RAFT聚合合成高分子量嵌段聚合物

以合成高分子量聚合物为目标,以苯基二硫代乙酸-1-苯基乙酯(PEPDTA)作为RAFT试剂,研究引发剂的种类(偶氮二异丁腈(AIBN)、1-1′-偶氮环己腈(ACC))、用量及聚合温度对苯乙烯/丙烯酸丁酯RAFT共聚合过程和聚合物结构的影响.结果发现,由于体系中RAFT浓度很低,相应的引发剂浓度要比传统自由基聚合低得多,只有采用较高的聚合温度和低分解速率常数的引发剂(ACC),才能制得无活性聚合物分率低(<0.1)、分子量高的聚合物,并进一步得到杂质含量少、分子量分布窄的嵌段聚合物.     

基于AIE效应的多重刺激响应性聚合物纳米微球的制备及其细胞示踪应用

基于AIE分子和智能响应性聚合物构筑的纳米材料,具有优良的AIE发光性能、环境刺激响应性和生物相容性,已在生命科学领域展现出诱人的应用前景. 本研究通过ATRP活性聚合方法, 以合成的TPE-BIB为引发剂, 引发具有多刺激响应特性的N-[2-(二乙氨基)-乙基]丙烯酰胺单体聚合, 成功制备具有温度/pH/CO₂三重响应性的两亲性聚合物: TPE-g-PDEAEAM, 并自组装形成约200 nm的纳米微球. 研究表明: 这种聚合物纳米粒子具有优良的水溶性、单分散性、稳定性及优异的AIE发光特性. 其相转变温度为60 ℃, 溶液荧光对环境温度、pH及CO₂均表现出快速敏感响应性能. 同时, 该纳米粒子表现出低细胞毒性, 能够有效示踪HeLa细胞增殖至11代以上, 有望作为一种活细胞荧光示踪探针材料.     

AIE荧光聚合物RAFT可控合成与表征及光物理性质研究

聚集诱导发光(AIE)分子是与传统的聚集态荧光淬灭染料分子具有截然相反的光物理性质的新型有机发光材料,可广泛应用于化学/生物传感、生物探针与成像、诊疗一体化和光电子器件等诸多领域中。本论文通过可逆加成-断裂链转移(RAFT)聚合方法,可控合成了侧链型四苯乙烯TPE聚丙烯酸酯AIE聚合物。通过实验条件的优化与探索,尤其采用半衰期较短、活性更高的偶氮二异庚腈(ABVN)取代常规的偶氮二异丁腈(AIBN)引发剂,将原来超过12 h的过夜反应前沿科研实验,改造为较短的3–5 h聚合反应时间内即可达到中等收率和较好的聚合物产品质量,使其成为一个适合本科教学环境的新创实验。本实验融合了无水无氧操作技术、柱层析分离纯化、RAFT可控聚合和GPC分子表征技术、FTIR、NMR、UV-Vis、荧光光谱等多种现代实验技术和表征方法,考查了所合成四苯乙烯TPE侧基的AIE聚合物的光物理性质,测定其溶液中的相对荧光量子产率达17%。     

原子转移自由基活性聚合合成PS-PMA-PS嵌段聚合物

本文采用氯化亚铜/α,α'-联吡啶配位化合物作催化剂.首先在130℃时用1-苯基氯乙烷在引发苯乙烯(St)进行原子转移自由基聚合,再以其产物PS-Cl作为大分子引发剂引发丙烯酸甲酯(MA)在反应温度为120℃时进行聚合,得到两嵌段聚合物PS-PMA-Cl.此两嵌段共聚物在特殊混合溶剂--丙酮/正丙醇(体积比7:3)中仍然可以作大分子引发剂引发苯乙烯进行原子转移自由基聚合,由于聚合体系接近于均相.所以表现出了较高的反应活性,并且合成的聚苯乙烯一聚丙烯酸甲酯一聚苯乙烯(PS-PMA-PS)三嵌段聚合物的分子量与设计值接近、分子量分布比较窄,反应的条件温和,可控性好.最后通过NMR技术对三元嵌段共聚物的结构迸行了表征.     

