COMPUTER SIMULATIONS ON UNPERTURBED CONFIGURATIONAL DIMENSIONS OF POLY (METHYL ACRYLATE)

A full-relaxation optimization of molecule and the popular MM2 force field are employed to obtain the geometry parameters and the conformational energy surface of a meso or a racemic dyad of poly(methyl acrylate) (PMA) with a specified carbonyl-bond orientation in side-groups. It is found that the conformational energy maps calculated here considerably differ from those calculated with the rigid molecular model as reported in the earlier studies. The g(-) state cannot be omitted in the obtained contour maps. Two important conformers tg(-) and g(-t) with energy minima were newly detected for a racemic dyad. The analysis on the conformations with energy minima confirmed that the ester groups are not always perpendicular to the plane defined by the two adjacent skeletal bonds and may change their relative orientations to meet the requirement of lower energies during the conformational state transition. Instead of the early way of adjusting the interaction energy parameters to fit the experimental data, we attempt to predict unperturbed chain dimensions via the reliable force field and the configurational statistical mechanics. The proposed scheme with three rotational states identified from the contour maps allowed us to satisfactorily reproduce the experimental dimensions of random PMA chains.

Redox active polymer metal chelates for use in flexible symmetrical supercapacitors:Cobalt-containing poly(acrylic acid)polymer electrolytes

The novel polymer metal chelate electrolytes(polychelates)were prepared by incorporation of cobalt sulfate(Co)into poly(acrylic acid)(PAA)host matrix.Quasi-solid state supercapacitor devices were fabricated using polychelates,PAA-Co X(X:3,5,7,and 10)where X represents the doping fraction(w/w)of Co in PAA.All polymer metal electrolytes were showed excellent bending-stretching properties,thermal stability and electrochemical durability with an optimum ionic conductivity of 3.15×10^(-4) S cm^(-1).Hierarchically porous activated carbon and nano-sized conductive carbon were used to form carbon composite symmetrical device electrodes.The electric double-layer capacitor(EDLC)and redox reactions of Co-incorporated polychelates at the interfaces of porous activated carbon provided an optimum specific capacitance of 341.33 F g^(-1) with a device of PAA-Co7,which is at least 15 times enhancement compared to the device of pristine PAA.The PAA-Co7 device also provided energy density of 21.25 Wh kg^(-1) at a power density of 117.69 W kg^(-1).A prolonged cyclic stability of the device exhibited superior capacitive performance after 10,000 charge-discharge cycles and the maintained 90%of its initial performance.In addition,the supercapacitor with a dimension of 1.5 cm×3 cm containing PAA-Co7 successfully operated the red-blue-green(RGB)LED light.

CONFORMATIONAL CHARACTERISTICS OF POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID)

A full-relaxation optimization of molecule and the Dreiding force field are employed to obtain the geometry parameters and the conformational energy surfaces of meso or racemic dyad of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Three different carbonyl-bond orientations of side-groups resulted in the differences in depth of potential wells in their energetic contours for a meso or a racemic dyad. These discrepancies are interpreted as a result of various fine structures corresponding to grid search conformations as well as thereby different interactions. The analysis on the most stable conformations of PMAA confirmed that the ester groups are nearly perpendicular to the plane defined by the two adjacent skeletal bonds but may possibly change their relative orientations to meet the requirement of lower energy during the conformational state transition. For each polymer, two global energy maps of a meso and a racemic dyad were finally constructed from the superposition of energy data for the three kinds of side-group orientations by the Boltzmann factors. From an ensemble average, the proposed scheme with three rotational isomeric states (RIS) allowed us to access the experimentally unperturbed dimensions of PAA chain via the configurational statistical mechanics. Although the calculation was based on the short-range, local interactions, it was interested to note that the experimental characteristic ratios just fell within the range calculated for atactic chains.

PREPARATION OF POLY(ETHYLENEGLYCOL-co-ACRYLIC ACID) MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.

CD POLY/Acrylic/Viscose混纺弹性织物气流机染色

用阳离子染料对CD POLY／Acrylic／Viscose混纺弹性织物进行一浴法染色，在大货生产中容易出现色差、折痕和毛头等问题。实验通过分段式升温，控制40-70℃升温速率为1．0℃／min，70-90℃升温速率为0．3℃／min，90-105℃升温速率为0．5℃／min，105℃保温30min能有效控制色差问题；气流机染色选用合适的行机条件也是控制质量问题的关键。设定行机条件为45％的风机，80％N差，机速350m／min，行一圈时间2．75min。大生产证明织物的布面品质良好。

Microstructure and Mechanical Properties of Poly (Vinyl Chloride) Modified by Silica Fume /Acrylic Core-Shell Impact Modifier Blends

