Synthesis of high solid content waterborne polyurethanes with controllable bimodal particle size distribution

A series of waterborne polyurethane dispersions were synthesized by one‐pot reaction and step‐wise reaction, respectively. The effects of synthetic methods and DMPA content on the particle size distribution (PSD), solid contents and viscosity were studied by laser particle size analyzer, Brookfield viscometer and TEM analysis. High solid content and low viscosity waterborne polyurethanes (WPUs) with controllable bimodal PSD were prepared by one‐pot reaction using 2,2‐dimethylol propionic acid (DMPA) as the only self‐emulsifier. Meanwhile, 40% solid content WPUs with unimodal PSD were obtained by step‐wise reaction at the same formula. With the increment of DMPA content, the ratio of large particles to small particles decreased and two peaks of the particle size finally became one peak by one‐pot reaction while the PSD remained unimodal by step‐wise reaction. The reason leading to the difference of PSD between one‐pot reaction and step‐wise reaction was analyzed and the relationships among PSD, viscosity and solid content were discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40420.     

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.     

高固含乳液压敏胶的粒径分析

运用多阶段乳液聚合法可以有效合成高固含乳液乳液粒径无论是单元分散还是多元分散均能实现高固含化在保持乳液稳定的条件下，如果乳液粒径是单元分散，当粒径足够大或者粒径分布足够宽时，乳液实现高固含的同时，可以达到低黏度目的如果是多元分散，粒径分布一般较宽，非常有利于实现乳液低黏度下的高固含化，当乳液的大粒子质量分数在80％左右时最容易达到目的.     

高固含量乳液性能与粒径分布及反应条件的关系

以乳胶粒粒径分布为切入点,讨论了制备高固含量乳液的反应条件与产品性能的关系     

高固含量聚合物乳液黏度的影响因素

综述了乳液粒径及分布、乳化剂、引发剂、单体配比、反应温度、功能单体、pH值等对聚合物黏度的影响，确定了实现高固含量低黏度乳液的最佳条件。     

高固含量多分散粒径分布乳液的研究2.二元种子法制备二元分散粒径分布乳液

通过在聚合过程中加入第２种子乳液,制备出了具有二元分散粒径分布的乳液,研究了第２种子乳液量对乳液粒径及粒径分布的影响。实验结果表明,通过改变第２种子乳液的量可以调节乳液搂闰径及粒径分布。当大粒子质量分数为８０％时,乳液粘度最小。通过粒径分布的多分散化,可显著降低乳液的最低成膜温度。     

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.     

高固含量醋酸乙烯-乙烯共聚乳液的研制

介绍了一种固含量在60％左右的醋酸乙烯-乙烯(VAE)共聚乳液的制备方法。讨论了乳化剂、聚乙烯醇、醋酸乙烯、乙烯、引发剂等对乳液合成及其性能的影响，并确定了合适的生产工艺，该工艺生产的产品固含量高、黏度低、柔韧性好，初粘性、快干性和耐水性均较常规产品有显著提高。     

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.     

An improved estimation of size distribution from particle profile measurements

Several methods are available to measure particle size. The majority of them, such as sieving, are off-stream techniques where samples must first be separated from the main stream for analysis.Therefore, the search for on-line particle size analysis systems has provided the impetus for the introduction of image-based particle size analysers to the mineral industry in the past three decades. Generally, the estimation of particle size distribution on the basis of image analysis depends on measuring a single parameter of particle profile. For example the equivalent area diameter (d_A) or mean Feret's diameter (d_F) distributions, then transforming this data to the equivalent size distribution. However, due to the irregularity of particles being analysed, it is believed that this kind of analysis may increase the error in estimation of particle size distribution since profiles of irregular particles carry more information than can be represented by a single parameter.In this paper, a proposed technique which measures two parameters, equivalent area diameter (d_A) and mean Feret's diameter (d_F), for each particle profile has been developed. The accuracy of the technique has then been investigated in the laboratory by successfully estimating (unfolding) the size distribution, where size refers to sieve size, of three samples of different particle shapes with known size distribution.     

