Surface modification of cellulose nanocrystals by grafting with poly(lactic acid)

The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L‐lactide by ring‐opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long‐term stability of a suspension of poly(lactic acid)‐grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X‐ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy. © 2013 Society of Chemical Industry     

坡缕石提纯和改性及其在NBR中的应用研究

对坡缕石进行提纯和改性，考察多种改性坡缕石对NBR胶料性能的影响。结果表明，提纯后坡缕石的质量分数达到0．93，平均粒径仅为0．92μm；硅烷偶联剂KH-560对坡缕石的改性效果较好；与填充未改性坡缕石相比，填充改性坡缕石NBR胶料的物理性能普遍提高；改性坡缕石在NBR中可替代炭黑N330。改性提纯坡缕石的价格仅为炭黑N330的1／5～1／4。     

聚乙烯吡咯烷酮的合成及其在定型剂啫喱中的应用

N-乙烯基吡咯烷酮(NVP)通过自由基溶液聚合方法合成聚乙烯基吡咯烷酮(PVP),通过调节引发剂偶氮二异丁腈(AIBN)的用量和催化剂NaHCO3溶液浓度调控PVP的质均分子量,制备出适用于定型剂啫喱所需的PVP。结果表明,当m(AIBN)∶m(NVP)为0.4%、NaHCO3溶液浓度为0.4 mol/L、聚合温度70℃、聚合时间2 h条件下,合成的PVP质均分子量为66 829;其所配制的定型剂啫喱对头发卷曲保持率为86.9%,且具有光泽度好、易清洗、不易发粘、梳理性好等性能。     

Melt‐compounded natural rubber nanocomposites with pristine and organophilic layered silicates of natural and synthetic origin

Composites based on natural rubber (NR) and containing organophilic and pristine layered silicates of natural and synthetic origin were produced by melt compounding and sulfur curing. The curing, thermomechanical, and mechanical properties of the mixes, which contained 10 phr (parts per hundred parts of rubber) silicates, were determined. The dispersion of the silicates was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Organophilic clays accelerated the sulfur curing of NR, which was believed to occur because of a complexation reaction in which the amine groups of the clay intercalants participated. The property improvements caused by the fillers were ranked as follows: organophilic clays > pristine synthetic layered silicate (sodium fluorohectorite) > pristine natural clay (purified sodium bentonite) > precipitated nonlayered silica (used as a reference). This was attributed to partial intercalation of the organophilic clay by NR on the basis of XRD and TEM results and to the high aspect ratio of the fluorohectorite. Apart from intercalation, severe confinement (i.e., the collapse of the interlayer distance) of the organoclays was observed. This peculiar feature was traced to the formation of a zinc coordination complex, which extracted the amine intercalant of the organoclays, thus causing the collapse of the layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 813–819, 2004     

PVP单体的合成研究进展及其应用

聚乙烯吡咯烷酮 ( PVP)是 N-乙烯基吡咯烷酮 ( NVP)经自由基聚合而成的一类高分子精细化学品。我国有关 PVP的研究工作分为 PVP单体 NVP的合成研究和 NVP聚合及其聚合物的应用。本文详细讨论了合成 NVP的催化剂种类、合成方法及工艺路线 ,简单介绍了 NVP合成研究的发展趋势。     

Performance and characterization of irradiated poly(vinyl alcohol)/polyvinylpyrrolidone composite hydrogels used as cartilages replacement

In this article, hydrogels were prepared by compounding polyvinylpyrrolidone (PVP) with poly(vinyl alcohol) (PVA), which is used as artificial cartilages, by means of repeating freezing and thawing and irradiation, for improving their mechanical and surface lubricative properties. The structures and properties, including gel content, crystallized degree, elastic modulus, and frictional coefficients of the compound hydrogels with different PVP contents and irradiative conditions, were examined and compared. The existence of PVP macromolecules interfered with the crystallization of PVA hydrogels resulted in the decrease of gel contents and elastic modulus, as well as the unstable external frictional coefficient in water. After irradiation treatment, these performances increased with irradiation intensity in lower dose ranges. The solubility and exudation of PVP in water were prevented and reduced because of the chemical crosslink of PVA and PVP, and the lubricative properties of PVA/PVP hydrogels in water were improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface modification of montmorillonite and application to the preparation of polybutadiene/montmorillonite nanocomposites

