氧化-还原低温引发苯乙烯/丙烯酸丁酯细乳液聚合粒度分布和成核机理的研究

用氧化还原引发剂(NH₄)₂S₂O₈/NaHSO₃研究了苯乙烯(St)/丙烯酸丁酯(BA)低温下的细乳液共聚合,细乳液单体液滴在亚微米级(100～400nm).测定了聚合过程中粒子大小及分布的变化,发现细乳液聚合随引发剂、乳化剂和共乳化剂浓度的增加,乳胶粒子尺寸变小,分布变宽,并且比相同条件下传统乳液聚合的粒子大.计算了聚合过程中粒子数变化规律及乳化剂覆盖率,讨论了细乳液与传统乳液中引发剂、乳化剂对反应过程的影响及成核机理的差异.     

Maximum Achievable Particle Size in Emulsion Polymerization: Modeling of Large Particle Sizes

A simplified model for particle formation in emulsion polymerization (comprising aqueous‐phase propagation to degrees of polymerization which may enter a pre‐existing particle and/or form new particles by homogeneous or micellar nucleation, coupled with the aqueous‐phase and intra‐particle kinetics of oligomeric radicals) is formulated to provide a model suitable for the simulation of systems containing large‐sized particles. The model is particularly useful to explore conditions for growth of large particles while avoiding secondary particle formation. Applied to the Interval II emulsion polymerization of styrene with persulfate initiator at 50°C, it is found that there is an effective maximum particle size that can be achieved if the formation of new particles is to be avoided. The parameter space of initiator concentration, particle number concentration and particle radius is mapped to show a “catastrophe” surface at the onset of new nucleation. Advanced visualization techniques are used to interpret the large number of simulations in the series, showing a maximum achievable particle diameter of around 5 μm.     

聚苯乙烯胶乳颗粒的成膜过程及尺寸效应

聚合物乳液成膜过程可分为介质蒸发、颗粒形变和相邻颗粒间高分子的扩散融合三个阶段.一般认为,环境温度达到或高于高分子的玻璃化转变温度(T_g)时颗粒才可能发生形变.Goudy等研究了粒径为0.24～1.05μm的聚苯乙烯(PS)胶乳的成膜过程,发现PS颗粒在368K(T_g约373K)热处理很长时间也不发生形变,而在378K热处理后,粒径较小的颗粒融合速度快于较大颗粒.     

MMA/BA/聚乙二醇马来酸单酯钠盐无皂乳液聚合的成粒机理

研究了在少量聚乙二醇马来酸单酯钠盐存在下,MMA/BA无皂乳液聚合成粒过程,发现聚合初期产生的初级粒子消失后,两次周期性地产生小粒子。经分析,是新的成核作用产生的,表明在聚合的中晚期,成核过程并未真正结束,而是处于成核-聚并的动态平衡之中。     

Study of poly(St/BA/MAA) copolymer latexes with trimodal particle size distribution

A new strategy was developed for producing a polymer latex with trimodal particle size distribution by adding a second seed of polymer particles and some additional surfactants during polymerization. The polymerization was investigated by following the variation of the particle size, the size distribution, the number of particles, the surface tension and surfactant surface coverage at different stages of the polymerization process. The results showed that both the size and the size distribution can be easily controlled by varying the amount of additional surfactants and the second seed of polymer particles. The secondary nucleation was achieved when the surface coverage of particles was over 70%, and the amount of small particles formed increased with increasing amount of additional surfactants. The introduction of the additional surfactants had no significant effect on the size and number of middle particles, but reduced the size of large particles and caused the number of large particles to remain more stable because of the suppression of limited flocculation. Copyright © 1998 John Wiley & Sons, Ltd.     

Modeling and Sensitivity Analysis of Particle Size Distribution and Chain Length Distribution in a Semibatch Emulsion Copolymerization Reactor

Summary: A comprehensive model is developed to predict the relationship between the particle size distribution and molecular weights of particles in an emulsion copolymerization reactor. A full population balance equation is used for the particle size distribution and extended to the model for the molecular properties using a continuous reactor approach. The numerical prediction clearly distinguishes the characteristics of molecular properties of particles by homogeneous nucleation from those by micellar nucleation with the dependence on the particle size. Sensitivity analysis of the proposed model under a variety of conditions shows that the compartmentalized feature of the emulsion system should be considered for better prediction of molecular properties, and provides information on the manipulated variables and lumped parameters which effectively decompose the correlation of both properties. Finally, a control strategy utilizing a lumped parameters tracking method is suggested for the regulation of both the particle size distribution and molecular properties.

Time evolution of number‐averaged molecular weights in the element under base conditions.     

