有机硅改性丙烯酸乳液的研制

采用预乳化法,以十二烷基磺酸钠/烷基酚聚氧乙烯醚为复合乳化剂,合成了乙烯基三(β-甲氧基乙氧基)硅烷改性丙烯酸酯乳液。     

高固含量丙烯酸酯乳液压敏胶制备及性能

以丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、丙烯酸（AA）、丙烯酸羟乙酯（HEA）为共聚单体，以烯丙氧基脂肪醇聚氧乙烯醚硫酸铵(SR-10)和烷基聚氧乙烯醚琥珀酸单酯磺酸二钠（A-102）作为环保型复合乳化剂，通过无种子半连续乳液聚合工艺制备了固含量高达62%的丙烯酸酯乳液压敏胶。考察了硬单体MMA用量对乳液压敏胶性能的影响。结果表明：当MMA用量为10%（以单体总质量计，下同）时，高固含量丙烯酸酯乳液压敏胶玻璃化转变温度（Tg）为-32.6 ℃，初始热分解温度为337 ℃，水接触角为108°，环形初黏为9.53 N/25mm，180°剥离强度为10.08 N/25mm，持黏力超过72 h；与未添加MMA的高固含量乳液相比，添加10% MMA后乳液黏度从361 mPa·s降至155 mPa·s，粒径从375 nm降至350 nm，粒径分布指数从0.144增至0.214。     

Hybrid emulsifiers enhancing polymerization stabilities and properties of pressure sensitive adhesives

In this study, a series of (anionic and nonionic) emulsifiers were investigated to prepare acrylic pressure sensitive adhesives (PSA) with core‐shell structure by semicontinuous emulsion polymerization. The cloud point of different emulsifiers was characterized to explain the emulsifier effects on the emulsification ability. It was interestingly found that the hybrid emulsifiers (anionic coupling with nonionic) with optimized compositions could enhance the stability of emulsion system and improve the properties of PSA compared with the mono‐emulsifier. The stability of emulsion polymerization, the appearance of the emulsion system and the properties of PSA were studied in details by changing the proportion and the content of hybrid emulsifiers. When the ratio of sodium dodecyl sulfate (SDS: anionic emulsifier) to polyoxyethylene alkyl phenyl ether (OP‐10: nonionic emulsifier) reached 2 : 1, the content of hybrid emulsifiers reached 3 wt % and the reaction temperature was around 80°C, a better emulsion system was obtained in terms of comprehensive properties. At this condition, the synthesized PSA demonstrated the good holding power and 180° peel strength properties with fair tacky property, which was promising for industrial applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

反应性乳化剂参与的醋丙多元共聚及其压敏胶性能研究

采用种子半连续乳液聚合法,将反应性乳化剂α-烯丙基烷基酚聚氧乙烯醚硫酸铵(HS-10)引入醋丙乳液聚合体系,制备了稳定的醋丙压敏胶乳液。红外光谱实验结果表明,HS-10参与了醋丙体系共聚合反应。所得乳液的表面张力、粒径及分布、粘度及180°剥离强度都随HS-10用量增加而减小。耐水性性能实验表明采用HS-10的醋丙压敏胶体系,吸水率仅为传统型的35．9％,较好地改善了聚合物耐水性能。     

Production of Saponin Biosurfactant from <Emphasis Type="Italic">Glycyrrhiza glabra</Emphasis> as an Agent for Upgrading Heavy Crude Oil

Saponins are the main group of phytogenic biosurfactants extracted from plants. One of the significant applications of these compounds is upgrading and viscosity reduction of heavy crude oil water in oil (W/O) emulsions. In this research, use of saponin extracted from Glycyrrhiza glabra was investigated for viscosity reduction of heavy crude oil and upgrading its API properties. The extracted saponin was characterized using Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Phase behavior analysis demonstrated a reduction in initial viscosity and improved API gravity of the heavy oil from 2350 mPa·s and 19 to 900 mPa·s and 27, respectively. In addition, the emulsification index (E ₂₄) was found to be 98 % at a saponin concentration of 8 % w/v. It was observed that the emulsions were stable in the pH range of 5.5–13, temperature from 30 to 80 °C and salinity up to 6 % w/v of NaCl solution. Average diameter of W/O droplets evaluated by dynamic light scattering (DLS) were in the range of 10–15 µm. The results obtained from the present research revealed that the extracted saponin improved the physical characteristics of heavy crude oil. We propose the use of saponin as a potential alternative to conventional emulsifiers for upgrading heavy crude oil in petroleum industry.     

