A Strategy for Preparation of Anionic Polyurethane/Acrylate Emulsions

In this article we proposed a new strategy for preparation of polyurethane/acrylate (PUA) hybrid emulsions. In the preparation of the polyurethane dispersion, methyl methacrylate (MMA) was used as the reactive solvent to reduce the viscosity of the reaction mixture, and 2-(Dimethylamino)ethyl methacrylate (DMEMA) as the reactive neutralizer. We then let MMA and DMEMA undergo further polymerization to form PUA hybrid emulsions. The morphology of the PUA hybrid emulsions was characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The structures of the waterborne polyurethanes (WPU) and PUA hybrid emulsions were characterized by Fourier transform infrared spectrometer (FTIR) and contact angle measurements.     

有机氟硅共改性水性聚氨酯乳液的合成及其性能

将异佛尔酮二胺(IPDA)和甲基丙烯酸十二氟庚酯(DFMA)进行Micheal加成反应,合成端仲胺基的有机氟化合物(DFMA-IPDA)。以该化合物为扩链剂、聚醚改性聚二甲基硅氧烷(PDMS)为二元醇,与异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、二羟甲基丙酸(DMPA)聚合制备了有机氟和硅改性的水性聚氨酯(WPU),研究了有机氟和/或硅用量对WPU乳液性能和胶膜性能的影响。结果表明:用该方法合成的DFMA-IPDA纯度达99.2%,和一定量的PDMS共改性可合成稳定的WPU乳液。随两者用量的增加,WPU乳液的平均粒径增大,胶膜的热稳定性、耐水性提高,表面水接触角增大。PDMS可提高WPU胶膜的柔性,而DFMA-IPDA可提高胶膜的韧性。用PDMS和DFMA-IPDA共改性能获得综合性能优异的WPU,当扩链剂完全采用DFMA-IPDA,PDMS用量为4%时,WPU胶膜的吸水率为4.5%,水接触角达到102.3°。     

功能化聚丙烯乳液制备方法研究进展

介绍了聚丙烯乳液制备方法的发展过程，主要包括低分子质量和高分子质量聚丙烯的乳化，以及不同乳化方法对乳液性能的影响。总结了聚丙烯乳化难易程度的主要影响因素。     

不同聚醚二元醇软段对光固化水性聚氨酯乳液性能的影响

以不同聚醚二元醇、异佛尔酮二异氰酸酯、2,2-双羟甲基丙酸、甲基丙烯酸-2-羟基乙酯为主要原料,通过丙酮法合成光固化水性聚氨酯(WPU)乳液,讨论了不同聚醚软段对光固化WPU乳液性能的影响.结果表明,由聚四氢呋喃醚二元醇PTMG1000和PTMG2000制备的光固化WPU乳液具有较小的粒径和粘度,其交联后的膜具有较高储...     

膜乳化和微流控法制备单分散W／O乳液的研究

以油相为连续相、水相为分散相,分别采用SPG膜乳化法和微流控技术制备出了单分散W／O乳液。对两种制备单分散乳液的方法进行了系统比较。结果表明,微流控技术不仅更易操作,而且制备出的W／O乳液单分散性更好。     

Properties and paper sizing application of waterborne polyurethanemicroemulsions: Effects of extender,cross‐linker,and polyol

A series of waterborne polyurethane (WPU) microemulsions were synthesized through self‐emulsification methodology, using toluene‐2,6‐diisocyanate, polytetramethylene glycol (PTMG), poly‐caprolactonediol (PCL), and dimethylol propionic acid (DMPA) as monomers; isophorone diamine (IPDA) as chain extender; and aziridine as cross‐linking agent. The resultant WPU microemulsions were utilized as surface‐sizing agents for cellulose fiber paper. The influences of IPDA content, PTMG/PCL molar ratio, and aziridine content on the physicochemical properties of the resultant emulsions and sized paper have been investigated in detail. The WPU microemulsion displayed better surface sizing properties when it was prepared under the following conditions: the IPDA content of 2.96%, PTMG/PCL molar ratio of 0:4, and aziridine content of 2.0 wt %. The relationships between the WPU structure and properties of WPU films and sized paper were clearly illustrated. The mechanical properties and water resistance of sized paper were not only depended on the interactions, chain entanglements, and cross‐linking density among the WPU chains, but also relied on the interactions among polymers and fibers, as well as the polarity and stiffness of surface sizing agent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43211.     

