Nanocomposite materials based on isosorbide methacrylate/Cloisite 20A

This paper reports experiments on grafting of a new polymerizable monomer onto organophilic montmorillonite. The monomer, 5‐methacryloyloxy‐1,4:36‐D ‐anhydrosorbitol (MAS), was synthesized by reacting methacryloyl chloride and isosorbide in the presence of Et₃N as base. Then, Cloisite 20A was reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety. Because the reaction liberates HCl, it was performed in the presence of sodium hydrogen carbonate to prevent the exchange of quaternary alkylammonium cations with H⁺ ions. Only the silanol groups on the edge of the clay react with vinyltrichlorosilane. After the reaction, the product maintained the same basal spacing as the precursor. The radical polymerization of the product with MAS as a vinyl monomer led to chemical grafting of the polymer onto the montmorillonite surface. The homopolymer formed during polymerization was separated from the grafted organoclay by Soxhlet extraction. Chemical grafting of the polymer onto Cloisite 20A was confirmed using infrared spectroscopy. The prepared nanocomposite materials and the grafted nanoparticles were studied using X‐ray diffraction and scanning and transmission electron microscopy. Exfoliated nanocomposite was obtained for 1 wt% clay loadings. The nanocomposites were studied using thermogravimetric and dynamic mechanical analyses. Improved thermal properties were observed for nanocomposites with 1–5 wt% clay content. © 2012 Society of Chemical Industry     

Elucidation of the nanoparticle effect on the grafting of vinyl monomers onto cotton fabric

The grafting emulsion polymerization of vinyl monomers onto cotton was carried out in the presence of double‐modified montmorillonite clay. The obtained results show that grafting with glycidyl methacrylate/montmorillonite gave a higher rate of grafting than grafting with methyl methacrylate/montmorillonite in all clay percentages, and also, the grafting yield of glycidyl methacrylate monomer onto cotton in the presence of montmorillonite clay had a higher value than that in the absence of the clay for all factors studied. Cotton grafted with glycidyl methacrylate/montmorillonite with a graft yield of about 50% was prepared according to the emulsion polymerization technique and was treated with different concentrations of dibutylamine solutions ranging from 1 to 4%. The obtained samples were characterized according to nitrogen content, thermal stability, scanning electron microscopy, mechanical properties, water absorption, and color strength according to acid, basic, and reactive dyes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of reactive mineral powders used for poly(sodium acrylate) composite superabsorbents

Reactive mineral powders were prepared with a vinyl monomer as an intercalating agent, which was grafted onto the surface of nanoclay layers, to offer crosslinking points between the nanoclay layers. According to IR characterization, the vinyl group of (3‐acrylamidopropyl)trimethylammonium chloride, grafted onto the clay, disappeared after polymerization was performed. This spectral evidence confirmed that the reaction occurred between the clay layers. Thermogravimetric curves showed that the weight percentage remaining at 750°C for the intercalated clay/sodium acrylate nanocomposites was about 5 wt % higher than that for organic poly(sodium acrylate). This indicated that the clay was not diminished in the polymerization, and this process produced intercalated mica with a quaternary ammonium content of approximately 38.8 mmol/100 g and intercalated montmorillonite with a quaternary ammonium content of approximately 45.36 mmol/100 g. We also investigated the effect of reactive clays on the crystalline morphology and water absorbency for these nanocomposite hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 855–861, 2005     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

The Effect of Presence of Glycopolymer Grafts in Poly N-Isopropylacrylamide/Clay Nanocomposite Hydrogels

Two types of poly-N-isopropylacrylamide (p-NIPAM)/Cloisite 30B clay nanocomposite (NC) hydrogels were synthesized where the first one contained Cloisite 30B without modification. However, the second one contained Cloisite 30B with glycopolymer units attached onto its surface by surface-initiated atom transfer radical polymerization. The main purpose of this article was to study the effect of surface grafting of glycopolymer onto Cloisite 30B clay surface on the physical properties of the resulting NC hydrogels such as swelling ratio, deswelling behavior and thermal behavior. It was found that NC hydrogels containing glyco-units had better properties than the first one.     