水性聚氨酯荧光材料的制备及其荧光性能

将4-胺基-4′-(N,N-二苯基氨基)-1,2-二苯乙烯(ADAS)溶解于N,N-二甲基甲酰胺(DMF)中后分别以混合和接枝的方式引入水性聚氨酯,制备了不同软段和扩链剂的水性聚氨酯荧光材料(FWPU)。采用傅里叶变换红外光谱、荧光光谱表征了FWPU的结构和荧光性能。结果表明:水性聚氨酯的软段和扩链剂结构均可影响FWPU的荧光强度;与溶解同样浓度ADAS的DMF溶液相比,混合法制备的FWPU其荧光强度最大可以增加76倍,接枝法制备的FWPU最大可增加47倍。     

水溶性聚合物和两性聚合物——Ⅰ.环氧乙烷-苯乙烯-环氧乙烷三嵌段聚合物(PEO—PSt—PEO)的合成和表征

用萘钠为引发剂的相继阴离子聚合合成了环氧乙烷-苯乙烯-环氧乙烷三嵌段聚合物(PEO-PSt-PEO),对经纯制的嵌段聚合物和母体聚苯乙烯用粘度法、GPC、¹H-NMR、折光指数增量(dn/dc)和溶解性测定等方法进行了表征。发现:1.在高引发剂浓度下,聚苯乙烯的[η]和M反而随[M]/[I]的减小而增加,说明存在引发剂的自抑制效应;2.嵌段聚合物在三种不同溶剂中的dn/dc与其组成有良好的线性关系,因此,dn/dc测定可作为确定嵌段聚合物组成的一个可靠方法;3.PEO-PSt-PEO三嵌段聚合物在THF中GPC谱图的峰值分子量与母体聚苯乙烯相似;4.聚苯乙烯含量较低的嵌段聚合物在THF中的溶解性较差。     

树状化-线形两亲嵌段聚合物的合成及自组装研究

合成了缩酮保护的一代甲基丙烯酸羟乙酯单体DHEMA(G1),通过顺序ATRP聚合方法,制备得到大分子引发剂PDHEMA(G1)-Br,再引发苯乙烯单体得到一代嵌段聚合物PDHEMA(G1)-b-PS.以PDHEMA(G1)-b-PS为反应前体,通过重复的缩酮保护和脱保护反应,进一步得到了二代和三代的树状化-线形两亲嵌段...     

含铽-水杨酸端基聚苯乙烯的合成及荧光性能研究

利用原子转移自由基聚合能对聚合物进行设计的优点,以水杨酸为原料,通过氯磺化制得5-氯磺酰基水杨酸,以此为引发剂,CuCl/2,2′联吡啶(Bpy)为催化体系,对苯乙烯(St)的聚合进行了研究,并且将制得的聚苯乙烯与铽离子配位.结果表明,聚合反应符合对单体浓度为一级的动力学关系;聚合物分子量随转化率呈线性增加;分子量分布较窄,Mw/Mn都在1.4以下;通过1H-NMR的端基分析,扩链反应都证明了聚合具有可控性;所有结果显示该聚合反应符合原子转移自由基聚合(ATRP)的特性.IR,UV-Vis和荧光光谱表明Tb(Ⅲ)与含水杨酸端基的聚苯乙烯配位成功,当用λ=305nm光激发,此配合物发射Tb(Ⅲ)的特征荧光.讨论了引发剂的浓度对聚合体系自由基活性特征的影响以及聚合物的分子量、配位条件对荧光强度的影响.     

双亲嵌段共聚物PSt-b-PAA在甲苯中的自聚集行为

以α-溴乙苯为引发剂,溴化亚铜为催化剂,2,2'-联吡啶为配体,用原子转移自由基聚合(ATRP)法合成了结构一定的嵌段共聚物聚苯乙烯-b-聚丙烯酸丁酯(PSt-b-PBA).经水解制备了双亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PSt-b-PAA);采用单溶剂溶解法配制了PSt-b-PAA在甲苯中的反胶束溶液;以极性荧光化合物N-1-萘乙二胺盐酸盐(NEAH)为极性微区探针,用荧光光谱法并配合透射电镜观察探索了双亲嵌段共聚物PSt-b-PAA在甲苯溶液中的自聚集行为,考察了双亲性嵌段共聚物浓度、链结构及温度等因素对反胶束化行为的影响规律.结果表明,亲水链PAA短而亲油链PSt长的双亲嵌段共聚物PSt-b-PAA,用单溶剂溶解法可使其在甲苯中发生自聚集,形成以亲水段为核,疏水段为壳的星状反胶束结构;反胶束为10-20nm的球形聚集态结构;PSt-b-PAA的自聚集行为及临界胶束浓度与分子链的微结构和温度等因素相关,且随着共聚物浓度的增大,小胶束会逐渐结合形成大的纺垂状聚集体.     

