Interfacial and Demulsifying Behavior of Novel Fluorinated Hyperbranched Polymers

In our previous study, a series of novel hyperbranched fluoropolymers with polyglycerol as the core and poly(hexafluorobutyl acrylate) as hydrophobic arms were synthesized. As potential demulsifier for lubricants, the demulsification behavior, dynamic interfacial tension, and dilational rheological properties of the fluorinated polymers were investigated in this paper. The influence of polymer concentration and molecular structure on the interfacial properties was analyzed. We conclude that the diffusion rate of the polymers and the viscoelastic properties of the water–oil interface are critical factors in determining the demulsification performance. The longer hydrophobic chains of the fluorinated polymers leads to a faster and more effective interfacial adsorption, which is favorable to improve demulsification efficiency. In contrast, the longer hydrophobic chain also enhances the elastic property of interface due to its entangled structure, which is unfavorable to demulsification. As a result, the polymer with medium hydrophobic chain length show the best demulsification performance.     

超支化聚氨酯氟代聚丙烯酸酯的合成与应用

以六亚甲基二异氰酸酯(HDI)、聚乙二醇(PEG-600)、三乙醇胺(TEOA)、丙烯酸羟乙酯(HEA)等为原料,合成以双键封端的超支化聚氨酯(HPU),再与全氟己基乙基丙烯酸酯(C6F)、甲基丙烯酸十八酯(SMA)、丙烯酸羟乙酯(HEA)、丙烯酸丁酯(BA)等,通过自由基聚合,合成超支化聚氨酯氟代聚丙烯酸酯(HPUFA)。通过红外光谱(FTIR)、场发射扫描电镜(SEM)、接触角测量仪等对产物结构、性能进行了测试。结果表明,当n(NCO)/n(OH)=1.4时,HPUFA用量1.5 g/100 g乙酸乙酯时应用效果较佳;经HPUFA处理的织物接触角达到137.5°,静态吸水时间达9.5 h,疏油等级6级。     

新型偶氮苯类的超支化大分子的合成

以对硝基苯胺、亚硝酸钠、盐酸、环氧氯丙烷为主要原料，经过重氮化、偶合、Williamson反应合成了对硝基偶氮苯酚（中间体A）和对硝基偶氮苯缩水甘油醚（中间体B）；以一定配比的偏苯三酸酐和环氧氯丙烷为原料经过酯化反应合成了一种全羧基超支化聚酯；利用超支化聚酯末端的羧基与偶氮苯缩水甘油醚的环氧基团开环反应，制备了偶氮苯功能化的超支化聚酯，并对其进行了表征。     

超支化聚合物用于材料制备和改性的研究

综述了近年来超支化聚合物在聚合物增韧、增塑、粉体填料的表面改性以及制备纳米粒子和纳米复合材料等方面的研究进展。     

超支化聚合物在共混改性中的应用

介绍了超支化聚合物的概况,综述了超支化聚苯、超支化聚酯、超支化聚酰胺、超支化聚醇和超支化聚苯乙烯等在聚合物共混改性中的应用。     

Modification of Some Hyperbranched Polyols with Oligo (Ethyleneoxide) Units on the Way to New Applications

Three different hyperbranched polymers (H₁, H₂, and H₃) were prepared. The H₁ and H₂ are hyperbranched polyesteramide polymers; however, H₃ is a poly(urea-urethane) hyperbranched polymer. The three polymers were treated with Br-ended surfactant units, which were prepared via simple reaction of Tergitol Np-50 (S) as surfactant with bromoisobutyrylbromide. New ended polymers resulted as H₁S, H₂S, and H₃S with new ethyleneoxide units. Critical micelle concentration (CMC) was studied for the newly prepared polymers (H₁S, H₂S, H₃S) and was compared with the original ones (H₁, H₂, H₃) on the way to involve the new modified polymers in various industrial applications. The CMC was determined by the surface tension technique employing the platinum ring method. It was found that CMC could be arranged in the following ascending order: H₃S < H₂S < H₁S < H₃ < S < H₂ < H₁.     

超支化聚合物改善聚乙烯性能的研究、

将超支化聚合物（HBP）添加到聚乙烯（PE）管道料中，采用SEM、DSC、成型工艺、拉伸实验等手段研究了不同邶P用量对PE结晶性能、注塑工艺、力学性能等的影响。结果表明：HBP的加入可使PE的结晶速率稍有提高，有效改善了PE注塑样条的表面光洁度，提高其熔体流动性，从而改善注塑加工工艺，同时提高了PE的拉伸强度。     

超支化聚酰胺合成与研究进展

介绍了超支化聚合物的结构、性能以及合成方法,重点对超支化聚酰胺的研究进展做了综述。     

Ionic Behavior Assessment of Surface-Active Compounds from Corn Steep Liquor by Exchange Resins

Depending on their ionic nature, biosurfactants can be classified as nonionic, anionic, cationic, or amphoteric. The ionic behavior of biosurfactants is an important characteristic that dictates their use in industrial applications. In this work, a biosurfactant extract obtained from corn steep liquor was subjected to anionic or cationic resins, in order to study the ionic behavior under different operational conditions using response surface methodology. The independent variables included in the study are the dilution of biosurfactant solution, the amount of cationic or anionic resin, and the extraction time, whereas the dependent variables studied consisted of the surface tension of biosurfactant aqueous solution, after contacting with anionic or cationic resin. The results showed that biosurfactant extracted from corn steep liquor is amphoteric, since both resins were able to entrap this biosurfactant, making it particularly suited for use in personal care preparations for sensitive skin.     

