主链含硅聚芳酯的合成及气体透过性能的研究

以双［对－酰氯苯基］二甲基硅烷和酚酞、四溴酚酞以及双酚Ａ为原料，合成了三种主链含硅聚芳酯，并对聚合物相关的物理性质进行了表征，制成了均质透明的薄膜．采用低真空法测定这些聚合物对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过速率，并计算出气体透过系数、扩散系数、溶解系数、分离系数．从气体透过性能与聚合物分子结构关系的角度，按照气体透过的溶解－扩散机制，对聚合物的气体透过性能进行了研究，而且着重讨论了聚合物的堆积密度对气体扩散系数的影响，以及聚合物主链中极性链段的百分含量对气体溶解系数和溶解选择性的影响。     

三甲基硅取代PPO和三苯基硅取代PPO及其气体选择透过性能

讨论了聚２，６－二甲基－１，４－苯撑氧（ＰＰＯ）与三甲基氯硅烷和三苯基氯硅烷的反应，合成了一系列取代含量不同的三甲基硅取代ＰＰＯ（ＴＭＳ－ＰＰＯ）和三苯基硅取代ＰＰＯ（ＴＰＳ－ＰＰＯ）．研究了取代基团不同和取代含量变化对聚合物的气体选择透过性能的影响，发现ＴＭＳ－ＰＰＯ的气体透过系数随三甲基硅取代量加大而增高，分离系数下降；ＴＰＳ－ＰＰＯ的气体透过系数和分离系数都随三苯基硅取代量的增加而下降，ＴＰＳ－ＰＰＯ与ＴＭＳ－ＰＰＯ的气体溶解系数相近，扩散系数差别较大．故二者气体透过系数的不同主要是由于扩散系数的差异．从化学结构与气体透过性能关系的角度来看，若在聚合物分子中引入有较小转动自由能的大基团，则有利于气体分子的扩散透过．     

含脂肪链聚苯并咪唑的合成及其气体透过性能

对含脂肪链聚苯并咪唑的聚合反应进行了比较系统的研究，在此基础上，合成了一系列含脂肪链聚苯并咪唑．以甲酸为溶剂，在减压下，制备了聚合物的均质膜．对聚合物的气体选择透过性能进行了研究，并从化学结构与气体透过性能关系的角度进行了讨论，发现同一聚合物对不同气体的透过系数符合一般玻璃态聚合物的规津；增加柔性链段中亚甲基数目，可提高聚合物的气体透过系数，降低分离系数；刚性链段中引入柔性基因，可增大气体透过系数；温度升高，聚合物的气体透过系数提高，分离系数一般下降．     

三甲基硅取代PPO和三苯基硅取代PPO及其气体选择透过性能

讨论了聚２，６－二甲基－１，４－苯撑氧（ＰＰＯ）与三甲基氯硅烷和三苯基氯硅烷的反应，合成了一系列取代含量不同的三甲基硅取代ＰＰＯ（ＴＭＳ－ＰＰＯ）和三苯基硅取代ＰＰＯ（ＴＰＳ－ＰＰＯ）。研究了取代基团不同和取代含量变化对聚合物的气体选择透过性能的影响。发现ＴＭＳ－ＰＰＯ的气体透过系数随三甲基硅取代量加大而增高，分离系数下降，ＴＰＳ－ＰＰＯ的气体透过系数和分离系数都随三苯基硅取代量的增加而下降，ＴＰ     

主链含硅的芳族聚酰胺的合成及其气体选择透过性能

采用界面缩合聚合方法，合成了一系列主链含硅的芳族聚酰胺，从化学结构与气体透过性能关系的角度研究了此类聚合物均质膜的气体透过性能，结果表明，此类聚合物膜对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过系数大小顺序符合一般玻璃态聚合物规律；在刚性强的高分子链段中引进柔性基因，可提高聚合物的气体透过系数；高分子主链有较强内旋转能力的聚合物，气体透过系数大；高分子主链的化学结构相同，苯环上带有侧甲基的聚合物有高的气体透过系数；硅原子上带有侧苯基的聚合物，其气体扩散系数大于而溶解系数小于硅原子上携有侧甲基的聚合物．结论为，在刚性高分子主链中引入柔性基团和提高刚性链间隙是增大气体透过含硅聚酰胺膜速率的有利因素．     

碱金属碳酸盐催化合成酚酞环氧树脂

在碱金属碳酸盐（Ｋ＿２ＣＯ＿３，Ｎａ＿２ＣＯ＿３）／Ｈ＿２Ｏ催化下制备了低分子量酚酞环氧树脂．用ＩＲ、￣１ＨＮＭＲ表征了其分子结构，测定了树脂产物的环氧值Ｅ和数均分子风及分子量分布，讨论了单体的摩尔比，催化剂含量及水含量对产物的影响，结果表明，在实验范围内，改变酚酞与环氧氯丙烷的摩尔比（１：１０～１：４）或酚酞与催化剂的摩尔比（１：２～１：１），均可以得到低分子量酚酞环氧树脂（５００～７００）．     

