Adhesion enhancement in waterborne acrylic latex binders synthesized with phosphate methacrylate monomers

The effect of the addition of a phosphoric acid group containing monomer on polymerization kinetics, copolymer microstructure and end-use properties of a latex prepared by seeded emulsion polymerization of MMA/BA/MAA/AAEMA/SIPOMER PAM100 was studied. It was found that despite of the surface activity of the phosphated monomer, the polymerization kinetics was not affected. Gel content increased with the concentration of phosphate monomer due mainly to the presence of divinyl ester phospate impurities. Gel improved the chemical resistance of the latex films. However, the most affected property was adhesion. Increasing amounts of the phosphated monomer led to a strong enhancement of the adhesion due to chemical interactions established with the metal surface. It was also found that the feeding strategy of the phosphated monomer played an important role in the adhesion enhancement. Latexes synthesized using a delayed addition of the phosphate monomer showed better performance than latexes prepared following a conventional addition strategy. The latexes synthesized during the investigation were evaluated as binders in a primer formulation. A primer with good adhesive and corrosion resistance properties was achieved using a 5 wt.% of the phosphated monomer.     

Measurement based modeling and control of bimodal particle size distribution in batch emulsion polymerization

In this article, a novel modeling approach is proposed for bimodal Particle Size Distribution (PSD) control in batch emulsion polymerization. The modeling approach is based on a behavioral model structure that captures the dynamics of PSD. The parameters of the resulting model can be easily identified using a limited number of experiments. The resulting model can then be incorporated in a simple learning scheme to produce a desired bimodal PSD while compensating for model mismatch and/or physical parameters variations using very simple updating rules. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

高转化率乳聚丁苯橡胶聚合过程中乳液相对分子质量分布与粒径分布考察

采用中石油吉化分公司乳聚丁苯橡胶高转化率大生产配方,考察了实验室聚合反应釜聚合反应单体转化率随反应时间的变化,采用激光粒度分析仪和凝胶渗透色谱仪测定了聚合反应不同单体转化率的胶乳的粒径分布与分子质量分布,结果表明：胶乳粒径呈正态分布,粒径主要集中分布在0.1μm附近,胶乳的平均粒径随反应时间的延长逐渐增大,但是增加的幅度越来越小;聚合反应时间在11 h前（即转化率小于72%）,胶乳的重均分子质量、Z均分子质量一直增大,而数均分子质量变化无明显规律;而分子质量分布宽度指数随反应的进行变小,表明调整的高转化率配方合成的丁苯橡胶可有效改善聚合生成的胶乳粒径分布。     

大粒径聚丙烯酸丁酯胶乳的制备

采用种子乳液聚合法制备了丙烯酸酯-苯乙烯-丙烯腈共聚物生产工艺中的基础胶乳聚丙烯酸丁酯(PBA),考察了配方和工艺条件对其粒径增大的影响。结果表明,在合成种子胶乳时可加入质量分数0.2%～0.8%的乳化剂十二烷基硫酸钠;在种子胶乳粒径放大试验时,加入质量分数0.3%的乳化剂十二烷基硫酸钠及补加的单体量为种子胶乳总固体物质量的33倍可以得到大粒径的PBA胶乳。采用种子乳液聚合法进行PBA胶乳粒径放大方法简便、效果明显。     

聚合条件对丁苯胶乳粒径的影响

通过乳液聚合方法合成了适用于聚氯乙烯(PVC)改性甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)的种子胶乳,利用一步法工艺获得一定粒径的丁苯胶乳,研究了乳化剂加入量、加入方式,聚合温度,聚合反应时间对粒径的影响,合成了粒径在200～300nm的丁苯胶乳。     

影响ABS树脂用EBR胶乳粒径的因素

考察了影响ABS树脂用乳液聚丁二烯橡胶（EBR）胶乳粒径的诸因素,包括初乳化剂用量、补加乳化剂用量、电解质用量、引发剂用量、初水配比及聚合温度等,得到了影响胶乳粒径各因素的线性关系。结果表明,影响EBR胶乳粒径的主要因素为初乳化剂、补加乳化剂及电解质用量,工业生产中应通过调节这些因素来实现不同EBR胶乳的生产。     

Bimodal particle size distribution polymer/oligomer combinations for printing ink applications

This paper describes a study in which anionically stabilised acrylic latices with a bimodal particle size distribution, produced by blending polymer particles of 50 and 350 nm in different blend ratios, are blended with oligomers. Reversibility, rheology, drying behaviour, film formation and blocking resistance of these systems were studied Reversibility appears to show two regions of linear dependence on the total particle surface area. The lower the surface area, the lower the amount of oligomer needed for good reversibility. The rheological data was fitted by the Krieger–Dougherty equation and it appeared that both in the presence and absence of oligomer an 80/20 large/small blend exhibited the highest maximum packing fraction. Short drying times were obtained with bimodal blends at high solids content and the drying profiles could be explained by the Croll model. The presence of oligomer was shown to exhibit a positive effect on film formation and when the oligomer is hard, the blocking resistance is already very good at low oligomer content, resulting in a very good MFT/blocking resistance balance. The latter can also be obtained when as well the size as the T_g of the polymer particles is varied.     