Hydrophobic organic montmorillonite (OMMT) which exists as stable dispersions in cyclohexane has been prepared by the combined modification of quaternary ammonium salts and coupling agents, and polybutadiene (PB)/OMMT nanocomposites (NCs) were successfully synthesized by in situ living anionic polymerization. The results showed that the interlayer spacing of OMMT increased dramatically on increasing the length of the long alkyl chain of C12, C16, C18 and C22 in n‐alkyltrimethylammonium ions and the number of long alkyl chains of 1C16, 2C16 and 3C16 in hexadecylmethylammonium ions. The interlayer spacings reached 4.9 and 5.07 nm, respectively, when C22 and 3C16 were used. The dispersion of MMT intercalated by quaternary ammonium salts was improved significantly after surface modification by different coupling agents, and the OMMTs could be disperses stably in cyclohexane for at least 72 h. In addition, the coupling agents did not change the inherent intercalation structure of OMMT. The results from a kinetic study and ¹H NMR analysis indicated that the incorporation of OMMT had little influence on the living polymerization and PB microstructure (proportions of 1,2‐ and 1,4‐units) when the OMMT content was below 3 wt%. However, the OMMT modified by different coupling agents had some influence on the molecular weight distribution. The results from transmission electron microscopy and X‐ray diffraction revealed that exfoliated structures of clay were obtained for all NCs. Furthermore, the results of differential scanning calorimetry and thermogravimetric analysis indicated that T_g and T_dc of NCs were increased compared to those of PB. Copyright © 2006 Society of Chemical Industry     

Compounding of nanocomposites by thermokinetic mixing

Nanocomposites have been prepared by melt mixing poly(propylene) (PP) and different levels of a premixed montmorillonite‐organoclay masterbatch (PP/clay concentrate). Melt mixing was achieved using a Gelimat, a high‐speed thermokinetic mixer. The Gelimat system is designed to handle difficult compounding and dispersion applications and can achieve mixing, heating, and compounding of products within a minute. Therefore, the thermal history of the compounded polymer is short, which limits degradation. The structure and properties of the nanocomposites prepared with a Gelimat were compared to ones prepared with a twin‐screw extruder. The structure and properties of PP/clay nanocomposites were compared by TEM, X‐ray diffraction, mechanical testing, and rheological analysis. Results indicate that a better dispersion of the clay can be achieved by thermokinetic mixing when compared to extrusion, resulting in better mechanical properties. Calculations, based on simplifying assumptions, showed that the shear rates generated in a Gelimat are at least one order higher than those generally generated in an extruder. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1557–1563, 2005     

Synthesis of polypropylene/clay nanocomposites using bisupported Ziegler‐Natta catalyst

In this article, preparation of polypropylene/clay nanocomposites (PPCNC) via in situ polymerization is investigated. MgCl₂/montmorillonite bisupported Ziegler‐Natta catalyst was used to prepare PPCNC samples. Montmorillonite (MMT) was used as an inert support and reinforcement agent. The nanostructure of the composites was characterized by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy techniques. Obtained results showed that silica layers of the MMT in these PPCNC were intercalated, partially exfoliated, and uniformly dispersed in the polypropylene matrix. Thermogravimetric analysis showed good thermal stability for the prepared PPCNC. Differential scanning calorimetric was used to investigate both melting and crystallization temperatures, as well as the crystallinity of the PPCNC samples. Results of permeability analysis showed significant increase in barrier properties of PPCNC films. Effective parameters on molecular weight and flow ability of produced samples such as Al/Ti molar ratio and H₂ concentration were also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of polyethylene–clay nanocomposites directly from Na+ montmorillonite by a melt intercalation method

Polyethylene (PE)/clay nanocomposites were prepared directly from Na⁺ montmorillonite by a melt intercalation technique, using hexadecyl trimethyl ammonium bromide (C16) as a reactive compatibilizer. Three other polymer–clay nanocomposites were also prepared by this new technique. Their structures were characterized by X‐ray diffraction and transmission electron microscopy. The mechanism of this new method was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2583–2585, 2003     

Morphology and properties of PVC/clay nanocomposites via in situ emulsion polymerization

