甲基丙烯酸三氟乙酯/甲基丙烯酸缩水甘油酯共聚物乳液的制备

以甲基丙烯酸三氟乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和苯乙烯为基本原料,用半连续滴加的方法制备了共聚物乳液。FT-IR证明了所用单体甲基丙烯酸三氟乙酯参与了共聚反应。讨论了氟单体用量对转化率的影响。讨论了乳胶膜的吸水率的影响因素。     

甲基丙烯酸三氟乙酯的制备

介绍了甲基丙烯酸三氟乙酯的制备方法及其性质.     

甲基丙烯酸三氟乙酯/十一烯酸钠无皂乳液的制备与性能研究

对甲基丙烯酸三氟乙酯/十一烯酸钠（TFEMA/SU）无皂乳液聚合体系进行了研究。考察了单体配比对聚合反应及乳液性质的影响,研究了SU的用量对乳液稳定性、黏度、乳胶粒粒径大小及分布等的影响。实验发现：以TFEMA和SU为单体可制得稳定性较好的无皂乳液,SU的用量是影响乳液稳定性、乳液黏度及乳胶粒粒径大小的关键因素。配方中SU的质量分数控制在3%～9%,制得的乳液稳定性较好,低于或高于此添加量,稳定性较差;当SU的质量分数由3%增大到9%时,乳液的电解质稳定性由1.6 mL增大到2.2 mL,黏度由102 mPa.s增大到379 mPa.s,说明SU量的增大对乳液的电解质稳定性及黏度提高是有利的。     

甲基丙烯酸2,2,2-三氟乙酯的ATRP乳液聚合

采用原子转移自由基聚合(ATRP)乳液聚合,合成了结构明确且相对分子质量分布窄的聚甲基丙烯酸2,2,2-三氟乙酯。催化剂、引发剂、乳化剂等都影响ATRP乳液聚合,使用非离子型乳化剂油醇聚氧乙烯醚所得乳液稳定,只有少量凝胶出现,所得聚合物相对分子质量实际值与理论值较为一致。随着乳化剂、催化剂、引发剂用量的增加,相对分子质量增大,聚合反应速率逐渐加快。ATRP乳液聚合可得到相对分子质量分布为1.44,乳胶粒粒径为105.0 nm,粒径分布为0.211,凝胶质量分数为15%,可稳定贮存三个月的聚甲基丙烯酸2,2,2-三氟乙酯乳液。     

甲基丙烯酸-2,2,2-三氟乙酯的制备

采用一锅法的工艺通过甲基丙烯酸先酰氯化,再与2,2,2-三氟乙醇在催化剂4-二甲氨基吡啶的催化下酯化的方法,方便快捷地制备了甲基丙烯酸-2,2,2-三氟乙酯,并根据实验结果讨论了影响反应的主要因素。最佳反应条件是:二甲基甲酰胺(DMF)和4-二甲氨基吡啶(DMAP)的用量为5%~10%(质量比),甲基丙烯酸∶氯化亚砜∶2,2,2-三氟乙醇=1.1∶1∶0.9(摩尔比),反应温度为50~60℃,收率达到95%以上。     

甲基丙烯酸3-三甲氧基硅丙酯/苯乙烯细乳液共聚合乳胶粒稳定性

研究了各聚合条件对甲基丙烯酸3-三甲氧基硅丙酯（MPS）和苯乙烯（St）细乳液共聚合体系乳胶粒稳定性的影响,聚合条件包括引发剂类型、MPS/St比例、乳化剂用量、共稳定剂用量和体系pH值。通过动态激光光散射测定初始液滴和乳胶粒的尺寸,气相色谱测定苯乙烯的转化率,总转化率由重量法测定。研究发现,油溶性引发剂偶氮二异丁腈（AIBN）引发的体系,MPS/St比例为1∶4时,聚合过程中乳胶粒尺寸基本不变,最终乳胶粒数与初始液滴数比值为0.97。相同MPS/St比例,水溶性引发剂过硫酸钾（KPS）引发的体系,随聚合反应进行乳胶粒尺寸增加,最终乳胶粒数和初始液滴数比值仅为0.55,乳胶粒发生明显聚并。随MPS/St比例增加,乳胶粒稳定性变差,乳化剂和共稳定剂量变化对乳胶粒数和初始液滴数比值影响不大。在酸性或碱性介质中,由于水解反应加剧,乳胶粒聚并严重,最终粒子数只占初始粒子数的0.25。     

