Prediction of Henry's constant in polymer solutions using PCOR equation of state coupled with an activity coefficient model

In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.

SOLID STATE VOLTAMMETRY OF ELECTROACTIVE SOLUTES IN POLYMER SOLVENTS(PEO)AT MICROELECTRODE

The present paper describes experiments aimed at delineating significant chemical characteristics of electrochemical reactions in polymeric solutions, including how rigid solvent environments affect mass transport rates, and also discusses the possibility that the microelectrode coated with poly(ethylene oxide)(PEO) film can be used as gas sensor.

Self-assembly synthesis of solid polymer electrolyte with carbonate terminated poly (ethylene glycol) matrix and its application for solid state lithium battery

A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.

Pressure-volume-temperature and excess molar volume prediction of amorphous and crystallizable polymer blends by equation of state

In this work the statistical mechanical equation of state was developed for volumetric properties of crystalline and amorphous polymer blends.The Ihm-Song-Mason equations of state(ISMEOS) based on temperature and density at melting point(T_m and ρ_m) as scaling constants were developed for crystalline polymers such as poly(propylene glycol) + poly(ethylene glycol)-200(PPG + PEG-200),poly(ethylene glycol) methyl ether-300(PEGME-350) + PEG-200 and PEGME-350 + PEG-600.Furthermore,for amorphous polymer blends containing poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) + polystyrene(PS) and PS + poly(vinylmethylether)(PVME),the density and surface tension at glass transition(ρ_g and γ_g) were used for estimation of second Virial coefficient.The calculation of second Virial coefficients(B_2),effective van der Waals co-volume(b) and correction factor(α) was required for judgment about applicability of this model.The obtained results by ISMEOS for crystalline and amorphous polymer blends were in good agreement with the experimental data with absolute average deviations of 0.84%and 1.04%,respectively.

LOW ENERGY PATHS AND REORIENTATION OF SIDE-GROUPS OF POLYMERS DURING CONFORMATIONAL STATE TRANSITION

INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation and phasetransitions of polymers. A description of the conformational state transition requires questions about; 1) howmany stable conformational states for a specific σ bond; 2) the barriers between the states; 3) the mechanismof the conformational transition; 4) any cooperative behavior during the transition. Flory and his coworkers

Emitting stability of poly(9,9-dialkylfluorene-co-N-butylcarbazole) by solid-state oxidative coupling polymerization

Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.

Study of the coordinative nature of alkylaluminum modified Phillips CrO_x/SiO_2 catalyst by multinuclear solid-state NMR

Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phillips CrOx/SiO2 catalysts were examined via ethylene homopolymerization.1H and 27Al magic angle spinning（MAS） nuclear magnetic resonance（NMR） spectra clearly demonstrated that the existing states of surface Al species in alkylaluminum-modified catalysts strongly depended on the type of alkylaluminum cocatalyst,concentration of alkylaluminum and the calcination temperature.1H MAS NMR spectra of alkylaluminum-modified Phillips CrOx/SiO2 catalysts,calcined at two different temperatures,exhibited similar trends in peak shift.1H spectra showed that with an increase of Al/Cr ratio and calcination temperature,the main peak shifted to high field,indicating that the dominant surface proton species changed from hydroxyl to ethoxyl and ethyl groups.27Al MAS NMR spectra showed the presence of three different coordination states（6-,5-,and 4-coordinated Al species） in the alkylaluminummodified Phillips catalysts.In comparison of different alkylaluminum cocatalysts,it was found that the reactivity of alkylaluminum modified Phillips catalyst decreased in the order of TEA〉DEAH〉DEAE.The amount of 4-coordinated Al species of Phillips catalysts modified by TEA,DEAE and DEAH also decreased in the order of TEA〉DEAH〉DEAE,indicating that the presence of 4-coordinated Al species is related to the polymerization activity.

Studies on Epitaxial Polymerization of 1,3-Bis(3-quinolyl)-1,4-butadiyne

During investigating what causes the low yield of the polymerization product of 1,4-bis(quinolyl)-1,3-butadiyne(DQ), we found that the DQ crystals formed on the surface of PDQ cauld be polymerized to give blue crystals, in which DQ could be sublimated and crystallized on the surface of PDQ film. According to the experimental results, the reason why the DQ crystals can be polymerized is that the sublimation of DQ changes the molecular orientation of DQ in the crystal. The crystals formed in epitaxial growth on the surface of DQ or PDQ during sublimation of DQ are suitable for 1,4-addition polymerization.

Modeling of Solid-state Polycondensation of Poly (ethylene terephthalate)

A mathematical model has been developed to handle the reactions in Poly(ethylene terephthalate) (PET) undergoing polycondensation reactions in the solid state. The effect of temperature on chain mobility was considered to estimate the rate constants of chemical reactions. The polymer crystalline fraction is modeled as containing only repeat units, thus concentrating end groups and conden-sates in the amorphous fraction. This model is compared with PET reaction data with good results.

