光敏共聚物P(St/VM-co-MA)自组装胶体粒子及其性能

以苯乙烯类光敏单体7-(4-乙烯基苄氧基)-4-甲基香豆素(VM)、苯乙烯(St)、马来酸酐(MA)为共聚单体,采用自由基聚合法制备了光敏性双亲共聚物P(St/VM-co-MA).在选择性溶剂(N,N-二甲基甲酰胺(DMF)/H2O)中对P(St/VM-co-MA)进行自组装,用透射电镜(TEM)和动态激光光散射(DLS)表征了自组装胶体粒子的形态、粒径大小及其分布.利用紫外光照使胶体粒子中香豆素基元发生光二聚反应,形成交联胶体粒子,并用紫外-可见光分光光度计(UV-Vis)跟踪其交联过程.用DLS研究了交联和未经交联胶体粒子的粒径和结构稳定性,用激光扫描共聚焦显微镜(LSCM)和光学显微镜考察了胶体粒子的乳化、包覆性能.结果表明:交联和未经交联胶体粒子均具有乳化性,且在乳化过程中可实现对油溶性染料的包覆.胶体粒子交联后,粒径有所减小,结构稳定性、乳化性能、包覆性能均有所提高.     

光敏感双亲性梳状SMA聚合物的合成及其胶束化

以含香豆素型苯乙烯类光敏单体(coumarin-containing styrene monomer, CS)与苯乙烯(St)、马来酸酐(MA)为反应单体, 以偶氮二异丁腈(AIBN)为引发剂制备了光敏感三元苯乙烯-马来酸酐共聚物(SMA)双亲交替聚合物P(St/CS-alt-MA), 再利用羧酸酐基元与正辛胺的室温胺解反应获得光敏感双亲性梳状聚合物P(St/CS-alt-MAA8). 用傅立叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、1H核磁共振(1H-NMR)等对该双亲梳状聚合物进行结构表征. 通过香豆素基元的光二聚作用, 使梳状聚合物溶解在DMSO中进行光照预交联; 非交联与预交联聚合物分别在选择性溶剂中自组装形成胶束; 利用羧酸基元与NaOH的离子化作用改变聚合物胶束的亲疏水性质. 动态激光光散射(DLS)与芘荧光探针实验表明预交联聚合物胶束较非交联胶束粒径大, 负载芘的能力强; 离子化作用使聚合物胶束解离重组成粒径更小的胶束, 但预交联胶束较非交联胶束小, 离子化后胶束疏水微区更加紧密, 负载芘的能力也增大.     

交替共聚物P(St-alt-Ma-Dopa)的自组装及乳化性能

以二甲亚砜(DMSO)为溶剂, 用多巴胺(Dopamine)胺解聚(苯乙烯-alt-马来酸酐)(P(St-alt-Man))制备双亲交替共聚物P(St-alt-Ma-Dopa). 在选择性溶剂(N,N-二甲基甲酰胺(DMF)/水)中对P(St-alt-Ma-Dopa)进行溶液自组装, 用紫外分光光度计(UV)、透射电镜(TEM)、荧光探针技术、zeta电位仪等技术研究了添加剂(HCl, NaOH或NaCl)对P(St-alt-Ma-Dopa)自组装行为的影响及其胶体粒子的乳化性能. 结果表明, P(St-alt-Ma-Dopa)链在选择性溶剂(DMF/水)中可自组装形成球状胶体颗粒, 其临界聚集水含量(CWC)明显大于P(St-alt-Man). 体系的pH值、盐浓度等对P(St-alt-Ma-Dopa)胶体粒子的性质(粒子大小、zeta电位、亲疏水性等)有较大的影响, 引入多巴胺结构使交替共聚物胶体粒子的乳化性能有所提高.     

4-PEG接枝苯乙烯-马来酸酐交替共聚物的合成及功能化

采用普通自由基聚合和可逆加成一断裂链转移（RAFT）自由基聚合方法合成了对位PEG取代苯乙烯（PEG-g-St）和马来酸酐的交替共聚物（P（（PEG—g—St）-alt-MA））,”CNMR分析表明PEG-g-St和马来酸酐单元采取交替的序列结构．利用反应性基团-马来酸酐单元的水解以及胺解可以制备功能性的PEG聚合物．以月桂胺为模型小分子研究了该聚合物的胺解,得到4-PEG-苯乙烯与羧酸基团以及疏水烷烃的交替序列聚合物,该双亲聚合物在水溶液中形成组装体．     