超支化聚(酰胺-酯)的合成与改性

以邻苯二甲酸酐和二乙醇胺为原料,制得AB2型单体;加入三羟甲基丙烷为核,采用一步法合成了超支化聚(酰胺-酯),并用硬脂酸对所得聚合物进行封端改性.应用红外光谱对改性前后超支化聚合物进行了表征.结果表明,所合成的聚合物与理论结构相吻合,且硬脂酸与端羟基发生了酯化反应,成功地接到了聚合物上.     

一种超支化聚(酰胺-酯)的合成及性能研究

以二异丙醇胺和六氢化苯二甲酸酐为原料,合成AB2型单体DH;DH和过量的二异丙醇胺在共沸带水剂-二甲苯中进行缩聚反应,合成超支化聚（酰胺-酯）。同时利用傅立叶红外光谱、化学滴定法和凝胶渗透色谱对DH和超支化聚（酰胺-酯）进行表征,并对超支化聚（酰胺-酯）的热稳定性、溶解性和流变性进行了研究。研究结果表明：超支化聚（酰胺-酯）具有较好的热稳定性,加热到300℃,超支化（酰胺-酯）才出现明显的失重;超支化聚（酰胺-酯）具有良好的溶解性能,能溶于醇类、酮类、四氢呋喃等极性溶剂,溶解度参数δ值为21．85～26．29（J／cm^3）^0.5;相对线型高分子,超支化聚（酰胺-酯）具有较好的流变性,在四氢呋喃溶液中,质量浓度高达40％时,黏度仅为6．61mPa·s。     

Synthesis and Characterization of UV-curable Hyperbranched Urethane Acrylate

The UV-curable hyperbranched urethane acrylate (HBUA) with a multi-hydroxyl functional hyperbranched polyester core was synthesized via a two-step procedure. The products were characterized by size exclusion chromatography, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, and thermogravimetric analysis. The mechanical properties of UV-cured HBUA films were also investigated. The polydispersity index of HBUA is 2.31 and the endcapped degree of acrylation is 79.8%. The viscosity of HBUA is relatively low in favor of mixing and spreading. The UV-cured films exhibit high hardness and good flexibility.     

氟化季铵盐表面活性剂的合成及其表面活性

以三氟乙酸乙酯和N,N-二甲基乙二胺为原料,经酰化反应制得中间体NDAET;然后将NDAET与溴代十二烷发生季铵化反应得到氟化季铵盐表面活性剂N,N-二甲基-N-{2-[(2,2,2-三氟乙酰基)氨基]乙基}-1-十二烷基铵溴化物(NDAET-12)。通过FTIR、13CNMR、1HNMR对其结构进行了表征。考察了反应物物质的量比、反应时间、反应温度、溶剂用量对NDAET-12产率的影响。在单因素实验的基础上,采用正交实验对NDAET-12的合成工艺进行了优化。NDAET-12的最佳合成工艺条件为:n(NDAET)∶n(溴代十二烷)=1.0∶1.3,NDAET质量为2.76g,反应时间12h,反应温度90℃,溶剂用量为20mL。在该条件下进行平行验证实验,得到NDAET-12的平均产率为86.75%。热重分析表明,NDAET-12是一种热稳定性较好的表面活性剂。对NDAET-12的临界胶束浓度(CMC)、表面活性和乳化性能进行了测定。NDAET-12的CMC为0.8 g/L,γCMC=25.15 mN/m,表面活性较好。与十二烷基三甲基溴化铵(DTAB)和十六烷基三甲基溴化铵(CTMAB)相比,NDAET-12从乳化体系中分出10mL所需要的时间最长,为473s,具有优异的乳化性能。     

Adsorption Behavior of Fatty Alcohol Ether Sulfonate at Different Interfaces

The equilibrium surface tension, dynamic surface tension, and interfacial tension (IFT) of fatty alcohol ether sulfonates (C_mE_nSO) were measured to investigate their adsorption behavior. The effect of NaCl and CaCl₂ concentrations on the IFT was also studied. The results showed that the number of EO units has no significant effect on the critical micelle concentration (CMC) and CMC decreases with increasing the length of the hydrophobic group. The surface tension at the CMC increases with the increase of the number of EO units and the length of the hydrophobic group. At dilute surfactant concentration, the adsorption process for C_mE_nSO is controlled by diffusion; at higher concentration, it becomes a mixed diffusion‐kinetic adsorption mechanism. The IFT between C_mE_nSO solution and dodecane remains around 10^?1 mN/m over a wide range of electrolyte concentrations (NaCl concentration from 25 to 210 g/L, CaCl₂ concentration from 0.1 to 10 g/L).     