Effect of Different Composition on Particle Size Chitosan-PMAA-PNIPAM Hydrogel

Chitosan-based (chitosan-poly(methacrylic acid)-poly(N-isopropylacrylamide) [Cs-PMAA-PNIPAM] copolymer hydrogels were synthesized by free radical emulsion polymerization to study the effect of different composition of monomer on hydrogel particle size. Chitosan usually applied for medical use such as drug delivery due to its biodegradability, bio-compatibility, and non-toxicity properties. Co-polymerized chitosan with MAA and NIPAM is an improvement of chitosan gel to be more responsive to the environment of human body included different pH, temperature, ionic strength, electric field, and enzyme activities. Small size of the particles is particularly important to ensure the particles reach the target site especially as a drug delivery. A full factorial experimental design (2³) was employed to identify which factors influenced most on the particle size. The design considered three factors which is amount of MAA, NIPAM and N,N’-Methylenebisacrylamide (MBA) while particle size are chosen as the responses of the variation on each composition. Particle size distribution was measured by laser diffractionin wet condition. From the design of experiment, NIPAM shows the main factor affected the particle size. However combination of the others factors also contributed on the whole size of the hydrogel.     

凝并和成核机理下颗粒尺度分布的Monte Carlo求解

颗粒的凝并和成核现象影响其尺度分布,现有的MonteCarlo方法描述颗粒尺度分布的时间演变过程存在若干困难.提出了一种新的多重MonteCarlo(MMC)算法,基于时间驱动,利用加权的虚拟颗粒的思想,在模拟过程中保持虚拟颗粒总数不变和计算区域体积不变.利用该算法对“常凝并核,一阶成核”的情况下颗粒尺度分布的时间演变过程进行了数值求解,所得结果与数值解相符,表明MMC算法具有高且稳定的计算精度.另外,MMC算法由于跟踪比实际颗粒数目少得多的虚拟颗粒而具有较低的计算代价.     

快淬NdFeB磁粉颗粒度对聚合物粘结NdFeB磁体永磁性能的影响

研究了快淬ＮｄＦｅＢ永磁粉颗粒及其分布对聚合物粘结ＮｄＦｅＢ永磁材料性能的影响。快淬Ｎｄ－ＦｅＢ永磁粉颗凿大小及其分布显著地影响聚合物结ＮｄＦｅＢ永磁材料的磁性能。适当尺寸的快淬ＮｄＦｅＢ磁粉组合可获得高的结ＮｄＦｅＢ永磁帝主要是由于快淬ＮｄＦｅＢ磁粉硬度高,呈鳞片状,其尺雨越大越难获得高密度,但尺寸太小又将破坏磁粉的结构,导致磁性能恶化。     

Particle Nucleation and Growth in the Emulsion Polymerization of Styrene: Effect of Monomer/Water Ratio and Electrolyte Concentration

This work is an extension of previous research results reported by our team (Colloid and Polymer Science 2013, 291: 2385-2398), where large scale and high solid content latexes of poly(n-butyl acrylate) were obtained with the particle coagulation method induced by the electrolyte. However, how to prepare controlled particle size distribution polymer latex has not been studied. Thus, in this study, the effect of the monomer/water ratios and electrolyte concentrations on particle formation and growth methods were studied by following the tracks of the evolutions of particle size, number and distribution as a function of reaction time or conversion. Experimental results showed that the length of time that particle nucleation occurred increased with increasing monomer charged for the systems without electrolyte. A point worthy of attention here is that homogeneous nucleation may occur at high monomer concentrations (30/70, 40/60). However, electrolyte added could be made the nucleation mechanism shift from micellar/homogeneous nucleation to micelle /coagulation nucleation. As a result, the final particle size distribution can be controlled by adding an appropriate electrolyte to regulate the nucleation mechanism. Spherical and uniformly sized particles could be obtained when electrolyte concentration is between 0.2 wt% and 0.4 wt% for water at the high monomer/water ratio (40/60). The effects of electrolyte concentration on nucleation mechanism mainly were expressed by decreasing the solubility of the monomer and interparticle potential, and then preventing homogeneous nucleation and enhancing particle coagulation.     

乙酸对阳离子型PVAc乳液粒径的影响

以醋酸乙烯酯(VAc)和甲基丙烯酰氧基乙基三甲基氯化铵为主单体,Gemini超支化双子型阳离子表面活性剂和OP-10为复合乳化剂,通过乳液聚合制得一系列阳离子型聚醋酸乙烯酯乳液(1n),考察了VAc的主要杂质乙酸对1n粒径的影响.研究结果表明,乙酸含量增多时,Gemini超支化阳离子表面活性剂的临界胶束浓度和表面张力都...     