Design strategy for waterborne polyurethane with sodium sulfonate groups on the soft segments

The field of waterborne polyurethane (WPU) is gaining a great deal of momentum from both a commercial and academic sense because of increasing environmental and sustainable awareness. For polyurethane (PU) to be dispersible in water, the hydrophilic groups are very important in the design of the polymer chains. Herein, we present a design strategy for WPU having hydrophilic groups on the soft segments through the reaction of as‐synthesized OH‐terminated poly(ε‐caprolactone) diols containing a sodium sulfonate group with diisocyanate. A stable aqueous dispersion was then obtained, and this was followed by a subsequent chain extension reaction and emulsification. We found that the PU dispersion particles were a core–shell structure with a good particle size distribution, and the obtained films exhibited a low tensile strength and a high elongation at break. This approach provided valuable information for fundamental research in the production, modification, property enhancement, and new applications of these materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39657.     

Macroporous polymers from particle-stabilized emulsions

Macroporous polymers are attractive materials due to their low density, low cost, recyclability and tunable mechanical and functional properties. Here, we report a new approach to prepare macroporous polymers from emulsions stabilized with colloidal polymeric particles in the absence of chemical reactions. Stable water-in-oil emulsions were prepared using poly(vinylidene difluoride) (PVDF), poly(tetrafluoroethylene) (PTFE), and poly(etheretherketone) (PEEK) as stabilizing polymeric particles in emulsions. The partial wetting of the polymeric particles by the two immiscible liquids drives particles at the water-oil interface during emulsification, leading to extremely stable water-in-oil emulsions. The particle-stabilized emulsions were processed into highly porous solid polymer components upon drying and sintering. The high stability of emulsions also allows for the preparation of hollow polymeric microcapsules. We describe the conditions required for the adsorption of particles at the liquid-liquid interface, we show the rheological behavior of the polymer-loaded wet emulsions and, we discuss the effect of the emulsions' initial compositions on the final sintered porous structures. This new approach for the fabrication of macroporous PVDF, PTFE, and PEEK polymers is particularly suited for the preparation of porous materials from intractable polymers but can also be easily applied to a variety of other polymeric particles.     

Preparation of water-in-oil and ethanol-in-oil emulsions by membrane emulsification

In this work, water-in-oil emulsions (W/O) and ethanol-in-oil emulsions (E/O) emulsions were prepared successfully by membrane emulsification. The emulsifiers selected were PGPR and MO-750 for the W/O and E/O emulsions, respectively. For W/O emulsions prepared with an oil pre-filled membrane, the dispersed flux was lower and the droplet size sharper than that obtained with a water pre-filled membrane. On the contrary, for E/O emulsions prepared with the membrane pre-filled with oil, the dispersed phase (ethanol) rapidly pushed out the oil from the membrane pores. Therefore, the pre-treatment of the membrane had almost no effect on the dispersed phase flux and on the droplet size. The droplet size distribution of the E/O emulsion was close to that obtained with a classical homogenizer. The dispersed phase fluxes were high and no fouling was observed for our experimental conditions (1.6 l emulsion, 10 wt% ethanol). These results confirm that membrane emulsification could be an interesting alternative for the preparation of E/O emulsions for the purpose of biodiesel fuels, considering the scale-up ability of membranes and their potentiality for industrial processes.     

