PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATIONPRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.

Lithium bis(oxalate)borate crosslinked polymer electrolytes for high-performance lithium batteries

Solid electrolytes play a vital role in solid-state Li secondary batteries,which are promising high-energy storage devices for new-generation electric vehicles.Nevertheless,obtaining a suitable solid electrolyte by a simple and residue-free preparation process,resulting in a stable interface between electrolyte and electrode,is still a great challenge for practical applications.Herein,we report a self-crosslinked polymer electrolyte(SCPE)for high-performance lithium batteries,prepared by a one-step method based on 3-methoxysilyl-terminated polypropylene glycol(SPPG,a liquid oligomer).It is worth noting that lithium bis(oxalate)borate(Li BOB)can react with SPPG to form a crosslinked structure via a curing reaction.This self-formed polymer electrolyte exhibits excellent properties,including high roomtemperature ionic conductivity(2.6×10^(-4) S cm^(-1)),wide electrochemical window(4.7 V),and high Li ion transference number(0.65).The excellent cycling stability(500 cycles,83%)further highlights the improved interfacial stability after the in situ formation of SCPE on the electrode surface.Moreover,this self-formation strategy enhances the safety of the battery under mechanical deformation.Therefore,the present self-crosslinked polymer electrolyte shows great potential for applications in high-performance lithium batteries.

A crosslinked polymer as dopant-free hole-transport material for efficient n-i-p type perovskite solar cells

A new crosslinked polymer,called P65,with appropriate photo-electrochemical,opto-electronic,and thermal properties,has been designed and synthesized as an efficient,dopant-free,hole-transport material(HTM)for n-i-p type planar perovskite solar cells(PSCs).P65 is obtained from a low-cost and easily synthesized spiro[fluorene-9,90-xanthene]-30,60-diol(SFX-OH)-based monomer X65 through a freeradical polymerization reaction.The combination of a three-dimensional(3 D)SFX core unit,holetransport methoxydiphenylamine group,and crosslinked polyvinyl network provides P65 with good solubility and excellent film-forming properties.By employing P65 as a dopant-free hole-transport layer in conventional n-i-p type PSCs,a power conversion efficiency(PCE)of up to 17.7%is achieved.To the best of our knowledge,this is the first time a 3 D,crosslinked,polymeric dopant-free HTM has been reported for use in conventional n-i-p type PSCs.This study provides a new strategy for the future development of a 3 D crosslinked polymeric dopant-free HTM with a simple synthetic route and low-cost for commercial,large-scale applications in future PSCs.

SYNTHESIS OF POLYMERIC β-CYCLODEXTRIN SUPPORTED BY CROSSLINKED POLY(ACRYLAMIDE-co-VINYLAMINE)AND ITS CATALYSIS OF THE HYDROLYSIS OF p-NITROPHENYL ACETATE

Polymeric β-cyclodextrin (β-CD) supported by crosslinked poly(acrylamide-co-vinylamine) was synthesized as anartificial analog of hydrolytic enzyme and its catalysis of the hydrolysis of p-nitrophenyl acetate (p-NPA) was theninvestigated. The result showed that the polymer-supported β-CD could accelerate the hydrolytic reaction of p-NPA morequickly than β-CD itself and crosslinked poly(acrylamide-co-vinylamine) alone. The acceleration rate of the polymer-supported β-CD was about 10 times as fast as that of free β-CD in 0.01 mol/L phosphate buffer (pH 7.4) containing 32%DMSO at 37±0.1℃ when the molar amount of β-CD units in the polymer was equal to that of free β-CD in the experiments.The enhanced acceleration of thc polymer-supported β-CD should be ascribed to the cooperative contribution of theinclusion effect of β-CD ring and the nucleophilic effect of amino groups on the polymeric support.

STUDY ON CASTOR OIL POLYURETHANE/POLY (METHYL METHACRYLATE) AB CROSSLINKED POLYMERS

Castor oil polyurethane/poly(methyl methacrylate) AB crosslinked polymers (ABCP) were synthesized by free radical copolymerization of MMA and vinyl-terminated castor oil polyurethane which was obtained from isocyanate-terminated castor oil polyurethane and hydroxyethyl methacrylate The mechanical properties, transition and relaxation, as well as compatibility and morphology of the ABCP were investigated by changing the component. The results show that the ABCP is a semicompatible system and the compatibility of the two components decreases with increasing content of the hard segment. The mechanical and damping properties of the ABCP are obviously superior to that of their homopolymers. The damping value is mainly controlled by cross[ink density of the ABCP but the T-g value by component.