This research explored replacing acrylic core-shell impact modifier （AIM） by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM （8 phr） were substituted by silica fume in PVC respectively, and then processed by dry blending and twin-screw extrusion. Severe silica fume agglomeration was observed by scanning electron microscope （SEM） in the PVC matrix when 8 phr pure silica fume was used and processed by screw speed of 20 rpm. Its tensile strength was thereby reduced by 38% comparing to unmodified PVC. The silica fume was successfully dispersed while the screw speed was slowed down to 10 rpm to give a stronger screw torque and a longer melt residential time in the extruder. The tensile strength was ’recovered’ to a level comparable to unmodified PVC. Impact test were performed on all formulations extruded at 10 rpm screw speed and synergetic toughening effect was found with 50% substitution and it had the impact strength that was comparable to 8 phr pure AIM toughened PVC.

Synthesis and Properties of IPN Hydrogels Based on Konjac Glucomannan and Poly(acrylic acid)

Novel interpenetrating polymer network （IPN） hydrogels based on konjac glucomannan （KGM） and poly（acrylic acid） （PAA） were prepared by polymerization and cross-linking of acrylic acid （AA） in the pre-fabricated KGM gel. The IPN gel was analyzed by FF-IR. The studies on the equilibrium swelling ratio of IPN hydrogels revealed their sensitive response to environmental pH value. The results of in vitro degradation showed that the IPN hydrogels retain the enzymatic degradation character of KGM.

Synthesis and application of a novel star-hyperbranched poly(acrylic acid) for improved dental restoratives

A new star-hyperbranched poly(acrylic acid) has been synthesized and incorporated into dental glassionomer cement for enhanced mechanical strengths. The effects of arm number and branching on viscosity of the polymer aqueous solution and mechanical strengths of the formed experimental cement were evaluated. It was found that the higher the arm number and the more the branching, the lower the viscosity of the polymer solution as well as the mechanical strengths of the formed cement. It was also found that the experimental cement exhibited significantly higher mechanical strengths than commercial Fuji II LC. The experimental cement was 51% in CS, 55% in compressive modulus, 118% in DTS, 82% in FS, 18% in FT and 85% in KHN higher than Fuji II LC. The experimental cement was only 6.7% of abrasive and 10% of attritional wear depths of Fuji II LC in each wear cycle. It appears that this novel experimental cement is a clinically attractive dental restorative and may potentially be used for high-wear and high-stress-bearing site restorations.

Preparation and Properties of Carrageenan-g-Poly(Acrylic Acid)/Bentonite Superabsorbent Composite

A novel biopolymer-based superabsorbent hydrogel composite based on kappa-carrageenan (κC) have been prepared via graft copolymerization of acrylic acid (AA) in the presence of bentonite powder using methylenebisacrylamide (MBA) as a crosslinking agent and ammonium persulfate (APS) as an initiator. The hydrogel structure was confirmed using FTIR spectroscopy and the morphology of the samples was examined by scanning electron microscopy (SEM). The affecting variables onto graft polymerization (i.e. AA, MBA and APS concentration, as well as the bentonite amount) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The results of Brunauer–Emmett–Teller (BET) analysis showed that the average pore diameter of the synthesized hydrogel was 11.5 nm. The effect of various salt media and solutions with different pHs on the swelling of the superabsorbent was also studied.

SYNTHESIS AND PROPERTIES OF NEW SIDE-CHAIN LIQUID CRYSTALLINE POLYMER WITH LATERALLY ATTACHED MESOGENS BY ESTER GROUP

New liquid crystalline monomer, 2,5-bis[(4'-methoxyphenoxy)carbonyl]phenyl acrylate was successfully synthesized. Polyacrylate with laterally attached mesogens via ei;ter linkage was also derived. This polymer forms an enantiotropic liquid crystal phase while its monomer exhibits a metastable nematic phase with respect to the crystalline state. However, its liquid crystallinity is very low as compared to that of poly{2,5-bis[(4'-methoxyphenoxy)carbonyl]-styrene}.

Development of flexible zinc–air battery with nanocomposite electrodes and a novel separator

In this paper, we present the development of flexible zinc–air battery. Multiwalled carbon nanotubes(MWCNTs) were added into electrodes to improve their performance. It was found that MWCNTs were effective conductive additive in anode as they bridged the zinc particles. Poly(3,4-ethylenedioxythiophene)polystyrene sulfonate(PEDOT:PSS) was applied as a co-binder to enhance both the conductivity and flexibility. A poly(acrylic acid)(PAA) and polyvinyl alcohol(PVA) coated paper separator was used to enhance the battery performance where the PVP–PAA layer facilitated electrolyte storage. The batteries remained functional under bending conditions and after bending. Multiple design optimizations were also carried out for storage and performance purposes.

