有机蒙脱石的制备新方法及性能表征

四甲基氯化铵(TMA)、十六烷基三甲基溴化铵(CTAB)、双氯乙酸丙二醇酯基双十二烷基四甲基氯化二铵(双子季铵盐GQAS)作为钠基蒙脱石(Na-MMT)的改性剂,分别采用一次插层法和两次插层法对Na-MMT进行有机化改性.X射线衍射(XRD)测试表明,Na-MMT的层间距(d001)值随着改性剂碳链长度的增长而增大,采用一次插层法时,d001值依次由Na-MMT的1.30nm增大至1.34nm、2.89nm和3.72nm,而采用两次插层法时(第一次用TMA,第二次用双子季铵盐插层)OMMT的d001值增大至3.99nm.热重分析(TGA)表明Na-MMT的失重率为13.4%,双子季铵盐一次插层的有机MMT(OMMT)的失重率为40.5%,而用TMA第一次插层,双子季铵盐第二次插层的OMMT的失重率为49.8%.傅里叶变换红外光谱(FT-IR)同样证实采用两次插层法,MMT层间吸附的阳离子与有机阳离子的交换更彻底.用双子季铵盐作为改性剂、通过两次插层法制备OMMT,鲜见文献报道.     

The properties of reactive hot melt polyurethane adhesives modified with novel thermoplastic polyurethanes

A reactive hot melt adhesive (RHMA) consisting of thermoplastic polyurethane (TPU) was modified with sodium montmorillonite (Na‐MMT) intercalated with poly(ethylene glycol) (PEG), and their effects on the adhesion, rheological, and mechanical properties of the RHMA were examined. The Na‐MMT intercalated with PEG (Na‐MMT/PEG) effectively enhanced the initial bond strength development of the RHMA, although the amounts of Na‐MMT/PEG in the RHMA were less than 0.2%. The increase of the complex viscosity and pseudo‐solid like behavior observed at low shear rate indicates that there are intimate interactions between the RHMA molecules and Na‐MMT/PEG. The improved modulus and tensile strength of the cured RHMA film in the presence of Na‐MMT/PEG demonstrates that Na‐MMT/PEG effectively reinforced the RHMA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Towards the synthesis of high solids content waterborne poly(methyl methacrylate-co-butyl acrylate)/montmorillonite nanocomposites

Small angle X-ray scattering of Na-montmorillonite (Na-MMT) aqueous dispersions showed that at concentrations below 1.5 wt%, clay platelets were fully dispersed with an average distance between platelets higher than 16 nm. At higher concentrations (3 wt%) platelet–platelet interaction was not negligible and SAXS measurements detected ordered stack structures composed of 2–3 platelets with an average distance of around 14–16 nm. Thus, initiating an emulsion polymerization of methyl methacrylate and butyl acrylate in an aqueous phase containing Na-MMT at concentrations below 1.5 wt% allowed the production of stable and coagulum free waterborne nanocomposites having 30 wt% solids content, with exfoliated structure. The in situ produced poly(methyl methacrylate-co-butyl acrylate)/Na-MMT nanocomposite latexes provided better mechanical, thermal and permeability properties than composites prepared by blending pristine latex with Na-MMT or the pristine copolymer synthesized in the same conditions. Furthermore, for the first time nanocomposite latexes with 45 wt% solids content and intercalated morphologies having enhanced mechanical properties were also produced by seeded semibatch emulsion polymerization. The intercalated structure was likely due to the higher clay concentration in the aqueous phase that favoured platelet–platelet interaction, increased the viscosity of the polymeric dispersion and prevented a complete exfoliation.     

插层有机纳米蒙脱土对脲醛树脂胶粘剂性能的影响

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,采用插层复合法制备了插层有机纳米MMT/脲醛树脂(UF)胶粘剂;讨论了有机纳米MMT用量对UF胶粘剂的表观黏度、拉伸剪切强度、耐水性及游离甲醛含量的影响。结果表明:与纯UF胶粘剂相比,插层有机纳米MMT/UF胶粘剂的表观黏度提高了2.05倍,拉伸剪切强度增加了17%,耐水时间增加了105min,游离甲醛含量由2.01%降至0.32%;经有机纳米MMT插层复合改性后,UF胶粘剂的综合性能明显提高,游离甲醛含量明显降低,符合世界环保产品的使用要求。     

