【作者】 冯光炷；

【导师】 崔英德；

【作者基本信息】 西北工业大学 ， 材料加工工程， 2007， 博士

【摘要】 随着可持续发展战略在全球范围内的进一步推广，来自石油化工，对人类和环境能够造成危害的材料在应用上逐渐受到限制，“环境亲合”和“绿色环保”材料将成为现代材料与化工领域发展的主导方向。本文以天然油脂加工产物——二聚脂肪酸为主要原料，系统地研究了二聚脂肪酸与乙二醇、聚乙二醇、聚丙二醇之间二元或三元缩聚反应的理论问题及合成物应用性能。作为研究工作的延伸，也研究了原料二聚脂肪酸的生产工艺；用于脂肪酸二聚化反应的新型催化剂的制备、表征和催化性能。研究结果如下：（1）研究与开发了一种二聚脂肪酸合成新工艺——自升压工艺。新工艺的基本原理和操作方法是：将一定量的水和原料脂肪酸一起添加到反应体系中，利用水气化后的水蒸汽将反应器内空气所含之氧带出，然后在残留水分和原料脂肪酸共同产生的压力下进行二聚化反应。与传统通入高纯氮气排氧加压工艺相比，新工艺具有可有效降低生产成本；防止催化剂高温下失活；减少脂肪酸在高温下发生脱羧、裂解和多聚等副反应的特点，并可提高二聚脂肪酸的产率。自升压工艺中，水的加入量对二聚脂肪酸的产率影响较大，加入量以2.00％（与原料脂肪酸物质量的比，w／w）为宜，量过少或过多均影响二聚脂肪酸的产率。在自升压制备二聚脂肪酸的工艺中，Li₂CO₃具有较好的协同和助催化作用，可提高二聚脂肪酸的产率和选择性，并能使产物色泽得到一定的改善。（2）采用一次或二次插层的方法，制备了系列有机蒙脱土，并将其用于催化不饱和脂肪酸二聚化反应。研究发现，在不饱和脂肪酸二聚化反应中，有机蒙脱土比蒙脱土具有更高的催化活性和效能，且其活性受插层剂的种类与结构、离子交换量大小的影响，与蒙脱土层间距在一定范围内呈正线性关系。当蒙脱土层间距从1.26mm增至2.19mm过程中，其催化活性和效能是线性增加的，二聚脂肪酸产率和选择性比蒙脱土催化有明显的提高；当离子交换量超过40，其催化活性开始快速降低，原因是蒙脱土层间活性金属离子数量减少而影响其催化活性和效能；蒙脱土经有机化处理后，可提高其在不饱和脂肪酸二聚化反应体系中的分配性能，在达到二聚反应所需传热和传质要求的条件下，可以降低聚合反应所需要的搅拌速度，减少功耗。（3）以二聚脂肪酸与乙二醇酯化反应为研究对象，研究和改进了多元酸和多元醇缩聚反应的工艺，确定了二聚脂肪酸-乙二醇聚酯合成的工艺条件。改进后的工艺采用初始阶段充氮气，后期抽真空的方法来带走反应中所生成的水以提高反应速率，抽真空排出的含少量乙二醇的水使用精馏装置进行分离。工艺改进后，可以很好地克服传统工艺所存在的反应时间长及消耗大量氮气的缺点，用于合成DFA-EG聚酯，取得了很好的效果。研究了二聚脂肪酸和乙二醇缩聚反应的动力学问题。对二聚脂肪酸与乙二醇缩聚反应体系进行了分析和简化，基于单体和聚合物端基等活性及不等活性的假设，采用已加入最优保存策略（Elitist Model）、变量数值扰动、龙格库塔积分（Runge-Kutta）算法、均匀分布的随机数发生器算子的遗传算法，建立了模型Ⅰ和模型Ⅱ，并利用C⁺⁺计算机语言编程来估算动力学模型的参数。比较后发现，单体和聚合物端基不等活性条件下的动力学模型更接近于反应体系的实际情况，能更为精确地描述二聚脂肪酸和乙二醇缩聚反应。通过实验，确定了二聚脂肪酸与乙二醇缩聚反应速率对羧基为2.0875级，对羟基为1级；也确定了C₃₆二聚脂肪酸-乙二醇聚酯平均分子量与特性黏度的关系：[n]=0.02696（?）^0.7758（25℃，以环己烷为溶剂）。（4）以二聚脂肪酸为原料，制备了二聚脂肪酸基不饱和聚酯，固化后得到二聚脂肪酸基聚酯树脂材料，研究了二聚脂肪酸基聚酯树脂的制备和性能。研究结果显示，二聚脂肪酸的引入，使聚酯树脂具有很好的力学性能、耐水性、断裂伸长率、柔韧性、生物降解性及耐燃性能（耐燃性能可达到GB 2408—80Ⅱ级），但也会使聚酯树脂的耐溶剂性能、硬度和拉伸强度下降。热分析实验结果表明，制备的二聚脂肪酸基聚酯树脂有很好的热稳定性，分解温度高于370℃，约510℃全部热分解，失重率约50.10％。随二聚脂肪酸含量的增加，二聚脂肪酸基聚酯树脂热分解温度提高，聚酯的热稳定性也更好。（5）以二聚脂肪酸和聚乙二醇400为原料，首先合成了DFA-PEG聚酯，再以DFA-PEG聚酯为衍生体，硫酸化或用松香封端，合成了两种DFA-PEG聚酯衍生物——DFA-PEG聚酯硫酸酯盐和松香酸封端DFA-PEG聚酯，通过正交试验，对合成的条件进行了优化。合成的DFA-PEG聚酯数均分子量为6135，重均分子量为7798，分子量分布为1.212，分子量呈窄分布。DFA-PEG聚酯及其衍生物为新型的高分子表面活性剂，其分子中含有特殊结构的亲水亲油性基团。性能测试表明，DFA-PEG聚酯及其两种衍生物均具有优良的乳化性能，乳液细腻且稳定；DFA-PEG聚酯及其硫酸酯盐水溶液的表面张力和临界胶束浓度较低：DFA-PEG聚酯松香酸酯还具有一定的抑泡性能，与DFA-PEG聚酯及其硫酸酯盐比，其水溶液表面张力和临界胶束浓度有所增加。研究了SnCl₂催化条件下，DFA与PEG 400缩聚反应动力学和热力学问题，结果为，DFA与PEG 400缩聚反应级数为0.998级；活化能E=97.18kJ·mol^-1；缩聚反应的Arrhenius方程为：1nk=21-39—11.689／T。（6）以二聚脂肪酸、聚乙二醇400和聚丙二醇2000为原料，系统研究了DFA-PEG-PPG共聚酯、封端的DFA-PEG-PPG共聚酯和（DFA-PEG）_m-（DFA-PPG）_n嵌段聚酯的合成规律及其应用性能，通过正交试验，优化了三种三元聚酯的合成工艺条件。通过实验，确定DFA与PPG 2000缩聚反应活化能E=108.4786 kJ·mol^-1，Arrhenius方程为：1nk=25.166—13.043／T，活化能比DFA与PEG 400缩聚反应的活化能大，因此，对于DFA／PEG／PPG三元共聚反应，须选用合适的工艺及工艺条件来控制共聚酯产率和分子结构。实验比较后表明，合成DFA-PEG-PPG三元共聚酯，连续加料工艺酯化率比一次加料工艺酯化率更高，所合成聚酯的分子量分布更窄，数均分子量也更大。性能研究发现，PPG的引入，可使DFA／PEG／PPG三元聚酯高分子表面活性剂的亲水亲油特性调节更为容易：在DFA／PEG／PPG三元共聚体系中，加入长链脂肪酸或脂肪醇，合成的封端型DFA-PEG-PPG共聚酯，结构上既含有长链的亲油性基团，还含有聚醚型的亲水基团，具有脂肪醇型消泡剂和聚醚型消泡剂复配增效的特性，其消泡性能优秀。这种新型结构聚酯的合成，为消泡剂分子结构的设计提出了一种的思路；采用嵌段聚合方法所合成的（DFA-PEG）_m-（DFA-PPG）_n嵌段聚酯型高分子表面活性剂，其分子量比DFA-PEG和DFA-PEG-PPG三元共聚酯的分子量更大，所表现出的乳化性能更为优秀。采用嵌段聚合的方法所合成的（DFA-PEG）_m-（DFA-PPG）_n嵌段聚酯，其分子结构更具有规整性，同时，通过调节预聚体的摩尔比，可以得到水溶或油溶聚酯醚型高分子表面活性剂。更多还原

