聚乳酸/田菁胶共混体系的加工流变性能研究

为了提高聚乳酸的黏度并降低其加工成本,采用田菁胶对聚乳酸进行共混改性。利用转矩流变仪对聚乳酸/田菁胶共混体系的加工流变性能进行研究,讨论了7种增塑剂(甘油、聚乙二醇4000、聚乙二醇6000、聚乙二醇10000、聚乙二醇20000、柠檬酸三丁酯和磷酸三苯酯)及其用量对共混体系加工流变性能的影响。结果表明,甘油的增塑效果不好,扭矩–时间曲线上并没有出现明显的塑化峰。当增塑剂用量为10~15份时,其它6种增塑剂均具有较好的增塑效果。以聚乙二醇6000增塑体系为例讨论了加工条件(加工温度和转速)对体系加工流变性能的影响。发现提高加工温度和转矩流变仪转速可以在一定程度上加快聚乳酸/田菁胶共混体系的塑化。需根据所用加工设备和工艺合理地选择增塑剂种类及其用量和加工条件。     

用于固体推进剂的新型热塑性聚氨酯弹性体的研究

基于环氧乙烷四氢呋喃共聚醚／聚乙二醇、异佛尔酮二异氰酸酯和１，４－丁二醇等合成了一系列具有优良力学性能、低玻璃化温度、低加工温度，并且与硝酸酯类增塑剂具有良好混溶能力的新型热塑性聚氨酯弹性体；比较了由环氧乙烷四氢呋喃共聚醚生成的热塑性聚氨酯和由环氧乙烷四氢呋喃共聚醚与聚乙二醇混合聚醚生成的弹性体的各种性质，指出在弹性体体系中加入少量聚乙二醇可以改善弹性体的各种性能     

增塑剂对聚氨酯密封胶性能的影响

以自制的聚氨酯预聚体为主体原料,配以填料、助剂等配制成单组分湿固化聚氨酯密封胶。讨论了增塑剂对聚氨酯密封胶老化性能的影响,结果显示：当增塑剂与聚氨酯体系的极性相近时,体系的耐迁移性随着增塑剂相对分子质量的增加而增加;当增塑剂与聚氨酯预聚体的相对分子质量相近时,增塑剂的极性与聚氨酯体系越接近,耐老化性能就越优越。通过老化实验表明：增塑剂的相对分子质量对于密封胶的耐紫外性能有一定的抑制作用,湿热是密封胶老化和增塑剂流失的关键原因之一。     

木材溶液制备聚氨酯胶粘剂的研究

研究了以苯甲基化木材溶液代替聚醚多元醇制备了聚氨酯胶粘剂，讨论了异氰酸酯用量、聚乙二醇用量、增塑剂用量及固化时间等对胶粘剂性能的影响，并获得了最佳的工艺条件。     

几种增塑剂对大豆蛋白质塑料拉伸性能的影响研究

采用了增塑剂聚乙二醇300,聚乙二醇400,聚乙二醇600及己内酰胺,对大豆蛋白质进行增塑,并测试了增塑后的大豆蛋白材料的拉伸性能,得到了这些塑增剂在增塑蛋白质中的最佳含量。     

光固化制备透明电解质及用于电致变色器件

采用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇2000 (PPG2000)、丙烯酸羟丙酯(HPA)和聚乙二醇(PEG600)制备了聚氨酯丙烯酸酯树脂,并与碳酸丙烯脂(PC)、高氯酸锂(LiClO_4)、2,4,6-(三甲基苯甲酰基)二苯基氧化膦(TPO)混合通过紫外辐照交联制备了凝胶电解质。通过电化学工作站,紫外光谱等方法对电解质性能及其应用的电致变色器件性能进行了表征。结果表明,制备的凝胶电解质薄膜在25℃下,电导率可达1. 61×10~(-3)S/cm,在可见光谱范围内平均透过率在92%以上。     

