两亲性聚合物修饰的大粒径金纳米粒子的相转移

通过对线性聚乙烯亚胺（linear polyethylenimineLPEI）的棕榈酸改性和季铵化制备了具有两亲性结构的线性聚合物。两亲性线性聚合物在没有诸如硫醇、四正辛基溴化铵（TOAB）等其它化学物质的协助下,通过氨基和柠檬酸钠负离子之间的离子键或氢键相互作用,成功将粒径为18nm柠檬酸钠保护的金纳米粒子（AuNP...     

两亲性超支化聚合物的研究进展

两亲性超支化聚合物作为一种新型功能性材料.近年来引起了人们的广泛关注.两亲性超支化聚合物的合成丰要是利用不同亲水性的链段对超支化聚合物端基进行改性,或者首先在超支化聚合物末端产生活性位点,再利用超支化分f作为大分子引发剂引发烯类单体进行斤环聚合、原子转移自由基聚合等得到以超支化聚合物为核的两亲性超支化共聚物;这些分子由...     

ZIF-67改性木质素磺酸钠/聚乙烯亚胺层层自组装膜的纳滤性能研究

基于木质素磺酸钠/聚乙烯亚胺纳滤膜的可行性,制备了ZIF-67改性的木质素磺酸钠/聚乙烯亚胺复合纳滤膜。通过层层自组装技术在聚砜基膜上沉积了ZIF-67改性的聚电解质阴/阳离子层,以不同的料液Mg SO_4、CaCl_2和NaCl为分离体系来探究ZIF-67改性木质素磺酸钠/聚乙烯亚胺复合膜的分离性能,发现本研究制备的ZIF-67改性木质素磺酸钠/聚乙烯亚胺复合膜在不降低截留率的前提下,渗透通量较木质素磺酸钠/聚乙烯亚胺纳滤膜可提高到约原来的两倍。本文运用层层自组装技术制备的ZIF-67改性的新型纳滤膜,可应用于水软化领域且简便可行。     

两亲性树状接枝己内酯共聚物的合成与表征

通过树状接枝聚己内酯的侧羟基及端羟基与氯甲酰化的聚乙二醇进行接枝反应,得到带有亲水性聚乙二醇链段的新型两亲性树状接枝共聚物.1H-NMR分析显示,接枝率为50%左右.GPC分析结果表明,共聚物分子量呈较窄的单峰分布,分子量与接枝前相比明显增高.两亲性共聚物能直接分散在水中形成胶束溶液.以芘为荧光探针的测试结果表明其临界胶束浓度有降低.动态光散射测得胶束平均粒径在16至31 nm之间,粒径分散指数适中,PDI在0.25至0.39之间.TEM显示胶束粒子为不规整球形,由更小的粒径为几个纳米的微粒聚集而成,这些微粒的大小刚好与单个大分子的尺寸相匹配.因此,两亲性树状接枝聚己内酯在水相中存在单分子胶束与多分子组装胶束的平衡.得益于支化聚合物结构中的纳米空腔,两亲性树状接枝聚合物胶束对紫杉醇具有优良的包载能力.     

两亲性梳状聚醚硅氧烷对相转化法聚偏氟乙烯多孔膜的共混改性作用研究

以聚醚链段为侧链的两亲性梳状聚醚硅氧烷(ACPS)为改性剂,研究了相转化法制备聚偏氟乙烯(PVDF)多孔膜的改性效果与机理.采用SEM、XPS、接触角、水通量等考察了ACPS对膜结构与性能的影响.研究发现,ACPS在相转化成膜过程中不流失,随着制膜液中ACPS含量的增加,相分离速度降低,膜中微孔由指状结构向蜂窝状结构发展,膜强度提高,亲水性显著提高.提出了ACPS在膜表面的富集现象和在膜中的稳定性机理和模型.结果表明,两亲性梳状聚醚硅氧烷在原理上是一类适合于相转化法制备聚合物微孔膜表面亲水化改性的有效物质.     

两亲性树形-线团大单体的合成及其丙烯酸共聚乳液的流变行为

将3,4,5-三(十六烷基氧基)苯甲酰氯先后与分子量为1000的聚乙二醇、甲基丙烯酰氯反应合成了一种新的可聚合两亲性树形-线团大单体——3,4,5-三(十六烷氧基)苯甲酰氧基聚氧乙烯甲基丙烯酸酯(6).通过核磁、红外、元素分析等对产物进行了表征.然后将其与甲基丙烯酸、丙烯酸乙酯进行乳液共聚合,制备了一种疏水树形侧链改性...     

