聚氨酯用丁二酸聚酯二醇的合成

研究了以丁二酸、乙二醇为主要原料制备聚氨酯用丁二酸聚酯二醇的方法,考察了原料酸醇比、反应温度、催化剂种类及用量、反应时间等对反应的影响。结果表明,当丁二酸与乙二醇摩尔比为1∶1.8、催化剂为辛酸亚锡、用量为原料总质量的0.3%、预酯化反应温度为180℃、减压缩聚温度为160℃、时间为5 h、真空度1.99 kPa时,酯化率达到99%,产品羟值为105 mgKOH/g,酸值为0.91 mgKOH/g。     

草酸亚锡催化合成PTT的研究

采用对苯二甲酸(PTA)和1,3-丙二醇(1,3-PDO)为原料,以自制的草酸亚锡为催化剂经酯化、缩聚,制得聚对苯二甲酸丙二醇酯(PTT)。探讨了反应条件对合成反应的影响。结果表明:草酸亚锡的催化活性优于丁基锡酸和辛酸亚锡。1,3-PDO／PTA的摩尔比为1．5／1、草酸亚锡用量为5×10-4mol／mol(相对PTA),酯化反应温度260℃,反应时间2 h;缩聚反应温度260℃,反应时间2 h,可制得PTT,其特性粘数为0．8950dL／g,端羧基含量为15 mol／t。     

亚锡类催化剂催化合成对苯二甲酸二异辛酯的研究

以3种亚锡类催化剂氧化亚锡、氯化亚锡、辛酸亚锡以及它们之间复配后作为催化剂,对对苯二甲酸二异辛酯酯化反应的催化活性进行了研究,实验结果表明,以氧化亚锡和辛酸亚锡复配后的催化活性最高,氧化亚锡和辛酸亚锡作为催化剂的酯化反应最佳合成工艺条件为:催化剂的加量为0.25%(重量比),反应温度为220℃,醇酸摩尔比为3.0?1,在最佳工艺条件下,产品的终点酸值为0.62 mgKOH/g,对苯二甲酸的转化率达99.75%。     

乙酰柠檬酸三丁酯合成工艺的改进

以柠檬酸、正丁醇和乙酸酐为原料,对甲苯磺酸为催化剂,通过酯化、脱醇、乙酰化、脱乙酸和乙酸酐、中和、水洗等步骤制备了乙酰柠檬酸三丁酯。和文献报道的工艺相比,节省了催化剂用量,减少了近一半的废水量。当反应物摩尔比n（柠檬酸）：n（正丁醇）：n（乙酸酐）：n（对甲苯磺酸）=1：4．3：1．10：0．041,酯化反应温度为130-140℃,酯化时间为4h,乙酰化反应温度为50℃,乙酰化反应时间为1h时,产品的产率为97．5％,酯含量为99．21％,酸值为0．14mgKOH／g,色度小于50（Pt—Co）,符合产品质量要求。     

乙撑双油酸酰胺的合成研究

对常压下以油酸和乙二胺为原料合成乙撑双油酸酰胺的方法进行了研究,考察了原料配比、催化剂种类及用量、反应温度及时间对合成反应的影响。确定了最佳工艺条件：n（油酸）：n（乙二胺）=1：0．52,催化剂为磷酸,m（磷酸）：m（油酸）=0．5％0,反应温度185-190℃,反应时间4～5h。在此条件下,产品的酸值〈7．0mgKOH／g,熔点112-118℃。     

碘催化无溶剂合成己二酸二乙酯

以碘作催化剂,无溶剂催化合成了己二酸二乙酯。考察了反应时间、原料配比、催化剂用量和反应温度对酯化率的影响。其最佳反应条件为：己二酸用量0．020mol,乙醇与己二酸的物质的量比6：1,碘用量0．060g,反应时间4．0h,反应温度84～85℃,此时酯化率可达94．68％。     

固体超强酸SO2- 4/TiO2/Nd3+催化合成肉桂酸异戊酯

采用稀土元素Nd^3＋对固体超强酸SO4^2-／TiO2进行改性,以肉桂酸和异戊醇为原料合成肉桂酸异戊酯。考察了各种因素对酯化率的影响。实验结果表明：最佳反应条件为催化剂焙烧温度450℃,催化剂用量1．0g,醇酸摩尔比1：4,反应时间2h。该催化剂可再生重复多次使用,产品的酯化率达93.8％。     

