Construction of Two Coordination Polymers Based on Two New 5-Substitued Tetrazole-based Ligands: Structures and Luminescent Properties

Two new coordination polymers(CPs) based on two new tetrazole-based ligands, namely, [Cu(TPP)]n(HTTP = 4-(3-(2 H-tetrazol-5-yl)phenyl)pyridine, 1) and {[Cd_2(TBCA)_2(H_2O)_2]·-H_2O}n(H_2TBCA = 3?-(2 H-tetrazol-5-yl)biphenyl-4-carboxylic acid, 2), were synthesized via solvothermal reactions. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a(3,6)-connected rtl network topology based on binuclear secondary building units(SBUs). Compound 2 presents a 2D framework composed of 1D SUBs formed by both carboxyl and tetrazole groups. The 2D network is linked into a 3D framework via various hydrogen bonds. They represent two examples of CPs construct from rigid 5-substitued tetrazole-based ligands with relatively longer spacer. The thermal stabilities and luminescent properties of compounds 1 and 2 were also explored.

Flexible Bis(benzimidazole)-based Ligands Directed the Structure Characteristics of Coordination Polymers Based on Diphenic Acid Co-ligands:Syntheses, Structures and Properties

Two new coordination polymers [Cu_2(bbim)(dpa)_2(C_2H_5OH)_2](1), [Co(dpa)_2(bbbm)](2)(H_2dpa = diphenic acid, bbim = 1,1?-(1,6-hexanediyl)bis-1H-benzimidazole, bbbm = 1,1?-(1,4-butanediyl)bis-1 H-benzimidazole) constructed from bis(benzimidazole)-based ligands with different lengths and diphenic acid co-ligand have been synthesized under solvothermal conditions.Complex 1 possesses Cu-dpa helical chains. The adjacent chains are connected by the bbim ligands into two-dimensional(2D) 3-connected(63) topology. Differently, the layer structure of 2 was consisted by one-dimensional chains containing alternated 8-and 18-membered rings. Furthermore,the thermal stability and fluorescence property for all crystalline materials have been investigated.

STUDY ON AB-CROSSLINKED POLYMERS Ⅰ. THE SYNTHESIS AND MECHANICAL PROPERTIES OF AB-CROSSLINKED POLYMERS BASED. ON PU/PS

The AB-crosslinked polymers (i.e. ABCP) with polystyrene as chain A and vinyl group blocked prepolymers of polyurethanes (PU) as chain B were synthesized and studied. The results of dynamic mechanical spectrometry (DMS) show that the compatibility between the components A and B can be improved greatly through chemical crosslinking during the formation of ABCPs. This effect is especially pronounced when short chain prepolymers is chosen as one of the components. It is apparent that the degree of crosslinking between the two components plays a major role in determining their compatibility. Copolymerizafion of styrene with maleic anhydride in chain A can improve the compatibility and broaden the damping temperature range. Mechanical properties of the sythesized ABCPs were also studied.

Heat Resistant Fluorenone-based Polyimines as Novel Light-emitting Polymers

Fluorenone-based polyamines, as novel light-emitting polymers, were synthesized by the condensation polymerization of 3,6-dibromo-9-fluorenone with different aromatic diamines by palladiumcatalyzed aryl amination reaction. The structures of the polymers were characterized by means of FT-IR, 1H NMR spectroscopy and elemental analysis. The experimental results show a good agreement with the proposed structures. TGA measurement exhibits that the polymers possess good thermal stabilities with high decomposition temperatures（T5 400 ℃）. Due to the photo-induced intramolecular charge-transfer（ICT） of fluorenone-based polyimines, these polymers show significantly strong photonic luminescence in N,Ndimethylacetamide.

A Review of Vegetable Oil-Based Polymers: Synthesis and Applications

The reviewed work addressed the shift in focus from conventional polymers to bio-based and renewable polymers. The environmental attributes of the renewable polymers make them preferred choice of matrix. The properties of the matrices from renewable origin could compete in high end applications. The composition of the fatty acids in plant seed oil was discussed and the determination of the level of unsaturation used the iodine value. This review also extensively discussed the values of various fatty acid components present in the oils. Areas of application of the thermosetting polymers obtained from plant seed oils were also discussed.