活性正离子聚合制备聚(异丁烯-b-α-甲基苯乙烯)嵌段共聚物

以2-氯-2,4,4-三甲基戊烷(TMPCl)/TiCl4/质子捕捉剂(DtBP)为引发剂体系,引发异丁烯聚合,随后加入1,1-二(4-甲基苯基)乙烯作为封端剂稳定末端碳正离子,再引入四异丙醇钛(Ti(OiPr)4),降低Lewis酸性,继续引发α-甲基苯乙烯聚合,实现活性正离子聚合制备聚(异丁烯-b-α-甲基苯乙烯)嵌段共聚物.考察了α-甲基苯乙烯聚合时间对单体转化率、产物的dn/dc值、分子量及其分布的影响以及四异丙醇钛对聚合速率的影响.并通过体积排斥色谱法/紫外检测器/示差折光指数/多角激光光散射、1H-NMR以及DSC以对产物进行表征.实验结果表明,嵌段共聚物分子量分布窄(MWD≤1.2),单体转化率与分子量呈线性关系,聚合速率对单体浓度呈一级动力学关系,具有活性聚合的特征.Ti(OiPr)4能有效稳定活性中心,降低聚合速率.聚(异丁烯-b-α-甲基苯乙烯)嵌段共聚物的DSC测试发现明显的两个Tg,表明存在微相分离结构.     

Effects of hectorite content on the temperature-sensitivity of PNIPAM microgels

A new method, adopting inorganic clay (synthetic hectorite) as a physical cross-linker, was used to prepare poly(N-isopropylacrylamide) (PNIPAM) microgels via surfactant-free emulsion polymerization. The effect of hectorite content on the temperature-sensitivity of PNIPAM microgels was investigated by means of DLS, UV/Vis and DSC. It was found that, in the absence of surfactant, with increasing hectorite content, the particle size tends to decrease to 300 nm at room temperature, while increases as weight ratio (WR) of hectorite and N-isopropylacrylamide (NIPAM) exceeds 21%. Furthermore, with increasing WR from 7% to 21%, the volume phase transition temperature of PNIPAM microgels has little shift, while decreases slightly when WR increases up to 28%.     

Activity of enzymes immobilized on microspheres with thermosensitive hairs

Poly(N-isopropylacrylamide)s (PNIPAMs) carboxylated at one chain end or both ends were prepared by polymerization using 4,4-azobis(N,N,-cyanopentanoic acid) (V-501) as an initiator and β-mercaptopropionic acid (MPA) as a chain transfer reagent. One end group of PNIPAM carboxylated at both ends was conjugated with latex particles, and another with trypsin using carbodiimide. Differential scanning calorimetry (DSC) revealed that PNIPAM on the particles exhibited a drastic phase transition, and that the transition temperature was largely elevated when the enzyme was immobilized at the chain end. Therefore, PNIPAM on the particles showed two phase transitions because of the coexistence of the enzyme-conjugated and non-conjugated PNIPAMs. The activity of trypsin immobilized on the particles with the PNIPAM spacer showed significant temperature dependence. The apparent relative activity increased above the transition temperature of non enzyme-conjugated PNIPAM on the particles. One of the reasons for this is that the diffusion of the substrate changed discontinuously around the transition temperature. Therefore, the temperature dependence of the enzymatic activity was significantly affected by the molecular size of the substrates. The enzymatic activity was also influenced by the surface density of trypsin and PNIPAM on the particle, and the molecular weight of the PNIPAM spacer.     

Aggregation-induced multicolor luminescent nanoparticles with adaptive and fixed cores derived from brominated tetraphenylethene-containing block copolymer

Aggregation-induced emission (AIE)-active nanoparticles (NPs) exhibiting multicolor fluorescence and high-quantum yields independent of the environment are important for the further development of next-generation smart fluorescent materials. In this work, AIE-active amphiphilic block copolymers were designed and synthesized by RAFT polymerization of a brominated tetraphenylethene (TPE)-containing acrylate (A-TPE-Br). The block copolymer exhibited typical AIE effects in selective solvents, which can be explained by hydrophobic TPE aggregated in the core during micelle formation. Luminescent core–shell NPs with a crosslinked AIE core (fixed structure) were synthesized by the Suzuki coupling reaction of the bromine groups of the assembled block copolymer and boronic acid compounds. The NPs composed of TPE/thiophene crosslinked core showed green emission in both diluted state and solid state, implying the ability to fluoresce regardless of environmental changes and molecular dispersion. Multicolor luminescent NPs capable of changing color from blue to red were synthesized by changing the coupling compounds, such as anthracene for electron-rich units and benzothiadiazole for electron-deficient units. The effects of the nature of the donor and acceptor, as well as their combination (TPE/donor/acceptor sequence), on the color and fluorescent intensity of the core crosslinked NPs in the nonpolar and polar solvents, and solid state, were investigated.     