对甲苯磺酸三氟乙酯的合成

在氢氧化钠催化下，三氟乙醇与对甲苯磺酰氯发生酯化反应生成对甲苯磺酸三氟乙酯，讨论了氢氧化钠用量、反应温度、反应时间、对甲苯磺酰氯与三氟乙醇的摩尔比等因素对酯化收率的影响。     

甲基丙烯酸2,2,2-三氟乙酯的原子转移自由基聚合

以α-溴代丙酸乙酯(EPN-B)/CuCl/ 联二吡啶(bpy)作为引发/催化体系、环己酮为溶剂,对甲基丙烯酸2,2,2-三氟乙酯(TFEMA)进行原子转移自由基聚合(ATRP),研究了TFEMA的反应动力学,并考察了引发/催化体系、引发剂EPN-B用量、配位剂bpy用量及单体配比对聚合反应的影响.结果表明,采用EPN-B/CuCl/bpy引发/催化体系对TFEMA进行ATRP,可得到窄分子量分布的聚甲基丙烯酸2,2,2-三氟乙酯(PTFEMA),在实验范围内,聚合速率对单体浓度呈一级动力学关系,该反应过程具有活性聚合特征;随着引发剂EPN-B和配位剂bpy用量的增加,聚合速率加快,当EPN-B相对摩尔用量为0.5,1.0,2.0时,其相应的表观链增长速率常数分别为3.143×10~(-4),3.478×10~(-4),4.435×10~(-4)s~(-1);增大[TFEMA]/[EPN-B](摩尔比),聚合速率明显降低,但无论[TFEMA]/[EPN-B]高与低,聚合物的分布指数均为1.15～1.23.     

对甲苯磺酸三氟乙酯合成的优化

为了提高对甲苯磺酸三氟乙酯的收率，本研究主要对其合成工艺进行优化，通过对甲苯磺酰氯和三氟乙醇的投料比、液碱滴加速率、静置时间的优化，有效提高酯的收率，最后考察试验的稳定性。得到以下结果：三氟乙醇和对甲苯磺酰氯的质量比为0.56，液碱的滴加速率为0.77 kg/min,最优静置时间为2 h，产品收率大于95%，水分含量小于0.2%。     

对甲苯磺酸三氟乙酯的应用进展

综述了对甲苯磺酸三氟乙酯的性质,并讨论它在农药、医药、含氟材料等中的应用。     

The effect of CO<Subscript>2</Subscript> in free-radical polymerization of 2,2,2-trifluoroethyl methacrylate

Carbon dioxide is an effective diluent for increasing the free volume of polymer. It has useful advantages with reductions of viscosity, surface tension and with an increase of diffusion into polymer. These properties are available in polymer processing and particle designing. We carried out free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) with AIBN as the initiator in carbon dioxide. This experiment was performed at fixed temperature (343 K), stirring speed and weight of monomer+initiator. Only weight ratios of carbon dioxide were changed. Molecular weight and T_g showed a minimum at 14.1 MPa and increased in the higher final pressure.     

