Pyrolysis-Gas Chromatography/Mass Spectrometry for Microstructure and Pyrolysis Pathway of Polyester-Polyether Multiblock Copolymer

The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.

Determination of Three Kinds of Polyether Drug Residues in Eggs by QuEChERS dSPE EMR-Lipid-LC/MS/MS

[Objectives] This study was conducted to establish an LC-MS/MS method for the determination of three kinds of polyether residues in eggs with QuEChERS dSPE EMR-Lipid as a pretreatment method, which was established according to Agilent Bond Elut enhanced lipid removal EMR-Lipid technology. [ Methods] Egg was extracted by acidified acetonitrile, purified by Bond Elut EMR-Lipid QuEChERS, and detected by HPLC-MS/MS. [ Results] The three kinds of polyether residues had good linear relationships in the range of 2.0 - 100 μg/L with peak areas, r 〉 0. 999. The recoveries ranged from 84.6% to 107.0%. [ Conclusions ] The method is convenient and accurate, and the quantitative results are accurate and reproducible. It is suitable for the determination of the three kinds of polyether residues in eggs.

Hydrogenation of SBS Catalyzed by Immobilized Ru-TPPTS Complex in Polyether Molten Salt

Catalytic hydrogenation of SBS was performed for the first time in polyether molten salt with Ru/TPPTS complex as catalyst. Experimental results showed that the hydrogenation degree can be enhanced significantly by the addition of triphenylphosphine (TPP). When the molar ratio of TPP, TPPTS and Ru is 2:5:1, 89% hydrogenation degree can be achieved after 12 h under reaction conditions of 5.0 MPa and 150°C. The ionic liquid containing catalyst can be reused three times without obvious changes in the catalytic selectivity and activity.

Novel Silica Gel Supported Polyether Ionic Liquids: Efficient Catalysts Applied in Transformation of Carbon Dioxide

Three new catalysts based on the silica gel supported polyether ionic liquids(ILs), i.e., [HO-PECH-MIM]ClSi, [H2N-PECH-MIM]Cl-Si, and [HOOC-PECH-MIM]Cl-Si, were prepared, and their chemical structures were characterized by infrared(IR) spectroscopy and nuclear magnetic resonance(NMR) spectroscopy. Thermogravimetric analyzer(TG), X-ray diffractometer(XRD) and scanning electron microscope(SEM) were used to evaluate their thermal stability,crystalline structure and apparent morphology, respectively. Surface areas of the prepared catalysts were calculated by the Brunauer-Emmett-Teller(BET) method. The catalytic reaction for the synthesis of propylene carbonate(PC) using CO_2 and propylene oxide(PO) in the presence of the prepared catalysts was studied. The influences of times of recycling and catalyst structure on catalytic performance were also investigated. The experimental results showed that the silica gel supported polyether ILs catalysts successfully prepared under mild condition could possess the advantages of high activity, excellent thermal stability, good selectivity and easy recycling, while the phase transition of the liquid polyether ILs catalysts was also achieved. When the reaction temperature was 90 °C, the CO_2 pressure was 2.0 MPa and the dosage of the catalyst was 2.5%, [HOOC-PECH-MIM]Cl-Si was found to have the best catalytic performance in the catalytic process, with the conversion rate reaching 100% and the selectivity equating to 98.2%. The conversion rate and selectivity still could reach more than 90% even after the catalyst was reused for 15 times.

Proton Conducting Composite Membranes from Sulfonated Polyether Ether Ketone and SiO_2

Proton conducting composite membranes from sulfonated polyether ether ketone and SiO2 for direct methanol fuel cell （DMFC） application were prepared with sulfonated polyether ether ketone（SPEEK） and tetracethoxy silane（TEOS） by sol-gel method. The covalent crosslinking structure was formed between —SO3H of SPEEK via SiO2. The SEM images show that the interfacial compatibility of SPEEK and SiO2 is improved obviously and SiO2 disperses uniformly in the polymer matrix and the particle diameter of SiO2 does not exceed 40 nm. The proton conductivity of composite membranes decreases slightly compared with the SPEEK membrane while the methanol permeability and swelling of composite membrane are improved remarkablely owing to covalent cross-linking between —SO3H and SiO2 .