【Abstract】 Along with the global further spreading of sustainable developrnent stratagem, thesematerials, which come froln petrochemicals and were harmful to human being andnatural environment, will be gradually restricted in application, the mainlydevelopment trend in the modern material industry and chemical industry field is toexplore "the environmental friendly material" and "the green chemicals".In this paper, the synthesis, performance and kinetics of C₃₆ DFA （dimer fatty acid）based di-polyester or tri-polyester and its derivant, their polyesters were synthesizewith DFA and EG （ethylene glycol） or PEG （polyethylene glycol） and PPG（polypropylene glycol）, were systemically and roundly studied. As the extending ofresearch work, at the same tirne rnanufacture process of DFA, synthesis and structurecharacterization as well as catalyzing performance of novel catalyst for dimerization offatty acid were studied, the research results were as follows:1. The dimerization reaction of the unsaturated fatty acid was catalyzed by a seriesof organ-intercalated montmorillomite, which was prepared by means of one ortwo-step intercalation. According to the research, it was found that organ-intercalatedmontmorillomite had better catalyzing activity and efficiency than montmorillomite indimerization reaction of the unsaturated fatty acid, and catalyzing activity oforgan-intercalated montmorillomite was influenced by kind and structure ofintercalating agent and CEC （cation exchange capacity）. Catalyzing activity of organ-intercalated montmoriliomite had a positive linear relationship with its interlayerdistance on certain condition. The catalyzing activity and efficiency of organ-intercalated montmorillomite was linearly increased when interlayer distance wasraised from 1.26 mn to 2.19 nm, meanwhile yield and selectivity of DFA wereevidently increased. When CEC exceeded 40, catalyzing activity and efficiency oforgan- intercalated montmorillomite began to obviously decrease, the possible reasonwas that the active metal ions is littler in layers of organ-intercalated montmorillomite.Distribution performance of organ-intercalated montmorillomite was better thanmontmorillomite in reaction system. Stirring speed and consumption of energy can bedecreased in polyesterification reaction when the requirements for heat and masstransfer are fulfilled.A novel synthesis process of DFA under autogenous pressure was studied and developed with safflower oil fatty acid. The basic theory and operation method ofnovel process were as follows: certain water and fatty acid were added into thereaction system together, air containing oxygen was taken away from reactor byboiling vapor, and then the polyesterification reaction occurred at the collectivepressure produced by residual water and fatty acid. Comparing with the traditionalremoving oxygen process by pure nitrogen, novel technology can effectively reduceproduction costs, prevent catalyst losing activity and decrease secondary reaction, suchas decarboxylase, decompositiob and multi-polymerization, etc. at high temperature.The yield of DFA can be also increased.Amount of adding water had obviously influence on the yield of DFA in autogenouspressure process, the appropriate amount of water was 2.00％of total amount of DFA（w/w）, too much or too little all affected the yield of DFA. Li₂CO₃ added in