改进型DMC催化剂制聚醚多元醇

用改进型双金属氰化物(DMC)催化剂合成了二官能、三官能聚醚多元醇,考察了催化剂用量、反应温度、反应压力等条件对聚合反应的影响。对小分子起始剂用改进型DMC催化剂直接起始进行了初步探索。     

聚合醇钻井液在水平井钻井中的应用

报道了在聚合物钻井液中加入3％市售聚合醇JCP-1得到的聚合醇钻井液的应用性能和在水平井钻井中的应用。在室内实验研究中发现，加入1％～3％JCP-1的聚合物钻井液，其漏斗粘度、滤失量、塑性粘度和动切力变化很小；在聚合物钻井液中加入3％JCP-1，使100℃滚动16h后页岩回收率由58％升至86％，使80℃下形成的滤饼摩擦系数由0．1降至0．038，摩阻降低63％；使储层岩心渗透率的恢复率由71％增至94％。在42口井水平井段钻井中使用聚合醇钻井液，均未出现钻井事故，这些井投产后有多口井自喷，3口井产油量超过100t／d。详细介绍了永12平4井概况和使用聚合醇钻井液的效果：井具与井壁间摩擦阻力由280kN降至90～110kN；无垮塌摔块现象。井径扩大率仅6．68％；地层渗透率恢复率由71．2％(聚合物钻井液，-1340m处)升至84．0％(-1560m)和87．0％(-1840m，水平段)。该井投产后产量是邻近直井的9倍。表2参3。     

钨基催化剂体系下甲醇开环环氧大豆油制备多元醇

以环氧大豆油和甲醇为原料,通过开环加成制备植物油基多元醇。在自制的二氯二氧化钨(WO2Cl2)作催化剂、三氟甲磺酸银(Ag OTf)作助催化剂的条件下,考察了催化剂用量、助催化剂用量、反应时间、温度和醇油物质的量比等对环氧大豆油开环转化率的影响,并对产物的环氧值进行了测试。结果表明,当催化剂用量为3%(以甲醇和环氧大豆油总质量为基准,下同),三氟甲磺酸银用量为4%,反应温度为70℃,反应时间为8 h,醇油物质的量比为28∶1时,环氧大豆油的开环转化率较高,为89.13%。对开环产物进行了FTIR、1HNMR、TG以及流变性分析。通过热重分析得出,多元醇的分解温度(334℃)比环氧大豆油的分解温度(305℃)高。流变性分析得出,随着温度的升高,环氧大豆油和多元醇的黏度逐渐下降。在温度较低时,大豆油多元醇的黏度明显低于环氧大豆油的黏度。     

Bio‐Based,Self‐Condensed Polyols

A new method for the synthesis of high‐molar‐mass (MM), bio‐based polyols for elastic polyurethanes is developed. This process is based on the self‐condensation of low MM polyols (M_n ≈ 1000) and vacuum removal of the resulting glycerol. Self‐condensation products are hyperbranched estolide polyols with average MMs close to 3000 and hydroxyl numbers in the range of 40–95 mg KOH g^?1. Three polyols, one with primary and two with secondary hydroxyls and different functionalities, are studied. The transesterification proceeded much faster with primary hydroxyls, leading to high‐viscosity products. The effect of functionality and reactivity of starting polyols on properties is discussed. Practical applications: The process is useful for upgrading the existing natural oil‐based polyols to higher MM, lower OH number and variable‐functionality polyols, for expanding application in the urethane field. The process is simple, involving just an oil‐based polyol, a catalyst, and heating under vacuum.     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料，成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP），用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性，氮气气氛下的初始分解温度为191.9℃，700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%，最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²，总产烟量从10.5 m²下降到5.3 m²。     

A physical method for preservation of cosmetic products

To date, the microbiological stability of cosmetics products is assured by means of chemical preservatives, with well-known possible side effects such as irritation or cutaneous allergic events. This paper describes a new concept to protect all types of cosmetic formulae from microbiological contamination: the osmotic effect of a particular form of glycerylpolyacrylate gels. The latter allows the formulator to conceive numerous preservative-free formulae. The basis of its activity lies in the strong osmotic properties of the hydrogel: it absorbs water from its surroundings, thus depriving germs of the vital aqueous environment needed for survival. Challenge tests on various microorganisms, repeat insult challenges and time-stability tests performed on these hydrogels in cosmetic formulas were carried out. At the same time, the hydrogel exhibited high skin moisturizing power. The hydrogel is non-toxic and non-irritant as the Primary Cutaneous Irritation Index observed after 48 h of occlusive patches in 10 adult volunteers is only of 0.10.     

