有机蒙脱土/BS乳液接枝改性制备粉末橡胶及在PVC中的应用

在丁苯（BS）乳液插层有机蒙脱土（OMT）过程中加入一定量的甲基丙烯酸甲酯（MMA）和二乙烯苯（DVB）进行反应制得接枝丁苯乳液（MMA—g—BS）,破乳后制得改性粉末丁苯胶（m-PSBR）,以质量分数为15％的OMT、25％MMA和1.2％DVB制得的m-PSBR粒径小于1mm．m—PSBR的热分解温度比粉末丁苯有明显提高。用该方法制得m—PSBR,用量为聚氯乙烯20％,共混制得m-PSBR／PVC复合材料,其拉伸强度比丁苯／OMT制得的粉末橡胶与聚氯乙烯的复合材料提高了25％、冲击强度提高了150％。     

聚丙烯／三元乙丙橡胶／改性蒙脱土纳米复合材料的制备和性能

用马来酸酐和苯乙烯改性蒙脱土得到改性蒙脱土（SMA-MMT），然后用熔融共混法制备了聚丙烯（PP）／三元乙丙橡胶（EPDM）／改性蒙脱土纳米复合材料，且加入接枝物PP-g-MAH-St作为相容剂。X射线衍射分析显示SMA-MMT的层间距达到3．98nm。透射电镜分析表明聚合物分子链已经插入蒙脱土片层中。接枝物含量为15％（质量分数，下同）时，复合材料的力学性能达到最好，拉伸强度和冲击强度分别为32．4MPa和79．5J／m。差示扫描量热分析结果表明，PP-g-MAH-St和SMA-MMT的加入可以改善PP的结晶性能，当PP-g-MAH-St和SMA-MMT含量分别为15％和2％时，复合材料中PP的结晶温度为120℃。     

右旋布洛芬/盐酸改性蒙脱土的制备及体外释放研究

目的：以酸改性蒙脱土为药物载体,制备右旋布洛芬/酸改性蒙脱土复合物,提高右旋布洛芬的载药量,并探索载药复合物在不同释放介质中的释放规律。方法：首先用浓度为5%~20%的盐酸对蒙脱土进行预处理,利用X-射线衍射（XRD）、比表面积测定（BET）、扫面电子显微镜（SEM）等表征方法对蒙脱土进行结构表征,筛选最佳酸处理浓度;然后用溶液插层法将右旋布洛芬负载于酸化后的蒙脱土上,制得右旋布洛芬/酸改性蒙脱土复合物;采用透析法对右旋布洛芬/酸改性蒙脱土复合体系进行体外释放实验。结果：经酸改性后蒙脱土的结构发生改变,当酸浓度为15%时,蒙脱土的比表面积达到最大值246 m2/g。上载右旋布洛芬后,载药量最大可达352.4 mg/g。体外释放实验表明,右旋布洛芬/酸改性蒙脱土的累积释药百分量受pH的影响,当pH为1.2时,其累积释药百分量为18.6%,当pH为6.8时,则为89.3%。结论：盐酸改性蒙脱土有助于提高药物的负载量,右旋布洛芬/酸改性蒙脱土复合物具有良好的缓释作用并有一定的pH响应性,有望制成肠道缓释口服药物制剂。     

环保型阻燃增强聚丙烯的研制

以氮-磷系阻燃剂,马来酸酐接枝聚丙烯（PP-g-MA）与阻燃用有机改性纳米蒙脱土（ONMMT-FR）的母粒作相容剂和阻燃协效剂、玻璃纤维增强剂,对聚丙烯（PP）进行阻燃增强改性,制得的纳米复合材料阻燃性达到UL-94 V-0级（1.6 mm）,且低烟,无熔滴,拉伸强度40.8~41.5 MPa,弯曲强度68.2~70.5 MPa,缺口冲击强度8.48~8.95 kJ/m2,热变形温度159~160℃（0.45 MPa下）。     

抗菌的季鳞阳离子改性蒙脱土的制备及表征

采用离子交换法将不同含量的十六烷基三丁基季鳞阳离子交换到蒙脱土的层间得到改性蒙脱土,并对其结构和性能进行了表征。热重分析（TGA）结果表明改性蒙脱土中季鳞阳离子的热分解起始温度都大于220℃,具有良好的热稳定性。通过X-射线衍射法（XRD）分析发现改性蒙脱土的层间距随着季鳞阳离子含量的增加而增加。扫描电镜观察结果发现：钠基蒙脱土为片状结构,粒子之间相互缠绕在一起;而改性蒙脱土的表面则显示出不规则的形状。随着改性蒙脱土中季鳞阳离子含量的增加,其抗菌活性逐渐增强。季鳞阳离子含量为22．61％（质量分数）的QPC—MMT2样品,其对E．coli和S．aureus的最低抑菌浓度（MICs）分别为1000mg·L^-1和30mg·L^-1,显示出良好的抗菌效果．     

