Sulfonated fluorinated multi-block copolymer hybrid containing sulfonated(poly ether ether ketone) and graphene oxide: A ternary hybrid membrane architecture for electrolyte applications in proton exchange membrane fuel cells

A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTALLINE MULTI-BLOCK COPOLYMERS,POLY[1,6-BIS(4-OXYBENZOYL-OXY)HEXANE TEREPHTHALATE]-b-BISPHENOL A POLYCARBONATE

A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chloride terminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.

PHASE STRUCTURE AND THERMAL BEHAVIOR OF LIQUID CRYSTALLINE MULTI-BLOCK COPOLYMERS,POLY[1,6-BIS(4-OXYBENZOYL-OXY)HEXANE TEREPHTHALATE]-b-BISPHENOL A POLYCARBONATE

Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 were synthesized in tetrachloroethane at 144 similar to 146 degrees C. The influence of segment length on the resulting phase structure and thermal behavior of block copolymers was also discussed. It is demonstrated by TEM and DMA that the resulting block copolymers show a considerable microphase separation. The degree of phase separation and the thermal behavior of the block copolymers are strongly dependent on the molecular weight of the segments incorporated.

Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Influence ofβ-nucleating Compound Agents on the Mechanical Properties and Crystallization Behavior of Polypropylene Random Copolymer

A novel polypropylene random(PPR)composite materials with optimized properties was developed by addingβ-nucleating compound agents(rare earth complex WBG-2 and aryl amide derivative TMB-5)and ternary compound modifier(TPE/WBG-2/CaCO_(3)).The effects of differentβ-nucleating agents and ternary compound modifier on the mechanical properties and crystallization behavior of PPR were analyzed.The results show that,compared with pure PPR materials,both WBG-2 and TMB-5 could significantly improve the impact strength of PPR.The crystallization temperature of PPR increased with the addition ofβ-nucleating agent.The modified PPR prepared with ternary compound modifier showed the most excellent comprehensive properties.

Research on the Marine Antifouling Ability and Mechanism of Acrylate Copolymers and Marine Coatings Based on a Synergistic Effect

Marine biofouling is an urgent global problem in the process of ocean exploitation and utilization.In our work,a series of zinc-based acrylate copolymers(ACZn-x)were designed and synthesized using benzoic acid,zinc oxide(ZnO)and a random quaternion copolymer consisting of ethyl acrylate(EA),butyl acrylate(BA),acrylic acid(AA)and methacrylic acid(MAA)by free radical polymerization and dehydration condensation.The ACZn-x with a zinc benzoate side chain is able to hydrolyze in natural seawater under static conditions,resulting in the formation of a smooth surface.We investigated and confirmed the antifouling(AF)behavior of ACZn-x in the laboratory and revealed that they have better antibacterial(86%for S.aureus and 72%for E.coli)and anti-algal(≥60.1%for N.closterium and≥67.5%for P.subcordiformis)activities.We also assessed the marine AF properties of ACZn-x and corresponding coatings in Qingdao,China;the ACZn-x exhibited ideal AF properties with little silt and biological mucosa adhered to the ACZn-x surface after 6 months,and corresponding coatings exhibited little biofouling after 16 months in the ocean.Importantly,possible AF mechanisms were further proposed at the cellular level.These results could be helpful for the development and application of effective AF coatings.

Highly efficient organic solar cells with improved stability enabled by ternary copolymers with antioxidant side chains

The stability of organic solar cells(OSCs)remains a major concern for their ultimate industrialization due to the photo,oxygen,and water susceptibility of organic photoactive materials.Usually,antioxidant additives are blended as radical scavengers into the active layer.However,it will induce the intrinsic morphology instability and adversely affect the efficiency and long-term stability.Herein,the antioxidant dibutylhydroxytoluene(BHT)group has been covalently linked onto the side chain of benzothiadiazole(BT)unit,and a series of ternary copolymers D18-Cl-BTBHTx(x=0,0.05,0.1,0.2)with varied ratio of BHT-containing side chains have been synthesized.It was found that the introduction of BHT side chains would have a negligible effect on the photophysical properties and electronic levels,and the D18-Cl-BTBHT0.05:Y6-based OSC achieved the highest power conversion efficiency(PCE)of 17.6%,which is higher than those based active layer blended with BHT additives.More importantly,the unencapsulated device based on D18-Cl-BTBHTx(x=0.05,0.1,0.2)retained approximately 50%of the initial PCE over 30 hours operation under ambient conditions,significantly outperforming the control device based on D18-Cl(90%degradation in PCE after 30 h).This work provides a new structural design strategy of copolymers for OSCs with simultaneously improved efficiency and stability.