Production of quasi-monodisperse emulsions with large droplets using a micromachined device

The development and operation of a modified method for the preparation of quasi-monodisperse (CV<16%) emulsions are reported. The device uses a microfabricated-nozzle (MN) array, produced by micromachining technology, to achieve a higher rate of emulsification [76.8 m³/(m²·h)] than previously reported for microchannel (MC) emulsification methods. The dispersed phase is extruded into a continuous phase through the MN, and the emulsions droplets are formed by viscous drag force of the continuous phase. The droplet diameter decreased with an increase in the flow velocity and viscosity in the continuous phase, which was explained by the theoretical model. The range of droplet diameters produced (130 to 370 μm) was larger than in previously reported MC emulsification, membrane emulsification, and shear-rupturing methods.     

手套涂饰剂用水性聚氨酯乳液的研制

以聚醚二元醇(N220、N240)、聚醚三元醇(N330)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)和蓖麻油(C.O)等为原料,采用丙酮法合成出水性聚氨酯(WPU)乳液。着重探讨了R值、C.O和TMP用量等对WPU乳液及成膜性能的影响。研究结果表明,当R值为5、m(N220):m(N240)=1:1、选择8%C.O作为交联剂时,所合成的WPU乳液外观好、拉伸强度大、断裂伸长率适中、附着力优良、胶膜光滑细腻丰满且符合手套涂饰剂的涂层要求;与国外同类产品相比,由该WPU乳液所配制的手套涂饰剂的透气性能和价格更胜一筹,完全可以替代同类进口产品。     

The effect of shear and oil/water ratio on the required hydrophile-lipophile balance for emulsification

Required hydrophile-lipophile balance (HLB) values were examined in terms of the nature of kerosene-water, both oil-in-water (O/W) and water-in-oil (W/O), emulsions formed using Span 80/Tween 80 surfactant blends. Both the nature of the emulsification method and the oil/water ratio were critical in determining the resulting emulsion type. Both high- and low-shear conditions were investigated. Under high shear, low internal phase emulsions formed using the surfactant mixtures that corresponded to the required HLB values for emulsification involving kerosene (6 for W/O and 14 for O/W). However, at low shear, high internal phase (concentrated) emulsions resulted. Furthermore, depending on the oil/water ratio, some of the high internal phase emulsions were opposite to the type expected, given the HLB of the surfactant blend used. From these results, it appears that the emulsification technique (applied shear and oil/water ratio) used can be of greater importance in determining the final emulsion type than the HLB values of the surfactants themselves.     

新型磺酸盐水性聚氨酯乳液的合成及其性能研究

以聚己二酸乙二醇酯二元醇、甲苯二异氰酸酯、乙二胺基己磺酸钠(N60)等为主要原料,制备了一系列不同N60用量的磺酸盐型水性聚氨酯(WPU)乳液。研究了N60用量对WPU乳液及其胶膜性能的影响,并通过FT-IR、TEM、TGA等方法进行表征。结果表明,磺酸盐型WPU乳液的贮存、冻融、高温稳定性均较好。随N60用量的增加,磺酸盐型WPU乳液粒径先减小后增大,粒径分布变窄,胶膜的拉伸强度、吸水率呈上升趋势、断裂伸长率下降。TEM图显示微粒分散性好,呈球形;相对于羧酸型WPU,磺酸盐型WPU胶膜的拉伸强度提高,热稳定性更好。     

Effect of emulsifiers on the preparation of food‐grade oil‐in‐water emulsions using a straight‐through extrusion filter

This paper describes the preparation characteristics of food‐grade soybean oil‐in‐water (O/W) emulsions using a novel straight‐through extrusion filter, named a silicon straight‐through microchannel (MC). Polyglycerol fatty acid ester (PGFE), polyoxyethelene sorbitan monolaurate (Tween 20), and sucrose fatty acid ester were tested as emulsifiers. Optical observations of the emulsification process exhibited that monodisperse oil droplets were stably formed from an oblong straight‐through MC for PGFE and Tween 20. The effect of the emulsifier on the straight‐through MC emulsification behavior is discussed. The selected PGFE‐ and Tween 20‐containing systems enabled us to prepare monodisperse O/W emulsions with droplet diameters of 38—39 μm and coefficients of variation below 3% using an oblong straight‐through MC with a 16 μm‐equivalent channel diameter.     