嵌入聚合法制备聚苯乙烯——蒙脱土混杂材料

添加少量的季铵盐改性蒙脱土的苯乙烯聚合制得混杂材料。研究了混杂材料的力学性能和耐热性,用ＩＲ、ＸＲＤ、ＤＳＣ和ＴＧ等证实了聚苯乙烯在改性蒙脱土夹层中的嵌入和苯乙烯在可聚合性季铵盐改性的蒙脱土片层上的接枝。结果表明,混杂材料的拉伸强度和冲击强度都有提高,ＣＴＡＢ－Ｍｔ－ＰＳ和ＭＢＤＡＣ－Ｍｔ－ＰＳ在蒙脱土含量超６％后,增加较小,在蒙脱土含量２％时,冲击强度有极大值。耐热性也有明显提高,最大热失重时的温度ＭＢＤＡＣ－Ｍｔ－ＰＳ达４０１．８℃比ＰＳ的３７１．４℃高得多。     

PVC／OMMT／WF纳米复合材料性能研究

对蒙脱土进行有机改性制得有机蒙脱土（OMMT），并制备了聚氯乙烯侑机蒙脱土／木粉（PVC／OMMT／WF）纳米复合材料。采用硅烷偶联剂对木粉表面进行改性，有效提高了聚氯乙烯／木粉（PVC／WF）复合材料的力学性能，其中加入1．5％（质量含量，下同）硅烷偶联剂可使复合材料的冲击强度和拉伸强度分别提高14．8％和18．5％。研究了OMMT的加入对木粉改性前后的PVC／WF复合材料力学性能、耐热性能及阻燃性能的影响，结果表明，木粉未经改性时，OMMT加入无助于PVC／OMMT／WF复合材料力学性能的提高；木粉用硅烷偶联剂改性后，添加少量的OMMT，可使PVC／OMMT／WF复合材料的冲击强度和拉伸强度明显提高。研究表明，添加OMMT可显著延迟复合材料的点燃时间，燃烧残余率也明显增加，OMMT是PVC／WF复合材料的高效阻燃剂。     

环氧树脂/蒙脱土纳米复合材料的制备及性能

实验采用长链烷基胺对原始蒙脱土进行有机化处理，再利用环氧树脂对有机蒙脱土插层，制得环氧树脂，蒙脱土纳米复合材料。实验表明，改性环氧树脂的冲击强度有所提高。     

纳米蒙脱土-脂肪族聚氨酯弹性体的合成与制备

采用聚四氢呋喃醚（PTMG1000）为软段,4,4’-二环己基甲烷二异氰酸酯（HMD1）、异佛尔酮二异氰酸酯（1PD1）为硬段,层间距分别为1．95nm和2．40nm的2种有机蒙脱土,以插层聚合法制备出不同硬段含量和有机蒙脱土含量的纳米蒙脱土．脂肪族聚氨酯弹性体,并研究了硬段含量、有机蒙脱土含量、二异氰酸酯和有机蒙脱土种类对脂肪族聚氨酯弹性体力学性能的影响。结果表明,硬段含量对材料力学性能影响最大,其次是有机蒙脱土含量。当硬段质量分数达40％时,拉伸强度最高达14．06MPa;有机蒙脱土少量加入可有效提高材料的撕裂强度和断裂伸长率。以HMD1、PTMG1000和MMT2为原料,硬段质量分数为40％时,所合成的纳米蒙脱土-脂肪族聚氨酯弹性体具有较好的力学性能。     

PP-g-GMA-St／蒙脱土／碳酸钙纳米复合材料的制备和表征

利用钙基蒙脱土的离子交换合成纳米碳酸钙,制得分散均匀的蒙脱土/碳酸钙复合粒子。采用反应挤出对极性很弱的PP进行接枝改性,得到接枝物PP-g-GMA-St,其中甲基丙烯酸缩水甘油酯(GMA)的接枝率为0.7%;然后将其按不同配比与蒙脱土/碳酸钙复合粒子熔融共混,X射线衍射分析显示,蒙脱土的层间距达到4.1nm左右;透射电镜分析也表明碳酸钙和蒙脱土分散得比较均匀。并且,在蒙脱土/碳酸钙复合粒子为3%(质量分数)时,复合材料的拉伸强度和冲击强度分别达到最大值(40.26MPa和30.65J/m),比纯PP有了较大幅度的提高。     