新型链行走烯烃聚合催化剂的合成及其催化活性

以二氯化镍为原料制得配合物(DME)Ni Cl2(1);以2,6-二异丙基苯胺和丁二酮为原料,经缩合反应制得α-二亚胺配体(2);1与2经络合反应合成了一种用于乙烯齐聚制备超支化聚乙烯的新型链行走催化剂(3),其结构经IR,XRD和元素分析表征。以乙烯齐聚为探针反应,考察了助催化剂,反应温度和反应时间对3催化活性的影响。结果表明:在较优反应条件[Al Et30.14 mol,n(Al)∶n(Ni)=600,于20℃反应0.5 h]下,3催化活性为2.5×106g PE·(mol·Ni·h·MPa)-1。齐聚产物为支化聚乙烯,部分支链中碳原子数大于4。     

荧光技术在两亲性聚合物研究中的应用

本文综述了应用荧光技术研究不同结构的两亲性聚合物性质的研究进展,涉及的不同结构两亲性聚合物主要有两亲性嵌段共聚物、两亲性接枝共聚物、两亲性树状聚合物以及其他结构的两亲性聚合物;说明了荧光技术可以用于研究聚合物疏水(或亲水)基团的结构参数(如骨架、长度、取代度和分子量)的变化,对两亲性聚合物的微环境性质(如微极性、微黏度、局部黏结力)、聚集行为(如临界聚集浓度)以及其他性质(如临界胶束浓度)的影响规律,以便对功能性更强的两亲性聚合物的合成提供理论指导。     

聚乙二醇-聚乳酸-聚甲基丙烯酸羟乙酯两亲性三嵌段聚合物的合成及其自组装研究

具有生物相容性的两亲性嵌段共聚物在水中易形成胶束,在医学诊断、体内药物缓释及药物靶向输送方面具有广阔的应用前景.利用二嵌段聚合物聚乙二醇-聚乳酸(PEG-PLA)引发甲基丙烯酸羟乙酯的原子转移自由基聚合,制备了两亲性三嵌段聚合物聚乙二醇-聚乳酸-聚甲基丙烯酸羟乙酯(PEG-PLA-PHEMA),利用凝胶渗透色谱(GPC),红外光谱(FT-IR),1H NMR表征了其聚合物组成;然后利用透析法制备了不同分子量的聚合物胶束,动态光散射(DLS)和透射电镜(TEM)结果表明其形貌规整、尺寸均一,而且胶束粒径在PEG和PLA链段长度不变的条件下,随PHEMA链段的变长而增大.PHEMA链上大量羟基的存在为聚合物胶束的功能化改性提供了反应位点,加上本身完全由具良好生物相容性的聚合物制备,使其在可控药物释放方面具有很大的应用潜力.     

基于Diels-Alder反应的热可逆交联聚乙烯的合成

分别以Ziegler-Natta催化剂和茂金属催化剂(rac-Et(Ind)_2ZrCl_2)引发乙烯/6-呋喃-1-己烯(FH)共聚合,合成了侧基含有呋喃取代基的聚乙烯。再以1,6-二马来酰亚胺基己烷(BMH)为交联剂,通过Diels-Alder反应制备了交联聚乙烯。利用~1H-NMR、DSC等对乙烯/FH共聚物结构进行了表征,利用FTIR、拉伸测试、蠕变实验等对交联聚乙烯的结构与性能进行测定。结果表明,通过改变马来酰亚胺与呋喃的比例可以调节聚乙烯的交联程度,同时Diels-Alder反应的热可逆性赋予交联聚乙烯重复加工性。     

Rodlike macromolecules through spatial overlapping of thiophene dendrons

Two novel dendritic macromonomers 7 and 8 functionalized with electroactive conjugated thiophene oligomers were synthesized by stepwise cross‐coupling reactions and the introduction of a vinyl group at the focal point. Both macromonomers were polymerized into dendronized polymers 9 and 10 by using a radical polymerization method. The photophysical and redox behaviors of dendronized polymers 9 and 10 are significantly different from those of the corresponding macromonomers. This difference may result from the spatial overlapping of thiophene dendrons through π–π interactions when the dendrons are connected to a polymer backbone. The dendronized polymers can organize into large‐area two‐dimensional sheets with a thickness of 4.8 nm. Polymer 9 , which has all‐dendritic thiophene side chains, exhibited enhanced conductivity by partial doping with iodine or nitrosonium tetrafluoroborate (NOBF₄). The novel amphiphilic dendronized polymer 15 was synthesized by the atom‐transfer radical polymerization of macromonomer 7 from a poly(ethylene glycol) (PEG) macroinitiator and was found to have a self‐organized structure in water.     