双亲性共聚物P(St/VBT-co-MA)自组装胶束的制备及其乳化性能

以1-(4-乙烯基苄基)胸腺嘧啶(VBT)、苯乙烯(St)、马来酸酐(MA)为共聚单体,采用自由基聚合法制备了双亲性共聚物P(St/VBT-co-MA)(PSVM)。PSVM在选择性溶剂N,N-二甲基甲酰胺(DMF)的水溶液中进行自组装可形成胶束。利用透射电镜(TEM)和动态激光光散射(DLS)表征了自组装胶束的形态和粒径分布。以该胶束作为颗粒乳化剂稳定白油-水体系形成乳液,研究了PSVM胶束浓度、pH、盐浓度等对其乳化性能的影响,并用光学显微镜(OM)表征了其乳液形态。结果表明:通过自由基聚合的方法成功合成了双亲共聚物PSVM,其自组装形成粒径分布均匀的球形胶束;该胶束具有优异的乳化效率,其乳液长期稳定且具有pH响应性及强耐盐性,静置四个月后,乳液仍具有良好的乳化效果且乳液层高度基本不变。     

光敏感三元共聚物的合成及溶液自组装

以一端为肉桂酸酯光交联基元、中间为聚己内酯长柔性链的甲基丙烯酸酯类大单体FM5C为第三单体,与马来酸酐(MAH)及苯乙烯(St)单体以AIBN引发共聚合,制备了光敏感三元共聚物P(FM5C-co-MAH-co-St).该三元共聚物可在选择性溶剂中形成纳米胶体粒子,并可先利用肉桂酸酯基元的光照交联作用使胶体粒子内聚合物交联,进而利用羧酸酐基元与2-氨基吡啶的室温氨解反应改变胶体粒子形态.用FTIR、GPC、1H-NMR等对该聚合物及其氨解产物进行了结构表征.用动态激光光散射(DLS)、透射电镜(TEM)、芘探针等技术研究了该聚合物胶体粒子微观形态、粒径与微环境在光照交联后及氨解后的变化.实验结果表明,P(FM5C-co-MAH-co-St)在选择性溶剂中可自组装成球形胶体粒子,肉桂酸酯光照交联作用使胶体粒子中的聚合物团聚得更加紧密,从而使其粒径更小、疏水区域更加集中;而进一步的室温氨解反应则使聚合物胶体粒子更松散、粒径变大.     

无规共聚物自组装球形胶束表面亲水性的耗散粒子动力学模拟

建立了含不同亲疏水粒子比的双亲性无规共聚物粗粒化模型. 采用耗散粒子动力学方法模拟了两亲性无规共聚物选择性溶剂自组装球形胶束表面的亲水性能. 模拟结果表明, 无规共聚物在选择性溶剂中自组装得到实心球形胶束, 球形胶束表面的亲水性与聚合物链亲水粒子含量、溶剂的选择性有关. 随着聚合物链所含亲水粒子增加, 球形胶束表面的亲水性增强. 球形胶束表面的亲水性随着疏水粒子与溶剂粒子间的排斥参数增大而增强, 模拟结果与实验结论一致. 该模拟方法给出的胶束微结构信息可以为双亲无规共聚物分子设计及自组装双亲胶束制备提供一定的理论指导.     

双亲性无规共聚物自组装胶束结构及其乳化性能

以不同交联度、溶胀程度的双亲无规共聚物聚[(苯乙烯-alt-马来酸酐)-co-(7-对乙烯基苄氧基-4-甲基香豆素-alt-马来酸酐)](PSMVM)胶束作为聚合物胶束乳化剂稳定甲苯/水体系, 重点研究光交联度对胶束结构及其乳化性能的影响. 结果表明, 胶束交联度、溶胀度和荷电性对胶束结构及乳化性能有较大影响.     

双亲性无规共聚物P（VM-co-AMPS）的自组装及其性能

以2-丙烯酰胺基-2-甲基丙磺酸（AMPS）和苯乙烯类光敏单体7-（4-乙烯基苄氧基）-4-甲基香豆素（VM）为共聚单体,采用自由基聚合法制备了光敏性双亲共聚物P（VM-co-AMPS）。P（VM-co-AMPS）在溶剂水中自组装胶束化,用原子力显微镜（AFM）表征了自组装胶体粒子的形态、粒径及其分布。紫外光照使胶体粒子中香豆素基元发生光二聚反应,用紫外-可见光分光光度计（UV-Vis）跟踪其光二聚交联过程,用光学显微镜考察了胶体粒子的乳化性能。结果表明：胶体粒子具有较好的紫外吸收性能和较好的乳化性能。该胶束制备工艺简单,条件温和,避免了溶剂的使用。     