Influence of particle size distribution on rheology and particle packing of silica-based suspensions

The effect of particle size, particle size distribution and milling time on the rheological behaviour and particle packing of silica suspensions was investigated using slurries containing total solids loading of 46 vol.%. Three silica powders with different average particle sizes (2.2, 6.5 and 19 μm), derived from dry milling of sand, and a colloidal fumed silica powder with 0.07 μm were used. Different proportions of colloidal fumed silica powder were added to each of the coarser silica powders and the mixtures were ball-milled for different time periods. The influence of these factors and of the particle size ratio on the rheological behaviour of the suspensions and densities of green slip cast bodies was studied.The results show that the flow properties of slips are strongly influenced by the particle size distribution. The viscosity of suspensions increases with the addition of fine particles, imposing some practical limitations in terms of volume fraction of fines that can be added. On the other hand, increasing the size ratio enhanced the shear thinning character of the suspensions, while decreasing the size ratio led to an accentuation of the shear thickening behaviour. For all mixed suspensions, green densities increased with increasing milling time, due to size reduction of silica powders and a more efficient deagglomeration of fumed silica. Increasing amounts of fumed silica led to a first increase of particle packing up to a maximum, followed by a decreasing trend for further additions. Good relationships could be observed between rheological results and packing densities.     

Synthesis and characterization of high solid content aqueous polyurethane dispersion

Aqueous polyurethane (APU) dispersions having a solid content of 50% were synthesized using dimethyol propionic acid (DMPA) as the stabilizing moiety. The principal diols used were poly‐1,4‐butylene adipate glycol (PBA). The diisocyanates used in this study were a 30:70 blend of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). All these samples were neutralized using triethylamine (TEA) and chain‐extended using ethylene diamine (EDA). The effects of the COOH content, NCO/OH molar ratio, and molecular weight (M_n) of PBA on the properties of APU dispersion and its cast film were studied. Dynamic light scattering results revealed that these high solid content dispersions shown broad particle size distributions as well as bimodal. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMA) results showed that as the hard segment content increased, the melting point (T_m) of the APU cast film increased, but the glass transition temperature (T_g) did not show significant alteration, when a PBA lower than 1000 M_n was used, the APU exhibited faint soft‐segment crystallization and tended to form amorphous polymer. Tensile and T‐peel strength tests attained excellent mechanical properties, such as a maximum Young's modulus of 166 MPa and the elongation at break reached to 2000%. T‐peel strength test (PVC/PVC) yielded a maximum peel strength value of 8.8 N/mm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

A particle analyser for measuring particle size distribution and shape,on-line or in the laboratory

Norsk Hydro has developed a Particle Analyser for on-line or laboratory use, which measures particle size, size distribution and the deviation from sphericity (called nonspherical).The principle for this system is that the particles fall in a monolayer curtain in front of a high resolution CCD camera. The computer unit in the analyser measures and calculates the particle size and a sphericity factor for each particle. The data are presented as four real time trend curves, shown simultaneously for the on-line version. These curves show % oversize and fines, d₅₀ and the percentage nonspherical particles. For the laboratory version the data are presented in table and cumulative form.The on-line particle analyser has been installed in two of Norsk Hydro's prilling plants in Norway. The analyser has in both plants improved the product quality during the two years of installation.     

高固含量鞋用水性聚氨酯胶粘剂的合成

以HDII、PDI和聚己二酸-1,4-丁二醇酯为基本原料,二氨基苯磺酸钠(SDBS)和二羟甲基丙酸为内乳化剂,通过丙酮法制备出高固含量(50%以上)、不含有机溶剂和储存稳定的鞋用水性聚氨酯胶粘剂。经红外光谱分析,证实其含有磺酸基团。研究了SDBS和丙酮用量对胶粘剂性能的影响,实验结果表明,其性能达到或超过市售U-54产品。     

Variation of particle size and its distribution during the synthesis of silicalite-1 nanocrystals

