窄分散大粒径交联聚苯乙烯功能微球的合成研究

用分散聚合法，以聚乙烯吡咯烷酮（PVP）为稳定剂，偶氮二异丁腈（AIBN）为引发剂，乙二醇二甲基双丙烯酸酯（EGDMA）为交联剂，一次加料法在醇水介质中制备数个微米交联聚苯乙烯（PS）微球。研究了苯乙烯（St)、丙烯酸（AA）、EGDMA的用量对粒子大小，粒径分布的影响。测量了微球表面羧基的含量。     

分散聚合制备羧基化单分散聚苯乙烯交联微球

以苯乙烯(St)、丙烯酸(AA)为单体,二乙烯基苯(DVB)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合和交联剂后滴加法合成了单分散羧基化交联聚苯乙烯微球。通过傅立叶红外光谱(FT-TR),扫描电子显微镜(SEM),激光粒度及Zeta电位分析仪等对微球结构进行了表征。结果表明,引发剂、分散剂用量和交联剂的加入方式对微球粒径及单分散性影响显著,当St用量为15%(wt)、DVB用量为1%(wt)、AA用量为1%(wt)、AIBN用量为2%(wt)、PVP用量为6%(wt)时所制备的微球具有良好的单分散性和球形形貌,粒径达到4μm,且微球表面带负电荷。     

膜乳化-液中干燥法制备单分散高分子微球

粒径可控的单分散高分子微球,在分析化学中可用作高效液相色谱填料^[1,2];在化学工业中可用作催化剂载体;在生物领域中用于药物释放、癌症与肝炎等临床诊断、细胞标记与识别等^[3].高分子微球的制备方法大致可分为两类,一是利用由单体出发的聚合反应或缩聚反应形成微球,二是高分子溶液经物理或物理化学手段处理后形成微球^[4]     

沉淀聚合法Poly(DVB-co-EGDMA-co-MAA)功能聚合物微球的制备及表征

采用二乙烯基苯-55(DVB-55)和乙二醇二甲基丙烯酸酯(EGDMA)作为混合交联剂,乙腈为溶剂,偶氮二异丁腈(AIBN)为引发剂,以甲基丙烯酸为功能单体采用沉淀聚合法合成了单分散或窄分散的、表面具有羧基的交联聚合物微球,所得微球的粒径变化范围为0.6～3.8μm.通过调节交联剂DVB-55和EGDMA的投料比,可以对微球的粒径、粒径分布、产率、热稳定性以及表面官能团含量进行有效控制.文中对混合交联剂DVB-55与EGDMA比例的改变对微球的粒径、粒径分布以及产率的影响机理给出了理论解释;对DVB和EGDMA的兼容性研究表明,制备的三元聚合物微球的核拥有比投料比稍多的DVB单元,而微球的外层则以在预聚混合物中占更大比例的交联剂为主.     

非离子型可聚合聚氨酯/苯乙烯的超浓乳液聚合

研究了以非离子型可聚合聚氨酯(PUAG)和苯乙烯(St)为混合单体的超浓乳液聚合, 并且考察了n(NCO)/n(OH)摩尔比、复合乳化剂体系质量浓度[E]、不同乳化剂的种类、引发剂质量浓度[I]、单体体积分数(或分散相体积分数, 也称内相比Φ)、聚合温度等因素对聚合稳定性、动力学的影响. 同时结合光相关光谱(PCS)测定了聚合物乳胶粒子大小和粒径分布, 用透射电子显微镜(TEM)观察了粒子形态, 结果表明: 当n(NCO)/n(OH)＝2∶1, T＝328 K, Φ＝80.39%, [I]＝0.8% g/g (PUAG-St), [E]＝0.22 g/mL H₂O, m(MS-1)/m(CA)＝2∶1, PVA＝0.01 g/mL H₂O时, 超浓乳液不仅有较好的聚合稳定性和较快的聚合速率, 而且粒径小分布均匀. 同时, 在此条件下的表观动力学表达式和表观活化能分别确定为R_p＝k[I]^0.50[E]^0.73[M]^0.54和 E_a＝29.7 kJ/mol. 热失重分析(TGA)进一步表明: 调节PUAG的含量可以达到对聚苯乙烯的改性, 提高聚苯乙烯的热稳定性.     

