聚砜-尼龙6嵌段共聚体的溶液性质及其与聚砜、尼龙6均聚物的相容性的研究

<正> 我们曾在前二篇文章中指出非晶型双酚A聚砜(以下用B表示)与结晶形尼龙6(以下用N表示)经共混得到的共混物很脆,而聚砜-尼龙6嵌段共聚物(以下用B-N和N-B-N表示)却具有较B或N更优的耐溶剂性和耐水性,但是嵌段共聚物中B组分含量不能超过25％,这样就限制了材料的使用范围,然而由于B-N(或N-B-N)在同一分     

聚砜-聚羟基醚嵌段共聚体的合成与表征

在碱性条件下由羟端基聚砜与双酚A环氧氯丙烷相互作用下制取了聚砜-聚羟基醚嵌段共聚物。溶解度试验、红外光谱、动态和静态力学试验等证明产物确是嵌段共聚物。     

双酚A聚砜链对对苯二酚聚砜链结晶性能的影响

本文报导了双酚A聚砜(B)与对苯二酚聚砜(H)两组份含量不同的嵌段共聚物的X射线衍射结果,B链的加入,使共聚物的结晶性能被破坏,B/H为0.48(摩尔比)时,所得共聚物已呈现出完全非晶相结构的特征.由IGC及DSC实验测定,表明这两种聚砜链是相容的.     

一种光学活性三嵌段共聚物的ATRP合成及表征

以溴代聚砜为大分子引发剂,三(2-二甲氨基乙基)胺(Me6TREN)/CuBr为催化体系,通过原子转移自由基聚合(ATRP)制备了结构预定且分子量分布窄的光学活性三嵌段共聚物,聚(N-甲基丙烯酰-L-亮氨酸甲酯)-嵌-聚砜-嵌-聚(N-甲基丙烯酰-L-亮氨酸甲酯)(PMALM-b-PSF-b-PMALM).通过核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、端羟基滴定等方法,研究了所合成的三嵌段共聚物的结构.利用差示扫描量热法(DSC)、热失重分析(TGA)以及圆二色谱(CD)研究了嵌段共聚物的热性能和旋光性能.根据TGA计算出的PMALM链段与PSF链段的重复单元数之比,与1H-NMR计算的结果能较好的吻合.共聚物在聚合过程中旋光度发生了反转,且比单体的旋光度的绝对值显著增加,这可能是由于聚合过程中分子主链感应出了手性的二级结构诱导出手性放大效应引起的.在CH3OH/CCl4混合溶剂中,共聚物比旋光度的绝对值随溶剂极性增大呈线性减小趋势,这一结果与CD一起证实了PMALM链段的无规卷曲结构.     

含有机硅三元多嵌段共聚物的研究──Ⅲ．不同硬段、半硬段对含有机硅三元多嵌段共聚物性能的影响

以双酚Ａ聚砜或酚酞作为硬段，聚对羟基苯乙烯、酚醛、聚羟基醚或聚羟基醚砜作为半硬段，聚二甲基硅氧烷作为软段合成了七种三元多嵌段共聚物，并对其稳定性、动态力学性能进行了比较详细的研究。结果表明这类共聚物在溶液中的稳定性及热稳定性主要与半硬段有关；它们的形态结构同属于微相分离，并在很宽的温度范围内表现出优良的弹性体性质。三元多嵌段共聚物中硬段与半硬段的相容性直接影响其力学性能，当两者的相容性好时，其强度高于对应的二元多嵌段共聚物。     

用薄层色谱法表征苯乙烯-二甲基硅氧烷嵌段共聚物的结构

常规的红外或核磁法不能区别嵌段共聚物与均聚物的共混物。不同类型嵌段共聚物间的区别更加困难.我们用薄层色谱法(TLC)来表征嵌段共聚物的结构.根据TLC吸附机理,利用展开剂的极性大小可将均聚物及嵌段共聚物迅速地区别、鉴定与分离.实验时应注意控制条件以抑制薄层吸附剂的分子筛效应,避免分子量及其分布的干扰.     