Recent studies imply that the external surface area of the nanozeolite product may, at least in some cases, be related to the average size of the particle population participating in aggregative nucleation, a population which itself is a product of aggregation of even smaller primary nanoparticles. This possibility puts more importance on our understanding of the variation of particle size and its distribution during the crystallization of zeolite nanoparticles. Variation of the particle size and PSD during nanoparticle silicalite-1 crystallization was followed with respect to time by a laser light scattering device with a scattering angle of 173°, for several starting synthesis compositions. Effects of varying TPAOH and water contents in the starting synthesis mixtures on the variation with time of the particle sizes and PSDs, especially across the two distinct aggregation events, were investigated. The products were also analyzed by XRD and AFM. Parallel to the decrease in the average particle size of the final product population with increasing alkalinity and organic template content, its PSD was observed to become narrower too. A reversal in the dependence on TPAOH content, of the average size of the population formed by aggregation, with respect to that of the population participating in aggregation, was observed across both aggregation events, implying that smaller particles aggregated to form larger particles, while larger particles aggregated to form smaller particles during these processes, and this was also seen from the AFM images, to be reflected to the surface features of the final product particles.     

Alkali-activated waste ceramics: Importance of precursor particle size distribution

The waste ceramics belongs to wide range of aluminosilicate materials which can be alkaline-activated to geopolymer cement – possible “green” alternative to conventional Portland cement. The studied ceramic material is generated during the size adjustment of ceramic building blocks by means of grinding. It means that most of the material is very fine, but it contains also some larger shards. This ceramic powder was used as geopolymer precursor “as received” and after removal of particles retained on 1, 0.5 and 0.125 mm sieves. These four types of precursor were activated by sodium silicate (SiO₂/Na₂O = 1) solution. The prepared mortars were tested for strength, basic physical properties, transport parameters and characterized by help of XRD and thermal analysis. It was found that the best mechanical performance provided the precursor after removal of particles retained on 0.5 mm sieve thanks to the highest geopolymerization rate. The presence of coarser particles in precursor gave rise to porosity, what consequently influenced transport parameter of geopolymers towards the lower thermal conductivity and faster moisture transport.     

高固含量阳离子水性聚氨酯的性能研究

以聚酯二元醇为软段、异佛尔酮二异氰酸酯(IPDI)和N-甲基二乙醇胺(N-MDEA)为主要原料,采用丙酮法合成了高固含量(约50%)的CWPU(阳离子水性聚氨酯),并着重探讨了N-MDEA含量、软段种类对该CWPU的基本性能、结晶性能、力学性能和粘接性能等影响。结果表明:当w(N-MDEA)=5.5%～7.0%(相对于预聚体质量而言)时,可制得稳定的高固含量CWPU;软段的结晶性越好,高固含量CWPU的力学性能和粘接性能越高;当软段为聚己二酸己二醇酯(PHA)时,相应高固含量CWPU的邵A硬度(84)、拉伸强度(55 MPa)和剥离强度(初始剥离强度、24 h剥离强度为68.2、90.4 N/25 mm)相对最大,可作为胶粘剂使用。     

Inferential closed-loop control of particle size distribution for styrene emulsion polymerization

In this work, a new control strategy for controlling the particle size distribution (PSD) in emulsion polymerization has been proposed. It is shown that the desired PSD can be achieved by controlling the free surfactant concentration which in turn can be done by manipulating the surfactant feed rate. Simulation results show that the closed-loop control of free surfactant concentration results in a better control of PSD compared to open-loop control strategy, in presence of model mismatch and disturbances. Since the on-line measuring of ionic free surfactant concentration is difficult, conductivity which is related to it is measured instead and used for control purposes. The closed-loop control of conductivity also results in a better control of PSD compared to open-loop control strategy, but its performance is not as good as controlling free surfactant concentration in presence of model mismatch.     

高固含量丁苯胶乳制备的研究进展

介绍了高固含量丁苯胶乳制备过程中存在的技术难题和该方面的理论、模型等,综述了提高丁苯胶乳固含量常用的方法,并结合现有的理论和实验基础对高固含量胶乳制备进行了展望。