影响苯丙乳液黏度与粒径的因素分析

采用种子乳液聚合法,以苯乙烯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯等为主要原料合成了用于制备胶粘剂的苯丙乳液。重点研究了引发剂、乳化剂及种子单体的用量及硬软单体不同配比对苯丙乳波黏度和粒径的影响。实验结果表明,当引发剂用量为0.5％（占单体总质量,后同）、乳化剂用量为1％、种子单体用量为8％、硬软单体配比为30／46的条件下,合成的笨丙乳液黏度较高、粒径小、粒度分布宽,用该乳液制备的胶粘剂具有优良的施工性能.     

激光粒度仪测定PTA粒径分布

介绍了激光粒度仪测定PTA粒径分布的分析方法 ,通过试验确定了分析条件 ,并与筛分法分析结果进行了对比。该方法简捷、快速、重现性好 ,适用于PTA产品的粒度分析。     

Preparation of mesoporous NiO with a bimodal pore size distribution and application in electrochemical capacitors

Mesoporous nickel oxide with a porous structure exhibiting a bimodal pore size distribution (2.6 and 30.3 nm diameter pores) has been synthesized in this paper. Firstly, a mesoporous precursor of coordination complex Ni₃(btc)₂·12H₂O (btc = 1,3,5-benzenrtricarboxylic acid) is synthesized based on the metal-organic coordination mechanism by a hydrothermal method. Then mesoporous NiO with a bimodal size distribution is obtained by calcining the precursor in the air, and characterized by transmission electron microscopy and N₂ adsorption measurements. Such unique multiple porous structure indicates a promising application of the obtained NiO as electrode materials for supercapacitors. The electrochemical behavior has been investigated by cyclic voltammogram, electrochemical impedance spectra and chronopotentiometry in 3 wt.% KOH aqueous electrolyte. The results reveal that the prepared NiO has high-capacitance retention at high scan rate and exhibits excellent cycle-life stability due to its special mesoporous character with bimodal size distribution.     

Measurement of particle size distribution of tripalmitin crystals in a model solution using a laser diffraction method

The form and size distribution of tripalmitin (PPP) crystals formed by quenching a solution in a batch crystallizer have been studied using scanning electron microscopy and a laser diffraction technique. Although the accuracy of the laser technique for particle sizing was affected by the nonsphericity of the crystals, the technique proved to be effective and very reproducible. Crystals recovered by filtration and sonication for laser sizing exhibited markedly different particle size distributions (PSD) and shapes compared to those prepared using another standard route, namely, suspension in butanol and centrifugation. Solutions of 2–10 wt% PPP in a paraffin solvent were crystallized at 25–40°C and displayed two ranges of behavior: (i) rapid growth under strongly supersaturated conditions, yielding narrow PSD of plate and needle-like crystals; and (ii) slow growth in the metastable regime, yielding spherulitic aggregates of platelets that broke down under sonication during preparation for laser sizing. Suspension in alcohol followed by centrifugation yielded aggregates that did not break down under sonication, indicating that the sample preparation route affected the result of the analysis.     

有机硅/丙烯酸酯乳液的粒径与分散行为研究

采用半连续乳液聚合法合成了以丙烯酸丁酯和甲基丙烯酸甲酯为成核单体,丙烯酸丁酯(MAA)、甲基丙烯酸甲酯(BA)、丙烯酸(AA)和γ―甲基丙烯酰氧基丙基三甲氧基硅烷为成壳单体的核壳结构乳液。采用马尔文纳米粒度仪等研究了乳液的粒径及其分布与引发剂和乳化剂用量之间的关系,粒径对乳液稳定性的影响以及乳液粒径与温度的关系,通过透射电镜对乳液微粒形态进行了分析。结果表明,乳液的粒径随着引发剂和乳化剂用量的增加而减小,乳液粒径在30～60℃时较为稳定,当引发剂过硫酸铵质量分数为0.55%,乳化剂十二烷基苯磺酸钠质量分数为2%时,制得的乳液粒径在120 nm左右,具有明显的核壳结构和较好的稳定性。     

Control of particle size distribution for the synthesis of small particle size high solids content latexes

A polymerization process to synthesize bimodal latexes with maximum particle diameters below 350 nm and solids content above 65 wt% has been developed.The process is based on an iterative strategy to determine the optimal particle size distribution that gives the maximum packing factor for a given range of particle sizes and at a given solids content. The calculated optimal bimodal PSD was experimentally obtained in a seeded semi-continuous emulsion polymerization reaction as follows: in the first step, a polymer seed latex was loaded in the reactor and grown, under monomer starved conditions, until a given particle size. At this point a fraction of the same seed was added to the reactor and the feed was continued until the desired particle size distribution and solids content were achieved. The point at which the seed was added again to the reactor and the amount of seed required were determined by the iterative strategy and depended on the competitive growth rate ratio of large and small particles that is an input for the iterative strategy.Implementation of the solution obtained from the iterative strategy, and for the first time in the open literature, led to the production of a coagulum free and stable bimodal latex with 70 wt% of solids content and particle sizes below 350 nm.     

