Preparation and characterization of graft copolymer from dealkaline lignin and styrene

Graft copolymerization of styrene onto dealkaline lignin by ferrous chloride and hydrogen peroxide coinitiator has been achieved successfully. The influence of temperature and reaction time as well as the amount of the styrene monomer, initiator, and catalyst on the grafting copolymerization was investigated. The optimum reaction conditions were determined as follows: c (styrene) = 20.00 mmol, c (H₂O₂) = 5.00 mmol, c (FeCl₂) = 0.10 mmol, T = 30°C and t = 48 h. The optimum yield (Y), total conversion (TC), grafting efficiency (GE), and degree grafted (DG) values were 96.6, 96.3, 59.5, and 53.7%, respectively. The copolymer of lignin grafted PS was separated and characterized by elemental analysis, differential scanning calorimetry, Fourier transform infrared, thermogravimetry analysis, field emission‐scanning electron microscopy, gel permeation chromatography, and nuclear magnetic resonance. It was demonstrated that the solubility what the copolymer exhibited turned out to be the very reverse of the original lignin. The surface properties and structure of lignin were completely changed after grafting copolymerization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41900.     

Propylene-ethylene Copolymer Filled Nanocomposites: Influence of Zn-ion Coating upon Nano-SiO2 on Structural,Thermal, and Dynamic Mechanical Properties

Propylene-ethylene copolymer (EP) nanocomposites based on nano-SiO₂ with and without Zn-ion coating were developed by conventional melt blending technique in a sigma internal mixer. Two composites each with 2.5 wt% filler were developed. The first composite was made by melt blending EP with nano-SiO₂ in a co-rotating sigma internal mixer. The second one was obtained by melt blending the same EP, but with Zn-ion coated nano-SiO₂. In case of Zn-ion coated nano-SiO₂ filled EP, wide-angle X-ray diffraction study (WAXD) showed a decrease in interplanar distance and lamellar polymer crystal size when compared to nano-SiO₂ filled EP. Differential scanning calorimetric (DSC) results showed Zn-ion coated nano-SiO₂ acting more as an effective nucleating agent than that of the nano-SiO₂. Thermogravimetric analysis (TGA) results showed improved thermal stability for EP in the presence of both the nanofillers. However, the thermal stability of Zn-ion coated nano-SiO₂ filled EP is higher than that of the nano-SiO₂ filled EP. Scanning electron microscope (SEM) study reveals that the Zn-ion coated nano-SiO₂ homogeneously distributed in the matrix, whereas nano-SiO₂ forms chainlike aggregates in the matrix phase. Dynamic mechanical analysis (DMA) study indicates that both the fillers increase storage modulus, E′; this increment is more prominent in nano-SiO₂ filled EP due to the formation of chain-type aggregates of nano-SiO₂.     

Pickering emulsion polymerization: Preparation of polystyrene/nano-SiO2 composite microspheres with core-shell structure

Polystyrene/nano-SiO₂ composite microspheres (PS/nano-SiO₂) with core-shell structure were successfully synthesized in a Pickering emulsion route using nano-SiO₂ particles as stabilizers, which were organically modified by methacryloxypropyltrimethoxysilane (MPTMS) which containing a reactive CC bond. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transformation infrared spectrum (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). In addition, bare PS spheres could also be obtained by changing synthetic conditions. It was found that the morphology of the resulting products depends on particle concentration, particle wettability and pH value of particle dispersion. A possible mechanism for the formation of the composites with different morphologies is proposed.     

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

Hydroxyl terminated poly(styrene‐r ‐methyl methacrylate) (P(S‐r ‐MMA )) random copolymers (RCPs ), with molecular weight (M _n) spanning from 1700 to 69 000 g mol^?1 and equal styrene unit content, were grafted at different temperatures onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder forming polystyrene‐b ‐poly(methyl methacrylate) (PS ‐b ‐PMMA ) block copolymer thin films. When the grafting temperature increases from 250 to 310 °C, a substantial increase in the grafting rate is observed. In addition, an increase in the surface neutralization efficiency occurs thus resulting in an increase in the robustness of the surface neutralization step. These data revealed that the neutralization of the substrate is the result of a complex interplay between RCP film characteristics and underlying substrate properties that can be finely tuned by properly adjusting the temperature of the grafting process. © 2016 Society of Chemical Industry     

Studies on the curing behaviour and mechanical properties of styrene/methyl methacrylate grafted deproteinized natural rubber latex