reactionsystem had well cooperative effect and assistant catalysis, could increase the yield andselectivity of DFA and get lighter color complex.3. The polyesterification reaction of DFA and EG was regarded as research object.The polyesterification reaction process of polyacid and polyalcohol was studied andimproved, and condition of synthesis reaction was determined. The improved processis as follows: the reactor was charged with nitrogen in the beginning, after certainreaction time the reactor was picked up suction in order to take away water producedin the course of reaction and elevates the reaction speed; water containing little EGwas separated with rectifier. The improved process could overcome the disadvantagesof the traditional process disadvantage such as long reaction time, consuming muchnitrogen, which was well used in synthesis of DFA-EG polyester.The kinetic of polyesterification reaction of DFA and EG was studied. The reactionsystem of polyesterification of DFA and EG was analyzed and simplified. Based on thehypothesis of equal and unequal activity of the end-group of monomer and polymer,the modelⅠand modelⅡfor estimating kinetic parameters were established usingimproved Genetic Algorithm, which was so improved by introducing the Elitist Model,Simulate annealing, Runge-Kutta method, proportional distribution randomizer etc.into the operators, and these models were more compatible with the estimation ofcomplex reaction kinetic model parameters. A program for calculating the parametersof modelⅠand modelⅡwas written with C⁺⁺ computer language. By comparison, itwas found that the kinetic model based unequal activity of end-group monomer andpolymer was more close to the fact and more accurately depict the polyesterification reaction of DFA and EG.By experiment, it was proved that the speed degree of polyesterification reaction ofDFA and EG was 2.0875 to carboxyl and 1 to hydroxyl respectively, and therelationship between average molecular weight and the inherent viscosity of DFA-EGpolyester was as follows: [η]=0.02696（?）0.7758 （25℃, taking cyclohexane as solvent）4. The preparation and performance of DFA based polyester resin were studied,which was prepared with DFA based unsaturated polyester, curing fixture and filler.The research results showed that the DFA based polyester resin had better mechanicalperformance, the water-fast performance, rate of elongation, flexility, the performanceof biodegradation and the burning-fast performance, but the chemical solvent-fastperformance, rigidity, tensile-strength were decreased.The experimental results of thermogravimetry analysis and differential thermalanalysis showed that the DFA based polyester resin had excellent thermal stability,decomposition temperature exceeded 370℃. It was completely decomposed around510℃, ratio of mass loss is 50.10％. The thermal stability and decompositiontemperature of the DFA based polyester resin was increased as the increase of theamount of DFA in the resin.5. DFA-PEG polyester was synthesized with DFA and PEG 400 at first, and then bysulfating DFA-PEG polyester with NH₂SO₃H or terminating DFA-EG polyester withrosin acid, two derivant, these are sulfated