Preparation of Phospholipid Microcapsule by Spray Drying

An experimental study of spray drying was carried out aimed at improvement of the phospholipid microencapsulation process. Three kinds of wall materials, maltodextrin blended with sodium caseinate, gelatin, and soy protein, respectively, were used to prepare phospholipid emulsion. Through examining the emulsion stability, a stable emulsion with the sodium caseinate contained system was obtained under 2.5 of mass ratio between maltodextrin and sodium caseinate, 70–80°C of emulsification temperature, 2.5% of emulsifier concentration, and 40 MPa of homogenization pressure. Phospholipid microcapsules with a mean size of 62 µm in apparent geometric diameter and good fluidity, dispersion, and dissolubility were prepared under 140°C of air inlet temperature, 30°C of feed temperature, and 20% of solids concentration. Up to 90% of phospholipid microencapsulation efficiency is achieved. In addition, phospholipid microcapsules have good dissolubility, fine appearance, and excellent fluidity and dispersion.     

柴油-水乳化燃料稳定性的影响因素

在柴油-水乳化燃料制备的过程中,从柴油本身性质、乳化温度、乳化剂及乳化助剂的用量、掺水率、pH值、乙醇及甲醇加入量、乳化剂加入方式和贮存温度等10个方面考虑了对乳化燃料稳定性的影响,从中找出了最佳条件使乳化油的稳定性增强,其中乳化剂加入量0.3%~0.5%,乳化助剂加入量0.08%,乙醇加入量20%,甲醇加入量25%,pH值4.9,掺水率10%~15%,水浴温度30~40°C,搅拌速率200 r/min,贮存温度低于40°C。     

醇酸交联型丙烯酸酯乳液的制备研究

以丙烯酸丁酯(BA)、丙烯酸甲酯(MA)和丙烯腈(AN)为主要原料,烷基酚聚氧乙烯醚(OP-10)和十二烷基磺酸钠(SDS)为复合乳化剂,过硫酸铵(APS)和亚硫酸氢钠(NaHSO3)为氧化还原型引发剂,采用种子乳液聚合法制备了丙烯酸酯乳液;然后以多元醇A作为丙烯酸酯乳液的交联改性剂,制备了醇酸交联型丙烯酸酯乳液,实现了热交联体系无甲醛化。结果表明:当聚合温度为70℃、w(引发剂)=2.4%、m(BA)∶m(MA)∶m(AN)=33∶11∶6、w(复合乳化剂)=5%且m(OP-10)∶m(SDS)=1∶1.5时,丙烯酸酯乳液的综合性能较好;当n(丙烯酸)∶n(多元醇A)=30∶1、w(丙烯酸)=1.0%时,交联改性乳液的固含量为51.40%、单体转化率为98.3%;交联改性乳液的胶膜吸水率(10.08%)比未改性乳液降低了82.4%,但两者的热稳定性均较高且相差不大。     

Sonocrystallization of Interesterified Fats with 20 and 30% of Stearic Acid at the sn-2 Position and Their Physical Blends

