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。     

响应面法优化废旧PET催化醇解工艺

常压下采用催化剂一步醇解废旧聚酯(PET)工艺制备聚酯多元醇,并采用物理发泡方式用该聚酯多元醇制备了硬质聚氨酯泡沫塑料,达到废旧PET的循环利用。以催化醇解得到聚酯多元醇的羟值、酸值和黏度为指标,筛选催化剂用量、醇解剂用量和醇解时间为主要因素,通过响应面法优化得到催化醇解废旧PET的最佳工艺条件,即:质量分数0.3%(占PET的质量,下同)的Sb2O3作为解聚的催化剂、质量分数100%的二甘醇为醇解剂,醇解反应时间为2.5 h,通过实验验证表明该条件可靠,实际得到的聚酯多元醇羟值503.9 mgKOH/g,酸值2.4 mgKOH/g,室温黏度1310 mPa·s,以该聚酯多元醇为原料制备硬质聚氨酯泡沫的导热系数为0.02～0.03 W/(m·K),密度为40～50 kg/m3,表明通过该方法实现废旧PET的循环利用是可行的,并提高了其循环利用价值。     

柠檬酸改性聚酯聚氨酯涂料的研究

以柠檬酸聚酯多元醇作为高固含量聚氨酯涂料的羟基树脂,通过正交试验优选了合成羟基树脂的工艺条件：n油酸：n柠檬酸：N1,4-丁二醇=1．0：1．0：3．5,反应在150～160℃下进行3h,再继续在190—200℃下反应2～3h。讨论了聚酯多元醇的羟值以及-NCO与-OH配比对涂膜性能的影响,当聚酯多元醇的羟值为148mgKOH／g,nNCO：nOH=1：2：1．0时,涂膜的各项综合性能最佳,达到了S01—3标准（聚氨酯清漆标准）。此外,研究发现催干剂二月桂酸二丁基锡浓度为mBTSL／m柠檬酸聚酯多元醇=0．08％-0．10％时,表干时间可达到25～30min。     

HFC-245fa型聚氨酯硬泡用聚醚多元醇的研究

通过对不同聚醚多元醇与HFC-245fa发泡剂相溶性及不同聚醚多元醇制备的组合聚醚发泡试验,确定了用于HFC-245fa发泡剂体系的基本配方,讨论了不同混合聚醚在HFC-245fa发泡体系中的流动性及所发聚氨酯硬泡物性。结果表明,采用羟值为403～419mgKOH/g,粘度为2000～2300mPa.s(25℃)的1#和2#聚醚多元醇混合物制备的HFC-245fa发泡体系,具有良好的流动性,所发泡沫具有优良的隔热性及尺寸稳定性。     

胀气慢回弹泡沫用聚醚多元醇的开发和应用研究

研究了聚醚多元醇的起始剂、环氧化物中环氧乙烷(EO)含量、羟值和封端等因素对胀气慢回弹聚氨酯泡沫回复时间、湿润感、胀气性和收缩性的影响。结果表明,在一定工艺条件下制备的EO质量分数为73%～82%、羟值为33～41 mgKOH/g的胀气慢回弹聚醚多元醇性能较好,由其制备的慢回弹聚氨酯软泡形状回复时间为3～5 s,湿润感较好,有胀气性而不收缩。     

组合多元醇对硬质聚氨酯泡沫塑料力学性能的影响

将中等羟值聚醚多元醇、低羟值聚醚多元醇、聚合物多元醇和苯酐聚酯多元醇分别与基础聚醚多元醇复配,制备了全水发泡硬质聚氨酯泡沫塑料,研究了4种不同组合多元醇对制品力学性能的影响,发现低羟值多元醇的加入使泡孔直径明显减小;过低羟值的TMN3050的加入对力学性能的提高不利;TMN700使泡沫体的压缩强度略为增加,冲击强度大幅提高,弯曲强度略为下降;聚合物多元醇TPOP36/28在低添加量下,制得硬泡泡孔直径明显减小,压缩强度和冲击强度大幅增加,弯曲强度降低;苯酐聚酯多元醇PS400A,使泡孔直径减小,制得硬泡的密度和力学性能大幅降低。     

二乙醇胺开环环氧大豆油制备大豆多元醇及其性能表征

以大豆油、冰乙酸和过氧化氢为原料,硫酸为催化剂,合成了不同环氧值的环氧大豆油。再由合成的环氧大豆油与二乙醇胺在四氟硼酸作催化剂的条件下．通过开环加成反应制备了羟基值分别为261mgKOH／g、285mgKOH／g、312mgKOH／g、340mgKOH／g的4种大豆多元醇。用滴定法测定多元醇羟值,用傅立叶变换红外光谱、差示扫描量热法、热重分析法对多元醇进行了分析和表征。结果表明4种多元醇的熔点和热稳定性都随多元醇羟值增大而增大。     

