聚醚共聚酰胺(PEBA)膜的溶胀和渗透汽化行为研究

用涂布法制备出PEBA均质膜,分别测试了膜在纯醋酸正丁酯、水以及醋酸正丁酯稀水溶液中的溶胀率,并考察了浸泡时间、温度和溶液浓度对溶胀率的影响;结果表明:PEBA膜在水中溶胀很小,对醋酸正丁酯具有优先吸附能力;溶胀率随浸泡时间的延长、浸泡液浓度和温度的升高而逐渐上升。渗透汽化实验表明膜对醋酸正丁酯的良好选择性,膜的渗透通量和分离因子随着浓度的增加而增加,渗透通量随着温度的升高而增加,但分离因子随温度的升高而减小;当原料液浓度为0.6%(wt)时,醋酸正丁酯的渗透通量为143.9g·m-2·h-1,分离因子达到236.9。     

聚氧乙烯链封端的聚酰胺-胺树状聚合物的合成与表征

采用酰氯法,用丙烯酰氯和不同相对分子质量的聚乙二醇为原料,制备出一系列具有丙烯酰端基的聚氧乙烯大单体(PEO-A)。实验证明,较佳的原料摩尔比n(PEG)∶n(CH2CHCOCl)∶n〔(CH3CH2)3N〕=2∶1∶1。然后以聚氧乙烯大单体为端基改性剂,在氮气保护下50℃四氢呋喃溶液中分别与G1.0～G4.0聚酰胺-胺树状聚合物进行Michael加成反应96h,合成出了聚氧乙烯(PEO)链封端的非离子型聚酰胺-胺树状聚合物,并用傅立叶变换红外光谱(FTIR)、核磁共振波谱(1HNMR,13CNMR)对其组成和结构进行了表征。     

Novel Ferrocene-Based Organometallic Poly(ether sulfone amide imide)s: Preparation, Characterization, and Properties

A new ferrocene-based diamine (ESAFDA) with built-in ether, sulfone, and amide groups was prepared via reaction of two synthetic precursors. Firstly, 1,1′-ferrocenedicarbonyl chloride was prepared from 1,1′-ferrocenedicarboxylic acid using oxalyl chloride. In another reaction, nucleophilic substitution reaction of 3-aminophenol with bis(4-chlorophenyl sulfone) was used for synthesis of 3,3′-(4,4′-sulfonyl bis(1,4-phenylene) bis (oxy)) dianiline (SBOD). Finally, the diamine was prepared via nucleophilic reaction of SBOD with 1,1′-ferrocenedicarbonyl chloride. The precursors and the diamine were characterized by conventional methods and the diamine was used for preparation of different ferrocene-based poly(ether sulfone amide imide)s through polycondensation with three different dianhydrides. The polymers were characterized by elemental analysis, FTIR and ¹H-NMR spectroscopy. Various properties of the polymers including inherent viscosity, molecular weight, solubility, thermal stability and behavior, flame-retardant nature, mechanical properties, and crystallinity were studied. Presence of ferrocene structure in companion to ether, sulfone, and amide units in the backbone of polyimides led to improved solubility of the polymers in polar aprotic solvents and enhanced thermal stability and flame-retardant character of polyimides.     

以TICT荧光探针对芳醚型树枝状聚合物构象的研究

树枝状聚合物由于其独特的结构特性引起了人们极大的兴趣．其高度的结构对称性、外围可带有大量官能团等结构特点，使这类化合物在高分子、催化、光化学、材料科学及光子器件等方面显示出广泛的应用前景．已有的研究表明，这类化合物的性质不仅决定于其化学结构，还强烈依赖于其构象，研究此类化合物的构象对推动相关各研究领域的发展有着重要的意义，     

芳醚树枝形聚合物体系的设计合成以及构象的研究

树枝形聚合物是一类围绕中心核外围链段随着代数的增加以指数级别增长的化合物，它具有高度的几何对称性、精确的分子结构、分子内存在空腔、分子本身具有纳米尺寸等特点．由于其具有精美的结构，树枝形聚合物在高分子、催化、光化学、材料科学等方面具有广泛的应用前景．材料的结构决定它的性能以及应用，为了拓宽树枝形聚合物的应用范围，对其结构以及构象的研究就显得颇为重要．     