温度和压力对六氟二酐型聚酰亚胺的透气性能的影响

本文研究了温度和压力对五种六氟二酐（６ＦＤＡ）型聚酰亚胺膜对Ｈ_２、ＣＯ_２、Ｏ_２、Ｎ_２和ＣＨ_４五种气体透过性能的影响．在３０－１００℃区间，五种聚酰亚胺的透气系数与温度的关系均符合Ａｒｒｈｅｎｉｕｓ关系式；在０．３－１．２ＭＰａ区间，压力对透气系数的影响很小．６ＦＤＡ－４，４＇－二氨基二苯酮（ＤＡＢＰ）和６ＦＤＡ－３，３＇－二甲基二苯甲烷二胺（ＤＭＭＤＡ）在１００℃仍然具有较大的透气选择系数，是比较好的气体分离膜材料．     

高分子气体分离膜材料的化学结构与气体透过性能之间的关系

本文以硅橡胶和聚酰亚胺为基础,从高分子的化学组成、分子链段的运动能力、侧基的大小及其作用等几个方面,讨论了聚合物的化学结构对其均质膜的气体选择透过性能的影响,以溶解扩散过程对气体分离膜材料的透气行为进行了剖析,井简述高分子化学结构对其成膜时结晶情况的影响及对气体透过的作用;还概述了气体分离膜科学发展的历史以及基本原理.     

新型聚合物／液晶复合膜的研究 Ⅱ．二氧化碳气体的分离性能

以顺丁橡胶（ｃｉｓ－ＰＢ）为高分子基质材料，与具有反应性基团的低分子液晶化合物溶液共混后成膜，后经Ｓ２Ｃｌ２气相硫化制得交联型聚合物／液晶复合膜．研究了测试温度、压力、交联时间以及成膜条件对膜的气体分离性能的影响。结果发现，制得的复合膜在５０℃以下有很好的富二氧化碳性能．在此实验条件下，Ｎ２、Ｏ２的透过系数很小，而ＣＯ２的透过系数为２．０－４．０×１０－８ｃｍ３（ＳＴＰ）ｃｍ／ｃｍ２·ｓ·ｃｍＨｇ。     

聚芳醚砜薄膜的气体透过行为

研究了一系列聚芳醚砜的Ｈ２、ＣＯ２、Ｏ２、Ｎ２和ＣＨ４气体透过性能，讨论了其气体透过的温度依赖性。与双酚Ａ聚砜（ＰＳＦ）相比，几种新型聚芳醚砜的气体透过系数和气体选择系数同时有所提高。通过聚合物的分子链段活动性和自由体积数据系列变化，讨论了气体透过速率与分子结构的关系。     

酚酞分子印迹聚合物的制备及特异吸附性能

以泻药酚酞为模板分子,4-乙烯基吡啶为功能单体制备了模板分子和功能单体不同比例的一系列酚酞分子印迹聚合物。利用扫描电镜对聚合物进行了表面形态分析,采用静态平衡实验法研究了聚合物对模板分子及其类似物的吸附行为和选择性识别能力。实验结果表明,所制备的分子印迹聚合物,吸附 3 h 后基本接近最大吸附量,其中模板分子、4-乙烯基吡啶和交联剂的摩尔比为 1∶6∶20的MIP2的印迹因子为 2.30,效果最佳。Scatchard 分析表明, 在所研究的浓度范围内,吸附过程存在两类结合位点,一类高亲和力结合位点的离解常数为Kd1= 0.63 mmol/L,最大表观结合量 Qmax1 = 25.4 umol/g,另一类低亲和力结合位点的离解常数为 Kd2 =3.5 mmol/L,最大表观结合量 Qmax2 = 61.9 umol/g,通过与酚酞类似物质在酚酞分子印迹聚合物上的吸附行为比较,表明对酚酞具有很好的选择性吸附。     

Gas transport properties of polyarylates part II: Tetrabromination of the bisphenol

The gas transport properties of a series of polyarylates based on isophthalic acid have been examined. The polyarylates were synthesized from the following bisphenol monomers with and without tetrabromo substitution: bisphenol A, hexafluorobisphenol A, phenolphthalein, and fluorene bisphenol, to study the effects of tetrabromination in combination with varying the bisphenol connector group size and shape. Substitution of a tertiary butyl group at position five on the isophthalate ring was used to increase polymer permeability. Tetrabromination of the bisphenol maintains or increases gas permeability and significantly increases permselectivity particularly for the O₂/N₂ gas pair as compared with the non-brominated analog. The substitution of t-butyl groups increases gas permeability by two-to fourfold but lowers permselectivity. Most of the increase in permeability can be related to an increase in the diffusion coefficient for each gas. All the brominated polyarylates have gas transport properties superior to most known glassy materials for O₂/N₂ separation with several materials close to a proposed empirical “upper bound” between permeability and selectivity. © 1995 John Wiley & Sons, Inc.     

