聚醚侧链接枝密度对聚醚硅油性能的影响

通过烯丙基聚醚与含氢硅油的硅氢加成反应制备聚醚硅油。保持含氢硅油摩尔质量基本不变,考察含氢硅油的活性氢质量分数,即聚醚侧链的密度对硅氢加成反应及聚醚硅油性能的影响。结果表明,随着含氢硅油中活性氢质量分数的增加,反应体系变澄清所需要的时间变长;含氢硅油的活性氢质量分数为0.25%时,聚醚硅油的浊点最高;活性氢质量分数为0.2%时,多种浓度的聚醚硅油水溶液均呈现较高的表面张力;同一结构的聚醚硅油水溶液的表面张力随着聚醚硅油浓度的增加快速下降,质量浓度大于0.02 g/L后表面张力下降缓慢。含氢硅油较佳的活性氢质量分数是0.25%,用此含氢硅油制备的聚醚硅油在质量浓度为0.10 g/L时,其水溶液的表面张力下降至44.8 mN/m。     

聚醚酯改性有机硅消泡剂的制备

以含氢硅油、十四酸烯丙基聚醚酯为原料,氯铂酸为催化剂,合成了聚醚酯改性硅油,对其结构进行了红外和核磁表征。探讨了温度、时间和原料比对Si—H转化率的影响,测定了其水溶液在不同质量浓度下的表面张力,并将其制成消泡剂乳液研究了消泡性能。结果表明,在85℃、6 h、n(CC)∶n(Si—H)=1.3∶1时,Si—H转化率为87.6%;聚醚酯改性硅油水溶液在质量浓度0.3 g/L时表面张力为28.6 mN/m;配制的消泡剂乳液消泡时间5 s,抑泡高度300 mL。     

不同结构聚醚改性硅油的制备与表征

以含氢硅油、（α-烯丙氧基,ω-羟基）聚氧乙烯聚氧丙烯醚（F-6）和（α-烯丙氧基,ω-甲氧基）聚氧乙烯聚氧丙烯醚（AEPM-1500）为原料,在氯铂酸催化剂作用下,通过硅氢加成反应,合成了一种聚醚改性硅油（AAMS）,并用红外光谱和核磁共振氢谱对其结构进行了表征。考察了反应时间、温度以及催化剂用量对Si—H转化率的影响,较佳合成工艺为：反应时间为6h、反应温度为105℃,氯铂酸用量为20μg/g,此时,Si—H的转化率可达94．6％;随着F-6与AEPM-1500的量之比的增大,产物AAMS水溶液的表面张力先降后升,浊点升高;当F-6与AEPM-1500量之比为4：1时,AAMS水溶液的表面张力可降至28．6mN／m,浊点为24℃。     

一种聚醚改性聚硅氧烷的合成与表征

以八甲基环四硅氧烷(D4)、四甲基环四硅氧烷(D4H)、六甲基二硅氧烷(MM)等为原料,经催化平衡化制备了一种低含氢量低分子量的侧链含氢硅油。在氯铂酸的催化下,制备的侧链含氢硅油与丙烯醇聚氧乙烯醚进行硅氢化加成,得到一种侧链聚醚改性聚硅氧烷。讨论了原料摩尔比、温度、催化剂浓度及反应时间对硅氢键转化率的影响。硅氢化反应最佳条件为:n(Si—H)∶n(CC)=1. 0∶1. 2,反应温度90℃,催化剂浓度13 mg/L,反应时间4 h。含氢硅油和产物的红外光谱进行了测试与解析,并测量了产物的粘度、浊点、表面张力等其它物化指标。     

支链聚醚原油破乳剂的合成与表征

以聚氧乙烯聚氧丙烯环氧基醚和聚氧乙烯聚氧丙烯甲基醚为支链,聚硅氧烷为主链,在异丙醇溶剂下,以氯铂酸为催化剂,通过硅氢加成反应,合成出聚醚聚硅氧烷类原油破乳剂。得到较佳的合成条件为:n(环氧醚)∶n(甲基醚)=1∶1,n(硅氢键)∶n(双键)=1∶1.15,反应温度105℃,反应时间5 h,催化剂用量30μg/g(相对于反应物总质量)和溶剂用量40%(以原料总质量计),在该条件下转化率达到92.62%,并通过FTIR和1HNMR对产物的分子结构进行了表征,谱图分析证明合成了预期产物。表面张力仪测定了其临界胶束质量浓度为0.7 g/L,最低表面张力24.2 mN/m。该破乳剂在破乳温度70℃,用量为100 mg/L条件下,对延长石油永平原油的脱水率达到88.42%,具有较好的破乳性能。     