新型白炭黑改性橡胶研究

采用2种新型白炭黑替代常用白炭黑来改性天然橡胶（NR）、顺丁橡胶（BR）、丁笨橡胶（SBR）、三元乙丙橡胶（EPDM）、丙烯酸酯橡胶（ACM）和硅橡胶。研究不同用量和不同种类的白炭黑对上述几种橡胶进行改性,通过对硬度、扯断伸长率、拉伸强度、磨耗和耐老化性能的测试,确定白炭黑的最佳用量和最适宜的种类。结果表明：白炭黑填料用量为80份时效果最好,普通白炭黑适合做EPDM的补强剂,碱法白炭黑对NR、SBR和ACM的改性效果更好,而酸法白炭黑改性的橡胶拉伸强度和硬度很小,不适于补强;白炭黑对硅橡胶的改性效果不好,得到的产品硬度很小,无法进行力学性能测试。     

Combining In‐Situ Organic Modification of Montmorillonite and the Latex Compounding Method to Prepare High‐Performance Rubber‐Montmorillonite Nanocomposites

Summary: To improve the interfacial interaction in MMT‐SBR nanocomposites, one type of UOAC was introduced to in‐situ modified MMT before latex compounding with SBR. The influence of the UOAC/MMT ratio on the structure and properties of MMT/SBR nanocomposites were carefully studied by XRD, TEM, and mechanical testing. It was found that through the in‐situ organic modification, a rubber‐intercalated structure of MMT was obtained in the nanocomposites, and the amount of rubber‐intercalated structure strongly depended on the UOAC/MMT ratio. The tensile strength of MMT‐SBR nanocomposites was enhanced dramatically from 4 to 18 MPa by in‐situ organic modification of MMT.

Stress‐strain diagram of SBR/clay nanocomposites.     

Organic interfacial tailoring of styrene butadiene rubber–clay nanocomposites prepared by latex compounding method

The styrene butadiene rubber (SBR)–clay nanocompounds were prepared by the latex compounding method, and then hexadecyl trimethyl ammonium bromide (C16) and 3‐aminopropyl triethoxy silane (KH550) were added into these nanocompounds on a two‐roll mill to prepare nanocomposites with strong interfacial interaction. The structure and properties of SBR–clay nanocomposites were carefully studied by X‐ray diffraction (XRD) studies, transmission electron microscopy (TEM), Rubber Process Analyzer (RPA), and mechanical testing. Compared with unmodified nanocomposites, the dispersion structure of modified SBR–clay nanocomposites is better with part rubber‐intercalated or part modifier‐intercalated structure. The tensile strength and the modulus at 300% elongation of modified SBR–clay nanocomposites are higher than three times of those of unmodified nanocomposites, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1826–1833, 2007     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

熔体法制备有机黏土/橡胶纳米复合材料的结构及性能

将有机黏土(OC)分别加入到天然橡胶(NR)、丁苯橡胶(SBR)、丁基橡胶(IIR)和三元乙丙橡胶(EPDM)中,通过熔体法制备了纳米复合材料。探讨了橡胶黏度及其分子结构对OC在复合材料中分散状况的影响,研究了复合材料的力学性能。结果表明,在以NR为基体的复合材料中。OC片层分散均匀,且剥离程度较高;在SBR,IIR,EPDM中,OC以插层结构为主,且插层效果从大到小的顺序依次为SBR,IIR,EPDM。与相应的纯胶相比,OC／NR纳米复合材料的定伸应力提高,拉伸强度和扯断伸长率有所下降;OC／SBR,OC／IIR,OC／EPDM纳米复合材料的定伸应力变化不大,拉伸强度和扯断伸长率明显提高,且OC／SBR和OC／EPDM复合材料的撕裂强度提高。     

纳米碳酸钙/二氧化硅复合粒子对丁苯橡胶物理机械性能的影响

采用溶胶沉淀法制备了纳米CaCO3/SiO2复合粒子,并用不同改性剂对其进行表面改性,考察了改性复合粒子对丁苯橡胶(SBR)物理机械性能的影响,同时与硬脂酸钠改性纳米CaCO3填充的SBR硫化胶做了比较。结果表明,CaCO3/SiO2复合粒子粒径为40～50 nm,大小均匀,表面粗糙,SiO2包覆在纳米CaCO3表面,具有核壳结构;硬脂酸钠改性复合粒子填充SBR硫化胶的拉伸强度、撕裂强度、永久变形和邵尔A硬度均大于改性纳米CaCO3填充SBR硫化胶,最大拉伸强度可达到13.6 MPa,两者的300%定伸应力和扯断伸长率相当;用硬脂酸钠和Si 69协同改性的纳米CaCO3/SiO2填充SBR硫化胶的拉伸强度、300%定伸应力、撕裂强度和邵尔A硬度均明显优于硬脂酸钠改性复合粒子填充的SBR硫化胶,最大拉伸强度达到14.1 MPa,扯断伸长率减小,低填充量时两者的永久变形差别不大,高填充量时前者的永久变形低于后者。     