Analysis and Investigation of Slow Light Based on Plasmonic Induced Transparency in Metal-Dielectric-Metal Ring Resonator in a Waveguide System with Different Geometrical Designs

In this paper we will try to create, propose and analyze structure of a slow light device, based on plasmonic induced transparency in a metal-dielectric-metal based ring resonator. Group index by first design about 37 and second design about 35 earned. The proposed dielectric material is Poly Methyl Meta Acrylate (PMMA) sandwiched by gold metal cladding. Finite Element Method-con- ducted Electromagnetic simulations are employed to evaluate the plasmonic designs for behavior of slow light. The signal and pump wavelength are assumed to be 830 nm and 1550 nm respectively in the systems. The overall length of the plasmonic slow light system is 600 nm. In a wide range of frequency bands, the optical properties of metals can be described with a plasma model. The optical signal can be achieved with the use of surface waves on the boundary between the insulating materials and metals with dimensions smaller than the diffraction limit. The main goal, is estimation of optical characteristics such as bandwidth, the Real and Imaginary parts of refractive index, group velocity and slow down factor in such optical devices. The obtained results and observations, can be useful in basic research and the production of highly integrated plasmonic devices.

Grafting of Poly（lauryl acrylate） onto Nano-silica by ‘Click Chemistry’

Poly（n-alkyl acrylate） with long side groups,namely,poly（lauryl acrylate）（PLA） was synthesized by reversible addition-fragmentation chain transfer（RAFT） polymerization,and the trithioester terminal groups were converted to thiol by reducing reaction.Grafting of the obtained polymer onto nano-silica modified with 3-（methacryloxy）propyl-trimethoxysilane（SiO2-MPS） was conducted by thiol-ene ‘click chemistry＇.PLA was characterized by proton nuclear magnetic resonance（1H NMR） and gel permeation chromatography（GPC）.Fourier transform infrared（FTIR） spectrometry and thermogravimetric analysis（TGA） were used to demonstrate the grafting reaction,and the grafted hairy nano-silica（SiO2-g-PLA） was viewed under a transmission electron microscope（TEM）.According to TGA,grafting ratio and grafting density of SiO2-g-PLA are 30.27％ and 0.013 chain/nm2,respectively.The static water contact angle of SiO2-g-PLA is （80.10±2.97）°,which ensures its hydrophobicity.Dispersion experiment was carried out to confirm its dispersibility in mixed solvents,indicating its potential application in coatings or composites.

Study on ChemFET NO_2 Gas Sensor Array

Based on conventional metal-oxide-semiconductor field-effect transistor (MOSFET),a novel kind of chemical field-effect transistor (ChemFET) gas sensor array has been designed and fabricated.The obtained sensor consists of self-assembly polyaniline (PAN) composite film containing poly(acrylic acid) (PAA) which was used as gate material of MOSFET instead of conventional metallic gate.The UV-Vis absorption spectra of PAN/PAA films were characterized.The NO_2 gas sensitive property of the ChemFET sensor array was also investigated.Results show that the drain current of devices increases with increasing of back-side voltage,and decreases with the increase of NO_2 concentration when the NO_2 concentration is below 20μg/g.The temperature dependence of ChemFET sensor array shows that the drain current of ChemFET sensor decreases with increasing of temperature.

A High-Strength Cement System for Improved Dental Restoratives

We have developed and studied a novel high-strength glass-ionomer cement system composed of poly(acrylic acid) with different molecular architectures. These poly(acrylic acid) polymers were synthesized via ATRP technique. The effects of arm number and branching on reaction kinetics, viscosity, and mechanical strengths of the formed polymers and cements were evaluated. The results showed that unlike the star-shaped polymer synthesis both hyperbranched and star-hyperbranched polymers syntheses proceed slowly at the early stage but accelerate at the later stage. The higher the arm number and initiator concentration are, the faster the ATRP reaction was. It was also found that the higher the arm number and branching that the polymer had, the lower the viscosity of the polymer aqueous solution is and the lower the mechanical strengths of the formed cement are. The mechanical strengths of three synthesized polymers-composed experimental cements were very similar to each other but much higher than those of Fuji II LC. The experimental cements were 31% - 53% in CS, 37% - 55% in compressive modulus, 80% - 126% in DTS, 76% - 94% in FS, 4% - 21% in FT and 53% - 96% in KHN higher than Fuji II LC. For wear test, the experimental cements were only 5.4% - 13% of abrasive and 6.4% - 12% of attritional wear depths of Fuji II LC in each wear cycle. The one-month aging study also showed that all the experimental cements increased their CS continuously during 30 days, unlike Fuji II LC.