分散共聚法制备窄分布P(St-co-nBA)微球

用分散共聚法制得窄分布苯乙烯(St)和丙烯酸正丁酯(nBA)的共聚物微球.采用1H-NMR、DSC、FTIR、SEM、LS等对共聚物的结构、形态、性能进行表征,考察了初始单体配比、温度、稳定剂浓度、分散介质极性、引发剂对微球粒径、粒径分布及转化率的影响.实验结果表明,初始单体比nBA/St增大,微球粒径增大,分布变宽,...     

沉淀聚合制备荧光聚脲微球及Fe3+检测

以异氟尔酮二异氰酸酯为单体, 以氨基功能化的1.8-萘二甲酰亚胺(AABD)为荧光基团, 在水/丙酮质量比为3/7的混合溶剂中, 通过沉淀聚合制备了表面洁净的高度单分散荧光聚脲微球(FPU). 通过FTIR及¹H NMR对AABD及FPU的化学结构进行了表征; 通过UV-Vis光谱确定FPU中嵌入的AABD荧光单元的含量; 通过荧光光谱研究了FPU固体粉末分散在水中及溶解在N-甲基吡咯烷酮中的荧光特性以及FPU分散在不同Fe³⁺浓度水溶液中的荧光变化. 结果表明, FPU的平均粒径(D_n)为5.24 μm, 粒径分布(D_w/D_n)为1.004, 具有强烈的绿色荧光(激发波长为420 nm, 最大发射波长为522 nm); FPU分散在水中不发生荧光自猝灭, 其荧光强度随着Fe³⁺浓度的增加(10^-4 ~10^-3 mol/L)呈线性降低.     

苯甲酸及其酯类衍生物的分子印迹机理的研究

分子印迹聚合物(M IP)是一种具有分子识别能力的新型高分子材料^[1～3].对其研究的重要问题之一是如何获得对相应模板化合物具有特异性结合的聚合物,这除了受模板分子结构特征的影响外,同时在很大程度上还受各种聚合物制备条件的影响,比如功能单体^[4～6]、溶剂^[7]及辅助金属离子的影响^[8]等.我们成功地通过计算模板分子与功能单体间的相互作用,预测了一些模板分子的印迹原性(产生印迹效应的性质)的强弱^[9],同时对几十种小分子化合物的分子印迹原性与结构之间的关系进行了讨论^[10].本文以苯甲酸、对氨基苯甲酸、对羟基苯甲酸及其酯的衍生物(结构见下式)为模板,在不同的功能单体和溶剂体系中制备了相应的分子印迹聚合物,研究了模板分子中不同取代功能基的印迹作用的相对强弱,探讨了功能基的印迹作用强弱与聚合反应体系溶剂极性间的相关性.     

水分散体系中苯乙烯和甲基丙烯酸甲酯梯度共聚物的合成与表征

以2-溴代异丁酸乙酯(EBiB)为引发剂,CuBr/CuBr₂/1,10-邻二氮菲(phen)为复合催化剂,十二烷基磺酸钠(SLS)为乳化剂,考察了水分散体系中苯乙烯(St)和甲基丙烯酸甲酯(MMA)的原子转移自由基共聚合的可控性和相对反应活性.在此基础上,通过反应进料法在水分散体系中进行了St和MMA的梯度共聚合,反应表现出“活性”聚合的特征,即所得共聚物的数均分子量随着单体转化率的增加而增大,分子量分布较窄(M_w/M_n<1.50).用¹HNMR跟踪分析了聚合反应过程中共聚物微观组成的变化规律,结果表明,共聚物链中MMA链节的累积含量和瞬时含量都随着共聚物相对链长的增加而增加,即随着聚合物相对链长的增加共聚物的微观组成从St链节占主导地位逐渐变化为以MMA链节占主导地位,表明确实形成了St和MMA的梯度或渐变共聚物.     

