CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅰ.POLY(P-PHENYLENE TEREPHTHALATE)

The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.

4天香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响

目的:探讨短期香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响。方法:BALB/c小鼠随机分为4组:对照组、熏烟组、poly(I:C)组和熏烟联合poly(I:C)组。检测支气管肺泡灌洗液(BALF)中总细胞数及细胞分类计数;普通光镜下观察各组细胞形态;荧光定量PCR检测肺组织细胞因子、趋化因子和干扰素及干扰素刺激基因表达。结果:与对照组相比,熏烟联合poly(I:C)组总细胞数计数、巨噬细胞与中性粒细胞计数明显升高(P<0.05),且熏烟联合poly(I:C)组巨噬细胞计数高于poly(I:C)组;与poly(I:C)组比较,熏烟联合poly(I:C)组小鼠气道灌洗液巨噬细胞体积较大,呈圆形或不规则形,细胞质较多空泡;与对照组相比,熏烟联合poly(I:C)组小鼠肺组织中性粒细胞趋化因子CXCL1(P<0.05)、CXCL2(P<0.01)和淋巴细胞趋化因子CCL2(P<0.01)mRNA表达升高,肺组织IL-1β、IL-6、TNF-αmRNA表达明显升高(P<0.01),肺组织IFN-β(P<0.01)、IFN-γ(P<0.05)、MX2(P<0.01)和IP-10(P<0.01)表达显著升高,且与poly(I:C)组小鼠相比,熏烟联合poly(I:C)组小鼠肺组织CXCL2(P<0.05)、TNF-α(P<0.01)和IFN-β(P<0.05)mRNA表达明显升高。结论:熏烟联合poly(I:C)诱导了小鼠肺部炎症反应和干扰素及干扰素刺激基因表达。同时,香烟暴露加剧了poly(I:C)诱导的小鼠肺部急性炎症反应和Ⅰ型干扰素表达。

Effect of Added Poly (vinyl pyrrolidone) during Condensation on Properties of Poly(p-phenylene terephthalamide)Pulp

Poly(p-phenylene terephthalamide)(PPTA)pulp was prepared by polycondensation of the p-phenylene diamine(PPDA)with terephthaloyl chloride(TPC)in the completely anhydrous solvent system of N-methyl pyrrolidone(NMP)having calcium chloride,in the presence of poly(vinyl pyrrolidone)(PVP)having a viscosity average molecular weight lower than 40 000.It was confirmed that the polycondensation could be accelerated,the inherent viscosity of the polymer could be increased,and the polymers could be fibrillated more easily by the addition of the PVP.FTIR and X-ray spectra proved that PVP had not combined into molecular chains of the resultant PPTA pulps.The morphology of the resultant pulps,the effect of viscosity average molecular weight,amount and adding mode of PVP on inherent viscosity,specific surface area,and mean length of the resultant pulps were discussed in detail.And the friction and wear properties of the compound reinforced by the resultant pulps were simply investigated.

Synthesis of Poly(p-phenyleneethynylene)s with Crosslinkable End or Side Groups and Its Solid State Structure and Optical Properties Before and after Crosslinking

Two crosslinkable poly（p-phenyleneethynylene）s（PPEs）： poly[2,5-di（2＇-ethyl-hexyloxy）-1,4-phenylenecthynylene] with end-capped vinyl（PPE1） and poly[2,5-di（allyloxy）-1,4-phenyleneethynylene-2,5-di（2＇-ethyl-hexyloxy）-1,4-phenyleneethynylene]（PPE2） were synthesized. Via the thermal addition reactions of vinyl end groups of PPE1 and allyloxy side groups of PPE2, crosslinked polymers C-PPE1 and C-PPE2 were obtained, respectively. The two polymers were characterized by wide-angle X-ray diffraction（WXRD）, ultraviolet-visible（UV-Vis） absorption, and photoluminescence（PL）. The results indicate that in the solid state, the polymer chains of PPE1 were packed with a low degree of crystallinity because of the sterically hindered（2＇-ethyl-hexyl）oxy branched side chains, but, because of the introduction of allyloxy side chains, the polymer chains of PPE2 were packed in an order fashion with a high degree of crystallinity. Because of the high crosslinking density in C-PPE2, the formation of aggregates and excimer was hampered by the formed crosslinking network more effectively in C-PPE2 film than in C-PPE1 film.