Transient state model of actin-based motility

We developed a transient model for actin-based motility.Diffusion of actin monomers was included in the formulation and its influence on the speed of actin-driven cargos was examined in detail.Our results clearly demonstrated how actin polymerization accelerates cargos that are initially stationary,as well as how steady-state is eventually reached.We also found that,due to polymerization and diffusion,actin monomer concentration near the load surface can be significantly lower than that in the rest of the comet tail,suggesting that many previous models may not be very accurate.

生物基耐高温PA5T/56的高效制备及表征

目前,耐高温尼龙(PA)的生产主要采用“预聚合+固相后聚合”法,然而固相后聚合过程中存在的制备周期长、副反应多等技术难题长期得不到有效解决。笔者以生物基戊二胺(PDA)、对苯二甲酸(TPA)和己二酸(AA)为原料,通过在固相后聚合过程前期加入适量水,高效制备了生物基耐高温PA5T/56。研究了TPA与AA的物质的量比对产物熔点的影响,结果表明当其物质的量比为6∶4时,产物(P64)的熔点为309℃,可以作为耐高温工程塑料使用。考察了固相后聚合阶段用水量、反应温度、保温时间和预聚物粒径对固相后聚合产物相对黏度的影响,确定了优化工艺条件:用水量与设备的体积比为1∶300、反应温度为260℃、保温时间为6h、预聚物粒径<0.1mm。通过傅里叶变换红外光谱仪和核磁共振氢谱确认了产物的分子结构。热性能测试结果表明,P64的熔点为309℃,起始热分解温度为375℃,即样品具有很宽的温度加工区间和良好的熔融加工温度窗口。力学性能测试结果表明,P64拉伸强度为85.7 MPa、断裂伸长率15.4%、缺口冲击强度为5.56kJ/m^(2),这与商品化PA6T共聚物的性能相近,表明该样品可以部分代替PA6T共聚物使用,拓宽了应用领域。

固相聚合对萘环液晶聚芳酯结构与性能的影响

为解决液晶聚芳酯熔融缩聚反应后期由于反应温度和熔体黏度过高导致的降解交联副反应以及成形加工困难等问题,以6-羟基-2-萘甲酸(HNA)、2,6-萘二羧酸(NDA)、对苯二甲酸(TA)、4,4'-二羟基联苯(BP)为原料,采用原位一锅熔融聚合法制备了低分子量萘环热致液晶聚芳酯,并对其进行固相聚合。通过差示扫描量热仪、热重分析仪、偏光显微镜、X射线衍射和熔融指数仪对固相聚合后的液晶聚芳酯结构与性能进行了测试。结果表明,液晶聚芳酯的熔融温度和结晶度受聚合时间和温度的影响较大,呈现出先增加后降低的变化趋势,但并不会改变聚芳酯的晶体结构,同样属于正交晶型。此外,固相聚合在温度305℃下反应12 h,液晶聚芳酯热学和结晶性能得到明显改善;高于此时间和温度时聚芳酯的熔点开始降低,热降解反应开始进行,热稳定性和结晶性能下降。

聚醚醚酮齐聚物固相增黏及聚合物性质研究

以环丁砜为溶剂合成齐聚物,采用齐聚物在双转子密炼机中进一步固相增黏的聚合方式制备了聚醚醚酮(PEEK)。研究了不同增黏时间对PEEK结晶、热学和流动性能等的影响。结果表明,随着聚合时间增加,PEEK结晶度和结晶完善程度逐渐降低,且增黏5 h制得的PEEK的结晶度较齐聚物降低约31.4%;所有聚合物900℃时残炭量仍大于50%,具有优异的热稳定性;PEEK熔体黏度随增黏时间增加逐渐增大,约为齐聚物的13~360倍。

导电聚合物基柔性固态超级电容器的组装及性能研究

导电聚合物基柔性固态超级电容器是一种具有高性能和广泛应用潜力的能量存储设备。为此研究导电聚合物基柔性固态超级电容器的组装方法,并对其性能进行测试。在组装过程中,首先需选择导电聚合物基材料,之后制备电极材料和聚合物电解质,最后对电容器进行组装封装。通过容量衰减率、能量密度、功率密度来测定电容器的循环稳定性及热稳定性,结果表明在适当的条件下,导电聚合物基柔性固态超级电容器具有优秀的性能,能提供高效的能量存储和快速释放,在极端条件下表现出色。

基于分段聚合和卡尔曼滤波的锂电池组SOC估算

针对原有的锂电池组荷电状态(state of charge,SOC)估算方式是在电池放电后进行测量,在电池内阻数值较大时难以获取明确的开路电压,导致其在锂电池组SOC估算上具有误差等问题,设计了基于分段聚合和卡尔曼滤波的锂电池组SOC估算方法.在构建等效电路模型的基础上,辨识锂电池参数,并定义开路电压等锂电池组SOC估算指标.分段聚合切换锂电池反馈路径,利用卡尔曼滤波线性递推估算锂电池组SOC数值.结果表明:以锂电池脉冲放电过程为测试条件,提出的方法估算结果与实际SOC值基本一致,在SOC为0.6时,该方法能将SOC估算相对误差控制在0~0.4%.