含铕荧光两亲接枝共聚物的制备及胶束化行为

以丙烯酸(AA)、 苯甲酸(BA)和邻菲啰啉(Phen)为配体, Eu³⁺为中心离子, 制备了可聚合荧光配合物单体, 并以此单体为功能单体, 聚乙二醇单甲醚甲基丙烯酸酯(MPEGMA)和甲基丙烯酸六氟丁酯(HFMA)为共聚单体, 通过溶液聚合制备出含铕两亲荧光接枝共聚物P-[HFMA-co-Eu(AA)(BA)₂Phen]g-PEG. 利用红外光谱(FTIR)和核磁共振波谱(¹H NMR和¹⁹F NMR)对共聚物的结构进行表征; 采用表面张力法测定共聚物的临界胶束浓度(cmc)为0.20 g/L; 通过透射电子显微镜(TEM)和动态光散射仪(DLS)观察胶束的形貌及其胶束化行为, 发现该共聚物可以形成大小均一的球形胶束, 且随着共聚物浓度的提高, 胶束粒径相应增大; 在溶液浓度达到临界胶束浓度时, 溶液荧光出现强度突变.     

Kinetics and mechanism of emulsifier-free emulsion copolymerization: Styrene-methyl methacrylate-acrylic acid system

The emulsifier-free emulsion copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process. The kinetics was investigated in detail using model function, Integrated Gamma Function. The morphology and size of particles were monitored continuously by TEM all along the polymerization. It was found that the nucleation, polymerization rate increase with increasing concentration of the functional monomer AA, initiator ammonium persulfate (APS), and polymerization temperature T, and APS plays a predominant role in the particle nucleation process. The particle nucleation stage ceased at about 10% conversion and the steady stage can be extended to about 70% conversion. The particle nucleation is likely to yield primary particle via the mechanism of homogeneous coagulative nucleation and coagulation of the primary particle to yield uniform particles. The particle growth in the postnucleation stage is via a shell growth mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2649–2656, 1999     

GRAFTING OF ETHYLENE GLYCOL DIMETHACRYLATE ONTO SILK IN AQUEOUS ALCOHOLIC SOLUTION

The grafting of ethylene glycol dimethacrylate (EGDMA) onto silk in aqueous alcohol systems using potassiumpersulfate (KPS) in the presence of air was investigated. Effects of grafting conditions, such as concentrations of monomer,initiator and formic acid, temperature and time, on the graft yield were determined. The optimum graft conditions were foundto be: T = 80℃, t = 30 min, [KPS] = 1.85% [on the weight ofmonomer (owm)]; [formic acid] = 0.2% (V/V); [EGDMA] =80% [on the weight of fiber (owf)]. The activation energy of grafting at 50-80℃ was found to be 71.31 kJ/mol for EGDMA.Grafting equations were also evaluated. The graft yield value can be regulated by the concentration of monomer. The graftcopolymerization of EGDMA onto silk is effective in improving the crease-proofing of silk fabrics.     

Butyl acrylate and vinyl acetate semicontinuous emulsion copolymerizations: study of stabilization performance

The use of small amounts of carboxylic monomers in industrial recipes with high solids content enhances colloidal stability due to the presence of carboxylic groups on the outer surface of the polymer particles. Understanding the relationship between several different but interdependent phenomena, including particle nucleation, kinetics, particle aggregation, monomer type, solids content, the role of the carboxylic monomer and the influence of reaction temperature may improve the control over particle size and latex stability. In this work, the kinetics and stabilization performance of semicontinuous vinyl acetate (VA) and butyl acrylate (BA) emulsion copolymerization reactions are studied under different reaction temperatures, acrylic acid (AA) concentrations, solids contents and monomer feed compositions. Results show that choosing optimal AA concentrations and reaction temperatures are key factors in order to enhance the stabilization performance in semicontinuous VA/BA emulsion copolymerization.     

