环保增塑剂TXIB的合成以及其对聚乳酸材料的改性研究
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摘要
以异丁酸和2,2,4-三甲基-1,3-戊二醇(TMPD)为原料,以对甲苯磺酸为催化剂,常压反应5 h(温度由150℃逐渐升温至195℃),减压反应1.5 h,真空度为-0.095 MPa,制备得到增塑剂TXIB。采用红外光谱(FT-IR)和核磁共振谱(~1H-NMR)对其进行表征;将该增塑剂与聚乳酸(PLA)按一定的质量比例共混后成膜,采用差示扫描量热仪(DSC)、动态热机械分析仪(DMA)和万能材料强力机对不同含量的增塑剂TXIB对PLA/TXIB共混膜的性能影响进行研究。结果表明:随着增塑剂含量的增加,PLA/TXIB共混体系的玻璃化温度(T_g)逐步降低,储能模量(E′)逐渐减小,拉伸强度由88.5 MPa下降至37.9 MPa,断裂伸长率由47.6%增至418.5%。
The plasticizer TXIB is prepared by using isoamyl acetate and TMPD as raw materials, p-toluene sulfonic acid as catalyst, with 5 h of atmospheric pressure reaction(temperature increased from 150℃ to 195℃), 1.5 h of decompression reaction,-0.095 MPa of vacuum degree. The samples are characterized by infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(~1H-NMR); the plasticizer is blended with PLA in a certain mass ratio to form a film. The effects of different amount of plasticizer TXIB on the properties of PLA/TXIB blend film are studied by differential scanning calorimetry(DSC), dynamic mechanical analyzer(DMA) and universal material strength machine. The results show that with the increase of plasticizer content, the glass transition temperature(T_g) of PLA/TXIB blends decreases gradually, the energy storage modulus(E') decreases gradually, the tensile strength decreases from 88.5 MPa to 37.9 MPa, and the elongation at break increases from 47.6% to 418.5%.
The plasticizer TXIB is prepared by using isoamyl acetate and TMPD as raw materials, p-toluene sulfonic acid as catalyst, with 5 h of atmospheric pressure reaction(temperature increased from 150℃ to 195℃), 1.5 h of decompression reaction,-0.095 MPa of vacuum degree. The samples are characterized by infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(~1H-NMR); the plasticizer is blended with PLA in a certain mass ratio to form a film. The effects of different amount of plasticizer TXIB on the properties of PLA/TXIB blend film are studied by differential scanning calorimetry(DSC), dynamic mechanical analyzer(DMA) and universal material strength machine. The results show that with the increase of plasticizer content, the glass transition temperature(T_g) of PLA/TXIB blends decreases gradually, the energy storage modulus(E') decreases gradually, the tensile strength decreases from 88.5 MPa to 37.9 MPa, and the elongation at break increases from 47.6% to 418.5%.
引文
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[3]Speranza V,Meo A D,Pantani R.Thermal and hydrolytic degradation kinetics of PLA in the molten state[J].Polymer Degradation&Stability,2014,100(1):37~41.
[4]袁理,李芬芬,康睿玲,等.聚乳酸增韧改性研究进展[J].中国塑料,2017,(01):7~12.
[5]杨光瑞.新型增塑剂的制备及其对PLA增塑效果的研究[D].天津科技大学,2015.
[6]陈荣圻.邻苯二甲酸酯增塑剂对人类健康的危害性[J].印染助剂,2016,(02):1~7.
[7]武阳,晏彪,焦铭,等.邻苯二甲酸二异壬酯致小鼠肾组织氧化损伤的研究[J].生态毒理学报,2015,(03):268~275.
[8]欧盟再次对中国产塑料玩具发出消费者警告[J].塑料工业,2015,07:55.
[9]万同,杨光瑞,张婕,等.柠檬酸醚酯增塑剂的合成及增塑聚乳酸[J].材料工程,2015,(05):67~74.
[10]Harte I,Birkinshaw C,Jones E,et al.The Effect of Citrate Ester Plasticizers on the Thermal and Mechanical Properties of Poly(DL-lactide)[J].Applied Polyer,2013,10:1997~2003.
[11]杜涛.新型柠檬酸酯增塑剂的合成与应用[D].天津科技大学,2014.
[12]张欣华,李泽天,王静,等.聚酯增塑剂增塑PVC最新研究进展[J].石油化工高等学校学报,2016,(04):13~17.
[13]Medhat S Farahat.On the heat stabilization efficiency of polyester for poly(vinyl chloride)(PVC)[J].Macromol Mater Eng,2001,286(2):88~93.
[14]杨秋杰.可控生物降解聚酯材料的制备及其性能研究[D].上海工程技术大学,2014.
[15]Cho M K,Ko D H,Lim Y H,et al.The synthesis and the s tructural analysis of advanced PVC plasticizer,2,2,4-trimethyl-1,3-pentanediol-1-butyrate-3-isobutyrate[J].Journal of the Korean Magnetic Resonance Society,2005,9(2):103~109.
[16]辛长征,张浩,王延伟,等.聚乳酸的多重熔融转变与冷结晶行为研究[J].塑料科技,2017,(01):74~77.
[17]桂宗彦.聚乳酸材料的改性研究[D].华东理工大学,2012.