高加成数壬基酚聚氧乙烯醚的合成及条件优化

本文在壬基酚乙氧基化反应研究与催化剂考察的基础上,提出了ZD-Ⅳ型三元高效聚合催化剂;通过四因素四水平正交实验考察了催化剂浓度、反应温度、反应压力及脱水时间四因素对高加成壬基酚聚氧乙烯醚合成反应的影响;考察了各因素对反应速度、产物分子量及产物色泽的影响程度,并确定了NP-50的最佳合成工艺条件。     

壬基酚聚氧乙烯醚的合成及条件优化

本文针对国内壬基酚聚氧乙烯醚(OP)生产中遇到的实际问题,通过催化活性、产物分子量分布以及产物后处理等方面的比较,采用了ZS—I新型催化剂,并按正交试验设计研究了壬基酚聚氧乙烯醚的合成。选择了催化剂用量(A)、脱水时间(B)、反应压力(C)和反应温度(D)四因素三水平,并以反应时间、浊点和PEG含量作为评价反应的三个指标,确定了各因素对反应影响大小的顺序,优选出最佳的合成条件,同时大大简化了产物的后处理。     

壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐的合成及其应用

本文介绍了以壬基酚聚氧乙烯醚、顺丁烯二酸酐、亚硫酸氢钠为原料,在催化剂的作用下,合成壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐的方法,以及产品的应用范围,并对有关问题进行讨论。     

2-磺基-4-壬基苯基聚氧乙烯醚的合成工艺研究

以壬基酚为原料，以发烟硫酸作磺化剂，合成了壬基酚磺酸钠；然后以氢氧化钾为催化剂，进行乙氧基化反应得到2-磺基-4-壬基苯基聚氧乙烯醚。分别考察了反应条件对磺化反应和乙氧基化反应的影响；并用IR验证了所合成产物的结构。结果表明：在温度为40℃，磺化剂用量为壬基酚体积的31％，反应时间2h下，磺化产物收率为99.88％；在150℃，0．3MPa，催化剂用量为壬基酚磺酸钠质量的0．5％下2-磺基-4-壬基苯基聚氧乙烯醚的磺化度为87．78％，聚乙二醇的含量为3．51％。     

OPS-1乳化剂的合成及应用

以壬基酚聚氧乙烯醚、顺丁烯二酸酐、无水亚硫酸钠为原料合成了壬基酚聚氧乙烯醚琥珀酸酯磺酸二钠盐,研究了反应温度和反应时间对酯化反应和磺化反应的影响,探讨了产品在乳液聚合等方面的应用     

HPLC-MS法测定纺织染整助剂中烷基酚及烷基酚聚氧乙烯醚

本文采用高效液相色谱-质谱法检测了纺织染整助剂产品中烷基酚及烷基酚聚氧乙烯醚,包括辛基酚(OP)、壬基酚(NP)、辛基酚聚氧乙烯醚(OPEO)、壬基酚聚氧乙烯醚(NPEO)。对样品前处理方法进行了优化和选择。     

光催化降解壬基酚聚氧乙烯醚的研究

研究了以悬浮态TiO2为催化剂,在H2O2存在的条件下,对壬基酚聚氧乙烯醚的光催化降解反应。分别考察了pH值、TiO2和H2O2的加入量、壬基酚聚氧乙烯醚的初始浓度以及光照时间对降解反应的影响。结果表明:在pH值为5,H2O2质量浓度为30mg/L的条件下,对初始质量浓度为50mg/L的壬基酚聚氧乙烯醚溶液光照4h后降解率达46.32%。     

新型润湿剂的合成

以壬基酚聚氧乙烯醚为原料，与顺酐酯化再与亚硫酸氢钠磺化，合成了壬基酚聚氧乙烯醚琥珀酸双酯磺酸钠。酯化反应适宜的反应条件为：n(壬基酚聚氧乙烯醚）：n(顺酐）＝2．7：1．0，酯化反应温度为160℃，酯化时间为6h，压强在1．3－8．0kPa，催化剂用量与顺酐量的质量比为0.04:1.00；磺化反应适宜的反应条件为：n(亚硫酸氢钠）：n(顺酐）＝1．05：1．00，在通氮气的条件下操作，磺化温度为85℃，磺化时间为3．2h。所得产品润湿力在10s左右。     