共溶剂性质对双亲性无规共聚物P(St-co-DM)胶束化行为及其性能的影响

以苯乙烯(St)和甲基丙烯酸二甲氨乙酯(DMAEMA)为共聚单体, 通过普通自由基溶液聚合合成了双亲性无规共聚物P(St-co-DM). 用傅里叶变换红外(FTIR)光谱、核磁共振氢谱(¹H NMR)、凝胶渗透色谱(GPC)和差示扫描量热(DSC)仪对聚合物结构进行表征. 研究了共溶剂的性质对P(St-co-DM)自组装胶束结构及其乳化性能的影响. 用透射电镜(TEM)和动态激光光散射(DLS)表征了自组装胶体粒子的形态、粒径大小及其分布. 通过测量胶束在甲苯/水界面的接触角表征胶束表面性能. 结果表明: P(St-co-DM)以四氢呋喃(THF)为共溶剂自组装时, 胶束的临界聚集水含量较大, 胶束表面亲水性较强, 流体力学半径较大; 用二氧六环或THF为共溶剂, 水为选择性溶剂, P(St-co-DM)自组装可以得到外层松散、内层比较密实的球状胶束, 用N,N-二甲基甲酰胺(DMF)为共溶剂时, 胶束整体呈现比较密实的球状胶束; 分别用DMF、二氧六环和THF为共溶剂制备的胶束, 其接触角均值都小于90°, 可形成O/W型(水包油型)乳液. 乳化实验结果表明, 以二氧六环和THF为共溶剂制备的胶束作为颗粒乳化剂制备的乳液性能较好.     

两种双亲性聚合物自组装胶束复合水溶液的乳化性能

以苯乙烯(St)、含香豆素光敏单体(VM)、丙烯酸(AA)为单体,偶氮二异丁腈(AIBN)为引发剂引发自由基共聚,合成了双亲性光敏无规共聚物P(St-co-VM-co-AA)(简称PSVA);又以St及甲基丙烯酸二甲胺乙酯(DMAEMA)为单体,AIBN为引发剂引发自由基共聚,制得二元双亲性无规共聚物P(St-co-D...     

Preparation of Quaternary Amphiphilic Block Copolymer PMA-b-P (NVP/MAH/St) and Its Application in Surface Modification of Aluminum Nitride Powders

Poly(methyl acrylate)-b-poly(N-vinyl pyrrolidone/maleic anhydride/styrene) (PMA-b-P (NVP/MAH/St)) quaternary amphiphilic block copolymer prepared by reversible addition-fragmentation chain transfer (RAFT) was used to improve the anti-hydrolysis and dispersion properties of aluminum nitride (AIN) powders that were modified by copolymers. Its structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and Hydrogen nuclear magnetic spectroscopy (¹H-NMR). The results demonstrate that the molecular weight distribution of the quaternary amphiphilic block copolymers is 1.35–1.60, which is characteristic of controlled molecular weight and narrow molecular weight distribution. Through charge transfer complexes, NVP/MAH/St produces a regular alternating arrangement structure. After being treated with micro-crosslinking, AlN powder modified by copolymer PMA-b-P(NVP/MAH/St) exhibits outstanding resistance to hydrolysis and can be stabilized in hot water at 50 °C for more than 14 h, and the agglomeration of powder particles was improved remarkably.     

微乳液法制备水溶性双亲丙烯酰胺-苯乙烯嵌段共聚物

分别以十二烷基硫酸钠 (SDS)、壬基酚聚氧乙烯醚 (OP 10 )为表面活性剂 ,丙烯酰胺 (AM)的水溶液为连续相 ,苯乙烯 (St)为分散相 ,构成微乳液共聚合体系 ,合成了水溶性双亲嵌段共聚物 ,并通过荧光探针技术、差示扫描量热 (DSC)测试及流变性能的测定表征了共聚物的嵌段性结构 ,用红外光谱 (FTIR)及紫外光谱 (UV)分析了共聚物的化学组成     

聚甲基丙烯酸甲酯-聚甲基丙烯酸两亲性嵌段共聚物的制备及自组装形态的研究

以2-溴异丁酸乙酯为引发剂, 氯化亚铜/联二吡啶为催化剂, 通过原子转移自由基聚合(ATRP)获得分子链末端含一个α-溴原子的聚甲基丙烯酸甲酯(PMMA-Br), 以此为大分子引发剂引发甲基丙烯酸铅[Pb(MA)₂]单体进行ATRP反应, 制得P[MMA-b-Pb(MA)_2]嵌段共聚物, 将此共聚物在盐酸中进行离子交换即得聚甲基丙烯酸甲酯-聚甲基丙烯酸的两亲性嵌段共聚物[P(MMA-b-MAA)]. 用FTIR, GPC, NMR和SEM方法对共聚物进行了表征.     