Preparation and characterization of eco-friendly poly(p-phenylenediamine) and its composite with chitosan for removal of copper ions from aqueous solutions

Poly(p-phenylenediamine)/chitosan (PPPDA/Chi) composite was prepared by in situ chemical oxidative polymerization of p-phenylenediamine (PPPDA) into chitosan (Chi) using ammonium persulphate (APS) as an oxidant. PPPDA and PPPDA/Chi composite were characterized by FT-IR spectra and SEM before and after copper loading. In batch adsorption method, the maximum removal of copper was experienced when 1 g/L of PPPDA and PPPDA/Chi composite dosages were used at pH 5.0 for PPPDA and 6.0 for PPPDA/Chi composite for 360 min for both sorbents. PPPDA showed adsorption capacity qemax of 650 mg/g whereas its composite achieved qemax of 573 mg/g. The experimental data correlate well with the Freundlich isotherm equation and the pseudo-second order kinetic model. The Cu(II), loaded PPPDA and its composite can be efficiently reused for as many as four cycles. The Cu(II)-loaded sorbents showed high antibacterial efficiency against Gram-positive and Gram-negative bacteria than their unloaded forms.

Stable Cycling of All-Solid-State Lithium Metal Batteries Enabled by Salt Engineering of PEO-Based Polymer Electrolytes

Poly(ethylene oxide)(PEO)-based polymer electrolytes show the prospect in all-solid-state lithium metal batteries;however,they present limitations of low room-temperature ionic conductivity,and interfacial incompatibility with high voltage cathodes.Therefore,a salt engineering of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium salt(LiHFDF)/LiTFSI system was developed in PEO-based electrolyte,demonstrating to effectively regulate Li ion transport and improve the interfacial stability under high voltage.We show,by manipulating the interaction between PEO matrix and TFSI^(-)-HFDF^(-),the optimized solid-state polymer electrolyte achieves maximum Li+conduction of 1.24×10^(-4)S cm^(-1)at 40℃,which is almost 3 times of the baseline.Also,the optimized polymer electrolyte demonstrates outstanding stable cycling in the LiFePO_(4)/Li and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li(3.0-4.4 V,200 cycles)based all-solid-state lithium batteries at 40℃.

Flexible and Robust Functionalized Boron Nitride/Poly(p‑Phenylene Benzobisoxazole)Nanocomposite Paper with High Thermal Conductivity and Outstanding Electrical Insulation

With the rapid development of 5G information technology,thermal conductivity/dissipation problems of highly integrated electronic devices and electrical equipment are becoming prominent.In this work,“high-temperature solid-phase&diazonium salt decomposition”method is carried out to prepare benzidine-functionalized boron nitride(m-BN).Subsequently,m-BN/poly(pphenylene benzobisoxazole)nanofiber(PNF)nanocomposite paper with nacremimetic layered structures is prepared via sol–gel film transformation approach.The obtained m-BN/PNF nanocomposite paper with 50 wt%m-BN presents excellent thermal conductivity,incredible electrical insulation,outstanding mechanical properties and thermal stability,due to the construction of extensive hydrogen bonds andπ–πinteractions between m-BN and PNF,and stable nacre-mimetic layered structures.Itsλ∥andλ_(⊥)are 9.68 and 0.84 W m^(-1)K^(-1),and the volume resistivity and breakdown strength are as high as 2.3×10^(15)Ωcm and 324.2 kV mm^(-1),respectively.Besides,it also presents extremely high tensile strength of 193.6 MPa and thermal decomposition temperature of 640°C,showing a broad application prospect in high-end thermal management fields such as electronic devices and electrical equipment.

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅱ. POLY(p-PHENYLENE 2,6-NAPHTHALATE)

Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that "curled up" off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius^2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm^3, space group P12_1/al.

