N-异丙基丙烯酰胺/丙烯酸胆甾醇酯共聚物研究

合成和表征了N 异丙基丙烯酰胺 (NIPAM)与丙烯酸胆甾醇酯 (CHA)的共聚物 .利用表面张力和荧光探针法研究了共聚物水溶液的表面活性性能 ,确定了其临界胶束浓度 (CMC) .利用浊度法和荧光探针法测定了共聚物的最低临界溶液温度 (LCST) .研究发现 ,在聚N 异丙基丙烯酰胺 (PNIPAM)分子链中引入疏水结构单元CHA会使其LCST下降 ;且随着共聚物中CHA含量的增加 ,LCST下降幅度增加 .在PNIPAM链段中引入少量的CHA就会使其表现出明显的两亲性 ,共聚物在水中能形成有壳核结构的稳定胶束 .通过将疏水化合物胆甾醇作为模拟药物包埋在胶束的疏水核中的研究 ,证实所得的胶束能包埋疏水药物 ,且随着包埋胆甾醇含量的增加 ,胶束平均粒径增大 .     

微波法制备聚(苯乙烯-N-异丙基丙烯酰胺)热敏性微球

聚(N-异丙基丙烯酰胺)(PNIPAM),由于其大分子链上同时具有亲水性的酰氨基和疏水性的异丙基,使得PNIPAM的水溶液,在32℃附近具有最低临界溶液温度(LCST)．PNIPAM及其共聚物表现出相转变,产生热敏性质．利用PNIPAM的热敏性质,可以制备多种智能高分子材料．这些高分子材料在生物医学、免疫分析、     

聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物的合成及其胶束制备

以聚丙烯酰胺(PAM)为大分子引发剂, 采用开环聚合方法, 在N,N-二甲基甲酰胺(DMF)中引发L-谷氨酸苄酯环内酸酐(BLG-NCA)聚合合成了两亲性聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物(PAM-g-BLG), 采用IR, 1H NMR和GPC方法对共聚物结构进行了表征; 用芘作荧光探针, 研究了共聚物胶束的形成及其临界胶束浓度(cmc), 利用动态光散射(DLS)和透射电镜(TEM)研究了胶束的粒径分布和形态. 结果表明, PAM能够引发BLG-NCA开环聚合得到接枝共聚物, 在一定条件下接枝共聚物能够形成球形的稳定胶束, cmc值和胶束粒径随着共聚物中疏水性聚L-谷氨酸苄酯(PBLG)链段含量的增加而减小.     

温度/pH敏感性P(MAA-g-DEAM)共聚物水溶液的相行为

利用大分子单体技术通过自由基共聚法合成了由甲基丙烯酸(MAA)和N, N-二乙基丙烯酰胺(DEAM)组成的几种不同组成的P(MAA-g-DEAM)接枝共聚物.通过UV-Vis 透光率的测定和荧光探针技术, 对共聚物水溶液的相行为进行了研究. 研究表明, 此接枝共聚物具有相互独立的温度和pH 敏感性；几种组成不同的P(MAA-g-DEAM)接枝共聚物具有基本相同的低临界溶解温度(LCST)；它们的临界相变pH与接枝共聚物的组成有关, 温敏性PDEAM 枝链的接枝率越高, 其临界相变pH 越高. pH > 5.5 时, 接枝共聚物的主链是一种较为松散的线团构象；pH < 5.5 时, 接枝共聚物的主链是一种较为压缩的线团构象. 这种接枝共聚物高分子聚集体在新的纳米复合材料的合成方面有可能获得应用.     

N-异丙基丙烯酰胺类共聚物温敏性研究

制备了N-异丙基丙烯酰胺(NIPAAm)与N,N-二甲基丙烯酰胺(DMAAm)和/或甲基丙烯酸羟乙酯(HEMA)的二元及三元共聚物,研究了组成和链转移剂用量对共聚物温敏性的影响,并在上述三元共聚物上接枝聚己内酯(PCL)得到温敏性两亲聚合物.结果表明,随着DMAAm增加、HEMA减少或共聚物分子量降低,共聚物的最低临界溶解温度升高,且PCL链段的接枝度和长度对聚合物的温敏性影响明显.     