原位有机改性法EPDM/Na-MMT纳米复合材料的结构和性能

直接将EPDM、未改性蒙脱土（Na-MMT）和插层剂共混，制备原位有机改性法EPDM／Na—MMT纳米复合材料，研究插层剂对复合材料结构和物理性能的影响。结果表明，添加Na-MMT和插层剂对EPDM的硫化反应有延迟效应，并可降低EPDM硫化胶的交联密度；原位有机改性法EPDM／Na-MMT纳米复合材料物理性能较未改性复合材料有较大幅度的提高，可达到剥离型EPDM／有机蒙脱土纳米复合材料的水平；Na—MMT以完全剥离、插层和未插层3种微观形态共存于EPDM基体中，未插层Na—MMT的存在基本上不影响完全剥离Na-MMT片层对EPDM的补强效果。     

Novel,synergistic composites of polypropylene and rice husk ash: Sustainable resource hybrids prepared by solid‐state shear pulverization

Rice husk ash (RHA) is an agrowaste byproduct resulting from the incineration of rice husks for power production; white RHA is ∼90 wt% or more silica, which makes it a potentially sustainable and inexpensive substitute for commercial (less “green”) silica filler. Past research on polypropylene (PP)‐RHA hybrids made by melt processing has yielded modest increments in Young's modulus, reduced yield strength, and drastic reductions in elongation at break relative to neat PP. Using the industrially scalable solid‐state shear pulverization (SSSP) process, PP‐RHA hybrids are made with 4–38 wt% RHA. As determined by microscopy and other methods, composites made by SSSP have much better RHA dispersion than composites reported in the literature made by twin‐screw extrusion. The superior dispersion leads to major enhancements in tensile modulus (up to 100% increases relative to neat PP) while maintaining the yield strength of neat PP and remarkably high values of elongation at break (e.g., 520% at 19 wt% RHA), far higher than composites made by melt processing. The properties of hybrids made by SSSP are competitive with and in some cases superior to those of PP hybrids made with commercial silica. The PP‐RHA hybrids also exhibit major increases in hardness, approaching that of polycarbonate in the case of a 38 wt% RHA hybrid. The 38 wt% RHA hybrid exhibits solid‐like rheology at low frequency. Nevertheless, all PP‐RHA hybrids made by SSSP exhibit viscosities at moderate to high shear rates that are little changed from that of neat PP. POLYM. COMPOS., 34:1211–1221, 2013. © 2013 Society of Plastics Engineers     

Influence of poly(ethylene glycol)/montmorillonite hybrids on the rheological behaviors and mechanical properties of polypropylene

The effects of poly(ethylene glycol) (PEG)/montmorillonite (MMT) hybrids on the phase morphology, rheological behaviors and mechanical properties of polypropylene (PP) were investigated. The analysis of transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) indicated that the PEG modified montmorillonite was intercalated and well dispersed into PP matrix. It was found that the addition of the PEG/MMT hybrids in PP matrix lead to a significant reduction of melt viscosity and enhancement in izod-notched impact strength and elongation at break, except that the tensile strength was without much obvious change. A quantitative analysis indicated that MMT was intercalated by PEG, which was responsible for the melt viscosity reduction of PP matrix. Differential scanning calorimetry (DSC) analysis indicated that the addition of PEG/MMT hybrids induced the formation of β-crystal of PP. Polarized light micrographs (PLM) analysis indicated that the dispersed MMT, which acted as a nucleating agent, lowered the spherulite dimension and increased the spherulite number, resulting in high izod-notched impact strength and elongation at break.     

Preparation of poly(lactic acid)/poly(ethylene glycol)/organoclay nanocomposites by melt compounding

Poly(lactic acid) (PLA)/organoclay nanocomposites were prepared by melt compounding in a co‐rotating twin screw extruder. Two types of commercialized organoclay (dimethyl benzyl stearyl ammonium ion and dimethyl distearyl ammonium ion intercalated between clay platelets named as Clay A and Clay B, respectively) and two grades of poly(ethylene glycol) (PEG) with different molecular weight (M_w = 2,000 and 300,000–500,000 named as PEG2k and PEG500k, respectively) were used in this study. The Young's modulus improved by the addition of organoclay to PLA matrix. The Young's modulus decreased with the addition of PEG to PLA/organoclay nanocomposites. The tensile strength and elongation of PLA/Clay B nanocomposites increased with the addition of PEG2k. The effect of the addition of PEG on d‐spacing of PLA/organoclay nanocomposites is dependent upon the kind of organoclay. The sizes of clay agglomerations in PLA/PEG/organoclay nanocomposites are larger than those of PLA/organoclay ones in the same organoclay. Addition of PEG to PLA/organoclay nanocomposites during melt compounding will not be useful for the preparation of PLA/organoclay having fully exfoliated clay platelets. The shear thinning properties of the nanocomposites are independent of the addition of PEG. On the whole, PEG2k is good plasticizer for PLA/organoclay nanocomposites. POLYM. COMPOS. 27:256–263, 2006. © 2006 Society of Plastics Engineers     

