含8-羟基喹啉侧基二嵌段共聚物的合成

以8-羟基喹啉和甲基丙烯酸羟乙酯为原料,经一系列反应得到含8-羟基喹啉配体结构的甲基丙烯酸甲酯类单体（HQMA）,再利用可逆加成-断裂链转移（RAFT）法实现该单体的活性可控聚合,然后以此聚合产物为大分子RAFT试剂,与苯乙烯实现活性可控聚合得二嵌段共聚物,并用1H NMR和GPC对其进行了表征,确定了其组成和结构;研究了所得共聚物在四氢呋喃（THF）（作共溶剂）和甲苯（Tol）（作选择性溶剂）混合溶剂中的自组装行为,结果表明,当共溶剂（THF)和选择性溶剂(甲苯)的体积比为V(THF):V（甲苯）=5:5和V(THF):V（甲苯）=4:6时,形成的胶束是球形的,当V(THF):V（甲苯）=2:8形成的胶束是蠕虫状的。     

PCL-b-PNAGA嵌段共聚物的制备及表征

聚己内酯(PCL)是一种性能优良的生物相容性及降解性良好生物材料,在生物医药方面有着巨大的潜能,但其具有很强的疏水性。本文利用N-丙烯酰基甘氨酰胺(NAGA)的亲水性通过可逆加成-断裂链转移聚合(RAFT)制备嵌段共聚物PCL-b-PNAGA,并通过FI-IR和1H-NMR表征证明了各个产物的成功制备。结果表明:成功制备了单体NAGA,大分子链转移剂PCL-CTA和嵌段共聚物PCL-b-PNAGA。     

温敏性嵌段聚合物的自组装性能

利用可逆加成-断裂链转移自由基聚合法(RAFT)制备了聚N-异丙基丙烯酰胺/聚丙烯酸乙酯(PNIPAM/PEA)的ABA型和BAB型三嵌段聚合物(A=PNIPAM,B=PEA),考察了共聚物的自组装性能和温度响应性能,探讨了各嵌段组分的用量和嵌段序列对共聚物性能的影响。结果表明:三嵌段共聚物都具有良好的温敏性和自组装性能;BAB型嵌段聚合物溶液的LCST值随着疏水组分PEA的增多呈现先增大后降低;在相同温度下,BAB型的胶束粒径明显小于ABA型的胶束粒径,并能在较低温度下发生相转变。     

通过RAFT法制备双亲性嵌段共聚物及诱导自组装行为

通过可逆-加成断裂链转移自由基聚合(RAFT)成功制备了聚甲基丙烯酸甲酯-聚丙烯酸叔丁酯嵌段共聚物(PMMA-b-PtBA),在三氟乙酸的作用下选择性水解,得到聚甲基丙烯酸甲酯-聚丙烯酸双亲性嵌段共聚物(PMMA-b-PAA),利用1HNMR,FTIR和GPC对两种产物的结构进行了表征。将Ln3+稀土离子与PMMA-b-PAA通过"配位诱导"作用在THF溶剂中形成配合物胶束,并用TEM和DLS测定了胶束的形貌和粒径。结果表明,共聚物与稀土离子配位而发生交联,导致配合物胶束粒径比单纯共聚物的胶束粒径明显增大。     

嵌段共聚物的合成及其组装行为

嵌段共聚物在选择性溶剂中可逆缔合形成以不溶性链段为核 ,溶解性链段为壳的胶束。广泛用作表面活性剂、增溶剂、药物载体和纳米材料等。综述了嵌段共聚物的合成方法 ,着重分析了浓度、温度、嵌段长度、溶剂、添加物及电荷等因素对嵌段共聚物在选择性溶剂中组装行为的影响及其形成机理。展望了嵌段共聚物组装行为的应用前景     

RAFT方法合成两亲性嵌段共聚物的研究进展

可逆加成一断裂链转移(RAFT)聚合是制备嵌段共聚物的重要方法之一,介绍了队RAFT聚合方法的基本原理及其所用的RAFT链转移剂基础上,综述了国内外利用RAFT聚合方法合成两亲性嵌段共聚物的研究现状.     

嵌段共聚物PBA-b-PDMAEA的合成及其分散性能研究

利用可逆加成断裂链转移自由基聚合(RAFT)的方法制备了AB型嵌段共聚物PBA-b-PDMAEA,用红外光谱(FT-IR)、核磁氢谱(1HNMR)和凝胶渗透色谱(GPC)等方法对其结构进行了表征。以PBA-b-PDMAEA为分散剂,分别制备了PBK7、PG7、PB15:3、PR101、PR112、PR254、PY42、PY74和PY154等色浆,利用激光粒度仪(LSPSA)和透射电镜(TEM)对色浆的粒度进行了测定,结果表明PBA-b-PDMAEA作为分散剂,性能优异且通用性好,对于炭黑、无机颜料和有机颜料都适用。     