芳醚树枝形聚合物体系中电子转移和能量传递研究

树枝形聚合物英文名为dendrimer，是具有类似树枝状结构的化合物，由核心、内层支化单元和外围基团三部分组成．树枝形聚合物具有与光合作用体系相似的结构，作为模拟光合作用体系被广泛研究．电子转移是光合作用中的重要过程，研究树枝形聚合物体系中的电子转移与能量传递具有重要的意义．本论文设计合成了一系列芳醚树枝形聚合物，用光物理和光化学方法研究了芳醚树枝形聚合物体系中电子转移和能量传递过程，得到了一系列有意义的结果．具体如下：     

Poly(ether ether sulfone amide)s as a new category of processable heat-resistant polymers

The aim of study was to prepare novel polyamides with improved solubility and processability without sacrifice of their thermal and mechanical properties. Polyamides containing ether and sulfone units were obtained via condensation of a special diamine with various diacid chlorides. Poly(ether ether sulfone amide)s were obtained in good inherent viscosities ranging from 0.72 to 0.84 dL/g. All the polyamides were amorphous and readily soluble in polar solvents and swelled in CH₂Cl₂ and tetrahydrofuran. Flexible films of polymers were obtained by solution casting. Polyamide films exhibited good mechanical and thermal stability including the temperature for 10% weight loss of 449–476 °C.     

Synthesis and properties of copolymers of poly(ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

Poly(aryl ether ketone)s (PAEKs) are a class of high‐performance engineering thermoplastics known for their excellent combination of chemical, physical and mechanical properties, and the synthesis of semicrystalline PAEKs with increased glass transition temperatures (T_g) is of much interest. In the work reported, a series of novel copolymers of poly(ether ketone ketone) (PEKK) and poly(ether amide ether amide ether ketone ketone) were synthesized by electrophilic solution polycondensation of terephthaloyl chloride with a mixture of diphenyl ether and N,N′‐bis(4‐phenoxybenzoyl)‐4,4′‐diaminodiphenyl ether (BPBDAE) under mild conditions. The copolymers obtained were characterized using various physicochemical techniques. The copolymers with 10–35 mol% BPBDAE are semicrystalline and have markedly increased T_g over commercially available poly(ether ether ketone) and PEKK due to the incorporation of amide linkages in the main chain. The copolymers with 30–35 mol% BPBDAE not only have high T_g of 178–186 °C, but also moderate melting temperatures of 335–339 °C, having good potential for melt processing. The copolymers with 30–35 mol% BPBDAE have tensile strengths of 102.4–103.8 MPa, Young's moduli of 2.33–2.45 GPa and elongations at break of 11.7–13.2%, and exhibit high thermal stability and good resistance to organic solvents. Copyright © 2010 Society of Chemical Industry     

聚酰胺-胺树枝状高分子及其研究进展

介绍聚酰胺胺树枝状高分子的结构和性能,聚酰胺胺的特殊结构决定了其独特的物化性质。同时,对其合成方法、及其经改性后的树枝状高分子在生物医药、表面活性剂、催化剂、污水处理和膜材料等方面的应用研究进展进行了综述。     

聚芳醚酮/含甲基侧基聚芳醚砜醚酮酮的合成与表征

以2，2’-二甲基-4,4'-二苯氧基二苯砜(o-CH3-DPODPS)、二苯醚(DPE)和对苯二甲酰氯(TPC)为单体，在无水A1C13、1，2-二氯乙烷和N，N-二甲基甲酰胺存在下，通过低温溶液缩聚反应。合成了一系列新型含甲基侧基的聚芳醚酮／聚芳醚砜无规共聚物。用FT-IR，WAXD，DSC和TG等方法对聚合物进行了表征。结果表明，随着2,2'-二甲基-4，4'-二苯氧基二苯砜含量的增加，共聚物的玻璃化转变温度逐渐提高，熔融温度则逐渐下降。     

Poly(ether amide) segmented block copolymers with adipic acid based tetraamide segments

Poly(tetramethylene oxide)‐based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration, which was varied between 3 and 44 wt %, were studied. The copolymers were characterized by differential scanning calorimetry and temperature‐dependent Fourier transform infrared, small‐angle X‐ray scattering, atomic force microscopy, and dynamic mechanical thermal analysis. The monodisperse tetraamide segments crystallized fast, forming crystalline ribbons with high aspect ratios, and the crystallinity of the tetraamide segments in the copolymers was typically 90%. The glass‐transition temperature of the poly(tetramethylene oxide) phase was low (?65 to ?70°C), and the modulus in the plateau region of the copolymers was virtually temperature‐independent. With increasing content of crystallizable amide segments in the copolymer, the storage modulus at room temperature increased from 1 to 102 MPa. This strong increase in the modulus with the tetraamide content could be approximated with a model for fiber‐reinforced polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

