Hybrid Porous Microparticles Based on a Single Organosilica Cyclophosphazene Precursor

Porous organosilica microparticles consisting of silane-derived cyclophosphazene bridges were synthesized by a surfactant-mediated sol-gel process. Starting from the substitution of hexachlorocyclotriphosphazene with allylamine, two different precursors were obtained by anchoring three or six alkoxysilane units, via a thiol-ene photoaddition reaction. In both cases, spherical, microparticles (size average of ca. 1000 nm) with large pores were obtained, confirmed by both, scanning and transmission electron microscopy. Particles synthesized using the partially functionalized precursor containing free vinyl groups were further functionalized with a thiol-containing molecule. While most other reported mesoporous organosilica particles are essentially hybrids with tetraethyl orthosilicate (TEOS), a unique feature of these particles is that structural control is achieved by exclusively using organosilane precursors. This allows an increase in the proportion of the co-components and could springboard these novel phosphorus-containing organosilica microparticles for different areas of technology.     

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

A procedure to synthesize poly(methyl methacrylate)‐grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N‐diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting “from”). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S_N2 mechanism. The study was performed with a Kieselgel® S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4‐(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT‐functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid‐state ¹³C and ²⁹Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and ¹H‐NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT‐functionalized Kieselgel® S used. Poly(methyl methacrylate)‐grafted silica microparticles bearing high length grafts ( about 100) were synthesized. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dispersivity of modified ZnO and characterization of polyurethane/ZnO composites

The properties of inorganic nanoparticles/polymer composites depend on the dispersivity of nanoparticles in a polymer matrix. The effect of surface modification on the dispersivity of ZnO nanoparticles in a polyurethane (PU) resin matrix was investigated. The nanocomposites were characterized by scanning electron microscopy (SEM), thermogravimetric analysis, and X‐ray diffraction. The scanning electron micrographs show that ZnO nanoparticles (CDI–SA–APS–ZnO), which were modified by aminopropyltriethoxysilane (APS) and activated stearic acid (SA) by N,N′‐carbonyldiimidazole (CDI), can be homogeneously dispersed and had been encapsulated in the PU phase. The interfacial compatibility between ZnO nanoparticles and PU matrix was significantly improved by hydrophobically modifying ZnO nanoparticles with APS and SA. The tensile strength and elongation at break of PU/CDI–SA–APS–ZnO nanocomposites increased by 82 and 64% respectively, compared with the pure PU material. The thermal stability and ultraviolet‐shielding properties were also improved by incorporating ZnO nanoparticles into the PU matrix. POLYM. COMPOS., 35:237–244, 2014. © 2013 Society of Plastics Engineers     

Reinforced chloroprene rubber by in situ generated silica particles: Evidence of bound rubber on the silica surface

Nano silica is generated in situ inside the uncrosslinked chloroprene rubber (CR) by the sol‐gel reaction of tetraethoxysilane (TEOS). This results in appreciable improvement in mechanical properties of the CR composites at relatively low filler content. Furthermore, exploitation of reactive organosilanes, γ‐aminopropyltrimethoxysilane (γ‐APS) in particular, in the silica synthesis process facilitates growing of spherical silica particles with a size distribution in the range of 20‐50 nm. The silica particles are found to be uniformly dispersed and they do not suffer from filler‐filler interaction. Additionally, it is observed that the silica particles are coated by silane and rubber chains together which are popularly known as bound rubber. The existence of the bound rubber on silica surface has been supported by the detailed investigations with transmission electron microscopy (TEM), energy filtered transmission electron microscopy (EFTEM) and energy dispersive X‐ray spectroscopy (EDAX). The interaction between rubber and silica, via bi‐functionality of the γ‐APS, has been explored by detailed FTIR studies. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43717.     

