氨基改性聚醚硅油的合成、结构表征及应用

在Pt催化剂的作用下，利用含氢硅油与烯丙基缩水甘油醚、烯丙基聚氧乙烯聚氧丙烯醚的硅氢化加成反应合成聚醚／环氧硅油中间体，然后分别用吗啉、乙二胺、N,N-二甲基丙二胺、N-氨乙基哌嗪等氨解开环，制得了一系列氨烃基改性聚醚硅油AMPES，对其进行了结构表征和应用。结果表明：增加含氢硅油的数均分子量，提高硅含量，可改善AMPES的柔软性，而对织物的吸湿性影响不大。     

聚醚聚氨酯-聚醚聚酰亚胺合金相结构的研究

通过不同分子量的对－氨基苯甲酸酯封端的聚（四次亚甲基）醚和均苯甲甲酸二酐反应,合成了聚醚聚酰胺酸;然后以不同重量比将聚醚聚氨酯和聚醚聚酰胺酸溶液混合反应亚胺化,制备了一系列不同硬段含量的聚醚聚氨酯－聚醚聚酰亚胺合金。用傅立叶变换红外光谱、动态力学分析、示差扫描量热、广角Ｘ－衍射、应力应变试验等分析测试方法对合金进行了研究,结果表明聚醚聚氨酯－聚醚聚酰亚胺合金具有很好的相分离结构,是一类新型耐高温、有韧性的热塑性弹性体。聚醚分子量相同的聚氨酯和聚酰亚胺形成的合金软段相容,合金具有两相结构;聚醚分子量不同的聚氨酯和聚酰亚胺形成的合金软段存在相分离,合金具有三相结构,表现在材料外观上分别为透明不透明的韧性膜,少量聚酰亚胺的掺入,能大大增加材料的耐热性能,而合金的材料力学性能没有明显变化。     

聚醚砜的磺化及表征

磺化是芳环聚合物改性的有效方法．引入的磺酸基以酸型、盐型和酯型存在,且可以继续制备其它衍生物．有关聚苯醚［１,２］、聚苯硫醚［３］、聚醚醚酮［４,５］和聚砜［６～８］的磺化研究和表征已有很多报道,这些聚合物引入磺酸基后亲水性增强,广泛用于制备反渗透膜...     

主链芳香型刚性链聚醚酮（砜）分子结构与其热性能的研究

通过模型化合物ＡｒＯＡｒＣＯＡｒＡｒＣＯＡｒＯＡｒ（Ａｒ为苯基或１，４－亚苯基）的全优化模型，得到芳环之间的平均二面角为３７．５°，由其结构参数建立了刚性链聚芳醚酮（砜）类均聚物分子结构与其熔点及玻璃化温度的关系式，据此较好地了预测了新品种均聚物的热性能。     

端乙酰乙酸酯基聚醚的合成与表征

以端羟基聚醚和双乙烯酮为原料合成了新型端乙酰乙酸酯基聚醚,通过FT-IR、~1H-NMR、~(13)C-NMR等方法对其结构进行了表征.结果表明:聚醚与双乙烯酮反应生成端乙酰乙酸酯基聚醚的同时生成了可以稳定存在的烯醇结构的互变异构体.所合成的新型端乙酰乙酸酯基聚醚与胺端基化合物反应生成具有优良力学性能的聚醚亚胺材料.     

支化聚醚电解质的研究：Ⅰ支化聚氧化乙烯的合成及表征

采用Ｗｉｌｌｉａｍｓｏｎ反应成功地合成了支化聚氧乙烯，并用ＩＲ、＾１３ＣＮＭＲ、ＤＳＣ对其进行了表征。结果表明，＾１３ＣＮＭＲ可半定量地表征支化度，链的支化可以降低玻璃化温度和结晶度。     

基质辅助激光解吸电离—飞行时间质谱表征6氟双酚A芳香环状聚醚酮（砜）

应用基质辅助激光解吸电离飞行时间质谱,在不同阳离子剂的存在下,对６氟双酚Ａ聚芳醚酮（砜）环状低聚物的结构进行了确认,研究了环状化合物对金属离子的选择性及激光质谱表征含氟环状低聚物的适宜条件。     

高分子冠醚毛细管柱的性能研究

本文报道了3种新的聚硅氧烷侧链冠醚作气相色谱固定液,并涂渍成弹性石英毛细管柱,这种毛细管柱具有优良的色谱性能,它们具有柱效高,热稳定性好,选择性强的特点,适于分离各种异构体。     

聚硅氧烷-聚醚接枝共聚物的合成及其碱金属盐络合物离子电导的研究

 本文采用环氧乙烷与环氧丙烷共聚合成了一系列低分子量的聚醚(PEP),并用PEP的单烯丙基醚借助氢化硅烷基化反应(Hydrosilylation)制备出一种新型聚硅氧烷接枝聚醚的高分子电解质主体材料(PAEPS).分别讨论了共聚物组成、盐的种类和浓度等因素对交联PAEPS与碱金属盐络合物电解质膜离子电导的影响.结果表明,PAEPS与碱金属盐络合物的室温电导率较纯线型PEO提高两至三个数量级,电导率随温度变化关系基本上符合VTF方程,属于典型的非晶电解质行为.     