Effects of silane grafting on the morphology and thermal stability of poly(ethylene terephthalate)/clay nanocomposites

An alkylammonium intercalated montmorillonite (A‐MMT) was modified by edge grafting with 3‐glycidoxypropyltrimethoxysilane. In comparison with poly(ethylene terephthalate) (PET)/A‐MMT, the resultant grafted clay, S‐A‐MMT, exhibited improved miscibility with PET matrix and revealed better dispersion state in the melting compounded PET/S‐A‐MMT nanocomposites. As a result, the PET/S‐A‐MMT nanocomposite had slower degradation rate owing to the enhanced clay barrier effect. Meanwhile, the nanocomposite exhibited lower degradation onset temperature under nitrogen because of the clay catalysis effect, which can be explained by the decreasing degradation reaction energy calculated from Coats–Redfern method of degradation kinetics. In the other hand, nanocomposite with better clay dispersion state exhibited increasing thermal oxidative stability due to clay barrier effect of hindering oxygen to diffuse in, which accorded with the continuous and compact char surface formed during polymer degradation. The clay catalysis and barrier effect of silicate layers were presented directly in isothermal oxidative TGA experiment. Furthermore, the mechanical and crystallization properties of PET/clay nanocomposites were investigated as well. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Polyethylene/Ethylene Vinyl Acetate and Ethylene Octene Copolymer/Clay Nanocomposite Films: Different Processing Conditions and Their Effect on Properties

Polymer nanocomposites based on a layered clay used as nanofiller and copolymers ethylene and vinyl acetate matrix (EVA, the content of vinyl acetate (VA) component 19 wt% and 5 wt%) and ethylene octene copolymer (EOC, 17% and 45% of octene) were prepared. KO Buss kneader and double screw extruder were used. The MMT Na+ and four types of commercial products such as Nanofil N5 and N3000, Cloisite 93A and 30B were used as nanofillers—5 wt% in relation to the content of montmorillonite. The aim was to evaluate the influence of copolymer composition and processing on prepared nanocomposite properties. The morphology of samples was examined by means of X‐ray diffraction (XRD) and transmission electronic microscopy TEM. Furthermore, mechanical and especially barrier properties were observed. Despite the fact that the XRD and microscopy results have revealed that complete exfoliation did not take place in any case, mechanical properties as well as the permeability showed that used 5 wt% of clay was enough to achieve the improvement of properties. Cloisite 30B might be the most suitable for the polyethylene/EVA matrix. In case of EOC copolymer the nanofiller Nanofil N3000 and mainly Cloisite 93A seems to be more suitable. The better properties were achieved for the version of EVA with lower VA content and also for EOC 17, but not for each evaluated property. POLYM. ENG. SCI., 59:2514–2521, 2019. © 2019 Society of Plastics Engineers     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

The effect of clay type and of clay–masterbatch product in the preparation of polypropylene/clay nanocomposites

Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ～ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

醋酸乙烯酯乳液与聚乙烯醇接枝反应的研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,作为保护胶体的聚乙烯醇与醋酸乙烯的接枝反应。发现聚乙烯醇的接枝主要发生在初期,而醋酸乙烯的接枝链一直增长到胶粒沉析;另外,保护胶体黏度对接枝率也有影响,黏度越大醋酸乙烯的接枝率越低。     

Effect of both silane‐grafted and ion‐exchanged organophilic clay in structural,thermal, and mechanical properties of unsaturated polyester nanocomposites

Unsaturated polyester (UPE) resin including styrene monomer was mixed with organophilic montmorillonite (MMT) clay and its crosslinking polymerization reaction was done in the presence of free‐radical initiator. MMT clay was modified with cetyl trimethly ammonium bromide and trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric and dynamic mechanical analyses (TGA and DMA). The exfoliated nanocomposite structure was obtained when the MMT clay was modified in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. The exfoliated UPE nanocomposite exhibited better thermal and dynamic mechanical properties when compared with pure UPE and other composites, even with 3 wt% clay loading. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effect of dispersion state of organoclay on cellular foam structure and mechanical properties of ethylene vinyl acetate copolymer/ethylene‐1‐butenecopolymer/organoclay nanocomposite foams

