对苯二甲酸二丁氧基乙酯增塑剂的合成及应用
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摘要
以对苯二甲酸二甲酯(DMT)和乙二醇丁醚(EB)为原料,采用酯交换一步合成法,制得含有醚键基团的对苯二甲酸二丁氧基乙酯(DBETP)增塑剂,并通过优化得到最适宜的制备工艺为:n(EB)∶n(DMT)=6∶1,催化剂CaO用量为3.0%(以DMT质量为基准,下同),反应时间3.0 h,反应温度140℃。在该条件下,DBETP收率达到93.6%。采用FTIR和1HNMR对产物结构进行了表征。将DBETP增塑的PVC试样(PVC-DBETP)和对苯二甲酸二异辛酯增塑的PVC试样(PVC-DOTP)进行性能对比,结果表明,PVC-DBETP热稳定性与PVC-DOTP基本相当;PVC-DBETP在蒸馏水、食醋、白酒及无水乙醇中的抽出质量损失率与PVC-DOTP相比分别升高了0.6%、1.0%、2.1%及0.3%,在大豆油中,则降低了1.1%;PVC-DBETP和PVC-DOTP的玻璃化转变温度(Tg)分别为31.4和34.7℃;PVC-DBETP与PVC-DOTP相比,拉伸强度提高了5.05%,断裂伸长率提高了8.73%。
A plasticizer containing ether bond,di(2-butoxy ethanol) terephthalate(DBETP),was synthesized by one-step transesterification using dimethyl terephthalate(DMT) and 2-butoxy ethanol(EB) as raw materials.The optimum process conditions of synthesizing DBETP were obtained as follows:n(EB)∶n(DMT)=6∶1,dosage of catalyst CaO 3.0%(based on the mass of DMT,the same below),reaction time 3.0 h,and reaction temperature 140℃.Under these conditions,the yield of DBETP reached 93.6%.The product was characterized by FTIR and 1 HNMR.Subsequently,DBETP was added to thermoplastic polyvinyl chloride(PVC),and mechanical properties of the resulting sample(PVC-DBETP) and diiooctyl terephthalate(DOTP) plasticized PVC(PVC-DOTP) were compared.The results showed that the thermal stability of PVC-DBETP was basically similar to that of PVC-DOTP.The pull-out resistance of plasticized PVC samples was performed in distilled water,vinegar,liquor and spirits,and ethyl alcohol.Compared with that of PVC-DOTP,the mass loss rate of PVC-DBETP increased by 0.6%,1.0%,2.1% and 0.3%,respectively.However,that decreased 1.1% in soybean oil.The glass transition temperature(Tg) of PVC-DBETP was 31.4 ℃,that of PVC-DOTP was 34.7 ℃.The tensile strength and elongation at break of PVC-DBETP increased by 5.05% and 8.73% compared with that of PVC-DOTP.
A plasticizer containing ether bond,di(2-butoxy ethanol) terephthalate(DBETP),was synthesized by one-step transesterification using dimethyl terephthalate(DMT) and 2-butoxy ethanol(EB) as raw materials.The optimum process conditions of synthesizing DBETP were obtained as follows:n(EB)∶n(DMT)=6∶1,dosage of catalyst CaO 3.0%(based on the mass of DMT,the same below),reaction time 3.0 h,and reaction temperature 140℃.Under these conditions,the yield of DBETP reached 93.6%.The product was characterized by FTIR and 1 HNMR.Subsequently,DBETP was added to thermoplastic polyvinyl chloride(PVC),and mechanical properties of the resulting sample(PVC-DBETP) and diiooctyl terephthalate(DOTP) plasticized PVC(PVC-DOTP) were compared.The results showed that the thermal stability of PVC-DBETP was basically similar to that of PVC-DOTP.The pull-out resistance of plasticized PVC samples was performed in distilled water,vinegar,liquor and spirits,and ethyl alcohol.Compared with that of PVC-DOTP,the mass loss rate of PVC-DBETP increased by 0.6%,1.0%,2.1% and 0.3%,respectively.However,that decreased 1.1% in soybean oil.The glass transition temperature(Tg) of PVC-DBETP was 31.4 ℃,that of PVC-DOTP was 34.7 ℃.The tensile strength and elongation at break of PVC-DBETP increased by 5.05% and 8.73% compared with that of PVC-DOTP.
引文
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[13]Hu Bing(胡兵),Tan Jihuai(谈继淮),Xie Bingxue(谢冰雪),et al.Synthesis of di[2-(2-butoxyethoxy)ethanol]terephthalate catalyzed by bronsted-lewis acidic ionic liquid[J].Fine Chemicals(精细化工),2015,32(8):910-916.
