纯水中PET的微波解聚研究
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摘要
本文对纯水中PET的微波解聚进行了研究。
PET纯水微波解聚是指：在微波辐射作用下，PET在不加碱、不加酸、不加催化剂的纯水中进行解聚。纯水中PET的微波解聚是一种新的回收利用废PET聚酯材料的绿色化学方法。本文主要对PET纯水微波解聚的解聚产物、解聚方式、解聚的影响条件及PET解聚反应动力学进行了研究。实验结果表明：在水与PET的质量比为10、220℃、2.0MPa、120min和微波功率为800W的反应条件下，PET的解聚率可以达到100％。解聚产物为对苯二甲酸(TPA)、乙二醇(EG)和少量的二甘醇(DEG)。在210℃、微波功率为600W、水与PET的质量比为10的反应条件下，PET纯水微波解聚的解聚方式为无规解聚。温度对PET解聚率有很大影响。水与PET的质量比对解聚率有影响，10为水与PET的最佳质量比。微波功率对PET的解聚率影响不大。经研究PET纯水微波解聚反应的活化能为38.5KJ／mol，微波对PET的解聚反应有降低活化能的作用。
本方法是绿色的化工过程，从原料到工艺条件都是绿色的，对环境没有污染。符合绿色化学的原则，是废PET聚酯再资源化的发展方向。
The depolymerization of polyethylene terephthalate(PET) by microwave radiation in pure water is investigated.
This process is that depolymerization of PET with microwave radiation needn't acid, base and catalyst .It is a new technology of recycling waste PET and of green chemistry. Some ways is investigated, for example: depolymerization products, chain scission mechanism, reaction conditions and PET depolymerization kinetics. The result approve that Under the condition of 220℃, 2.0 MPa, 120 min, water /PET10 and 800W, PET is depolymerized completely, conversion of PET is 100%. It is testified that the depolymerized products are terephthalic acid(TPA), ethylene glycol(EG) and trace diethylene glycol(DEG). At the condition of the microwave irradiation power 600W, water/PET 10, 210℃, reaction mechanism is the random chain scission mechanism. Reaction temperature has important effection on the degree of PET depolymerization. weight ratio of water to PET has Effect on the degree of PET depolymerization, water to PET 10 is optimal. Microwave power has little effect on the degree of PET depolymerization. Activation energy
is 38.5KJ/mol, microwave radiation have impaction on PET depolymerization with lowing activation energy.
The depolymerization of polyethylene terephthalate(PET) by microwave radiation in pure water is green chemistry and in according with green chemistry principles. It is the powerful one of the depolymerization of polyethylene terephthalate ways .
PET纯水微波解聚是指：在微波辐射作用下，PET在不加碱、不加酸、不加催化剂的纯水中进行解聚。纯水中PET的微波解聚是一种新的回收利用废PET聚酯材料的绿色化学方法。本文主要对PET纯水微波解聚的解聚产物、解聚方式、解聚的影响条件及PET解聚反应动力学进行了研究。实验结果表明：在水与PET的质量比为10、220℃、2.0MPa、120min和微波功率为800W的反应条件下，PET的解聚率可以达到100％。解聚产物为对苯二甲酸(TPA)、乙二醇(EG)和少量的二甘醇(DEG)。在210℃、微波功率为600W、水与PET的质量比为10的反应条件下，PET纯水微波解聚的解聚方式为无规解聚。温度对PET解聚率有很大影响。水与PET的质量比对解聚率有影响，10为水与PET的最佳质量比。微波功率对PET的解聚率影响不大。经研究PET纯水微波解聚反应的活化能为38.5KJ／mol，微波对PET的解聚反应有降低活化能的作用。
本方法是绿色的化工过程，从原料到工艺条件都是绿色的，对环境没有污染。符合绿色化学的原则，是废PET聚酯再资源化的发展方向。
The depolymerization of polyethylene terephthalate(PET) by microwave radiation in pure water is investigated.
This process is that depolymerization of PET with microwave radiation needn't acid, base and catalyst .It is a new technology of recycling waste PET and of green chemistry. Some ways is investigated, for example: depolymerization products, chain scission mechanism, reaction conditions and PET depolymerization kinetics. The result approve that Under the condition of 220℃, 2.0 MPa, 120 min, water /PET10 and 800W, PET is depolymerized completely, conversion of PET is 100%. It is testified that the depolymerized products are terephthalic acid(TPA), ethylene glycol(EG) and trace diethylene glycol(DEG). At the condition of the microwave irradiation power 600W, water/PET 10, 210℃, reaction mechanism is the random chain scission mechanism. Reaction temperature has important effection on the degree of PET depolymerization. weight ratio of water to PET has Effect on the degree of PET depolymerization, water to PET 10 is optimal. Microwave power has little effect on the degree of PET depolymerization. Activation energy
is 38.5KJ/mol, microwave radiation have impaction on PET depolymerization with lowing activation energy.
