Approaches for Making High Performance Polymer Materials from Commodity Polymers

A brief surrey of ongoing research work done for improving and enhancing the properties of commodity polymers by the author and author’s colleagues is given in this paper. A series of high performance polymers and polymer nanomaterials were successfully prepared through irradiation and stress-induced reactions of polymers and hydrogen bonding. The methods proposed are viable, easy in operation, clean and efficient. 1. The effect of irradiation source (UV light, electron beam, γ-ray and micr…     

STUDY ON HYDROLYSIS OF POLYIMIDE AND POLYPHENYLQUINOXALINE

Although polyimide (PI) and polyphenylquinoxaline (PPQ) are both heat resistant polymers, their hydrolytic stabilities are quite different. In this paper, the electron densities of two model compounds——N-phenylphthalimide and 2,3-diphenylquinoxaline are calculated by moans of CNDO/2 method. On the other hand, hydrolysis of model compounds and polymers is carried out. The theoretical calculation and experiments both prove that PPQ has excellent hydrolytic stability while PI is completely hydrolyzed under the same experimental condition. The mechanism of hydrolysis is also predicted.     

Synthesis of chiral polyphenylenes through Bergman cyclization of enediynes with pendant chiral amino ester groups

Chiral enediynes with pendant chiral amino ester groups are synthesized through Sonogashira reactions and subjected to thermal triggered Bergman cyclization at elevated temperatures either in bulk or in solvents to produce chiral polyphenylenes. The disappearance of enediyne monomers are evidenced by FTIR and NMR spectroscopies. The formation of polyphenylenes is further confirmed by UV-Vis and MALDI-TOF mass spectroscopies(MS). Isotope pattern analysis of the MS spectra shows that the polymers prepared in solvents are terminated by the solvent molecules, whereas the chain ends of the polymers prepared in bulk consist of considerable amount of unmasked free radicals, which is further confirmed by EPR analysis. Circular dichroism(CD) spectra of the chiral polymers show blue shifts of the Cotton peaks, indicating the occurrence of the cycloaromatization reaction. A new set of peaks mirrored at the horizontal axis show up in the long wavelength range, which are assigned to main chain chirality of the polyphenylenes.     

SYNTHESIS AND POLYMERIZATION OF OLIGO (OXYETHYLENE) MACROMONOMER

This paper reports the synthesis of methoxyoligo (oxyethylene) methacrylate (MEO_n , n is the repeating unit number of (CH_2CH_2O) in the macromonomer), and its polymerization in different solvents. MEO_n is prepared through such two independent reactions as (1) anionic polymerization of oxirane initiated by potassium alkoxide and (2) end-capping of methoxy oligo(oxyethylene) by methacrylic group. The n value can be conveniently controlled over the range of 5 ～30 by varying the molar ratio of oxirane to initiator and the molecular weight distribution of MEO_n be narrowed by increasing reaction time only in step (1). MEO_n thus obtained shows a rapid polymerization in water and benzene respectively, and both give water-soluble polymers as long as suitable conditions are used.     

Chemical synthesis, spectral characterization and stability of some electrically conducting polymers

<正>The synthesis,characterization,thermal degradation and stability of polyaniline(PANI),poly(m-nitroaniline), poly(m-chloroaniline) and poly(o-methylaniline) were reported.Different properties were measured and compared with PANI to find out the effect of electron donating groups(-CH_3) and electron withdrawing groups(-Cl,- NO_2).It was found that the presence of any type of substitution in the benzene ring of aniline increased the solubility but reduced the yield,thermal stability and electrical conductivity.Two probe methods were used to measure the electrical conductivity of these polymers.The structural properties of these polymers were characterized by using FTIR and UV-Vis spectroscopic methods.Thermal degradation and stability of these polymers were explained by using thermogravimetric analysis(TGA) and conductivity measurements.     

The World of Synthetic Polymers. An Industrial Perspective

Synthetic polymers have become the building block in almost every aspects of our daily life. Billions of pounds of polymers are produced each year and the demand is continuously growing both in terms of volume and advanced performance. The general property of a class of polymers is often bounded by the synthetic process that produces the polymer. For example, polyolefins, are non-polar polymers due to the poor tolerance of transition metal catalysts toward polar monomers. Conversely, latices a…     

A CIDEP study of photolysis benzophenone radicals in the microheterogeneous phase systems

The chemically induced dynamic electron polarization (CIDEP) of photolyzed benzophenone radicals in the microheterogeneous phase systems has been made by using the time-resolved electron spin resonance (TRESR) spectrometer. In the AEO_9/isoproanol/H_2O/C_8H_(18) liquid crystal system, the TRESR spectrum of Ph_2COH shows an unusual CIDEP of spin correlation radical pair (SCRP). The SCRP formation in these systems resulting from the character microenvironment and the related physical-chemistry property are discussed.     