Mechanical Property and Crystal Structure of Poly(p-phenylene terephthalamide)(PPTA) Fibers during Heat Treatment under Tension

The relationship between property and structure of poly( p-phenylene terephthalamide)( PPTA) was investigated for the purpose of obtaining products with better performance. PPTA fiber subjected to heat treatment under different conditions was intensively studied. Simultaneous wide-angle X-ray diffraction( WAXD) technique was introduced to study the changes of crystal structure. It was found that the tensile modulus was strongly sensitive to the levels of temperature and tension. The structure parameters including crystal size and crystal orientation after heat treatment evolve similarly to the tensile modulus,indicating a direct structure-property relationship. The lattic c-dimension increases after heat treatment and is greatly affected by the tension. An optimal temperature can be found around 400 ℃,where big change can happen in the crystal structure due to α-relaxation in the crystal region as supported in dynamic mechanical analysis( DMA).

The Synthesis and Electronic Characteristics of Poly(p-Phenylene Vinylene) Derivatives

A series of soluble poly(p-phenylene vinylene) (PPV) derivatives were synthesized through dehydrochlorination with the p-metaoxy phenol as starting materials. The electronic characteristics of PPV derivatives were studied.

Study on the behaviors of poly（p-phenylene benzobisoxazole） in coagulation

Poly（p-phenylene benzobisoxazole）（PBO） is a candidate of high performance materials for many applications. PBO materials＇ properties are considered to be closely related to their fabrication process, especially coagulation. In this paper, the coagulation effect on the chemical and microstructure of PBO was investigated with the help of a PBO model compound, 2, 2＇-（ 1,4-phenylene） bis （5-amino-6-benzoxazolole）. During coagulation, the hetero-cyclic ring of the PBO structure was experienced cleavage and even being broken down completely under some extreme conditions. Wide-angle X-ray diffraction （WAXD） analysis showed that different coagulants could cause the microstructure difference in PBO materials. In a slow coagulation process, PBO molecular chains aligned more orderly in the side-by-side direction （200）.

SYNTHESIS,CHARACTERIZATION AND QUENCHING BEHAVIOR OF A CATIONIC POLY(p-PHENYLENEVINYLENE) RELATED COPOLYMER

A cationic poly(p-phenylene vinylene) related copolymer without bulky phenylene substitutents attached to the conjugated backbone was prepared through Wittig reaction.The molecular structure and optical properties were highly investigated through ~1H-NMR,UV and PL spectroscopy.The quenching behavior was also investigated,and the results demonstrate that incomplete quenching exists,which is consistent with the cationic poly(p-phenylene vinylene) related copolymer containing bulky phenylene substitutents,prob...

A STUDY OF PACKING STRUCTURE OF POLY(P-PHENYLENE BENZOBISTHIAZOLE)BY MOLECULAR SIMULATION

Molecular simulation technique was used in an examination of the possibilities of chain packing in the crystalline state for poly(ρ-phenylene benzobisthiazole).It has been found that one reason of hardly forming very ordered crystal of the polymer is the existence of so many stable positions of interchain interaction along chain axis.

The Electroluminescence Characterization of Poly(p-phenyleneethynylene)——The π-conjugated Backbone Interrupted by a Butylene Unit

π -Conjugated poly( p -phenyleneethynylene) with the interruption of the conjugation by a butylene unit was synthesized. Its absorption, PL and EL spectra were investigated respectively. The spectral peaks shifted to the higher energy side with the interruption of the conjugation lengths. The model compound was synthesized, by which the results were proved. The thermal characteristics of the polymer was determined by DSC and TGA, indicating that the polymer has a good thermal stability. The electroluminescence(EL) in the green region of the spectrum with a maximum at 500 nm was observed from the polymer films sandwiched between indium-tin-oxide and an Al electrode.

Innovative approach to boosting the chemical stability of AZ31 magnesium alloy using polymer-modified hybrid metal oxides

Meeting the demands of complex and advanced applications requires the development of high-performance hybrid materials with unique properties.However,the integration of polymeric frameworks with MgO/WO_(3) composite layers faces challenges due to the lack of understanding of the formation mechanism and the challenge of determining the impact of self-assembled architecture on anticorrosive properties.In this study,we aimed to enhance the corrosion resistance of the MgO layer produced by plasma electrolysis(PE)of AZ31 Mg alloy by incorporating WO_(3) with partially phosphorated poly(vinyl alcohol)(PPVA).Two types of porous MgO layers were produced using the PE process with an alkaline-phosphate electrolyte,one with and one without WO_(3) nanoparticles,which were subsequently immersed in an aqueous solution of PPVA.Incorporating PPVA into the WO_(3)-MgO layer resulted in hybrids being deposited in a fragmented manner,creating a“laminar reef-like structure”that sealed most of the structural defects in the layer.The PPVA-sealed WO_(3)-based coating exhibited superior corrosion resistance compared to the other samples.Computational analyses were employed to explore the mechanism underlying the formation of PPVA/WO_(3) hybrids on the MgO layer.These findings suggest that PPVA-WO_(3)-MgO hybrid coatings can potentially improve corrosion resistance in various fields.