碳酸钙在聚合物胶束控制下的仿生合成

合成了温敏性的聚(N-异丙基丙烯酰胺)-b-聚(L-谷氨酸)(PNIPAM-b-PLGA)嵌段共聚物,在较高温度下制备了以PNIPAM为核、以PLGA为壳的自组装胶束,研究了胶束对碳酸钙晶体生长的控制作用.使用扫描电镜和X射线衍射表征了碳酸钙晶体的形貌和晶型.当聚合物胶束浓度较高时,得到纤维状的文石;当胶束浓度较低时,...     

P(AA-g-NIPAM)与PNIPAM间络合作用的荧光技术研究

利用UV透光率、荧光探针和荧光各向异性研究了稀水溶液中聚N-异丙基丙烯酰胺(PNIPAM)与接枝共聚物聚丙烯酸接枝聚N-异丙基丙烯酰胺[P(AA-g-NIPAM)]间的络合作用. 结果表明, PNIPAM和P(AA-g-NIPAM)之间通过氢键作用形成络合物. 络合作用依赖于溶液pH及P(AA-g-NIPAM)接枝共聚物中AA的相对含量. 溶液pH越小, AA相对含量越高, 络合作用越强. 这种络合作用使得聚合物主链变得较为收缩, 体系亲水性降低, 表现出一定的疏水性.     

基于葡萄糖和苯硼酸基元之间的可逆共价键构筑多重响应性高分子复合物胶束

通过可逆加成-断裂链转移(RAFT)的聚合方法,合成了分别含有苯硼酸基元和葡萄糖基元的聚(N-异丙基丙烯酰胺)-b-聚(丙烯酰胺基苯硼酸)(PNIPAM-b-PAPBA)和聚(N-异丙基丙烯酰胺)-b-聚(丙烯酰葡萄糖胺)(PNIPAM-b-PAGA)二嵌段聚合物.由于苯硼酸和葡萄糖基元之间在弱碱性条件下(pH9.3)形成硼酸酯共价键,两种二嵌段聚合物的水溶液混合后能自发形成以PAPBA/PAGA络合物为核,PNIPAM为壳层的高分子复合物胶束.由于硼酸酯共价键在pH值和葡萄糖浓度改变时能可逆形成和断裂,以及胶束PNIPAM壳层的温敏性,所制备的基于苯硼酸/葡萄糖可逆共价键的高分子复合物胶束对pH、葡萄糖和温度具有多重响应性.     

共聚N-异丙基丙烯酰胺单链微凝胶

聚 N -异丙基丙烯酰胺 (PNIPAM)的水溶液具有下临界共溶温度 LCST(约 3 2℃左右 ) ,即当体系温度高于 3 2℃时 ,高分子链的构象发生 Coil- to- Globule的变化 [1～ 3 ] ,而由 N -异丙基丙烯酰胺制备的水凝胶亦存在体积相转变 ,该转变与网络链的构象变化相关 ,文献 [1 ,4,5 ]对从大块凝胶到微米级凝胶的性质进行了研究 .本文成功地制备了聚 N -异丙基丙烯酰胺的单链微凝胶 ,与相应的线性高分子在分子量和化学组成上完全相同 ,初步研究了它们与十二烷基硫酸钠 (SDS)的混合水溶液的粘度性质 ,从而在两者之间建立了直接而明确的联系 .1…     

聚谷氨酸基双重响应性纳米胶束的制备及药物控释性能

首先制备端氨基聚(N-异丙基丙烯酰胺-co-聚乙二醇)大分子引发剂,再通过端氨基引发L-谷氨酸-γ-苄酯-N-羧酸酐开环聚合,制备了聚(N-异丙基丙烯酰胺-co-聚乙二醇)与聚(L-谷氨酸-γ-苄酯)的嵌段共聚物,将其中的γ-苄酯基团转化为酰肼基团后与阿霉素(DOX)共价结合,最后在水溶液中自组装成纳米胶束,制备了温度和pH值双重响应性纳米胶束。胶束外层由亲水性聚(N-异丙基丙烯酰胺-co-聚乙二醇)组成,具有温敏性,低临界溶液温度为38℃;胶束内层由聚(L-谷氨酸-γ-酰肼-阿霉素)组成。该胶束对于药物的释放具有温度和pH双重敏感性。     

高分子表面活性剂P(AM-co-OPMA)的合成与表征

辛基酚聚氧乙烯醚(10)(OP-10)与马来酸酐在95℃下反应,合成了辛基酚聚氧乙烯醚马来酸单酯(OPMA);并在水溶液中与丙烯酰胺(AM)单体进行共聚合,获得了高分子表面活性剂P(AM-co-OPMA);考察了引发剂用量、单体组成、单体总浓度及反应温度对共聚物特性粘数与阴离子度的影响.通过红外光谱、紫外光谱、荧光发射光谱和电导滴定对共聚物结构和组成进行了表征;利用视频光学接触角测量仪分别测定了共聚物表面和界面张力.结果表明,在聚丙烯酰胺分子主链上引入OPMA链节后,不仅保持了PAM优良的增稠能力(特性粘数达764.31 mL/g),且赋予了共聚物较高的表面活性(浓度为1.5 g/L共聚物水溶液的表面和界面张力分别可达53.94 mN/m和5.41 mN/m).     

