Biodegradable surfactants derived from corn starch

Polyol glucosides, prepared by reacting corn starch with ethylene glycol or glycerol, were used to make biodegradable surfactants. The hydroxyl sites of the glycosides were first partially polyalkoxylated with ethylene oxide or a mixture of ethylene and propylene oxides. The resulting derivatives then were reacted with various long chain epoxides or fatty esters. A good hydrophilic-lipophilic balance in these products was achieved by controlling the number of alkoxide and aliphatic groups/anhydroglucose unit. Surface active properties of these products were destroyed rapidly by the bacteria of an activated sludge. This excellent biodegradability property was attributed to the presence of the glycoside unit.     

Polyoxyethylene ethers of some polyol glycosides and their fatty esters

Starch heated with a polyol, such as ethylene glycol, propylene glycol, or glycerol, in the presence of an acid catalyst undergoes transglycosidation and forms a mixture of polyol glycosides. This mixture is sufficiently heat-stable to permit polyetherification with ethylene oxide. The preparation and properties of a number of glycoside polyoxyethylene ethers are described. Nonionic emulsifying agents were prepared by reacting glycoside polyethers with either saturated or unsaturated long-chain fatty acids and linseed oil. In general, the esterified glycoside polyethers exhibited good emulsifying action, and the unsaturated esters of the polyethers possessed film-forming properties. Presented at the AOCS meeting in New Orleans, La., 1962. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Preparation of detergents from formaldehyde

A process was developed for condensing different mol ratios of dodecanol, formaldehyde and ethylene oxide to form a series of adducts with useful detergent properties. These products are analogous to the commercially important class of nonionic surfactants produced by treating fatty alcohols with ethylene oxide to produce a homologous series of adducts. The structures were shown to be represented by RO[(CH₂O)_x(CH₂CH₂O)_y]R where R is either dodecyl or hydrogen, x and y are integers (including zero), and it is understood that the oxymethylene and oxyethylene groups are intermingled in the ether chains. Unfortunately, we were unable to produce commercially viable detergent compositions. For these, our calculations indicate that a dodecanol:HCHO:EO mol ratio between 1:3:4 and 1:5:2 would be necessary both for good detergency and good economics. With acidic catalysts such as BF₃, the condensation is facile and product with desired overall mol ratios can be produced. However, much of the formaldehyde and ethylene oxide are incorporated into by-products that either detract from the detergency properties (e.g., terminal ethers where both R groups are dodecyl) or make the mixtures unacceptable as detergents (e.g., 1,4-dioxane). Because of the presence of terminal ethers, the detergent properties are similar to those of propylene oxide adducts rather than ethylene oxide adducts. With selected basic catalysts most of the harmful by-products can be eliminated, but the reaction rates and conversions are unsatisfactory. Basic catalysts that give high reaction rates convert most of the formaldehyde fed to methyl formate.     

Supercritical fluid chromatographic analysis of the propoxylated glycerol esters of oleic acid

Capillary supercritical fluid chromatographic methods were developed for the separation and quantitation of oligomers of propoxylated glycerols and fatty acid-esterified propoxylated glycerols. Samples containing mole ratios (propylene oxide to glycerol) of 5, 8 and 14 were chromatographed. Separations depended primarily upon the molecular weight or the number of the propylene oxide units. The oligomer distributions in the propoxylated glycerol and the oleic acid-esterified propoxylated glycerol samples were determined.     

Preparation of block copolymers with polymeric azocarbamate as an initiator

Block copolymers containing polystyrene and poly(ethylene oxide) or poly(propylene oxide) segments were prepared via chemical reactions. A stepwise procedure was first employed to prepare macroazocarbamates by capping poly(ethylene oxide) glycols or poly(propylene oxide) glycols and an aliphatic diisocyanate and subsequently by reacting this intermediate with an azobisalcohol. This macroazocarbamate was later used to initiate free radical polymerization at elevated temperatures. Styrene contents, molecular weights, and elastic modulus-temperature relationships were determined.     