高性能粒度调配水泥及其在混凝土中的应用研究

通过设计和调配水泥组分的细度和颗粒分布,制备了一种高性能粒度调配水泥,并测试了该水泥及其配制的混凝土的物理力学性能。试验结果表明:粒度调配水泥的标准稠度用水量与普通球磨水泥相当;在相同熟料含量条件下,粒度调配水泥比对比水泥的抗压强度提高3～4MPa;在混凝土应用中,粒度调配水泥和普通球磨水泥相比具有更为明显的性能优势,利用粒度调配水泥配制的C60高强混凝土不但工作性能良好,而且力学性能优异,28d抗压强度达到了96.1MPa。     

In-line evaluation of average particle size in styrene suspension polymerizations using near-infrared spectroscopy

The main objective of this article is evaluating the influence of average polystyrene particle size upon the near-infrared (NIR) spectra collected during suspension polymerization experiments and observing whether NIR spectroscopy may be used for in-line monitoring and control of average particle size. It is shown that NIR spectra are sensitive to changes of the average particle size, and that standard empirical models (PLS—partial least squares—and NN—neural networks) may be built to correlate average particle size and light absorbance at certain wavelengths fairly well. Finally, it is shown that these models allow the in-line evaluation of average particle size in styrene suspension polymerizations with NIR spectroscopy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1737–1745, 1998     

粒径分布对嵌段聚醚氨基硅乳液性能的影响

通过机械搅拌、均质化等制备了一系列pH=5.9的嵌段聚醚氨基硅(BPEAS)乳液,用激光粒度分布仪和透射电子显微镜对乳液粒径和结构进行了表征,并探讨了不同粒径分布的乳液对整理织物性能的影响,确定了合适的粒径范围。结果表明,中位径(D50)分布在32.67～52.48 nm,粒径在58.77～98.82 nm时的累积分布达到90%以上的乳液具有较好的稳定性;经整理后的织物白度基本不变,弯曲刚度明显下降,亲水性增强,综合应用性能优异。     

New measurement of particle size distribution by a buoyancy weighing-bar method

The rates which particles from JIS Test Powders 1, Class 2 (silica sand), Class 3 (silica sand), Class 16 (calcium carbonate, heavy), and JIS Test Powder 2, Class GBM-20 (barium titanate glass) settled out of homogenous suspensions were determined using the principles of the buoyancy weighing-bar method as well as a sedimentation balance. Samples were standardized by Japanese Industrial Standard, and the dispersing agent was NaPP or NaHMP, while the viscosity improver was a starch syrup solution. Although constructing a handmade sedimentation balance is difficult, developing a handmade weighing tool capable of measuring particle size distribution is easy. Herein three weighing-bars, which were composed of aluminum, stainless steel, and copper, were used to measure the particle size distribution. However, an aluminum slit-cylinder occasionally replaced the weighing-bars. The weighing data obtained via an analytical balance were controlled by connecting the balance to a personal computer with an RS-232C interface, and the determined particle size agreed well with the data obtained by Andreasen analyses and the sedimentation balance.     

Measurement of the floating particle size distribution by a buoyancy weighing-bar method

The particle size distribution of cylinder-shaped solid particles was measured using a buoyancy weighing-bar method where the liquid phase density was adjusted to settle or float the particles. The particle size distribution obtained in our experiment agrees with the particle size measured by other method. The present study demonstrates that a buoyancy weighing-bar method, a novel method for measuring the particle size distribution, is suitable for measuring the particle size distribution of a floating solid. The precision of the resulting particle size distribution is comparable to that of a laser diffraction/scattering method as well as a direct measurement with a micrometer. Moreover, this buoyancy weighing-bar method can measure the particle size distribution even in a mixture of two particles with different sizes.     

用乳液法合成丙烯酸丁酯-甲基丙烯酸共聚胶乳

采用乳液聚合法合成了丙烯酸丁酯和甲基丙烯酸共聚胶乳,用红外光谱对胶乳的结构进行了表征,讨论了加料方式、水油体积比和引发剂与胶乳性能的关系。结果表明,聚合中分3次加料可使反应更平稳地进行;控制水油体积比在1.50左右更易于反应的控制,胶乳性能也较好;引发剂质量分数为0.2%~0.4%时反应体系稳定,胶乳中的单体残留量少,共聚胶乳的性能较好。