低聚醚磺酸锂／梳形聚醚复合物的单离子导电性

低聚醚磺酸锂／梳形聚醚复合物的单离子导电性郑云贵，万国祥（中国科学院成都有机化学研究所成都６１００４１）关键词低聚醚磺酸锂，单离子导体，阳离子迁移数聚合物阳离子导体一般采用单体盐与能促进离子迁移的单体通过共聚或将其均聚物共混的方式制备’‘－‘’．由于...     

THERMAL BEHAVIOR AND IONIC CONDUCTIVITY OF POLY[LITHIUM-N(4-SULFO-PHENYL) MALEIMIDE -CO-METHOXY OLIGO(OXYETHYLENE) METHACRYLATE]

Poly[lithium-N(4-sulfophenyl) maleimide -co- methoxy oligo-(oxyethylene) methacrylates] [P(LiSMOE_n)s] with three different oligoether side chains and different salt concentrations were synthesized. The copolyelectrolytes are essentially random in structure, with blocks of methoxy oligo(oxyethylene) meth-acrylate (MOE_nM) recurring sporadically in between the salt units of N(4-sulfophenyl) maleimide. They all show two glass transitions in the temperature range of ?100 to 100°C. The first one below ?30°C is assigned to the oligo(oxyethylene) side chain (T _g1), while the second one located between 20 and 50°C is attributed to the main chain of the polymer host (T _g2). The maximum ionic conductivity of the copolymer electrolytes, 1.6 × 10^?7 S cm^?1 at 25°C, occurs at lithium salt concentration [Li⁺]/[EO] = 2.2 mol%. The ionic conductive behavior of the copolyelectrolytes follows the Vogel-Tammann-Fulcher (VTF) equation. Moreover, a special VTF behavior exists in the copolymers with shorter oligoether side chain and higher salt concentration. Sweep voltammetric results indicate that these copolyelectrolytes have a good electrochemical stability window.     

CATIONIC CONDUCTIVITY FOR THE CROSSLINKED P [OLIGO (OXYETHYLENE) METHACRYLATE-COoMETHACRYLOYL ALKYLSULFONIC ACID LITHIUM]

Crosslinked copolymers with single Li~+-ionic conductivity were prepared from oligo (oxyethylene) methacrylate (MEO_n), methacryloyl alkylsulfonic acid lithium (SAMLi), and oligo (oxyethylene) dimethacrylate (DMEO_n). Li~+-ionic conductivity of the copolymer is improved by crosslinking and presented as a function of polymerization degree (n) in MEO_n, comonomeric salt concentration (O/Li), and crosslinking degree. The crosslinked copolymer P (0.7 MEO_(14)-0.3DMEO_(14)-SHMLi) without other small molecular additives exhibits an optimum Li~+-ionic conductivity of 1.2×10~(-6) S/cm at 25℃. Dc polarization test in the cell composed of Li/copolymer/Li shows a constant dc ionic conductivity which closes gradually to the ac one with decreasing dc polarization potential.     

SYNTHESIS AND POLYMERIZATION OF OLIGO (OXYETHYLENE) MACROMONOMER

This paper reports the synthesis of methoxyoligo (oxyethylene) methacrylate (MEO_n , n is the repeating unit number of (CH_2CH_2O) in the macromonomer), and its polymerization in different solvents. MEO_n is prepared through such two independent reactions as (1) anionic polymerization of oxirane initiated by potassium alkoxide and (2) end-capping of methoxy oligo(oxyethylene) by methacrylic group. The n value can be conveniently controlled over the range of 5 ～30 by varying the molar ratio of oxirane to initiator and the molecular weight distribution of MEO_n be narrowed by increasing reaction time only in step (1). MEO_n thus obtained shows a rapid polymerization in water and benzene respectively, and both give water-soluble polymers as long as suitable conditions are used.     

Single-Ion Conduction and Electrochemical Characteristics of Poly (Oxyethylene)/ Lithium Methoxy Oligo(Oxyethylene) Sulfate Blend

Abstract

The ion conduction of a blend of poly(oxyethylene) (PEO) and lithium methoxy oligo(oxyethylene) sulfate (SAL₈) and its electrochemical characteristics were studied. The maximum ambient conductivity of the blend reaches 1.2 × 10^?6 S/cm. The blend exhibits single-ion conduction, excellent mechanical performance, and electrochemical stability. A battery of Li/PEO + SAL₈/Li_1+xV₃O₈ has a constant discharge capacity at different discharge current densities up to a certain voltage, while the discharge capacity of Li/P (MEO_16-AM) + LiClO₄/Li_1+xV₃O₈ decreases with an increase of the discharge current density.     

SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE CONTAINING OLIGO(OXYETHYLENE)SULFATE SALT

Solvent-free polymeric alkali-metal ion conductors, consisting of a comb-like polysiloxane with oligo(oxy-ethylene) side chains and pendant sulfate groups were synthesized by the hydrosilylation of allyl oligo(oxyethylene) sulfatesalt and allyl methoxy oligo(oxyethylene) with poly(methylhydrosiloxane). The factors influncing the ionic conductivity ofthe resulting polymer such as the electrolyte content and the nature of the alkali-metal were investigated. The temperaturedependence of conductivity was determined, and the ionic conductivity of the polymer follows the Vogel-Tammann-Fulcher(VTF) equation.     

Single-Ionic Conductivityin Poly(Sodium 2-Methacryloyl 3-[Ω-Methoxyl Oligo(Oxyethylene)]Propylsulfonate)

Abstract

Sodium 2-methacryloyl 3-[ω-methoxyl oligo(oxyethylene)] propylsulfonate was synthesized, from which homopolymer-based polyelectrolyte was prepared. The polyelectrolytes thus obtained show single Na⁺ionic conductivity at ambient temperature, neither adding plasticizer nor hybridizing small molecular salt. The conductivity depends considerably on the length of oligo(oxyethylene) side-chain. Optimally, the highest conductivity of 6.0 × 10^?6 S/cm at 25°C is obtained when the number of (CH₂CH₂O) repeating units equals 16. Results indicate that the conductivity data follow WLF and VTF equations. The WLF parameters are found to be comparable with “universal” values, and analysis of the configuration entropy model suggests that the conduction of Na⁺ ions is carried out by an association mechanism.     

Polymers designed to control nucleation and growth of inorganic crystals from aqueous media

Water soluble graft polymers prepared by copolymerization of either methacrylic acid (MAA) or vinylsulfonic acid (VS) with α‐methoxy‐ω‐methacroyl‐oligo(oxyethylene)s (PEO_n‐MA) serve to control nucleation and crystal growth during precipitation of inorganic crystals from aqueous media. Precipitation of zinc oxide crystals (‘zincite’) is used as example for such mineralization processes. Homogeneous and narrow crystal size distributions are obtained in presence of ppm‐amounts of graft copolymers. Copolymer is incorporated into the crystals demonstrated by using latex particles with ‐CO₂H‐group rich surfaces as controlling additives. Incorporation of these particles leads to single crystals with pores of the size of the particles (‘Swiss cheese’ morphologies).     

Excess Molar Volumes of Oligo(Oxyethylene Glycol) Monodecyl Ethers in n-Dodecane, and Apparent Dipole Moments of {(Oligo(Oxyethylene Glycol) Monodecyl Ethers?+?n-Heptane, n-Decane or n-Dodecane} at T?=?298.15?K

Excess molar volumes and relative permittivities at a frequency of 30?kHz of oligo(oxyethylene glycol) monodecyl ethers (C₁₀E _m ) for m?=?1?C8 in n-heptane, n-decane or n-dodecane solutions were determined for the mole fraction range 0?<?x?<?0.04 at the temperature of 298.15?K. By using Frohlich??s equation the apparent dipole moments, ??, of C₁₀E _m were calculated, and the limiting values, ?? ₀, were determined by extrapolating to infinite dilution. The values of ?? ₀ increase linearly with increasing number of oxyethylene units (m) of oligo(oxyethylene glycol) monodecyl ethers in the range m?=?2?C8, while ?? ₀ of C₁₀E₁ is less than its extrapolated value. By comparing the present results with our previous ones measured in n-heptane and decane, a solvent effect on ?? ₀ was found. The excess partial molar volumes of oligo(oxyethylene glycol) monodecyl ethers at infinite dilution increase with increasing m. Those results are discussed from the viewpoint of the interactions between oligo(oxyethylene glycol) monodecyl ethers and solvent molecules.     

POLYMERIC IONIC CONDUCTORS MODIFIED WITH POLAR GROUPS:PART Ⅰ. IONIC CONDUCTION AND MECHANICAL PROPERTY OF LI-COMPLEX BASED ON ACRYLAM ID E-COPOLYMERIZED METHACRYLATES

Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex based on the resultant copolymer was investigated. The introduction of the polar constituent raises chain rigidity, retards crystallization of oligo(oxyethylene) domain and promotes the dissociation of lithium salt. The factors work on the mechanical and conduction properties synergistically, therefore both of the properties are improved simultaneously as the consequence of acrylamide-introduction.