PREPARATION AND CHARACTERIZATION OF SHISH-KEBAB TYPE LIQUID CRYSTALLINE POLY(p-PHENYLENEVINYLENE)

Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tributylstannyl） ethylene （monomer 2）. The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

Dual-salt poly(tetrahydrofuran) electrolyte enables quasi-solid-state lithium metal batteries to operate at -30 ℃

The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migration.Herein,we prepare a dual-salt poly(tetrahydrofuran)-based electrolyte consisting of lithium hexafluorophosphate and lithium difluoro(oxalato)borate(LiDFOB).The Li-salt anions(DFOB−)not only accelerate the ring-opening polymerization of tetrahydrofuran,but also promote the formation of highly ion-conductive and sustainable interphases on Li metal anodes without sacrificing the Li^(+)conductivity of electrolytes,which is favorable for Li^(+)transport kinetics at low temperatures.Applications of this polymer electrolyte in Li||LiFePO_(4)cells show 82.3%capacity retention over 1000 cycles at 30℃and endow stable discharge capacity at−30℃.Remarkably,the Li||LiFePO4 cells retain 52%of their room-temperature capacity at−20℃and 0.1 C.This rational design of dual-salt polymer-based electrolytes may provide a new perspective for the stable operation of quasi-solid-state batteries at low temperatures.

Efficient and selective upcycling of waste polylactic acid into acetate using nickel selenide

The conversion of waste polylactic acid(PLA)plastics into high-value-added chemicals through electrochemical methods is a promising and sustainable approach.However,developing efficient and highly selective catalysts for lactic acid oxidation reaction(LAOR)and understanding the reaction process are challenging.Here,we report the electrooxidation of waste PLA to acetate at a high current density of 100 mA cm-2 with high Faraday efficiency(~95%)and excellent stability(>100 h)over a nickel selenide nanosheet catalyst.In addition,a total Faraday efficiency of up to 190%was achieved for carboxylic acids,including acetic acid and formic acid,by coupling with the cathodic CO_(2) reduction reaction.In situ experimental results and theoretical simulations revealed that the catalytic activity center of LAOR was dynamically formed NiOOH species,and the surface-adsorbed SeO_(x) species accelerated the formation of Ni~(3+)species,thus promoting catalytic activity.The mechanism of lactic acid electrooxidation was further elucidated.Lactic acid was dehydrogenated to produce pyruvate first and then formed CH_3CO due to preferential C-C bond cleavage,resulting in the presence of acetate.This work demonstrated a sustainable method for recycling waste PLA and CO_(2) into high-value-added products.

TOPCon太阳电池背面叠层poly工艺的优化及其对电性能的影响

通过增加TOPCon太阳电池poly层中的磷掺杂浓度可以增强poly层与硅基底之间的钝化效果并提高poly层与金属电极间的接触能力,但过高的掺杂浓度会导致磷原子扩散到硅基底,破坏氧化层与硅基底之间的界面钝化效果。为了解决这一问题,提出在poly层中间增加一层薄的氧化层作为阻挡层(即叠层poly工艺,下文简称为“叠层工艺”)的方案,将原本单一的poly-Si磷掺杂进行双层分布,底层poly-Si轻掺杂,表层poly-Si重掺杂;对常规工艺和叠层工艺制备TOPCon的太阳电池进行对比试验后,进一步优化叠层工艺,调整中间氧化层厚度,并研究不同中间氧化层厚度的叠层工艺对TOPCon太阳电池电性能的影响。实验结果表明:1)叠层工艺可以提高TOPCon太阳电池的电性能;2)当中间氧化层厚度提升至1.5 nm时,太阳电池的光电转换效率达到最高值(25.66%)。但中间氧化层的厚度是一个需要精确控制的工艺参数,需找到最佳的厚度平衡点,以提高太阳电池性能。