The effect of acrylic acid amount on the colloidal properties of polystyrene latex

Poly(styrene-co-acrylic acid) (St/AA) latices were prepared by using a batch soap-free emulsion copolymerisation in non-buffered medium. Polymerisation kinetics, followed by gravimetric method, revealed that increasing AA comonomer concentration was directly proportional to the copolymerisation rate, while adding AA comonomer caused a strong decrease of particle size of final St/AA latex particle without affecting the size distribution. Transmission electron microscopy indicated that the particles were monodispersed and spherical in shape irrespective of AA amount used in the investigated range. The colloidal stability of the latices was increased upon increasing the AA concentration; owing to the electrosteric stabilisation originated from AA-rich layer on the particle surface. In addition, electrophoretic mobility of formed particles versus polymerisation conversion exhibited the constancy of the surface charge density during the polymerisation process and was inferred for discussion of the polymerisation mechanism of this system.     

Preparation of styrene/acrylic acid copolymer microspheres: polymerization mechanism and carboxyl group distribution

 Poly(styrene-co-acrylic acid) (St/AA) copolymer microspheres were prepared by batch emulsifier-free emulsion copolymerization of St with AA. The monomer conversion, the morphology and the composition of the particles along the polymerization process were monitored by a gravimetric method, transmission electron microscopy observation and Fourier transform IR analysis, respectively. A shift of the polymerization locus from inside the particles to “outside” the particles in the postnucleation stage was proposed. The results of the study of the distribution of carboxyl groups by a combination of elemental and X-ray photoelectron spectroscopy analyses implied a core/shell structure for the St/AA copolymer microspheres. By chemical metal deposition, nickel particles were formed and deposited on the surface of St/AA microspheres, forming polymer/metal composite particles. Received: 16 February 2001 Accepted: 8 August 2001     

Uniform polymer particles by dispersion polymerization in alcohol

Uniform polystyrene particles in 1–10 μm size range and up to 40% solid contents have been prepared by polymerizing styrene in ethyl alcohol with azo-type initiators and a polymeric stabilizer polyvinylpyrrolidone along with an anionic, nonionic, or comonomeric co-stabilizer. Effects of polymerization parameters, such as monomer concentration, type of co-stabilizer, initiator type and concentration, crosslinking monomer, and diluent on average particle size and size distribution have been studied. Functional groups such as hydroxyl, carboxyl, amine, amide, silane, polydimethylsiloxane, and silacrown have been successfully incorporated onto the particles by copolymerization. A mechanism for particle formation and growth in dispersion polymerization is presented.     

PARAMETERS AFFECTING PARTICLE SIZE OF POLYBUTYL-ACRYLATE MICROGELS

The factors affecting particle size of reactive microgels formed during the self-emulsifying copolymerization of unsaturated polyester (UP)with butyl acrylate (BA)have been studied. The parameters discussed are: the proportion of the UP in the monomer mixture, the molecular weight and the carboxyl value of the UP, the phase ratio, the electrolyte concentration and the polar solvent additive. The seeding emulsion polymerization is discussed as well.It turned out that the particle size of the reactive microgels can be controlled in a definite range by changing the experimental conditions. However the particle size distribution becomes broader as the average diameter increases. It is suggested that the agglomeration of primary particles plays an important role during the growth of microgel particle.     

以阳离子乳化剂进行丙烯酸丁酯－苯乙烯乳液共聚的动力学研究

采用十二烷基二甲基苄基氯化铵（１２２７）乳化剂，对丙烯酸丁酯（ＢＡ）－苯乙烯（Ｓｔ）进行乳液共聚，研究了影响聚合速度的各种因素，得出了聚合速率方程和表观活化能．