Synthesis of LDHs and Rheological Properties of Laponite／LDHs Dispersions

The chemical composition, morphology of the particles of positively charged layered double hydroxides (LDHs) were studied by ICP, Mastersizer, TEM. The preliminary results indicated that with adding LDHs to 1% laponite dispersion the yield stress of laponite/LDHs mixed dispersions increased at first, then decreased dramatically to a minimum, and the yield stress rose again when LDHs increased further.     

PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE(SPI)/MONTMORILLONITE(MMT) BIONANOCOMPOSITES

 The bionanocomposites of soy protein isolate (SPI)/montmorillonite (MMT) have been prepared successfully via simple melt mixing, in which MMT was used as nanofiller and glycerol was used as plasticizer. Their structures and properties were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermogravimetric analysis and tensile testing. XRD、TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by simple melt processing. The exfoliated MMT layers were randomly dispersed in the protein matrix as MMT content was low (less than 5 wt%), an incomplete exfoliation was evident from SEM results, and some primary particles were observed as the MMT content was high (from 5 wt% to 9 wt%). A significant improvement of the mechanical strength and thermal stability of SPI/MMT nanocomposites has been achieved. Our work suggests that simple melt processing is an efficient way to prepare SPI/MMT nanocomposites with exfoliated structure.     

Preparation of polystyrene/silica nanocomposites by radical copolymerization of styrene with silica macromonomer

A two-stage process has been developed to generate the silica-based macromonomer through surface-modification of silica with polymerizable vinyl groups. The silica surfaces were treated with excess 2,4-toluene diisocynate (TDI), after which the residual isocyanate groups were converted into polymerizable vinyl groups by reaction with hydroxypropylacrylate (HPA). Thus, polystyrene/silica nanocomposites were prepared by conventional radical copolymerization of styrene with silica macromonomer. The main effecting factors, such as ratios of styrene to the macromonomer, together with polymerization time on the copolymerization were studied in detail. FTIR, DSC and TGA were utilized to characterize the nanocomposites. Experimental results revealed that the silica nanoparticles act as cross-linking points in the polystytene/silica nanocomposites, and the glass transition temperatures of the nanocomposites are higher than that of the corresponding pure polystyrene. The glass transition temperatures of nanocomposites increased with the increasing of silica contents, which were further ascertained by DSC.     

ENHANCED MECHANICAL PROPERTIES OF POLYPROPYLENE/SILICA NANOCOMPOSITES WITH SURFACE MODIFICATION OF NANO-SILICA VIA IN SITU COPOLYMERIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

Nano-sized silica particles were modified with methacryloxy-propyltrimethoxysilane(MPS) followed by in situ copolymerization of methyl methacrylate(MMA) and butyl acrylate(BA).These modified nanoparticles were compounded with polypropylene(PP) to prepare PP/silica nanocomposites.PMMA grafted on nano-silica enhances the dispersion of the nanoparticles and interfacial adhesion,decreases the size of PP spherulites in nanocomposites and leads to increasing the Young's modulus and toughness of PP/silica nanoc...     

Effect of polyaniline as a surface modifier of TiO2 nanoparticles on the properties of polyvinyl chloride/TiO2 nanocomposites

Surface of TiO2 nanoparticles was modified with the in situ chemical oxidative polymerization of aniline. Polyaniline modified TiO2 nanoparticles (PANI-TiO2 ) were characterized with the FT-IR, XRD, SEM and TEM techniques. Results confirmed that PANI was grafted successfully on the surface of TiO2 nanoparticles, therefore agglomeration of nanoparticles decreased dramatically. Polyvinyl chloride nanocomposites filled with 1 wt% 5 wt% of PANI-TiO2 and TiO2 nanoparticles were prepared via the solution blending method. PVC nanocomposites were analyzed with FT-IR, XRD, SEM, TG/DTA, DSC and tensile test techniques. Effect of PANI as surface modifier of nanoparticles was discussed according to the final properties of PVC nanocomposites. Results demonstrated that deposition of PANI on the surface of TiO2 nanoparticles improved the interfacial adhesion between the constituents of nanocomposites, which resulted in better dispersion of nanoparticles in the PVC matrix. Also PVC/PANI-TiO2 nanocomposites showed higher thermal resistance, tensile strength and Young’s modulus compared to those of unfilled PVC and PVC/TiO2 nanocomposites.     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.     