Construction of coal pitch-based HA-K grafted poly condensates and their excellent anti-temperature and viscosity-reducing properties

Humic acids(HAs)are widely used as filtrate and viscosity reducers in drilling fluids.However,their practical utility is limited due to poor stability in salt resistance and high-temperature resistance.Hightemperature coal pitch(CP)is a by-product from coal pyrolysis above 650℃.The substance's molecular structure is characterized by a dense arrangement of aromatic hydrocarbon and alkyl substituents.This unique structure gives it unique chemical properties and excellent drilling performance,surpassing traditional humic acids in drilling operations.Potassium humate is prepared from CP(CP-HA-K)by thermal catalysis.A new type of high-quality humic acid temperature-resistant viscosity-reducer(Graft CP-HA-K polymer)is synthesized with CP-HA-K,hydrolyzed polyacrylonitrile sodium salt(Na-HPAN),urea,formaldehyde,phenol and acrylamide(AAM)as raw materials.The experimental results demonstrate that the most favorable conditions for the catalytic preparation of CP-HA-K are 1 wt%catalyst dosage,30 wt%KOH dosage,a reaction temperature of 250℃,and a reaction time of 2 h,resulting in a maximum yield of CP-HA-K of 39.58%.The temperature resistance of the Graft CP-HA-K polymer is measured to be 177.39℃,which is 55.39℃ higher than that of commercial HA-K.This is due to the abundant presence of amide,hydroxyl,and amine functional groups in the Graft CP-HA-K polymer,which increase the length of the carbon chains,enhance the electrostatic repulsion on the surface of solid particles.After being aged to 120℃ for a specified duration,the Graft CP-HA-K polymer demonstrates significantly higher viscosity reduction(42.12%)compared to commercial HA-K(C-HA-K).Furthermore,the Graft CP-HA-K polymer can tolerate a high salt concentration of 8000 mg.L-1,measured after the addition of optimum amount of 3 wt%Graft CP-HA-K polymer.The action mechanism of Graft CP-HA-K polymer on high-temperature drilling fluid is that the Graft CP-HA-K polymer can increase the repulsive force between solid particles and disrupt bentonite's reticulation structure.Overall,this research provides novelty insights into the synthesis of artificial humic acid materials and the development of temperature-resistant viscosity reducers,offering a new avenue for the utilization of CP resources.

Electrochemical Performance of Nickel Hydroxide/Activated Carbon Supercapacitors Using a Modified Polyvinyl Alcohol Based Alkaline Polymer Electrolyte

Polyvinyl alcohol （PVA）-sodium polyacrylate （PAAS）-KOH-H2O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method. Polymer Ni（OH）2/activated carbon （AC） hybrid supercapacitors with different electrode active material mass ratios （positive to negative） were fabricated using this alkaline polymer electrolyte, nickel hydroxide positive electrodes, and AC negative electrodes. Galvanostatic charge/ discharge and electrochemical impedance spectroscopy （EIS） methods were used to study the electrochemical performance of the capacitors, such as charge/discharge specific capacitance, rate charge/discharge ability, and charge/discharge cyclic stability. Experimental results showed that with the decreasing of active material mass ratio m（Ni（OH）2）/m（AC）, the charge/discharge specific capacitance increases, but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.

Double-layer Modifi cation of Water-based Aluminum with SiO2 and Polyacrylic Acid by Solgel Process and in situ Polymerization

A double-layer aluminum consisting of an aluminum core and a shellof SiO2 and polyacrylic acid was synthesized.This modified aluminum was used to improve the corrosion resistance and dispersive property of aluminum in waterborne media.TEM,FTIR,XPS,and EDX determination showed that PAA and SiO2 were coated on the surface of aluminum.Evolved hydrogen detection showed that the corrosion resistance of composite particle had been markedly improved.Maximum corrosion inhibition efficiency of SiO2 coated aluminum（SiO2@Al）was 95.1% while that of double-layer coated aluminum（PAA/SiO2@Al）was 98.8%.Meanwhile,polyacrylic acid layer improved the agglomeration of aluminum significantly.According to the dispersibility test,the particle size of 50% volume fraction [d（0.5）] of aluminum,SiO2@Aland PAA/SiO2@Alwere 42,53,and 34 μm,respectively.

PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4'-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4＇-methylenebis（cinnamaldehyde）ethylenediimine] （PMBCen）, poly[4,4＇- methylenebis（cinnamaldehyde）1,2-propylenediimine] （PMBCPn）, poly[4,4＇-methylenebis（cinnamaldehyde）1,3-propylenediimine] （PMBCPR）, poly[4,4＇-methylenebis（cinnamaldehyde） 1,2-phenylenediimine] （PMBCPh）, poly[4,4＇-methylenebis（cinnamaldehyde）meso-stilbenediimine] （PMBCS）, poly[4,4＇-methylenebis（cinnamaldehyde）urea] （PMBCUR）, poly[4,4＇- methylenebis（cinnamaldehyde）semicarbazone] （PMBCSc）, poly[4,4＇-methylenebis（cinnamaldehyde）thiosemicarbazone] （PMBCTSc） and poly[4,4＇-methylenebis（cinnamaldehyde）hydrazone] （PMBCH） were formed by polycondensation of 4,4＇- methylenebis（cinnamaldehyde） with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and ^1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.

Polymerization of Norbornene via an Iron-Based Complex/MAO Catalytic System

Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.

Performance and Stability of Polymer Solar Cells Based on the Blends of Poly(3-Hexylthiophene) and Indene-C_(60) Bis-Adduct

The performance and morphology stability of polymer bulk heterojunetion solar cells based on poly（3-hexylthiophene） （P3HT） as the donor and indene-C6o bisadduct （ICBA） or methanofullerene [6,6]-phenyl C61-butyric acid methyl ester （PCBM） as the aeceptor are compared. Effect of the different donor and aeeeptor weight ratios on photo- voltaic performance of the P3HT：ICBA device is studied. The optimal device achieved power conversion emeiency of 5.51~o with dso of l0.86mA/cm2, Voc of 0.83 V, and fill factor （FF） of 61.1 % under AM 1.5G （lOOmW/cm2） simulated solar illumination. However, the stability measurement shows that cells based on P3HT：ICBA are less stable than those of the device based on P3HT：PCBM. Atomic force microscope results reveal that the morphol- ogy of the P3HT：ICBA film changed considerably during the storage periods due to unstable interpenetrating D-A network. This observation can be explained by the fact that there is lack of intermolecular hydrogen bonds in the P3HT：ICBA system. However, in the P3HT：PCBM system the molecules in the blend film are firmly held together in the solid state by means of intermoleeular hydrogen bonds originating from C-H. ~. Os bonds （where Os comes from the singly-bonded 0 atom of PCBM）, forming a stable three-dimensional network. The measured PL decay lifetimes for P3HT：PCBM and P3HT：ICBA systems are 33.66 ns and 35.34 ns, respectively, indicating that the P3HT：ICBA system has a less efficient exciton separation eftleiency than that of P3HT：PCBM, which may result in the interracial photogenerated charges accumulated on the D： A interface. Such progressive phase segregation between P3HT and ICBA eventually leads to the degradation in performance and deteriorates the stability of the device. We also present an approach to enhance the stability of P3HT：ICBA systems by adding PCBM as the second acceptor. Our results show that by carefully tuning the contents of PCBM as the second acceptor, more stable polymer solar cells can be obtained.

Poly (N-Isopropyl Acrylamide-<i>Co</i>-Vanillin Acrylate) Dual Responsive Functional Copolymers for Grafting Biomolecules by Schiff’s Base Click Reaction

This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.

Humanoid Based Intelligence Control Strategy of Plastic Cement Die Press Work-Piece Forming Process for Polymer Plastics

The plastic cement belongs to a sort of polymer material, the chemical composition is very complex, and the plastic cement work-piece is generally manufactured by die press forming. Aimed at being difficult to control in parameters of forming process, the paper explored the humanoid based intelligence control strategy. In the paper, it made the anatomy in control puzzle resulted in uncertainty such as chemical component of plastic cement etc., summarized up the characteristic of cybernetics in forming process, researched on the humanoid based intelligence control strategy, and constructed the control algorithm of forming process in plastic cement work-piece. Taking the process experiment of temperature and pressure control as an example, it validated the good dynamic and static control quality through simulation of control algorithm constructed in this paper. The experimental results show that the control algorithm explored in this paper is reasonably available.

Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

SYNTHESIS AND CHARACTERIZATION OF NOVEL BIPOLAR PPV-BASED COPOLYMER CONTAINING TRIAZOLE AND CARBAZOLE UNITS

Two new blue light-emitting PPV-based conjugated copolymers containing both an electron-withdrawing unit (triazole-TAZ) and electron-rich moieties (carbazole-CAR and bicarbazole-BCAR) were prepared by Wittig condensation polymerization between the triazole diphosphonium salt and the corresponding dialdehyde monomers. Their structures and properties were characterized by FT-IR, TGA, DSC, UV-Vis, PL spectroscopy and electrochemical measurements. The resulting copolymers are soluble in common organic solvents and thermally stable with a T-g of 147degreesC for TAZ-CAR-PPV and of 157degreesC for TAZ-BCAR-PPV. The maximum photoluminescence wavelengths of TAZ-CAR-PPV and TAZ-BCAR-PPV film appear at 460 nm and 480 nm, respectively. Cyclic voltammetry measurement demonstrates that TAZ-BCAR-PPV has good electrochemical reversibility, while TAZ-CAR-PPV exhibits the irreversible redox process. The triazole unit was found to be an effective pi-conjugation interrupter and can play the rigid spacer role in determining the emission colour of the resulting copolymer.