基于植物油基多元醇的无溶剂型双组分聚氨酯胶黏剂的研究

以绿色可再生的蓖麻油（CO）和环氧大豆油（ESBO）为原料制备了植物油基多元醇,用植物油基多元醇代替传统的石油类多元醇,与异氟尔酮二异氰酸酯（IPDI）和聚乙二醇（PEG）400或CO制备的预聚体在无溶剂条件下混合制备了4种脂肪族聚氨酯胶黏剂。并对制备的聚氨酯胶黏剂涂膜进行了热重分析、差示扫描量热分析、拉伸性能测试、剥离及剪切强度测试。结果表明,以PEG400和植物油基多元醇共同改性的聚氨酯胶黏剂剥离强度达到约200 N/m,剪切强度最高为4.9 N/mm^2;完全以植物油类原料制备的聚氨酯胶黏剂胶膜具有更好的耐热分解性能以及耐水性。     

新颖离子导电型聚氨酯弹性体

以低聚二氧戊环磺酸盐(SPDXL)为离子源和增塑剂,聚己二酸乙二醇酯聚氨酯弹性体(EGPU)为基质,设计了一种新颖的正离子导电型聚氨酯弹性体,并对其结构、形态及性能进行了研究。结果表明,通过选取适当平均相对分子质量的磺化低聚醚以及通过控制磺化低聚醚的质量分数,可以优化聚氨酯固体电解质体系的离子导电性能。对于EGPU/SPDXL固体电解质体系,采用SPDXL800的样品具有较高的离子导电性能,其室温离子电导率均达到10-6S/cm以上。     

聚乙二醇400对水性复膜胶合成及性能的影响

将聚乙二醇(PEG)作为空间位阻型乳化剂、润湿剂和增塑剂引入到原水性干法复膜胶的反应体系中,讨论了PEG的相对分子质量(M_n)和用量对乳液的合成及使用性能的影响。结果表明:当w(PEG-400)=1.15%(相对于总单体而言)时,聚合反应的稳定性最佳,乳液的粘接性能和机械适应性明显提高。     

不同浓度和溶剂对剪切增稠液流变性能的影响

本文考察不同浓度以及不同溶剂聚乙二醇200、聚乙二醇400、复配型的聚乙二醇/丙三醇(PEG/Gl)对二氧化硅/聚乙二醇(SiO2/PEG)剪切增稠体系的影响,采用流变仪测试该剪切增稠液的稳态流变性能。测试表明,复配型分散介质的增稠效果不如单一分散介质,临界剪切速率PEG400PEG200SiO2/PEG400/GlSiO2/PEG200/Gl,因此当需要在较小剪切速率条件下增稠时,应选用分子量较大的聚乙二醇单一分散介质;同时,分散相质量分数越高,体系的增稠现象也愈明显。     

Preparation and electrochemical properties of nonwoven reinforced solid polymer electrolytes

Summary Reinforced PEO-based polymer electrolytes were prepared by UV curing method. In this study, nonwoven sheets which were polyethylene terephthalate and polypropylene were used for that purpose. To enhance the ionic conductivity of reinforced PEO-based polymer electrolytes, oligomeric poly(ethylene glycol) dimethyl ether was added as a plasticizer, which is a sort of nonvolatile chemicals. The reinforced PEO-based polymer electrolytes showed the ionic conductivity of around 1.2 × 10⁻⁴ S/cm at 30°C, which was a little bit lower than the value of not reinforced one, that is pristine UV cured SPE. Even though the reinforced PEO-based polymer electrolytes didn't have any organic solvent such as ethylene carbonate, lithium ionic type polymer cell containing the polymer electrolyte showed reasonable specific discharge capacity of 116 mAh/g at room temperature. Received: 25 February 2000/Accepted: 14 April 2000     

Electrochemical studies on composite gel polymer electrolytes for lithium sulfur‐batteries