PVC/Na⁺–montmorillonite (MMT) nanocomposites were prepared via a simple technique of emulsion polymerization at several different MMT clay concentrations. X‐ray diffraction and transmission electron microscopy studies revealed the formation of a mixture of intercalated and exfoliated nanostructure. Tensile testing results showed that the tensile modulus of the nanocomposites increased with the addition of clay, while the tensile strength decreased little. The notched impact strength of the nanocomposites was also improved. For systems containing clay in the range of 2.1 to 3.5 wt %, the impact strength was almost two times as large as that of pure PVC. However, those mechanical properties began to decrease with the continuously increasing amount of clay. The fracture surface of pure PVC and the nanocomposites was observed by scanning electron microscope. Thermal properties of the nanocomposites were found to increase as a result of clay incorporation. The glass transition temperatures of the PVC/clay nanocomposites were nearly identical to that of pure PVC. The Vicat softening points exhibited a progressively increasing trend with the clay content added. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 277–286, 2004     

Synthesis and properties of new fluoroelastomer nanocomposites from tailored anionic layered magnesium silicates (hectorite)

In the field of polymer clay nanocomposites, naturally occurring smectite group of clays are the most commonly used nanofillers. In the present work, smectite group clay, hectorite was synthesized in the laboratory with an intention to understand the structure–property relationship of polymer nanocomposites, with special reference to the characteristics of the nanoclays. The nanocomposites were prepared using these synthetic clays and fluoroelastomer by a solution mixing process. The clays and their nanocomposites were characterized by using X‐ray diffraction, X‐ray fluorescence, infra‐red spectroscopy, and transmission electron microscopy. It was observed that clay formation was a function of the concentration of the constituent materials. The gallery spacings and surface areas of synthetic clays are higher than those of the natural clay. Mechanical, dynamic mechanical, swelling, and thermal properties of these nanocomposites were also studied. The properties of these nanocomposites were compared with the nanocomposites obtained from natural clays, available commercially. Synthetic clay filled samples showed better properties than the natural clay filled samples, e.g., synthetic hectorite filled sample exhibited 75% increment in tensile strength and 24% improvement in 100% modulus compared with the natural hectorite based system. The results were explained with the help of thermodynamics and morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyethylene/aluminum nanocomposites: Improvement of dielectric strength by nanoparticle surface modification

The effect of the surface modification with a silane coupling agent (octyl‐trimethoxysilane) of aluminum (Al) nanoparticles on the dielectric breakdown behaviors of polyethylene (PE)/Al nanocomposites was investigated in comparison of the influence of the improvement of the interfacial adhesion between Al nanoparticles and PE using a compatibilizer (maleic anhydride grafted polyethylene). It was found that when compared with the other modification approaches, the surface‐treated Al nanofiller with the silane coupling agent makes it possible for the PE/Al nanocomposites to still keep the relatively higher breakdown strength even in the higher Al loading level above 14 vol %, which can be understood in terms of the better interfacial adhesion between the surface‐treated particle dispersion and the matrix. The combined effects of the Al nanoparticles on the different factors which influence the dielectric breakdown processes in polymer matrix such as microstructure, conductivity, and crystallinity of the nanocomposites were discussed in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polypropylene nanocomposites produced by in situ grafting of n‐butyl acrylate

Nanocomposites of polypropylene and organophilic clay are produced by in situ functionalization of PP with n‐butyl acrylate (BA) during melt mixing. Three strategies for incorporating materials into the mixer are analyzed and the effect of clay concentration is evaluated. The materials are examined by FTIR spectroscopy, X‐ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetry, and rotational rheometry. The results show that all composites prepared in the presence of BA have similar intercalated clay structure, and that the largest degree of exfoliation is obtained using the sequential mixing technique. This method, which consists in adding the initiator and functionalizing agent to the molten polypropylene followed by the addition of the clay, also produces the largest reduction in molecular weight of the polymer and the largest increase of the elastic modulus. All polymers show similar crystallization and degradation processes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42585.     