The graft copolymerization of styrene/methyl methacrylate (MMA) onto deproteinized natural rubber (DPNR) latex was carried out using ammonium peroxy disulfate (N₂H₈O₈S₂) as the initiator. The presence of the grafted polystyrene (PS) and polymethyl methacrylate (PMMA) on the rubber backbone was confirmed by FTIR spectroscopy. The effects of monomer concentrations on curing characteristics and mechanical properties were studied. It was found that the cure time and scorch time were increased with increasing monomer concentration whereas the torque_max–min value was slightly decreased. It was also noted that the increase in the monomer concentration resulted in stiffer rubber with increased modulus and reduced elongation at break.     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on the mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂/polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both percentage grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. Due to partial chain scission and deterioration of the ordered structure of PP during the graft polymerisation, the grafted PP exhibits worse thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂/PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have important influences on the toughening effect of the functionalised PP.     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂ /polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both per cent grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. As a result of partial chain scission and deterioration of ordered structure of PP during the graft polymerisation, the grafted PP exhibits poorer thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂ /PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have an important influence on the toughening effect of the functionalised PP.     

Effects of nanosilica filler surface modification and compatibilization on the mechanical,thermal and microstructure of PP/EPR blends

Polypropylene/ethylene-propylene rubber/nanosilica (PP/EPR/nano-SiO₂) composites were prepared by a melt blending masterbatch process using a Brabender mixer. In order to improve the interfacial adhesion and achieve diverse desired properties of the composites, nanosilica surface silylation by means of two silane coupling agents: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (AEAPTMS) and 3-methacryloxypropyltrimethoxysilane (MPTMS) was explored. The composites were also compatibilized using three compatibilizers: methyl methacrylate grafted PP (MMA-g-PP), glycidylmethacrylate grafted PP (GMA-g-PP) and maleic anhydride grafted PP (MAH-g-PP). The properties of the blends and the composites were examined using tensile and Izod impact tests, differential scanning calorimetry (DSC), thermogravimetric analysis (ATG) and scanning electron microscopy (SEM). According to the mechanical property evaluations, the incorporation of nano-SiO₂ particles into PP/EPR blend improved the tensile strength and Young’s modulus of the composites. The elongation and Izod impact strength were adversely affected. A significant improvement in the mechanical properties was obtained for the composites with AEAPTMS-SiO₂ and MAH-g-PP. The DSC results indicated that the incorporation of the modified silica and MAH-g-PP increased the crystallinity of the composites. However, no significant variation in the crystallinity was observed as a result of the addition of MMA-g-PP and GMA-g-PP. The TGA results revealed that the composites exhibit a higher thermal stability than that of the neat matrix. SEM micrographs of the fractured surfaces revealed a two-phase morphology with EPR nodules being dispersed in the PP matrix. SEM also indicated that the incorporation of MAH-g-PP into PP/EPR composites contributes to a better dispersion of the EPR phase and nano-SiO₂ particles in the polymer matrix.     

SiO2-g-PS纳米微球的制备及其在增韧PP中的应用

采用乳液聚合方法在纳米SiO₂粒子表面接枝苯乙烯（St）单体,制备了具有核/壳结构的SiO₂-g-PS纳米微球,用FTIR、TEM、XPS和TG分析了SiO₂-g-PS的结构。结果表明,乳液聚合产物基本呈球形、SiO₂为核、PS为壳的核壳结构。通过熔融共混工艺制备聚丙烯（PP）基复合材料,并对其力学性能进行了分析,结果表明,当SiO₂-g-PS填充量较低［4%～6％（质量）］时,SiO₂-g-PS/PP复合材料的冲击强度和拉伸强度明显提高,并对PP的结晶有明显的异相成核作用。     

Surface‐initiated atom transfer radical polymerization from Mg(OH)2 nanoparticles to prepare the well‐defined polymer‐Mg(OH)2 nanocomposites

Well‐defined polymer‐Mg(OH)₂ nanocomposites were prepared by atom transfer radical polymerization (ATRP). The ATRP initiators were covalently attached to the Mg(OH)₂ by esterification of 2‐chloropropionyl chloride with hydroxyl group. The amount of polymer grafted from Mg(OH)₂ can be controlled using a different catalyst system and adding a small amount of polar solvent. The well‐defined diblock copolymer, consisting of poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) were synthesized. The products were characterized by nuclear magnetic resonance, Fourier transform infrared, differential scanning calorimetry, and thermal gravimetric analysis. The morphologies of PS/PMMA and PS/PMMA/Mg(OH)₂‐g‐PS‐b‐PMMA blends are compared by using a scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3680–3687, 2007     

Kinetics-controlled compatibilization of immiscible polypropylene/polystyrene blends using nano-SiO2 particles

