高羟值大豆油多元醇的合成与表征

以环氧大豆油(ESO)、异丙醇为主要原料合成了高羟值大豆油多元醇.讨论了水和催化剂用量等因素对合成反应的影响,并对反应产物进行了红外(IR)及核磁共振氢谱(1H-NMR)分析.结果表明,水的用量为50 g、催化剂的质量分数为0.75%时,大豆油多元醇的羟值相对较高,达到266.3 mgKOH/g,粘度为33500 mPa·s;同时推测了产物的基本结构.     

废弃大豆油环氧改性制备多元醇及其表征分析

传统大豆油多元醇的合成具有反应温度高、时间久、需要添加溶剂等缺点。为了使其合成方法简单易行、节能环保,对传统多元醇合成方法进行了优化改进。以废弃大豆油(SBO)自制的环氧大豆油(ESO)为主体,以异丙醇、正丁醇、正戊醇3种一元醇为原料,四氟硼酸(HBF4)为催化剂,在室温下,不添加水和其他溶剂,通过开环反应快速生成3种羟值不同的环氧大豆油多元醇低聚物。利用傅里叶红外光谱、差示扫描量热法、热重分析法、核磁共振氢谱等对聚合产物进行表征,并对产物结构和性质进行分析。结果表明,无需添加溶剂,室温下环氧大豆油开环聚合,反应时间不超过1 min,产物羟值达406 mg/(KOH) g,环氧大豆油转化率达95. 5%。     

聚氨酯用高羟值大豆油多元醇的合成与表征

本文以大豆油为原料,采用过氧甲酸氧化法制备了高环氧值环氧大豆油(ESO);以氢氧化锂为催化剂,并通过三羟甲基丙烷对其开环合成了高羟值的大豆油多元醇(TESO),研究了反应温度、反应时间对反应进程的影响。用傅里叶红外光谱及1HNMR对其进行表征,结果表明在在190℃下反应4h可以得到高羟基的大豆油多元醇。     

响应面法优化乌桕梓油多元醇合成工艺

以环氧乌桕梓油、甲醇、水为原料,以氟硼酸为催化剂,对环氧乌桕梓油进行醇解开环合成乌桕梓油多元醇工艺进行了研究。结果表明,最佳工艺参数为:催化剂用量0.3%,甲醇环氧基摩尔比12.9∶1,醇水摩尔比4.3∶1,转速200 r/min,反应时间73 min,反应温度73℃。在此条件下,乌桕梓油多元醇羟值为212.67 mgKOH/g,转化率达96.5%。     

小桐子油脂肪酸聚酯多元醇及聚氨酯泡沫的制备和性能

研究了脂肪酸环氧-开环-酯化三步反应制备聚酯多元醇,比较了3种不同碘值的脂肪酸原料制备的聚酯多元醇及其聚氨酯泡沫（PUF）性能。脂肪酸碘值越高多元醇的羟值也越高：1#、2#和3#聚酯多元醇羟值分别为：261.47 mgKOH/g、370.28 mgKOH/g和434.49 mgKOH/g。3种多元醇的相对分子量为600～2000。3种泡沫的压缩和弯曲性能与泡沫密度成正比。泡沫SEM分析显示：羟值较高的多元醇泡沫2#和3#泡沫孔结构较规则,以正五边形和正六边形居多;1#泡沫泡孔不规则,易变形。对3种泡沫的TG-DSC、DTG分析结果表明：3种泡沫的热分解温度都约为300 ℃,具有较好热稳定性。     

磁性固体酸催化制备高羟值植物油基多元醇

以ZrOCl_2·8H_2O和纳米Fe_3O_4为原料,用共沉淀法制备了ZrO_2/Fe_3O_4载体,并以浸渍法将SO_4~(2–)负载于ZrO_2/Fe_3O_4载体上作为活性中心,制得SO_4~(2–)/ZrO_2/Fe_3O_4催化剂。利用FTIR、EDS、XRD等对催化剂的组成、结构、表面酸性、磁性能进行了表征。将此磁性固体酸催化剂应用于甘油作为开环剂的环氧大豆油制备多元醇反应体系中,考察了催化剂用量、温度、反应时间等对开环转化率及产物羟值的影响。结果表明,最佳反应条件为:催化剂用量为环氧大豆油质量的1%,反应温度80℃,反应时间6 h。在该条件下环氧大豆油开环转化率达99%,产物羟值达365 mg KOH/g。     