In this study, our goal is to obtain lower density of ethylene‐vinyl acetate copolymer (EVA)/ethylene‐1‐butene copolymer (EtBC) foams without sacrificing mechanical properties. For this purpose EVA/EtBC/organoclay (Cloisite 15A, Closite 30B) nanocomposite foams were prepared. To investigate the effect of compatibilizer on the dispersion state of organoclay in cellular foam structure and mechanical properties of the EVA/EtBC/organoclay foams composites were prepared with and without maleic anhydride grafted EtBC (EtBC‐g‐MAH). The dispersion of organoclay in EVA/EtBC/organocaly foams was investigated by X‐ray diffraction and transmission electron microscopy. The EVA/EtBC nanocomposite foamswith the compatibilzer, especially EVA/EtBC/Cloisite 15A/EtBC‐g‐MAH foams displayed more uniform dispersion of organoclay than EVA/EtBC nanocomposite foams without the compatibilzer. As a result, EVA/EtBC/Cloisite 15A/EtBC‐g‐MAH foams have the smallest average cell size and highest 100% tensile modulus followed by EVA/EtBC/Cloisite 30B/EtBC‐g‐MAH foams. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3879–3885, 2007     

Bulk polymerization of styrene in the presence of organomodified montmorillonite

The effect of montmorillonite (Cloisite 6A) on the bulk polymerization of styrene initiated by benzoyl peroxide (BPO) was studied by the dilatometric determination of the polymerization rates. The bulk polymerization rates increased as the montmorillonite input quantity increased. The effect became greater when the BPO concentration decreased. Under the assumption that clay participated in the radical initiation reaction of the chains, the reaction orders for clay and BPO were determined to be approximately 1.0 and 0.5, respectively. X‐ray diffraction and thermogravimetric analysis studies showed that the structure and properties of the obtained polystyrene (PS)/montmorillonite nanocomposites were greatly affected by the BPO concentration. With lower BPO concentrations, a larger interlayer distance and a higher extent of delamination for the clay were observed in the obtained PS/montmorillonite nanocomposites. The nanocomposites prepared with lower BPO concentrations also showed higher heat‐decomposition‐resistance temperatures. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1146–1152, 2005     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Grafting and adsorption of poly(vinyl) alcohol in vinyl acetate emulsion polymerization

Poly(vinyl alcohol) is often used in vinyl acetate emulsion polymerization as a protective colloid, but its role is complex and controversial since it partakes in grafting reactions with the monomer, influencing process mechanisms, and affecting the colloidal properties of the latex. Furthermore, in industrial operations, the wide scatter of macromolecular properties of the commercial types of poly(vinyl alcohol) causes process irreproducibilities. In this work different types of polyvinyl alcohol were used to perform a series of polymerizations, and their kinetics were compared. A selective solubilization procedure was applied to separate the three fractions of poly(vinyl alcohol) in the final latex: free in the water phase, physically adsorbed onto the polymer particles and chemically grafted. These results were compared with those obtained from pure adsorption measurements of polyvinyl alcohol onto ‘emulsifier-free’ polyvinyl acetate dispersions. The rheological behavior of the different latexes was also compared, and the results were used to formulate an hypothesis on the interaction mechanisms acting in these systems.     

Preparation and characterization of maleated thermoplastic starch‐based nanocomposites

Biodegradable nanoscale‐reinforced starch‐based products were prepared from an in situ chemically modified thermoplastic starch and poly(butylene adipate‐co‐terephthalate) (PBAT) through reactive processing. Natural montmorillonite (hydrophilic Cloisite Na) and organophilic Cloisite 30B were studied. In situ chemically modified thermoplastic starch (MTPS) was first prepared starting from (nano)clay (previously swollen in glycerol as plasticizer), and maleic anhydride (MA) as an esterification agent. Then, these nanoscale‐reinforced MTPS was reactively melt‐blended with PBAT through transesterification reactions promoted by MA‐derived acidic moieties grafted onto the starch backbone. The tensile and barrier properties of resulting (nano)composites were studied. High‐performance formulations with superior tensile strength (>35 MPa as compared with 16 MPa for the PBAT‐g‐MTPS copolymer) and break elongation (>800%) were obtained, particularly with Cloisite30B. Better water vapor and oxygen barrier properties of nanoscale‐reinforced MTPS‐g‐PBAT were achieved rather than the PRECURSORS. Wide angle X‐ray diffraction and transmission electronic microscopy analyses show that partial exfoliation of the clay platelets was observed within the PBAT‐g‐MTPS graft copolymer‐Cloisite 30B nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of poly(vinyl alcohol)-clay nanocomposite materials