Toughening of ethylene-propylene random copolymer/clay nanocomposites: Comparison of different compatibilizers

Ethylene/propylene-random-copolymer(PPR)/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers,including an ethylene-octene copolymer grafted maleic anhydride(POE-g-MA) and three maleic-anhydride-grafted polypropylenes(PP-g-MA) with different melt flow indexes(MFI),were used to improve the dispersion of organic clay in matrix.On the other hand,the effects of organic montmorillonite(OMMT) content on the nanocomposite structure in terms of clay dispersion in PPR matrix,thermal behavior and tensile properties were also studied. The X-ray diffraction(XRD) and transmission electron microscopy(TEM) results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites.Moreover,a PP-g-MA compatibilizer(compatibilizer B) having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers.With the introduction of compatibilizer D(POE-g-MA),most of the clays are dispersed into the POE phase,and the shape of the dispersed OMMT appears elliptic,which differs from the strip of PP-g-MA.Compared with virgin PPR,the Young’s modulus of the nanocomposite evidently increases when a compatibilizer C(PP-g-MA) with medium MFI is used.For the nanocomposites with compatibilizer B and C,their crystallinities(X_c) increase as compared with that of the virgin PPR. Furthermore,the increase of OMMT loadings presents little effect on the melt temperature(T_m) of the PPR/OMMT nanocomposites,and slight effect on their crystallization temperature(T_c).Only compatibilizer B can lead to a marked increases in crystallinity and T_c of the nanocomposite when the OMMT content is 2 wt%.     

PREPARATION OF POLY（METHYL METHACRYLATE）/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly(methyl methacrylate)(LDHs/PMMA)nanocomposite was prepared by in situ solution polymerization of methyl methacrylate(MMA)in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs).MgAl-VBS LDHs was prepared by the ion exchange method,and the structure and composition of the MgA1-VBS LDHs were determined by X-ray diffraction(XRD),infrared spectroscopy and elemental analysis.XRD and transmission electron microscopy(TEM)were employed to examine the structure of LDHs/PMMA nanocomposite.It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix.The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.     

Preparation of POE/PS blends with fine particle sizes by diffusion and subsequent polymerization of styrene in POE pellets

Ethylene-α-octene copolymer(POE)/polystyrene(PS) blend pellets with fine particle sizes were prepared by diffusion and subsequent polymerization of styrene in POE pellets through a one-pot procedure.The effects of the amounts of styrene and BPO on PS content,monomer efficiency and monomer conversion were investigated.The blend pellets were characterized by Micro-FTIR and FESEM,showing homogeneous diametrical distributions of PS and particle size.After melt-processing into rods,the average particle sizes are almost doubled,but still in submicron scale.Compared to neat POE rods,the blend rods with PS content higher than 15% exhibit improved tensile modulus and tensile strength without significantly losing ductility,being attributed to the small sizes,complex nature of particles and the existence of POE-g-PS copolymer that result in good interfacial adhesion.POE/PS pellets were compared with the previously reported PP/PS pellets,and the differences between the two systems are attributed to the different morphology of the two matrices: POE is completely amorphous at the diffusion and polymerization temperature,while i PP is semicrystalline.Without efficient impediment of the crystal lamellae in POE pellets,styrene diffuses easily in POE pellets.     

Dispersion stability and rheological behavior of suspensions of polystyrene coated fumed silica particles in polystyrene solutions

Polystyrene coated silica（SiO₂@PS） core-shell composite particles with averaged diameter of about 290 nm were prepared by in situ emulsion polymerization of styrene on the surface ofγ-methacryloxypropyltrimethoxysilane grafted SiO₂ nanoparticles of 20-50 nm in diameter.Rheological behavior and dispersion stability of SiO₂@PS suspension in 10 wt%PS solution were compared with suspensions of untreated SiO₂ and silane modified SiO₂ nanoparticles.Suspensions of the untreated and the silane modified SiO₂ exhibited obvious shear thinning.The SiO-2@PS suspension exhibits shear viscosity considerably smaller than suspensions of untreated and silane modified SiO₂ at low shear rates.Transmission electron microscopy showed that the composite particles can uniformly and stably disperse in PS solution compared to other suspensions,implying that the PS shell can effectively enhance the particle compatibility with PS macromolecules in solution.     