双亲水嵌段共聚物MA-b-APEC自组装阻止磷酸钙垢析出

利用透射电镜(TEM)和X射线衍射(XRD)法,通过与水解聚马来酸(HPMA)对磷酸钙晶体析出的对比研究,初步揭示了双亲水嵌段共聚物马来酸酐-烯丙氧基聚乙烯氧基羧酸钠(MA-b-APEC)阻止磷酸钙晶体析出的作用机理.TEM表明,MA-b-APEC在阻止磷酸钙垢析出时MA-b-APEC分子存在自组装且形成水溶性的壳核结构,MA链段中的羧基与钙作用后形成相应的核,亲水性强的聚乙烯氧基长侧链形成相应的壳.XRD研究表明,在MA-b-APEC作用下,磷酸钙晶体有着择优取向生长的趋势.研究显示,聚合物MA-b-APEC可以充当循环水用良好的阻磷酸钙阻垢剂.     

偏氯乙烯活性自由基聚合及其嵌段共聚物合成研究进展

偏氯乙烯(VDC)是重要含氯单体之一,通过活性自由基聚合可以制备分子量可控、分子量分布窄的VDC聚合物,并可进一步制备VDC嵌段共聚物,提高VDC聚合物的性能、拓展其应用。本文对VDC活性自由基聚合(主要是可逆加成-断裂链转移聚合)及其嵌段共聚物合成研究进行了综述。     

三嵌段离子液体共聚物P2VP(Bu)TFSI-b-PS-b-P(POEGMA)合成与表征

在链转移剂S-十二烷基-S′-(α,α′-二甲基-α″-乙酸)-三硫代碳酸酯的调控下,偶氮二异丁腈引发单体2-乙烯基吡啶、苯乙烯和聚乙二醇单甲醚甲基丙烯酸酯连续聚合,制备了含有聚2-乙烯基吡啶(P2VP)、聚苯乙烯(PS)和聚(聚乙二醇单甲醚甲基丙烯酸酯)[P(POEGMA)]链段的三嵌段共聚物P2VP105-b-PS...     

Photo-responsive block copolymer containing azobenzene group: Synthesis by reversible addition-fragmentation chain transfer polymerization and characterization

The design and synthesis of a new azobenzene-based methacrylate monomer (Azo-IEM) was demonstrated, and its polymerization behavior during reversible addition-fragmentation chain transfer (RAFT) polymerization was investigated. Well-defined homopolymer and amphiphilic block copolymer containing Azo-IEM monomeric units were successfully prepared as evidenced by NMR and GPC analysis. Moreover, the photo-triggered reversible isomerization of polymer products in selected solvents was investigated. Finally, TEM analysis showed that there were significant differences in the nanoparticle morphologies when the block copolymer samples were irradiated with different wavelengths of light (i.e., UV and visible). The size and shapes of the p(HEMA-b-Azo-IEM) polymer capable of transitions upon changes in Vis/UV light exposure which prepared from MeOH/CHCl₃ mixture solvent. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47870.     

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS₃) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (M_w/M_n ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)₃ (PS-b-PNIPAAM)₃, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and ¹H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ in mixed solution (DMF/CH₃OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ decreased with the increase of relative length of PS in the block copolymers.     

聚(丙烯酸-丙烯酰胺)接枝辛基酚聚氧乙烯醚丙烯酸酯两亲性共聚物的合成及表征

以辛基酚聚氧乙烯醚丙烯酸酯(C8PhEO10Ac)为大分子单体,丙烯酸(AA)、丙烯酰胺(AM)为共聚单体,采用大分子单体接枝共聚法,制备了一种两亲性接枝共聚物(AA-AM-g-C8PhEO10Ac),用静态光散射(SLS)与GPC联用技术测得接枝共聚物的分子量为9.51×105,用FTIR、1H NMR和TG/DTA等手段对共聚物的结构及性能进行了表征。采用透射电子显微镜(TEM)对聚合物在水溶液中的自组装行为进行了初步研究。结果表明,AA-AM-g-C8PhEO10Ac在水溶液中自组装,形成球型胶束,随着浓度增大,趋向于形成更大的自组装体。     

Self-assembly of telechelic polymers bearing adamantane groups via host-guest inclusion complexes with cyclodextrin polymer

Self-assembly and supramolecular inclusion complexations between telechelic polymers bearing one or double adamantane groups and linear poly(β-cyclodextrin) (P(β-CD)) were investigated in water. An adamantane (Ada) attached to poly (acrylic acid) (PAA) was prepared by reversible addition-fragmentation chain transfer polymerization using s-1-dodecyl-s″ -(α,α′-dimethyl-α″-acetic acid) trithio-carbonate functionalized Ada with tert-butyl acrylate, followed by functional modification. Additionally, two Ada groups capped triblock copolymer F127 were obtained via an esterification reaction. The dynamic light scattering, transmission electron microscope and ¹H 2D NOSEY NMR spectroscopy were conducted to characterize the self-assembly behaviors. With the inclusion complexation of Ada/CD in 1:1 M ratio in water, the spherical micelles were enlarged at 25°C than that of the adamantyl polymer precursors. Due to the PPO segment of Ada-F127-Ada, the micelles aggregation showed temperature dependence from 4 to 37°C for precursor and corresponding inclusion complexation; while in Ada-PAA/P(β-CD) system, the hydrodynamic diameters decreased with pH decreasing.     