Micellization and Adsorption Parameters of Poly(Propylene Oxide)/Poly(Ethylene Glycol) Block and Graft Copolymers in Aqueous Medium

This work aims to measure the adsorption and micellization parameters of new water soluble nonionic amphiphilic block and graft copolymers based on hydrophilic poly (ethylene glycol) (PEG) and hydrophobic poly (propylene oxide) (PPO) at ambient temperature and normal atmospheric pressure. The chemical composition and molecular weights of the prepared copolymers were determined from ¹H NMR analyses. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration, and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration, the area per molecule at interface and the effectiveness of surface tension reduction were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption and micellization process were calculated and are discussed.     

Micellization and Thermogelation of Poly(ether urethane)s Comprising Poly(ethylene glycol) and Poly(propylene glycol)

A series of multiblock poly(ether urethane)s comprising poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. Their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 8 to 12 wt%. The composition and structural information of the copolymers were studied by GPC and ¹H NMR. The critical micellization concentration (CMC) and thermodynamic parameters for micelle formation were determined at different temperatures. The temperature response of the copolymer solutions were studied and found to be associated with the composition of the copolymers.     

Micellar characteristics of diblock polyacrylate-polyethylene oxide copolymers in aqueous media

The formation and structural features of micelles from low molecular weight diblock copolymers of poly(methylmethacrylate-b-ethylene oxide) PMMA-PEO (varying in total molecular weight) and poly(butylmethacrylate-b-ethylene oxide) PBMA-PEO in water, aqueous NaCl and urea solutions were examined by surface tension, dye spectral, cloud point, viscosity and small angle neutron scattering (SANS) measurements. The increasing concentrations of NaCl reduce the onset concentration of micellization and phase separation, while urea has reverse effect. The analysis of the SANS curves revealed the presence of prolate ellipsoidal micelles in diblock copolymers at various experimental concentrations and temperatures studied. The effect of temperature, NaCl and urea on the neutron scattering profiles are more or less the same which is well supported by viscosity and surface tension measurements. The diblock copolymers form spherical micelles of aggregation number in the range of 522-664. The micelles are very temperature stable.     

Micelles and gels of mixed triblock copoly(oxyalkylene)s in aqueous solution

The micellization in dilute aqueous solution of a 50/50 wt% mixture of two triblock copolymers, E45B14E45 and E62P39E62, and the gelation of concentrated micellar solutions have been investigated over a range of temperatures. Here E, B, and P denote oxyethylene, oxubutylene, and oxypropylene chain units. Comparison is made with aqueous solutions of the individual copolymers. The results of light scattering measurements are consistent with effectively separate micellization of the two copolymers in the mixture. Hard gel formed when the extent of micellization was high for both copolymers. Because of the relatively high critical micellization temperatures of copolymer E62P39E62, the low-temperature boundary of the hard gel was high for this copolymer and for the mixture. The minimum concentration for hard-gel formation was higher for the mixture than for either of the individual copolymers, as would be expected for packing of two distributions of micelles of different average size.     

含磺酸基团的含氟嵌段共聚物的溶液性能及其应用

利用原子转移自由基聚合以及随后的磺化反应合成了一系列具有不同含氟量和磺化度的嵌段共聚物P(SSt b FNEMA) (PSSF) .通过溶液粘度和表面张力的测定 ,研究了该含氟嵌段共聚物独特的溶液行为 .实验结果表明 ,PSSF能显著降低N 甲基吡咯烷酮溶液的表面张力 .然而 ,与N 甲基吡咯烷酮溶液的表面性能不同 ,PSSF不能显著地降低水溶液的表面张力 ;当PSSF中和成钠盐后 ,水溶液的表面张力趋于一致 .进一步通过TEM、1 H NMR考察了PSSF在不同溶液中的形态 ,发现PSSF在水溶液中以核壳结构存在 ,而在N 甲基吡咯烷酮溶液中主要以胶束的形式存在 .初步考察了PSSF对聚氨酯脲 丙烯酸酯 (PUA)复合水分散液的改性效果 ,发现只需加入少量的PSSF ,就可使PUA膜的吸水率从原来的 10wt%下降到 4wt% .     