Influence of organophilic montmorillonite and polypropylene on the rheological behaviors and mechanical properties of ultrahigh molecular weight polyethylene

The effects of organophilic montmorillonite (OM)/poly(ethylene glycol) (PEG) hybrids and polypropylene (PP) on the phase morphology, rheological behaviors, and mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE) were investigated. The presence of the OM/PEG hybrids and PP in UHMWPE was found that it was able to lead to a significant reduction of melt viscosity and enhancement in tensile strength, and elongation at break of UHMWPE. A quantitative analysis indicated a larger affinity of the OM to the PEG than to PP or UHMWPE in the composites, suggesting that OM was intercalated by PEG. This was proposed to be responsible for the reduction of viscosity. Polarizing optical microscopy analysis, on the other hand, indicated that the dispersed OM, which acted as a nucleating agent, lowered the spherulite dimension and increased the spherulite number, resulting in high tensile strength and elongation at break. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

不同结构聚苯乙烯/蒙脱土复合材料的熔体流动行为研究

分别将聚苯乙烯树脂(PS)与钠基蒙脱土(Na-MMT)和有机化蒙脱土(OMMT)通过熔融复合制备纳米黏土改性的复合材料。通过X射线衍射(XRD)对复合材料的微观结构进行了分析,采用HAAKE流变仪和熔体流动速率仪研究了复合材料的熔体流动行为。结果表明,Na-MMT在与PS熔融复合前后,其片层间距没有发生变化,PS分子链没有插入蒙脱土片层之间,所形成的是一种填充型复合材料。OMMT在熔融复合后,片层间距显著增大,与PS分子链形成了插层复合结构。蒙脱土含量相同时,PS/Na-MMT复合体系的熔体流动性能比PS/OMMT体系更好。研究认为,熔融复合过程中PS分子链的断链和2种复合材料结构上的差异是影响2种材料流动性能的主要因素。     

高能推进剂NEPE组分PEG与铝颗粒模型的分子动力学模拟

在COMPASS力场下,对高能推进剂NEPE组分PEG／Al球型包覆模型进行了分子动力学模拟。以预测PEG／Al模型结构的静力学性能和界面结合能。模拟结果得出PEG／Al的力学性能（拉伸模量、泊松比、体积模量、剪切模量）及其界面结合能,这对NEPE推进剂体系的进一步研究奠定了理论基础,从而为在推进剂中固体颗粒与黏结剂的脱粘研究提供一定的理论依据。     

Utilization of rice husk ash in green natural fiber-reinforced cement composites: Mitigating degradation of sisal fiber

This study aims to explore a novel approach to improve the durability of sisal fiber in cement composites by using by-products of biomass power plant: rice husk ash (RHA). The effects of two RHAs on the fiber's degradation were investigated indirectly by testing flexural behavior of sisal fiber-cement composite beams and directly by means of uniaxial tensile properties, thermal decomposition, crystallinity indices and microstructures of embedded fibers, after exploring up to 30 wetting and drying cycles. Allowing the distinction between pozzolanic activities, the efficiency of RHA was compared with two fly ashes and combinations of two clay minerals (metakaolin and nanoclay) with a cement substitution level of 30 wt.%. The durability of composites was improved considerably by incorporating RHA owing to the mitigation of fiber's degradation: the ultimate tensile strength and cellulose fraction of embedded fibers were improved by 384% and 45%, respectively. Fine RHA and the combination of metakaolin and nanoclay yield similar efficiency in mitigating degradation of sisal fiber, and are better than the coarse RHA and fly ashes. The correlations between cement hydration and sisal fiber degradation were analyzed. The results indicate that degree of hydration, calcium hydroxide content and alkalinity of the cement matrix play decisive roles in alkali attacks and mineralization of fiber's cell walls.     

Evaluation of amine functionalized polypropylenes as compatibilizers for polypropylene nanocomposites

The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH₂ which was subsequently protonated to form PP-g-NH₃⁺. Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no improvement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.     

The Properties of Reactive Hot Melt Polyurethane Adhesives: Effects of Molecular Weight and Reactive Organoclay

We studied the affect of molecular weight on the adhesion properties of reactive hot melt adhesive (RHA), which has polyurethane prepolymer as its major component. The RHAs that were prepared by the two-shot method and were of a higher average molecular weight showed improved initial bond strength development compared to that of RHAs prepared by the one shot method but with the same recipe. However, the viscosity of the RHA was increased by this method, which reduced the cross-linking in the cured RHA. This was confirmed by its deteriorated tensile properties and increased tan δ value. The reactive organoclay, Cloisite 30B, also improved the initial bond strength development and raised the viscosity of the RHA, thereby reducing cross-linking in the cured RHA.     

