P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

基于偏氯乙烯嵌段共聚物的多级多孔炭的制备

采用可逆加成-断裂链转移（RAFT）活性自由基聚合制备了聚苯乙烯-b-聚偏氯乙烯-b-聚苯乙烯嵌段共聚物（PS-b-PVDC-b-PS）,以此嵌段共聚物为碳前驱体,直接碳化制备微孔-中孔复合多级多孔炭。采用凝胶渗透色谱仪和核磁共振仪表征了嵌段共聚物结构,表明通过RAFT聚合可制得分子量较高（M_n^GPC >6000 g·mol^-1）和分子量分布较窄（PDI<1.5）的PS-b-PVDC-b-PS。采用热重分析表征嵌段共聚物热解特性,采用扫描电镜、N₂吸脱附表征多孔炭形貌和孔隙结构。结果表明嵌段共聚物同时具有PVDC和PS链段的热失重峰,PS链段可完全热解而具有形成中孔的模板作用,PVDC链段热降解形成含微孔的炭骨架,最终形成兼有微孔和中孔的多级多孔炭;随着PS嵌段含量的增加,嵌段共聚物的成炭率逐渐降低,孔隙尺寸逐渐增大;当PS/PVDC聚合度比为4.3时,多孔炭的比表面积、中孔率和平均孔径达到最大,分别为839 m²·g^-1、54%和2.02 nm。     

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.     

RAFT法合成超分散剂PS-b-PAA及其分散性能研究

以苯乙烯(St)和丙烯酸(AA)为单体,二硫代苯甲酸苄酯为链转移剂,偶氮二异丁腈(AIBN)作为引发剂,采用可逆加成-断裂链转移(RAFT)活性自由基聚合方法合成了两亲性嵌段共聚物分散剂聚苯乙烯-b-聚丙烯酸(PS-b-PAA),探讨了影响聚合反应的主要因素,用GPC、IR、1H NMR对其结构进行了表征.结果表明,用RAFT法制得的共聚物分子量分布为1.1～1.3,聚合反应在80℃下24h内转化率达95%.进一步的分散性能研究表明,超分散剂PS-b-PAA对SiO2粉体在水中有着较好的分散效果.     

聚(偏氯乙烯-co-丙烯酸甲酯)-b-聚丙烯酸丁酯共聚物的合成和相态结构

采用可逆加成-断裂链转移(RAFT)活性自由基乳液聚合法制备聚(偏氯乙烯-co-丙烯酸甲酯)-b-聚丙烯酸丁酯共聚物(P(VDC-co-MA)-b-PBA),并研究了不同组成嵌段共聚物的相态结构和热失重特征。发现以端基为2-(十二烷基三硫代碳酸酯基)-2-异丁酸的聚丙烯酸-b-聚苯乙烯共聚物为大分子RAFT试剂和乳化剂,并加十六烷助乳化剂,可得到稳定的P(VDC-co-MA)共聚物和P(VDC-co-MA)-b-PBA共聚物乳液;随着大分子RAFT试剂浓度减小,共聚物的数均分子量增加,聚合具有可控特性。P(VDC-co-MA)-b-PBA共聚物溶液成膜和胶乳热成型膜均具有微相分离特征,随P(VDC-co-MA)/PBA摩尔比由11/1增加到2.2/1再到1/1,共聚物呈现从PBA粒状分散、PBA线条状分散、双连续分布的变化,并在热失重过程中出现分别对应于P(VDC-co-MA)共聚物和PBA的热失重温度区间。     

PS-b-PNVIm(Bu)BF_4离子液体嵌段聚合物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯为链转移剂,制备了窄分布的聚苯乙烯大分子链转移剂,再用该大分子链转移剂制备聚苯乙烯-b-聚N-乙烯基咪唑(PS-b-PNVIm)两嵌段聚合物。通过与溴代正丁烷发生季铵化反应并与氟硼酸钠进行阴离子交换,得到聚苯乙烯-b-聚1-丁基-3-乙烯基咪唑氟硼化物[PS-bPNVIm(Bu)BF4]。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,结果表明,嵌段聚合物为PS160-b-PNVIm82,分子量分布为1.52,合成过程具有活性/可控聚合特征。PS-bPNVIm具有两亲性,原子力显微镜观察到水溶性球形胶束,胶束以PNVIm链段为壳,PS链段为核。     