含三氟甲基聚芳醚酮的合成与表征

以六氟双酚A和4,4′–二氟二苯酮为原料,以N–甲基吡咯烷酮为溶剂采用新的合成工艺合成含三氟甲基聚芳醚酮,采用傅里叶变换红外光谱、核磁共振波谱及X射线衍射等对聚合物的结构和性能进行分析和表征。结果表明,采用新工艺合成的聚芳醚酮与传统工艺合成的树脂的热性能基本一致,具有良好的耐热性能,其玻璃化转变温度为162.6℃,氮气中5%热失重温度为517.1℃;80 kHz下含三氟甲基聚芳醚酮的介电常数为1.55,具有良好的电绝缘性;室温下能溶解于N–甲基吡咯烷酮、氯仿、四氢呋喃等有机溶剂。     

Synthesis and properties of novel copolymers of poly(ether ketone diphenyl ketone ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

New monomers, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP) and N,N′‐bis(4‐phenoxybenzoyl)?4,4′‐diaminodiphenyl ether (BPBDAE), were conveniently synthesized via simple synthetic procedures from readily available materials. Novel copolymers of poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) and poly(ether amide ether amide ether ketone ketone) (PEAEAEKK) were synthesized by electrophilic Friedel‐Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of BPOBDP and BPBDAE, over a wide range of BPOBDP/BPBDAE molar ratios, in the presence of anhydrous AlCl₃ and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by different physico‐chemical techniques. The copolymers with 10–40 mol% BPBDAE are semicrystalline and had remarkably increased T_gs over commercially available PEEK and PEKK due to the incorporation of amide and diphenyl linkages in the main chains. The copolymers IV and V with 30–40 mol% BPBDAE had not only high T_gs of 185–188°C, but also moderate T_ms of 326–330°C, having good potential for the melt processing. The copolymers IV and V had tensile strengths of 101.7–102.3 MPa, Young's moduli of 2.19–2.42 GPa, and elongations at break of 13.2–16.6% and exhibited high thermal stability and excellent resistance to organic solvents. POLYM. ENG. SCI., 54:1757–1764, 2014. © 2013 Society of Plastics Engineers     

干法纺丝用聚间苯二甲酰间苯二胺溶液的流变性能

研究了聚间苯二甲酰间苯二胺溶液的固体质量分数、相对分子质量、温度对溶液流变性能的影响。结果表明:聚间苯二甲酰间苯二胺溶液的流变性能受溶液固体质量分数、相对分子质量、温度的影响明显,聚合物相对分子质量增大、溶液固体质量分数增加均使溶液表观黏度增大,温度升高使溶液表观黏度减小,溶液表观黏度随剪切速率的变化幅度较小。试验结果表明:适合干法纺丝的聚间苯二甲酰间苯二胺溶液的固体质量分数为31%³5%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为5035%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为50¹20℃。     

醋酸丁酯酯化反应体系组分在PEBA膜中的吸附性能

采用实验和模型计算两种方法研究了醋酸丁酯酯化反应体系组分在涂布法制备的用于渗透汽化分离的PEBA膜材料中的吸附行为.分别用Flory-Huggins和ONIQUAC模型预测了全浓度范围内的水/有机物二元混合液在PEBA膜中的吸附量.用溶解度参数法得到Flory-Huggins模型中的相互作用参数;用纯溶剂与膜的平衡吸附数据拟合得到UNIOUAC模型中溶剂与膜的二元相互作用参数,而溶剂之间的二元相互作用参数可用文献中汽液平衡数据关联拟合.结果表明PEBA膜材料的亲有机物性能良好,对于四种组分的选择吸附性顺序为:醋酸正丁酯>正丁醇>醋酸>水,并且两种模型的计算结果基本一致.     