Application of rice husk ash as fillers in the natural rubber industry

Rice husk ash (RHA) obtained from agricultural waste, by using rice husk as a power source, is mainly composed of silica and carbon black. A two‐stage conventional mixing procedure was used to incorporate rice husk ash into natural rubber. For comparison purposes, two commercial reinforcing fillers, silica and carbon black, were also used. The effect of these fillers on cure characteristics and mechanical properties of natural rubber materials at various loadings, ranging from 0 to 40 phr, was investigated. The results indicated that RHA filler resulted in lower Mooney viscosity and shorter cure time of the natural rubber materials. The incorporation of RHA into natural rubber improved hardness but decreased tensile strength and tear strength. Other properties, such as Young's modulus and abrasion loss, show no significant change. However, RHA is characterized by a better resilience property than that of silica and carbon black. Scanning electron micrographs revealed that the dispersion of RHA filler in the rubber matrix is discontinuous, which in turn generates a weak structure compared with that of carbon black and silica. Overall results indicate that RHA can be used as a cheaper filler for natural rubber materials where improved mechanical properties are not critical. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 34–41, 2005     

新型超分散有机蒙脱土的制备和表征

采用十六烷基三甲基溴化铵为插层剂,通过先机械搅拌后超声振荡的复合工艺对钠基蒙脱土进行了有机改性,制备了超分散蒙脱土并对其进行了表征.FTIR表明有机插层剂进入蒙脱土层间;XRD结果表明超分散蒙脱土层间距由改性前的1.01 nm增加到3.13 nm;SEM和TEM表明蒙脱土已被剥离成单个片层.粒径分析表明超分散蒙脱土有很好的亲油性和分散性;沉降对比实验说明超分散蒙脱土分散性好,可长时间悬浮在熔融己内酰胺中.     

PS/MMT溶液插层复合材料的制备及流动性能研究

研究了溶剂种类和混合时间对聚苯乙烯(PS)在溶液中与不同种类蒙脱土的插层行为的影响以及所制备的复合材料的流动性能。结果表明:PS分子链在溶液中能够插入有机蒙脱土(OMMT)片层之间形成插层型复合材料,而与钠基蒙脱土(Na-MMT)只能形成填充型复合材料,溶剂种类和混合时间对插层效果没有影响;两种复合材料的流动性能与纯PS相比显著改善,其中PS/Na-MMT的流动性能优于PS/OMMT。     

LDPE/PEG插层剥离改性氮化硼导热复合材料的制备及其性能

以聚乙二醇(PEG)为插层剂,通过机械球磨法制备了PEG插层剥离改性氮化硼.以低密度聚乙烯(LDPE)为基体,PEG插层剥离改性氮化硼为导热填料,采用双辊开炼、压片成型制备LDPE/PEG插层剥离改性氮化硼导热复合材料,研究了改性氮化硼用量及粒径对复合材料导热性能、力学性能和电绝缘性能的影响.结果表明:随着PEG插层剥...     

蒙脱石有机化对PVA/蒙脱石复合薄膜的性能影响

以精制钠基蒙脱石(Na-MMT)、有机化蒙脱石(OMMT)和聚乙烯醇(PVA)为原料,通过水溶液插层-流延成膜法制备纳米复合薄膜。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和热重分析(TGA)对复合材料的结构和性能进行表征,重点探讨蒙脱石有机化对PVA/MMT复合薄膜性能的影响。结果表明Na-MMT和OMMT纳米颗粒在PVA基体中均得到了良好分散;有机改性剂的存在促使PVA/MMT复合薄膜的MMT片层间距扩撑更大,但由于其与PVA相容性较差,导致有效插入MMT片层间的PVA分子较少,PVA/MMT复合薄膜的热稳定性改善效果不明显。     

Thermodynamically and kinetically favored locations of rice husk ash particles in the phase structure,and the properties of epoxidized natural rubber/thermoplastic polyurethane blends

This article aims to study the influences of the selective location of rice husk ash (RHA) particles on morphological, mechanical, and dynamic properties of epoxidized natural rubber and thermoplastic polyurethane blends (ENR/TPU). Thermodynamic aspects, that is, interfacial tension and work of adhesion were assessed from estimates based on surface tension. It was found that the RHA particles had stronger interactions with the ENR than the TPU, of the co‐continuous phases. The phase structure was mainly controlled by kinetic factors, particularly by the mixing sequence, and to a lesser degree by thermodynamics. Furthermore, the microstructure with RHA particles dispersed in the ENR co‐continuous phase was found to give enhanced mechanical properties. This might be attributed to the higher work of adhesion between ENR and RHA that stabilized the encapsulated RHA particles against shear and elongational stresses, during melt mixing and in the final products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46681.