具有多重玻璃化转变的梳状聚合物的合成,表征和导电性：侧链 …

以分子量为５５０的聚乙二醇单甲醚为侧链,苯乙烯／马来酸酐共的为骨架,合成了苯乙烯／马来酸酐共聚物多缩乙二醇酯。用红外光谱、元素分析、ＤＳＣ、热失重等方法,对合成条件、产物结构和性能进行了研究。结果表明：反应严格按照反应方程进行,精制产物是非晶的梳状聚合物。玻璃化转变温度为３０．６８℃,分解温度为１２０℃。对动态这性能及其锂盐复合物离子导电性进行了研究,表明α转变温度和β转变温度分别是２８℃他－４７     

玻璃化转变在室温附近的一种新型梳状聚合物的合成和表征：——— …

以分子量为５５０的聚乙二醇单甲醚为侧链,苯乙烯／马来酸酐共聚物为骨架,合成了苯乙烯／马来酸酐共聚物多缩乙二醇酯,用红外光谱、元素分析、ＤＳＣ、热失重等方法,对合成条件、产物结构和性能进行了研究,结果表明;反应严格按照反应方程进行,精制产物是非晶的梳状聚合物。玻璃化温度为３０．６８℃,分解温度为１２０℃,对动态力学性能及其锂盐复合物离子导电性进行研究表明α转变温度和β转变温度分别是２８℃和４７．７℃     

具有多重玻璃化转变的梳状聚合物的合成、表征和导电性--侧链分子量为550的聚乙二醇单甲醚

以分子量为550的聚乙二醇单甲醚为侧链,苯乙烯/马来酸酐共聚物为骨架,合成了苯乙烯/马来酸酐共聚物多缩乙二醇酯.用红外光谱、元素分析、DSC、热失重等方法,对合成条件、产物结构和性能进行了研究.结果表明:反应严格按照反应方程进行,精制产物是非晶的梳状聚合物.玻璃化转变温度为30.68 ℃,分解温度为120 ℃.对动态力学性能及其锂盐复合物离子导电性进行了研究,表明α转变温度和β转变温度分别是28 ℃和-47.7 ℃.随着盐浓度的增加, 盐浓度与电导率的关系呈现出双峰或多峰.电导率与温度的依赖关系符合VTF方程.室温电导率最高可达4.2×10-5 S·cm-1.     

新型梳状聚合物电解质的离子导电性 Ⅱ.侧链是分子量为550的聚乙二醇单甲醚

以乙烯／马来酸酐共聚物为骨架，聚乙二醇单甲醚（Ｍ＝５５０）为侧链，通过两步酯化，合成了梳状乙烯／马来酸酐共聚物多缩乙二醇酯，用ＩＲ、元素分析、交流复阻抗谱等对产物及其ＬｉＣｌＯ４盐复合物进行了研究。结果表明：所合成的产物为非晶的梳状聚合物，并严格按反应方程式生成半酯。盐浓度与电导率的关系在所研究的浓度范围内存在两个峰，一峰在Ｏ／Ｌｉ＋＝８；另一峰在Ｏ／Ｌｉ＋＝３０。用侧链ＰＥＯ玻璃化转变温度作Ｔ０，以ｌｏｇσ对１／Ｔ－Ｔ０作图，电导率与温度关系呈典型的ＶＴＦ行为，该体系室温电导率最高可达２．５８×１０－５Ｓ／ｃｍ。     

聚合物单阳离子导体的制备—羧酸型梳状单离子导体

本文报道一种制备聚合物单阳离子导体的新方法。马来酸酐－醋酸乙烯酯及马来酸酐－苯乙烯共聚物以聚乙二醇单甲醚醇解，使酸酐环打开而得到带有聚乙二醇侧链的羧酸型梳状聚合物，其锂盐在加入适当增塑剂成膜后，可作为聚合物单阳离子导体，其结构以非晶态为主，具有较低的玻璃化转变温度及较好的热稳定性，增塑后的室温电导率最高可达１０＾－６Ｓ／ｃｍ。此外还研究了聚合物结构、阳离子半径、增塑剂、温度及外加额率等因素对电导率     