聚(芳基醚1,3,4-噁二唑)类聚合物的磺化及表征

为了探索影响芳香族聚噁二唑的磺化反应的因素,分别以发烟硫酸和氯磺酸为磺化试剂对几种含醚键聚芳噁二唑(PEODs)进行磺化,研究了以氯磺酸为磺化试剂时磺化反应时间、用量对磺化反应的影响,并分析了PEODs用于质子交换膜的潜在应用.磺化产物的结构与性能通过傅里叶红外(FT-IR)、氢谱(1H-NMR)、离子交换当量、热重分析(TGA)和溶解性等测试进行了表征.结果表明:发烟硫酸磺化产物磺化度不可控制,磺化度较氯磺酸的磺化产物高;采用氯磺酸磺化时,磺化时间对磺化反应没有影响,氯磺酸用量仅对侧苯基双酚A型聚噁二唑有影响;邻叔丁基型聚噁二唑的氯磺酸磺化产物有用于质子交换膜的潜力.     

耐高温聚芳醚砜的合成与表征

以联苯甲醛与2,6-二甲基苯酚为原料合成了一种新型双酚单体,与4,4’-二氟二苯砜进行缩聚,得到了一种新型含联苯结构的聚芳醚砜聚合物。测试了聚合物的溶解性,并用^1H NMR、DSC、TGA、GPC等方法进行了表征。结果表明,所合成的聚合物在NMP、DMF、DMSO等强极性非质子溶剂及CH2C12、THF、CHCl3等普通溶剂中具有较好的溶解性;具有高的摩尔质量（Mn=4．3×10^4g／mol）;玻璃化温度（Tg）为261℃,5％的热分解温度为421℃,说明其具有突出的耐高温性能。     

Semi-aromatic copoly(ether ether amide): Synthesis and properties

A series of semi-aromatic copoly(ether ether amide)s (hydroquinone (HQ) (0%)-HQ (100%)) were synthesized by 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BHPPE), 1,4-benzenediol (HQ) and 1,6-N,N′-bis(4-fuorobenzamide) hexane (BFBH) in this work. The inherent viscosities of copoly(ether ether amide)s were in the range of 0.487–0.769 dl g⁻¹. Following with increase of the content of HQ, the resultant polymers were converted from amorphous to crystalline. The copolymers were found to have high glass transition temperatures (T_g) of 141.4–155.6°C and weight-loss temperature (T_5%) of 423.3–434.3°C. They can be hot-pressed into films with tensile strength of 63.3–87.6 MPa, and storage modulus over 0.8 GPa at about 150°C, indicating good thermal and mechanical property of the obtained copolymers. The results of rheological property showed that the copolymers had good melt flowability and thermal stability. Additionally, the introduction of HQ improved the corrosion resistance of copolymers, the obtained polymers HQ (60%), HQ (80%) and HQ (100%) exhibited better corrosion resistance than that of HQ (0%). Especially, HQ (80%) and HQ (100%) were insoluble in organic polar solvents such as DMSO, DMF because of their crystalline nature, indicating that they had potential to be applied to the corrosion-resistant materials.     

新型含偶氮结构聚芳醚砜醚酮酮的合成与表征

在无水AlCl3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将含砜基芳二醚类单体与含偶氮苯结构芳二甲酰氯进行低温付-克缩聚反应,合成了一类新型含偶氮结构聚芳醚砜醚酮酮树脂。用IR、TG、WAXD及元素分析等技术进行了结构表征和性能测试。结果表明:所合成的聚合物树脂具有预期结构且为非晶态聚合物;在N2气氛中质量损失5%的温度(Td)分别为445～463℃;聚合物除了能在浓硫酸、CF3COOH/CHCl3等强极性质子型溶剂中溶解外,还能溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等强极性非质子型溶剂中,也能在普通溶剂,如氯仿(CHCl3)、1,2-二氯乙烷(DCE)、四氢呋喃(THF)等中溶解。     

Dispersion of Poly(phenylene ether) in a Poly(phenylene sulfide)/Poly(phenylene ether) Alloy

We have devised and developed a new method for the preparation of a poly(phenylene sulfide)/poly(phenylene ether) (PPS/PPE) alloy, which has micro‐dispersed PPE in the PPS matrix. PPS was chemically treated to activate the reactivity of the PPS end‐group by extrusion in the presence of diphenylmethane diisocyanate (MDI) in its molten state at 300°C. The reactive processing of the MDI‐treated PPS with maleic anhydride‐modified PPE gave a PPS/PPE alloy with micro‐dispersed PPE in the PPS matrix. The PPS/PPE alloy showed mechanical properties superior to those of PPS at elevated temperature (150°C) and also showed precision‐molding ability superior to that of PPS.