Preparation and characterization of wood/styrene‐acrylonitrile copolymer/MMT nanocomposite

Wood polymer nanocomposite (WPNC) was prepared by impregnating Simul (Salmalia malabarica) wood with styrene‐acrylonitrile copolymer (SAN), glycidyl methacrylate(GMA), and a reactive polymerizable surfactant modified montmorillonite (MMT). The physical and mechanical properties of WPNC were investigated by using XRD, tensile tester, SEM, and FTIR. The polymer loading, dimensional stability, water uptake, mechanical property, and thermal stability were found to improve due to inclusion of MMT. SEM micrographs showed the presence of polymer and MMT into cell wall and cell lumen. FTIR analysis confirmed the presence of MMT and SAN in WPNC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

有机粘土／SBR纳米复合材料的结构与性能研究

采用十六烷基三甲基溴化铵（CTAB）和十八烷基三甲基溴化铵（STAB）分别对无机粘土进行有机改性,然后制备有机粘上／SBR纳米复合材料,研究不同季铵盐类改性剂对无机粘土的改性效果。结果表明：CTAB改性有机粘土与STAB改性有机粘土的片层间距分别从无机粘土的1．26nm增加到3．77nm和4．39nm;CTAB改性有机粘土的片层结构较稳定,而且在橡胶基体中的分散效果较好;所制备的有机粘土／SBR纳米复合材料的片层结构较多,力学性能较好。     

SYNTHESIS OF POLY(METHYL METHACRYLATE)—CLAY NANOCOMPOSITES

Poly(methyl methacrylate)/clay nanocomposites were synthesized via in situ free radical polymerization of methyl methacrylate (MMA) in the presence of functionalized clay. Montmoril-lonite (MMT), a smectic type of clay, was treated with a commercial cationic surfactant, benzalkonium chloride (BAC), and a synthesized zwitterionic surfactant, octadecyldimethyl betaine (CI8DMB) Functionalized MMT was prepared via an ion exchange between Na,ions in the clay and the surfactant cations in aqueous medium. The intercalation of the surfactant in the clay galleries was determined using X-ray diffraction (XRD). The interlayer spacing for C18DMB was 2.03nm, higher than 1.86nm observed for BAC. This is due to longer chain length of C18DMB. Both organophilic clays formed a viscous gel when dispersed in the monomer, MMA. Poly(methyl methacrylate) (PMMA) nanocomposites were obtained by polymerizing the dispersions. XRD and transmission electron microscopy (TEM) indicate predominant exfoliation of the silicate layers in the polymer matrix for MMT treated with C18DMB, and partial exfoliation for MMT treated with BAC     

加拿大一枝黄花纤维素合成吸油材料的工艺条件与吸附性能

以加拿大一枝黄花纤维为基材,采用悬浮聚合接枝共聚法制备吸油材料。考察了引发剂过氧化苯甲酰(BPO)用量、交联剂十六烷基三甲基溴化铵(CTAB)用量和甲基丙烯酸甲酯(MMA)与甲基丙烯酸正丁酯(BMA)单体质量比对该产物吸油性能的影响,并通过红外光谱(IR)和扫描电镜(SEM)考察了加拿大一枝黄花接枝前后的性质。结果表明:产物表面附有聚合物,且原材料中的C=O键断裂,产生醚键。这说明加拿大一枝黄花表面已接枝甲基丙烯酸酯。在单体甲基丙烯酸甲酯与甲基丙烯酸正丁酯的质量比为0.75,引发剂BPO质量分数为0.7%和交联剂CTAB质量分数为1.2%的条件下制备吸油材料,其吸附葵花籽废油的性能较好,吸油倍率为21.036 g/g,且重复吸油性能较好。     

Use of acrylic based surfmers for the preparation of exfoliated polystyrene–clay nanocomposites

