| 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 ?h equation model was used to correlate the solubility data and the results showed that Apelblat model is better than ?h 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 reach20?m.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 reach3?m.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. |
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