Effect of organosilica isomers on the interfacial interaction in polyimide/aromatic organosilica hybrids

We report the effect of organosilica precursor isomers on the interfacial interaction between polyimide and organosilica in polyimide/organosilica hybrid composite films. Poly(4,4′‐oxydianiline biphenyltetracarboxamic acid) (BPDA‐ODA PAA) was used as the polyimide precursor, while the organosilica was made using o‐substituted, m‐substituted, and p‐substituted phenyl organosilica precursor isomers. For the preparation of precursor hybrid films, BPDA‐ODA PAA and organosilica precursors were mixed and then the organosilica precursors were converted to corresponding organosilica via sol–gel process. Finally, these precursor films were converted to corresponding polyimide/organosilica hybrid films by the thermal imidization of BPDA‐ODA PAA, which results in poly(4,4′‐oxydianiline biphenyltetracarboximide) (BPDA‐ODA PI). The polyimide/organosilica hybrid films were characterized using three distinctive nuclear magnetic resonance spectroscopies (¹H NMR, ¹³C‐CPMAS‐NMR, and ²⁹Si‐MAS‐NMR), wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and peel strength measurement. We found that the m‐substituted phenyl organosilica shows poorer interfacial interaction with BPDA‐ODA PI than do the o‐ or p‐substituted phenyl organosilicas. It was observed, however, that the peel strength of the hybrid films against an aluminum substrate increased with increasing contents of organosilicas, regardless of the nature of the organosilica isomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2507–2513, 2007     

Inverse emulsion free‐radical polymerization of acrylamide terpolymer for enhanced oil recovery application in harsh reservoir conditions

A free‐radical inverse emulsion polymerization formulation has been developed for preparation of acrylamide (AAm)/sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPSNa)/N‐vinylpyrrolidone (VP) terpolymers. An aqueous solution of a blend of monomers is emulsified in n‐decane using Tween 85 (Tw85). Ammonium persulfate (APS) and dicumyl peroxide (DCP) were used as initiators for water and oil phases, respectively. The reactions were catalyzed by temperature and by a redox pair; the former is achieved at 60°C and the latter by adding tetramethylethylenediamine (TEMED) and sodium bisulphite (BisNa) to activate the initiator in water and oil phase, respectively. The emulsion type, stability, conversion, and rate of polymerization were analyzed. The obtained terpolymer was characterized by elemental analysis, infrared spectroscopy (FTIR), ¹³C nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology. Thermal catalyzed emulsion polymerization initiated with DCP showed the best performance as viscosity control agent and as polymeric precursor for in situ gel forming, for water mobility control and flow diversification, respectively. Both application for enhanced oil recovery purposes in harsh oil reservoir conditions are presented. POLYM. ENG. SCI., 57:1214–1223, 2017. © 2017 Society of Plastics Engineers     

Chemical modification‐induced improvement in the electrical characteristics of radiation‐functionalized polypropylene sheets

The development of conducting or semiconducting polymers is a highly interesting area due to the urgent need for new materials that combine several unique properties to be applied in a great variety of electrochemical devices. Polypropylene sheets were functionalized by radiation‐induced grafting of acrylonitrile to import reactive nitrile groups into the inert polymer sheets. To improve the electrical characteristics, such as electrical conductivity, of the radiation‐grafted sheets, a conjugated structure was developed via the repetition of the two‐step condensation polymerization of p‐phenylenediamine and glyoxal using the grafted nitrile groups as starting point. The grafted and treated polypropylene sheets were characterized using Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). FTIR spectra confirmed the occurrence of the grafting as well as the treatment of the grafted cyanide groups with p‐phenylenediamine and reaction with glyoxal. TGA traces showed an improvement in the thermal stability of the grafted sheets by grafting and a reduction of such stability by chemical treatment. The electrical characteristics of the grafted and treated sheets were evaluated and compared with those of untreated polypropylene. The effects of degree of grafting and conjugated chain length on the electrical characteristics of the grafted sheets were also investigated. The results showed that the development of a conjugated chemical structure in the polypropylene sheets increases the conductivity by about five orders of magnitude. The electrical conductivity of polypropylene was significantly increased as a result of the chemical development of a conjugated double‐bond chain structure in the radiation‐functionalized form. Copyright © 2009 Society of Chemical Industry     