聚醚与甲基丙烯酸十二烷基酯共改性硅油的制备与表征

以氯铂酸为催化剂,烯丙醇聚氧乙烯聚氧丙烯醚(F-6)、甲基丙烯酸十二烷基酯(LMA)和含氢硅油(PHMS)为原料,通过硅氢加成制备了聚醚与甲基丙烯酸十二烷基酯共改性硅油(PMS),并用红外光谱和核磁共振氢谱对其结构进行了表征。考察了硅氢键与碳碳双键的量之比、反应温度、反应时间、催化剂用量对Si—H转化率的影响,确定了最佳工艺为:甲苯的质量分数30%～40%,Si—H与CC的量之比1.00∶1.20,催化剂用量为30×10-6,反应温度为90℃,反应时间为6 h,Si—H转化率达到92.35%。产物水溶液的临界胶束浓度为0.6 g/L,PMS的临界表面张力为22.236 mN/m,表现出低表面能的特点。     

聚环氧丙醇/环氧丙烷超支化聚合物的抗乳化性能

在对不同结构聚环氧丙醇/环氧丙烷超支化聚合物水数、表面张力、浊点表征的基础上,考察了聚合物添加质量浓度、温度对150SN基础油抗乳化性能的影响。结果表明,HLB值、质量浓度均显著影响各体系的抗乳化性能。当质量浓度为2.0×10-2g/L时,HLB值(亲水-亲油平衡值)14.7～14.9(水数法)、浊点58.6～65.1℃的超支化聚合物显示了较好的抗乳化性能。此外,升高温度有利于抗乳化性能的提升。     

有机硅表面活性剂的制备及乳化性能

以烯丙基聚氧乙烯醚、低含氢硅油为原料,氯铂酸的异丙醇溶液为催化剂,在无溶剂条件下合成出有机硅表面活性剂,并用红外光谱对其结构进行表征。正交实验表明,较佳的合成条件为:原料中SiH与C=C的量之比为1∶1.1,催化剂用量为10μg/g(以铂含量计),反应温度100℃,反应时间6 h,聚醚转化率达88.58%;在此条件下制得的有机硅表面活性剂的最低表面张力为27.8 mN/m、浊点为60℃、临界胶束质量浓度为0.32 g/L。将其与Span 60复配后用于乳化二甲基硅油,可制得稳定的硅油乳液。激光粒度仪测得乳液平均粒径为17.556μm,与一般Span/Tween复配乳化剂乳化的硅油乳液相比,乳液粒径更小,乳液更稳定。     

氟硅非离子表面活性剂的制备及性能

以含氢硅油(PMHS)、N-甲基-N-烯丙基-2-全氟-2-甲基-3-氧代己酰胺(NF2)和烯丙基聚醚(F6)为原料,在Karstedt催化剂作用下,通过硅氢加成反应制备了氟硅非离子表面活性剂PF2F6;采用FT-IR、1H NMR和19F NMR对产物结构进行了表征,并测定了产物的溶解度、浊点、表面张力和润湿性。结果表明,PF2F6在弱极性溶剂中具有良好的溶解度,在水中的溶解度随着F6物质的量的增大而增大;当n(Si-H)∶n(NF2)∶n(F6)=2∶0.7∶1.3时,临界胶束浓度(cmc)和平衡表面张力(γcmc)最小,其值分别为0.13 g/L和22.8 mN/m;随着反应体系中F6物质的量的增加,PF2F6的浊点增加,而在有机玻璃(PMMA)表面的接触角减小。     

不同封端聚醚共改性硅油的合成及其破乳性能

以异丙醇为溶剂、氯铂酸为催化剂,将单烯丙基封端聚氧乙烯聚氧丙烯醚(AEP)、单烯丙基封端聚氧乙烯聚氧丙烯环氧基醚(AEPH)和单烯丙基封端聚氧乙烯氧聚丙烯乙酰基醚(AEPC)同时与含氢硅油进行硅氢加成反应,合成了羟基封端聚醚、环氧基封端聚醚和乙酰基封端聚醚共改性硅油破乳剂。通过IR和1H NMR对产物结构进行表征,证实得到了预期产物。通过单因素实验法考察了碳碳双键与硅氢键的量之比[n(CC)∶n(Si—H)]、反应时间、反应温度和催化剂用量对活性氢转化率的影响,确定的最佳反应条件为:n(CC)∶n(Si—H)=1.20∶1,反应时间6 h,反应温度100℃,催化剂用量40μg/g(相对于反应物总质量),在此条件下活性氢转化率达到93.72%。将该聚醚改性硅油进行原油破乳性能测试,结果显示,在聚醚改性硅油用量为100 mg/L、破乳温度70℃条件下,加入聚醚改性硅油2 h后,原油脱水率达到90.54%,具有较好的破乳性能。     

