新型聚合物季铵盐改性蒙脱土的研究进展

聚合物改性蒙脱土具有比小分子改性更好的热稳定性,更多的结构变化性,聚合物改性蒙脱土可以赋予蒙脱土更多的表面性能和物理机械性能.综述了近年来此领域的最新研究进展,详细介绍了不同聚合物季铵盐、共聚物季铵盐和层间聚合的季铵盐作为改性剂的情况和效果.重点介绍了聚合物有机改性剂的组成、结构、性质及改性后纳米复合材料的性能和应用,并对未来的研究趋势进行展望.     

Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation: mechanical, thermal and rheological properties

(Nano)composites of poly(ε-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na⁺ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based quaternary ammonium cations, such as dimethyl 2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Microcomposites or nanocomposites were prepared depending on whether neat or modified montmorillonites was used, as assessed by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were studied as a function of the filler content by tensile testing, Izod impact testing, thermogravimetric analysis and differential scanning calorimetry. The rheological behaviour at 80 °C was also analysed in relation to the structure and content of the layered silicate. Effect of exfoliated silicates on the mechanical properties, thermal stability and flame resistance of PCL was considered. Stiffness and thermal stability improved with the filler loading until a content of 5 wt%. Further loading resulted in the levelling off and possibly in a decrease of these properties. A marked charring effect was observed upon exposure to a flame.     

Styrene-acrylonitrile (SAN) layered silicate nanocomposites prepared by melt compounding

Poly(styrene-co-acrylonitrile) (SAN) nanocomposites were successfully made by melt compounding and exhibited improved thermal stability and reduced flammability. The organoclays used in these nanocomposites were based upon fluorinated synthetic mica (FSM) or montmorillonite (MMT). Four different organic treatments were used on the clay surface to study the effect of organic treatment on clay dispersion: dimethyl, bis(hydrogenated tallow) ammonium (DMHTA), methyl tallow bis-2-hydroxyethyl ammonium (MTBHA), triphenyl, n-hexadecyl phosphonium (TPHDP), and 1,2-dimethyl-3-n-hexadecyl imidazolium (DMHDI). Along with studying the effect of clay organic treatment on the nanocomposite formation and flammability, the effect of acrylonitrile content in the SAN on nanocomposite formation and flammability was also studied. The overall findings suggest that dispersion of clay into SAN is rather facile, but certain combinations of organic treatment and clay type resulted in microcomposites rather than nanocomposites. Flammability of these materials was measured by pulse-combustion flow calorimetry (PCFC), also known as micro-cone calorimetry.     

Preparation of polystyrene/clay nanocomposite by suspension and emulsion polymerization

Organophilic montmorillonite was prepared using ion‐exchange method between sodium ions in clay layers and four kind of quaternary ammonium salt. The montmorillonite has the largest d₀₀₁‐spacing, as determined by X‐ray diffraction in modified by di(hydrogenated tallowalkyl) dimethyl ammonium chloride. Polystyrene montmorillonite nanocomposites were obtained by suspension and emulsion polymerization of styrene in the dispersed organophilic montmorillonite. The d₀₀₁‐spacing of clay was determined by X‐ray diffraction (XRD). The thermal stability of organophilic montmorillonite was investigated by thermogravimetric analysis (TGA). POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Formation of polymer nanocomposites with various organoclays

The role of the type of organic modifier used with montmorillonite (MMT) on the formation of polymer/clay nanocomposites in the melt compounding process was investigated. Various organoclays including primary [12‐aminolauric acid (12ALA)], secondary [dioctylamine (DOA)], tertiary [trioctylamine (TOA)], and two commercial quaternary (Cloisite 30B and 20A) MMTs were melt compounded with carefully selected polymers including polypropylene, polystyrene, styrene–acrylonitrile copolymer, poly(methyl methacrylate), poly(vinylidene fluoride), and acrylonitrile–butadiene copolymer (NBR). X‐ray diffraction and transmission electron microscopy characterizations confirmed that the two quaternary ammonium organoclay (Cloisite 30B and 20A) have superior compatibility compared to the primary (12ALA), secondary (DOA), and tertiary (TOA) ammonium organoclay. DOA and TOA can form polymer/clay nanocomposites only with the most polar polymer (NBR). Cloisite Na⁺ and 12ALA can not form nanocomposite with any polymers. The large organic surface area of the quaternary ammonium organoclay could be the reason of the best compatibility with polar polymers. It is estimated that long alkyl ammonium chains of organic modifier can spread over the clay surface more effectively than short alkyl chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1888–1896, 2005     