A novel method to graft carbon nanotube onto carbon fiber by the use of a binder

A novel method is developed for grafting multiwall carbon nanotubes (MWNTs) onto the surface of polyacrylonitrile‐based high strength (T300GB) carbon fiber. Functionalized MWNTs were well dispersed in the PVA solution and the carbon fiber was dip‐coated in this solution. After heat treatment of the coated carbon fiber under a nitrogen atmosphere, MWNTs with carboxyl groups were grafted onto the functionalized carbon fiber via chemical interaction. The resulting materials were characterized by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), Field emission scanning electron microscopy (FESEM), Raman spectrum and mechanical testing. FESEM observations revealed uniform coverage of carbon nanotubes on carbon fiber. The carbon fiber grafted with MWNTs improved the tensile strength by 12% with respect to the pristine carbon fiber. These results are supportive of good interfacial bonding between the carbon nanotubes (CNTs) and carbon fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characteristics of polypropylene-graft-maleic anhydride anchored micro-fibriled cellulose: its composites with polypropylene

The surface modification of micro-fibriled cellulose (MFC) was carried out through the hydrolysis–condensation reaction using (3-aminopropyl)triethoxysilane (APS) and then was subsequently treated with polypropylene-graft-maleic anhydride (MAPP) to give desired MAPP-anchored MFC (MAPP-a-MFC). The confirmation of surface modification for the pristine MFCs was characterized by FTIR, EDX, and XPS measurements. The polypropylene (PP) composites with MAPP-a-MFC were prepared via typical melt-mixing method. The effects of MAPP-a-MFC on the physical properties of the PP composites were investigated. From the results of mechanical properties, thermal behaviors, and the morphology of the composites, it was found that there was an improved interfacial adhesion between the MAPP-a-MFC and PP matrix in the composites.     

Synthesis and fluorescence properties of aromatic‐aliphatic copolyamides

The aromatic‐aliphatic copolyamides were synthesized by condensation polymerization of aromatic diamine PPD (or APS, where PPD is p‐phenylene diamine and APS is aminophenyl sulfone), aliphatic diamine HDA (or EDA, where HDA is hexanediamine and EDA is ethylenediamine), and TPC (where TPC is terephthalyl chloride) with different molar ratios of aromatic diamine to aliphatic diamine. The steady‐state fluorescence of these condensed copolymers was investigated. These copolyamides exhibit strong blue‐to‐green fluorescence. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 315–321, 2005     

Base‐Catalyzed Condensation of 2‐Hydroxybenzaldehydes with α,β‐Unsaturated Aldehydes – Scope and Limitations

The base‐catalyzed condensation of α,β‐unsaturated carbonyl compounds with 2‐hydroxybenzaldehydes yielding tetrahydroxanthones and dihydrobenzopyrans has been investigated. A novel access to highly functionalized dihydrobenzopyrans via a mild generation of the dienol of senecialdehyde and subsequent conjugated aldol reaction has been reported.     

Enhanced swelling and methylene blue adsorption of polyacrylamide‐based superabsorbents using alginate modified montmorillonite

Polyacrylamide/sodium alginate modified montmorillonite (PAM/SA‐MMT) superabsorbent composites were synthesized by free‐radical polymerization under normal atmospheric conditions. They were characterized by X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy (FTIR). Their water absorbency and methylene blue (MB) adsorption behaviors were studied. Compared with PAM/MMT composites, PAM/SA‐MMT composites demonstrated greater water absorbency (863 g g^?1 in distilled water and 101 g g^?1 in 0.9 wt % NaCl solution) and higher adsorption capacity of 2639 mg g^?1 for MB. The adsorption behaviors of the composites showed that the isotherms and adsorption kinetics were in good agreement with the Langmuir equation and pseudo‐second‐order equation, respectively. FTIR analysis suggested that the MB adsorption of PAM/SA‐MMT composites via a mechanism combined electrostatic, H‐bonding and hydrophobic interaction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40013.     