可再生聚酯多元醇的合成及其在聚氨酯材料中的应用

采用油酸为主要原料合成了羟值为236mgKOH／g、酸值为2．8mgKOH／g的可再生聚酯多元醇,并以此聚酯多元醇为原料制备了聚氨酯硬质泡沫。研究了该聚酯多元醇用量对泡沫发泡和力学性能的影响。结果表明,随着聚酯多元醇加入量的增加,形成聚氨酯硬质泡沫的反应速度增加;与纯聚醚多元醇制备的聚氨酯硬质泡沫相比,加入20％～30％的该聚酯多元醇制备的聚氨酯泡沫的尺寸稳定性和压缩强度增加。     

大豆油-油酸多元醇改性聚氨酯胶黏剂的合成及性能

以环氧大豆油(ESBO)、改性油酸为原料,在无溶剂无催化剂的条件下,通过开环反应合成了环氧大豆油-油酸多元醇(P-OA-ESBO),通过红外(FTIR)和核磁(1HNMR)对环氧大豆油-油酸多元醇(P-OA-ESBO)的结构进行了表征。然后以P-OA-ESBO、异氟尔酮二异氰酸酯(IPDI)为原料,以绿色可再生的甘油为扩链剂,在无催化剂条件下合成了环保型包装用聚氨酯胶黏剂,不使用传统的石油类多元醇和有机锡类催化剂。利用热重分析(TGA)、差示扫描量热法(DSC)、拉伸力学性能测试、PE/OPP复合膜的剥离强度测试及剪切强度测试考察了不同R(NCO/OH)比聚氨酯胶黏剂涂膜的耐热、机械和粘接性能。结果表明,大豆油-油酸多元醇成功改性聚氨酯胶黏剂。当R值为1.3~1.5时合成的聚氨酯胶黏剂的力学拉伸和剪切能较好,R值在1.7时合成的聚氨酯胶黏剂剥离强度较优异,可满足PE/OPP膜的基本复合要求。     

绿色增塑剂环氧大豆油的合成与表征

用自制的催化剂合成了一种环氧大豆油。通过L16(45)正交试验考察了双氧水用量、催化剂用量、反应时间和反应温度对环氧大豆油环氧值的影响。结果表明:在双氧水用量100份、催化剂用量0.5份(大豆油用量定为100份)、反应温度50℃、反应时间12.5 h的最佳工艺条件下,产品的环氧值为6.58%,碘值为0.83 gI/100g。产品通过红外和核磁共振表征,确定大豆油被环氧化生成环氧大豆油。     

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。     

Network structure and properties of polyurethanes from soybean oil

Vegetable oils are very heterogeneous materials with a wide distribution of triacylglycerol structures and double‐bond contents. The hydrogenation of epoxidized soybean oil (ESO) produces polyols having a functionality distribution related to that of soybean oil. Therefore, these polyols are convenient substances for studying the impact of structural heterogeneity on network formation and properties. Polyols of hydroxyl numbers ranging from 225 to 82 mg KOH/g and weight‐average functionalities ranging from 4.4 to 2.7 were obtained by the variation of the time of hydrogenation of ESO. An analysis of the functionality distribution in polyols shows that gel points with diisocyanates vary from 54 to 76% conversion. The molecular weights of the network chains of polyurethanes prepared from these polyols and diphenyl methane diisocyanate varied from 688 to 1993. Polyols with hydroxyl numbers above 200 mg KOH/g gave glassy polymers, whereas those below that value gave rubbers. The heterogeneity of polyols had a negative effect on the elastic properties only at low crosslinking densities. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and Characterization of the Different Soy-Based Polyols by Ring Opening of Epoxidized Soybean Oil with Methanol, 1,2-Ethanediol and 1,2-Propanediol