Polymericaly modified clays to preparation of polystyrene nanocomposite by nitroxide mediated radical polymerization and solution blending methods

Polymericaly modified clays that contain an oligomeric poly(styrene‐co‐chloromethyl styrene) ammonium salt have been prepared and used to preparation of polystyrene (PS) nanocomposites. First, PS and poly(styrene‐co‐chloromethyl styrene) [P(St‐co‐CMSt)] were synthesized by nitroxide mediated living free radical polymerization (NMRP) by TEMPO iniferter .Then the copolymer was coupled with N, N‐dimethyl hexadecyl amine to prepare polymeric modifier by anion exchange of chlorine group of chloromethyl styrene (CMSt) by quaternary amine. The synthesized polymeric modifier was mixed with nanoparticle of silica to change the property of clay surface from hydrophilic to hydrophobic via cation exchange of Na⁺ with alkylammonium ions. For synthesizing of nanocomposites, we used polymericaly modified montmorillonite and PS that was synthesized by NMRP technique. Intercalated nanocomposites and in some cases, exfoliated or mixed intercalated/exfoliated nanocomposites of all of these polymers have been produced by solution blending method. The prepared materials were characterized by X‐ray diffraction, Transmission electron microscopy, Fourier‐transform infrared, ¹H nuclear magnetic resonance, and gel permeation chromatography techniques. Effect of layered silicates on thermal properties and glass transition temperature of PS was investigated using TGA and DSC techniques. POLYM. COMPOS., 38:1127–1134, 2017. © 2015 Society of Plastics Engineers     

Influence of the type of quaternary ammonium salt used in the organic treatment of montmorillonite on the properties of poly(styrene‐co‐butyl acrylate)/layered silicate nanocomposites prepared by in situ miniemulsion polymerization

Hybrid latices of poly(styrene‐co‐butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer‐MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

几种常用织物柔顺剂的性能研究

通过研究6种柔顺剂原料对织物的白度、柔软性能、表面抗静电性能及再润湿性能的影响,得出氨基硅油乳液、酰胺季铵盐与咪唑啉季铵盐对方巾白度影响较大;双烷基二甲基季铵盐柔软效果最好,聚醚硅油柔软效果最差;季铵盐类柔顺剂抗静电效果优于硅油类柔顺剂;酯基季铵盐与双烷基二甲基季铵盐的再润湿性能较差。     

Effect of Clay Types on the Mechanical,Dynamic Mechanical and Morphological Properties of Polypropylene Nanocomposites

In the present investigation Polypropylene–Maleic anhydride grafted polypropylene–organically modified MMT (PP-MAPP-OMMT) nanocomposites were prepared by melt mixing in a twin screw extruder followed by injection molding. The effect of clay chemistry and compatibilizer on the properties of the nanocomposites has been studied. Sodium montmorillonite has been organically modified using quaternary and alkyl amine intercalants. A comparative account with commercial quaternary ammonium modified clays i.e Cloisite 20A, Cloisite 15A and Cloisite 30B has been presented. Storage modulus of PP matrix also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of organically modified nanoclays. The morphology of the nanocomposites has been examined using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Morphological findings revealed efficient dispersion of organically modified nanoclays within the PP matrix. MAPP compatibilized PP/Cloisite 15A nanocomposites displayed finely dispersed exfoliated nanomorphology as compared with other systems.     

