酚酞型聚芳醚砜共聚物与共混物－(PP/BiS-T) PES共聚物和(PPS/PES-C)、(PPO/PES-C)共混物的合成、结构与性能研究

本工作旨在通过共聚、共混技术制备酚酞型聚芳醚砜共聚物(PP/BiS-T) PES和共混物(PPS/PES-C)、PPO/PES-C，以便改善酚酞型聚芳醚砜（PES－C）的加工性能（特别是注射加工性能）和耐溶剂性能。通过研究共聚物和共混物的微观结构，聚集态结构与性能的关系，探索改善酚酞型聚芳醚硕性能的有效途径第一部分：(PP/BiS-T) PES共聚物的合成、结构与性能(PP/BiS-T) PES共聚物是以4，4'二氯二苯砜（DCDPS）、酚酞（PP）和4，4'－二羟基二苯硫醚(BiS-T)为单体，采用固体无水K_2CO_3/NMP/TMSO_2 混合溶剂反应体系合成的。共聚反应规律研究表明：在NMP/TMSO_2混合溶剂中，共聚反应可以顺利进行，避免了交联反应的发生，并成功地合成了高分子量的(PP/BiS-T) PES共聚物。DSC分析结果表明(PP/BiS-T) PES系列属于无定形的均相共聚物体系，每一组成比例对应的共聚物只具有一个玻璃化转变温度。且随组成比例的改变呈线性变化，TBA分析结果与DSC基本一致，并证实了(PP/BiS-T) PES属于均相共聚物体系，而不是均聚物的共混物。TG分析表明：共聚物具有良好的耐热氧化稳定性BiS-T链节在分子链中起到了提高自身抗氧性的作用。1R光谱对共聚物的结构进行表征。~(13)C-NMR分析确认共聚物多属于无规共聚物。动态力学试验表明共聚物(PP/BiS-T) PES以及PES－C，在－100 ℃附近和0－100 ℃，存在着次级松驰与转变，并发现水分子的存在对这种转变（次级松驰）有一定的影响。共聚物的熔融流动性试验和溶解性试验表明共聚物(PP/BiS-T) PES具有稍好于PES－C的熔融流动性；溶解性与PES－C类似。力学试验说明共聚物属于强而硬类型的聚合物。第二部分：PPS/PES－C共混物的制备、聚集态结构与性能PPS/PES－C共混物是以联苯/二苯硕混合物为溶剂，采用溶液沉析方法制备的，DSC、WAXD，SEM和1R分析手段对共混物的聚集态结构和微观结构进行了表征。DSC分析认为共混物属于多相体系，PPS的结晶性随着PES－C含量增加而降低。DSC和SEM观察结果表明：相转变发生在PPS占40％左右。PPS占25％时，DSC曲线呈现出界面相玻璃化转变温度。共混物具有良好的耐热氧化稳定性和耐热分解稳定性。微晶大小计算结果：PES－C存在导致了PPS微晶大小降低。WAXD曲线表明PPS占50％，共混物中的PPS具有较好的结晶性。SEM观察发现：随着PES－C含量增加，PES－C由分散相（PES－C50％）变为连续相（PES－C70％）。PPS占50％或低于50％时，共混物体系不仅发生了微观相分离，而且发生了宏观相分离。M.I.指数表明共混物中PPS为连续相时，共混物具有良好的熔融流动性。溶解性试验结果：共混物具有较好的耐溶剂性。第三部分：PPO/PES－C共混物的合成、结构与性能 PPO/PES－C共混物系用溶液－涂膜法，以氯彷为溶剂制备的。讨论了由同一共混物溶液浓度下制备的共混物的互溶性随组成的改变而变化。DSC分析结果：PPO/PES－C属于部分相溶性体系。利用Fox方程推导式计算结果表明PPO在富PES－C相中具有良好的分散性；而PES－C在富PPO相中的分散性较差。共混物(PPO/PES－C)试样经丙酮浸泡后，PPO（>50％）发生了溶剂诱导结晶现象，同时丙酮促使共混物发生完全相分离。结晶溶化热显示共混物中少量的PES－C存在有利于PPO的溶剂诱导结晶。TG分析表明共混物具有良好的耐热分解稳定性和耐热氧化分解稳定性。偏光显微镜下观察到PPO球晶的存在。SEM和FT－1R分别对共混物的形态结构和微观结构进行了表征。WAXD试验证实了丙酮处理的(PPO/PES－C)（70/30），（90/10）共混物中PPO的结晶性。溶解性试验表明：PPO掺入有助于 PES－C的耐溶剂性提高。