Gas sorption and transport in UV-irradiated polyarylate copolymers based on tetramethyl bisphenol-A and dihydroxybenzophenone

Gas sorption and transport properties at 35°C are reported for a series of ultraviolet irradiated polyarylates prepared from tetramethyl bisphenol-A (TMBPA), 4,4′-dihydroxybenzophenone (DHB), and 5-tertiary-butyl isophthalic acid dichloride (tBIA). UV irradiation induces crosslinking and photo-Fries rearrangements in these polymers. The gas permeability of the polyarylates decreases with UV irradiation due to reductions in the diffusion coefficient; however, the ideal selectivity for all gas pairs increases with UV irradiation. The effect of UV irradiation on the gas transport properties of the polyarylates is compared with that reported in the literature for similar polyimide materials. The polyimides show much greater improvement in selectivity than do the current polyarylate materials. The photo-Fries rearrangements limit the amount of crosslinking achievable in these polyarylate materials in spite of the fact that additional benzophenone units are formed.     

Polymers with improved flammability characteristics. II. Phenolphthalein related copolycarbonates

Analysis of phenolphthalein and bisphenol-A copolycarbonates reveals a linear correlation between oxygen index (OI) and char yield (Y): OI = 0.34Y + 19.6, which can be compared with the empirical equation QI = 0.4Y + 17.5 proposed by D. W. Van Krevelen for other polymers. Analysis also suggests that no chemical interction occurs between the two comonomers during pyrolysis, which leads neither to enhanced char yield nor to enhanced oxygen index. Each copolymer component contributes to the char yield and oxygen index on an additive basis. Study of 4,5,6,7-tetrabromophenolphthalein and phenolphthalein copolycarbonates shows that some enhancement of char yield does occur and that the lower the char yield, the higher the oxygen index, which is an indication of the predominance of a vapor-phase bromine effect over that related to char. Study of 4,5,6,7-tetrabromophenolphthalein and bis-phenol-A copolycarbonates is interpreted on the basis of two factors—the char effect that prevails over the vapor phase radical scavenging effect at lower bromine content and the reverse order at higher bromine content.     

Mass spectrometric study of the bromination of technical mixtures of polychlorinated biphenyls

The products of bromination of polychlorinated biphenyls (PCBs) that constitute Trichlorobiphenyl and Sovol PCB technical mixtures were studied by gas chromatography–mass spectrometry. On the basis of mass spectrometric data, the reaction was shown to result in formation of a mixture of poly(bromochloro)biphenyls containing from one to five bromine atoms and from two to six chlorine atoms in different combinations. It was found that the content of monobromo derivatives increases while the content of di-, tri-, and tetrabromo PCB derivatives decreases when the chlorination degree of the initial PCBs increases.     

由聚合物结构预测气体的透过性能

本文利用基团加和法,对20多种常见聚合物的自由体积和内聚能进行了计算。发现氧气和氮气在聚合物膜中的透过率与自由体积和内聚能的比值有直接关系。此比值越大,气体的透过率越大,透过率的对数与自由体积和内聚能的比值基本呈线性关系。据此,对未知聚合物可根据其化学结构,从已有的基团数据计算该比值,从而预测它对氧气和氮气的透过性能。     

Influence of side chains assembly on the structure and transport properties of comb-like polysiloxanes in hydrocarbon separation

We have synthesized a number of comb-like polysiloxanes with linear, branched, cyclic and silicon-containing substituents; most of them are new and previously not studied polymers. The physicochemical properties of comb-like polysiloxanes have been systematically investigated. Differential-scanning calorimetry and wide-angle X-ray scattering data revealed the side-chain microphase assembly for polymers with linear aliphatic substituents, while the polymers with bulky substituents did not form a microphase. It is shown that the ratio of microphase in the polymer is greater, the closer the values of the thickness of the microphase layer and the length of the cross-link. The effect of the side-chain substituent on the hydrocarbon transport properties of comb-like polysiloxanes was studied. All synthesized polymers are promising as membrane materials for a vital process of hydrocarbon separation. This is associated with an increase in the solubility selectivity of n-butane/methane because the solubility coefficient of methane sharply decreases when long side chains are introduced into the polysiloxane. It was shown for the first time that microphase forming polymers have a significantly higher butane/methane selectivity (23.2–27.5) than polysiloxanes not forming a microphase (selectivity 12.3–20.0). The effect is demonstrated on polysiloxanes with various types of side substituents. It was revealed that for the comb-like polysiloxanes, the diffusivity selectivity and permselectivity are proportional to the fraction of the side-chain microphase in the polymer. With the increase in the hydrocarbon microphase share, the diffusion coefficient of the permanent gas methane is decreasing more rapidly than n-butane, which dissolves well in hydrocarbons and plasticizes polymer. Consequently, the polymers forming the microphase have a higher selectivity C₃₊/CH₄ in the separation of a multicomponent hydrocarbons mixture.