Grafting of hydrophilic monomers onto aminopropyl‐functionalized sodium montmorillonite via surface‐initiated redox polymerization

Hydrophilic polymer/sodium montmorillonite (Na‐MMT) hybrid nanomaterials were prepared via surface‐initiated redox polymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (PAMPS‐g‐MMT), acrylamide (PAAm‐g‐MMT) and styrenesulfonic acid sodium salt (PSSA‐g‐MMT) from surface of aminopropyl‐functionalized sodium montmorillonite (AMMT) dispersed in an aqueous medium. Cerium(IV) ammonium nitrate/nitric acid and aminopropyl groups on the surface of AMMT were used as oxidant and reducing groups, respectively. AMMT was prepared by covalently attaching 3‐aminopropyltriethoxysilane onto the surface of Na‐MMT. Hydrophilic monomers (AMPS, AAm and SSA) were then grafted onto AMMT dispersed in water via redox initiation at 40 °C. Structure, morphology and thermal properties of the AMMT, PAMPS‐g‐MMT, PAAm‐g‐MMT and PSSA‐g‐MMT hybrid materials were characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD) and thermogravimetric (TGA) analyses, respectively. FTIR results indicated that hydrophilic monomers were successfully grafted onto the surface of MMT. Grafting amounts of the hydrophilic polymers were estimated from TGA thermograms to be 28.8, 118.8 and 14.4% for PAMPS, PAAm and PSSA, respectively. XRD patterns showed an exfoliated morphology for PAMPS‐ and PAAm‐grafted MMT hybrid nanomaterials and an intercalated/exfoliated morphology for the PSSA‐grafted MMT one. The effect of the nature of hydrophilic monomer on the grafting efficiency is discussed in detail. © 2013 Society of Chemical Industry     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

HDPE composites strengthened–toughened synergistically by l‐aspartic acid functionalized graphene/carbon nanotubes hybrid nanomaterials

Ethylenediamine (EDA) covalently functionalized graphene sheets (GS‐EDA) and acidized carbon nanotubes (MWNTs‐COOH) were first prepared, followed by synthesizing l ‐aspartic acid functionalized GS‐EDA/MWNTs‐COOH (LGC) hybrid nanomaterials by using l ‐aspartic acid as a bridging agent. Then nanocomposites of high density polyethylene‐g ‐maleic anhydride (HDPE‐g ‐MAH) synergistic strengthening–toughening using LGC hybrids were prepared via melt compounding method. The surface structure of filler was characterized by using infrared (FTIR) and Raman spectrum. The synergistic strengthening–toughening effects of LGC hybrids on the HDPE‐g ‐MAH were investigated by scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), thermal gravimetric analysis (TGA), tensile, and impact tests. FTIR showed that EDA has been grafted on the graphene sheets, and ? COOH group has been introduced into MWNTs. The l ‐aspartic acid connected GS‐EDA and MWNTs‐COOH through chemical bonds. SEM observations showed that LGC hybrids were homogeneously dispersed in HDPE‐g ‐MAH nanocomposites. Tensile and impact tests indicated that the mechanical properties of nanocomposites were improved obviously when LGC hybrid nanomaterials were incorporated simultaneously. DMA analysis indicated that the storage modulus of composites was higher than that of pure HDPE‐g ‐MAH matrix. TGA results revealed that the maximum decomposition temperature of HDPE‐g ‐MAH composites containing 0.75 wt % of LGC showed 11.5 °C higher than that of HDPE‐g ‐MAH matrix. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45055.     

Preparation and in vitro characterization of poly(sebacic acid‐co‐ricinoleic acid)‐based tamoxifen citrate‐loaded microparticles for breast cancer

This study was aimed to develop an injectable polymeric drug delivery system for tamoxifen citrate (TC) using poly(sebacic acid‐co‐ricinoleic acid) [poly(SA‐RA) 70 : 30 w/w] as a drug carrier for the treatment of estrogen receptor positive breast cancer. Injectable biodegradable microparticles of TC were produced by solvent displacement technique of microencapsulation and were characterized by surface morphology (scanning electron microscopy), particle size, size distribution, physical and chemical interaction (Fourier transform infrared), nature and physical state of drug [DSC and X‐ray diffraction (XRD)], and in vitro release studies. TC loading over different concentrations was analyzed by high performance liquid chromatography (HPLC) technique. Polyanhydride microparticles obtained after lyophilization were nearly spherical in shape with smooth surface and size less than 2.5 μm. TC was dispersed in the form of amorphous state, and TC remains intact and stable during the process of microencapsulation. In vitro drug release studies demonstrated prolonged controlled release of TC with zero‐order kinetics. Stability studies revealed that the production process of microparticles itself did not affect the chemical stability of the drug and polymer forming the particle matrix. Significant difference in drug release capacity was observed in microparticles with different drug loadings, and the drug release was more sustained in microparticles prepared with high TC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of PVA/SA composite nanofiltration membranes

Nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) were prepared by coating PVA/SA (95/5 in wt %) mixture solutions on microporous polysulfone (PSF) supports. For the formation of a defect free thin active layer on a support, the PSF support was multi‐coated with a dilute PVA/SA blend solution. The PVA/SA active layer formed was crosslinked at room temperature by using an acetone solution containing glutaraldehyde as a crosslinking agent. The prepared composite membranes were characterized with a scanning electron microscopy (SEM), a Fourier transform infrared spectroscopy (FTIR), an electrokinetic analyzer (EKA) and permeation tests: The thicknesses of the active layers were about 0.25 μm and 0.01 μm depending on the preparation conditions. The crosslinking reaction of the active layers were completed in less than three minutes via the formation of acetal linkage. The surface of the PVA/SA composite membrane was found to be anionic. The permeation properties of the composite membrane were as follows: 1.3 m³/m² day of flux and > 95% of rejection at 200 psi for 1000 ppm PEG600 solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 347–354, 2000     

Fluorescent DNA Labeling by N‐Mustard Analogues of S‐Adenosyl‐L‐Methionine

Azide and alkyne‐functionalized N‐mustard analogues of S‐adenosyl‐L ‐methionine have been synthesized and were demonstrated to undergo efficient methyltransferase‐dependent DNA alkylation by M.TaqI and M.HhaI. Subsequent labeling of the DNA with a fluorophore was carried out using copper‐catalyzed azide–alkyne cycloaddition chemistry and was visualized by fluorescence scanning. This work demonstrates the utility of functionalized N‐mustard analogues as biochemical tools to study biological methylation and offers a facile way to site‐selectively label substrates of DNA methyltransferases.     

Interpolymer complex microparticles based on polymethacrylic acid‐chitosan for oral insulin delivery

In the present study, microparticles composed of polymethacrylic acid‐chitosan (PMAA‐CS) were prepared by a novel interionic gelation method. Free‐radical polymerization of methacrylic acid was carried out in the presence of CS, using a water‐soluble initiator, and application of these microparticles toward oral insulin delivery was evaluated. Microparticles obtained were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) studies. From SEM studies, it was observed that microparticles had an aggregated morphology with size ～20 μm, while FTIR confirmed the presence of ionic interaction between PMAA and CS chains. Protein loading was done by diffusion filling method, and from in vitro release study, it was observed that insulin‐loaded microparticles displayed a pH depended release profile at alkaline/acidic pH. Microparticles exhibited sustained release of insulin for 3–4 h at neutral pH, and enzyme linked immunosorbent assay (ELISA) proved that encapsulated protein maintained 100% biological activity at neutral pH. Preliminary study suggests that these microparticles can serve as good candidate for oral protein delivery. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 506–512, 2006     

纳米锑掺杂氧化锡的表面改性

将纳米锑掺杂氧化锡(antimony doped tin oxide,ATO)分散于乙醇与水的混合改性介质中,利用硅烷偶联剂KH-570与纳米ATO表面羟基的脱水反应以及硅烷偶联剂间的缩合反应,制得了KH-570包覆的纳米ATO粉体。用FTIR、XPS、TG、TEM对纳米ATO粉体的表面结构进行了表征,并通过亲油性的测试,考察了其分散稳定性。结果表明,在ATO纳米粒子表面接枝上了7.36%～7.73%(质量分数)的KH-570,改性后的纳米ATO粒子的亲油性及分散性得到大幅度提高,改性ATO在正丁醇中能够稳定分散100 h以上。