Synthesis and characterization of exfoliated polystyrene/ZnAl layered double hydroxide nanocomposite via emulsion polymerization

Exfoliated polystyrene (PS)/ZnAl layered double hydroxide (LDH) nanocomposites have been synthesized via emulsion polymerization in the presence of N-lauroyl-glutamate surfactants and long-chain n-hexadecane. The samples were characterized using elemental analysis, Fourier transform infrared (FTIR) spectrum, X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The XRD and TEM results demonstrate that the exfoliated ZnAl-LDH layers of 50-70 nm width and about 1 nm thickness were well dispersed at molecular level in the PS matrix. And the completely exfoliated PS/LDH nanocomposites can be obtained even at the 10 wt% LDH loading. When the 50% weight loss was selected as a comparison point, the decomposition temperature of exfoliated PS/LDH sample with 5 wt% LDH was ca. 28 degrees C higher than that of pure PS.     

乳液聚合法制备聚苯乙烯/Mg-Al层状双氢氧化物纳米复合材料

采用乳液聚合法制备阻燃性聚苯乙烯MgAl层状双氢氧化物(LDHs)纳米复合材料.通过对不同合成条件下复合材料的XRD谱,讨论了纳米复合材料的形成过程;经SEM图证实了LDHs是以剥离的纳米级层片分散在基体中的;TG和DSC谱图揭示了LDHs纳米层板可有效提高PS的热稳定性,并可使PS的玻璃化转化温度明显提高;当层状双氢氧化物在插层复合材料中含量为14.92%时,纳米复合材料的氧指数可达23.5%,其用量比在PS中直接添加纳米LDHs时要少约一倍.文中还分析了纳米复合材料的形成过程.     

Preparation of polystyrene/montmorillonite nanocomposites using a new radical initiator-montmorillonite hybrid via in situ intercalative polymerization

Polystyrene/montmorillonite (PS/MMT) nanocomposites were prepared by in situ free radical intercalative polymerization, using 1, 3 and 5 wt% of a new cationic radical initiator-MMT hybrid. The corresponding nanocomposites were designated as PS/MMT-1, PS/MMT-3 and PS/MMT-5, respectively. The silicate layers were well exfoliated and randomly dispersed in the PS/MMT-1 and PS/MMT-3, but were less exfoliated in the PS/MMT-5, due to the predominant extra-gallery polymerization over the intra-gallery polymerization. The unique properties of nanocomposites resulted from the strong interactions between the nano-sized silicate layer surfaces and the polymer chains. The onset temperature of thermal degradation, and the glass transition temperature, increased with increasing hybrid content, up to 3 wt%. The molecular weights of the PS in the PS/MMT-1 and PS/MMT-3 were less than those calculated theoretically, due to the predominant intra-gallery polymerization.     

蒙脱土负载型引发剂的制备及在苯乙烯乳液聚合中的应用

通过正离子交换将引发剂AIBA负载在蒙脱土上制得负载型引发剂V50-MMT.进而采用原位乳液聚合方法引发苯乙烯聚合制备PS/MMT纳米复合材料.采用XRD、TGA、DSC、TEM和抽提等方法对负载型引发剂和纳米复合材料进行了表征.结果表明,负载过程中引发剂AIBA进入了MMT的片层之间;聚合过程中介于片层间的引发剂因发生分解一方面产生自由基引发St聚合,另一方面MMT发生了剥离分散;由此法制备的PS/MMT纳米复合材料,MMT片层无规、均匀地分散于PS基体中,片层厚度在几个纳米至十几个纳米之间,长度为几十至几百个纳米不等;大量的PS链段以化学键接枝在MMT的片层上,接枝在MMT片层上的PS的分子量及其分布与游离的PS不同.     