反应型聚氨酯表面活性剂的制备及性能

以聚乙二醇(PEG)、异佛尔酮二异氰酸酯(IPD I)和2,2,6-三甲基-4H-1,3-二口恶烷-4-酮为主要原料,合成了一种带有乙酰乙酸基团的聚氨酯表面活性剂。用FTIR1、HNMR对合成产物的结构进行了表征,采用表面张力仪对其表面活性进行了测定。考察了温度、相对分子质量及外加电解质对表面活性的影响,测定了其电导率和浊点。结果表明,以PEG-1000、IPD I及2,2,6-三甲基-4H-1,3-二口恶烷-4-酮所制备的产物Ⅰ,在浓度为0.003mol/L时,可以将溶液的表面张力降低至37.5 mN/m(25℃),浊点为80℃。     

羧酸盐表面活性剂与两亲聚合物相互作用研究

根据黏度和表面张力的测定数据研究了羧酸盐表面活性剂(HF-E)与两亲聚合物的相互作用,结果表明,HF-E/两亲聚合物混合溶液的表观黏度随HF-E质量浓度的增加先升高后下降;两亲聚合物的质量浓度越大,HF-E/两亲聚合物混合溶液表面张力越高;随着水的矿化度的升高,HF-E/两亲聚合物混合溶液的表观黏度先略有增加,到一定值后反而降低,而表面张力则随矿化度的增加而降低;温度升高,HF-E/两亲聚合物混合溶液的表观黏度随之降低而其与大庆模拟油间的界面张力则升高。优化后的高黏度低界面张力二元体系配方为HF-E和两亲聚合物的质量浓度分别为3和1.5 g·L-1;此外,还加入质量浓度为1 g·L-1的烷基醇酰胺(NS)。     

Solution properties of homogeneous polyglycerol dodecyl ether nonionic surfactants

The synthesis and solution properties of a homologous series of polyglycerol dodecyl ethers (R₁₂G_n) are described. The phase behavior, surface tension, cloud point and HLB value (hydrophile lipophile balance) of these surfactants in aqueous solutions and in mixed solutions of water/oil have been investigated and compared with values for polyoxyethylene dodecyl ether (R₁₂EO_n). The surface tension measurements showed that R₁₂G_n have sufficiently low values of surface tension and critical micellization concentration (cmc) to serve as useful nonionic surfactants. The mesophases appearing in the R₁₂G_n systems were more stable in a high temperature range than the mesophases of the R₁₂EO_n systems. The cloud point and HLB data indicated that addition of one glycerol group was equivalent to the addition of three oxyethylene units, as far as the hydrophilic property was concerned. The phase diagrams of the R₁₂G_n/dodecane/water systems showed that the solubilizing and emulsifying powers of R₁₂G_n were greater than those of R₁₂EO_n. It is concluded that the polyglycerol chain can be even more useful as the hydrophilic part of nonionic surfactants than the conventional oxyethylene chain.     

New non-ionic surfactants: Alkyl polyoxyethylene diethers of isomeric dimethylxanthines

Novel isomeric nonionic surfactants of the poly-oxyethylene (POE) ether type possessing terminal dimethylxanthine functions related to caffeine have been prepared using a polyoxyethylene cetyl mono-ether as the starting material. The surface tension pro-perties indicate that, compared to the parent com-pound and its chloride derivative, these derivatives show pronounced changes in the critical micelle con-centration (CMC) and pre-CMC slope but relatively minor changes in the minimum surface tension value. The findings are discussed also in terms of efficiency and effectiveness of surfactants. The evidence indi-cates that the structure of the terminal hydrophilic portion can have a significant effect on interfacial packing. The cloud points of the chloride derivative and the xanthine derivatives were considerably lower than that of the parent ether. Cloud point curves for the ether, the chloride, and the xanthines over the dilute concentration range show similar features.     

