【作者】 刘伟；

【导师】 刘国际；

【作者基本信息】 郑州大学 ， 化学工艺， 2014， 博士

【摘要】 随着化石资源的日益枯竭,如何利用可再生资源已引起全世界的关注。腰果壳提取液的催化加氢产物是间十五烷基酚(PDP),能够替代石油类酚,属绿色可再生资源。基于PDP间位长链烷烃空间自由体积大的特性,本文将其作为超分散剂的溶剂化链段,能够提供较大的空间位阻效应,设计合成丙烯酸聚酯型和端氨基嵌段聚酯型超分散剂。研究分散剂制备方法和工艺条件,并对两种新型超分散剂的分散效果及吸附性能进行研究。以PDP和丙烯酰氯为原料,咪唑类离子液体为催化剂,三乙胺为敷酸剂,制备间十五烷基丙烯酸苯酯(PDPA)单体,通过红外、核磁、质谱和元素分析确认结构。利用响应面分析法对PDPA的合成工艺条件进行优化,得适宜工艺条件为：咪唑类离子液体用量2.02%,底物摩尔配比n(丙烯酰氯)：n(PDP)=1.15:1,反应时间8.25h,反应温度57。C。在此工艺条件下,PDPA的收率可达87%。对PDP与丙烯酰氯的酯化反应进行动力学研究,得无催化剂和无缚酸剂条件下,酯化反应动力学方程为：在离子液体催化和三乙胺为缚酸剂下,酯化反应动力学方程为：测定PDPA在乙醇和甲醇混合溶剂以及甲苯等六种有机溶剂中273K-297K范围内的溶解度。利用Apelblat方程和λh方程模型对所测溶解度数据进行关联,结果显示Apelblat模型优于λh模型。采用Apelblat方程和范德霍夫方程对溶解过程的溶解熵和溶解焓进行计算,表明溶解过程都是熵驱动的自发过程。由基团贡献法估算PDPA的溶度参数,对不同溶剂中PDPA的溶解度大小进行比较。通过自由基无规共聚,合成PDPA、甲基丙烯酸(MAA)和丙烯酸丁酯(BA)三元聚酯型超分散剂,其制备适宜工艺条件为：偶氮二异丁腈(AIBN)用量为单体总质量2%;链转移剂用量为AIBN等摩尔比;反应温度70。C;反应时间8h。采用红外光谱和核磁氢谱对聚合物进行结构表征。研究PDPA/MAA/BA三元聚酯型超分散剂对钛白粉分散体系黏度和细度影响,结果表明：其适宜的重均分子量为6000左右;三种单体质量配比为PDPA:MAA:BA=1.2:1:10;钛白粉体系(固含量30%)黏度可降低到50mPa·s,细度可达20μm。在303K、313K、323K温度下,甲苯、异丙醇和乙酸乙酯三种溶剂中钛白粉对丙烯酸聚酯型超分散剂的等温吸附数据用四种常用模型进行拟合比较,结果表明Fritze-Schlunder模型拟合最好。钛白粉吸附超分散剂前后红外光谱无变化，说明钛白粉对丙烯酸聚酯型超分散剂在三种溶剂中的吸附主要为物理吸附。由Dubinin–Radushkevich方程计算结果表明，钛白粉在三种溶剂中对丙烯酸聚酯型超分散剂的平均自由吸附能在2.09～3.11kJ·mol-1之间，远小于化学吸附平均自由吸附能，证实吸附过程主要是物理吸附。碳黑是最难分散的颜料之一，为达到在溶剂体系中分散碳黑的目的，本课题结合PDP的分子结构特点，设计合成一种新型的嵌段聚酯型超分散剂。首先，以PDP引发己内酯开环聚合，制备端羟基聚酯，适宜工艺条件为：钛酸丁酯为催化剂，用量为5‰；反应温度110℃；反应时间16h。然后，马来酸酐与端羟基聚酯反应，制备端羧基聚酯，适宜工艺条件为：反应温度90℃，马来酸酐：端羟基聚酯=2.5：1（mol），反应时间10h。最后，端羧基聚酯与二乙烯三胺进行酰胺化反应，其适宜工艺条件为：反应温度120℃，反应时间12h。用红外光谱和核磁氢谱对嵌段聚酯分散剂进行结构表征。研究端氨基嵌段共聚物对碳黑分散体系黏度和细度影响，结果表明：其适宜的重均分子量为3000左右；胺值为20mgKOH/g；碳黑分散体系（固含量为30%）黏度可降低到30mPa·s，细度可达5μm。在303K、313K、323K温度下，甲苯、异丙醇和乙酸乙酯三种溶剂中碳黑对端氨基嵌段聚酯型超分散剂的等温吸附数据用四种常用模型进行拟合比较，结果表明Tempkin模型拟合最好。红外图谱间接证实碳黑对端氨基嵌段聚酯型超分散剂在三种溶剂中的吸附为物理吸附。由Dubinin–Radushkevich方程计算结果表明，碳黑在三种溶剂中对端氨基嵌段聚酯型超分散剂的平均自由吸附能在1.31～2.62kJ·mol-1之间，证实吸附过程主要是物理吸附。综合以上研究结果表明，以PDP制备丙烯酸聚酯型超分散剂和端氨基嵌段聚酯型超分散剂，在溶剂型体系中对钛白粉和碳黑均有较好的分散能力，对于拓展PDP在涂料行业的应用具有一定的指导意义。更多还原