光催化降解壬基酚聚氯乙烯醚的研究

研究了以悬浮态TiO2为催化剂，在H2O2存在的条件下，对壬基酚聚氧乙烯醚的光催化降解反应。分别考察了pH值、TiO2和H2O2的加入量、壬基酚聚氧乙烯醚的初始浓度以及光照时间对降解反应的影响。结果表明：在pH值为5，H2O2质量浓度为30mg／L的条件下，对初始质量浓度为50mg／L的壬基酚聚氧乙烯醚溶液光照4h后降解率达46．32％。     

附着态TiO2光催化降解壬基酚聚氧乙烯醚的研究

采用Sol-Gel法制备TiO2薄膜.以该薄膜为催化剂,研究了在H2O2存在的条件下,对内分泌干扰物质壬基酚聚氧乙烯醚的光催化降解反应.分别讨论了pH值、H2O2的加入量、壬基酚聚氧乙烯醚的初始浓度、光照时间对降解反应的影响.结果表明在pH=5、30 mg·L-1的H2O2中对初始浓度为50 mg·L-1的壬基酚聚氧乙烯醚溶液光照4 h,有较好的降解效果.     

Refractive index of alcohol nonionics

Refractive index is a rapid and consistent method of analysis for alcohols and nonionics from normal alcohols and ethylene oxide. Correlations of refractive index with hydroxyl number of alcohols and nonionics are excellent and measurement error is considerably lower for refractive index. Refractive index affords a measurement of the amount of ethylene oxide in nonionics and can be used as a replacement for the 1% cloud point analysis. The ethylene oxide adduct distribution has no effect on refractive index. Specific adducts, a narrow range of adducts made by acid catalyzed ethoxylation and a broad range of adducts made by base catalyzed ethoxylation give the same refractive index value for any given ethylene oxide content. Applications for the refractive index method for the laboratory and plant are: alcohol blending control, calculation of ethylene oxide requirements for ethoxylation, nonionic control analysis, calculations of hydroxyl number for sulfations. Also, refractive index can help identify laboratory samples, indicate the 1% cloud point and predict the phase character of nonionics.     

苯酚乙氧基化反应的工艺研究

研究用乙酸钙为催化剂的苯酚乙氧基化反应，着重考察了催化剂用量、反应压力等因素对产物相对分子质量分布的影响。与传统催化剂氢氧化钠相比，用乙酸钙为催化剂，其反应的相对选择性指标Q值提高了60％，表明产物的相对分子质量分布比用氢氧化钠的要窄得多。     

窄分布吐温—80的合成研究

通过对几种碱金属、碱土金属盐催化剂的考察,研究了斯本－８０的乙氧基化反应,筛选出ＤＦ－１型新型催化剂。以该催化剂为重点,对其催化活性、反应影响因素等作了深入的考察。ＤＦ－１型乙氧基化催化剂不但具有催化活性较好,产物分子量分布较窄,色泽较浅等特点,而且在合成工艺上与传统生产工艺相比,具有操作简单的优点,可望在工业生产上获得广泛的应用。     

Ethoxylation of fatty amines

It is well known that long chain alcohols and phenols cannot react with ethylene oxide in the absence of catalysts, whereas primary fatty amines can take up at least two moles of oxide to form tertiary amines. It has been found that further ethoxylation of this two mole adduct in the absence of added catalyst can proceed only if ethoxylation temperatures are lowered considerably. The present paper demonstrates that this low-temperature ethoxylation is really catalyzed by a previously overlooked highly alkaline compound generated during the course of the reaction. It is shown that this is a long-chain quaternary ammonium compound, and the mechanism of its formation is described. As the addition of ethylene oxide proceeds, this quaternary gradually decomposes and the reaction essentially comes to a halt when it has all disappeared.     