Two polymerizable cationic surfactants, (11-acryloyloxyundecyl)dimethyl(2-hydroxyethyl)ammonium bromide (hydroxyethyl surfmer) and (11-acryloyloxyundecyl)dimethylethylammonium bromide (ethyl surfmer), were used for the modification of montmorillonite (MMT) clay. The modification of MMT dispersions was carried out by ion exchange of the sodium ions in Na⁺-MMT by surfactants in aqueous media. Modified MMT clays were then dispersed in styrene and subsequently polymerized in bulk by a free-radical polymerization reaction to yield polystyrene–clay nanocomposites. An exfoliated structure was obtained using the ethyl surfmer-modified clay, whereas a mixed exfoliated/intercalated structure was obtained using the hydroxyethyl surfmer-modified clay. Nanocomposite structures were confirmed by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The nanocomposites exhibited enhanced thermal stability and an increase in glass transition temperature, relative to neat polystyrene. The nanocomposites also exhibited enhanced mechanical properties, which were dependent on the clay loading. Intercalated polystyrene–clay nanocomposites were obtained using the non-polymerizable surfactant-modified clay (cetyltrimethylammonium bromide). Nanocomposites made from mixtures of surfmer-modified and CTAB-modified clays were also prepared, showing intermediate properties. However, when the nanocomposites were prepared in solution only intercalated morphologies were obtained. This was attributed to the competition between the solvent molecules and monomer in penetrating into clay galleries. These nanocomposites also exhibited enhanced thermal stability relative to the virgin polystyrene prepared by the same method. Similar temperatures of degradation (at 50% decomposition) were found for these nanocomposites relative to those prepared by bulk polymerization.     

表面活性剂对聚乙烯醇基薄膜透光性及机理的影响

针对聚乙烯醇（PVA）与表面活性剂能组成复配体系,制备了聚乙烯醇基亲水性薄膜材料,研究了表面活性剂的掺量对聚乙烯醇基薄膜的微观结构、孔隙度、透光性能、PVA结晶度及晶粒尺寸的影响。采用紫外分光光度计考察了各薄膜的透光性;采用扫描电子显微镜观察了聚乙烯醇/表面活性剂的横截面微观结构;采用X射线衍射仪考察了不同表面活性剂的添加量对复合薄膜的晶相组成及PVA晶粒尺寸的影响,结果表明当表面活性剂添加量在6%~10%（质量分数,下同）时,阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）明显地降低聚乙烯醇的结晶度,而阴离子表面活性剂十二烷基苯磺酸钠（SDBS）则没有此效果;CTAB的加入使聚乙烯醇/CTAB体系中PVA晶粒尺寸增大,SDBS的加入使聚乙烯醇/SDBS体系中PVA晶粒尺寸减小。最后对聚乙烯醇与表面活性剂相互作用机理示意图进行了预测。     

Some Surface Properties of Polysorbates and Cetyl Trimethyl Ammonium Bromine Mixed Systems

Mixed surfactant solutions consisting of cationic/nonionic surfactants were prepared in different compositions of the components in aqueous solution in order to determine the surface properties. The critical micelle concentration (CMC) of aqueous solutions of the individual surfactants cetyl trimethyl ammonium bromide (CTAB) and polysorbate nonionics, and their mixtures are determined at different proportions. The results show that there is synergistic behavior in mixtures at higher mole fraction of nonionic surfactant. The effect of the alkyl chain on the CMC is also determined.     

复合插层有机蒙脱土的制备及表征

以钠基蒙脱土、十六烷基三甲基溴化铵(CTAB)和己内酰胺为原料,制备了复合插层有机蒙脱土。红外光谱分析(IR)、热重分析(TGA)和X-射线衍射分析(XRD)表明,有机插层剂已进入蒙脱土的层间,CTAB/己内酰胺复合插层有机蒙脱土的层间距大于单阳离子CTAB插层有机蒙脱土的层间距。Molau实验结果表明,这种有机蒙脱土在有机介质中表现出很好的分散性。     

Morphology,Thermal and Mechanical Properties of Poly (Styrene-Acrylonitrile) (SAN)/Clay Nanocomposites from Organic-Modified Montmorillonite