Synthesis and Characterization of Multi-block(β)±butyrolactone(BL)-ethylene Oxide(EO) Copolymer

ＳｙｎｔｈｅｓｉｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＭｕｌｔｉ－ｂｌｏｃｋ（β）±ｂｕｔｙｒｏｌａｃｔｏｎｅ（ＢＬ）－ｅｔｈｙｌｅｎｅＯｘｉｄｅ（ＥＯ）ＣｏｐｏｌｙｍｅｒＣＨＥＮＸｉａｎ－ｈａｉ（ＮＳＦＢｉｏｄｅｇｒａｄａｂｌｅＰｏｌｙｍｅｒ...

Copolymer 1保护高眼压大鼠视神经的免疫学机制

目的探讨Copolymer 1(Cop 1)对实验性高眼压性青光眼视神经保护作用的相关免疫学机制。方法对27只大鼠采用烧灼巩膜上静脉制作双眼高眼压模型,在眼压升高的第3周,取12只模型大鼠于后脚皮内注射100μg Cop 1和等体积的完全弗氏佐剂(CFA)混合乳化液(实验组);另取12只模型大鼠作为对照组,后脚皮内注射等体积PBS和CFA的混合乳化液;其余3只模型大鼠作为空白对照组,不做任何处理。1周后取出大鼠脾淋巴细胞,采用流式细胞仪检测T细胞亚群的变化;ELISA法检测T细胞分泌细胞因子的变化;[3H]thymidine标记检测淋巴细胞的增殖。结果实验组大鼠的CD4+CD25+Treg/CD4+比值显著高于对照组和空白对照组(P<0.05)。实验组IL-10分泌量和分泌浓度均显著高于对照组和空白对照组,差异有统计学意义(P<0.05),但三组间INF-γ分泌量和分泌浓度比较差异均无统计学差异(P>0.05)。三组间体外刺激淋巴细胞指数比较差异无统计学意义(P>0.05)。结论 Cop 1能诱导CD4+CD25-向CD4+CD25+Treg转化,促进Th1转化为Th2,并增加IL-10的分泌。

Copolymer1保护视神经的作用及作用机制

Copolymer1(Cop1)是美国FDA批准的一种用于治疗多发性硬化的多聚肽类药物。许多实验用Cop1免疫动物,发现Cop1对钳伤和高眼压造成的视神经损伤有保护作用。我们对Cop1作用的免疫学机制的研究进展进行综述。

Synthesis and Flocculation Property of Chitosan-Acrylamide Graft Copolymer

Chitosan, as a kind of natural polymer, has many advantages, such as abundant sources, biological degradation, no secondary contamination and facile modification. In this work, we prepared modified chitosan flocculants with double electrical behavior via polymerizing chitosan, acrylamide and sodium carboxymethyl cellulose together by using ammonium persulfate as the indicator in water. The product is a comb-type of chitosan copolymer and a polymeric ampholyte. And then we studied the product by FTIR, UV-Vis, TG, DSC spectrometeries and viscometry, etc. We also performed CACM′s water treat experiment. The effects of pH values, reaction time and dose of the new floccalant on treating various of waste water have been investigated, too.

Synthesis and application of lignin-based copolymer LSAA on controlling non-point source pollution resulted from surface runoff

In this article,alkali lignin separated from paper pulp waste was grafted into a novel copolymer LSAA (a copolymer of lignin,starch, acrylamide,and acrylic acid).Its practical application effect and environmental safety were studied.The results of field simulation experiment indicated that the application of LSAA significantly affected the output of the runoff and pollutants.The runoff quantity was decreased by 16.67%-47.00%and the loads of total suspended solids (TSS),chemical oxygen demand (COD),total nit...

Rapid synthesis of biodegradable poly(epsilon-caprolactone-co-p-dioxanone) random copolymers under microwave irradiation

Biodegradable poly(epsilon-caprolactone-co-p-dioxanone)(PCDO) random copolymers have been synthesized by ring-opening polymerization of epsilon-caprolactone(CL) and p-dioxanone(PDO) under microwave irradiation.The effects of irradiation time and different CL/PDO molar feed ratios on the microwave-assisted ring-opening polymerization(MROP) of PCDO have been discussed.The resultant products were characterized by ~1H NMR,GPC and DSC.It was found that the polymerization was completed within 20 min at 140℃.In th...

Synthesis of new EVA graft copolymer and its pour point depressant performance evaluation for Daqing crude oil

EVA was widely used as the pour point depressant for waxy oil.In order to improve its effect,some graft copolymerization methods should be used to modify EVA's property.EVA has long side chains and nitrogen polar groups to enforce its adaptability and effect of waxy oil.The pure amine,maleicanhydride and their reaction product were tested using infrared spectra and the NMR spectral.The results show that when the modified EVA is added into oil,the wax deposits not only on the main chain but also on the side chains.And the polar groups have the function to avoid and resist the wax crystals connection each other to form the net.Using the reaction product of maleicanhydride and high carbonic amine(C12,C16,C18 amine) as the graft component,the toluene as the solvent and BPO as the initiator,the series of new EVA graft copolymer with special side chains are prepared under controlled condition.A series of cylmaleimide exist indeed in modified EVA and the highest grafted percentage is 18.8%.EVA-16,the new graft copolymer,is better than EVA about 3 ℃ more in depressant the pour-point of Daqing waxy crude oil.

