侧链结构对侧链型磺化聚砜质子交换膜性能的影响

以双酚A型聚砜(PS)为基础,与自制的1,4-二氯甲氧基丁烷反应制备氯甲基化聚砜(CPS),接着与2-萘酚-6,8-二磺酸钾(NSK)进行亲核取代反应制备萘磺酸型侧链磺化聚砜(PS-NS)。采用溶液浇注法制备相应的质子交换膜(PEMs),结合前期研究的脂肪磺酸型侧链磺化聚砜(PS-ES)和苯磺酸型侧链磺化聚砜(PS-BS) PEMs,考察侧链结构对PEMs的吸水率、吸水溶胀率和尺寸稳定性的影响关系。结果表明,与主链型芳香聚合物PEMs相比,3种侧链型磺化聚砜PEMs由于亲水基团远离疏水主链,能够形成类似于Nafion膜的相分离结构,在高吸水率下保持更好的尺寸稳定性;在相同的离子交换膜容量(IEC)下,PS-ES、PS-BS和PS-NS膜随着侧链刚性苯环数目的增加,侧链的运动能力减弱,导致PEMs的尺寸稳定性增加,相应的质子传导率减小; PS-ES膜在25℃和85℃的质子传导率分别达到0. 072和0. 141 S/cm,PS-NS在25℃和85℃的尺寸溶胀性仅为21. 8%和51. 5%,性能与商业化的Nafion115膜十分接近。     

GRAFTED STYRENE-DIVINYLBENZENE COPOLYMERS CONTAINING BENZALDEHYDES AND THEIR WITTIG REACTIONS WITH VARIOUS PHOSPHONIUM SALTS

A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared.The degree of functionalization with aldehyde groups is well suited for the subsequent use of the products as Wittig reagents.The polymer bound aldehyde was reacted with Wittig reagents to give olefin groups grafted on styrene-divinylbenzene copolymers.The reactions were carried out in phase transfer catalysis conditions.A simple procedure for the calculation of the degree of functionalization and the statistical modeling of the structural repetitive unit of the copolymer are reported.     

A hyper-cross-linked polystyrene with nano-pore structure

Chloromethylated polystyrene (CMPS) beads were prepared by suspension polymerization of vinylbenzyl chloride (VBC), divinylbenzene (DVB) and styrene (St) in the presence of porogen. The same feed volume ratio of DVB leads to similar cross-linking degree for all CMPS, but decreasing VBC content provided a progressively reduced content of chloromethyl groups in each CMPS. Hyper-cross-linked polystyrene (HCLPS) beads were obtained by post cross-linking reaction of CMPS in dichloroethane (DCE) containing Friedel-Crafts catalyst. The role of porogen and its influence on nano-pore structure of HCLPS were investigated. The results showed that different types of porogen had significant effect on the nano-pore structure of the final products, such as specific surface area, average pore size and total pore volume. Using the mixture of toluene and cyclohexanol as inner porogen can yield the highest specific surface area for HCLPS beads. Moreover, higher amount of VBC lead to greater specific surface area and total pore volume. It was therefore indicated that nano-pore structure of HCLPS can be controllably prepared via changing porogen type and VBC concentration. Finally, the unprecedented swelling capacity was found for the hyper-cross-linked species derived from different porogen types.     

HALOMETHYLATION OF POLYSTYRENE AND SUBSEQUENT PYRIDINATION VIA A HOMOLYTIC PATHWAY

Chloromethylation of polystyrene （PS） with two different chloromethylating systems methylal/thionyl chloride and paraformaldehyde/trimethylchlorosilane was studied. Soluble chloromethylated polystyrene with a degree of substitution of 89% was obtained. The Conant-Finkelstein reaction on the chloromethylated PS afforded soluble iodomethylated polystyrene with a degree of substitution as high as 96%. The reaction conditions of Minisci were employed to radically pyridinate PS via its iodomethylated derivative. Polyelectrolytes were formed which could be converted to normal polymers by treatment with a 20% aqueous solution of NaOH.     