Poly(ethylene oxide)‐based composite gel polymer electrolytes (CGPE's) were prepared for various concentrations of magnesium aluminate (MgAl₂O₄) and LiTFSI as salt with a combination of 1,3‐dioxolane (DOL) and tetraethylene glycol dimethyl ether (TEGDME) as plasticizer by a simple solution casting technique. The addition of plasticizers has significantly improved the ionic conductivity of the gel electrolytes. The prepared CGPEs were subjected to scanning electron microscopy, thermal, and FT‐IR analysis. The electrochemical properties such as ionic conductivity, compatibility, and charge–discharge behavior have also been studied. Preliminary studies revealed that the prepared CGPE can be employed as a potential electrolyte for lithium–sulfur (Li–S) batteries. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44594.     

用Williamson法合成四甘醇双甲醚

以四甘醇 (C8H18O5)、氯甲烷 (CH3Cl)及固体碱性氢氧化物 (MOH)为原料 ,按n (C8H18O5)∶n (CH3Cl)∶n (MOH) =1∶( 2～ 3)∶( 2～ 5) ,采用Williamson法合成四甘醇双甲醚。反应温度为55～ 90℃ ,反应压力 0 6MPa ,反应时间为 3h ,四甘醇转化率大于 99% ,双醚选择性为 78 6%。同时以四甘醇的副产四、五甘醇混合物为原料合成四、五甘醇双甲醚混合物 ,反应只需约 2h即可完成 ,双醚选择性为 93 5%。     

乙酰乙酸乙酯金属配合物催化丁二酸二甲酯和碳酸乙烯酯的耦合反应

研究了乙酰乙酸乙酯金属配合物催化碳酸乙烯酯(EC)和丁二酸二甲酯(DMSu)同时合成聚丁二酸乙二醇酯(PES)预聚体和碳酸二甲酯(DMC)耦合反应新工艺。结果表明,以乙酰乙酸乙酯锌为催化剂,反应温度205～215℃,n(乙酰乙酸乙酯锌)/n(EC+DMSu)=0.001,n(EC)/n(DMSu)=4,反应时间1 h时,DMC收率为52.3%,PES的特性黏度为0.117 4 dL/g。     

碳酸二甲酯做甲基化试剂合成2,6-二氯苯甲醚

采用碳酸二甲酯(DMC)代替传统的有毒有害试剂作甲基化试剂,以2,6-二氯苯酚(DCP)为原料,在固体碱与相转移催化剂(PTC)作用下,合成了2,6-二氯苯甲醚(DCA)。考察了PTC种类及用量、物料配比、反应时间、反应温度和碱性催化剂用量对反应的影响,得到最佳反应条件为:以聚乙二醇400(PEG-400)为PTC,x(PEG-400)=0.2%,n(DMC)∶n(DCP)∶n(K2CO3)=0.1∶0.05∶0.003,温度150℃,时间5h,在该条件下,DCA的收率为87.3%,DCP的转化率为100%。优化条件下的重复实验表明,该反应易于控制,重复性好。     

Polymer gel electrolytes synthesized by photopolymerization in the presence of star-shaped oligo(ethylene glycol) ethers (OEGE)

The photoinitiated cross-linking polymerization of tri(ethylene glycol) dimethacrylate and its copolymerization with cyanomethyl methacrylate in the presence of LiCF₃SO₃ and of various oligo(ethylene glycol) methyl ethers as plasticizer was studied for potential use of the resulting polymer gel electrolytes in lithium batteries. Comparing linear and star-shaped (three and four arm molecules) oligo(ethylene glycol) methyl ethers, the influence of the architecture of the plasticizers on the polymerization course was investigated by means of differential scanning calorimetry. Linear and star-shaped plasticizers with molar masses < 1000 g/mol differ from each other concerning the dependence of their viscosity on their molar mass but not concerning the influence of the viscosity on the polymerization rate. Compared with linear plasticizers, the star-shaped ones have as an essential advantage a distinctly lower tendency to crystallize which is even completely suppressed in some cases. The gels were characterized with regard to the network density of their polymer matrix, to their thermal transitions, thermo-mechanical properties and ionic conductivity. The conductivity of solutions and gels with star-shaped plasticizers was slightly lower than that with linear ones at temperatures above room temperature.     