Three soy-based polyols intended for application in polyurethanes were prepared by ring opening the epoxy groups in epoxidized soybean oil (ESO, 0.385 mol/100 g epoxy rings) with methanol, 1,2-ethanediol and 1,2-propanediol in the presence of tetrafluoroboric acid catalyst. The effect of the different opening reaction reagents, different low molecular weight alcohols, on the polyols was investigated by spectroscopic, chemical and physical methods. The viscosities, viscous-flow activation energies, molecular weight and melting point of the samples increased in the following order: polyol (3) > polyol (2) > polyol (1) > ESO [polyol (1); polyol (2) and polyol (3) represented the samples synthesized from the same epoxidized soybean oil generated by opening reactions with methanol, 1,2-ethanediol and 1,2-propanediol, respectively]. All the samples were crystalline solids below their melting temperature, displaying multiple melting point peaks. Compared with polyol (1), polyol (2) had a primary hydroxyl group, promoting the reactive activity of the polyol with isocyanates; polyol (3) contained large numbers of hydroxy groups, improving the properties of polyurethanes.     

Thermal and mechanical properties of cast polyurethane resin based on soybean oil

The soy polyols were prepared from epoxidation of soybean oil followed by ring opening of oxirane obtained by using methanol as the ring opener. Polyols of hydroxyl (OH) numbers ranging from 128 to 174 mg of KOH/g were obtained by the variation of epoxidation time of soybean oil. A novel cast polyurethane resin has been synthesized by these polyols and 2,4‐toluene diisocyanate. Swelling of networks in toluene showed that the sol fraction varies from 1.13 to 72.06%. The thermal and mechanical properties of cast resins were characterized by differential scanning calorimetry and thermogravimetric analysis. The results showed that the glass transition temperature increases with the increase of OH number and that the thermal stability of the resins was slightly decreased with the increasing OH number. The tensile strength at break increases with the increase of OH number. Polyols with OH number of 174 mg of KOH/g gave glassy polymers, whereas those below this value gave rubbers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Di-Hydroxylated Soybean Oil Polyols with Varied Hydroxyl Values and Their Influence on UV-Curable Pressure-Sensitive Adhesives

Di-hydroxylated soybean oil (DSO) polyols with three different hydroxyl values (OHV) of 160, 240, and 285 mg KOH/g were synthesized from epoxidized soybean oils (ESO) by oxirane cleavage with water catalyzed by perchloric acid. The DSO were clear, viscous liquids at room temperature. The structure and physical properties of DSO were characterized using titration methods, Fourier-transform infrared spectroscopy (FTIR), gel permeation chromatography, rheometer, differential scanning calorimetry, and thermogravimetric analysis. The number average molecular weight of DSO160, DSO240, and DSO285 were 1,412, 1,781, and 1,899 g/mol, respectively, indicating that oligomerization occurred during DSO synthesis, which was further confirmed by FTIR. All DSO polyols exhibited non-Newtonian, shear thinning behavior. DSO with higher OHV were more viscous than those with lower OHV. All DSO were thermally stable up to 380 °C. These three DSO were formulated into pressure-sensitive adhesives (PSA) by copolymerizing with ESO using UV curing. The peel adhesion strength of the PSA was significantly affected by the OHV of DSO and DSO content. Maximal PSA adhesion strength of 4.6 N/inch was obtained with DSO285 and a DSO/ESO weight ratio of 0.75.     