Physical blends (PB) of high oleic sunflower oil and tristearin with 20 and 30% stearic acid and their interesterified (IE) products where 20 and 30% of the fatty acids are stearic acid at the sn-2 position crystallized without and with application of high intensity ultrasound (HIU). IE samples were crystallized at supercooling temperatures (ΔT) of 12, 9, 6, and 3 °C while PB were crystallized at ΔT = 12 °C. HIU induced crystallization in PB samples, but not in the IE ones. Induction in crystallization with HIU was also observed at ΔT = 6 and 3 °C for IE C18:0 20 and 30% and at ΔT = 9 °C only for the 30% samples. Smaller crystals were obtained in all sonicated samples. Melting profiles showed that HIU induced crystallization of low melting triacylglycerols (TAGs) and promoted co-crystallization of low and high melting TAGs. In general, HIU significantly changed the viscosity, G′, and G″ of the IE 20% samples except at ΔT = 12 °C. While G′ and G″ of IE 30% did not increase significantly, the viscosity increased significantly at ΔT = 9, 6, and 3 °C from 1526 ± 880 to 6818 ± 901 Pa.s at ΔT = 3 °C. The improved physical properties of the sonicated IE can make them good contenders for trans-fatty acids replacers.     

一种环保型乳化剂复配体系的研究

研究了淀粉糖苷非离子表面活性剂与脂肪醇聚氧乙烯醚硫酸酯钠盐阴离子型表面活性剂、脂肪醇聚氧乙烯醚非离子表面活性剂的混合体系的乳化力的变化规律,找出复配体系的最佳配方,将其乳化性与常用的烷基酚聚氧乙烯(10)醚进行比较。结果表明,复配后的体系有较低的表面张力,对菜油的乳化性与烷基酚聚氧乙烯(10)醚相当,对变压器油的乳化性优于烷基酚聚氧乙烯(10)醚。且该体系浊点高,泡沫稳定,乳化性能好。     

秸秆基环氧树脂乳液的制备及其涂膜性能

以脂肪醇聚氧乙烯醚(AEO-9)和十二烷基硫酸钠(SDS)复配为乳化剂,通过相反转技术乳化秸秆基环氧树脂,考察了复配乳化剂的HLB值、用量以及乳化温度和搅拌速率对乳液临界含水量Rf值、粒径及稳定性的影响,获得了如下较佳的乳化工艺条件:HLB值17,复合乳化剂用量8%,乳化温度35°C,搅拌速率800 r/min。以此工艺制得的乳液稳定性较好,平均粒径为1.57μm。以水性聚酰胺为固化剂,将此乳液制成清漆,固化后所得漆膜综合性能良好。     

乳液型CPP-g-MAH复膜胶的研制

以酯溶性CPP-g-MAH(马来酸酐接枝改性氯化聚丙烯)、BA(丙烯酸丁酯)、HEA(丙烯酸羟乙酯)和β-CEA(β-羧乙基丙烯酸酯)为共聚单体,DNS-86[烯丙氧基壬基酚丙醇聚氧乙烯(10)醚硫酸铵]为反应型乳化剂,采用半连续预乳化乳液聚合法制备乳液型CPP-g-MAH复膜胶。研究结果表明:当m(BA)∶m(CPP-g-MAH)=9∶4、聚合温度为82⁸5℃、聚合时间为4 h、w(DNS-86)=3.0%(相对于配方中各物料总质量而言)和w(引发剂)=0.5%(相对于聚合单体总质量而言)时,制得的乳液型复膜胶具有环保、成本低等优势,并且其黏度、初粘力(2.5 cm)和180°剥离强度(5.1 N/cm)俱佳。     

Gas chromatographic analysis of nonionic surfactants by acid cleavage of ether linkages

The gas chromatographic analysis of various kinds of nonionic surfactants has been carried out after chemical decomposition using the mixed anhydride of acetic and p-toluene sulfonic acids which acts as a reagent for cleavage of ether linkages. The gas chromatographic peaks of the reaction products show the alkyl distributions of the hydrophobic groups of ethylene oxide adducts. The alkyl compositions closely agree with those of the starting materials. In this way, the hydrophobic groups of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl amine, and polyoxyethylene alkyl thioether have been analyzed. At the same time, the hydrophilic group, namely polyoxyethylene group, can be identified in the form of ethylene glycol diacetate.     