CH3OK催化乙氧基化反应合成异十三醇聚氧乙烯醚-7的研究

以异十三醇和环氧乙烷为原料,经CH3OK催化乙氧基化反应合成异十三醇聚氧乙烯醚-7(简称E1307),以解决目前宽分布产品的低温透明度和润湿力不敌窄分布产品的问题。并考察了碱催化乙氧基化反应参数对E1307品质,特别是对最低透明温度和润湿力的影响,结果表明,原料水分残留量和催化剂用量对产品品质的影响较大。异十三醇在100 oC下抽真空除水分1 h,用异十三醇质量0.3%的CH3OK催化剂在0.3 MPa和120 oC下进行乙氧基化反应,得到E1307的最低透明温度为10 oC,润湿力为163 s,品质好于目前市售窄分布产品。     

Determination of molar mass distribution of alkyl polyethylene glycol ethers

A process based on gas chromatographic separation and on the computerized evaluation of the results has been developed for the determination of the distribution and distribution coefficients of alkyl polyglycol ethers, formed in the competitive, consecutive reaction of fatty alcohol and ethylene oxide. A comparison of experimental and theoretical distributions showed that the distribution is the Weibull-Nycander-Gold type for potassium hydroxide catalyst, and the Flory type in the antimony pentachloride catalyst. The characteristic of the distribution does not change with reaction parameters in either type of distribution, though actual distribution is slightly modified by temperature. In determinations of Weibull-Nycander-Gold's c and Natta-Mantica's c_i-s distribution coefficients, the Weibull-Törnquist effect, i.e., the changing of the distribution coefficients with ethoxylation, has been experimentally proven in the example of ethoxylation catalyzed with potassium hydroxide.     

Component distribution of alcohol ethylene oxide adducts

The relative reaction constants for the base-catalyzed ethoxylation of primary straight chain alcohols have been determined for the unreacted alcohol and the first three ethylene oxide adducts. The distribution of the ethoxylates was found using molecular distillation, nuclear magnetic resonance analysis and gas liquid partition chromatography. A mathematical model describing the distributions was set up and programmed on a 7090 digital computer. Solution of the program gave the relative reaction constants for the alcohol and the first three adducts. The relative reactivities of the adducts in the base-catalyzed ethoxylation of primary straight chain alcohols are shown to increase with adduct number, but tend to a constant value as the adduct number increases. Results also show that alcohols from C₆ to C₁₈ are equally reactive to ethylene oxide on a molar basis.     

复合型碱土金属乙氧基化窄分布催化剂及其性能研究

研制出复合型碱土金属乙氧基化催化剂（简称ＦＨ型）。通过辛基酚和月桂醇的乙氧基化反应考察了其催化活性和产品的分子量分布。结果表明，这种催化剂的催化活性高，合成乙氧基化产物分子量分布窄，色泽好。     

The prediction of ethylene oxide distributions in mixed alcohol ethoxylates

Supercritical fluid Chromatographic analyses of ethoxylates of 2- ethylhexanol in the pure state and in mixtures were used to determine relative propagation- to- initiation ethoxylation rate constants. Earlier work with normal octanol was verified in that ethylene oxide distributions were found to be unaffected by the presence of other alcohols in the ethoxylation of mixed alcohols. An apparent decrease in the relative ethoxylation rates with increasing number of ethylene oxide monomers in ethoxylates is attributed to truncation of the measured distributions and is eliminated by adding small amounts of higher ethoxylates to the distribution. The Weibull- Tornquist effect of decreasing relative rate constants as the overall average ethylene oxide- to- alcohol ratio increases was again observed. Rate constants of the ethoxylation of 2- ethylhexanol and its ethylene oxide adducts relative to the ethoxylation of normal octanol were determined from the analysis of ethoxylates of their mixtures. A computer model using averaged relative rate constants was developed that effectively predicts the ethylene oxide distributions in ethoxylates of alcohol mixtures. To whom correspondence should be addressed at Exxon Chemical Company, Intermediates Technology Division, P.O. Box 241, Baton Rouge, LA 70821     

Influence of catalyst structure on direct ethoxylation of fatty methyl esters over Al-Mg composite oxide catalyst

During direct ethoxylation of fatty methyl ester over Al-Mg composite oxide catalyst, the activity was nearly proportional to the total number of active Al acidic sites on the catalyst surface per unit weight of catalyst. Lower active Al acidic site densities resulted in a narrower ethylene oxide (EO) adduct distribution of obtained ethoxylate. We developed a new catalyst with a large surface area on which many acidic sites are distributed uniformly by partially poisoning the Al acid sites of high-Al content Al-Mg composite oxide with alkali. This catalyst was used for direct ethoxylation of fatty methyl esters to obtain ethoxylated fatty methyl esters with narrow EO adduct distribution efficiently.