丁苯嵌段共聚物(SBS,SB-4A)与均聚物PPO,PBD共混体系相容性的研究

本工作对不同分子构成的丁苯嵌段共聚物SBS（SB三嵌段共聚物）和SB－4A（SB四臂星型嵌段共聚物）分别与均聚物PPO，以及分别与不同分子量的均聚物PBD的共混体系进行了研究，探讨了嵌段共聚物分子构造，均聚物分子量和共混组成对共混体系的相容性和形态结构的影响。

Theoretical estimation of thermodynamic properties of the system PS/PPO on the basis of modified combining rule of Sanchez-Lacombe lattice fluid model

The three scaling parameters described in Sanchez-Lacombe lattice fluid theory (SLLFT), T*, P* and rho* of pure polystyrene (PS), pure poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their mixtures are obtained by fitting corresponding experimental pressure volume-temperature data with equation-of-state of SLLFT. A modified combining rule in SLLFT used to match the volume per mer, v* of the PS/PPO mixtures was advanced and the enthalpy of mixing and Flory-Huggins (FH) interaction parameter were calculated using the new rule. It is found that the difference between the new rule and the old one presented by Sanchez and Lacombe is quite small in the calculation of the enthalpy of mixing and FH interaction parameter and the effect of volume-combining rule on the calculation of thermodynamic properties is much smaller than that of energy-combining rule. But the relative value of interaction parameter changes much due to the new volume-based combining rule. This effect can affect the position of phase diagram very much, which is reported elsewhere [Macromolecules 34 (2001) 6291]

The glass transition temperatures of PS/PPO blends: Couchman volume-based equation and its verification

The glass transition temperatures (T-g) of PS/PPO blends with different compositions were studied under various pressures by means of a PVT-100 analyzer. A general relation of T-g and pressure of the PS/PPO system was deduced by fitting the experimental T-g's. Couchman volume-based equation was testified with the aid of those data. It was found that the experimental T-g's do not obey the Couchman equation of glass transition temperature based on thermodynamic theory. According to our studies, the major reason of the deviation is caused by the neglect of DeltaV(mix). (C) 2001 Published by Elsevier Science Ltd.

Morphology and properties of [PPO-PDMS-PHS](n) segmented ternary copolymers

The morphology and properties of [ PPO-PDMS-PHS](n) segmented ternary copolymers were investigated by DMA, TEM and SAXS techniques. It is shown that the continuous phase of [PPO-PDMS-PHS](n) is the compatible phase composed of PDMS, PPO and PHS segments, and that there exist two dispersed phases, i, e. the PDMS phase and a mixed phase of half hard ( PHS) and hard ( PPO) segments. The tan delta vs. T curve of the segmented ternary copolymer with 66.7% (W/W) PDMS shows a rather high plateau in the temperature range from -120 degrees C to 200 degrees C, which indicates that the copolymer has the characteristics of microphase separation as well as compatibility of block copolymers, respectively. Meanwhile, it has good tensile properties, which means that [PPO-PDMS-PHS](n) has overcome the weakness of low strength of block or segmented copolymers containing PDMS.

具有双重相互作用PPO-PDMS-PHS_n/PPO共混相容性的研究

利用ＤＳＣ和ＤＭＡ研究了一种新的含有机硅三元多嵌段共聚物ＰＰＯ－ＰＤＭＳ－ＰＨＳ与均聚物ＰＰＯ共混体系的相容性，结果表明，均聚物ＰＰＯ与ＰＰＯ－ＰＤＭＳ－ＰＨＳ中的两种嵌段（ＰＰＯ和ＰＨＳ）有相容性，两种嵌段协同作用的结果提高了共混相容性的临界值，当均聚物ＰＰＯ的Ｍｎ为２００００时，ＰＰＯ嵌段的Ｍｎ为２００００，ＰＨＳ嵌段的Ｍｎ为５１６０时，ＰＰＯ－ＰＤＭＳ－ＰＨＳ／ＰＰＯ共混物为一相容体系。