The effect of organic modifier‐12‐aminolauric acid on morphology and thermal properties of polylactide nanocomposites

A novel organically modified montmorillonite (OMMT) based on a bifunctional organic modifier‐12‐aminolauric acid (ALA) was synthesized. Polylactide (PLA) nanocomposites with this new and traditional OMMT were prepared by solution casting method. The effects of the organic modifiers on structure, morphology and thermal properties of PLA nanocomposites have been investigated using Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results indicate that ALA has distinct effects on the dispersion of MMT platelets into the PLA matrix, where partial exfoliated as well as intercalated structures have been obtained, when compared with ordinary modifier, cetyltrimethyl ammonium bromide (CTAB). TGA data verifies that PLA nanocomposites with ALA‐MMT organoclay display enhanced thermal stability. The optimal clay loading of ALA‐MMT occurs at 3%wt, leading to the best compromise between clay dispersion and thermal properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Intercalation process and rubber–filler interactions of polybutadiene rubber/organoclay nanocomposites

The intercalation process and microstructural development of polybutadiene rubber (BR)/clay nanocomposites cured with sulfur were systematically investigated with respect to the organic modifier (primary and quaternary ammonium compounds) of the clay. X‐ray diffraction spectra were recorded at various stages of processing to obtain information about the intercalation process. The rubber–filler interactions was examined on the basis of the surface free energy, stress‐softening effect, and crystallization behavior. A well‐ordered intercalated structure was obtained in the primary ammonium modified clay (P‐OMMT) and quaternary ammonium modified clay (Q‐OMMT) filled with BR composite. The BR/Q‐OMMT composites showed higher mechanical properties and higher hysteresis under tension and lower crystallization abilities than the BR/P‐OMMT composites. The results also show that higher interfacial interactions existed between Q‐OMMT and BR than between P‐OMMT and BR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

有机膨润土吸附废水中苯酚的机理

以C12阳离子烷基多糖苷季铵盐对膨润土改性制备有机膨润土,探讨了有机膨润土的制备因素对去除废水中苯酚效果的影响,结果表明,在有机改性剂/膨润土的质量比为40 mg/g,反应温度为30℃,pH=8的条件下,反应30 min制备的有机膨润土,对初始浓度为50 mg/L的含苯酚废水去除率达到89.50%,其对苯酚的吸附符合Freundish方程。     

Vulcanization behavior and mechanical properties of organoclay fluoroelastomer nanocomposites

The vulcanization behavior and mechanical properties of clay/fluoroelastomer nanocomposites produced by melt‐mixing of Dyneon FPO 3741 (a terpolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene) with 10 phr of unmodified montmorillonite (CloisiteNA) or di(hydrogenated tallow‐alkyl) dimethyl ammonium‐modified montmorillonites (Cloisite15A and Cloisite20A) were studied. The properties of clay/FKM nanocomposites were compared with composites prepared using 10 and 30 phr of carbon black. The effects of clay surfactant and surfactant concentration on the vulcanization behavior, mechanical, and dynamical properties of peroxide cured composites were studied. XRD results of cured composites showed a decrease in d‐spacing and indicated deintercalation of the clays after the vulcanization process. It was also found that organoclays retard the FKM peroxide vulcanization process. Significantly, higher maximum torque on vulcanization was obtained with organoclays versus unmodified clay and carbon black. Although the morphologies of organoclay/FKM nanocomposites studied by XRD and TEM suggest similar intercalated/exfoliated structures, the organoclay with the lowest concentration of surfactant (95 meq/100 g clay) resulted in the highest increase in torque, modulus, hardness, and tear strength in the clay/FKM nanocomposites. It was also found that organoclays can increase both the hydrodynamic reinforcement and hysteresis loss of FKM nanocomposites. © 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。     

Influence of intercalated structure on the properties of montmorillonite/high-temperature vulcanized silicone rubber nanocomposites

In this article, montmorillonite/high-temperature silicone rubber hybrid nanocomposites were prepared via melt mixed process. The resulting hybrid nanocomposites were characterized by fourier transform infrared analysis (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), tensile testing and swelling experiment etc. The results proved that the nanocomposites with montmorillonite treated with double octadecyl dimethyl ammonium chloride prepared by melt mixed could form intercalated structure. Double octadecyl dimethyl ammonium chloride has a better effect on enhancing hydrophobicity of montmorillonite layers and expanding the lamellar spacing of montmorillonite than dodecylamine. Furthermore, the mechanical property of the hybrids was improved. The intercalated structure could improve the apparent crosslinking degree of montmorillonite/high-temperature silicone rubber hybrid nanocomposites. Moreover, a novel strategy is proposed to study the effect of intercalated structure on degree of crosslinking.     