Preparation of monodisperse water-in-oil-in-water emulsions using microfluidization and straight-through microchannel emulsification

Water-in-soybean oil-in-water (W/O/W) emulsions with an internal water phase content of 10–30% (vol/vol) were prepared by a two-step emulsification method using microfluidization and straight-through microchannel (MC) emulsification. A straight-through MC is a silicon array of micrometer-sized through-holes running through the plate. Microfluidization produced water-in-oil (W/O) emulsions with submicron water droplets of 0.15–0.26 μm in average diameter (d _av,w/o) and 42–53% in CV (CV_w/o) using tetraglycerin monolaurate condensed ricinoleic acid esters (TGCR) and polyglycerin polycondensed ricinoleic acid esters (PGPR) as surfactants dissolved in the oil phase. The d _av,w/o and viscosity of the W/O emulsions increased with an increase in internal water phase content. Straight-through MC emulsification was performed using the W/O emulsions as the to-be-dispersed phase and polyoxyethylene (20) sorbitan monooleate (Tween^® 80) as a surfactant dissolved in the external water phase. Monodisperse W/O/W emulsions with d _av,w/o/w of 39.0–41.0 μm and CV_w/o/w below 5% were successfully formed from a straight-through MC with an oblong section (42.8×13.3 μm), using the TGCR-containing systems. The d _av,w/o/w of the monodisperse W/O/W emulsions decreased as the internal water phase content increased because of the increase in viscosity of the to-be-dispersed phase. Little leakage of the internal water droplets and no droplet coalescence or droplet break-down were observed during straight-through MC emulsification.     

Fluoro-silicone Modified Polyacrylate Latex Emulsified with Green Surfactants

Fluoro‐silicone modified polyacrylate latex was successfully prepared by semi‐continuous seeded emulsion polymerization in the presence of a green mixed emulsifier consisting of cashew phenol polyoxyethylene ether sulfonate (BCE‐10B) anionic surfactant and alkyl polyglycoside (APG) nonionic surfactant, in which the mixed monomers were initiated with potassium persulfate (KPS). The structure and properties were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA), respectively. Results show that the optimal conditions of synthesizing the novel emulsion are as follows: the total concentration of mixed emulsifiers is 5.0%; the optimum mass ratio of APG to BCE‐10B is 2:1; the amount of initiator is 0.6%; the composition of main monomers of MMA:BA = 1:1; and the concentrations of HFMA and VTES are 4.0 and 6%, respectively. In this case, the resultant emulsion showed good thermal stability and hydrophobicity.     

含水乙醇汽油体系相稳定剂的研究

通过向乙醇汽油中加入相稳定剂的方法,获得稳定的含水乙醇汽油体系,从而降低其成本,促进乙醇汽油在我国的推广应用。对4种非离子表面活性剂:月桂醇聚氧乙烯醚(AEO-3)、壬基酚聚氧乙烯醚(NP-4)、辛基酚聚氧乙烯醚(OP-4,OP-6)的相稳定效果进行研究。结果表明:对E15,E20和E25乙醇汽油,相稳定剂用量(体积分数)大于3%时,AEO-3的相稳定效果最优;对E5,E10乙醇汽油,随各表面活性剂的HLB值逐渐增大,相稳定效果依次增强。温度一定,体系的最大增溶水量与表面活性剂用量、乙醇配比均成正比。     

烷基酚聚氧乙烯醚的定性分析

利用氢碘酸作裂解剂处理烷基酚聚氧乙烯醚试样 ,采用气相色谱 质谱联用技术对其进行定性分析。根据气相色谱图及质谱检测得到的特征峰分析其组成 ,可得知油剂中的未知组分     

Micellization and Adsorption Behaviors of New Reactive Polymerizable Surfactants Based on Modified Nonyl Phenol Ethoxylates