DMS AND ^(13)C NMR STUDIES ON THE COMPATIBILITY AND DYNAMICS OF LATEX BIDIRECTIONAL IPNS AND LATEX IPN OF PVAc/PBA

The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ^(13)C linewidths of PBA and temperature is also discussed.

Self-healing poly(acrylic acid) hydrogels fabricated by hydrogen bonding and Fe^(3+) ion cross-linking for cartilage tissue engineering

Autonomous self-healing hydrogels were achieved through a dynamic combination of hydrogen bonding and ferric ion(Fe^(3+))migration.N,N′-methylenebis(acrylamide)(MBA),a cross-linking agent,was added in this study.Poly(acrylic acid)(PAA)/Fe^(3+)and PAA–MBA/Fe^(3+)hydrogels were prepared by introducing Fe^(3+)into the PAA hydrogel network.The ionic bonds were formed between Fe^(3+)ions and carboxyl groups.The microstructure,mechanical properties,and composition of hydrogels were characterized by field emission scanning electron microscopy and Fourier transform infrared spectroscopy.The experimental results showed that PAA/Fe^(3+)and PAA–MBA/Fe^(3+)hydrogels healed themselves without external stimuli.The PAA/Fe^(3+)hydrogel exhibited good mechanical properties,i.e.,the tensile strength of 50 kPa,the breaking elongation of 750%,and the self-healing efficiency of 82%.Meanwhile,the PAA–MBA/Fe^(3+)hydrogel had a tensile strength of 120 kPa.These fabricated hydrogels are biocompatible,which may have promising applications in cartilage tissue engineering.

Miscibility and Crystallization of PHB/PMA Blends

The miscibility, crystallization behavior and morphological structure of PHB/PMA blends have been studied by the differential scanning calorimeter (DSC) and polarized optical microscopy (POM). The chemical repeat units of the two components of the blend are isomers. The results indicate that PHB and PMA are miscible in the melt. The addition of PMA into PHB results in a depression in the spherulite growth rate of PHB. With increasing PMA content in the blends, the texture of PHB spherulite becomes more open.

One-Pot Synthesis and Strong Near-Infrared Upconversion Luminescence of Poly(acrylic acid)-Functionalized YF3:Yb^(3+)/Er^(3+) Nanocrystals

This paper describes the synthesis of new upconverting luminescent nanoparticles that consist of YF_(3):Yb^(3+)/Er^(3+)functionalized with poly(acrylic acid)(PAA).Unlike the upconverting nanocrystals previously reported in the literature that emit visible(blue-green-red)upconversion fluorescence,these as-prepared nanoparticles emit strong near-infrared(NIR,831 nm)upconversion luminescence under 980 nm excitation.Scanning electron microscopy,transmission electron microscopy,and powder X-ray diffraction were used to characterize the size and composition of the luminescent nanocrystals.Their average diameter was about 50 nm.The presence of the PAA coating was confirmed by infrared spectroscopy.The particles are highly dispersible in aqueous solution due to the presence of carboxylate groups in the PAA coating.By carrying out the synthesis in the absence of PAA,YF_(3):Yb^(3+)/Er^(3+)nanorice materials were obtained.These nanorice particles are larger(~700 nm in length)than the PAA-functionalized nanoparticles and show strong typical visible red(668 nm),rather than NIR(831 nm),upconversion fluorescence.The new PAA-coated luminescent nanoparticles have the pottential be used in a variety of bioanalytical and medical assays involving luminescence detection and fluorescence imaging,especially in vivo fluorescence imaging,due to the deep penetration of NIR radiation.

Highly Stretchable and Self-healing Hydrogels Based on Poly(acrylic acid) and Functional POSS

Herein, we present a novel way for the production of self-healing hydrogels with stretch beyond 4200% than their initial length and relatively high tensile strength （0.1-0.25 MPa）. Furthermore, the hydrogel was insensitive to notch. Even for the samples containing V-notches, a stretch of 2300% was demonstrated. The hydrogels were developed by in situ crosslinking of the self-assembled colloidal poly（acrylic acid） （PAA）/functionalized polyhedral oligomeric silsesquioxane （POSS） micelles. This was achieved by the addition of functionalized polyhedral oligomeric silsesquioxane with tertiary amines and hydroxyls （POSS-AH） into the PAA reaction solution. The POSS-AH led to micellar growth, then the dual- crosslinked network was constructed. One type of crosslink was formed by hydrogen-bonding and ionic interactions between PAA chains and POSS-AH, the other type of crosslink was formed by covalent bonds between PAA and bis（N,N＇-methylene- bis-acrylamide）.