Surface modification of polypropylene sheets by UV‐radiation grafting polymerization

1,6‐Hexanediol diacrylate (HDDA) was grafted onto polypropylene (PP) substrates in the presence of benzophenone (BP) and isopropylthioxanthone (ITX) photoinitiators, and then polyurethane acrylate formulations were coated onto the HDDA‐g‐PP substrates, using UV radiation. The amount grafted and the grafting efficiency of the polymerizations were determined gravimetrically. The effects of the photoinitiator concentration and the UV radiation intensity on the physicochemical surface properties and the grafting efficiency of the UV‐radiation grafting polymerizations were characterized in detail using contact‐angle measurements, Fourier transform infrared spectroscopy with attenuated total internal reflection, and scanning electron microscopy. The results showed that the amount grafted and the surface polarity of the HDDA‐g‐PP substrates both increased linearly with increasing BP photoinitiator concentration and UV radiation intensity, and that the addition of a small amount of ITX markedly enhanced both parameters, probably due to photosensitization. The adhesion of the UV‐cured coating onto the HDDA‐g‐PP substrates was evaluated using the crosshatch adhesion test. The results indicated that the amount of HDDA grafted onto the PP substrates should exceed about 1 mmol/cm² for satisfactory adhesion with the UV‐cured coating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1446–1461, 2006     

Reaction kinetics and characteristics of polyurethane/clay nanocomposites

The reaction behavior and physical properties of polyurethane (PU)/clay nanocomposite systems were investigated. Organically modified clay was used as nanofillers to formulate the nanocomposites. Differential scanning calorimetry was used to study the reaction behavior of the PU/clay nanocomposite systems. The reaction rate of the nanocomposite systems increased with increasing clay content. The reaction kinetic parameters of proposed kinetic equations were determined by numerical methods. The glass transition temperatures of the PU/clay nanocomposite systems increased with increasing clay content. The thermal decomposition behavior of the PU/clay nanocomposites was measured by using thermogravimetric analysis. X‐ray diffractometer and transmission electronic microscope data showed the intercalation of PU resin between the silicate layers of the clay in the PU/clay nanocomposites. A universal testing machine was used to investigate the tensile properties of the PU/clay nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1641–1647, 2005     

Crystallization behavior of syndiotactic polystyrene nanocomposites for melt‐ and cold‐crystallizations

Analyses of the effects of montmorillonite (clay) on the crystallinity and crystallization behavior of syndiotactic polystyrene (s‐PS) were investigated by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The dispersibility of the clay in s‐PS nanocomposites was studied by X‐ray and transmission electron microscopy (TEM). The clay was dispersed into the s‐PS matrix by melt blending on a scale of 1–2 nm or few tenths–100 nm, depending on the surfactant treatment. On adding clay, the crystallization behavior of the s‐PS tends to convert into the β‐crystal from the α‐crystal after being cold‐crystallized because the clay plays a vital role in facilitating the formation of the thermodynamically favored β‐form crystal when the s‐PS is cold‐ or melt‐crystallized. This phenomenon leads to a change in a conventional mechanism of molecular packing for the s‐PS. Evidently, the clay significantly affects the crystallinity and crystallization behavior of the s‐PS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2492–2501, 2002     

Phase morphology and clay distribution of poly(trimethylene terephthalate)/polypropylene/montmorillonite nanocomposites

Poly(trimethylene terephthalate) (PTT)/polypropylene (PP) blend nanocomposites were prepared by melt mixing of PTT, PP, and organically modified clay. The phase morphologies of the PTT/PP nanocomposites and the distribution of the clay in the nanocomposites were investigated using scanning electron microscopy, transmission electron microscopy (TEM), and wide angle X‐ray diffraction. When PP is the dispersed phase, the domain size of the PP phase is decreased significantly with increasing the clay content from 0 to 5 wt %. In contrast, when PTT is the dispersed phase, the dimension of the PTT phase is a little larger in the presence of 2 wt % clay compared with the case of without clay. TEM observations indicate that the clay is mainly distributed at the phase interfaces along the phase borderlines. In addition, some intercalated clay tactoids (multilayer particles) are observed in the PTT matrix whereas no discernable clay particles can be found in the PP phase, indicating that the affinity of clay with PTT is higher than with PP. In the presence of 5 wt % PP‐graft‐maleic anhydride, the phase morphology is much finer, and most clay is exfoliated and distributed at the phase interfaces forming phase borderlines in polygonal shape. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel preparation of poly(propylene)–layered silicate nanocomposites

We used a novel approach to prepare poly(propylene)–clay nanocomposite starting from pristine montmorillonite and reactive compatibilizer hexadecyl trimethyl ammonium bromide. The nanocomposite structure was revealed by X‐ray diffraction and high‐resolution electronic microscopy. The thermal properties of the nanocomposite were investigated by thermogravimetric analysis. An increase of thermal stability was observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2586–2588, 2003     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.