Rigid inorganic filler has been long time used as a reinforcement agent for polymer materials. Recently, more work is focused on the possibility that using filler as a compatibilizer for immiscible polymer blends. In this article, we reported our efforts on the change of phase morphology and properties of immiscible polypropylene(PP)/polystyrene(PS) blends compatibilized with nano-SiO₂ particles. The effects of filler content and mixing time on the phase morphology, crystallization behavior, rheology, and mechanical properties were investigated by SEM, DSC, ARES and mechanical test. A drastic reduction of PS phase size and a very homogeneous size distribution were observed by introducing nano-SiO₂ particles in the blends at short mixing time. However, at longer mixing time an increase of PS size was seen again, indicating a kinetics-controlled compatibilization. This conclusion was further supported by the unchanged glass transition temperature of PS and by increased viscosity in the blends after adding nano-SiO₂ particles. The compatibilization mechanism of nano-SiO₂ particles in PP/PS blends was proposed based on kinetics consideration.     

Preparation and characterization of grafting styrene onto LLDPE by cyclohexane compatibilization in suspension polymerization

A novel method of grafting styrene onto linear low‐density polyethylene (LLDPE) by suspension polymerization was systematically evaluated. Cyclohexane as a compatibilizer was introduced to swell and activate the surface of LLDPE molecular chain for amplifying the contact point of styrene monomer with LLDPE. A series of copolymer of grafting polystyrene (PS) onto LLDPE, known as LLDPE‐g‐PS, were prepared with different ratios of cyclohexane/styrene monomer and various LLDPE dosages. FTIR and ¹H NMR techniques both confirmed successful PS grafting onto the LLDPE chains. In addition, SEM images of LLDPE‐g‐PS particles showed that the cross‐section morphology becomes smooth and dense with suitable cyclohexane dosages, indicating a better compatibility between LLDPE and PS. The highest grafting efficiency was 28.4% at 10 mL/g cyclohexane and styrene monomer when 8% LLDPE was added. In these conditions, the LLDPE‐g‐PS elongation at break increased by about 30 times compared with PS. Moreover, thermal gravimetric analysis (TGA) demonstrated that LLDPE‐g‐PS possesses much higher thermal stability than pure PS. Therefore, the optimal amount of cyclohexane as compatibilizer could increase the grafting efficiency and improve the toughness of PS. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41671.     

Syntheses of an azo‐group‐bound silica initiator and silica–polystyrene composites

In this article, we present a facile method for the synthesis of an azo‐group‐bound silica (SiO₂–azo) initiator. The azo groups were introduced onto the surface of silica (SiO₂) nanoparticles via facile condensation between 4,4′‐azobis‐4‐cyanopentanoic acid and the alkyl–hydroxyl groups ‐ immobilized on the SiO₂ nanoparticle surface under ambient conditions. The polystyrene (PS) chains were grafted onto the SiO₂ nanoparticle surface by in situ polymerization with the resulting SiO₂–azo as an initiator, and then, the SiO₂–PS composite was prepared. The syntheses and properties of the SiO₂–azo initiator and the composite were characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermogravimetric analysis, gel permeation chromatography, and differential scanning calorimetry techniques. The results confirm that the SiO₂–azo initiator and the composite were synthesized successfully. Styrene was polymerized with the initiation of SiO₂–azo, and the resulting PS domain accounted for 48.6% of the total amount of composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graft polymerization of styrene onto waste rubber powder and surface characterization of graft copolymer

The surface of waste rubber powder (WRP) was graft-modified with styrene (St) by bulk polymerization method. The effects of styrene content, initiator mass, time of reaction, and temperature on the graft efficiency were investigated. The results showed that the graft efficiency (%) was highest when 89 wt% styrene and 0.11 g of initiator were added for reaction time of 25 h at 85 °C. The surface of graft-modified rubber powder was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), energy dispersive X-ray (EDXS) analysis, and thermogravimetric (TG/DTG) analysis. The results showed that polystyrene (PS) was grafted onto waste rubber powder, which formed a WRP/PS core–shell structure.     

The study of polystyrene blends: The relationship of phases and structure in blends of polystyrene with ethylene–propylene diene monomer rubber and its grafted copolymer

Pressed films of blends of polystyrene (PS) with ethylene–propylene diene monomer rubber (EPDM) or grafted copolymer of styrene (St) onto EPDM (EPDM-g-St) rubber were examined by small-angle X-ray scattering (SAXS), and scanning electron microscope (SEM). Small-angle X-ray scattering from the relation of phase was analyzed using Porod's Law and led to value of interface layer on blends. The thickness of interface layer (σ_b) had a maximum value at 50/50 (PS–EPDM-g-St) on blends. The radius of gyration of dispersed phase (domain) and correlation distances a_c in blends of PS–EPDM-g-St were calculated using the data of SAXS. The morphology and structure of blends were investigated by SEM. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 805–810, 1998     