一种梳状高分子固体电解质的合成及LiSCN盐复合物的导电性

以乙烯／马来酸酐共聚物为骨架，分子量为３５０的聚乙二醇单甲醚为侧链，合成了新型的乙烯／马来酸酐共聚物多缩乙二醇酯聚合物固体电解质。用红外对该聚合物的合成过程进行了跟踪。用红外、ＤＳＣ、元素分析等对终产物进行分析，表明酯化反应进行完全，并按合成路线生成严格的半酯。产物的成膜性能好，比较柔软，电导率与盐浓度的关系在所研究的范围内存在两个峰，电导率与温度的关系符合ＶＴＦ行为。     

马来酸酐—醋酸乙烯酯梳状聚合物单阳离子导体的制备及表征

马来酸酐－醋酸乙烯酯交替共聚物以聚乙二醇单醚醇解，得到带有不同长度的聚醚氧侧链的羧酸型梳状聚合物，其碱金属盐在加入适当增塑剂成膜后，可作为聚合物单阳离子导体，其结构以非晶态为主，具有较低的玻璃化转变温度及较好的热稳定性，增塑后的室温电导率最高可达１０－５Ｓ／ｃｍ．研究发现，适当增加侧链的长度有利于提高聚合物膜的离子电导率．此外，还详细探讨了增塑剂、阳离子半径、温度及外加频率等因素对电导率的影响．     

低相对分子质量苯乙烯-马来酸酐交替共聚物的合成

将引发剂偶氮二异丁腈(AIBN)、共聚单体苯乙烯(St)和马来酸酐(MA)溶解于甲苯中,采用沉淀聚合法合成苯乙烯-马来酸酐共聚物(SMA).分别研究了反应温度、引发剂用量、反应时间、单体配比和单体浓度对聚合物得率和酸酐含量的影响.采用正交实验确定最优反应条件为:单体浓度20%,单体物质的量比为1∶1,引发剂用量为0.60%,反应温度为86℃,反应时间2h,产物得率为86.86%,酸酐含量为50.28%.并利用傅里叶变换红外光谱(FTIR)、核磁共振碳谱(~(13)C NMR)、凝胶渗透色谱(GPC)和热分析法分别研究聚合物的分子结构、相对分子质量及相对分子质量分布和热稳定性.结果表明产物是苯乙烯-马来酸酐交替共聚物,相对分子质量分布较窄,具有良好的热稳定性.     

马来酸酐—苯乙烯本体自由基聚合反应

在杷来酸酐－苯乙烯本体聚合反应过程中，于７０℃和低引发剂浓度（０．５９－１．８×１０＾－３ｍｏｌ／Ｌ条件下，共聚物组成与单体的配比无关，生成无规共聚物；在高引发剂浓度（２×１０＾－２ｍｏｌ／Ｌ），随马来酸酐单体含量的增加，趋向生成１：１交替共聚物，温度的提高可以使生砀共聚物结构向１：１组成移动，当温度超过１４０℃时将生成无规共聚物，在本体聚合反应体系中，存在共聚反应和苯乙烯的均聚反应，而且随着的提     

苯乙烯-N-苯基马来酰亚胺-马来酸酐三元共聚物的合成与性能

以过氧化对苯二甲酸二叔丁酯为引发剂, 以一次投料方式, 采用溶液聚合法合成了苯乙烯-N-苯基马来酰亚胺-马来酸酐三元共聚物. 通过控制单体配比, 实现产物中N-苯基马来酰亚胺质量分数在48%~63%之间可调. 采用FTIR, ¹H NMR, ¹³C NMR和GPC技术对三元共聚物的化学组成、链序列结构和分子量进行了测试. 利用FOX方程计算的共聚物NPMI含量与¹H NMR核磁测试结果一致. DSC和TGA测试的结果表明, 当N-苯基马来酰亚胺质量分数>48%时, 共聚物的玻璃化转变温度(T_g)从202 ℃提高到215 ℃, 5%热失重温度高于363 ℃, 所以三元聚合物是一种优异的聚合物耐热剂.     

聚苯并咪唑-锂盐-聚乙二醇单甲醚共混全固态聚合物电解质的制备及性能

使用共混后浇铸成膜的方法,制备了聚苯并咪唑-锂盐-聚乙二醇单甲醚组成的锂离子电池共混全固态聚合物电解质。通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、差示扫描量热(DSC)、拉伸与交流阻抗测试表征了共混全固态电解质的结构与性能。研究了不同锂盐以及各组分含量对共混全固态电解质的力学性能与电导率的影响。结果表明:聚苯并咪唑与聚乙二醇单甲醚之间存在氢键;共混全固态电解质中聚乙二醇单甲醚处于无定形态;锂盐的加入使聚乙二醇单甲醚的玻璃化转变温度下降;聚乙二醇单甲醚含量越高,共混膜强度越低,电导率越高,并且使用三氟甲磺酸锂作为锂盐时其电导率最高,室温下可以达到3.58×10~(-5) S/cm,高温下可以达到3.3×10~(-3) S/cm,高温下满足对锂离子电池的使用需求。     