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide),PEG-b-(PNIPAM)_2,were successfully synthesized through atom transfer radical polymerization(ATRP).A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether(PEG).The copolymers were obtained via the ATRP of N-isopropylacrylamide(NIPAM) at 30℃with CuCl/Me_6TREN as a catalyst system and DMF/H_2O(v/v = 3:1) mixture as solvent.The resulting copo...     

Molecular motions in low cross-linked poly(N-isopropylacrylamide) microgels

Non-ionic N-isopropylacrylamide (PNIPAM) microgel is employed to investigate the molecular motion of polymer chains in the swollen and collapsed states. This study is performed using incoherent elastic (IES) and quasielastic neutron scattering (IQNS). IES measurements show an increase of both, the elastic intensity and the oscillations of the polymer network vibrational amplitude at the transition temperature. IQNS was measured at two different selected temperatures 290 K and 327 K corresponding to the swollen and collapsed states, respectively. The diffusion constant from IQNS experiments decreases nearly two orders of magnitude when the microgel de-swells and finally collapses.     

Controlled radical polymerization of tert‐butyl acrylate at ambient temperature: Effect of initiator structure and synthesis of amphiphilic block copolymers

Controlled and very rapid ambient temperature polymerization of tert‐butyl acrylate (tBA) via atom transfer radical polymerization (ATRP) and single electron transfer living radical polymerization (SET‐LRP) conditions is reported. Two initiators, one that would generate a secondary radical and another that would generate a primary radical, upon activation, are used. A very active catalyst CuBr/Me₆TREN was found to initiate rapid polymerization whether it was the primary or the secondary initiator. The polymerization was well controlled and very rapid. The initiator that produces secondary initiating site is found to result in more rapid polymerization than the one that produces primary initiating site. To explore the possibility of rapid ambient temperature polymerization through the SET‐LRP mechanism, the polymerization was also carried out in the presence of DMSO. It was found that the polymerization was much faster compared to the bulk ATRP, without loss of control. Styrene was block copolymerized from PtBA macroinitiators and vice versa. In both the cases, block copolymers with controlled molecular weights were obtained. The tBA block of the polymer was selectively hydrolyzed to get amphiphilic block copolymers. This amphiphilic block copolymer was found to be useful in preparing stable cadmium sulfide (CdS) nanoparticulate dispersion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

温敏性纤维素/聚N-异丙基丙烯酰胺复合水凝胶的固体核磁共振表征及动力学研究

利用半互穿网络方法将具有温度响应的高分子聚N-异丙基丙烯酰胺(PNIPAM)与天然纤维素复合得到温敏性水凝胶. 通过固体核磁共振的 ¹H, ¹³C CP/MAS(交叉极化/魔角旋转)和QCP(定量交叉极化)等实验手段对复合凝胶的结构进行了定性及定量研究, 并利用固体静态变温核磁共振实验和偶极滤波-自旋扩散实验研究了复合凝胶中PNIPAM分子链段的动力学行为.     

Organic/inorganic hybrid star-shaped block copolymers of poly(l-lactide) and poly(N-isopropylacrylamide) with a polyhedral oligomeric silsesquioxane core: Synthesis and self-assembly