Thermo-and photo-driven soft actuators based on crosslinked liquid crystalline polymers

Crosslinked liquid crystalline polymers（CLCPs） are a type of promising material that possess both the order of liquid crystals and the properties of polymer networks.The anisotropic deformation of the CLCPs takes place when the mesogens experience order to disorder change in response to external stimuli; therefore,they can be utilized to fabricate smart actuators,which have potential applications in artificial muscles,micro-optomechanical systems,optics,and energyharvesting fields.In this review the recent development of thermo-and photo-driven soft actuators based on the CLCPs are summarized.

STUDY OF THE MOLECULAR MOTION AND COMPATIBILITY IN AB-CROSSLINKED POLYMER BASED ON POLYURETHANE AND POLYSTYRENE-co-ACRYLIC ACID BY SOLID STATE HIGH RESOLUTION NMR

The ^(13)C T_(1s) of --CH_3 side group in PPU/P (St-co-AA), AB-crosslinked polymers (i. e.ABCP) was studied by using high resolution solid state NMR. The rotation motion of --CH_3 sidegroup in PPU was analyzed by means of the average spectral density functions of internal rota-tion. The results showed that the rotation of the --CH_3 side group is related closely to the com-patibility between the two components. The compatibility was studied by analyzing the protonspin-lattice relaxation in rotating frame, spin-spin relaxation and spin-diffusion. The resultsshowed that the hydrogen bonds between the components play a major role in determining thecompatibility. Through spin diffusion studying, the soft phase domain size was calculated. Bystudying proton spin-spin relaxation, the content of each component in each phase and that ofeach phase in the samples can be obtained. The result shows that the content of interphase is related closely to the compatibility.

Crosslinked solubilizer enables nitrate-enriched carbonate polymer electrolytes for stable,high-voltage lithium metal batteries

High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density batteries.However,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium.N,N-dimethylacrylamide(DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate(LiNO3)in carbonate-based electrolytes and to form gel polymer electrolytes(GPEs)through in situ polymerization.The Lit solvation structure of the GPEs is regulated using LiNO3 and DMAA,which suppresses the decomposition of LiPFe and facilitates the formation of an inorganic-rich solid electrolyte interface.Consequently,the Coulombic efficiency(CE)of the LillCu cell assembled with a GPE increases to 98.5%at room temperature,and the high-voltage LillNCM622 cell achieves a capacity retention of 80.1%with a high CE of 99.5%after 400 cycles.The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.

CALCULATION OF MOLECULAR INTERNAL ROTATING STERIC FACTOR OF FLUOROPOLYMERS BY RADIATION CROSSLINKING METHOD

In this paper, the relationship between radiation crosslinking parameter β and the molecular internal rotating steric factor (σ) for fluoropolymers were studied. An expression calculating the molecular internal rotating steric factor of fluoropolymers, σ=1.44+(β-0.206)/1.946, was established. σ value obtained by this method is in agreement with that given in the literature.

Thiol-ene crosslinked cellulose-based gel polymer electrolyte with good structural integrity for high cycling performance lithium-metal battery

Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.

POLYMER-SUPPORTED GRIGNARD REAGENT AND ITS USE IN THE FUNCTIONALIZATION OF POLYMER

Polymeric Grignard Reagent (PGR) based on the chloromethylated poly(ST-co-DVB) resinhas been prepared by means of anthracene-magnesium complex in THF (Anth-Mg-THF), andpolymer matrix with long polymethylene spacer was synthesized via the coupling reaction betweenPGR and α, ω-dibromoalkanes. Based on the studies of factors affecting the coupling, such ascatalyst,reaction time,the length of spacer etc.,this paper offers the optimal reaction conditionsand three typical experiment procedures. The mechanism for the formation and coupling reactionof PGR are also discussed.

SYNTHESIS AND FLUORESCENCE STUDY OF St／DVB COPOLYMERS LABELLED WITH PYRENE GROUPS

Two kinds of St/DVB copolymer beeds containing (1 - pyrenyl) formyl and(1 -pyrenyl) methyl groups respectively have been synthesized by both functionalization and copolymerization. The fluorescence spectra of the swollen polymers synthesized are similar in shape to those of the corresponding model compounds, whilethe intensity ratio of excimer to monomer shows clear dependence on the contents ofthe pyrene groups.