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have successfully been prepared by melt intercalation method. The hexadecyl triphenyl phosphonium bromide (P16) and cetyl pyridium chloride (CPC) are used to modify the montmorillonite (MMT). The structure and thermal stability property of the organic modified MMT are, respectively characterized by Fourier transfer infrared (FT-IR) spectra, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results indicate that the cationic surfactants intercalate into the gallery of MMT and the organic-modified MMT by P16 and CPC has higher thermal stability than hexadecyl trimethyl ammonium bromide (C16) modified MMT. The influences of the different organic modified MMT on the structure and properties of the SAN/clay nanocomposites are investigated by XRD, transmission electronic microscopy (TEM), high-resolution electron microscopy (HREM), TGA and dynamic mechanical analysis (DMA), respectively. The results indicate that the SAN cannot intercalate into the interlayers of the pristine MMT and results in microcomposites. However, the dispersion of the organic-modified MMT in the SAN is rather facile and the SAN nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The thermal stability and the char residue at 700°C of the SAN/clay nanocomposites have remarkably enhancements compared with pure SAN. DMA measurements show that the silicate clays improve the storage modulus and glass transition temperature (Tg) of the SAN matrix in the nanocomposites.     

原位聚合法制备聚丙烯腈/蒙脱土插层共混材料初探

用十六烷基三甲基溴化铵(CTAB)对蒙脱土进行有机化处理,以过硫酸铵为引发剂,使丙烯腈单体在有机化蒙脱土层间进行原位聚合.对这种插层复合材料的的燃烧性能和热性能进行了初步研究,并且用红外光谱和X射线衍射对其结构进行了分析与表征.结果表明:PAN/MMT共混复合物的阻燃性能有一定提高,其极限氧指数从18%提高到了22%;耐热性能得到一定程度改善.红外光谱和X射线衍射分析结果显示:在蒙脱土片层之间通过原位聚合生成了聚丙烯腈大分子,使蒙脱土层间距有一定程度的增大.     

Synthesis and characterization of novel poly(o‐toluidine) montmorillonite nanocomposites: Effect of surfactant on intercalation

The investigation of clay based polymer nanocomposites has opened the door for the development of novel, ecofriendly advanced nano materials that can be safely recycled. Because of their nanometer size dispersion, these nanocomposites often have superior physical and mechanical properties. In this study, novel nanocomposites of poly(o‐toluidine) (POT) and organically modified montmorillonite (MMT) were synthesized using camphor sulfonic acid (CSA), cetyl pyridinum chloride (CPCl), and N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) to study the role of surfactant modification on the intercalation. The in situ intercalative polymerization of POT within the organically modified MMT layers was analyzed by FTIR, UV–visible, XRD, SEM as well as TEM studies. The average particle size of the nanocomposites was found to be in the range 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of silica nanopowder on the properties of wood flour/polymer composite

Low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polypropylene (PP), and polyvinyl chloride (PVC) (1:1:1:0.5) were solution blended by using a mixture of solvents consisting of xylene and tetrahydrofuran (THF) (70:30). SiO₂ nanoparticles were modified by cetyl trimethyl ammonium bromide (CTAB). Wood polymer composites (WPC) were prepared by using polymer mixture, polyethylene‐co‐glycidyl methacrylate (PE‐co‐GMA), wood flour, and modified SiO₂. X‐ray diffraction (XRD) studies showed that the intensity of the peaks of polymer mixture decreased due to incorporation of SiO₂. The dispersion of SiO₂ nanoparticles and morphological characteristics were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The interaction between SiO₂ nanoparticles, PE‐co‐GMA, polymer mixture, and wood was studied by Fourier transform infrared spectroscopy (FTIR). Tensile and flexural properties of the composites improved significantly due to the incorporation of SiO₂ nanoparticles. Thermal stability, hardness, flame retardancy, and water resistance capacity were also found to enhance. Maximum improvement in properties was observed by the inclusion of 3 phr modified SiO₂ in WPC. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Effects of modified attapulgite on the properties of attapulgite/epoxy nanocomposites