PPO作为PPO-PDMS-PHS_n/PS增容剂的研究

导了一种新的共混增容体系，以均聚物ＰＰＯ作为不相容共混体系ＰＰＯ－ＰＤＭＳ－ＰＨＳ／ＰＳ的增容剂。ＤＳＣ和ＤＭＡ的研究结果表明，ＰＰＯ对ＰＰＯ－ＰＤＭＳ－ＰＨＳ／ＰＳ共混体系确有增容作用，ＰＰＯ的含量在１３．５％以下时，ＰＳ、ＰＰＯ和ＰＰＯ－ＰＤＭＳ－ＰＨＳ中的硬段相容为一相；ＰＰＯ的含量在２３．８％以上时，ＰＰＯ分布在ＰＳ相和ＰＰＯ－ＰＤＭＳ－ＰＨＳ中的硬段相中，经ＰＰＯ增容后，材料的拉伸性能明显提高。

PPO-PDMS-PHS_n三元多嵌段共聚物的形态结构和性能

利用DMA,TEM和SAXS对以聚苯醚(PPO)为硬段、聚对羟基苯乙烯(PHS)为半硬段和聚二甲基硅氧烷(PDMS)为软段的三元多嵌段共聚物(?)PPO-PDMS-PHS(?)_n的形态结构和性能进行了研究.结果表明,(?)PPO-PDMS-PHS(?)_n以三种嵌段相容相为连续相,PPO与PHS的相容相和PDMS相为两种分散相,其tanδ随温度变化曲线在-100℃至200℃一直是一很高的平台,并具有优异的力学性能,较好地解决了含有机硅类嵌段共聚物强度低的弱点,同时又保留了嵌段共聚物微相分离的特性.

STUDIES ON THE SULFONATION OF POLY(PHENYLENE OXIDE) (PPO) AND PERMEATION BEHAVIOR OF GASES AND WATER-VAPOR THROUGH SULFONATED PPO MEMBRANES .3. SORPTION BEHAVIOR OF WATER-VAPOR IN PPO AND SULFONATED PPO MEMBRANES

Water vapor absorption and desorption by poly (phenylene oxide) (PPO) and sulfonated PPO (SPPO) membranes were studied at a constant temperature of 30-degrees-C and over a broad range of water activity (0.05 less-than-or-equal-to a < 0.8) by the weighing

STUDIES ON THE SULFONATION OF POLY(PHENYLENE OXIDE) (PPO) AND PERMEATION BEHAVIOR OF CASES AND WATER-VAPOR THROUGH SULFONATED PPO MEMBRANES .1. SULFONATION OF PPO AND CHARACTERIZATION OF THE PRODUCTS

Poly(2,6-dimethylphenylene oxide) (PPO) was sulfonated to varying degrees using different sulfonating agents. Physical properties such as solubility, density, and thermal properties were studied for both PPO and sulfonated PPO (SPPO) with different degree

STUDIES ON THE SULFONATION OF POLY(PHENYLENE OXIDE) (PPO) AND PERMEATION BEHAVIOR OF CASES AND WATER-VAPOR THROUGH SULFONATED PPO MEMBRANES .2. PERMEATION BEHAVIOR OF CASES AND WATER-VAPOR THROUGH SULFONATED PPO MEMBRANES

The permeation behaviors of water vapor and gases were studied for both PPO and SPPO of different sulfonation degree. It was found that the permeability of water vapor increased, and those of oxygen and nitrogen decreased; thus the selectivity for water v

PHB／PPO共混体系的相容性和结晶

采用溶液共混方法对聚β－羟基丁酸酯（ＰＨＢ）／聚氧化丙烯（ＰＰＯ）共混体系的相容性和结晶行为进行了研究。ＤＳＣ、ＰＯＭ、ＷＡＸＤ等实验结果表明，该体系是不相容体系。但在特殊的组成比下有相容的第三相存在。ＰＰＯ对ＰＨＢ的结晶结构无影响，但对ＰＨＢ的结晶速率和结晶完整性有很大作用。

溴代及胺交联聚苯醚(PPO)膜的气体透过行为

对聚苯醚(PPO)进行了苯环溴代、甲基溴代以及胺交联,发现苯环溴代可提高O_2、N_2透过率(P),而选择性(α)基本不变。甲基溴代则相反,P降低、α有明显提高。调节两者比例可得到P、α兼优的O_2、N_2分离膜。甲基溴代后进一步胺交联可得到α更高、耐溶剂的膜材料。