Preparation of monodispersed emulsion with large droplets using microchannel emulsification

Microchannel (MC) emulsification is a novel technique for producing monodispersed emulsions with coefficients of variation of less than 5%. To produce emulsions with large droplets, we designed three MC with large dimensions. The MC structure consists of two parts: a channel and a terrace. Terrace length was defined as the length from the exit of the MC to the end of the terrace. The MC plates used in this study have deeper channels and longer terraces. The size limit of droplets prepared by MC emulsification was studied. Monodispersed emulsions with droplets as large as 100 μm were prepared using an MC with a depth of 16 μm and a terrace length of 240 μm. The average diameter (coefficient of variation) of the emulsion droplets was 98.1 μm (2.5%). Emulsions with larger-diameter droplets were prepared using an MC with a longer terrace. The effect of the applied pressure on emulsification behavior was studied and discussed from the viewpoint of the droplet formation mechanism. At low applied pressures, droplet diameters were independent of the applied pressure, and monodispersed emulsions were produced. The pressure ranges of constant droplet diameter for large-droplet emulsions were narrower than those for the 5 to 30 μm droplet size emulsions because interfacial tension is more significant on a smaller scale compared with the other forces.     

赖氨酸扩链的生物基水性聚氨酯的制备与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃二醇(PTMG-2000)为主要原料,二羟甲基丙酸(DMPA)、赖氨酸(Lys)等作为小分子扩链剂,制备了含赖氨酸成分的水性聚氨酯(WPU)乳液.讨论了Lys用量对WPU乳液及胶膜性能的影响,并采用FT-IR、TGA等检测方法进行表征.结果表明:随着Lys用量的增大,WPU乳...     

催化剂对复合薄膜用水性聚氨酯胶粘剂性能的影响

采用丙酮法制备了复合薄膜用的水性聚氨酯(WPU)乳液胶粘剂,研究了催化剂用量对WPU反应速率及其性能的影响。研究结果表明,适量的催化剂能明显加快聚氨酯(PU)预聚体的反应速率;当催化剂质量分数为0.1%时,WPU乳液的粘度和复合薄膜的T型剥离强度最大,但WPU胶膜的玻璃化转变温度(Tg)降低,由未加催化剂时的-25.5℃降低到-29.1℃。     

双酚A环氧树脂改性水性聚氨酯的合成及性能研究

以环氧树脂(EP)、异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇和二羟甲基丙酸(DMPA)等为原料,合成了一系列不同EP含量的水性聚氨酯(WPU)分散体,讨论了EP、亲水基团含量对EP改性WPU分散体的储存稳定性、胶膜力学性能等影响。结果表明:当u(EP)≤3%、w(羧基)=1.6%时,EP改性WPU分散体及其胶膜的综合性能良好;利用WPU中残留的-NCO与EP中羟基反应,使EP被包覆在PU链段中,乳化后EP可稳定存在于WPU中,并且具储存稳定性、耐水性、耐溶剂性及力学性能等俱佳。     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

制备单分散含单体O/W乳液的SPG膜乳化过程

采用Shirasu多孔玻璃（SPG）膜乳化法制备了单分散含对苯二甲酰氯（TDC）单体的O/W乳液,系统地研究了SPG膜乳化过程的影响因素.实验结果表明,采用SPG膜乳化法制备单分散O/W乳液时,选择阴离子表面活性剂比考虑亲水亲油平衡（HLB）匹配更重要;增大分散相或连续相的黏度,能够改善乳液的单分散性和稳定性;随着单体浓度增加,乳液的单分散性变差,液滴的平均粒径逐渐变小.当SPG膜孔径大于1.0 μm左右时,可得到单分散的含TDC单体乳液;而当孔径小于1.0 μm左右时,水分子更容易扩散并溶解到油水界面甚至油相内部与TDC生成对苯二甲酸（TPA）,TPA积累到一定程度在油水界面上析出将膜孔堵塞,从而无法制得单分散乳液.随着乳化时间增长,乳液的平均直径逐渐变小、单分散性逐渐变差.