氯甲基化聚苯乙烯后交联过程中的氧化反应研究

在１２０℃将氯甲基化聚苯乙烯进行Ｆｒｉｅｄｅｌ—Ｃｒａｆｔｓ后交联制备超高交联聚苯乙烯的过程中，伴随有氧气对氯甲基化聚苯乙烯的氧化作用而使超高交联聚苯乙烯含有极性基团羰基约２．５ｍｍｏｌ／ｇ，而在较低的温度下，通过后交联制备超高交联聚苯乙烯时，则没有氧化反应发生。     

基于原子转移自由基聚合制备新型螯合树脂及其吸附性能

以氯甲基化聚苯乙烯树脂(CMPS)为基质, 通过表面引发原子转移自由基聚合(SI-ATRP)反应将聚甲基丙烯酸缩水甘油酯(PGMA)接枝到树脂表面, 再与亚氨基二乙酸(IDA)反应, 制备了一种新型螯合树脂. 采用红外光谱、 元素分析及比表面积与微孔分析仪对其结构进行表征. 树脂表面甲基丙烯酸缩水甘油酯(GMA)接枝量和IDA含量及对Ni(Ⅱ), Cu(Ⅱ)和Pb(Ⅱ)的吸附容量均随聚合时间的延长而增大, 聚合时间为18 h时, 最大吸附容量分别为1.29, 1.19和0.83 mmol/g. 结果表明, SI-ATRP是制备高吸附容量及吸附容量可控的螯合树脂的可行方法.     

CHLOROMETHYLATION OF POLYMERS MADE FROM TECHNICAL DIVINYLBENZENE AND PROPERTY OF THE CHLOROMETHYLATED POLYMERS

The goal this paper was to reveal the feasibility of chloromethylation of polymers made from technical divinylbenzene so as to introduce functional groups into polymeric adsorbents.Forthis study,the factors,that effect the chloromethylation reaction,such as the pore structure of the polymer,the ratio of the reactants to catalyst,the reaction temperature and reaction time and so on were investigated.and the pore structure and property of the chloromethylated polymers were studied.The results showed that polymers of technical divinylbenzene could be chloromethylated successfully,and the adsorptive property of the chloromethylated resin was different from that of the initial resin.     

相转移催化法制备侧链带有醛基的聚苯乙烯交联微球

首先使氯甲基聚苯乙烯交联微球（CCMPSt）在有机相中充分溶服,然后通过相转移催化剂（季铵盐）的作用,将水相中对羟基苯甲醛所产生的负氧离子转移至有机相,使之与CCMPSt微球表面的苄氯基团发生亲核取代反应,从而将CCMPSt微球转变为侧链带有醛基的聚苯乙烯交联微球（Aldehyde—CPSt）．本研究重点考察了各种因素对液-液-固三相体系中相转移催化过程及取代反应的影响规律,较深入地探讨了反应机理．研究结果表明,通过相转移催化剂的作用,可将亲核取代试剂对羟基苯甲醛负氧离子不断地从水相转移至有机相,在有机相与交联微球CCMPSt的界面发生取代反应,从而将CCMPSt微球顺利地转变为功能微球Aldehyde—CPSt．有机溶剂的极性越强,对CCMPSt微球的溶服性能越好,取代反应速率越快;相转移催化剂季铵离子上的碳链对称性越好及碳链越长,相转移催化的效果越好;有机相与水相的比例对相转移催化效果也有较大的影响．     

聚苯乙烯三乙醇胺树脂的合成与表征

由氯甲基聚苯乙烯与三乙醇胺反应合成了聚苯乙烯三乙醇胺树脂,通过元素分析,交换容量,溶胀性和ＩＲ对其进行表征,研究了其可能结构和某些性能。     

CHLOROMETHYLATION OF POLYMERS MADE FROM TECHNICAL DIVINYLBENZENE AND PROPERTY OF THE CHLOROMETHYLATED POLYMERS

1. INTRODUCTIONMacroporous polymers of technical divinylbenzene are often used as polymeric adsorbents for adsorptive separation. These resins may be advantageous compared to other polymeric adsorbents due to the high specific surface area and high porosity. However, the ability of these resins to adsorb polar compounds is very weak because the resins are non-polar and the values of the swelling capacity in aqueous solution are relatively low, and thus these resins are limited for adsorpti…