Rylene diimide and dithienocyanovinylene copolymers for polymer solar cells

Two polymers containing(E)-2,3-bis(thiophen-2-yl)acrylonitrile(CNTVT) as a donor unit, perylene diimide(PDI) or naphthalene diimide(NDI) as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells(OSCs). Both polymers exhibit broad absorption in the region of 300–850 nm. The LUMO energy levels of the resulted polymers are ca. –3.93 eV and the HOMO energy levels are –5.97 and –5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency(PCE) of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.     

A novel microwave absorber — BaAl2Fe10O19/poly(m-toluidine) composite: Preparation and electromagnetic properties

BaFe10Al2O19 /poly(m-toluidine)(BFA/PMT) composites were synthesized by in-situ polymerization of m-toluidine in the presence of BaFe10Al2O19 particles.The structure,composition and morphology of the obtained samples were characterized by using XRD,FT-IR,UV-visible spectroscopy,SEM and TEM techniques.Their electrical conductivity,magnetic property and microwave absorbing property were measured by the four-probe meter,the vibrating sample magnetometer and the vector network analyzer,respectively.The results indicated that BFA particles were coated effectively by PMT polymer and some interactions between PMT and BFA particles existing in the composites.The conductivity of BFA/PMT composite is smaller than that of pure polymers and its saturation magnetization is a little smaller than that of pure BFA.The influence of the constitution and film thickness of absorbent on its microwave absorbing property is evident.The microwave absorbing properties of the BFA/PMT composites are better than those of pure BFA and PMT.When optimizing the mass rate of BFA/PMT to 0.3,the absorbent with 2 mm film thickness has the minimum reflection loss of 28.26 dB at approximate 14.24 GHz,and the maximum available bandwidth of 8.8 GHz,respectively.The results show that these composites can be used as advancing absorption and shielding materials due to their favorable microwave absorbing property.     

Phase Transition and Micellization of Temperature Responsive Dextran—graft—poly（N—isopropylacrylamide）Polymers

Phase behavior and micellization of dextran-graft-poly(N-isopropylacrylamide)(PNIPAAm)polymers in aqueous solution are investigated in this paper using DSC and AFM methods.It is found that with the increase of grafting(G%) of the copolymers the endothermic enthalpy during the phase transition increases significantly and the transition temperature decreases slightly.The phase transition behavior of the copolymers is scanning rate dependent.Micelles are formed whenever the solution temperature is raised above the LCST of the copolymers.It is proposed that by using this thermal responsive property of the copolymers,drugs could be incorporated into the micelles without employing any organic solvent.     

A TRILAYER DERMAL EQUIVALENT CONTAINING SILVER NANOPARTICLES WITH ENHANCED ANTIBACTERIAL PROPERTY

A dermal equivalent having a trilayered structure was designed by combining a silver nanoparticles incorporated chitosan film with a bilayer collagen-chitosan/silicon membrane dermal equivalent(BDE).The silver nanoparticles prepared at different conditions were characterized by UV-Vis and transmission electron microscopy(TEM).The macroscopic sharp and the microstructure of the trilayer dermal equivalent(TDE) were also studied.Then,the in vitro antibacterial property of TDE was evaluated by the antibacter...     

Synthesis and properties of novel soluble poly(aryl amine ketone)s as high-performance polymers

A series of poly(aryl amine ketone)s have been obtained by the condensation polymerization of different aromatic dibromides with different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of polymers are characterized by means of FT-IR, 1H NMR spectroscopy, and elemental analysis. The results show an agreement with the proposed structures. DSC and TG measurements show that polymers possess high glass transition temperature (Tg>170℃) and good thermal stability with high decomposition temperatures (TD>450℃). These novel polymers also exhibit good mechanical behaviors and good solubility.     

Action mechanism of antioxidation and anticorrosion and molecular design for perfluoropolyether fluid additives (Ⅰ)——Action mechanism of additive and property of donating-accepting electron

The combination energy and chemical adsorption energy of N-substituted perfluoropoly-alkyletherphenylamide (PFPEA) additive to perfluoropolyalkylether oxygen radical (RfO.) and to Fe atom have been calculated by quantum chemical methods. Structural characteristics, action mechanism, property of donating-accepting electron and substituent effect for antioxidant and anticorrosive additive are investigated. It is found that HOMO of the additives is a π-molecular orbital with lone pair electron of heteroatom. The HOMO of PFPEA additive reacts with LUMO of Fe atom to result in chemical adsorption. The LUMO of additive can interact with the SOMO of RfO. and accept electron of RfO. to form stable addition product. The additives have the property of donating-accepting electron. The electron-releasing group, particularly, the phenyl group, introduced to N atom of phenylamide can increase the combination energy and chemical adsorption energy, and enhance the antioxidant and anticorrosive efficiency. The research achi     