涤纶POY油剂单体的合成及性能研究

以碳酸二乙酯为原料,与丙二醇聚醚反应,合成了低级聚碳酸酯,再用自制的不同脂肪醇聚氧乙烯醚封端,合成了改性聚碳酸酯;将改性聚碳酸酯与其他单体复配,配制成涤纶POY油剂,考察脂肪醇聚氧乙烯醚的起始剂、环氧乙烷(EO)与环氧丙烷(PO)加成数,碳酸二乙酯与丙二醇聚醚的摩尔比对POY油剂性能的影响。结果表明:使用辛醇为起始剂,与EO按摩尔比1:8缩合合成脂肪醇聚氧乙烯醚,1,2-丙二醇与PO按摩尔比1:8缩合合成丙二醇聚醚,碳酸二乙酯与丙二醇聚醚按摩尔比4:3缩合成低级聚碳酸酯,低级聚碳酸酯与脂肪醇聚氧乙烯醚按摩尔比1:1合成的改性聚碳酸酯作为单体复配的涤纶POY油剂,其润湿性能、热性能较好,表面张力较高。     

Ethoxylated glycerol and propylene glycol glycoside palmitates from lactose

Polyoxyethylene polyol glycoside palmitates were prepared by the following successive reactions: transglycosylation of lactose by glycerol and propylene glycol to yield crude mixtures of the polyol glucosides and galactosides; alkoxylation with ethylene oxide; and tranesterfication by methyl palmitate. Almost all the solid waxy products exhibited low surface and interfacial tensions and good emulsion stability; they are expected to be effective food emulsifiers, cosmetic surfactants and biodegradable industrial surfactants. ARS, USDA.     

Effect of the degree of soft and hard segment ordering on the morphology and mechanical behavior of semicrystalline segmented polyurethanes

The hierarchical microstructure responsible for the unique energy-absorbing properties of natural materials, like native spider silk and wood, motivated the development of segmented polyurethanes with soft segments containing multiple levels of order. As a first step in correlating the effects of crystallinity in the soft segment phase to the hard segment phase, we chose to examine the morphology and mechanical behavior of polyurethanes containing polyether soft blocks with varying tendencies to crystallize and phase segregate and the evolution of the microstructure with deformation. A series of high molecular weight polyurethanes containing poly(ethylene oxide) (PEO) (1000 and 4600 g/mol) and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) (1900 g/mol) soft segments with varying hard segment content were synthesized using a two-step solution polymerization method. The presence of soft segment crystallinity (PEO 1000 g/mol) was shown to improve the storage modulus of the segmented polyurethanes below the T_m of the soft block and to enhance toughness compared to the PEO-PPO-PEO soft segment polyurethanes. We postulate that this enhancement in mechanical behavior is the result of crystalline soft regions that serve as an additional load-bearing component during deformation. Morphological characterization also revealed that the microstructure of the segmented polyurethanes shifts from soft segment continuous to interconnected and/or hard domain continuous with increasing hard segment size, resulting in diminished ultimate elongation, but enhanced initial moduli and tensile strengths. Tuning the soft segment phase crystallinity may ultimately lead to tougher polyurethane fibers.     

便携式气相色谱法快速测定空气中的环氧乙烷和环氧丙烷

建立一种利用便携式气相色谱仪快速测定空气中环氧乙烷和环氧丙烷的方法,两者能实现完全分离,检出限分别为0.6 mg/m^3、0.7 mg/m^3,方法的精密度与准确度较好,且检测结果与实验室常规固定式气相色谱法的检测结果差异无统计学意义（p〉0.05）。该方法经实际应用,效果良好。     

聚酯醚型消泡剂的一步法合成及消泡性能研究

以月桂酸甲酯、环氧乙烷(EO)、环氧丙烷(PO)为原料,MCT-09为催化剂,一步法合成了脂肪酸甲酯无规聚醚(FMERP)聚酯醚型消泡剂.反应条件优化为:反应温度195～200 ℃,压强0.3～0.4 MPa,搅拌速率600 r/min,催化剂用量6.05 g Cat./mol脂肪酸甲酯.通过红外光谱(IR)、核磁共振谱图(1HNMR、13CNMR)对产品进行了表征,结果表明所合成的产品为目标产物.产品与市场聚醚消泡剂L-61进行了比较,表明FMERP的消泡和抑泡性能比L-61好,消泡效率和抑泡效率最高分别达到72.2%和61.1%.     