含有机硅多嵌段及其接枝共聚物的表面组成

利用ＸＰＳ对聚二甲基硅氧烷与聚砜或／和聚对羟基苯乙烯组成的二元和三元多嵌段和接枝共聚物及其共混物进行了研究。结果表明溶液成果的聚合物样品的表面都存在有机硅富集，共混物的表面富集程度等于接枝共聚物，更高于多嵌段共聚物，讨论了有机硅含量和键接结构对有机硅表面富集的影响。     

嵌段共聚物三维软受限自组装

嵌段共聚物在三维软受限条件下能够组装形成结构有序的聚合物胶束,其在催化、电子器件、光学传感等领域有广泛的应用价值,已经引起了广大科研工作者的关注。众所周知,嵌段共聚物自身性质及组装体内部结构和外部形状都会显著影响嵌段共聚物组装体性质及应用。本文简述了近年来嵌段共聚物三维软受限自组装的方法,分析了影响嵌段共聚物组装结构的内在和外在因素,内在因素主要指嵌段共聚物自身性质,包括嵌段共聚物种类、分子量及嵌段比;外在因素主要包括受限空间尺寸、界面性质、热或溶剂退火等。本文讨论了无机纳米粒子与嵌段共聚物三维软受限共组装,探讨了纳米粒子引入对组装结构影响及其在嵌段共聚物组装体中的分布及排列规律,以及组装结构的潜在应用。最后还讨论了目前嵌段共聚物三维软受限自组装存在的问题,同时对未来的发展方向进行了展望。     

结晶/无定形PMMA-b-PHBV-b-PMMA三嵌段共聚物的合成及热稳定性表征

以生物质聚酯聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)为结晶组分、聚甲基丙烯酸甲酯(PMMA)为无定形组分,通过原子转移自由基聚合法(ATRP)制备了ABA型结晶/无定形三嵌段共聚物.采用凝胶色谱法(GPC)、傅里叶红外光谱(FTIR)和核磁共振氢谱(1H-NMR)表征了三嵌段共聚物的分子量及其分子量分布和化学结构;使用热失重分析仪(TG)测试了三嵌段共聚物的热稳定性,并通过Horowitz-Metzger法计算了嵌段共聚物的降解表观活化能.研究表明,三嵌段共聚物的最大转化产率为92.39%;当单体与大分子引发剂的比例为8∶1时,三嵌段共聚物的T0、T5%、T max温度分别提高25 K、15 K和40 K,三嵌段共聚物降解表观活化能E a可由纯PHBV的428.25 kJ·mol-1降低至169.83 kJ·mol-1.     

含有机硅三元多嵌段共聚物的研究──Ⅱ．（PSF－PDMS－PHS）_n的动态力学性能研究

以双酚Ａ聚砜（ＰＳＦ）为硬段、聚对羟基苯乙烯（ＰＨＳ）为半硬段、聚二甲基硅氧烷（ＰＤＭＳ）为软段合成了三元多嵌段共聚物，并对其动态力学性能和抗张性能进行了比较详细的研究，结果表明该三元多嵌段共聚物为多相结构；在引入半硬段ＰＨＳ后两相间的界面相增宽，粘接力增大，其强度和模量高且稳定，使含有机硅高分子材料强度低的弱点得以改善。扭辩分析（ＴＢＡ）结果显示，这种三元多嵌段共聚物具有多重转变，且在－２０℃至５０℃间有两个较大的几乎重叠的吸收峰；这表明这种三元多嵌段共聚物的相分离结构较为复杂，并有良好的阻尼性能。     

Synthesis and characterization of nanostructured-segmented block copolyetheramide based on nylon6 and poly(ethylene oxide)

<正>Segmented block copolymer based on nylon6(N6) and polyethylene oxide(PEO) with stochiometric ratio was synthesized via a two-step process.The first step represents end capping of N6 in the presence of adipic acid leading to carboxy terminated N6,and the second one is polycondensation of the latter product with PEO in the presence of catalyst and thermostabilizer to form a high molecular weight multi-block copolymer.Several methods were applied to characterize the synthesized copolymer such as Fourier transform infrared spectroscopy,proton nuclear magnetic resonance spectroscopy,differential thermal analysis,differential scanning calorimetry,X-ray diffraction and atomic force microscopy. The obtained results confirmed the multi-block structure for copolymer with a very high degree of micro-phase separation. Atomic force microscopy micrographs indicated that the morphology was the dispersion of high stiffness nanostructured polyamide(PA) domains in the amorphous region of PEO matrix,which can be very important in their performance for membrane processes.     