梳状P(MMA-co-MAh)-g-PEGME共聚物的合成及结构与性能

用自制的甲基丙烯酸甲酯和马来酸酐的共聚物P(MMA-co-MAh)为反应物,聚乙二醇单甲醚(PEGME)为接枝单体,合成了梳状P(MMA-co-MAh)共聚物多缩乙二醇酯(P(MMA-co-MAh)-g-MPEG).采用傅立叶红外光谱(FTIR)、核磁共振(NMR)13C谱、1H谱以及H,C-COSP谱对所合成的梳状共聚物结构进行表征;热失重分析(TGA)和示差扫描量热法(DSC)对所合成的共聚物的物理性能进行了分析.FTIR及NMR结果表明,聚乙二醇单甲醚通过酯化反应接枝到P(MMA-co-MAh)共聚物上,形成以MMA/MAh共聚物为主链,聚乙二醇单甲醚为侧链的梳状共聚物,其在马来酸酐上的接枝率大约为20%;热性能分析结果表明,合成的梳状共聚物热分解温度与共聚物P(MMA-co-MAh)的分解温度相差不大,接枝后的梳状共聚物也具有高的热稳定性,起始热分解温度在325.9℃左右,且该梳状共聚物具有两个玻璃化转变温度,一个是由于侧链的玻璃化转变引起的,温度为32℃左右;一个是主链的玻璃化转变引起的,温度为120℃左右.在主链玻璃化转变温度以下,侧链是可以移动的,有利于电活性物质和离子等在聚合物基体中的扩散和迁移.     

无定形梳状高分子固体电解质的二重玻璃化转变及典型VTF特征

研究了交替马来酸酐共聚物多缩乙二醇酯(CP350)-LiNO₃络合物的热行为及离子导电性。实验表明:CP350/LiNO₃络合物在所研究的[Li]/[EO]配比范围呈均相无定形并具有二重玻璃化转变。2个玻璃化转变温度均随盐含量的增加而上升。离子电导率随盐浓度的变化出现1个极大值,室温电导率最大可达3.72×10^-5S/cm.导电行为呈典型VTF特征。     

The effect of crosslinked networks with poly(ethylene glycol) on sulfonated polyimide for polymer electrolyte membrane fuel cell

To investigate the effect of crosslinking by a hydrophilic group on a sulfonated polyimide electrolyte membrane, sulfonated polyimide end‐capped with maleic anhydride was synthesized using 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl, 2,2′‐disulfonic acid, 2‐bis [4‐(4‐aminophenoxy)phenyl] hexafluropropane and maleic anhydride. The sulfonated polyimides end‐capped with maleic anhydride were self‐crosslinked or crosslinked with poly(ethylene glycol) diacrylate. A series of the crosslinked sulfonated polyimides having various ratios of sulfonated polyimide and poly(ethylene glycol) diacrylate were prepared and compared with uncrosslinked and self‐crosslinked sulfonated polyimides. The synthesized sulfonated polyimide films were characterized for FTIR spectrum, thermal stability, ion exchange capacity, water uptake, hydrolytic stability, morphological structure, and proton conductivity. The formation of sulfonated polyimide was confirmed in FTIR spectrum. Thermal stability was good for all the sulfonated polyimides that exhibited a three‐step degradation pattern. Ion exchange capacity was the same for both the uncrosslinked and the self‐crosslinked sulfonated polyimides (1.30 mEq/g). When the crosslinked sulfonated polyimides with poly(ethylene glycol) were compared, the ion exchange capacity was decreased as 1.27 > 1.25 > 1.23 mEq/g and water uptake was increased as 23.8 < 24.0 < 24.3% with the increase in poly(ethylene glycol) diacrylate content. All the crosslinked sulfonated polyimides with poly(ethylene glycol) diacrylate were stable for over 200 h at 80 °C in deionized water. Morphological structure and mean intermolecular distance were obtained by WAXD. Proton conductivities were measured at 30, 50, 70, and 90 °C. The proton conductivity of the crosslinked sulfonated polyimides with poly(ethylene glycol) diacrylate increased with the increase in poly(ethylene glycol) diacrylate content despite the fact that the ion exchange capacity was decreased. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1455–1464, 2005     