A Structure-properties Study of MDI-based Hydrophilic Polyether-polyester Polyurethane

A series of segmented polyether-polyester polyurethane with amorphous hydrophilic soft segment domains were prepared from 4,4'- diphenylmethane diisocyanate (MDI), polybutylene adipate (Glycol) 2000 (PBA2000), and polyethylene glycol 1000 (PEG1000), with 1,4-butanediol (BDO) as the chain extender. Furthermore, several representative properties of the polyurethanes, such as moisture permeability, water resistance, hydrophilic property, and phase inversion temperature, were investigated. The studies show that the structure and concentration of soft segment have a remarkable effect on the main application properties of polyurethane. On the contrary, the functional properties of the polyurethane are almost not affected by its hard segment.

SYNTHESIS AND CHARACTERIZATION OF A FLAME RETARDANT HYPERBRANCHED POLYETHER

A brominated hyperbranched polyether has been synthesized from cyanuric chloride and sodium salt of tetrabromobisphenol-A by an A2 ＋ B3 approach. The synthesized polyether was characterized by ^1H-NMR, ^13C-NMR, UV, FTIR spectroscopy and X-ray diffraction studies, measurements of solution viscosity, molecular weight and solubility and elemental and thermogravimetric analyses. The flame retardancy of the synthesized polyether and its blends with commercially available plasticized poly（vinyl chloride） （PVC） and low density polyethylene （LDPE） was investigated by measurements of limiting oxygen index （LOI） value and thermogravimetric analysis. The properties are compared with a non-halogenated similar type of bisphenol-A based aromatic polyether after blending at different dose levels with the same base polymers. The LOI values of these blends indicated that these hyperbranched polyethers acted as flame retardant additives, and antimony trioxide had prominent synergistic effect with the bromo hyperbranched polyether for the above base polymers, and an increment of 4 to 6 units in LOI values was observed.

Isocyanate-terminated Polyethers Toughened Epoxy Resin:Chemical Modification,Thermal Properties,and Mechanical Strength

The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanateterminated polyethers （ITPE） was investigated. The progress of the reaction and the structural changes during modification process were studied using FTIR spectroscopy. The studies support the proposition that TDI （tolylene diisocyanate） acts as a coupling agent between the epoxy and polyethers, forming a urethane linkage with the former and the latter, respectively. Me THPA-cured ER/ITPs blends were characterized using dynamic mechanical analysis （DMA） and thermogravimetric analysis （TGA）. It is indicated the glass transition temperature （T） of systems was lower than the T of pure epoxy resin and overfull ITPE separated from the modified epoxy resin and formed another phase at an ITPE-content of more than 10wt%. The thermal stability was decreased by the introduction of ITPE. The impact strength and the flexural strength of the cured modifiedepoxy increased with increasing the ITPE content and a maximum plateau value of about 24.03 kJ/m^2 and 130.56 MPa was measured in 10wt% ITPE. From scanning electron microscopy （SEM） studies of the fractrue surfaces of ER/ITPE systems, the nature of the micromechanisms responsible for the increases in toughness of the systems was identified.

Alkylation of Isobutane and Isobutene in Acidic Polyether Ionic Liquids

The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.

Synthesis of Arsamacrocyclic Polyethers

The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.

SOLID-STATE VARIABLE-TEMPERATURE NMR STUDY ON THE PHASE SEPARATION OF POLYETHER POLYURETHANE ZWITTERIONOMERS

Polyether-polyurethane zwitterionomers based on 4, 4'-diphenylmethane diisocyanate(MDI), methyl diethanolamine (MDEA), and polytetramethylene oxide glycol (PTMO) werestudied with variable-temperature wide-line ~1H NMR. It is found that upon ionization, degree ofphase separation in the polymer system decreased at first due to the loss of hard segmentregularity, while further ionization increased the degree of phase separation through increasinghard phase cohesion and difference of polarity between hard and soft segments.

IMMOBILIZATION OF POTENTIALLY BIOACTIVE MOIETIES ONTO POLYETHER WITH POLY(ETHYLENE GLYCOL)-SULFONATE SPACER

A new reactive graft copolymer, poly(tetramethylene glycol)-graft-omega-propyl sodium sulfonate-poly(ethylene glycol) (PTMG-g-PEG-CH2CH2CH2SO3-Na+), was synthesized by the cationic polymerization of alpha-omega-bifunctional PEG macromonomer ((sic)CH2-PEG-CH2CH2CH2SO3Na) and THF. The obtained copolymer exhibits the expected structure as indicated by the result of characterization. Two amino acids (L-arginine, L-tyrosine) were covalently attached to the copolymer after converting the sulfonate group, to sulfonyl chloride. So the new reactive graft copolymer (PTMG-g-PEG-CH2CH2CH2SO3-Na+) is expected to be very useful in attachment of potentially bioactive moieties to polymer via a hydrophilic PEG spacer.