Preparation and characterization of poly(styrene‐co‐butadiene) and polybutadiene rubber/clay nanocomposites

Poly(styrene‐co‐butadiene) rubber (SBR) and polybutadiene rubber (BR)/clay nanocomposites have been prepared. The effects of the incorporation of inorganically and organically modified clays on the vulcanization reactions of SBR and BR were analysed by rheometry and differential scanning calorimetry. A reduction in scorch time (t_s1) and optimum time (t₉₅) was observed for both the rubbers when organoclay was added and this was attributed to the amine groups of the organic modifier. However, t_s1 and t₉₅ were further increased as the clay content was increased. A reduction in torque value was obtained for the organoclay nanocomposites, indicating a lower number of crosslinks formed. The organoclays favoured the vulcanization process although the vulcanizing effect was reduced with increasing clay content. The tensile strength and elongation of SBR were improved significantly with organoclay. The improvement of the tensile properties of BR with organoclay was less noticeable than inorganic‐modified clay. Nevertheless, these mechanical properties were enhanced with addition of clay. The mechanical properties of the nanocomposites were dependent on filler size and dispersion, and also compatibility between fillers and the rubber matrix. Copyright © 2004 Society of Chemical Industry     

Nanocomposite Formation in Hydrogenated Nitrile Rubber (HNBR)/Organo‐Montmorillonite as a Function of the Intercalant Type

Summary: Hydrogenated acrylonitrile butadiene rubber (HNBR) was melt compounded with montmorillonite (MMT) and organophilic modified MMTs prior to sulfur curing. In contrast to the micro‐composite formation resulting from the compounding of the HNBR and pristine MMT, the modified MMTs (i.e., octadecylamine: MMT‐ODA, octadecyltrimethylamine: MMT‐ODTMA, methyltallow‐bis(2‐hydroxyethyl) quaternary ammonium: MMT‐MTH intercalants) produced nanocomposites. It was found that the organoclay with primary amine intercalant (cf. MMT‐ODA) gave confined structures along with the exfoliated/intercalated structures. This was traced to its reactivity with the curatives. By contrast, the organoclays containing less reactive quaternary ammonium compounds (cf. MMT‐ODTMA, MMT‐MTH) were exfoliated and intercalated based on X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results. The hydroxyl functional groups of the MMT‐MTH supported the clay dispersion. The better adhesion between MMT‐MTH and HNBR was explained by hydrogen bonding between the hydroxyl groups of the intercalant and the acrylonitrile group of the HNBR matrix. This HNBR/MMT‐MTH nanocomposite showed the best mechanical properties as verified by tensile mechanical tests and dynamic mechanical thermal analysis (DMTA). The high tensile strength along with the high elongation at break for the rubber nanocomposites were attributed to the ability of the ‘clay network’ to dissipate the input energy upon uniaxial loading.

Scheme of failure development in rubber/organoclay mixes with poor (a) and good (b) dispersion of the clay layers.     

Novel fabrication of disorderly exfoliated sodium montmorillonite in a styrene–butadiene rubber matrix

Using industrial technologies, we prepared a sodium montmorillonite (Na‐MMT) slurry and an irradiated styrene–butadiene rubber (SBR) latex, and then spray dried them to produce a novel, ultrafine fully vulcanized powder SBR (UFPSBR)/Na‐MMT nanocompound powder in which the nanoscale UFPSBR particles and exfoliated Na‐MMT were isolated and stuck together. When the UFPSBR/Na‐MMT nanocompound powder was mixed with crude SBR, the exfoliated Na‐MMT was disorderly dispersed in the SBR matrix because of the carrier nature of the UFPSBR particle, which is compatible with SBR and disperses easily in the SBR matrix, and the SBR/UFPSBR/Na‐MMT ternary nanocomposite was prepared. When compared with SBR/Na‐MMT binary composites, the SBR/UFPSBR/Na‐MMT ternary nanocomposite has a shorter vulcanization time, higher strength, and better flame retardancy because of the good dispersion of exfoliated Na‐MMT in the SBR matrix with a Na‐MMT loading range of 4 phr. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2013     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005