RAFT miniemulsion polymerization of methyl methacrylate

It has been well documented that RAFT miniemulsion polymerization has broader molecular weight distribution, compared with its bulk polymerization counterpart. Interestingly, it was found that the PDI value of RAFT miniemulsion polymerization of methyl methacrylate (MMA) mediated by 2-cyranoprop-2-yl dithiobenzoate (CPDB) was still as low as its corresponding bulk polymerization did. PDI could be as low as 1.13 even with typical sodium dodecyl sulfate (SDS, 1 wt%, surfactant) and n-hexadecane (HD, 2 wt%, costablizer) concentrations. When the polymerization was carried out at 60 °C, a dramatic increase in PDI (>1.4) was observed after 80% monomer conversion since RAFT addition reaction became diffusion-controlled. Increasing the polymerization temperature to 80 °C could reduce the PDI to 1.2 even at 100% monomer conversion. The compartmentalization effect of radicals was surprisingly absence before 30% monomer conversion but became pronounced afterwards in the miniemulsion polymerization. Thus, it still took less time to finish the miniemulsion polymerization with the increase of the surfactant levels.     

Synthesis, characterization, and energy transfer studies of dye-labeled poly(butyl methacrylate) latex particles prepared by miniemulsion polymerization

Poly(butyl methacrylate) (PBMA) latex particles have been copolymerized with new fluorescent naphthalimide dyes by miniemulsion polymerization. A new pair of naphthalimide dye monomers was synthesized and copolymerized with butyl methacrylate (BMA) via miniemulsion polymerization, producing approximately 80 nm diameter particles with a narrow size distribution. We were able to prepare polymers with molecular weights in excess of 100,000 g/mol. We also prepared 30,000 g/mol polymers using 1-dodecanethiol as a chain transfer agent. GPC and UV characterization suggest that nearly all of the dye monomers were incorporated into the PBMA polymer chains. The polymerized naphthalimide dyes can be used as a donor-acceptor pair for fluorescence resonance energy transfer (FRET) experiments. The analysis of FRET experiments is complicated by the slightly non-exponential decay of the donor naphthalimide dye. We propose a simple method to deal with this non-exponential behavior in the data analysis. Using our approach, we find that the Förster radius (R_o) between the donor and the acceptor dyes incorporated in the PBMA latex is 3.8 nm. This value is similar to the 3.6 nm Förster radius of a comparable model dye pair in ethyl acetate obtained by a different method.     

Synthesis of polystyrene encapsulated nanosaponite composite latex via miniemulsion polymerization

The synthesis and characterization of polystyrene encapsulated nanosaponite composite suspension via miniemulsion polymerization are reported in this study. The particle size of nanoclay and its pre-modification are critical to successfully producing a stable complex suspension. The final products were characterized by X-ray diffraction spectra, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thin window energy dispersive spectroscopy (EDS), and light scattering. The results show that ar-vinylbenzyltrimethylammonium chloride (VBTAC) modified nanosaponite could be fully exfoliated and encapsulated inside the polystyrene latex via in situ miniemulsion polymerization. When the concentration of hexadecane (a co-stabilizer used in the miniemulsion polymerization) was high, the final composite particles are composed mainly of spherical particles with size less than 100 nm, and a small number of hemispherical or bowl-structured particles of size ∼100 nm to 1000 nm. The phase separation due to the existence of large amounts of hexadecane accounted for the formation of a variety of morphologies.     

Comparison of RAFT polymerization of methyl methacrylate in conventional emulsion and miniemulsion systems

In this study, we have conducted the reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in two heterogeneous systems, i.e. conventional emulsion and miniemulsion, with identical reaction conditions. The main objective is to compare the living character in both systems according to the nucleation mechanism, the latex stability, the particle sizes and particle size distributions of latexes, the molecular weights and molecular weight distributions (or polydispersity index, PDI) of PMMA, and the kinetics of the RAFT polymerization. The RAFT agent used in both systems was 2-cyanoprop-2-yl dithiobenzoate (CPDB). The effects of an oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN) and a water-soluble initiator kalium persulfate (KPS) on the RAFT/emulsion and RAFT/miniemulsion polymerizations were investigated. Methyl-β-cyclodextrin (Me-β-CD) was used as a solubilizer. The average molecular weights and molecular weight distributions (PDIs) of dried PMMA samples were characterized by gel permeation chromatography (GPC). The experimental results showed that the RAFT/miniemulsion polymerization of MMA exhibited better living character than that of RAFT/emulsion polymerization under the conditions of our experiment. The PDI of PMMA in RAFT/miniemulsion polymerization was decreased with the addition of Me-β-CD. However, Me-β-CD did not have influence on the PDI of PMMA prepared in RAFT/emulsion polymerization.     