月桂醇聚醚及其消泡性能研究

以月桂醇为起始剂,在高压反应釜中通过控制加料次序制备了5种不同链段结构的分子量在1 000-1 200的聚醚。分别考察了这5种聚醚的表面张力、浊点与消泡性能之间的关系后发现,随着聚醚浊点温度的降低,其消泡性能基本呈升高趋势,而聚醚的表面张力并不对其消泡性能起决定性作用。     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

Mixed Micelles of Trisiloxane Based Silicone and Hydrocarbon Surfactants Systems in Aqueous Media: Dilute Aqueous Solution Phase Diagrams, Surface Tension Isotherms, Dilute Solution Viscosities, Critical Micelle Concentrations and Application of Regular Solution Theory

Mixtures of trisiloxane type nonionic silicone surfactant (SS) with sodium dodecylsulfate, tetradecyltrimethylammonium bromide or tert-octylphenol ethoxylated with 9.5 ethylene oxide groups were studied in water at 30 °C by dilute aqueous solution phase diagrams, surface tension and dilute solution viscosity methods. The cloud points for the silicone surfactant aqueous solutions increased upon addition of hydrocarbon surfactants indicating the formation of hydrophilic complexes in mixture solutions. The scrutiny of the surface tension isotherms plotted as a function of SS concentration revealed that competitive adsorption effects are the characteristic features in these mixtures depending upon the SS concentration. Otherwise the isotherms exhibited two break points and the difference of concentration between the two break points increased with the increase in SS concentration indicating the cooperative nature of interactions. The micellar mole fractions of individual surfactants were determined by Rublingh's regular solution theory; interaction parameters and activity coefficients were evaluated and interpreted in terms of synergistic type interactions in these mixtures. The surface active parameters in mixture solutions were estimated and their analysis shows that the molecular species in the mixture solutions have a preferential tendency for adsorption at the air/water interface than in association form in the bulk solution. The effect of hydrocarbon surfactants on the intrinsic viscosity of SS micelles was monitored and related to the enhanced hydration in mixed micelles.     

Hydrotrope-Induced Enhancement of Room Temperature Surface Activity for High Krafft Point Fluorinated Surfactants

Potassium perfluorooctane sulfonate (KPFOS) and sodium perfluorooctane sulfonate (NaPFOS) exhibit poor surface activities in aqueous solution at room temperature because of their high Krafft points. In this work, we attempted to increase the solubility of KPFOS and NaPFOS and consequently improve their surface activities at room temperature with sodium p‐methylbenzene sulfonate (BS) and urea, which are typical hydrotropes in industrial applications. The effects of BS and urea on the surface tension of the aqueous solutions of KPFOS and NaPFOS were investigated at 25 °C. When the hydrotropes were added, the effectiveness of KPFOS and NaPFOS in surface tension reduction was greatly enhanced and KPFOS showed higher efficiency in surface tension reduction than NaPFOS. On the other hand, BS had much stronger ability than urea to reduce the surface tension of KPFOS and NaPFOS in water. In particular, with the assistance of BS the minimum surface tension of KPFOS approached 19 mN/m at 25 °C. It was worth noting that in the presence of BS, the surface tension of an apparently “saturated” solution (i.e., with coexisting surfactant solid) continuously decreased with increasing surfactant concentration. This behavior was ascribed to enrichment of branched PFOS isomers in aqueous phase with the assistance of BS, as evidenced by high‐resolution ¹⁹F NMR. Hydrotropes were able to recover the inherent character of KPFOS and NaPFOS as highly surface‐active fluorinated surfactants by increasing the solubility of branched isomers. This is an easy way to enhance the effectiveness in surface tension reduction at room temperature for fluorinated surfactants with high Krafft points.     

Synthesis,Characterization and Surface Activities of Cationic Polysaccharide (Aloe) Schiff Base Surfactants

Synthesis of cationic polysaccharide (Aloe) Schiff base surfactants was described and their chemical structures were confirmed by using FTIR spectroscopic, H‐NMR and UV analysis. The surface activities of these surfactants were measured, including surface tension, critical micelle concentration, effectiveness, efficiency, maximum surface excess and minimum surface area at 25 °C, interfacial tension and emulsification power at 25 °C. Adsorption and micellization free energies of these amphiphiles in their solutions showed a good tendency towards adsorption at the interfaces.