Fine polystyrene latexes with reactive poly(ethylene oxide) –poly(propylene oxide)–poly(ethylene oxide) triblock macrosurfactants in modified miniemulsion polymerization

Polystyrene latexes were produced via a newly accessible miniemulsion polymerization where reactive poly(ethylene oxide)–poly(propylene oxide) –poly(ethylene oxide) triblock macrosurfactants were used to impart the interfacial activity during the emulsification and the reactivity in the polymerization. Through atomic force microscopy studies, it was found that the polystyrene latexes produced were extremely small to about 50 nm in a proper experimental condition, and covered richly with poly(ethylene oxide) groups. The polystyrene latexes were expected to have great applicability in the production of structured latex films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 328–332, 2002     

Synthesis of nitrogen-functionalized polyolefins with metallocene/methylaluminoxane catalysts

Summary Thirteen differently substituted long-chain amide- and amine-functional alkenes were synthesised and used as comonomers in zirconocene/methylaluminoxane-catalysed copolymerizations with ethylene and propylene. Characterization of the prepared copolymers showed the formation of functionalized copolymers with isolated comonomer units. The incorporation level of the comonomers ranged from 0.24 to 1.3 mol % with ethylene and from 0.04 to 0.96 mol % with propylene. The molar masses of the copolymers were lower than those of the corresponding homopolymers. End group analysis of the copolymers by NMR suggested that the dominant chain termination mechanism was chain transfer to aluminium. Received: 8 December 2000/Accepted: 12 February 2001     

Die mit Natriumphenolat katalysierte Addition von Äthylenoxid-Propylenoxid-Gemischen an Monophenylmonoalkylenglykole. I. Die Kinetik der Epoxid-Alkohol-Reaktion

Four separate reactions necessary to describe the copolyaddition of ethylene oxide and propylene oxide mixtures to monophenylmonoalkylene glycol with sodium phenoxide as catalyst have been studied kinetically. The rate of reaction for homoaddition of ethylene oxide and propylene oxide at a molar ratio ≥ 1 of epoxide to the corresponding alkylene glycol is proportional to the catalyst concentration. However, for heteroreactions i. e. in case the glycol used as initial OH-component is not of the same nature (as that produced after the first reaction step), the concentration of the initial alcohol also appears in the rate equation.     

Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

Practical and theoretical molecular weights in polyaddition reactions of ethylene and propylene oxide

The addition reactions of ethylene oxide and/or propylene oxide catalyzed by KOH and initiated with compounds containing free hydroxyls are followed by secondary reactions which vary the expected molecular weight. By using ethylene oxide, diols are formed and by using propylene oxide, both diols and unsaturated monofunctional compounds are formed. These products are usually characterized by their hydroxyl number. The average molecular weight is found by taking into consideration the starter functionality only. There are often some behavioral differences among similar products owing to the different quantity and chain length of the secondary products contained therein. The secondary products are analyzed and the quantity of the secondary products were determined from the hydroxyl number values and from the unsaturation of reagents and products. In the case of monofunctional adducts using the calculation method, the results have been experimentally confirmed.     

Lactose- derived surfactants(III): Fatty esters of oxyalkylated lactito

Lactitol was oxyalkylated with propylene or ethylene oxide. The resulting ether-alcohols were transesterified with a series of fatty acid esters in order to produce long chain ether-esters of lactitol. These compounds were found to be more water soluble than related lactitol derivatives prepared by transesterification prior to oxyalkylation. Improved lime soap dispersant requirements (LSDR) and emulsification times were obtained from the new derivatives.     