邻苯二甲酸二(乙二醇醚)酯绿色合成及增塑PVC性能

以邻苯二甲酸酐和低毒型乙二醇醚（乙二醇甲/乙/丁醚、二乙二醇甲/乙/丁醚）为原料,固体酸\mathrm{S}{\mathrm{O}}_{\mathrm{4}}^{\mathrm{2}-}/TiO₂为催化剂,采用直接酯化法催化合成邻苯二甲酸二(乙二醇醚)酯（酯化率?97.0%）,并利用傅里叶红外光谱（FTIR）、¹H核磁共振（¹H NMR）确定产物结构。对合成产物邻苯二甲酸二(乙二醇醚)酯的基本物性（酯含量、酸度、黏度、加热减量等）及其增塑后聚氯乙烯（PVC）制品的力学性能、热稳定性以及抗迁移性能进行测试。结果表明,邻苯二甲酸二(乙二醇醚)酯的增塑性能与其结构中乙氧基数目成正比,而与其末端烷基碳链长度呈现先增加后下降趋势。与邻苯二甲酸二辛酯（DOP）增塑后PVC制品（PVC/DOP）相比,邻苯二甲酸二(二乙二醇乙醚)酯增塑后PVC制品（PVC/DEEEP）的断裂伸长率和拉伸强度分别提高87.4%和3.4MPa,初始热分解温度（T_5%）提高21.5℃。     

Properties of Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline Conductive Films: The Effect of Poly(ethylene glycol) Diglycidyl Ether

The effect of polyaniline and poly(ethylene glycol) diglycidyl ether on tensile properties, morphology, thermal degradation, and electrical conductivity of poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films was studied. The poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films were prepared using a solution casting technique at room temperature until a homogeneous solution was produced. Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline/poly(ethylene glycol) diglycidyl ether conductive films exhibit higher electrical properties, tensile strength, modulus of elasticity but lower final decomposition temperature than poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films. Scanning electron microscopy morphology showed that the polyaniline more widely dispersed in the poly(vinyl chloride)/poly(ethylene oxide) blends with the addition of poly(ethylene glycol) diglycidyl ether as surface modifier.     

Electrolyte additives for enhanced thermal stability of the graphite anode interface in a Li-ion battery

The influence of electrolyte additives on the thermal stability of graphite anodes in a Li-ion battery has been investigated. The selected additives are: ethyltriacetoxysilane, 1,3-benzoldioxole, tetra(ethylene glycol)dimethylether and vinylene carbonate. These compounds were added in 4% to an electrolyte consisting of 1M LiBF₄ ethylene carbonate (EC)/diethyl carbonate (DEC) solvent mixture. Differential scanning calorimetry (DSC) was used to investigate the thermal stability. The electrochemical performance was investigated by galvanostatic cycling and the formed solid electrolyte interphase (SEI) was characterised by photoelectron spectroscopy (PES) using Al Kα and synchrotron radiation (SR). The onset temperature for the thermally activated reactions was found to increase for all electrodes cycled with additives compared to electrodes cycled without additives. The onset temperature increased in the order: no additive < tetra(ethylene glycol)dimethyl ether < 1,3-benzoldioxole < ethyl-triacetoxysilane < vinylene carbonate. Features in the PES spectra found to be associated with high onset temperatures for thermally activated reactions are: (i) no discernible graphite peak, (ii) small amount of salt species of the type LiF and Li_xBF_yO_z and (iii) larger amounts of organic compounds preferably with a high oxygen content.     

Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic-inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

Organic-inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO₄ via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10⁻³ S/cm at 30 °C. Variable temperature ⁷Li-{¹H} magic angle spinning (MAS) NMR demonstrated that the Li⁺ cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the ⁷Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.