maleic anhydride (MAH‐g‐EPDM) was used as a compatibilizer and greatly affected the dispersion of OMMT. When OMMTs were modified by octadecyltrimethyl ammonium chloride and distearydimethyl ammonium chloride, the EPDM/OMMT/MAH‐g‐EPDM composites (100/15/5) had an exfoliated structure, and they showed good mechanical properties and high dynamic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 638–646, 2004     

有机蒙脱土和氢氧化镁对PS的协同阻燃作用研究

将聚苯乙烯(PS) 树脂与有机蒙脱土(OMMT) 和表面改性的氢氧化镁(MH) 直接熔融复合制备了PS/MH/OMMT复合材料,采用X射线衍射对复合材料的微观结构进行了分析,分别用水平燃烧试验、氧指数试验和高温处理试验研究了复合材料的阻燃性能。结果表明：OMMT 与PS熔融复合后,其片层间距从1.46 nm增加至3.30 nm,表明与PS分子链形成了插层复合结构,MH的引入并不影响纳米插层结构的形成。OMMT与MH并用时可以显著减少复合材料在燃烧时的滴落和发烟性,材料在高温下更加稳定,阻燃性能更好,从而可以减少阻燃剂的用量。     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers     

聚乳酸/蒙脱石复合材料的溶液插层法制备及其性能表征

的界面相容性良好.聚乳酸/蒙脱石复合材料的热失重曲线移向高温端,其热分解温度提高,表明其热稳定性比PLA基材提高.聚乳酸及聚乳酸/蒙脱石复合材料在不同环境中的初步降解实验结果表明该复合材料具有较好的生物可降解性.     

Thermal stability of organo‐montmorillonite‐modified wood flour/poly(lactic acid) composites

In this research, wood flour (WF) was modified using sodium–montmorillonite (Na‐MMT) at four different concentrations (0.5, 1.0, 2.0, and 4.0 wt%, respectively) and didecyl dimethyl ammonium chloride (DDAC) in a two‐step process to form organo‐montmorillonite (OMMT) inside the WF or attached to the WF surface. The thus‐modified WF was then mixed with poly(lactic acid) (PLA) to produce WF/PLA composites. The thermal stability of these composites with respect to their resistance against both thermal deformation and thermal decomposition was characterized by stress relaxation, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. Besides, the activation energies for thermal decomposition of the composites were calculated. The results showed the following: (1) The modification of WF by OMMT improved the resistance against thermal deformation of the composites at appropriate OMMT loadings (lower than 1 wt% in this study). However, after introducing excessive OMMT, the enhancements in thermal stability diminished. Composite containing WF modified by 0.5 wt% of OMMT showed the optimal thermal deformation stability in this study, reflected in the highest values of thermal properties such as the glass transition temperature, melting temperature, crystallization temperature, and slowest stress relaxation rate. (2) OMMT showed a negative effect on the resistance against thermal decomposition. Namely, OMMT accelerated the thermal decomposition of the composites, probably by the easier degradation of the organic surfactant used for the WF modification. However, this behavior might be favorable for achieving fire retardancy. POLYM. COMPOS., 37:1971–1977, 2016. © 2015 Society of Plastics Engineers     

Processing thermal stability and degradation kinetics of poly(vinyl chloride)/montmorillonite composites

Thermal stability of polyvinyl chloride (PVC) based montmorillonite composites with either sodium montmorillonite (MMT) or alkyl ammonium ion modified montmorillonite (OMMT) were investigated by thermogravimetric analysis. The apparent activation energies associated with the first thermal degradation stage were calculated by the methods of Flynn–Wall–Ozawa and Kissinger in nitrogen atmosphere at several different heating rates. The processing thermal stability of PVC and PVC/MMT(OMMT) composites was also discussed. Increase of mixing torque did not result in a larger intercalation extent of PVC on MMT; instead, it unexpectedly induced discoloration of PVC and then deteriorated the processing stability, especially in the presence of OMMT. The apparent activation energies in the first thermal degradation stage exhibited little difference among PVC, PVC/MMT, and PVC/OMMT composites, and the kinetic compensation effect of S_p^* kept a constant value, indicating that the thermal stability and thermal degradation mechanism of PVC were not affected by the presence of either MMT or OMMT, although the processing discoloration of PVC is observed for PVC/OMMT composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1521–1526, 2004     

SEBS/蒙脱土复合材料结构及热性能研究

采用十二烷基三苯基溴化膦(DTPB)改性钠基蒙脱土(Na+-MMT),利用熔融插层法制备氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)/蒙脱土复合材料。采用X射线衍射仪、红外光谱仪、场发射扫描电镜、热重分析仪对样品进行结构表征和性能测试,比较不同有机化蒙脱土(OMMT)对SEBS/OMMT复合材料的影响。结果表明:无论是MMT还是OMMT都起到了阻止SEBS热失重进程的发展,且携带苯基的DTPB有机改性剂有利于OMMT与SEBS复合材料的相容性。     

有机蒙脱土对PVC复合材料热降解性能的影响

采用热重分析研究了有机蒙脱土(OMMT)用量对聚氯乙烯(PVS)复合材料热降解过程的影响,并采用Flynn-wall-Ozawa方法分析计算得到了复合材料体系的表观活化能.研究表明,在PVC材料降解初期(转化率小于30%),OMMT的加入使得PVC降解活化能都有不同程度的下降;但随着降解过程的继续,PVC的降解活化能又开始逐渐增大.