Oxypropylation of fatty alcohols,and the sulfation products

Reaction of propylene oxide, rather than ethylene oxide, with fatty alcohols, gives a higher yield (50%) of mono-oxyalkylation product because the secondary alcohol formed is less reactive than the primary alcohol formed with ethylene oxide. Rate of further reaction is about half the rate of the parent primary alcohol. Distributuon of propylene oxide reaction products follows the Weibull-Nycander equation. Analysis of reaction products was accomplished by gas-liquid chromatography of the acetylated ether alcohol mixtures. Pure mono-oxypropylated alcohols ROCH₂CHOHCH₃ and in some cases dioxypropylated alcohols R[OCH₂CH(CH₃)]₂OH were separated by fractional distillation. Individual ether alcohols and products with a known average number of oxypropyl groups were sulfated and evaluated in terms of Krafft point, critical micelle concentration, detergency, foam height and lime soap dispersing properties. Incorporation of one oxypropyl group was more effective than the same degree of oxyethylation, and improved solubility with no significant loss in foaming and detergency. Ether alcohol sulfates from propylene oxide are stable to alkaline hydrolysis and nearly equal to the sulfates from ethylene oxide in their stability to acid hydrolysis. Presented at the AOCS Meeting in Cincinnati, 1965. E. Utiliz. Res. Dev. Div., ARS. USDA.     

Nonionic surfactant polarity index determination by inverse gas chromatography

Polyglycol nonionic surfactants are widely used in industrial and consumer products. Two classes of these surfactants, made from selected combinations of 1,2-butylene oxide, propylene oxide and ethylene oxide, were compared to alcohol ethoxylate (AE) and nonyl phenol ethoxylate nonionic surfactants in this study. Polyglycol copolymers consisted of either a polypropylene glycol (PPG) or polybutylene glycol (PBG) central hydrophobe. Ethoxylation of the hydrophobes produced polyethylene glycol hydrophilic blocks. Differences in hydrophobe polarity were determined by inverse gas chromatography (IGC). IGC is a useful analytical method by which the physical and chemical characteristics of a material are studied. The stationary surfactant material under study was coated onto an inert support and used as the packing for the column. A probe mixture, containing simple organic molecules of varying polarity, was injected, and the retention characteristics were measured. The retention characteristics of the standard probe mixture were used to reveal relative polarity information about the stationary surfactant coatings. Polarities of the four hydrophobes were (in decreasing order): PPG, PBG, nonyl phenyl and fatty alkyl. Comparisons were then made between the calculated hydrophile-lipophile balance values and polarity indices of the hydrophobes and their ethoxylates. The effects of hydroxyl groups on polarity were also studied and quantified.     

Graft copolymers of poly(methyl methacrylate) backbone and poly(propylene oxide-b-ethylene oxide) branches

Summary Two mono-functional macromonomers of poly (propylene oxide-b-ethylene oxide) were synthesized by reaction with methacryloyl chloride. The macromonomers have the same molecular weight and ratio of ethylene oxide and propylene oxide sequences. The reactive methacrylate group can be linked to the ethylene oxide (BuPPOPEO) or to the propylene oxide (BuPEOPPO). These macromonomers showed self-gelling in one week even at low temperature and under a dry atmosphere. Graft copolymers were obtained by reaction of these macromonomers with methyl methacrylate upon free-radical initiation and they were characterized by GPC, VPO, IR and ¹H NMR spectra.     

环氧丙烷开环聚合反应的工程研究 (Ⅰ)环氧丙烷开环聚合反应动力学

本文对环氧丙烷在氢氧化钾作催化剂,丙三醇作起始剂条件下的开环聚合动力学问题进行了研究。研究结果表明,聚合反应对催化剂浓度和环氧丙烷浓度,均为一级反应,而与丙三醇浓度无关。