二聚酸二丁氧基乙酯的合成与增塑性能

以二聚酸和乙二醇丁醚为原料,在催化剂钛酸四丁酯催化作用下,采用直接酯化法工艺合成了二聚酸二丁氧基乙酯。考察了原料配比、催化剂用量、带水剂用量、反应时间等因素对酯化反应的影响。结果表明：当乙二醇丁醚和二聚酸摩尔比为2.5∶1,钛酸四丁酯用量为二聚酸质量的1.0%,带水剂环己烷用量为二聚酸质量的17.5%,反应时间5h时,酯化率可达99.6%。建立了酯化反应表观动力学模型,反应速率方程为：r=9.2×10⁵e^-49.1/RTc_A。通过FTIR和¹H NMR对产物结构进行表征,并将二聚酸二丁氧基乙酯和DOP分别加入到PVC树脂中,通过溶剂铸膜法制成PVC塑料试片,对比其性能,二聚酸二丁氧基乙酯有良好的耐油、耐水抽出及热稳定性,可作为DOP的升级产品使用。     

酸化膨润土催化酯化合成癸二酸二正己酯

以酸化膨润3a（SO4^2-／Bentonite）固体酸为催化剂、癸二酸和正己醇为原料合成了癸二酸二正己酯。考察了反应温度、原料配比、催化剂用量和反应时间等因素对酯化反应的影响,得到了较佳酯化反应工艺条件：正己醇与癸二酸的物质的量比为4．0：1,SO4^2-／Bentonite用量为醇酸总质量的4．17％、反应温度不高于160℃、反应时间为3h,此条件下癸二酸的转化率达到99．05％。催化剂重复使用3次,癸二酸的转化率仍可达93％以上。     

抗氧剂168的合成工艺研究

研究了酯化法合成抗氧剂168[亚磷酸三（2,4二叔丁基苯基）亚磷酸酯]的工艺条件。以68．8g（1／3mol）2,4-二叔丁基苯酚和15．4g（1／9mol）三氯化磷为原料,催化剂三乙胺,反应温度140—150℃、反应时间2．5h的条件下进行酯化反应,经异丙醇结晶后得三（2,4-二叔丁基苯基）亚磷酸酯。平均收率95％。     

阳离子可染聚酯酯型改性剂的合成研究

以质量分数15%的硫酸为催化剂,将己二酸与乙二醇进行酯化反应,合成了阳离子可染聚酯的改性剂己二酸乙二醇酯,对催化剂用量、反应温度、反应时间、投料比等因素进行了探讨,采用红外光谱法对产物进行了表征。结果表明:当催化剂质量分数为0.05%,乙二醇:己二酸(摩尔比)为3.2:1,反应温度115~120℃,反应时间3.5 h时,其酯化率超过90%,且粘度低于0.05 Pa.s。红外光谱分析表明,产物中含有酯键,说明己二酸与乙二醇发生了酯化反应。     

β-二酮铝和β-二酮酯铝催化合成聚对苯二甲酸乙二醇酯

采用对苯二甲酸(TPA)和乙二醇(EG)为原料,以自制的β-二酮铝和β-二酮酯铝为催化剂经酯化、缩聚,制得聚对苯二甲酸乙二醇酯(PET).探讨了反应条件对合成反应的影响.结果表明:β-二酮酯铝和乙酰丙酮铝优于其他β-二酮铝.EG与TPA的摩尔比为1.2∶1、催化剂的用量为0.5%(与TPA的摩尔比),酯化反应温度为26...     

Synthesis of poly(alkylene succinate) biodegradable polyesters I. Mathematical modelling of the esterification reaction

Synthesis of three biodegradable aliphatic polyesters, namely poly(ethylene succinate), poly(propylene succinate) and poly(butylene succinate) is presented using the appropriate diols and succinic acid in the presence of tetrabutoxytitanium as catalyst. A theoretical mathematical model for the esterification reaction, based on the functional group approach, is developed and applied successfully in the simulation of all experimental data. Values for the kinetic rate constants are proposed for different catalyst molar ratios and comonomer chemical structure. It was found that the presence of the metal catalyst used leads to a poor activity of self-catalyzed acid and the main kinetic rate constant of the esterification reaction correlates well with the square root of the catalyst concentration. Different glycols do not influence much the number average degree of polymerization (NADP) values of the oligomers produced, even thought they slightly affect esterification rates in the order BG>PG>EG. In contrast, these values are affected by the amount of catalyst, with larger catalyst molar ratio giving polymer with bigger average molecular weight. These results were verified from measurements of the final polyester average molecular weight obtained at different polycondensation temperatures. Finally, from theoretical simulation results it was found that although higher initial ratios of glycol to succinic acid are useful to increase the esterification rate, they lower the NADP of the oligomers formed at a fixed conversion of acid end groups.     