微交联聚吡咯衍生物的合成与光学性能

有机共轭聚合物因具有独特的结构和光电性能,在发光材料及器件领域有着广泛的研究和应用。以吡咯和单醛基苯甲醛为线形单体,以对苯二甲醛为交联单体,采用溶液缩聚法制备了4种蓝光微交联聚吡咯衍生物,并对其分子结构、聚集态结构、微观形貌、热行为、紫外-可见吸收和荧光性能等进行了分析,考察了取代基类型对其结构和光学性能的影响。研究表明,微交联聚吡咯衍生物具有较高的玻璃化转变温度和热稳定性能,为非晶态和亚微米级的球形堆积体;在340nm左右紫外光的激发下,微交联聚吡咯衍生物能够产生约473nm的可见光,属于蓝色发光材料;不同类型的取代基对微交联聚吡咯衍生物的结构和光学特性有所影响。该微交联聚吡咯衍生物制备简单,结构可调可控,在聚合物发光二极管领域有着潜在的应用。

水驱油藏聚乙烯亚胺交联聚合物凝胶体系研究进展

聚乙烯亚胺(PEI)是一种低毒性环保材料,它与聚合物交联的凝胶体系具有适用温度范围广、成胶时间可控、成胶后强度大、高温稳定时间长、几乎不受储层岩石矿物影响等优点。本文回顾了以PEI作为交联剂的各类凝胶体系的研究动态,阐明了PEI与各类聚合物的交联反应机理及其凝胶体系特点,分析了各类因素对凝胶性能的影响,并列举了改善凝胶性能的方法和成功的矿场应用实例,重点分析了提高凝胶体系交联活性的方法研究。最后,提出聚丙烯酰胺(PAM)/PEI凝胶体系作为环保型调驱体系在中低温油藏深部调控方面具有非常大的应用前景,应继续深入研究提高PAM/PEI凝胶体系交联效率的方法及其作用机理,以降低聚合物与交联剂用量,为这一体系的推广应用提供理论依据与实验基础。

动态化学交联聚烯烃类弹性体研究进展

聚烯烃类弹性体是由乙烯与丙烯或其他高碳α-烯烃共聚而成的高端聚烯烃材料,具有出色的化学稳定性、耐候性和电绝缘性,广泛应用于光伏、汽车、电缆等领域。通过动态化学交联可在保证其加工性的前提下,进一步提高其力学性能与热稳定性,拓展应用范围。综述了动态化学交联聚烯烃弹性体的制备工艺,包括一步法直接交联和功能化后再交联(多步法)。详细介绍了后功能化、乙烯与功能化单体共聚等功能化方法。讨论了动态化学交联聚烯烃类弹性体的表征手段及其链结构、聚集态结构和性能之间的关系。展望了动态交联聚烯烃类弹性体的未来发展。为动态化学交联聚烯烃类弹性体的可控制备、构效关系研究以及高值应用提供理论指导与技术支持,推动高端聚烯烃材料的创新和发展。

卡宾在聚合物交联反应中的研究进展

归纳分析了三氟甲基类卡宾化合物、重氮酯类卡宾化合物、N-杂化卡宾化合物等稳定结构的卡宾前驱体的结构、性能特点,并重点介绍了其在聚合物改性领域的应用研究进展。

聚乙烯醇基凝胶电解质的制备及在储能器件中的应用

由于在电化学能源存贮与转化器件中所展现出的巨大潜在应用前景,固态聚合物电解质膜的开发受到研究界的广泛关注。基于柔性储能与转换器件的发展,以聚乙烯醇(Polyvinyl alcohol, PVA)为基体的凝胶聚合物电解质(Gel polymer electrolytes, GPEs)因亲水性强,无毒,良好的兼容性以及优异的化学稳定性,是当前研究较多的理想电解质材料。本文从PVA基水凝胶电解质的制备合成原理、方法和性能表征出发,总结和讨论了其基本物理特性和电化学性能,并就PVA基水凝胶电解质在超级电容器、柔性锌空电池、锂离子电池以及太阳能水热电池中的研究和应用进展进行了综述,并对其在该领域未来的发展做出展望。

海藻酸钠-聚乙烯包覆贝得石复合材料(SA-Bd@PE)去除低浓度铀酰试验研究

针对低浓度含铀废水的处理效果不理想、成本较高的问题,采用天然吸附材料并转化聚乙烯(PE)的能量来提高材料对铀酰(UO_(2)^(2+))的吸附能力。以贝得石(Bd)、海藻酸钠(SA)和PE为原料,通过交联法制备SA-Bd@PE,采用XRD、FTIR、Raman光谱、SEM和Zeta电位等分析手段对SA-Bd@PE进行表征,并对所制备的SA-Bd@PE复合材料进行吸附试验,结果表明:Bd结构发生了坍塌,SA表面更加粗糙,PE的加入使得材料结构变得松散,孔洞增多,且分散性更好;SA-Bd@PE_(10)比SA-Bd@PE_(0)的吸附性能更好,其对UO_(2)^(2+)的最大吸附量为49.71 mg/g;最佳吸附pH为5.0;吸附行为与Pseudo-second-order动力学模型和Langmuir等温吸附模型的拟合度均高达0.99,表明该吸附属于表面单层化学吸附。