Preparation of liquid‐filled micelles based on an amphiphilic triblock copolymer

A series of novel amphiphilic triblock poly(ethylene glycol)‐b‐poly(2‐aminoethyl methacrylate hydrochloride)‐b‐poly(heptadeca‐fluorodecyl acrylate) (PEG‐b‐PAEMA‐b‐PHFDA) comprised of two hydrophilic PEG and PAEMA segments and one hydrophobic PHFDA segment was designed and synthesized. The structure of the triblock copolymer was characterized by ¹H‐NMR and GPC analysis. The amphiphilic triblock copolymer was capable of self‐assembling into liquid‐filled micelles that consisted of PHFDA and liquid perfluorocarbons (PFCs) as the core and PEG as outer shell. PAEMA can be used as cross‐linking sites to increase the stability of the liquid‐filled micelles. The shape, size, and Acoustic properties of the obtained liquid‐filled micelles were investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

基于RAFT聚合策略合成功能化聚烯烃嵌段聚合物的研究进展

首先介绍了可逆加成-断裂链转移聚合（RAFT）的聚合机理及其常用的RAFT试剂,并与其它两种活性可控自由基聚合[氮氧化合物媒介的自由基聚合（NMP）和原子转移自由基聚合（ATRP）]进行了简单的优缺点对比。其次,介绍了近些年在基于RAFT聚合制备功能化聚烯烃嵌段聚合物研究中取得的进展,重点综述了制备功能化聚烯烃嵌段聚合物时所采用的6种方法,包括①烯烃配位聚合与RAFT聚合相结合;②阴离子聚合与RAFT聚合相结合;③阳离子聚合与RAFT聚合相结合;④Click反应与RAFT聚合相结合;⑤开环聚合与RAFT聚合相结合;⑥叶立德活性聚合与RAFT聚合相结合。最后,对基于RAFT聚合策略设计合成功能化聚烯烃嵌段聚合物的研究前景与实际应用进行了展望。     

One-step synthesis of poly(2-oxazoline)-based amphiphilic block copolymers using a dual initiator for RAFT polymerization and CROP

A range of poly(2-oxazoline) (POx)-based amphiphilic block copolymers were synthesized using 4-cyano-4-(dodecylthiocarbonothioylthio)pentyl-4-methylbenzenesulfonate (CDPS) as a dual initiator for reversible addition-fragmentation chain transfer (RAFT) polymerization and cationic ring-opening polymerization (CROP) in a one-step procedure. Methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, and N-isopropylacrylamide were polymerized for the hydrophobic block, and 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline were used as the hydrophilic block. RAFT polymerization and CROP proceeded independently in a controlled manner and resulted in amphiphilic block copolymers with a narrow molecular weight distribution. CDPS was found to be a useful dual initiator for the one-step synthesis of POx-based amphiphilic block copolymers via a combination of RAFT polymerization and CROP.     

Emulsion polymerization of styrene with amphiphilic random copolymer as surfactant: Predominant droplet nucleation

Amphiphilic random copolymer consisting of monomeric units of poly (butyl acrylate) and poly (maleic acid salt) was synthesized and characterized. The emulsion polymerization kinetics of styrene stabilized by this copolymer was investigated. The influencing factors, including polymeric surfactant concentration, initiator concentration and polymerization temperature, were systematically studied. The kinetic data show that the polymerization rate (R_P) increased with the increase of the polymeric surfactant concentration ([S]) and polymerization temperature (T). At the higher [S], droplets nucleation and micelle nucleation coexisted in the polymerization system; at the lower [S], only the droplets nucleation process existed. The polymerization did not follow Smith‐Ewart Case II kinetics. Dynamic light scatter and transmission electron microscope were utilized to measure the sizes and shapes of the particles, respectively. It would be speculated that a kind of large heterogeneous particles with multiple‐active‐sites was formed in the polymerization system. The increasing of R_P with increasing initiator concentration ([KPS]) was rapid at a medium [KPS], but the slowly increasing was observed at a lower or higher [KPS]. It was attributed to the barrier effect of the polymeric surfactant around the monomer droplets. The polymerization activation energy was 60.29 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

水溶性紫杉醇两亲性共聚物纳米胶束研究

聚乙二醇聚己内酯聚乙二醇采用三嵌段共聚物为载体包载紫杉醇形成纳米胶束,胶束具有明显的核壳结构,有效地改善了紫杉醇的水溶性。研究表明,采用蒸发溶剂法、透析法和熔融法制备的胶束对紫杉醇都呈现良好的包封效果,其中,以熔融法制得的胶束粒径最小,分布最窄。文中还考察了蒸发溶剂法实验条件对胶束的影响,发现低沸点有机溶剂有利于获得小粒径胶束,胶束平均粒径随着载药量的提高相应增大。体外释药的结果表明,载药量高的胶束释药率却相对较小。