PS-b-PNVIm(Bu)BF_4离子液体嵌段聚合物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯为链转移剂,制备了窄分布的聚苯乙烯大分子链转移剂,再用该大分子链转移剂制备聚苯乙烯-b-聚N-乙烯基咪唑(PS-b-PNVIm)两嵌段聚合物。通过与溴代正丁烷发生季铵化反应并与氟硼酸钠进行阴离子交换,得到聚苯乙烯-b-聚1-丁基-3-乙烯基咪唑氟硼化物[PS-bPNVIm(Bu)BF4]。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,结果表明,嵌段聚合物为PS160-b-PNVIm82,分子量分布为1.52,合成过程具有活性/可控聚合特征。PS-bPNVIm具有两亲性,原子力显微镜观察到水溶性球形胶束,胶束以PNVIm链段为壳,PS链段为核。     

pH和CO_2响应性嵌段共聚物的合成及其自组装行为

采用可逆加成-断裂链转移自由基聚合(RAFT)和开环聚合(ROP)合成一种具有双重敏感性的聚甲基丙烯酸N,N-二甲氨基乙酯-b-聚乳酸(PDMAEMA-b-PLA)嵌段共聚物。利用傅里叶变换红外光谱(FTIR)、核磁共振波谱(1HNMR)对双亲性嵌段共聚物的结构进行表征;用紫外-可见分光光度计(UV-Vis)、Zeta电位及粒度分析仪和扫描电子显微镜(SEM)研究了其自组装行为及聚集体的大小、形态变化,结果表明,嵌段共聚物在酸性和中性条件下有pH敏感性和CO2响应性,且具有良好的可逆性。     

荧光法研究PSt-b-PCA-b-PSt与牛血清白蛋白的相互作用

采用可逆加成-断裂链转移聚合方法(RAFT)合成了聚苯乙烯-b-聚肉桂酸-b-聚苯乙烯两亲性三嵌段聚合物(PSt-b-PCA-b-PSt),采用荧光光谱法研究了PSt-b-PCA-b-PSt与牛血清白蛋白的相互作用。结果表明,PSt-b-PCA-b-PSt在选择性溶剂中自组装形成半径约为50nm的胶束;根据Stern-Volmer方程计算得到双分子猝灭过程速率常数、结合常数和结合数,表明三嵌段聚合物PSt-b-PCA-b-PSt与牛血清白蛋白之间发生了较强的静态荧光猝灭作用。     

单电子转移-蜕化链转移活性自由基细乳液聚合制备PS-b-PBA-b-PS共聚物

以碘仿为引发剂、连二亚硫酸钠/碳酸氢钠为催化体系、十二烷基硫酸钠/十六烷为乳化体系,通过单电子转移-蜕化链转移(SET-DT)活性自由基细乳液聚合合成碘端基化聚丙烯酸丁酯(I-PBA-I),进而以其为大分子引发剂引发苯乙烯聚合,制备聚苯乙烯-b-聚丙烯酸丁酯-b-聚苯乙烯(PS-b-PBA-b-PS)三嵌段共聚物,并进行共聚物结构和性能表征。发现两个阶段的SET-DT细乳液聚合均具有大的反应速率,碘仿引发剂用量少,可获得高分子量PBA和PS-b-PBA-b-PS共聚物。PS-b-PBA-b-PS共聚物具有微相分离和热塑性弹性体特征,PS质量分数为50%的嵌段共聚物的拉伸强度达9.8 MPa,断裂伸长率为660%。     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

Thermoresponsive biotinylated star amphiphilic block copolymer: Synthesis,self-assembly,and specific target recognition

A novel star amphiphilic block copolymer star poly(ε-caprolactone)-b-poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide)-DDAT [SPCL-b-P(NIPAAm-co-DMAAm)-DDAT] (DDAT: S-1-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)trithiocarbonate) was synthesized by combination of ring-opening polymerization (ROP) and reversible addition-fragment chain transfer (RAFT) polymerization. DDAT-terminated groups were further transformed into hydroxyl groups by one-pot strategy for aminolysis of DDAT and Michael addition reaction of an α,β-unsaturated ester of 2-hydroxyethyl acrylate (HEA). Biotinylated star copolymer SPCL-b-P(NIPAAm-co-DMAAm)-Biotin was obtained by coupling of biotin to the hydroxyl-terminated star copolymer using carbodiimide coupling chemistry. These star copolymers with DDAT, hydroxyl, and biotin end groups were capable of self assembling into core–shell structural micelles in aqueous solution. The variation of end groups significantly affected the micellar characters, such as hydrodynamic diameter (D_h), critical micellar concentration (CMC), and lower critical solution temperature (LCST). Biotinylated micelle exhibited a phase transition at 41.4 °C. The amount of biotin on the micelle surface as well as the specific recognition between biotinylated micelle and avidin was determined by 4′-hydroxyazobenzene-2-carboxylic acid/avidin (HABA/avidin) binding assay and dynamic light scattering (DLS). In addition, the biotinylated star copolymer displayed good biocompatibility according to a preliminary cytotoxicity study. The novel polymeric micelle with biodegradability, thermoresponse, and specific target recognition was expected to be a promising polymeric carrier material for targeted drug delivery.     