【Abstract】 While Petrochemical resources is drying up, how to make use of the renewable resources has attracted attentions of all the world.3-Pentadecylphenol(PDP) is the product of catalytic hydrogenation of cashew nut shell liquid, which could replace Petroleum phenol, so it’s a kind of green renewable resources. Because of the Characteristics for PDP that the meta-position long-chain alkane has big free volume, in this paper, PDP is used as solvation segment of hyperdispersant, which will provide sufficient steric hindrance effect. The polyester acrylate type and amino terminal block polyester type of hyperdispersant were prepared to make a study on synthesis methods and synthesis techniques of the two hyperdispersants, which are used for the dispersion and adsorption research on titanium oxide and carbon black.Using PDP and acryloyl chloride as materials, imidazolium ionic liquids as catalyst, triethylamine as acid binding agent,3-pentadecylphenyl acrylate(PDPA) was prepared and its structure was characterized using FTIR, NMR, MS and EDS. Synthetic technological conditions of PDPA was optimized using Response Surface Methodology and the optimum conditions were as follows:usage of imidazolium ionic liquids2.02%(wt.%), molar ratio of acryloyl chloride to PDP1.15:1, reaction time8.25h, reaction temperature57℃. At this condition, the yield of PDPA can reach to87%. Kinetic study was made on the esterification reaction between acryloyl chloride and PDP, and when there were no catalyst and acid binding agent, kinetic equation of the esterification reaction was as follows: When ionic liquids as catalyst and triethylamine as acid binding agent exist, kinetic equation of the esterification reaction was as follows:The solubility of PDPA in mixed solvent of ethanol and methanol, toluene and other five organic solvents was measured at the temperature ranging from273K-297K, and Apelblat equation and λh equation model was used to correlate the solubility data and the results showed that Apelblat model is better than λh model. The dissolution enthalpy and entropy of PDPA were predicted with the solubility data using Apelblat equation and Van’t Hoff equation, and the results showed that the dissolve process is an entropy-driven spontaneous process. Solubility parameter ofPDPA was got through group contribution method, and solubility data of PDPA indifferent solvent was compared.The acrylic polyester type of hyperdispersant including PDPA, methacrylicacid(MAA) and butyl acrylate(BA) was synthesized through free radicals randomcopolymer. The optimum conditions of preparation were as follows: usage ofazodiisobutyronitrile(AIBN) as initiator2%(wt.%), usage of chain transfer agent thesame molar as AIBN, reaction temperature70℃, reaction time8h. The structure ofthe polymer was characterized by FTIR and H-NMR. The influence of the acrylicpolyester type of hyperdispersant including PDPA, MAA and BA on the viscosity andfineness of titanium dioxide disperse system was also studied. The results indicatedthat: the optimum weight-average molecular weight6000, the quality ratio of PDPA：MAA：BA=1.2：1：10, viscosity of titanium dioxide disperse system (solid content30%) can reach50mPa·s, fineness can reach20μm.At the temperature of303K,313K and323K, the isothermal adsorption data oftitanium dioxide to the polyester acrylate type of hyperdispersant in the solvents oftoluene, isopropanol and ethyl acetate were fitted and compared using differentmodels, and the result showed that Fritze-Schlunder model was optimum. The FTIRdata also indicated that the adsorption of titanium dioxide to the polyester acrylatetype of hyperdispersant in the three solvents was mainly physical absorption. Theresult of Dubinin-Radushkevich equation showed that the average adsorption freeenergy of titanium dioxide to the polyester acrylate type of hyperdispersant in thethree solvents was2.09～3.11kJ·mol-1, which indicated that the adsorption wasmainly physical absorption.Carbon black was one of the hardest dispersed pigments, in order to disperse thecarbon black in the solvent system, a new block polyester type of hyperdispersant wasprepared in this paper combining with the structural character of PDP. Firstly, ring-opening polymerization of caprolactone was triggered by PDP to prepare hydroxyl-terminated polyester, and the optimum conditions of preparation were as follows:usage of butyl titanate as catalyst5‰, reaction temperature110℃, reaction time16h.Secondly, the carboxyl end group was got by the reaction between maleic anhydrideand hydroxyl-terminated polyester, and the optimum conditions were as follows:reaction temperature90℃, molar ratio of maleic anhydride to hydroxyl-terminatedpolyester2.5：1, reaction time10h. Finally, amidation occurred between the carboxyl end group and diethylenetriamine, and the optimum conditions were as follows:reaction temperature120℃, reaction time12h. The structure of the block polyestertype of hyperdispersant was characterized by FTIR and H-NMR, and the influence ofthe amino block copolymer on the viscosity and fineness of carbon black dispersesystem was also discussed. The results indicated that: the optimum weight-averagemolecular weight about3000, amine value20mgKOH/g, viscosity of carbon blackdisperse system (solid content30%) can reach30mPa·s, fineness can reach3μm.At the temperature of303K,313K and323K, the isothermal adsorption data ofcarbon black to amino terminal block polyester type of hyperdispersant in the solventsof toluene, isopropanol and ethyl acetate were fitted and compared using differentmodels, and the result showed that Tempkin model was optimum. The FTIR data alsoindicated that the adsorption of carbon black to amino terminal block polyester typeof hyperdispersant in the three solvents was mainly physical absorption. The result ofDubinin–Radushkevich equation showed that the average adsorption free energy ofcarbon black to amino terminal block polyester type of hyperdispersant in the threesolvents was1.31～2.62kJ·mol-1, which indicated that the adsorption was mainlyphysical absorption.Generally speaking, the above results suggest the polyester acrylate type andamino terminal block polyester type of hyperdispersant prepared by PDP both hadpreferable dispersive capacity to titanium dioxide and carbon black in solvent-bornesystem, which will has guiding sense to development of PDP in coating industry.更多还原