纳米复合全固态聚膦腈电解质

为了进一步提高聚合物电解质的室温离子电导率和锂离子的迁移数,通过对纳米二氧化硅的表面修饰,并采用可聚合的带氧化乙烯-氧化丙烯共聚侧链取代的聚膦腈大单体制备了纳米复合的全固态电解质.通过X射线光电子能谱,扫描电镜,差热扫描分析对纳米复合电解质的性能和形貌进行了分析,并通过交流阻抗考察了电解质与电极间的界面稳定性,用循环伏安表征了电解质的电化学稳定窗口,考察了锂盐含量对电解质离子电导率的影响,测试了电解质的离子电导率随温度的关系,并对锂离子的迁移数进行了测定.研究结果表明,通过纳米复合的方法,提高了聚合物电解质的离子电导率,降低了界面电阻,提高了锂离子迁移率.     

梳状聚合物电解质的合成与表征

用1H -NMR方法对苯乙烯 /马来酸酐共聚物多缩乙二醇酯的合成进行了表征 ,说明用1H -NMR的方法进行该类化合物的合成研究是简便准确的。并且通过热失重对该电解质的热稳定性进行了研究。     

The stability of semi-interpenetrating polymer networks based on sulfonated polyimide and poly(ethylene glycol) diacrylate for fuel cell applications

A series of the semi-interpenetrating polymer network (semi-IPN) membranes based on sulfonated polyimide and poly(ethylene glycol) diacrylate were prepared and characterized comparing with pure sulfonated polyimide membrane and commercially available membrane, Nafion^® 117. The proton conductivity increased with the increase of poly(ethylene glycol) diacrylate contents in spite of the decrease in ion exchange capacity which is a key factor to improve the proton conductivity. The water stability of semi-IPN membranes containing poly(ethylene glycol) diacrylate is higher than the pure sulfonated polyimide membrane. Morphological structure showed that amorphous nature of the films also increased with the poly(ethylene glycol) diacrylate contents, which could make a crosslink, so that the crystallinity of polyimide could disappear. Semi-IPN membranes based on sulfonated polyimide and poly(ethylene glycol) diacrylate, which show good conductivity comparable to Nafion^® 117 in the range of 20-50% content of poly(ethylene glycol) diacrylate, could be promising proton conducting membranes in fuel cell application.     

Influence of PEG-borate ester on thermal property and ionic conductivity of the polymer electrolyte

We have focused on the poly(ethylene glycol) (PEG)-borate ester as a new type plasticizer for solid polymer electrolyte for lithium ion secondary battery. Adding the PEG-borate ester into the electrolyte shows the increase in the ionic conductivity of the polymer electrolyte. By measuring the glass-transition temperature of the polymer electrolytes with DSC, it is found that the increase in ionic conductivity of the polymer electrolyte is due to the increase in ionic mobility. By investigating the temperature dependence of the ionic conductivity of the polymer electrolytes using William-Landel-Ferry type equation, we considered that the PEG-borate ester does not have any influence for dissociation of Li-salt. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anionic synthesis and detection of fluorescence‐labeled polymers with a terminal anhydride group

To monitor polymer–polymer coupling reactions between two different monofunctional polymers in dilute polymer blends, fluorescence‐labeled anhydride‐functional polystyrene (PS) and poly(methyl methacrylate) (PMMA) were prepared by conventional anionic polymerization. Sequential trapping of lithiopolystyrene by 1‐(2‐anthryl)‐1‐phenylethylene (APE) and then di‐t‐butyl maleate (4) provided, after pyrolysis, anhydride‐functional fluorescent PS. Fluorescent PMMA anhydride (8) was synthesized with sec‐butyllithium/APE as an initiator for the anionic polymerization of methyl methacrylate, trapping by 4, and pyrolysis. These polymers could be reacted with amine‐functional polymers by melt blending, and the reaction progress could be monitored by gel permeation chromatography coupled with fluorescence detection. This technique not only allows monitoring of the coupling reaction with high sensitivity (ca. 100 times more sensitive than refractive index detection) but also permits selective detection because unlabeled polymers are invisible to fluorescence detection. This highly sensitive and selective detection methodology was also used to monitor the coupling reaction of 8 with PS‐NH₂ at a thin‐film interface, which was otherwise difficult to detect by conventional methods. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2177–2185, 2000