The depolymerization of polyethylene terephthalate(PET) by microwave radiation in pure water is green chemistry and in according with green chemistry principles. It is the powerful one of the depolymerization of polyethylene terephthalate ways .
引文
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[43]. A.G.Whittaker and D.M.P.Mingos,journal of Microwave Power and Electromagnetic Energy,1991, 29(4), 195.
[44]. 李杰，赵建青，沈家瑞。微波作用下的甲基丙烯酸甲酯的本体聚合[J]高分子材料科学工程。1999(2):155.
[45]. Wei J ,Hawley M C.Delong J D.Comparison of Microwave and Thermaclcune of Epoxy resins[J]. Polymer.1993,33(17): 1132-1140.
[46]. Marand E. Baker H R.Graybeal J D.Comparison of reaction Mechanisms of Epoxy Resins undergoing Thermal and Microwave Cure from in-situ Measurements of Microwave Diielectric Properties and Infrared Spectroscopy[J].Macromoleculars. 1992,25(8):2243～2252.
[47]．田一光．孙健飞，李广军等。微波加热离子交换制备La.Sm L分子筛催化剂[J]。沈阳化工学院学报，2000(1)5～9．
[48]．戴长虹，杨静漪。溶胶-凝胶法微波合成AIN纳米微粉的研究[J]。科学通报2000。45(8)：835～838
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[50]．陈莉月，徐立强，分析仪器，1997，(4)，12。
[51]．韩铠，国外分析仪器，1994，(3)，26。
[52]．H.Matusiewiez,J.Anal.Atom.Spectrom,1986,58,2534．
[53]．杨俊杰，低渗油气藏勘探开发技术，北京石油工业出版社，1995．
[54]. Ben-Zu Wan,Chih-Yu Kao,Wu-Hsun Cheng: Ind Eng .Chem.Res.2001,40,509～514.
[55]. A.Ballara and J.Verdu, Polym.Degrad,stab,26,361～374(1989).
[56]. H.Zimmerman and N.T.Kim,Polym.Eng.Sci,20,680～683(1980).
[57]. D.A.S.Ravens and and I.M.Ward.trans.Farad.Soc,57,150～159(1961).
[58]. Campanelli,J.R;Kamal,M,R;Cooper, D.G.J Appl Polym Sci 1993,48,443.
[59]．仪征化纤工业联合公司企业标准QJ／YH03-3015-89．
[60]．金日光，华幼卿。高分子物理．化学工业出版社，1991，256．
[61]. Campanelli J R, Cooper G, et aI.ANTEC 1992,50:270.
[62]．仪征化纤工业联合公司企业标准QJ／YH08-3016-89．
[63]. CampanelliJR, CooperDG, KammalMR.J.Appl.Poly. Sci., 1994,53:985～991.
[64]. B.-K.Kim,C.-C. HUANG,S.-C.BAE,S.-C. YI,H.KUMAZAWA Journal of Applied Polymer Science.Vol.81.2102-2108(2001).
[2]．黄发荣，等．高分子材料的循环利用。北京：化学工业出版社，1999：2．
[3]．GB patent 784 248，1957．
[4]．杨勇，吕毅军，徐元源，相宏伟．化学进展2001．1，13卷1期68～72．
[5]．胡常伟，李贤均．绿色化学原理和应用[M]．北京：中国石化出版社，2002．
[6]．宋新，张先德合成技术及应用2000。16卷1期22～27．
[7]. PolyesterWasterRecycling: Sources,ProcessingMethods&EndUses[J].IFJ, 1999,(6): 18～24.
[8]．王德诚．世界聚酯工业发展的特点和趋势[J]．聚酯工业，2000，13(2)：1～5．
[9]. PureTechInternational,Inc[J].IFJ, 1995,10(3):20～22.
[10]．潘祖仁等。高分子化学第二版1997,202～203．
[11]. Wellman,Inc.ThefibersDivision[J].IFJ, 1995,10(3): 14～18.
[12]. RecyclingandRe-useofpolyester. ChemFibersIntem, 1998,48(3):245.
[13]．罗伟国．日本用回收聚酯瓶切片生产纺粘无纺布[J]．中国化纤信息,2000,(7)：22．
[14]. JanzerL.PolyesterWasterRecyclingTechnology.PETryc.ChemfibersIntern, 1998,48(5):390～392.
[15]. Buhler.PETBottletoBottleProcess. ChemafibersInter,1999,(5):387.
[16]. EastmanChemical. PETRecyclingtechnology.ChemFibersIntern. 1999,(5):383.
[17]. USP 4605762,1986.
[18]. USP 3403115,1968.