含超支化枝状羟基官能聚酯的清漆组合物

本发明涉及一种带≥1种超支化枝状羟基官能聚酯（羟值≥180mgKOH／g）的清漆组合物和种羟值≥180mgKOH／g超支化枝状羟基官能聚酯。     

一种改性MDI用聚醚多元醇的合成及应用研究

采用不同官能度的醇类化合物为起始剂,氢氧化钾(KOH)为催化剂,通过低挥发性有机物(VOC)聚合工艺,与环氧丙烷(PO)、环氧乙烷(EO)进行开环加成反应,合成了羟值约为24mgKOH/g的低VOC聚醚多元醇JQN-6034D。该聚醚多元醇与异氰酸酯MDI-100、MDI-50、PM-200反应合成了高回弹泡沫用改性MDI,用其制备的高回弹聚氨酯泡沫具有气味小、密度低(37 kg/m3左右)、开孔性良好以及物理性能优良的特点。     

汽车中涂用水性丙烯酸改性聚酯树脂的合成及其性能

合成了一种用于汽车中涂漆的水性丙烯酸改性聚酯树脂,讨论了E10P、MAH、聚酯中间体分子量、酸值和羟值对该聚酯水分散体的性能影响。结果表明引入一定量的E10P利于合成丙烯酸改性聚树脂,当MAH质量分数为2.5%左右(基于聚酯中间体)、聚酯中间体分子量为800～1200、酸值为30mgKOH/g以上、羟值为100～120mgKOH/g时,制备的丙烯酸改性聚酯性能最佳。与常规水性聚酯相比,合成的丙烯酸改性聚酯具有更好的水稀释性和触变性,由该改性聚酯树脂制备的水性中涂漆具有优异的配套性、综合机械性能、化学抗性和施工性。     

原材料对聚氨酯硬泡抗压性能的影响

以环氧丙烷聚醚多元醇、苯酐聚酯多元醇、多苯基甲烷多异氰酸酯PM-200、发泡剂一氟二氯乙烷(HCFC-141b)、泡沫稳定剂硅油AK-8801等为主要原料,采用一步法合成了聚氨酯硬泡,考察了不同种类多元醇及其配比、发泡剂、泡沫稳定剂种类及用量等对聚氨酯硬泡抗压性能的影响。结果表明:高羟值、高官能度的环氧丙烷聚醚多元醇可提高泡沫的压缩强度,且当环氧丙烷聚醚多元醇4110为100份,并加入20份左右苯酐聚酯多元醇580及10份左右聚醚403,泡沫稳定剂用量1～2份,发泡剂水用量0.5～1份,HCFC-141b用量30～35份,催化剂用量0.5～1.5份时,所得聚氨酯硬泡性能较好。     

聚酯多元醇的羟值测定

采用醋酐加热酰化法,在酰化剂中加入少量高氯酸,测定聚酯多元醇的羟值,计算得到相对分子质量(M_W),并与凝胶色谱法(GPC)所得的M_W进行比较,以评价该方法的准确性。结果表明:该方法简便、快速、准确、经济,测定结果的相对平均偏差为0.19%～0.87%,对于M_W低于5 000的聚酯多元醇其测定结果的误差较低,该方法测定的M_W与GPC法测定的M_W具有较好的一致性。     

Kraft Lignin-Based Rigid Polyurethane Foam

Abstract

Kraft pine lignin was derivatized to a liquid polyol through oxypropylation. The resulting polyol was characterized by GPC, FT-IR, H¹, C¹³, and P³¹ NMR and was compared to commercial polyols in view of the mechanical property of the corresponding rigid polyurethane foams for the first time. A series of lignin-based PU was synthesized by replacing varying weight percentages of the amount of sucrose polyol and glycerol polyol, two commonly used commercial polyols employed in the control foam preparation. All foams had a low density of ～30 Kg m^?3 and showed typical linkages of PU in the FT-IR spectra. The diameter of closed-cells was ～650 μm for most of the foams as revealed by SEM images. The optimal compressive property of rigid PU foams was obtained using lignin polyol without the addition of any other commercial polyols primarily attributed to the rigidity of lignin aromatic structure and the high functionality of lignin hydroxyl groups.     