One-pot synthesis of poly(N-vinylcaprolactam)-based biocompatible block copolymers using a dual initiator for ROP and RAFT polymerization

Thermosensitive, biocompatible poly(ε-caprolactone)-b-poly(N-vinylcaprolactam) (PCL-b-PVCL), poly(δ-valerolactone)-b-PVCL, and poly(trimethylene carbonate)-b-PVCL block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate (HECP), as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The hydrophobic blocks were first synthesized by the ROP of cyclic monomers using diphenyl phosphate (DPP) as a catalyst and the RAFT polymerization of the PVCL block was followed by adding N-vinylcaprolactam (VCL) and 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) (V-70) as an initiator to the reaction mixture. This novel one-pot process is convenient and powerful method for the synthesis of the PVCL-based biocompatible block copolymers. The lower critical solution temperature (LCST) of the PVCL-based biocompatible block copolymer can be readily tuned by controlling the hydrophobicity of the block copolymers. By copolymerizing a hydrophilic N-vinylpyrrolidone moiety to the PVCL blocks by RAFT copolymerization, the LCST of the copolymer was matched with the body temperature for its future biomedical applications.     

Polyurethane tri‐block copolymers—Synthesis,mechanical, elastic,and rheological properties

A series of polyurethane tri‐block copolymers were synthesized by reacting a 4,4′‐methylenebis(phenyl isocyanate) (MDI)‐endcapped poly(tetramethylene oxide) (PTMO, M_n = 2,000 g/mol) with a monoamine‐diamide (6T6m) hard segment (HS). The concentration of the HS in the copolymer was varied between 9 and 33 wt % by changing the length of the soft mid‐block segment. The structure of the copolymers was analyzed by nuclear magnetic resonance, the amide crystallinity was investigated by Fourier transform infra‐red and the thermal properties were studied by differential scanning calorimetry. The mechanical and elastic properties of the tri‐block copolymer were subsequently explored by dynamic mechanical analysis, compression set and tensile experiments, and the melt rheological behavior was studied by a parallel plate method. The amide end groups displayed a high crystallinity and the modulus of the tri‐block copolymers was relatively high. The fracture strain increased strongly with the molecular weight and the copolymers demonstrated a ductile fracture behavior for molecular weights above 6000 g/mol. Good compression set values were obtained for the tri‐block copolymers despite their low molecular weight. In the molten state, the tri‐block polymers displayed a gelling effect at low frequencies, which was believed to be a result of a clustering of the end‐segments. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Synthesis of polydimethylsiloxane‐containing block copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization

Low polydispersity polydimethylsiloxane (PDMS) was end functionalized with a reversible addition fragmentation chain transfer (RAFT) agent by the esterification of hydroxyl terminated PDMS with a carboxylic acid functional RAFT agent. These PDMS‐RAFT agents were able to control the free radical polymerization of styrene and substituted styrene monomers to produce PDMS‐containing block copolymers with low polydispersities and targeted molecular weights. A thin film of polydimethylsiloxane‐block‐polystyrene was prepared by spin coating and exhibited a microphase separated morphology from scanning force microscopy measurements. Controlled swelling of these films in solvent vapor produced morphologies with significant long‐range order. This synthetic route will allow the straightforward production of PDMS‐containing block copolymer libraries that will be useful for investigating their thin film morphological behavior, which has applications in the templating of nanostructured materials.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl₂ initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both ¹H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE₆₁-b-NIPAM₁₅₀) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (T_ps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVE_n-co-BVCT_m)-g-NIPAM_x (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above T_ps of poly(NIPAM) graft chain unlike the case of block copolymers.     

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。     

Synthesis and properties of gradient copolymers of butyl methacrylate and fluorinated acrylate via RAFT miniemulsion copolymerizations

A series of gradient fluorinated copolymers with a broad variation of the monomer units in the polymer chain were synthesized via semibatch CPDB‐mediated RAFT miniemulsion polymerization technique. In the presence of RAFT agent 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB), the copolymerization of BMA and FMA in miniemulsion exhibited typical features of a controlled molecular weights and narrow polydispersities. The macromolecular structure and thermal behavior of the synthesized fluorinated copolymers were investigated in detail. The DSC analyses show that the gradient copolymers showed a unique thermal behavior with broad range of transition temperature. It was also confirmed that the fluorinated gradient copolymer exhibited obvious surface segregation structure and ultra‐low surface energy between 16.8 and 20.3 mN/m. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42936.     

Adsorption of block copolymers at latex surface and their utilization in emulsion polymerization

Amphiphilic block copolymers have been investigated for their utilization in emulsion polymerization of butyl methacrylate. Special attention has been paid to the adsorption mechanism of the block copolymers from systematic measurements of equilibrium adsorption isotherms. A series of well-defined water-soluble amphiphilic block copolymers, composed of poly(butyl methacrylate) and poly(sodium methacrylate) blocks, were synthesized by anionic polymerization of butyl methacrylate and tert-butyl methacrylate followed by the thermal deprotection of the tert-butyl ester groups and final hydrolysis. The number density of emulsion polymer particles N_P varied as [copolymer]^α, α lying between 0.44 and 0.73 according to the hydrophilic content of the copolymers. In contrast with SDS taken as a reference emulsifier, the adsorption of the copolymers was very strong and this provided quite an efficient stabilization of the polymer particles during emulsion polymerization, even at low concentrations (<10⁻⁴ mol L⁻¹) and low coverages (<10% of the interfacial area).