聚肽接枝共聚物的自组装行为研究

Polymeric micelles of poly(γ-benzyl L-glutamate)(PBLG)-poly(ethylene oxide)(PEO) graft copolymer were prepared by the dialysis method in deionized water. Fluorescence spectroscopy, nuclear magnetic resonance(NMR) and transmission electron microscope(TEM) were used for the investigation of the self-assembly of PBLG-PEO graft copolymer. Fluorescence spectrosco0y measurements suggest that PBLG-PEO graft copolymer associates to form polymeric micelles in water. ^1H NMR measurements further prove that in aqueous medium PBLG-PEO graft copolymer could assemble into polymeric micelles with PBLG segments as the hydrophobic inner core and PEO segments as the hydrophilic shell. The results of the TEM observations show that the polymeric micelles of PBLG-PEO graft copolymer are almost spindly shaped, which are different from the morphology of the spherical micelles formed by PBLG-PEO block copolymer. Polymeric micelles formed by polypeptide copolymer have potential application as drug carrier in controlled-release delivery system.     

Block polymers from isocyanate-terminated intermediates. II. Preparation of butadiene–ϵ-caprolactam and styrene–ϵ-caprolactam block polymers

Polystyrene–nylon 6 and polybutadiene–nylon 6 block copolymers have been prepared from isocyanate-terminated prepolymers. From extraction and fractionation data the products obtained were found to be mixtures of both homopolymers and pure block copolymer. The polybutadiene–nylon 6 copolymers are extremely pliable at ambient temperatures even at high ?-caprolactam contents (70–80 wt-%). This is true even though these copolymers show a crystalline melting point at 213°C similar to poly-?-caprolactam. Presumably this unusual behavior occurs because of the nature of the synthesis which renders the butadiene portion of these copolymers the continuous phase. Plasticity measurements indicate that pliability is dependent on the molecular weight of the block poly-?-caprolactam.     

Nanocrystallization-locked Network of Poly(styrene-b-isobutylene-b-styrene)-g-Polytetrahydrofuran Block Graft Copolymer

Poly(styrene-b-isobutylene-b-styrene) triblock copolymer(SIBS), a kind of thermoplastic elastomer with biocompatibility and biostability containing fully saturated soft segments, could be synthesized via living cationic copolymerization. A novel poly[(styrene-comethylstyrene)-b-isobutylene-b-(styrene-co-methylstyrene)]-g-polytetrahydrofuran(M-SIBS-g-PTHF) block graft copolymer was prepared to increase the polarity and service temperature of SIBS by grafting polar PTHF segments onto SIBS. A series of the above block graft copolymers with average grafting numbers from 2 to 6 and molecular weights of PTHF branches ranging from 200 g·mol~(-1) to 4200 g·mol~(-1) were successfully synthesized via living cationic ring-opening polymerization of tetrahydrofuran(THF) coinitiated by AgClO_4. The introduction of PTHF branches led to an obvious microphase separation due to thermodynamic incompatibility among the three kinds of segments of polyisobutylene(PIB),polystyrene(PS) and PTHF. Moreover, the microphase separation promotes the rearrangement of PTHF branches to form the nanocrystallizationlocked physically cross-linked network after storage at room temperature for 2 months, leading to insolubility of the copolymers even in good solvents. The melting temperature and enthalpy of PTHF nanocrystallization locked in hard domains of M-SIBS-g_5-PTHF~(-1).1 k block graft copolymer increased remarkably up to 153 °C and 117.0 J·g~(-1) by 23 °C and 11.6 J·g~(-1) respectively after storage for long time. Storage modulus(G')is higher than loss modulus(G') of M-SIBS-g-PTHF block graft copolymer at temperatures ranging from 100 °C to 180 °C, which is much higher than those of the SIBS triblock copolymer. To the best of our knowledge, this is the first example of high performance M-SIBS-g-PTHF block graft copolymers containing segments of PIB, PS and PTHF with nanocrystallization-locked architecture.     

热处理对尼龙6及其与聚酰胺嵌段共聚物共混体系晶体熔融行为和结晶结构的影响

采用溶液共混-共沉淀的办法获得尼龙6及聚酰胺嵌段共聚物/尼龙6共混体系粉末,样品在260℃下熔融之后经程序降温的方法得到非淬火样品,然后分别在190℃下高温退火不同时间(0~48 h),采用示差扫描量热仪(DSC)、广角X射线衍射仪(WAXD)、偏光显微镜(POM)等表征手段研究热处理对体系晶体熔融行为和结晶结构的影响.结果表明,(1)在相同的热历史条件下,嵌段共聚物的存在影响了尼龙6的结晶行为及结晶结构;(2)退火处理对两种样品有着不同的影响,对于尼龙6体系,退火处理促进了非晶相向晶相的转变,大大提高样品的结晶完善程度和结晶度;对于共混体系,退火处理同样促进了非晶相向晶相的转变,同时形成新的α型和γ型结晶,体系的结晶完善程度明显提高,退火48 h后,结晶度比原始样品提高约84%.     