A “click” approach to ROMP block copolymers

Amphiphilic block copolymers can be conveniently prepared via convergent syntheses, allowing each individual polymer block to be prepared via the polymerization technique that gives the best architectural control. The convergent “click‐chemistry” route presented here, gives access to amphiphilic diblock copolymers prepared from a ring opening metathesis polymer and polyethylene glycol. Because of the high functional group tolerance of ruthenium carbene initiators, highly functional ring opening metathesis polymerization (ROMP) polymer blocks can be prepared. The described synthetic route allows the conjugation of these polymer blocks with other end‐functional polymers to give well‐defined and highly functional amphiphilic diblock copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2913–2921, 2008     

Modification of porous poly(vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase inversion process

Three kinds of amphiphilic polymers, including the tri-block copolymer of (polyethylene oxide)–(polypropylene oxide)–(polyethylene oxide) (I, EPTBP), the comb-like copolymer of polysiloxane with polyethylene oxide and polypropylene oxide side chains (II, ACPS) and the hyperbranched star copolymer of polyester-g-methoxyl polyethylene glycol (III, HPE-g-MPEG), were blended with PVDF to fabricate porous membranes via a phase inversion process, respectively, and the effects of the different structures of the amphiphilic polymers on the properties of the blend membranes were compared. The membranes were characterized by scanning electron microscopy (SEM), elemental analysis, X-ray photoelectron spectroscopy (XPS) analysis, mercury porosimetry, water contact angle measurements, etc. The anti-fouling properties of the prepared membranes were evaluated by static and dynamic bovine serum albumin (BSA) adsorptions. Specially, the stabilities of these amphiphilic polymers in the final membranes were estimated by continuous leaching tests. At the same time, the properties of the membranes using the amphiphilic polymers as modifiers were compared with those of the membrane using poly(ethylene glycol) (PEG) as modifier.     

Postpolymerization modification of poly(pentafluorophenyl methacrylate): Synthesis of a diverse water‐soluble polymer library

This article explores the feasibility of poly(pentafluorophenyl methacrylate) (PPFMA) prepared by reversible addition fragmentation chain transfer (RAFT) polymerization as a platform for the preparation of diverse libraries of functional polymers via postpolymerization modification with primary amines. Experiments with a broad range of functional amines and PPFMA precursors of different molecular weights indicated that the postpolymerization modification reaction proceeds with good to excellent conversion for a diverse variety of functional amines and is essentially independent of the PPFMA precursor molecular weight. The RAFT end group, which was well preserved throughout the polymerization, is cleaved during postpolymerization modification to generate a thiol end group that provides possibilities for further orthogonal chain‐end modification reactions. The degree of postpolymerization modification can be controlled by varying the relative amount of primary amine that is used and random polymethacrylamide copolymers can be prepared via a one‐pot/two‐step sequential addition procedure. Cytotoxicity experiments revealed that the postpolymerization modification strategy does not lead to any additional toxicity compared with the corresponding polymer obtained via direct polymerization, which makes this approach also of interest for the synthesis of biologically active polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4332–4345, 2009     

Multiblock poly(4‐vinylpyridine) and its copolymer prepared with cyclic trithiocarbonate as a reversible addition–fragmentation transfer agent

The polymerization of 4‐vinylpyridine was conducted in the presence of a cyclic trithiocarbonate (4,7‐diphenyl‐[1,3]dithiepane‐2‐thione) as a reversible addition–fragmentation transfer (RAFT) polymerization agent, and a multiblock polymer with narrow‐polydispersity blocks was prepared. Two kinds of multiblock copolymers of styrene and 4‐vinylpyridine, that is, (ABA)_n multi‐triblock copolymers with polystyrene or poly(4‐vinylpyridine) as the outer blocks, were prepared with multiblock polystyrene or poly(4‐vinylpyridine) as a macro‐RAFT agent, respectively. GPC data for the original polymers and polymers cleaved by amine demonstrated the successful synthesis of amphiphilic multiblock copolymers of styrene and 4‐vinylpyridine via two‐step polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2617–2623, 2007     

Vine-twining polymerization: a new preparation method for well-defined supramolecules composed of amylose and synthetic polymers