金属-有机框架材料基固态电解质快离子导体的功能化设计及其在锂金属电池中的应用

固态电池与传统的锂离子电池和液态电池相比,在提高能量密度和安全性方面具有更大的潜力。然而,现有的固态电解质在提升电导率和克服锂枝晶产生等问题时遇到不少挑战。为解决此问题,选用MIL-101(Cr)的金属-有机框架材料(Metal-organic framework,MOF)作为主体材料,将高电导率的有机单体1,3-二氧戊环(DOL)负载在MIL-101(Cr)上,设计制备了一种新型固态电解质。该方法不仅解决了DOL电化学稳定性差的问题,还充分利用了MIL-101(Cr)富含不饱和金属位点的特点,限制了阴离子的自由移动,加速了锂离子的解离过程,从而提升锂离子迁移数。结果表明,MIL-101(Cr)@DOL材料表现出优异的离子电导率(0.92 mS·cm^(-1)),稳定的电化学窗口(4.65 V)和较高的锂离子迁移数(0.57)。此外,使用MIL-101(Cr)@DOL材料组装的Li//LiFePO_(4)电池也表现出了优异的倍率和循环性能,在0.2 C下经过140次循环后放电比容量仍然维持在128.9 mAh·g^(-1),容量保持率达到82.9%。将有机单体DOL负载在MIL-101(Cr)上合成的新型固态电解质的方法,对于开发新型的固态电解质材料和寻找新的离子传导机制起到了启发的作用,为提升锂金属电池性能提供了新的途径和可能性。

高炉矿渣的组成和结构对其在碱性环境中早期水化特性的影响

以不同组成和结构的高炉矿渣作为研究对象,借助XRD、ICP-MS以及29Si MAS NMR等微观测试手段,探究了高炉矿渣在碱性环境中的离子溶出特性、硅氧四面体聚合状态随水化龄期变化的影响规律。研究表明:高炉矿渣中玻璃体的活性受其化学组成和结晶相含量影响,结晶相及铝氧结构单元的存在和增多降低了玻璃体结构的聚合度;网络改性剂在玻璃体结构中表现为不均匀分布,不同网络形成体结构单元的水解会伴随不同的水化特性;在碱性环境下,高炉矿渣玻璃体结构中硅氧四面体含量较大时,其硅氧结构更易被破坏,溶液中硅离子的浓度较高,溶液pH值维持在较低水平,生成的水化产物中高聚态硅氧四面体较多;高炉矿渣玻璃体结构中铝氧四面体含量较大时,其铝氧结构更易被破坏,溶液中铝离子及钙离子的浓度较高,液相pH值维持在较高水平,生成的水化产物中高聚态硅氧四面体较少。

聚乳酸合成研究进展

针对直接法和二步法合成聚乳酸的共性,从单体纯度、催化剂选择到共沸脱水、微波辅助、超临界流体介质,以及到固相聚合、反应挤出、扩链等各个方面,对近年来聚乳酸合成研究的新进展进行了综述,指出各种新方法、新技术的复合应用是提高聚乳酸分子量、降低其成本的关键。

聚酯切片结晶行为与固相缩聚过程新流程方案

研究了聚酯基础切片在氮气环境、水相环境以及热台偏光显微镜中的结晶特性。发现．氮气环境中90℃及以下聚酯切片的结晶度很小（约6％），温度高于100℃结晶度明显增加，二次高温结晶的结晶度与一次低温结晶温度有关；水相环境中80℃～90℃的结晶度（25％～35％）明显比氮气环境中的结晶度高；球晶生长速率在180℃～190℃范围内最大。创新提出“聚酯热水介质造粒与结晶集成”的新方法并确定了基本工艺条件：热水温度90℃～95℃，切片在热水中的停留时间2S左右；气相结晶的热空气温度175℃～185℃，停留时间约5min。

超大多孔水凝胶的制备及吸附性能研究

以Na2CO3为发泡剂,聚(氧化乙烯/氧化丙烯)(PF127)为泡沫稳定剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸铵(APS)及N,N,N′,N′-四甲基乙二胺(TMEDA)为氧化还原引发剂,利用发泡技术合成了羧甲基纤维素钠(CMC)接枝丙烯酸(AA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)超大多孔水凝胶(SPH),并应用于处理阳离子红染料溶液。研究表明,该水凝胶具有超大多孔结构且具有良好的热稳定性;在m(AA)∶m(AMPS)=8∶2,w(MBA)=0.02%,w(Na2CO3)=65%,w(PF127)=0.2%时制得的凝胶吸蒸馏水倍率及吸0.9%盐水倍率分别达1281、143g/g,10min时已基本达到溶胀平衡;该SPH对阳离子红染料溶液具有良好的脱色效果,脱色率达98%。