Morphological investigations of block sulfonated poly(arylene ether ketone) copolymers as potential proton exchange membranes

A series of block sulfonated poly(arylene ether ketone) (SPAEK) copolymers with different block lengths and ionic contents were synthesized by a two‐stage process. The morphology of these block SPAEK copolymers was investigated by various methods, such as differential scanning calorimetry (DSC), transmission electron microscope (TEM), and small angle X‐ray scattering (SAXS). Dark colored ionic domains of hundreds of nanometers spreading as a cloud‐like belt were observed in TEM images. The sizes of the ionic domains as a function of block copolymer composition were determined from SAXS curves. The results for the evolution of ionic domains revealed that the block copolymers exhibited more clearly phase‐separated microstructure with increasing ionic contents and hydrophobic sequence lengths. Proton conductivity is closely related to the microstructure, especially the presence of large interconnected ionic domains or ionic channels. Block SPAEK membranes have interconnected ionic clusters to provide continuous hydrophilic channels, resulting in higher proton conductivity. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and morphology of all‐conjugated donor–acceptor block copolymers based on poly(3‐hexylthiophene) and poly(naphthalene diimide)

A series of all‐conjugated diblock and triblock copolymers comprised of poly(naphthalene diimide) (PNDI)‐based n‐type and the poly(3‐hexylthiophene) (P3HT) segments could be synthesized via the Kumada catalyst‐transfer polycondensation process. The crystalline structures and chain orientation of the block copolymer thin films were systematically studied by grazing incident wide‐angle X‐ray scattering (GIWAXS). The GIWAXS results indicated that both the P3HT and PNDI segments in the block copolymers form exclusive crystalline domains in which the P3HT domain aligns with an edge‐on rich orientation, and the PNDI domain aligns with a face‐on rich orientation. In contrast, the blend films of the P3HT and PNDI homopolymers also show two distinguished crystalline domains in which the P3HT domain aligns with an edge‐on rich orientation, and the PNDI domains align in different ways depending on the chemical structure of n‐type polymers, that is, PNDI1Th is isotropically dispersed, while PNDI2Th aligns with a face‐on rich orientation. In addition, the effect of thermal annealing on the crystalline behavior of the block copolymers is reported. The GIWAXS results indicated that thermal annealing increases the crystallinity of both segments without affecting their chain orientation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1139–1148     

Anionic block copolymerization of ϵ-caprolactam

?-Caprolactam anionic homopolymerization was studied in the presence of different model activators. On the basis of the results ester- and isocyanate-terminated polymers were used as macroactivators and nylon-6–polyvinyl or polydiene block copolymers were synthesized in high yields. The physical properties and morphology of a nylon–polybutadiene triblock copolymer were characterized.     

聚芳醚腈-聚硅氧烷嵌段共聚物的合成

采用4-烯丙基-2-甲氧基苯酚(Eugenol)为端基的聚二甲基硅氧烷与氟代苯端基含杂萘联苯结构聚芳醚腈,以碳酸钾为催化剂,二甲基亚砜与邻二氯苯为溶剂的条件下进行芳香亲核取代反应(SNAr),合成了一种高分子量的聚芳醚腈-聚硅氧烷嵌段共聚物,并采用FTIR和1H-NMR对该产物的结构进行了表征.DSC测试结果表明该类嵌段共聚物具有两个玻璃化转变温度(Tg),分别为-98～-90℃和255～287℃,而且共聚物具有优良的耐热性,10%的热失重温度(Td)在450℃以上.采用原子力显微镜和透射电镜观测发现该共聚物存在明显的相分离特征.     

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

A block copolymer composed of a flexible polar poly(ethylene glycol) (PEG) and a less polar liquid crystalline poly(allene) segments is prepared by the living coordination polymerization of an allene derivative possessing trans‐azobenzene‐containing mesogenic substituent by the use of a π‐allylnickel macroinitiator bearing PEG segment. The thin film of the block copolymer is prepared by the spin coating of its solution onto mica or silicon wafer which proves to possess perpendicularly oriented nanocylindrical microphase separated structures as supported by the differential calorimetric, polarized optical microscopic, grazing‐incidence small‐angle X‐ray scattering, transmission electron microscope, and atomic force microscope measurements.