Influence of four different types of organophilic clay on the morphology and thermal properties of polystyrene/clay nanocomposites prepared by using the γ-ray irradiation technique

Polystyrene (PS)/clay nanocomposites were successfully prepared by the γ-ray irradiation technique. Four different types of organophilic clays were used: three of the four contained a reactive group, while the other did not. Exfoliated PS/clay nanocomposites can be obtained by using reactive organophilic clay and intercalated PS/nanocomposites can be formed by using non-reactive ones, which was confirmed by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). In the formation of exfoliated PS/nanocomposites, the effect of the double bond of the clay-intercalated agents is much more important than the alkyl chain length. The enhanced thermal properties of PS/nanocomposites were characterized by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). In particular, the enhancement of the thermal properties of PS/nanocomposites made using the reactive organophilic clay was much higher than that of the thermal properties of PS/nanocomposites incorporating non-reactive clay.     

Preparation and characterization of exfoliated polystyrene/clay nanocomposites using a cationic radical initiator-MMT hybrid

The exfoliated polystyrene (PS)/clay nanocomposites were prepared via in situ polymerization using a cationic radical initiator-intercalated montmorillonite hybrid. The exfoliated structure resulted from the predominant intra-gallery polymerization over the extra-gallery polymerization owing to the anchored radical initiator inside the clay galleries. Several critical properties of the nanocomposites such as the initial thermal degradation temperature, glass transition temperature, storage modulus, Young’s modulus, and tensile strength were estimated and compared with earlier reported literature values. The improvements in such properties were either comparable or much greater than the reported literature values, mainly due to the efficient exfoliation and dispersion of the clay in the PS matrix.     

sPS/PA6/蒙脱土纳米复合材料的制备与性能

讨论了间规聚苯乙烯 (sPS) 尼龙 6(PA6) 磺化间规聚苯乙烯 (SsPS H) 蒙脱土纳米复合材料的制备技术和新材料的结构与性能特征 .蒙脱土经层间改性处理后 (MTN) ,可分别将SsPS H和aPS(无规聚苯乙烯 )插入其纳米层间 ,制备出插层型纳米复合物MTN SsPS和MTN aPS .在sPS/PA6/SsPS H三组分共混体系中加入MTN SsPS或MTN aPS ,进行四组分熔融共混即可制备出sPS/PA6/SsPS H/蒙脱土纳米复合材料 .TEM测定证实了蒙脱土在基体中的层厚分布约为 5 0nm .此外 ,采用DSC、DMA、XRD及力学性能测试仪等现代分析方法对sPS/PA6/SsPS H/蒙脱土纳米复合材料的结构与性能进行了详细研究 .研究结果表明这种纳米复合材料具有优良的综合性能     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

新型纳米层状硅酸盐Magadiite主体材料的制备、表征、结构和生成机理研究

利用简单的插层反应方法成功地制备了四丁基氢氧化铵(TBAOH)插层的层状硅酸盐Magadiite纳米复合材料,在室温下该材料溶胶放置30d可以保持稳定,粉体长期保存结构稳定,而且反应时间短,只需30min.利用XRD,FTIR,SEM和HRTEM等方法对样品进行了结构表征.结果表明,TBA⁺离子在层间以双分子层排列,并与层状硅酸盐结合在一起,TBAOH插层后的纳米粒子在玻璃片上进行了重组,粒径分布在10～100nm之间;HRTEM电镜照片进一步证实了剥离的层状硅酸盐纳米粒子在玻璃片上的自组装过程.根据实验结果阐述了TBAOH插层反应形成纳米溶胶的机理.     

Thermal properties of polystyrene nanocomposites formed from rigid intercalation agent‐treated montmorillonite

Polystyrene (PS)/clay nanocomposites were prepared with two different new intercalation organophilic clays, the phosphonium salt (APP) and the ammonium 4‐(4‐adamantylphenoxy)‐1‐butanamine (APB) salts, by emulsion polymerization technique. X‐ray diffraction and transmission electron microscopy were performed to characterize the layered structures of APB‐ and APP‐treated polymer–clay nanocomposites, and both resulted in exfoliated structures. Molecular weights of PS obtained from these nanocomposites are slightly lower than the virgin PS formed under similar polymerization conditions. Coefficient of thermal expansion showed approximately a 44–55% decrease for APB‐ and APP‐intercalated clay nanocomposites relative to the pure PS. Both T_g and thermal decomposition temperature of the PS component in the nanocomposite are higher than the virgin PS, implying that the presence of clay is able to enhance thermal stabilities of the PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1781–1787, 2007