In this article we describe a new method of polymerization called "vine-twining polymerization" for preparation of well-defined supramolecules, which are amylose-polymer inclusion complexes. The method was achieved by enzymatic polymerization of alpha-D-glucose-1-phosphate catalyzed by phosphorylase in the presence of various synthetic polymers such as polyethers, polyesters, poly(ester-ether), and amphiphilic block copolymer. Powder X-ray diffraction (XRD) and 1H-NMR measurements determined the structures of the products to be inclusion complexes. The XRD patterns were completely different from those of amylose and guest polymers. The 1H-NMR spectra of the products indicated that the structures were composed of amylose and guest polymers. The formation process of the inclusion complexes during the enzymatic polymerization was also evaluated. In addition, we revealed that the bulkiness of the end groups and the hydrophobicity of the guest polymers strongly affected the formation of the inclusion complexes. By means of this method of polymerization, a graft polymer having inclusion complexes as side chains was prepared. Furthermore, as an evolution of the "vine-twining polymerization," we attempted a system of parallel polymerization to form an inclusion complex of amylose with a strongly hydrophobic guest polymer.     

两亲性杂侧链聚合物刷的合成及其乳化功能

报道了一种随机高密度接枝亲水、疏水聚合物侧链的刷形两亲性聚合物.首先,结合可逆加成-断裂链转移(RAFT)聚合和后修饰方法,得到含叠氮侧基的聚甲基丙烯酸缩水甘油酯(PGMA-N3)作为主链;再分别合成端炔基聚苯乙烯(PS)和端炔基聚环氧乙烷(PEO),然后通过铜催化的叠氮-炔环加成反应,将疏水性PS和亲水性PEO同时高效的接到PGMA主链上,制得两亲性杂侧链的聚合物刷.由凝胶渗透色谱(SEC)分析得知,在主链叠氮基团与两侧链总炔基的摩尔投料比为1∶1的条件下,PS和PEO的接枝效率很高,都大于90%.通过调节主链长度和2种侧链的投料比,获得不同组成的聚合物刷.通过等质量的甲苯/水混合体系,考察两亲性聚合物刷的乳化能力,发现主链聚合度为100,PS∶PEO比例为70∶30的聚合物刷表现出最佳的乳化性能.     

Hyperbranched‐upon‐dendritic macromolecules as unimolecular hosts for controlled release

Novel amphiphilic hyperbranched‐upon‐dendritic polymers with a dendritic polyester core, a linear poly(ε‐caprolactone) (PCL) inner shell, and a hyperbranched polyglycerol outer shell have been prepared. The structures of the hyperbranched‐upon‐dendritic polymers were characterized by using NMR spectra. The critical aggregating concentrations (CACs) of those amphiphilic hyperbranched‐upon‐dendritic polymers were measured by using pyrene as the polarity probe. To study the encapsulation performances of those hyperbranched‐upon‐dendritic polymers as unimolecular hosts, inter‐molecular encapsulation was carefully prevented by controlling the host concentrations below their CACs and by washing with good organic solvents. The study on encapsulation of two model guest molecules, pyrene and indomethacin, was performed. The amounts of encapsulated molecules were dependent mainly on the size of inner linear shells. About three pyrene molecules or five indomethacin molecules were encapsulated in hyperbranched‐upon‐dendritic polymers with average PCL repeating units of two but different hyperbranched polyglycerol outer shells, whereas about five pyrene molecules or about 12 indomethacin molecules were encapsulated in those with PCL repeating units of nine. The encapsulated molecules could be released in a controlled manner. Thus, the hyperbranched‐upon‐dendritic polymers could be used as unimolecular nanocarriers with controllable molecular encapsulation dosage for controlled release. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4013–4019, 2010     

Preparation and characterization of conjugated polymers made by postpolymerization reactions of alternating polyketones

Conjugated polymers possessing a poly(2,5-dimethylene-2,5-dihydrofuran) backbone were prepared through postpolymerization reaction of styrenic polyketones with bromine in one-pot reactions. The modification is proposed to proceed via condensation of two repeating units to form a fully characterized polymer with a poly(2,5-dimethylenetetrahydrofuran) backbone. Subsequent bromination and elimination of HBr yield a polymer with a fully conjugated carbon backbone. The new conjugated polymers were characterized by NMR, IR, and UV-vis spectroscopies and by CV. These polymers have strong absorption in the visible region, with the absorption peaks shifted to the NIR region upon doping with acids. The ease of the synthesis of the starting polyketone and of the modifications allows large-scale preparation of those conjugated polymers.