One New Zinc Coordination Polymer Based on 2-Chloro-benzoate and 4,4'-Bipyridine: Synthesis, Crystal Structure and Luminescence

A Zn-based coordination polymer [Zn（2-cb）2（4,4′-bpy）0.5]n （1, 2-cb = 2-chloro- benzoate, 4,4＇-bpy = 4,4′-bipyridine） was prepared by hydrothermal synthesis using 2-chloro- benzoic acid and 4,4′-bipyridyl as ligands. The compound was characterized by elemental analysis, IR, TGA, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group PI with a = 8.0471（5）, b = 9.7338（6）, c = 11.7830（7） A, a = 96.2230（10）, β = 92.542（2）, γ = 103.7560（10）°, V = 888.84（9） A3, Z = 2, Mr = 454.57, Dc = 1.698 g/cm3,μ（MoKa） = 1.708 mm.1, F（000） = 458, the final R = 0.0359 and wR = 0.0936 for 3167 observed reflections with I 〉 2σ（I）. The crystal analysis indicates that 1 exhibits a 1-D chain structure constructed by 4,4′-bpy and a dicaryon secondary-building-unit of [Zn2（2-cb）4]. Luminescence analysis revealed that compound 1 emits blue fluorescence with a fluorescence lifetime of 55.03 ns.

Model for a UV Laser Based Local Polymer Surface Halogenation Process Using a Gaseous Precursor

An analytical model describing the physical relations of a UV-based process for halogenation of polymeric surfaces is presented. The process allows, depending on the parameters, a local halogenation with sharp edges at the interfaces to areas where no halogenation is desired. This is achieved via a nonreactive halogen-containing gaseous precursor and a UV source providing photons which dissociate the precursor photolytically. Thus, only where the UV photons affect the precursor, halogens are generated and the polymer is being halogenated.

Effect of Polymer-based Grinding Aid on Sulfate Attacking Resistance of Concrete

Influences of polymer-based grinding aid（PGA） on the damage process of concrete exposed to sulfate attack under dry-wet cycles were investigated. The mass loss, dynamic modulus of elasticity（Erd）, and S and Ca element contents of concrete specimens were measured. Scanning electron microscopy（SEM）, mercury intrusion porosimetry（MIP）, and X-ray diffractometry（XRD） were used to investigate the changing of microstructure of interior concrete. The results indicated that PGA was capable of reducing the mass loss and improving the sulfate attack resistance of concrete. X-ray fluorescence（XRF） analysis revealed that PGA delayed the transport process of sulfate ions and Ca ions. In addition, MIP analysis disclosed that the micropores of concrete with PGA increased in the fraction of 20-100 nm and decreased in the residues of 200 nm. Compared with the blank sample, concrete with PGA had more slender and well-organized hydration products, and no changes in hydration products ratio or type were observed.

A New 3D Pb(Ⅱ) Coordination Polymer [Pb(L)]_n Based on a Long Flexible Octane-1,8-dicarboxylic Acid:Crystal Structure and Physical Properties

A new Pb（II）-based coordination polymer, [Pb（L）]n （1）, was hydrothermally synthesized and its structure was determined by single-crystal X-ray diffraction （H2L = octane- 1,8-dicarboxylic acid）. Compound 1 crystallizes in orthorhombic, space group Pnma with a = 32.061（4）, b = 7.2597（8）, c = 4.8084（5） A, V= 1119.2（2） A3, Z = 4, C10H1604Pb, Mr = 407.42, Dc = 2.418 g/cm3, F（000） = 760, μ（MoKa） = 15.066 mm-1, R = 0.0270 and wR = 0.0666. In 1, each Pb（II） cation is coordinated by six carboxylate oxygen atoms from four L2- anions. Each L2- anion bridges three Pb（ll） atoms in a μ3：η2：η1：η1 mode to form a 3D framework. The structure of 1 was characterized by IR spectrum and thermogravimetric analysis. Moreover, solid state luminescent property of 1 was also investigated.