A series of polymer-clay nanocomposite (PCN) materials that consist of poly(vinyl alcohol) (PVA) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic PVA matrix via an in situ free radical polymerization with AIBN as initiator. Organic vinyl acetate monomers are first intercalated into the interlayer regions of organophilic clay hosts and followed by a one-step free radical polymerization. The prepared poly(vinyl acetate)-clay (PVAc-clay) solution are then saponified via direct-hydrolysis with NaOH solution to form PVA-clay nanocomposite materials. The as-synthesized PCN materials are typically characterized by Fourier-Transformation infrared (FTIR) spectroscopy, wide-angle X-ray diffraction and transmission electron microscopy.The molecular weights of poly(vinyl alcohol) (PVA) extracted from polymer-clay nanocomposite (PCN) materials and bulk PVA are determined by gel permeation chromatography (GPC) analysis with THF as eluant. The viscosity property of PCN materials with different feeding amount of MMT clay is studied by an ubbelohode capillary viscometer. The morphological image of as-synthesized materials is studied by scanning electron microscopy (SEM) and optical polarizing microscope (OPM). Effects of the material composition on the thermal stability, mechanical strength, optical clarity of PVA along with a series of PCN materials, in the form of fine powder and free-standing film, are also studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analyzer (DMA) and UV-visible transmission spectra, respectively.     

Synthesis of effective poly(4‐vinylpyridine) nanocomposites: in situ polymerization from edges/surfaces and interlayer galleries of clay

Poly(4‐vinylpyridine) (P4VP) nanocomposites have been prepared by using an in situ polymerization method in the presence of organically modified montmorillonite (MMT) clays with a quarternary salt of cocoamine containing a vinyl group, as well as trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. This resultant exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance when compared to the other nanocomposites, even with 2 % clay loading. Copyright © 2005 Society of Chemical Industry     

Preparation of grafted copolymers via oxidized polypropylene

A new and novel class of oxidized polypropylene containing bound peroxide functionalities can be used as polymerization initiators to produce polypropylene‐grafted copolymers. Upon heat treatment, the peroxide functionalities in the oxidized polypropylene act as a source of free radicals, reacting with the unsaturated double bonds of the monomer and initiating polymerization. The grafting reaction is carried out in the solid state in a reactor. The advantage of grafting via this new class of oxidized polypropylene is the elimination of expensive and environmentally unfriendly organic peroxides. A number of monomers have been grafted using oxidized polypropylene, including vinyl acetate, vinyl pyrrolidinone, methacrylic anhydride, and maleic anhydride. Oxidized polypropylene‐grafted copolymers are effective compatibilizers for PP/ETP blends and good coupling agents in glass‐ reinforced formulations. Preparation, characterization, and mechanical properties of terpolymers prepared from sequential grafting of oxidized polypropylene are also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and UV weathering of polyethylene nanocomposites

Polyethylene / montmorillonite (PE/MMT) nanocomposites films were prepared by blending in the molten state: Low-density polyethylene (LDPE), montmorillonite clay, and polyethylene grafted maleic anhydride (LDPE-g-MA) or zinc neutralized carboxylate ionomer (Surlyn B) as compatibilizers. A chemically modified clay Cloisite 20A has been used. Nanocomposites were prepared by melt blending in a twin-screw extruder by using two-step mixing. Characterization of the nanocomposites was performed by mechanical properties, X-ray diffraction, light transmittance, infrared spectroscopy (FTIR) and transmission electronic microscope (TEM) techniques. Changes in UV irradiated nanocomposites film samples were characterized by FTIR. The results were analyzed in terms of the effect of the compatibilizing agent in the clay dispersion, and UV degradation of the nanocomposite.