A chlorinated copolymer donor demonstrates a 18.13% power conversion efficiency

The rapid development of low-bandgap(LBG)nonfullerene acceptors and wide-bandgap(WBG)copolymer donors in recent years has boosted the power conversion efficiency(PCE)of organic solar cells(OSCs)to the 18%level[1−21].The commercialization of OSCs is highly expected.However,critical issues like the cost and the stability also determine whether OSCs can enter the market or not[22].

Selective swelling of polysulfone/poly(ethylene glycol) block copolymer towards fouling-resistant ultrafiltration membranes

Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.

Copolymerization of Ethylene with Dicyclopentadiene Using a Constrained Geometry Cyclopentadienyl-phenoxytitanium Catalyst

The copolymerization of ethylene with dieyclopentadiene （DCP） in the presence of a constrained geometry tetramethylcyclopentadi-enyl-phenoxytitanium catalyst [ 2,4-＇ Bu2-6-（ 2,3,4,5-Me4 -Cp ） -PhO ] TICl2, combined with AI（ iBu）3/Ph3C^＋ B（ CsF5 ）4^- cocatalyst system was studied. The copolymers that were formed were characterized by ＇ H and ,3 C NMR, differential scanning calorimetry （ DSC）, SEM, and X-ray diffraction （XRD） analyses. The re- suits of the analysis indicate that the copolymers of ethylene with dicyclopentadiene are amorphous and display two or more melting temperatures in their DSC diagrams. Moreover, the morphologies of the copolymers are quite different from that of polyethylenes.

Synthesis and Properties of a New Kind of High Performance Composite Resin Matrix-Poly (Aryl Ether Ketones)/Poly (Ether Sulfone) Block Copolymers

A new kind of high performance composite resin matrix PEEK/PES, PEEKK/PES block copolymers have been prepared from the corresponding oligomers via a nucleophilic aromatic substitution reaction. The different properties of the copolymers are investigated by differential scanning calorimetry (d. s. c), thermogravimetric analysis (t. g. a) and dynamic mechanical analysis (d. m. a). The results show that the relationship between Tg and the compositions of the copolymers approximately follows the formula 1/Tg=W1/Tg1 +W2/Tg2 for PEEKK/PES block copolymers, and Tg=Tg1W1 +Tg2W2 for PEEK/PES block copolymers. The PES content and the segment length of the copolymers have a significant influence on their melting point. The thermal properties and dynamic mechanical behaviour of the copolymers are also studied. The introduction of PES segment into the molecular main chain increases the glass transition temperature of poly aryl ether ketones and decreases their melting temperature, that is to say it decreases their melting processing temperature. The block copolymers keep the high temperature stability and solvent resistance of poly aryl ether ketones. They are expected to be a new kind of high performance composite resin matrix.

Comparison of selective flocculation of low grade goethitic iron ore fines using natural and synthetic polymers and a graft copolymer

This study aims to beneficiate low grade goethitic iron ore fines using a selective flocculation process. Selective flocculation studies were conducted using different polymers such as starch amylopectin(AP), poly acrylic acid(PAA), and a graft copolymer(AP-g-PAA). The obtained results were analyzed; they indicate the enhancement of the iron ore grade from 58.49% to 67.52% using AP-g-PAA with a recovery of 95.08%. In addition, 64.45% Fe with a recovery of 88.79% was obtained using AP. Similarly, using PAA, the grade increased to 63.46% Fe with a recovery of 82.10%. The findings are also supported by characterizing concentrates using X-ray diffraction(XRD) and electron probe microanalysis(EPMA) techniques.

IMPACT PROPERTIES OF METALLOCENE - CATALYZED ETHYLENE-α-OLEFIN COPOLYMERS

The impact properties of two selected metallocene-catalyzed ethylene-butene copolymers and one conventionalcopolymer were evaluated using Izod impact test. It is found that the metallocene-catalyzed copolymer shows superior impactproperties. This result was explained on the basis of the more homogeneous inter-molecular composition distribution andnarrower molecular weight distribution, which leads to more homogeneous morphology with fewer defects. Stepwisecrystallization improves the impact properties, especially in the crack propagation process, to a large extent. This is due to thedecrease of entanglements by stepwise crystallization, which is advantageous for the chain slip and shear. The polymer withheterogeneous intra-molecular composition distribution exhibits a more evident improvement of impact properties understepwise crystallization.