UV固化超支化双酚A衍生物环氧丙烯酸酯的合成与性能研究

利用自制的双酚A衍生物Ph-BPA、三羟甲基丙烷为原料,通过A2+B3缩聚反应的方法,合成超支化双酚A衍生物环氧树脂(HPHEP),再对其末端基团进行改性,成功合成出超支化双酚A衍生物环氧丙烯酸酯(HPHEA)。通过红外光谱、紫外可见光谱以及核磁共振氢谱对其结构进行表征。HPHEA的热失质量曲线表明,其主要失质量温度区间为320~450 ℃,具有良好的耐热性。UV固化后,HPHEA涂膜展现出优良的力学性能。     

Synthesis and Surface Activities of Novel Succinic Acid Double-Tailed Sulfonate Fluorinated Surfactants

In this study, four environmentally friendly succinic acid double-tailed sulfonate fluorinated surfactants were synthesized from maleic anhydride, fluoroalkyl alcohols, namely 1-(1H,1H,7H-Dodecafluoroheptyloxy) ethanol, 1-(1H,1H,5H -octafluoropentyloxy) ethanol, 1-(1H,1H,3H-tetrafluoropropoxy) ethanol, and 1-(1H,1H -trifluoroethyoxy) ethanol, and sodium hydrogensulfite. The surfactant structure was characterized by FT-IR, ¹H NMR, and ¹⁹F NMR . Thermogravimetric results showed that the fluorinated surfactants were stable up to relatively high temperature. The Krafft points of the four novel succinic acid double-tailed sulfonate fluorinated surfactants were all below 0 °C. The lowest CMC value for the synthesized four double-tailed fluorine surfactants is about 0.076 mmol L^?1, far less than that of ammonium perfluorooctanoate (PFOA), demonstrating that double-tailed surfactants have higher surface activity than surfactants with one fluoroalkyl chain. The replacement of alkyl groups with oxyethylene groups enhances the hydrophilicity of the obtained fluorinated surfactants. Based on these findings, the synthesized surfactants may be environmentally friendly alternatives to PFOA and exhibit promising potential in industry applications.     

用接触角法测量聚合物共混体系的表面性能

利用接触角的方法研究了聚合物HDPF、PET及其共混物HDPE／PET的表面自由能、极化度以及与不同液体一水和甘油间界面张力的大小。     

Synthesis of Hyperbranched Polyglycerol in a Continuous Flow Microreactor

Hyperbranched polymers have been synthesized in a microreactor for the first time, employing the known ring‐opening multibranching polymerization of glycidol. Microreactors are well‐known to be beneficial for highly exothermic reactions because of their capability to enhance mass and heat transfer due to short diffusion pathways and large interfacial areas per volume. The characteristics of the microstructured reaction system were utilized to engineer a continuous flow process for the preparation of well‐defined hyperbranched polyglycerols with molecular weights up to 1,000 g/mol. Increased flow rates, as well as the use of highly polar solvents, led to the partial formation of very narrowly distributed (M_w/M_n = 1.05–1.15) high molecular weight fractions (M_n up to 150,000 g/mol). NMR‐ and MALDI‐ToF spectra confirmed incorporation of the multifunctional initiator core into the hyperbranched polymer structure.     

Synthesis and Characterization of Ferrocene-Containing Hyperbranched Poly(aroylarylene)s

Ferrocene-containing hyperbranched poly(aroylarylene)s are prepared in satisfactory yields by one-pot copolycyclotrimerization of bis(aroylacetylene)s with a ferrocene-containing monoyne. The ferrocene content of the polymers can be varied by changing the monomer feed ratio, and copolymers with up to 41 mol% of ferrocene moiety can be readily prepared. All the polymers are thermally stable, losing little of their weights when heated to 340 °C. This article is dedicated to Professor Didier Astruc.     

超支化聚(酰胺-酯)的合成及其光致变色性能研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料,在冰水浴条件下合成AB_3型单体,然后进行熔融缩聚制得超支化聚(酰胺-酯)(HBP);再将含羧基的螺吡喃光致变色基元通过反应活性基团羧基与AB_3超支化聚合物末端羟基的反应而引入到AB_3超支化聚合物末端上,得到具有光致变色性能的超支化聚合物(MHBP)。利用红外、核磁等对其结构进行了表征,利用紫外可见分光谱对超支化聚合物光致变色性进行了研究。结果表明:MHBP同时具有超支化聚合物的性能和光致变色性能。