Micellization and gelation of aqueous solutions of star-shaped PEG-PCL block copolymers consisting of branched 4-arm poly(ethylene glycol) and polycaprolactone blocks

Star-shaped block copolymers consisting of non-toxic poly(ethylene glycol) and biodegradable polycaprolactone ((PEG5K-PCL)₄) were synthesized by ring-opening polymerization of the ε-caprolactone monomer with hydroxyl-terminated 4-armed PEG as initiator. These biodegradable, amphiphilic star block copolymers showed micellization and sol-gel transition behaviors in aqueous solution with varying concentration and temperature. In the dilute aqueous solutions of star block copolymers, micellization behavior occurred over specific concentration. The 1,6-diphenyl-1,3,5-hexatriene (DPH) solubilization method was used to determine the critical micellization concentration (CMC) of star block copolymers. The obtained micelle size increased with increasing hydrophobic PCL block length. In high-concentration solutions, the star block copolymers showed temperature-sensitive sol-gel transition behavior. The morphology of the micelle and gel was investigated by atomic force microscopy (AFM). As a result, the micelles showed a core-corona spherical structure at concentration near CMC, while the gel showed a mountain-chain-like morphology picture. It was proposed that with increasing the micelle concentration the worm-like micelle clusters formed firstly and the gel was constructed by the packing of micelle clusters.     

Synthesis and self-assembly behavior of thermoresponsive triblock copolymer

Block copolymers comprising thermosensitive poly(N-isopropylacrylamide) (PNIPAM) and hydrophobic poly(n-butyl acrylate) (PBA) blocks, were synthesized using the reversible addition-fragmentation chain transfer polymerization (RAFT), their thermosensitive behavior was studied by ultraviolet spectrophotometer (UV) and dynamic light scattering (DLS). The lower critical solution temperature (LCST) was strongly correlated to the hydrophobic/hydrophilic ratio of the copolymers. Their micellization and self-assembly behavior in dilute aqueous solution were studied by surface tension (SFT), DLS and TEM. The resulting block copolymers reversibly formed or deformed micellar assemblies during their LCSTs. The critical micelle concentration (CMC) was controlled by the composition of PBA and PNIPAM, indicating the successful formation of the block copolymers.     

丙烯酰胺型阴离子表面活性单体与丙烯酰胺共聚物水溶液的流变特性

以丙烯酰胺型阴离子表面活性单体2-丙烯酰胺基十四烷基磺酸钠(NaAMC14S)为共单体,与丙烯酰胺(AM)的水溶液均相共聚合,使NaAMC14S的浓度分别处于临界胶束浓度上下,分别制备了具有无规结构与微嵌段结构的两类共聚物;用红外光谱法对共聚物的结构进行了表征,使用乌氏粘度法测定了特性粘数,相对表示出了共聚物的分子量;采用荧光探针法与表观粘度法重点研究了两类共聚物的疏水缔合性与水溶液的流变特性.研究结果表明,具有微嵌段结构的共聚物具有很强的疏水缔合性,当其水溶液的浓度达0.2wt%后,表观粘度迅速提高;其水溶液的切力变稀行为具有明显的可逆性,表现出强的抗剪切性能.本研究中特别发现,具有微嵌段结构的共聚物其盐水溶液的表观粘度远高于纯水溶液的表观粘度,当共聚物浓度为0.3wt%、CaCl2浓度为2wt%时,溶液的表观粘度竟然提高了3个数量级,表现出独特的正性盐敏性(即遇盐变稠).     

聚氧乙烯-聚氧丙烯嵌段共聚物在水溶液中的胶束化作用

本实验采用表面张力法,苯红紫可见光吸收法测定L64,AE32,AP221等三种不同结构的聚氧乙烯-聚氧丙烯嵌段共聚物的临界胶束形成浓度CMC,发现L64与AE32在低浓度下形成单分子胶束,在高浓度下形成聚集胶束。AP221则只在较低的浓度下形成聚集胶束。不同温度下CMC的测定结果表明温度对L64形成单分子胶束的CMC影响较小,而聚集胶束的浓度则随着温度升高而迅速下降,后者胶束形成热ΔH较高,为140.6kJ/mol。