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[15]Tan Jihuai(谈继淮),Chen Muhua(陈慕华),Xie Bingxue(谢冰雪),et al.Synthesis of di[2-(2-butoxyethoxy)ethanol]terephthalate[J].Progress in Chemistry(化工进展),2015,34(4):1109-1114.
[16]Sangjun Lee,Kwang-Hwan Ko,Jihoon Shina,et al.Effects of the addition of dimer acid alkyl esters on the properties of ethyl cellulose[J].Carbohydrate Polymers,2015,121:284-294.
[17]Jia Puyou,Zhang Meng,Hu Lihong,et al.Synthesis and application of novel environmental castor oil based polyol ester plasticizers for poly(vinyl chloride)[J].Acs Sustainable Chemistry&Engineering,2015,3(9):2187-2193.
[2]Wang Duoren(汪多仁).Green plasticizer[M].Beijing:Science and Technology Literature Press(科学技术文献出版社),2011:10-13.
[3]Li Min(李敏),Li Hongchun(李红春),Niu Yongsheng(牛永盛).Research progress of plasticizers for polyvinyl chloride[J].Polyvinyl Chloride(聚氯乙烯),2016,44(12):10-12.
[4]Wan Yuhui(万玉辉),Yang Shue(杨树娥).Research progress and prospects on the novel non-toxic plasticize[J].Journal of Salt Science and Chemical Industry(盐业与化工),2014,43(7):1-3.
[5]Greco A,Ferrari F,Del Sole R,et al.Use of cardanol derivatives as plasticizers for PVC[J].Journal of Vinyl&Additive Technology,2016,28(9):63-69.
[6]Li Zhiying(李志莹),Jiang Pingping(蒋平平),Huang Yuandan(黄元旦),et al.Preparation and evaluation of the environment-friendly plasticizer di(2-propylheptyl)-1,2-cyclohexane dicarboxylate[J].Fine Chemicals(精细化工),2015,32(7):794-798.
[7]Rishikesh M,Steve W,Hong M,et al.Biological impact of phthalates[J].Toxicology Letters,2013,217(1):50-58.
[8]Rodrigo Navarro,Mónica Pérez Perrino,Myriam Gómez Tardajos,et al.Phthalate plasticizers covalently bound to PVC:plasticization with suppressed migration[J].Macromolecules,2010,43(5):2377-2381.
[9]Dumont L J,Baker S,Dumont D F,et al.Exploratory in vitro study of red blood cell storage containers formulated with an alternative plasticizer[J].Transfusion,2012,52(7):1439-1445.
[10]Marcilla A,García S,García-Quesada J C.Study of the migration of PVC plasticizers[J].Journal of Analytical&Applied Pyrolysis,2004,71(2):457-463.
[11]Latini G,De F C,Verrotti A.Plasticizers,infant nutrition and reproductive health.[J].Reproductive Toxicology,2004,19(1):27-33.
[12]Sun Yongtai(孙永泰).The synthesis process and application of dioctyl terephthalate[J].Polyester Industry(聚酯工业),2008,21(3):44-45.
[13]Hu Bing(胡兵),Tan Jihuai(谈继淮),Xie Bingxue(谢冰雪),et al.Synthesis of di[2-(2-butoxyethoxy)ethanol]terephthalate catalyzed by bronsted-lewis acidic ionic liquid[J].Fine Chemicals(精细化工),2015,32(8):910-916.
[14]Shi Wancong(石万聪),Shi Zhibo(石志博),Jiang Pingping(蒋平平).Plasticizer and its application[M].Beijing:Chemical Industry Press(化学工业出版社),2002:39-40.
[15]Tan Jihuai(谈继淮),Chen Muhua(陈慕华),Xie Bingxue(谢冰雪),et al.Synthesis of di[2-(2-butoxyethoxy)ethanol]terephthalate[J].Progress in Chemistry(化工进展),2015,34(4):1109-1114.
[16]Sangjun Lee,Kwang-Hwan Ko,Jihoon Shina,et al.Effects of the addition of dimer acid alkyl esters on the properties of ethyl cellulose[J].Carbohydrate Polymers,2015,121:284-294.
[17]Jia Puyou,Zhang Meng,Hu Lihong,et al.Synthesis and application of novel environmental castor oil based polyol ester plasticizers for poly(vinyl chloride)[J].Acs Sustainable Chemistry&Engineering,2015,3(9):2187-2193.