The star-shaped organic/inorganic hybrid poly(l-lactide) (PLLA) based on polyhedral oligomeric silsesquioxane (POSS) was prepared using octa(3-hydroxypropyl) polyhedral oligomeric silsesquioxane as initiator via ring-opening polymerization (ROP) of l-lactide (LLA). The molecular weight of POSS-containing star-shaped hybrid PLLA (POSSPLLA) can be well controlled by the feed ratio of LLA to initiator. The POSSPLLA was further functionalized into the macromolecular reversible addition-fragmentation transfer (RAFT) agent for the polymerization of N-isopropylacrylamide (NIPAM), leading to the POSS-containing star-shaped organic/inorganic hybrid amphiphilic block copolymers, poly(l-lactide)–block–poly(N-isopropylacrylamide) (POSS(PLLA–b–PNIPAM)). The self-assembly behavior of POSS(PLLA–b–PNIPAM) block copolymers in aqueous solution was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). DLS showed the PNIPAM block in the aggregates is temperature-responsive and its phase-transition is reversible. TEM proved that the star-shaped POSS(PLLA–b–PNIPAM) amphiphilic block copolymers can self-assemble into the vesicles in aqueous solution. The vesicular wall and coronas are composed of the hydrophobic POSS core and PLLA, and hydrophilic PNIPAM blocks, respectively. Therefore, POSSPLLA and POSS(PLLA–b–PNIPAM) block copolymers, as a class of novel organic–inorganic hybrid materials with the advantageous properties, can be potentially used in biological and medical fields.     

Study on interaction between Tb(III) and poly(N-isopropylacrylamide)

A new kind of the thermo-sensitive and fluorescent complex of poly(N-isopropylacrylamide) (PNIPAM) and Tb(III) was synthesized by free radical polymerization, in which PNIPAM was used as a polymer ligand. The complex was characterized by using X-ray photoelectron spectroscopy (XPS), ultraviolet-visual (UV), Fourier transform infrared (FT-IR) and fluorescence spectroscopy. The results from the experiments indicated that there is a strong interaction between PNIPAM and Tb(III), leading to a decrease in the electron density of nitrogen and oxygen atoms and an increase in the electron density of Tb(III) in the PNIPAM containing Tb(III) by contrast with PNIPAM and Tb(III), respectively, meanwhile, exhibiting that the Tb(III) is mainly bonded to oxygen atoms in the polymer chain of PNIPAM and formed the complex of PNIPAM-Tb(III). After forming the PNIPAM-Tb(III) complex, the emission fluorescence intensity of Tb(III) in the PNIPAM-Tb(III) complex is significantly enhanced because the effective intramolecular energy transfer from PNIPAM to Tb(III). Especially, the emission intensity of the fluorescence peak at 547 nm can be increased as high as 145 times comparing with that of the pure Tb(III). The intramolecular energy transfer efficiency for fluorescence peak at 547 nm can reach as high as 68%. The fluorescence intensity is related the weight ratio of Tb(III) and PNIPAM in the PNIPAM-Tb(III) complex. When the weight ratio is 1.4%, the maximum fluorescence enhancement can be obtained. Nevertheless, the lower critical solution temperature of PNIPAM containing a low content of Tb(III) has not obviously changed after the formation of the complex of PNIPAM-Tb(III) by the interaction between PNIPAM and Tb(III). This novel thermosensitive and fluorescence characterization of the PNIPAM-Tb(III) complex may be useful in the fluorescence systems and the biomedical field.     

One-step preparation of branched PEG functionalized AIE-active luminescent polymeric nanoprobes

The synthesis of amphiphilic aggregation-induced emission(AIE) dyes based organic nanoparticles has recently attracted increasing attention in the biomedical fields. These AIE dyes based nanoparticles could effectively overcome the aggregation caused quenching effect of conventional organic dyes, making them promising candidates for fabrication of ultrabright organic luminescent nanomaterials. In this work, AIE-active luminescent polymeric nanoparticles(4-NH_2-PEG-TPE-E LPNs) were facilely fabricated through Michael addition reaction between tetraphenylethene acrylate(TPE-E) and 4-arm-poly(ethylene glycol)-amine(4-NH_2-PEG) in rather mild ambient. The 4-NH_2-PEG can not only endow these AIE-active LPNs good water dispersibility, but also provide functional groups for further conjugation reaction. The size, morphology and luminescent properties of 4-NH_2-PEG-TPE-E LPNs were characterized by a series of techniques in detail. Results suggested that these AIE-active LPNs showed spherical morphology with diameter about 100–200 nm. The obtained 4-NH_2-PEG-TPE-E LPNs display high water dispersibility and strong fluorescence intensity because of their self assembly and AIE properties of TPE-E.Biological evaluation results demonstrated that 4-NH_2-PEG-TPE-E LPNs showed negative toxicity toward cancer cells and good fluorescent imaging performance. All of these features make 4-NH_2-PEG-TPE-E LPNs promising candidates for biological imaging and therapeutic applications.