Preparation of sulphonate-containing polymer particles <Emphasis Type="Italic">via</Emphasis> semi-continuous emulsion copolymerizaion of styrene and sodium styrene sulphonate

Submicron-sized P(St-NaSS) latexes were prepared via a semi-continuous emulsion copolymerization of styrene (St) and sodium styrene sulphonate(NaSS) in the presence of anionic surfactant,in which NaSS aqueous solution and St were separately dropwise charged into the polymerization system at the same time.The hydrodynamic diameter of the latex particles was measured by dynamic light scattering(DSL) method,and the NaSS unit content of the purified copolymer by water extraction was calculated based on the elementary analysis.Results showed that the copolymerization could be performed smoothly with the monomer conversion more than 96%in the absence of crosslinker,and PNaSS homopolymer could be removed from the latex product by water extraction for 28 h.The weight loss in the water extraction tended to decrease and the NaSS unit content of the purified copolymer tended to increase with the increase of monomer feeding time, and both of them increased with the increase of NaSS/St mole ratio in the charge.The introduction of divinyl benzene (DVB) could decrease the weight loss in the water extraction and increase the NaSS unit content of the purified copolymer. When 25/75 mole ratio of NaSS/St and 11 mol%DVB of total NaSS and St were used in the recipe,and the monomer feeding time was 3 h in copolymerization,the NaSS unit content of the purified copolymer reached 7.31 mol%.     

一种含假芪型偶氮生色团两亲性嵌段共聚物的合成与表征

利用原子转移自由基聚合（ATRP）合成了一种新型的含假芪型偶氮生色团的两亲性嵌段共聚物P（HEMA-b-6CNAzo）。首先,采用ATRP引发剂引发三甲基硅保护的羟乙基甲基丙烯酸酯（HEMA—TMS）聚合,得到大分子引发剂P（HEMA—TMS）;接着进一步引发单体甲基丙烯酸6-（N_甲基苯胺基）己酯进行ATRP反应,得...     

Pickering Emulsion Stabilized by Self-Assembled Micelles of Amphiphilic Random Copolymer P(St-co-DM)

Self-assembled polymeric micelles can be used as efficient particulate emulsifiers. Styrene (St) and dimethylaminoethyl methacrylate (DM) were used to synthesize the amphiphilic random copolymer P(St-co-DM). This copolymer self-assembles into spherical polymeric micelles. The polymeric micelles show surface activity and pH sensitivity for producing Pickering emulsion. The experiment shows that the stability of the emulsion increases with the micelle concentration. The emulsion can only be formed when the salt concentration is below a certain limiting value. Using the white oil as the oil phase, polymeric micelles have emulsification in a large pH range. The emulsifying performance of the polymeric micelles could be enhanced by raising the water/oil volume ratio.      

Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene‐co‐2‐hydroxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] using sequential controlled polymerization

A well‐defined amphiphilic copolymer of ‐poly(ethylene oxide) (PEO) linked with comb‐shaped [poly(styrene‐co‐2‐hydeoxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] (PEO‐b‐P(St‐co‐HEMA)‐g‐PCL) was successfully synthesized by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with ring‐opening anionic polymerization and coordination–insertion ring‐opening polymerization (ROP). The α‐methoxy poly(ethylene oxide) (mPEO) with ω,3‐benzylsulfanylthiocarbonylsufanylpropionic acid (BSPA) end group (mPEO‐BSPA) was prepared by the reaction of mPEO with 3‐benzylsulfanylthiocarbonylsufanyl propionic acid chloride (BSPAC), and the reaction efficiency was close to 100%; then the mPEO‐BSPA was used as a macro‐RAFT agent for the copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) using 2,2‐azobisisobutyronitrile as initiator. The molecular weight of copolymer PEO‐b‐P(St‐co‐HEMA) increased with the monomer conversion, but the molecular weight distribution was a little wide. The influence of molecular weight of macro‐RAFT agent on the polymerization procedure was discussed. The ROP of ε‐caprolactone was then completed by initiation of hydroxyl groups of the PEO‐b‐P(St‐co‐HEMA) precursors in the presence of stannous octoate (Sn(Oct)₂). Thus, the amphiphilic copolymer of linear PEO linked with comb‐like P(St‐co‐HEMA)‐g‐PCL was obtained. The final and intermediate products were characterized in detail by NMR, GPC, and UV. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 467–476, 2006