MOLECULAR DESIGN OF FUNCTIONAL POLYMERS BASED ON UNIQUE PROPERTIES OF POLYMER CHAINS

The inclusion complex formation of α-CD, β-CD, and γ-CD with various water-soluble polymers has beeninvestigated, and the relationship between the chain cross-sectional areas of the polymers and the diameters of the cavities ofcyclodextrins (molecular recognition) was found. Polyrotaxanes and tubular polymers were prepared on the basis ofmolecular recognition. Several kinds of polymers having tetraphenylporphyrin (TPP) and paramagnetic metallotetraphenyl-porphyrin (AgTPP, CuTPP, VOTPP or ZnTPP) have been prepared by radical polymerization of the correspondingmonomers. Visible spectra of these polymers show hypochromism in the Sorer bands of TPP moieties as compared withthose of monomers. Polymer effects were observed in the magnetic behavior and oxygen adsorption of paramagneticmetallotetraphenylporphyrin moieties. Moreover, polymer effects on photophysical and photochemical behavior were foundin the amphiphilic polymers covalently tethered with small amounts of zinc(Ⅱ)-tetraphenylporphyrin (ZnTPP).     

Tunable UCST thermoresponsive copolymers based on natural glycyrrhetinic acid

Water-soluble thermoresponsive polymers present either upper critical solution temperature(UCST) or lower critical solution tempe rature(LCST) depending on the location of their miscibility range with water at high temperatures or at low temperatures.Compared with LCST polymers,the water-soluble UCST polymers are still less explored until now.In this work three copolymers of P(AAm-co-GAA) were synthesized by copolymerizing two acrylamide monomers,acrylamide(AAm) and acrylamide functionalized with natural glycyrrhetinic acid(GAA),using reversible addition-fragmentation chain transfer(RAFT) polymerization.These copolymers exhibited the typical UCST thermoresponsive behavior,and their phase transition temperatures could be easily tuned to around 37℃ for potential biological applications.Moreover,the UCST of P(AAm-co-GAA) can be adjusted not only by the content of glycyrrhetinic acid(GA) and polymer concentrations,but also by the host-guest interactions between GA and cyclodextrins(β-and γ-CD).The suitable value of UCST and the biocompatible nature of GA and CDs may endow these copolymers with practical applications in biomedical chemistry.     

Synthesis and Characterization of Small Band-gap Conjugated Polymers - Poly(pyrrolyl methines)

A kind of small band-gap conjugated polymers-poly (pyrrolyl methines) and their precursors-(poly pyrrolyl methanes) have been synthesized by a simple method and characterized by 1HNMR, FT-IR, TGA and UV-Vis. These polymers can be dissolved in high polar solvents such as DMSO, DMF or NMP. The results reveals that the band-gap of the synthesized conjugated polymers are in the range of 0.96～1.14 eV and they all belong to the small band-gap polymers. The conductivity of doped products with iodine is in the range of semiconductor.     

Synthesis of Poly（N-vinylpyrrolidone） Nanofibers Containing Gold Nanoparticles via Electrospinning Technique

Poly(N-vinylpyrrolidone)(PVP)nanofibers containing gold nanoparticles were prepared by electrospinning method.This simple route was used to prepare composites on a large scale,and the syntheses are simple.The optical property of gold nanoparticles in PVP aqueous solution was investigated by UV-Visible absorption spectra.The morphology of the fibers and the distribution of particles were characterized by transmission electron microscopy.The structure of the composite was characterized by Fourier transform infrared spectroscopy.     

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.     

Synthesis and characterization of Bi-functional photorefractive polymers with high molecular weight and low glass transition temperature

Carbazole-based bi-functional photorefractive polyacrylates were prepared via free radical polymerization and post-azo-coupling reaction. The structure of polymers was characterized by Fourier transform infrared spectroscopy(FTIR) and proton nuclear magnetic resonance(1H-NMR) spectroscopy. The differential scanning calorimetry(DSC) and the thermal gravimetric analysis(TGA) were used to characterize the thermal property of polymers. The results indicate that though the glass transition temperature(Tg) of polymers increases with increasing the ratio of NLO groups, the polymers with different ratios of NLO groups still all show low glass transition temperatures around 60 °C, and good thermal stability, which are favorable to the practical application of these polymers. The gel permeation chromatographic(GPC) result indicates that these polymers all have high-molecular-weight which is favorable to the long term stability of the material. Further, these polymers have good solubility in chloroform solvent, and the solutions can easily be fabricated into optically transparent films. Gain coefficients of 75 cm-1, 185 cm-1 and 66 cm-1 can be observed at zero external electric field without any addition agent or pre-poling for polymers P-2, P-3 and P-4 respectively. The different contents of NLO groups result in the different properties of polymers P-2, P-3 and P-4.     

Synthesis of Methyl—substituted Phthalazinone—based Aromatic Poly（amide imide）s

A series of novel aromatic poly (amide imide)s containing phthalazinone moietics were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with our diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36-0.65 dL/g. These polymers had high glass transition temperatures above 300℃ and they lost 10% weight between 426-475℃ in N2. The structure of diamine 1 and the polymers was confirmed by IR,^1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP,m-cresol etc. and easily cast into tough,flexible films. The X-ray indicated that they are all amorphous.