Novel crosslinking system with hydroxyl-containing polymer, alicyclic polyepoxide and polyalkoxysilane

The crosslinking system based on the reaction among alicyclic epoxide group, hydroxyl group and alkoxysilyl group in the presence of aluminum β-diketone chelate have been developed. Five kinds of reaction are possible, and the result of gas chromatography and infrared analyses indicated that the main reaction is the ring-opening reaction of alicyclic epoxide group with hydroxyl group and/or hydroxysilyl group. The acrylic resin obtained by free radical polymerization of these three kinds of functional monomers and non-functional monomers showed good curing property, and the film was superior in acid rain resistance and outdoor durability. The resin is suitable to use in automotive 2coat–1bake clear coat. The viscosity of this binder system was remarkably reduced by addition of a low molecular weight alicyclic polyepoxide compound and an alkoxysilane oligomer without affecting to its good curing property. Such a system made it possible to design novel high solid coatings. It was found that the crosslinking could be extended to the combination of a polyester polyol, an alicyclic epoxide compound and an alkoxysilane oligomer. In this case, it was necessary that the polyester polyol contained highly reactive terminal hydroxyl group in the branch chains.     

用天然和可再生原料改性醇酸树脂研究进展

介绍了天然片状屏蔽型颜填料和可再生的多元醇-植物油脂肪酸为基础的高官能化合物改性醇酸树脂情况。片状云母氧化铁提高了醇酸树脂的耐候性,煅烧处理的片状高岭土和氧化铁红配合可使气干醇酸色漆涂膜具有耐水28 d的优良等性能。蔗糖多元醇-植物油脂肪酸化合制成多脂肪酸酯,具高官能度和低黏度,在气干性高固体醇酸涂料中具潜在应用前景;多脂肪酸酯进一步环氧化生成多酯多元醇,能代替羟基型醇酸和聚酯树脂在氨基醇酸和聚氨酯涂料中应用、提高固体分和改进性能。     

Preparation and properties of waterborne polyurethanes with natural dimer fatty acids based polyester polyol as soft segment

Waterborne polyurethanes (WPUs) with natural dimer fatty acids (DA) based polyester polyols as soft segments were prepared via the acetone process, and characterized by Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). The thermal and mechanical properties were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and tensile tester. Water contact angle on the surface of the WPU films increased from 80° to 93° with increasing DA weight content in dicarboxylic acid of polyester polyol from 0 to 100%. The results indicated that among the synthesized WPUs, those containing DA exhibited excellent water resistance (water uptake decreased from 13.2% to 2.42%), outstanding hydrolytic resistance (weight loss decreased from 14.2% to 5.85%) and superior thermal stability (decomposition temperature of 50% weight loss and maximum weight loss, increased from 384 to 443 °C and from 409 to 464 °C, respectively). Compared to toluene resistance and mechanical properties of WPUs containing no DA, those of WPUs containing DA were low. For the WPU films based on polyester polyol derived from 100% DA as dicarboxylic acid, the interesting delamination occurred in special solvents, probably due to dissolution of low molecular weight molecules, and the presence of long hydrophobic branched chains and the high degree of phase separation.     

新型芳香族聚酯多元醇的合成与性能研究

用对苯二甲酸、苯酐、二元醇、三元醇等多元醇为原料制备新型芳香族聚酯多元醇,考察了聚酯多元醇酸值、羟值与其醇酸摩尔比的关系,以及酸值与反应时间的关系,并将其用于制备硬质聚氨酯泡沫塑料,讨论了新型聚酯多元醇对硬质聚氨酯泡沫塑料的性能影响。     

脂肪酸甘油酯的色谱分析

应用高效液相色谱法和高分辨凝胶渗透色谱法建立了脂肪酸甘油酯中单酯、双酯和三酯的族分离方法 ,采用乙醇作流动相的非水反相色谱法可以将饱和脂肪酸甘油酯按族进行分离 ,不饱和脂肪酸甘油酯在反相色谱条件下族分离效果不理想 ;相比于HPLC方法 ,采用四氢呋喃作流动相的GPC法可以迅速地将各种多元醇酯按族进行分离 ,而且具有快速、简便等特点     

Synthesis of Transesterified Palm Olein‐Based Polyol and Rigid Polyurethanes from this Polyol

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm‐based polyol. The objective of this study was to synthesize transesterified palm olein‐based polyol via a three‐step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g^?1. The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring‐opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein‐based polyol has hydroxyl value between 300 and 330 mg KOH g^?1 and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein‐based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum‐based polyol with the transesterified palm olein‐based polyol. It was observed that by increasing the amount of transesterified palm olein‐based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.