基于二聚酸/己二酸聚酯多元醇的合成及表征

以二聚酸、己二酸和新戊二醇为原料,在高温氮气保护下,合成一种相对分子质量为2000的二聚酸类聚酯多元醇。考察醇酸比、最高反应温度、反应时间、保温脱水时间、催化剂种类及用量对反应结果的影响。通过红外光谱分析表征了产物中的基团。结果表明:合成基于二聚酸聚酯多元醇的最优条件是醇酸比为1.24∶1,总反应时间为8 h,最高反应温度为220℃,二月桂酸二丁基锡为催化剂且质量分数为0.12%。     

以生物基二聚脂肪酸制备聚氨酯丙烯酸酯树脂及其性能研究

为了减缓石油资源消耗,利用可再生二聚酸制备聚氨酯丙烯酸酯。将二聚脂肪酸(DA)与乙二醇(EG)以不同的物质的量比缩合制得3种不同羟值的聚酯二元醇(A-1、A-2、A-3),再依次通过与甲苯二异氰酸酯(TDI)、丙烯酸羟乙酯(HEA)反应引入丙烯酸酯基团,从而制得3种可光固化的聚氨酯丙烯酸酯树脂(B-1、B-2、B-3)。利用傅立叶变换红外光谱(FT-IR)对原料及合成产物进行了结构表征;采用实时红外分析(RT-IR)研究了不同条件下树脂的光固化性能;采用万能试验机、差示扫描量热仪(DSC)、热重分析仪(TGA)分析测试了固化膜的力学性能、玻璃化转变温度和热稳定性;同时测试了固化膜的接触角及铅笔硬度等。结果表明:随着二聚酸含量的升高,所制得的聚酯二元醇黏度和数均相对分子质量增大,羟值降低。最终所制备的聚氨酯丙烯酸酯树脂固化膜的热稳定性和附着力基本相同,但随着羟值含量的降低,软段部分增加,双键含量降低,交联密度下降,导致固化膜铅笔硬度、吸水率降低,柔韧性增加。     

Green polyurethane from dimer acid based polyether polyols: Synthesis and characterization

In this study, dimer acid (DA) obtained from waste soybean oil was used together with propylene oxide (PO) to obtain novel polyether polyols [prepolymers for polyurethanes (PUs)] through ring‐opening polymerization reaction. The average molecular weight of polyols was estimated by gel permeation chromatography and titration method. The substantial reaction between DA and PO was evident from FTIR and nuclear magnetic resonance spectroscopy. Subsequently, the polyols were reacted with chain extender [ethylene glycol, (EG)] and 4, 4 ‐ Diphenylmethane diisocyanate (MDI) to prepare green PUs. The effect of molar ratio variation of EG and MDI with a fixed amount of polyols was estimated by measuring hydrophobicity and mechanical strength of PUs. The molar ratio such as 1 : 4 : 5.7 of polyol : EG : MDI was found to exhibit maximum hydrophobicity and improved mechanical strength that were comparable with typical PU sample prepared from commercially available polyol, such as polypropylene glycol. FTIR spectroscopic analysis confirmed the chemical changes and possible crosslinking in PUs. Thermalgravimetric analysis and differential scanning calorimetry analysis also showed substantial thermal stability of the green PUs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41410.     

Synthesis and Kinetic Studies on Dimer Fatty Acid/Polyethylene Glycol Polyester

Dimer fatty acid polyethylene glycol polyester, a new kind of non-ionic polymeric surfactant, was synthesized by using dimer fatty acid and polyethylene glycol (400) as materials in this paper. The optimum reaction conditions of esterification were as follows: the molar ratio of dimer fatty acid (DFA)/PEG (400) is 1 / 1.20, the preferable catalyst is stannous chloride and the amount is 0.3% (w/w) of the mass of DFA, reaction temperature is 200°C, reaction time is 6 h. The conversion ratio of polyesterification can reach 98.11%. A new kinetic model of polyesterification reaction catalyzed with stannous chloride was presented. The Genetic Algorithms and Runge–Kutta were used to estimate the parameters of the kinetic model. The results of experiments and computer operations indicated that the reaction order is 0.998 to the carboxyl and 1 order to the hydroxyl. The activation energy obtained from Arrhenius plot is 97.18 kJ mol⁻¹, and the pre-exponential frequency factor is lnA = 21.39 kg² mol⁻² min⁻¹ at temperature range of 160 ∼ 190°C.     

Sol-Gel负载磷钨酸催化合成乙二醇单乙醚醋酸酯

以醋酸和乙二醇单乙醚为原料,硅酸乙酯为硅源,通过溶胶-凝胶法(Sol-Gel)负载磷 钨酸为催化剂,合成了乙二醇单乙醚醋酸酯。实验结果表明:当正硅酸乙酯:水(mol／mol)=1∶4, 正硅酸乙酯:磷钨酸(W/W)=10∶1,醋酸:醇醚(mol／mol)=1．4∶1,催化剂用量为醇醚质量的 10％,带水剂甲苯用量为反应物质量的15％,反应时间为60 min时,收率可达96％以上。比较了 以硅胶直接负载磷钨酸作为催化剂的使用情况。