聚醚多元醇新型催化剂的技术经济分析

概述了聚醚多元醇新型催化剂的研制背景 ,描述了新技术的创新点及优势 ,对年产 5 0t新型催化剂装置进行了经济分析     

Oligomeric Composition of Polyols From Fatty Acid Methyl Ester: The Effect of Ring‐Opening Reactants of Epoxide Groups

Commercial availability of fatty acid methyl ester (FAME) from palm oil targeted for biodiesel offers a good feedstock for the production of structurally well‐defined polyols for polyurethane applications. The effect of molecular weight (MW), odd and even carbon numbers, and the linear and branched structure reactants used in the ring‐opening reaction of epoxidized fatty acid methyl ester (E‐FAME) on the properties of polyols was investigated. Conversions of E‐FAME to PolyFAME polyols were confirmed by Fourier transform infrared analysis, oxirane oxygen content, and hydroxyl number. Gel permeation chromatography (GPC) calibrated against polyether polyols as a standard and vapor pressure osmometry were used for MW determination. GPC chromatograms of PolyFAME polyols clearly demonstrated the formation of oligomers during ring‐opening reactions. MW, and odd and even carbon numbers in a structure of linear diols and branched diol used in the syntheses of PolyFAME polyols did not have an effect on crystallinity, glass transition, or melt temperatures measured using Differential scanning calorimetry (DSC). PolyFAME polyols ring‐opened with water, methanol, and 1,2‐propanediol contained secondary hydroxyl groups, whereas PolyFAME polyols ring‐opened with linear diols contained a mixture of primary and secondary hydroxyl groups. It was found that the concentration of primary hydroxyl groups increased significantly by increasing the number of carbons from C2 to C3 in the linear diols. The viscosity of PolyFAME polyols also increased with the MW of linear diols used in the E‐FAME ring‐opening reaction. These findings would be beneficial for formulators in choosing the most cost effective polyols for polyurethane formulations.     

膜分离法精制低不饱和度聚醚多元醇

采用聚醚砜超滤膜对ZSN-330低不饱和度聚醚多元醇进行精制,粗聚醚多元醇由正己烷1∶1体积比稀释,精制效果很好,大部分检测时间下锌、钴离子截留率高达90%以上,含量低于1 mg/g。采用红外分析并验证了截留物中含有双金属氰化络合物催化剂（DMC）成分。考察了膜截留分子量、料液黏度、操作压力、料液流速等对膜通量的影响,确定了较佳的超滤条件为膜截留分子量为150 kDa、由正己烷1∶1稀释、操作压力0.5 MPa、料液流速40 L/h。分别采用去离子水、2‰氢氧化钠溶液、正己烷溶剂超声清洗污染的膜,2‰氢氧化钠溶液的清洗效果较好,膜通量恢复率达66.4%。     

纤维素选择性催化转化为重要平台化合物的研究进展

纤维素是自然界中最丰富的植物生物质组分,拓宽纤维素的利用对于减少化石资源使用和可持续发展非常重要。本文综述了以纤维素为原料,通过化学催化转化得到平台化合物葡萄糖、羟甲基糠醛、乙酰丙酸、多元醇的方法,包括离子液体催化、固体酸催化和贵金属催化加氢等,以及上述平台化合物后续转化的途径。如羟甲基糠醛的氧化与还原,乙酰丙酸制备γ-戊内酯、烃、1,4-戊二醇和甲基四氢呋喃,以及多元醇催化重整制备液体燃料。提出纤维素催化制备平台化合物的研究成果将为可再生资源替代化石资源的可持续发展提供有力的理论支持和实践指导。