The aim of this work is to figure out the true effects of filler modification in attapulgite (ATP)/epoxy (EP) nanocomposites through comparing the properties of composites containing pristine or modified ATP clay. ATP particles were first pretreated by a silane coupling agent KH550 and cationic surfactant cetyl trimethyl ammonium bromide (CTAB) separately, and then a series of nanocomposites were prepared with varied clay loadings. Fourier transform infrared spectroscopy and thermogravimetric analysis were used to confirm the modification. The wicking experiment showed the compatibility of ATP with EP increased after modification, especially for CTAB‐ATP, which was discovered to exhibit the highest affinitive ratio. Mechanical and thermal properties of the composites were enhanced on the introduction of ATP. Regarding the efficiency of mechanical reinforcement, KH550 was superior to CTAB at lower ATP loadings (<2 wt%), whereas CTAB became relatively more effective at higher loadings. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

有机MMT对高密度聚乙烯改性的研究

采用十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和双十八烷基二甲基氯化铵4种阳离子表面活性剂对钠基蒙脱土(MMT)进行有机化处理,制备了有机MMT(OMMT)。将OMMT与高密度聚乙烯(HDPE)进行熔融插层制备了HDPE／OMMT纳米复合材料,研究了OMMT的层间距同季铵盐烷基链的关系。结果表明,OMMT的层间距随烷基链长度的增加而增大;随着OMMT含量的增加,HDPE／OMMT纳米复合材料的断裂伸长率和拉伸强度降低,弯曲弹性模量增加,弯曲强度出现极大值,使该纳米复合材料的力学性能得到了一定的改善。     

Phosphonium‐based layered silicate—Poly(ethylene terephthalate) nanocomposites: Stability,thermal and mechanical properties

PET‐clay nanocomposites were prepared using alkyl quaternary ammonium and phosphonium modified clays by melt‐mixing at 280°C using a micro twin screw extruder. The latter clays were prepared by synthesizing phosphonium surfactants using a simple one‐step method followed by a cation exchange reaction. The onset temperature of decomposition (T_onset) for phosphonium clays (>300°C) was found to be significantly higher than that of ammonium clays (around 240°C). The clay modified with a lower concentration (0.8 meq) of phosphonium surfactant showed a higher T_onset as compared to the clay modified with a higher concentration (1.5 meq) of surfactants. Nanocomposites prepared with octadecyltriphenyl phosphonium (C18P) modified clay showed a higher extent of polymer intercalation as compared with benzyltriphenylphosphonium (BTP) and dodecyltriphenylphosphonium (C12P) modified clays. The nanocomposites prepared with ammonium clays showed a significant decrease in the molecular weight of PET during processing due to thermal degradation of ammonium surfactants. This resulted in a substantial decrease in the mechanical properties. The molecular weight of PET was not considerably reduced during processing upon addition of phosphonium clay. The nanocomposites prepared using phosphonium clays showed an improvement in thermal properties as compared with ammonium clay‐based nanocomposites. T_onset increased significantly in the phosphonium clay‐based nanocomposites and was higher for nanocomposites which contained clay modified with lower amount of surfactant. The tensile strength decreased slightly; however, the modulus showed a significant improvement upon addition of phosphonium clays, as compared with PET. Elongation at break decreased sharply with clay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The dispersion behavior of clay particles in poly(L‐lactide)/organo‐modified montmorillonite hybrid systems

Hybrids of poly(L‐lactide)/organoclay (PLACHs) have been prepared via a melt‐compounding process using poly(L‐lactide) (PLLA) and three types of surface‐treated montmorillonite modified with ammonium salts (M1, trimethyl octadecyl‐; M2, dimethyl dioctadecyl‐, and M3, bis(4‐hydroxy butyl) methyl octadecyl‐ammonium). The dispersed state of the clay particles in the PLLA matrix was examined by use of wide‐angle X‐ray diffraction, transmission electron microscopy, and polarizing optical microscopy. On melt‐compounding PLLA and two organoclays (M1, M2) modified with the surfactants both carrying homogenous alkyl chains, we obtained intercalated hybrids with relatively uniform dispersion of nanometer‐sized clay particles. On the other hand, the organoclay (M3) modified with a surfactant carrying alkyl chains end‐capped with hydroxyl groups yielded the composite with flocculated particles. The flocculation of the particles originates from the hydrogen bonding among the hydroxyl groups of the component surfactant, those of the clay edge and those of both ends of PLLA chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2711–2720, 2004     