超声衰减谱测量电池浆料的粒度分布

电池浆料中颗粒状活性物质的粒度大小和分散均匀性对电池的内阻、 电压、 局部表面电流和总极化程度等性能有直接影响, 实现对其的在线实时测量对电池的质量控制具有重要意义. 基于电池浆料的高固含量、 高黏度和低透光性的特点, 本文利用超声衰减谱的方式测量了其粒度分布(PSD). 应用于电池浆料的粒度分布测量的最大难点是其利用超声衰减谱法预测粒度分布的模型需要难以获得的分散相和连续相的物性参数. 本文采用主成分分析(PCA)结合误差反向传播(BP)神经网络建立预测模型解决了超声衰减谱法的难点, 并引入遗传算法(GA)优化BP神经网络的初始阈值和权值. 通过以LiCoO₂为活性物质的电池浆料进行了验证, 结果表明, PCA-GA-BP神经网络能够有效对不同固含量电池浆料的粒度分布进行预测, 预测值与真实值的峰形重合度高, 峰高偏差小, 两者的均方误差为0.1358, 拟合度(R²)为0.9816, 说明超声衰减谱法可作为测量电池浆料粒度分布的重要方式.     

种子乳液聚合物胶粒形态及胶膜结构研究

以醋酸乙烯酯和丙烯酸丁酯为单体，用乳液聚合方法，以极性小的ＰＢＡ为种子进行了ＶＡ种子聚合，用透射电镜染色及皂液滴定方法对胶粒形态进行了表征，结果，上述聚合反应能形成ＰＢＡ／ＰＶＡ核壳结构的胶粒，而以ＰＶＡ为种子对ＰＢＡ进行聚合，则不能形成ＰＶＡ／ＰＢＡ核壳结构的胶粒，其胶粒亦具有类似ＰＢＡ／ＰＶＡ核壳结构或半包囊结构，将胶乳制成胶膜，其耐水性能测试表明成膜后胶粒基本保持了其分散阶段的形态。     

分散聚合法制备窄分布聚苯乙烯微球

窄分布聚合物微球有相当广泛的用途，如用于色谱柱填料，过滤器效能和孔径的测定标准，生化反应的载体等［１］．制备聚合物微球的方法有多种：如悬浮聚合物法可以制得微米级球体，但粒径分布较宽［２］；超微乳液聚合法，却仅能制得小于１μｍ的超微球［３］；唯有分散聚...     

超细钛硅分子筛粒径的激光粒度分析

研究了试样浓度、超声波强度、分散时间及分散剂的加入对钛硅分子筛粒度测定结果的影响，结果表明，试样浓度低或高，粒度测定结果偏大；超声波强度的增大和超声波分散时间适当的延长有利于粒子的分散，也有利于粒度的准确测定；加入分散剂六偏磷酸钠后，测试结果重复性好。     

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.     

毛细管区带电泳测定纳米粒子粒度分布的研究

建立了一种用毛细管区带电泳测定纳米粒子平均粒径及粒径分布的新方法。该方法通过外标定量法对样品的原始电泳谱图进行定量校正,从而得到样品的粒径分布图及平均粒径。外标定量法包括迁移时间-粒径校正曲线的建立及不同粒径含量校正曲线的建立。该方法所需样品量少,且粒度分布结果具有统计代表性。     

苯乙烯/丙烯酸正丁酯乳液聚合反应过程中残余单体含量的实时监测

采用近红外光谱分析技术在线测量苯乙烯(St)/丙烯酸正丁酯(BA)乳液聚合体系中残余单体的含量. 共设计9个半连续方式的St/BA乳液共聚反应, 在反应过程中实时取样测量其残余单体含量, 并记录取样时刻对应的聚合体系的近红外光谱. 采用多元散射校正法(MSC)处理光谱, 有效地克服了乳胶粒子散射效应对近红外光谱分析的影响. 采用主成分分析法(PCA)对乳液体系的近红外光谱数据进行了解析. 选取6个聚合反应对应不同反应时间的72个样品, 用于建立校正模型, 另外3个聚合反应共取36个样品用于校正模型的验证, 并在反应设计上体现了乳化剂用量的变化, 从而使校正模型对乳化剂用量的变化具有一定的适应性. 研究结果表明, 所得模型对残余单体St和BA含量的预测结果标准差(SEP)分别为0.08026和0.05305.     

Styrene Emulsion Polymerization above the CMC: New Evidence on Particle Nucleation by means of AFFFF

Summary: The number (N) and size distribution of particles (PSD) of a styrene emulsion polymerization above the CMC were studied by means of asymmetric flow‐field flow fractionation (AF⁴). Bimodal PSDs were obtained, suggesting that coagulation of the primary particles is not as extensive as would be expected, according to the coagulative mechanism. AF⁴ allowed it to be demonstrated that N is constant during interval II, and that the resolution limit of other particle sizing techniques can lead to erroneous mechanistic inferences, from the evolution of N.

Particle size distribution measured at low conversion for the emulsion polymerization of styrene, obtained by AF⁴ and DLS. The initial surfactant (S₀), initiator (I₀) and monomer (M₀) concentrations are indicated in the figure.