[19]．杨始堃(YangSK)．合成纤维工业(ChinaSyntheticFiberIndustry),1978，4：8．
[20]．佐古猛。工业材料，1978(4)：8．
[21]．邹盛欧。塑料科技，1998，26(4)：54．
[22]．王汉夫，孙辉等。吉林大学自然科学学报．2000，(4)：39。
[23]. Collins M J,Zeronian S H,Marshall M L. J Macromol Sci Chem,1991,A28:775.
[24]. Blackmon K P, et al .EP 365 842 1998.
[25]. Ind Patent 154 774.1985.
[26]．黄发荣，陈涛，沈学宁。高分子材料的循环利用。化学工业出版社，2000：273．
[27]. C Birdladeanu, C Vasile,I A Schneider.Makromol Chem,1976,177:121
[28]. IP 163385,1985.
[29]. Yoshioka, etal. JAppl Polym sci, 1994 (52): 1353.
[30]. Paszum D, spychaj T. Ind Eng Chem Res,1997 (36): 1373.
[31]. Rollick K L.WO9510 499.1995.
[32]. EP597751, 1994.
[33]. Rosen BJ. US 5095 145, 1991.
[34]. GB Patent 824 624.1960.
[35]. GB Patent 2 123 403.1984.
[36]. Gallagher F G. US 3 321 510,1967.
[37]．金钦汉等，微波化学。科学出版社1999：5．
[38]．金钦汉等，微波化学。科学出版社1999：7～13．
[39]．杨伯伦，贺拥军。现代化工2001第12卷4期6～12．
[40]. Thostenson E T, Chou T W.Microwave Processing:Fundamentals and Application.composites;Part A,199,30(9):1055-1071.
[41]. Clark D, Folz D,West J.Processing Materials with Microwave Energy[J]. Materials Science and Engineering:A,2000,287(2):153～158.
[42]. Bose A K,Banik B K,Manhas M S. Stereocontrol of βlactam Formation Using Microwave Irradiation[J].Tetrahe dron Letters, 1995,36(2):213～216.
[43]. A.G.Whittaker and D.M.P.Mingos,journal of Microwave Power and Electromagnetic Energy,1991, 29(4), 195.
[44]. 李杰，赵建青，沈家瑞。微波作用下的甲基丙烯酸甲酯的本体聚合[J]高分子材料科学工程。1999(2):155.
[45]. Wei J ,Hawley M C.Delong J D.Comparison of Microwave and Thermaclcune of Epoxy resins[J]. Polymer.1993,33(17): 1132-1140.
[46]. Marand E. Baker H R.Graybeal J D.Comparison of reaction Mechanisms of Epoxy Resins undergoing Thermal and Microwave Cure from in-situ Measurements of Microwave Diielectric Properties and Infrared Spectroscopy[J].Macromoleculars. 1992,25(8):2243～2252.
[47]．田一光．孙健飞，李广军等。微波加热离子交换制备La.Sm L分子筛催化剂[J]。沈阳化工学院学报，2000(1)5～9．
[48]．戴长虹，杨静漪。溶胶-凝胶法微波合成AIN纳米微粉的研究[J]。科学通报2000。45(8)：835～838
[49]．金钦汉等，微波化学。科学出版社1999：126～134．
[50]．陈莉月，徐立强，分析仪器，1997，(4)，12。
[51]．韩铠，国外分析仪器，1994，(3)，26。
[52]．H.Matusiewiez,J.Anal.Atom.Spectrom,1986,58,2534．
[53]．杨俊杰，低渗油气藏勘探开发技术，北京石油工业出版社，1995．
[54]. Ben-Zu Wan,Chih-Yu Kao,Wu-Hsun Cheng: Ind Eng .Chem.Res.2001,40,509～514.
[55]. A.Ballara and J.Verdu, Polym.Degrad,stab,26,361～374(1989).
[56]. H.Zimmerman and N.T.Kim,Polym.Eng.Sci,20,680～683(1980).
[57]. D.A.S.Ravens and and I.M.Ward.trans.Farad.Soc,57,150～159(1961).
[58]. Campanelli,J.R;Kamal,M,R;Cooper, D.G.J Appl Polym Sci 1993,48,443.
[59]．仪征化纤工业联合公司企业标准QJ／YH03-3015-89．
[60]．金日光，华幼卿。高分子物理．化学工业出版社，1991，256．
[61]. Campanelli J R, Cooper G, et aI.ANTEC 1992,50:270.
[62]．仪征化纤工业联合公司企业标准QJ／YH08-3016-89．
[63]. CampanelliJR, CooperDG, KammalMR.J.Appl.Poly. Sci., 1994,53:985～991.
[64]. B.-K.Kim,C.-C. HUANG,S.-C.BAE,S.-C. YI,H.KUMAZAWA Journal of Applied Polymer Science.Vol.81.2102-2108(2001).