Radiation-induced admicellar polymerization of isoprene on silica: Effects of surfactant's chain length

This research compared radiation-induced admicellar polymerization with the traditional thermal process and studied the influence of the hydrocarbon chain length of different surfactants on film formation. Three types of surfactants were used in this study: dodecyl trimethyl ammonium bromide (DTAB), tetradecyl trimethyl ammonium bromide (TTAB) and cetyl trimethyl ammonium bromide (CTAB). Isoprene was used as a monomer for the formation of thin film inside the surfactant bilayers, called admicelle, adsorbed on silica surface. The results showed that an optimum dose can lead to a better film formation on silica, compared with the thermal method. However, when the dose was over the optimum value, the formation of polyisoprene film was diminished. The formation of polyisoprene film was found to depend not only on the hydrocarbon chain length of the surfactant, but also on the density of adsorbed surfactant on silica surface.     

丙烯酸酯核壳纳米粒子的合成及其改性环氧树脂

以丙烯酸丁酯(BA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体和甲基丙烯酸缩水甘油脂(GMA)为官能单体,采用乳液聚合法合成出具有活性结构的BA/MMA/GMA核壳纳米粒子,并以此作为环氧树脂(EP)的增韧改性剂。研究结果表明:当w(核壳粒子)=10%、m(BA):m(MMA):m(GMA)=80:20:10时,与纯EP体系相比,改性EP体系的断裂伸长率提高了42.5%,剥高强度提高了近3倍,25℃和150℃时的剪切强度分别提高了48.6%和31.2%,坡璃化转变温度变化不大;红外光谱(FT-IR)证实,该核壳纳米粒子具有典型的特征吸收峰;透射电镜(TEM)观察结果表明,合成粒子具有纳米级核壳结构。     

插层有机纳米蒙脱土改性骨胶胶粘剂的制备与性能研究

用十六烷基三甲基溴化铵和十二烷基三甲基溴化铵对蒙脱土(MMT)进行有机化处理,得到有机纳米MMT;将骨胶插层到有机纳米MMT中,再经环氧氯丙烷(ECH)交联改性,得到插层有机纳米MMT改性骨胶胶粘剂。通过单因素试验探讨了各种工艺因素对胶粘剂黏度的影响。结果表明:制备插层有机纳米MMT改性骨胶胶粘剂的最佳工艺条件为酸解温度60℃,接枝共聚温度50℃,m(ECH)≈0.5 g,接枝共聚时间90 min,m(MMT)=0.35 g;在此工艺条件下制取的骨胶胶粘剂,其适用期增至60 d,凝固点降至-4℃,克服了传统骨胶储存期短、常温呈固态以及使用时要现用现熬等缺点,具有良好的应用前景。     

Effect of tethering chemistry of cationic surfactants on clay exfoliation, electrospinning and diameter of PMMA/clay nanocomposite fibers

We examine the influence of tethering chemistry of cationic surfactants on exfoliation of montmorillonite (MMT) clay dispersed in methyl methacrylate (MMA) followed by in-situ polymerization to form poly(methyl methacrylate) (PMMA) nanocomposites, the effect of exfoliation and clay loading on the rheology of polymer/clay dispersions in dimethyl formamide, and the diameters of nanocomposite fibers formed from these dispersions by electrospinning. Incorporation of an additional reactive tethering group of methacryl functionality significantly improves the intercalation and exfoliation of clays in both in-situ polymerized PMMA nanocomposites and the corresponding electrospun fibers. The proper surfactant chemistry also increases the dispersion stability, extensional viscosity, extent of strain hardening and thus the electrospinnablity of the nanocomposite dispersions, especially at low nanocomposite concentrations. The degree of the enhancement in electrospinnability by clays with proper tethering chemistry is at least the same as or greater than that obtained with three times higher loading level of clay particles without proper tethering chemistry in the nanocomposites. These results suggest a new strategy to produce smaller diameter fibers from very dilute polymer solutions, which are otherwise not electrospinnable, by incorporating a small amount of well-exfoliated clays.