Simulation studies on the origin of the limiting conversion phenomenon in hybrid miniemulsion polymerization

Hybrid systems of acrylic monomers are studied as they undergo miniemulsion free radical polymerization in the presence of unsaturated alkyd resins. The goal of such polymerizations is to induce grafting between the acrylic and alkyd components, which would retard microdomain phase separation, and produce materials with the crosslinking capability of alkyd coatings (normally applied from a solvent system) with the environmental and cost benefits of an aqueous system. In this paper, the observed limiting monomer conversion phenomenon will be explored via simulation studies.Two mathematical models describing the kinetics of bulk hybrid polymerization of an alkyd-acrylate system were developed. The first was a homogenous model in which the kinetics of retardive chain transfer was used to attempt to simulate the observed phenomenon of limiting conversion. The second model was a core-shell model in which polymerization takes place in an acrylic-rich shell, while the alkyd-rich core serves as a reservoir for acrylic monomer and alkyd. Based on the results from these models, the cause of limiting conversion was attributed to the combined role of the glass effect and the partitioning effect of the monomer into a core-shell system and its subsequent entrapment. Retardive chain transfer was not capable of producing the observed limiting conversion.     

Hyperbranched poly(methyl methacrylate)s prepared by miniemulsion polymerization and their (non)-Newtonian flow behaviors

Miniemulsion polymerization is most suitable for the targeted synthesis of vinyl copolymers than the conventional emulsion polymerization, because in miniemulsion polymerization each monomer nanodroplet is a nanoreactor, and the monomers in each droplet are in situ converted to the corresponding polymers. Soluble and hyperbranched poly(methyl methacrylate)s (PMMA) were prepared with quantitative monomer conversion and without gelation by the miniemulsion copolymerization with di- and tri-acrylate and mediated with 1-dodecyl thiol (DDT). DDT acted both as a gelation prohibitor and as a reactive cosurfactant. The PMMAs with varied “X” or “Ж” shaped branches, depending on the di- and tri-functional acrylate used as the branching agent, are characterized and interpreted in terms of the repeating units per part, parts and branches per macromolecule, average molecular weight, latex particle size and size distribution. Effects of topology changes of the branched PMMAs on the rheological behaviors are observed for the first time: from Newtonian flow for the densely branched PMMAs to the non-Newtonian flow with pronounced shear thickening for the PMMA samples with high-molecular-weight and longer parts.     

甲基丙烯酸2，2，2-三氟乙酯的制备及聚合

甲基丙烯酸2，2，2-三氟乙酯是一种重要的有机含氟聚合物单体，具有独特的物化性质，被广泛应用于涂料、光学纤维和接触镜片等领域。     

Synthesis and thermoanalysis of suspension copolymer of N-cyclohexylmaleimide and methyl methacrylate

Copolymers of N-cyclohexylmaleimide (CHMI) and Methyl Methacrylate (MMA), in which CHMI content ranged from 5-80% (in Wt.), were synthesized by suspension polymerization. The thermal properties of copolymer at different CHMI feed content were investigated by TBA and TGA. The results show that the glass transition temperature (T g ) and the decomposition temperature of copolymers increased with increasing CHMI feed content. M ¥ n and M ¥ w of copolymers were determined by GPC. The resultS show that there exists a maximum value when the CHMI feed content lay between 50 and 60%. The mechanical properties (tensile strength and impact strength) of the copolymers decreased with increasing CHMI content. The rheological behavior of copolymers in the melt was that of pseudoplastic liquid, and the flow index n increased with increasing CHMI feed content from 5 to 30%.     

Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.