水性大豆油-松香基超支化聚酯的合成与表征
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摘要
以松香、大豆油、顺丁烯二酸酐和丙三醇为原料制备水性大豆油-松香基超支化聚酯,采用FTIR、GPC、TG对聚酯的结构进行了表征。研究表明,制备该聚酯的较佳条件为:大豆油投料量为松香质量的50%,顺丁烯二酸酐投料量为松香质量的20%,加入丙三醇使物料羟羧比为0.86,恒温酯化反应温度250℃,恒温反应时间为3 h。该条件下得到超支化聚酯数均分子量(M_n)1776,重均分子量(M_w)5305;酸值为49.9 mg/g,软化点为67℃,乳化3 h可得黄色透明胶体溶液;TG结果表明,该聚酯分解主要集中在350～450℃,表明其具有较高的热稳定性能。该超支化聚酯胶体溶液粒径分布图显示整个体系的平均粒径为22.14nm,说明该聚酯在水中乳化分散性能良好。
The waterborne soybean oil-rosin-based hyperbranched polyester was prepared from rosin,soybean oil, maleic anhydride and glycerol and characterized by FTIR, GPC and TG. The results showed that the preferred conditions for the preparation of the polyester were as follows: the dosage of soybean oil was 50% by mass of rosin, that of maleic anhydride was 20% by mass of rosin, and the hydroxyl-carboxyl ratio of raw materials was 0.86 by adding glycerol, esterification reaction temperature was 250 ℃, and reaction time was 3 h. Under these conditions, the number average molecular weight(M_n) of the prepared hyperbranched polyester was 1776, the weight average molecular weight(M_w) was 5305, the acid value was49.9 mg/g and softening point was 67 ℃. The yellow transparent colloid solution was obtained after 3 hours of emulsification. TG results indicated that the decomposition of polyester was mainly concentrated in the ranging from 350 ℃ to 450 ℃, indicating that it had higher thermal stability. The particle size distribution of the hyperbranched polyester colloidal solution demonstrated that the average particle size of the whole system was 22.14 nm, which revealed that the polyester had good emulsifying and dispersing properties in water.
The waterborne soybean oil-rosin-based hyperbranched polyester was prepared from rosin,soybean oil, maleic anhydride and glycerol and characterized by FTIR, GPC and TG. The results showed that the preferred conditions for the preparation of the polyester were as follows: the dosage of soybean oil was 50% by mass of rosin, that of maleic anhydride was 20% by mass of rosin, and the hydroxyl-carboxyl ratio of raw materials was 0.86 by adding glycerol, esterification reaction temperature was 250 ℃, and reaction time was 3 h. Under these conditions, the number average molecular weight(M_n) of the prepared hyperbranched polyester was 1776, the weight average molecular weight(M_w) was 5305, the acid value was49.9 mg/g and softening point was 67 ℃. The yellow transparent colloid solution was obtained after 3 hours of emulsification. TG results indicated that the decomposition of polyester was mainly concentrated in the ranging from 350 ℃ to 450 ℃, indicating that it had higher thermal stability. The particle size distribution of the hyperbranched polyester colloidal solution demonstrated that the average particle size of the whole system was 22.14 nm, which revealed that the polyester had good emulsifying and dispersing properties in water.
引文
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[14]Zhang Haibo(张海波),Min Denghao(闵邓昊),Chen Yuxiang(陈玉湘),et al.Synthesis of hyperbranched polyester by maleopimaric acid(MPA)and PEG-400 and its UV curing[J].Thermosetting Resin(热固性树脂),2015,30(5):20-23.
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[16]Tang Bingtao(唐炳涛),Zhao Jie(赵杰),Zhang Shufen(张淑芬).Synthesis of styrene-maleic anhydride alternating copolymers by solution polymerization[J].Fine Chemicals(精细化工),2010,27(3):217-221.
[2]Liu Xiongmin(刘雄民),Qin Rongxiu(秦荣秀),Huang Pinxian(黄品鲜),et al.Oxidation reaction kinetics of abietic acid and rosin under ultraviolet light irradiation[J].Acta Phys-chim Sin(物理化学学报),2010,26(8):2115-2120.
[3]Li Dongmei(李冬梅),Li Qian(李前),Zhao Zhendong(赵振东),et al.Study on preparation of bio-fuel oil from rosin residue in industria ldeep processes[J].Biomass Chemical Engineering(生物质化学工程),2010,44(4):13-16.
[4]Chen Yuxiang(陈玉湘),Zhao Zhendong(赵振东),Gu Yan(古研),et al.Study on composition variation relationships of pimaric-type resin acids in rosin at acidic conditions[J].Fine Chemicals(精细化工),2009,26(8):818-823.
[5]Gulacti T,Ramazan E,Osman C,et al.Diterpenes from the berries of Juniperus excelsa[J].Phytochemistry,1999,50(7):1195-1199.
[6]Smith E,Williamson E,Zloh M,et al.Isop imaric acid from pinus nigra shows activity against multidrug-resistant and emrsa strains of Staphylococcus aureus[J].Phytotherapy Research,2005,19(6):538-542.
[7]Wang Chunping(王春平),Lei Fuhou(雷福厚),Li Hao(李浩),et al.Synthesis and structural characterization of the plasticizer tri-lauryl maleopimarate[J].Chemistry and Industry of Forest Products(林产化学与工业),2011,31(4):46-52.
[8]Liu He(刘鹤),Xu Xu(徐徐),Gao Hong(高宏),et al.Synthesis and properties of maleopimaric acid polyester polyol[J].Paint&Coatings Industry(涂料工业),2013,43(1):53-55.
[9]Ge C,Greenland B W,Lampard C,et al.Hyperbranched polymers containing oxazoline monomers and succinic anhydride:Applications in fast drying,low solven coating formulationss[J].Progress in Organic Coatings,2014,77(10):1516-1522.
[10]Asif A,Wen F S.Synthesis and properties of UV curable waterborn hyperbranched aliphatic polyester[J].European Polymer Journal,2003,39(2):933-938.
[11]Tomuta A,Ferrando F,Serra A,et al.New aromatic-aliphatic hyperbranched polyesters with vinylic end groups of different length as modifiers of epoxy/anhydride thermosets[J].Reactive&Functional Polymers,2012,72(1):556-563.
[12]Atta A M,Nassar I F,Bedawy H M.Unsaturated polyester resins based on rosin maleic anhydride adduct as corrosion protections of steel[J].Reactive&Functional Polymers,2007,67(7):617-626.
[13]Sun Liting(孙丽婷),Chen Yuxiang(陈玉湘),Xu Jian(徐建),et al.Synthesis and terminal modification of rosin based hyperbranched polyester[J].Chemistry and Industry of Forest Products(林产化学与工业),2013,33(3):1-6.
[14]Zhang Haibo(张海波),Min Denghao(闵邓昊),Chen Yuxiang(陈玉湘),et al.Synthesis of hyperbranched polyester by maleopimaric acid(MPA)and PEG-400 and its UV curing[J].Thermosetting Resin(热固性树脂),2015,30(5):20-23.
[15]Mosiewicki M A,Aranguren M I.A short review on novel biocomposites based on plant oil precursors[J].European Polymer Journal,2013,49(6):1243-1256.
[16]Tang Bingtao(唐炳涛),Zhao Jie(赵杰),Zhang Shufen(张淑芬).Synthesis of styrene-maleic anhydride alternating copolymers by solution polymerization[J].Fine Chemicals(精细化工),2010,27(3):217-221.