The synthesis and characterization of a series of polymerizable surfactants based on alkyl phenol ethoxylate backbone and carboxylic or anhydride chain ends were investigated. Surface activities of these polymerizable surfactants were investigated to correlate their structure and their performances. The new bifunctional surfmers were prepared by reacting polyoxyethylene 4-nonyl-2-propylene-phenol nonionic reactive surfactants with maleic anhydride. The chemical structure of the prepared surfactants was characterized by ¹³C and ¹H NMR analyses. The surface activities of the modified polymerizable surfactants were measured from the adsorption isotherm measurements which were determined from the relationship between the concentrations and surface tension of surfactants in aqueous medium at different temperatures. Critical micelle concentration (CMC) values were determined for water soluble surfactants. It was found that CMC decreases with the incorporation of the anhydride and acid groups in the chemical structure of polyoxyethylene 4-nonyl -2-propylene-phenol nonionic surfactant. surface-active parameters such as area per molecule at the interface (A _min), surface excess concentration (Γ_max) and the effectiveness of surface tension reduction (π_CMC) were measured from the adsorption isotherms of the modified surfactants. Some thermodynamic data for the adsorption process were calculated and discussed. The data indicated that the new surfmers are more reactive than the simple polyoxyethylene 4-nonyl-2-propylene-phenol and more adsorbed at interfaces. We have performed a preliminary experiment to explore the emulsification efficiency of the newly synthesized reactive surfactants in equal volume oil–water emulsions. Different emulsion types and stabilities were obtained.     

新型乳化剂对苯丙乳液性能的影响

采用半连续法制备苯丙乳液,通过改变乳化剂的种类和用量,比较了新型乳化剂烯丙氧基壬基酚聚氧乙烯（10）醚（ANPEO10）、烯丙氧基壬基酚聚氧乙烯（10）醚单磷酸（ANPEO10-p1）和聚氧乙烯-4-酚基醚硫酸铵盐（C0436）对乳液性能的影响。结果表明,用乳化剂ANPEO10制得的乳液冻融稳定性和聚合稳定性较好;而用ANPEO10-P1和CO436制得的乳液稀释稳定性较好;乳液的黏度随着乳化剂用量的增加而增大,且用ANPEO10-P1制得的乳液黏度相对较低;这3种乳化剂所制备的乳胶膜都具有良好的耐水性。     

Synthesis and Physico-Chemical Characterization of Halogenated Partly Aromatic Cardo Copolyesters

Copolyesters of 1,1′-bis(3-methyl-5-chloro-4-hydroxy phenyl) cyclohexane (0.0025 mol), ethylene glycol/propylene glycol/1, 4-butanediol/1,6-hexanediol (0.0025 mol) and terephthaloyl chloride (0.005 mol) have been synthesized by interfacial polycondensation technique by using water-chloroform (4:1 v/v) as an interphase, sodium hydroxide (0.125 mol) as an acid acceptor and cetyl trimethyl ammonium bromide (50 mg) as an emulsifier. The reaction time and temperature were 3 h and 0°C, respectively. The yield of copolymers was 85–87%. Copolyesters are soluble in common solvents and possess moderate molecular weights. The structures of copolyesters are supported by FT-IR and ¹HNMR spectral data. Copolyesters are characterized for their viscosity in chloroform and 1,2-dichloroethane at 30, 35 and 40°C, densities by floatation method (1.139–1.2775 g cm^?3). It is observed that both [η] and density of copolyesters decreased with increase in alkyl chain length. Copolyesters possess excellent hydrolytic stability against water and 10% each of acids, alkalis and salt at room temperature. The observed wt. % change is ±3.15% in the selected environments. A 30 μm thick C1MPT film has 17.8 MPa tensile strength, 50.1 kV mm^?1 electric strength and 2.2 × 10¹² ohm cm volume resistivity. Copolyesters possess high T_g (148–172°C) and are thermally stable up to about 411–426°C and followed single step degradation kinetics involving 70–75% weight loss with 20–24% residual weight above 650°C. Copolyesters followed 1.19–1.94 order degradation kinetics. Activation energy and frequency factors are increased with alkyl chain length.