DFA-PEG polyester and terminateDFA-PEG polyester, were synthesized. The reaction conditions of synthesis wereoptimized by orthogonal experiments.The molecular weight of product was analyzed by GPC. The number averagemolecular weight of DFA-PEG polyester is 6135, and average weight molecularweight is 7798. Distribution of molecular weight is 1.212, and it is distributed innarrow range.DFA-PEG polyester and its derivant were novel macromolecule surface activityreagent, its molecule contains special structural hydrophilic and lipophilic group.Results of test showed that DFA-PEG polyester and its derivant had excellentemulsification performance, and emulsion was exquisite and steady, the surfacetension and critical micelle concentration （CMC） of DFA-PEG polyester and sulfatedDFA-PEG polyester were very low, DFA-PEG polyester terminated with rosin acid hadcertain antifoaming performance, but surface tension and CMC increase to extent. Thermodynamics and dynamics of polyesterification reaction of DFA and PEG 400were studied taking SnCl₂ as catalyst. The research results showed that the speeddegree of polyesterification reaction of DFA and PEG 400 was 0.998, activation energywas 97.18 kJ·mol^-1. Arrhenius equation is as follows: lnk=21.39-11.689/T.6. Synthetical regularity and applicable performance of DFA-PEG-PPG tripolymerpolyester synthesized with DFA, PEG 400 and PPG 2000 as reactant, DFA-PEG-PPGtripolymer polyester terminated with oleic acid, （DFA-PEG）_m-（DFA-PPG）_n blockcopolymer synthesized with DFA-PEG and DFA-PPG, were studied systemically. Atthe same time synthesis reaction conditions were optimized by orthogonal experiment.Activation energy of polyesterification reaction of DFA and PPG 2000 was108.4786 kJ·mol^-1. Arrhenius equation is as follows: lnk=25.166-13.043/T. As forthe tripolyesterification reaction, it is necessary to choose appropriate processconditions to control the yield and molecular structure of tripolymer polyester. Bycomparison, it was found that esterification rate of continuously adding reactant washigher than one-off adding reactant for synthesis of DFA-PEG-PPG tripolymerpolyester, distribution of molecular weight was narrower and number averagemolecular weight was larger.It was also found that the balance of hydrophilic and lipophilic of DFA-PEG-PPGtripolymer polyester macromolecule surface activity reagent was easily adjusted bychanging the adding amount of PPG. Terminated DFA-PEG-PPG tripolymer polyester,which was synthesis by adding long chain fatty acid or fatty alkanol into the reactionsystem, contained not only chain lipophilic group but also polyester-polyether group,and had the building effection of alkanol antifoaming reagent and polyether one. Thenovel design theory for structure of antifoaming reagent was put forward by studyingperformance of product. The molecular weight of （DFA-PEG）_m-（DFA-PPG）_n blockcopolymer synthesized with DFA-PEG and DFA-PPG was larger than the molecularweight of DFA-PEG polyester and tripolymer DFA-PEG-PPG polyester, theemulsification performance was better. At the same time it is easy to obtainwater-solubility or oil-solubility polyester macromolecule surface activity reagent.更多还原