THE COORDINATION BETWEEN SILVER NITRATE AND OPEN CHAIN POLYETHER

A complex of silver nitrate with 1.8-bis（8’-quinolyloxy）-3.6-dioxaoctane （noted as ligand L） was synthesized. The results of element analysis show that it consists of the calculated values of [Ag4L3]（NO3）4. It is clear from the IR, UV and ’HNMR spectra that the ligand L coordinated to Ag+ ion with its N and 0 atoms which connected with the terminal quinolyloxy group.

SYNTHESES OF POLYSTYRENE RESINS CONTAINING POLYETHER OLIGOMERS AND THEIR EXTRACTION FOR GOLD (Ⅲ)

Three polystyrene resins containing polyether oligomers as extractants were synthesized andtheir extraction properties were studied. Gold (III) ion could be extracted rapidly by the resins(T_(1/2),<lmin. )with high efficiency and capacity (for LS-B resin that were 99. 8% and 95. 8mg/gRrespectively) from aqueous solution but most of the co-existing metal ions such as Pd (II),Cu(II), Zn (II), Pb (II) and Cd (II) were remained. The extraction capacity and strippingpercentage for gold (III) remained unchanged in four extraction-stripping cycles. The resins also showed good column extraction-elution properties.

IONIC CONDUCTIVITY IN THE COMPLEXES OF COMB-SHAPED POLYETHER WITH LITHIUM AROMATIC SULFONATE

Complexes of comb-shaped polyether and lithium aromatic sulfonates bearing different negative charge number were prepared by in situ thermal polymerization. Their conductivity depends deeply on salt content, ambient temperature and negative charge number of the added salts. Results show that anions can be partly immobilized by increasing their negative charges at lower temperature. Against discharge time the short circuit current of the battery (Li/complex film/Li_x V_3O_8) is stabilized by increasing the anionic charge number of the complex.

ION CONDUCTION IN COMPLEX OF ACRYLONITRILE-COPOLYMERIZED COMB POLYETHER WITH LITHIUM PERCHLORATE

Poly (oligoether methacrylate-co-acrylonitrile) s, P (MEOn- AN), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of polymer structure. At proper copolymer composition, lithium concentration and pendant length, the ion conductivity reaches 7.0×10^(-5)S/cm at ambient temperature, together with improved mechanical strength. The ion transport in the polymer media is assisted by segmental relaxation, which is confirmed both by the consistency between ion conductivity and T_g and by the study of TSC.

IONIC CONDUCTIVITIES OF SEGMENTED POLYETHER POLYURETHANEUREA COMPLEXES WITH LiClO_4

Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10^(-4) S·cm^(-1) at 353K and～1.0×10^(-5)S·cm^(-1) at 306K were achieved. The ionic conductivity data were analyzed using the VTF (Vogel-Tamman-Fulcher) equation and WLF (Williams-Landel-Ferry) type equation. Values have been estimated for the 'apparent' activation energies of ion transport from VTF equation and they lie in the range 2.70—5.53 kJ·mol^(-1).

TEMPERATURE—DEPENDENCE OF CARRIER ION NUMBER IN SOLID POLYETHER MEDIA

The temperature—dependence of cationic conductivity,mobility and carrier generation in the blend of macromolecular lithium salt and copoly- ether were investigated.The population of free—ions was found to decrease exponentially with rising temperature.However,this“anomalous”behavior of salt—dissociation has little effect on the temperature—dependence of con- ductivity,since it is ion mobility rather than carrier ion number which predominates ion transport process.

Synthesis and Characterization of EO/PO Random Copolyethers

Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.

CATIONIC CONDUCTION IN BLEND COMPLEX OF LITHIUM METHOXY OLIGO (OXYETHYLENE) SULFATE AND COMBLIKE POLYETHER

Two kinds of lithium methoxy oligo(oxyethylene) sulfate LiSAEO_8 and LiSAEO_(12) were synthesized. The blend complexes of the salts with P(MEO_(16)—AM) show high cationic conductivity, the transference numbers of lithium ion(t_+)in [P(MEO_(16)—AM)/LiSAEO_8] and [-P(MEO_(16)—AM)/LiSAEO_(12)] are 0.93 and 0.98 at 50℃, and their ambient conductivities are 1.4×10^(-5)/cm and 7.7×10^(-6)S/cm respectively.