In situ studies of bovine serum albumin adsorption onto functionalized polystyrene latices monitored with a quartz crystal microbalance technique

The adsorbability of bovine serum albumin (BSA) onto poly(styrene‐co‐itaconic acid) (PS–IA), poly(styrene‐co‐hydroxyethyl methacrylate) (PS–HEMA), poly(styrene‐co‐acrylic acid) (PS–AA), and poly(styrene‐co‐methacrylic acid) (PS–MAA) latices were investigated with a quartz crystal microbalance. The amount adsorbed onto the functionalized latices, except for PS–MAA, was greater than that adsorbed onto polystyrene (PS) latex. To explain this result, two kinds of interaction forces were considered, hydrogen bonding and hydrophobic interactions, whereas electrostatic interaction was assumed to be small. When comparing the two extremes of hydrophobic interaction and hydrogen bonding, the latter was stronger. The corrected adsorption mass suggested that the BSA molecules were adsorbed onto the PS–MAA latex in a side‐on mode. However, in the case of the PS, PS–IA, PS–HEMA, and PS–AA latices, the BSA molecules were probably adsorbed in multiple layers. The presence of the BSA in the latex particle surface was verified by attenuated total reflectance/Fourier transform infrared spectroscopy and atomic force microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42055.     

Synthesis and properties of polystyrene‐g‐mSiO2 filled polypropylene nanocomposites

Hydrophobically modified nanosilica was prepared from tetraethoxysilane (TEOS) and γ‐methacryloxypropyltrimethoxysilane (MPS) by a two step sol‐gel process. The polystyrene‐grafted‐modified nanosilica (PS‐g‐mSiO₂) hybrid particles were prepared by grafting polystyrene onto the resulting hydrophobically modified nanosilica by dispersion polymerization. The hybrid nanoparticles were subsequently used as the filler to fabricate polypropyrene (PP) nanocomposites. The crystallization kinetics, crystal morphology and crystallization phase component of PS‐g‐mSiO₂/PP nanocomposite were studied using a differential scanning calorimeter (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (XRD). Crystallization half life (t_1/2) decreased, while the Arami exponent (n) of PS‐g‐mSiO₂/PP nanocomposite increased compared with that of virgin PP. A rheological study allowed the unambiguous characterization of the dispersibility of nanosilicas in PS‐g‐mSiO₂/PP nanocomposite. The storage modulus, melt viscosity and the elongation to break of the PS‐g‐mSiO₂/PP nanocomposite were found to be strongly dependent on the grafting of PS on nanosilicas. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Polystyrene–polyisobutylene network composites from in situ polymerizations

Crosslinked networks of butyl rubber [polyisobutylene (PIB) with 2 mol % unsaturation] were swelled with various amounts of styrene containing 0.25–4.6 wt % benzoyl peroxide as initiator. Polymerization of the styrene in situ, by increase in temperature, gave novel elastomeric composites. Scanning electron micrographs suggest phase separation which is locked in at the microscopic level, with no evidence for the particulate domains seen in the similarly prepared polystyrene-polydimethylsiloxane system. The wt % polystyrene (PS) extractible increased with increase in initiator concentration, which is consistent with decrease in the lengths of the PS chains being formed and grafted onto the PIB. Mechanical properties obtained in continuous extension showed maxima in their dependence on composition. Specifically, the ultimate strength (f/A^*)_m, maximum extensibility ε_r, energy E_r required for rupture, and permanent set ΔL/L₀ generally showed maxima in the vicinity of 50 wt % PS. The shortest-chain PS samples generally showed the largest values of (f/A^*)_m, ε_r, and E_r, and the smallest values of ΔL/L₀.     

Grafting of polypropylene with N-cyclohexylmaleimide and styrene simultaneously using supercritical CO2

Monomer mixture of styrene (St) and N-cyclohexylmaleimide (ChMI) and initiator benzoyl peroxide (BPO) were first impregnated into isotactic polypropylene (iPP) films simultaneously using supercritical carbon dioxide (SC CO₂) as a solvent and swelling agent at 35.0 °C. The composites were obtained after the monomers were grafted onto the iPP matrix at 70 °C. The effects of various conditions, such as pressure, monomer concentration, and the molar ratio of the two monomers in the soaking process, on the composition of the composites were determined. The molar ratios of St to ChMI in the composites were estimated by Fourier transform infrared spectroscopy. The thermal properties, the morphology, and the mechanical properties of the composites were characterized by different techniques. The results demonstrated that the phase size of the grafted St-ChMI was very small and the phase boundary was very ambiguous. The composites had better thermal stability than the original iPP film. The Young's modulus and tensile strength of the film increased continuously with increasing grafting percentage. The two grafted monomers in the composites had good synergetic effect.