竹屑常压酸催化液化产物的制备与表征

在常压酸催化作用下对竹屑进行多元醇液化,对液化产物的羟值和粘度进行了测定,并通过红外光谱、凝胶渗透色谱及GC-MS等对液化产物进行分析表征。结果表明:液化产物的羟值为350mgKOH/g,粘度为750mPa·s,相对分子质量分布范围在18~20 372之间,为连续分布形式,满足制备中强度硬质聚氨酯泡沫的要求。     

Oxirane Cleavage Kinetics of Epoxidized Soybean Oil by Water and UV‐Polymerized Resin Adhesion Properties

Di‐hydroxylated soybean oil (DSO), a biobased polyol synthesized from epoxidized soybean oil (ESO) could be used to formulate resins for adhesives; however, current DSO synthesis requires harsh reaction conditions that significantly increase both cost and waste generation. In this paper, we investigate the kinetics of oxirane cleavage in ESO to DSO by water and elucidate the role of different process parameters in the reaction rate and optimization of reaction conditions. Our kinetic study showed that ESO oxirane cleavage was a first‐order reaction and that the ESO oxirane cleavage rate was greatly influenced by tetrahydrofuran (THF)/ESO ratio, H₂O/ESO ratio, catalyst content, and temperature. Optimized reaction parameters were THF/ESO of 0.5, H₂O/ESO of 0.25, catalyst content of 1.5 %, and reaction time of 3 h at 25 °C. DSO with hydroxyl value of 242 mg KOH/g was obtained under these conditions. We also characterized the structure, thermal properties, adhesion performance, and viscoelasticity of UV‐polymerized resins based on this DSO. The resin tape exhibited peel adhesion strength of 3.6 N/in., which is comparable to some commercial tapes measured under similar conditions.     

Polyols and polyurethanes prepared from epoxidized soybean oil ring‐opened by polyhydroxy fatty acids with varying OH numbers

Bio‐based polyols from epoxidized soybean oil and different fatty acids were successfully prepared using a solvent‐free method in order to investigate the effect of the polyols' OH numbers on the thermal and mechanical properties of the polyurethanes prepared using them. Epoxidized soybean oil/epoxidized linseed oil was ring‐opened by methanol/glycol followed by saponification to prepare polyhydroxy fatty acids. These fatty acids and epoxidized soybean oil were then used for further solvent‐free ring‐opening reactions with DBU as catalyst, which facilitated the carboxylic ring‐opening. Gel permeation chromatography revealed that a molar ratio of carboxylic acid from polyhydroxy fatty aicds and epoxy group of 0.5 : 1 resulted in optimized polyols containing the smallest amounts of residual starting materials. The obtained polyols had varying OH numbers and the acquired polyurethane films were comprehensively characterized. With increasing OH number of the polyols the PUs displayed an increase in crosslinking density, glass transition temperature (T_g), tensile strength and Young's modulus, and a decrease in elongation and toughness. This work provides Supporting Information on the effect of OH number of polyols obtained via a solvent‐free ring‐opening method on the mechanical and thermal properties of polyurethanes, of particular interest when designing PU products for specific purposes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41213.     

低不饱和度高活性聚醚多元醇的研制

使用双金属氰化物络合催化剂,首先制备了低不饱和度高相对分子质量聚氧化丙烯多元醇,再采用碱金属化合物催化剂,用环氧乙烷封端,制得高活性聚醚多元醇,所得聚醚二醇及聚醚三醇的羟值约为26mgKOH/g,不饱和度约0.007mmol/g,伯羟基摩尔分数大于85％。     

Thermal and mechanical properties of acrylated expoxidized‐soybean oil‐based thermosets

A series of epoxidized‐soybean oil (ESO) with different epoxyl content were synthesized by in situ epoxidation of soybean oil (SBO). The acrylated epoxidized‐soybean oil (AESO) was obtained by the reaction of ring opening of ESO using acrylic acid as ring opener. The acrylated expoxidized‐soybean oil‐based thermosets have been synthesized by bulk radical polymerization of these AESOs and styrene. The thermal properties of the resins were characterized by differential scanning calorimetry (DSC) and thermo‐gravimetric analysis (TG). The results showed that these resins possess high thermal stability. There were two glass transition temperature of each resin due to the triglycerides structure of the resins. The tensile strength and impact strength of the resins were also recorded, and the tensile strength and impact strength increased as the iodine value of ESO decreased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010