Recycled PET‐organoclay nanocomposites with enhanced processing properties and thermal stability

Preparation of thermally stable recycled PET‐organoclay nanocomposites with improved processing and mechanical properties is a challenging task from the environmental as well as industrial and commercial point of view. In this work, both modification of sodium‐type montmorillonite with 1,2‐dimethyl‐3‐octadecyl‐1H‐imidazol‐3‐ium chloride and additional treatment with [3‐(glycidyloxy)propyl]trimethoxysilane was performed. Thermal stability of the organoclays and nanocomposites prepared by melt compounding was tested by thermogravimetric analysis, differential scanning calorimetry, and melt rheology. In comparison with the organoclays modified with quaternary ammonium compounds, the prepared clays showed substantial suppression of matrix degradation during melt mixing. The increase in interlayer distance of silicate platelets and homogeneity of dispersions in the recycled and virgin PET matrices have been evaluated by transmission electron microscopy and wide‐angle X‐ray scattering. The higher degree of delamination in the nanocomposites filled with imidazole organoclays was in a good agreement with improved rheological characteristics and led to significant enhancement in mechanical properties and thermal stability. A difference in structure (besides the level of delamination and homogeneity of silicate platelets) of recycled versus virgin PET nanocomposites was detected by X‐ray diffraction patterns. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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。     

橡胶／改性膨润土纳米复合材料研究——不同改性剂的影响

用不同的烷基长碳链季铵盐对膨润土进行有机改性,并将改性膨润土与天然胶乳共沉制得插层型纳米复合材料,研究了结构性能的关系,筛选出一种实用的有机改性剂。     

Advances in quaternary ammonium biocides

Several generations of structurally variable quaternary ammonium biocides were developed from approximately 1935 until the present. Demand for products with improved microbiological performance guided each successive step of development. Commercial availability of dialkyl dimethyl ammonium chlorides in 1965 set the stage for significant advances in quaternary biocide practices in the USA and Europe. This trend is continuing today with development of new, fourth-generation quaternary biocides. Regulatory requirements by the US Environmental Protection Agency (organic soil tolerance) and specific consumer/marketing demands (hard water tolerance) provided a renewed challenge for quaternaries meeting those requirements. Development and properties of new, fourth-generation quaternary biocides meeting those challenges are discussed. Some of the functional advantages of quaternaries are outlined. Development of the fourth-generation quaternary biocides has led to products demonstrating significantly superior broad spectrum biocidal activity, specifically designed to meet the new challenges of organic soil and hard water contamination. Strong market gains, made by quaternary biocides over the recent past, have been primarily as a result of the type of work described herein, but some of the gains in quaternary usage can be ascribed to concern over adverse toxicological and environmental impact of other traditional biocides such as phenolics and aldehydes. The outlook for a continued increase in the use of modern-day quaternary biocides is encouraging.     

Technical Relevance of Epoxy/Clay Nanocomposite with Organically Modified Montmorillonite: A Review

This review covers almost all known categories of compounds used for nanoclay surface modification with special emphasis on organic modification of layered silicate montmorillonite. Commonly used organic modifiers include quaternary ammonium ions, quaternary phosphonium ions, and amino acids. Dispersion of organomodified nanoclays in epoxy is particularly focused upon in this article. Epoxy-based materials are used as convenient matrices for montmorillonite dispersion since years due to superior properties of resulting polymeric nanocomposites, such as mechanical strength, electrical conductivity, flammability, and thermal stability. Owing to their high performance epoxy nanocomposites have endless applications in aerospace, automotives, construction, electrical, adhesives, and coating industries.