过渡金属Mn取代多金属氧簇催化醇解废旧PET
|
摘要
合成了一种具有三明治结构的过渡金属Mn取代的多金属氧簇(POMs)催化剂Na12[WZnMn2(H2O)2(ZnW9O34)2],用于催化聚对苯二甲酸乙二醇酯(PET)的醇解过程,对反应温度、反应时间和催化剂量等实验条件进行了优化。结果表明,在催化剂量为PET质量的1.0%、质量比PET/EG(乙二醇)为1:4及190℃的条件下反应80 min,PET降解率可达100%,对苯二甲酸乙二醇酯(BHET)的收率达84.42%。
Poly(ethylene terephthalate)(PET) is a kind of thermoplastic polymer resin and has been widely used in many fields because of its excellent thermodynamics and mechanics performance, such as synthetic fiber, plastic film, food packaging, water and soft-drink bottles and so on. However, with the extensive use of PET materials and their inherently hard-to-degrade characteristics, our environment is facing significant challenges in environmental protection and resource reuse. Therefore, it is verynecessary to carry out research on the recycling of PET. The recycling methods for PET are mainly divided into physical and chemical methods. Since chemical methods can degrade PET into raw materials and then reuse them, these methods have received more and more attention. Alcoholysis is a relatively mild method in chemical methods with the advantages of mild reaction conditions and easy separation of products. In order to achieve rapid and gentle degradation of PET and to obtain high conversion and selectivity, ethylene glycol was chosen as a solvent and polyoxometalate(POM) as catalysts for degradation of waste PET. In this study, a kind of transition-metal-substituted POM Na12[WZnMn2(H2 O)2(ZnW9 O34)2] with a sandwich structure was synthesized and it was used to catalyst the alcoholysis of poly(ethylene terephthalate)(PET). The effects of reaction time, reaction temperature, and the amount of catalyst on PET degradation were researched, the conditions was optimized. The results showed that PET could be 100% degraded at 190℃ for 80 min under the conditions of catalyst amount was 1.0 wt% of PET and mass ratio of PET to ethylene glycol(EG) was 1:4, the yield of bis(hydroxyethyl) terephthalate(BHET) achieved 84.42%. In addition, in order to determine the structure and properties of the degradation products, the degradation products were characterized by NMR, IR, TGA, DSC, HPLC and other instruments. The final experimental results showed that the catalyst can efficiently catalyze the alcoholysis reaction of PET and obtain high-purity BHET products.
Poly(ethylene terephthalate)(PET) is a kind of thermoplastic polymer resin and has been widely used in many fields because of its excellent thermodynamics and mechanics performance, such as synthetic fiber, plastic film, food packaging, water and soft-drink bottles and so on. However, with the extensive use of PET materials and their inherently hard-to-degrade characteristics, our environment is facing significant challenges in environmental protection and resource reuse. Therefore, it is verynecessary to carry out research on the recycling of PET. The recycling methods for PET are mainly divided into physical and chemical methods. Since chemical methods can degrade PET into raw materials and then reuse them, these methods have received more and more attention. Alcoholysis is a relatively mild method in chemical methods with the advantages of mild reaction conditions and easy separation of products. In order to achieve rapid and gentle degradation of PET and to obtain high conversion and selectivity, ethylene glycol was chosen as a solvent and polyoxometalate(POM) as catalysts for degradation of waste PET. In this study, a kind of transition-metal-substituted POM Na12[WZnMn2(H2 O)2(ZnW9 O34)2] with a sandwich structure was synthesized and it was used to catalyst the alcoholysis of poly(ethylene terephthalate)(PET). The effects of reaction time, reaction temperature, and the amount of catalyst on PET degradation were researched, the conditions was optimized. The results showed that PET could be 100% degraded at 190℃ for 80 min under the conditions of catalyst amount was 1.0 wt% of PET and mass ratio of PET to ethylene glycol(EG) was 1:4, the yield of bis(hydroxyethyl) terephthalate(BHET) achieved 84.42%. In addition, in order to determine the structure and properties of the degradation products, the degradation products were characterized by NMR, IR, TGA, DSC, HPLC and other instruments. The final experimental results showed that the catalyst can efficiently catalyze the alcoholysis reaction of PET and obtain high-purity BHET products.
引文
[1]Sorrentino L,Di Maio E,Iannace S.Poly(ethylene terephthalate)foams:correlation between the polymer properties and the foaming process[J].Journal of Applied Polymer Science,2010,116(1):27-35.
[2]Sharma V,Parashar P,Srivastava P,et al.Recycling of waste petbottles using dimethyl sulfoxide and hydrotalcite catalyst[J].Journal of Applied Polymer Science,2013,129(3):1513-1519.
[3]Liu F S,Cui X,Yu S T,et al.Hydrolysis reaction of poly(ethylene terephthalate)using ionic liquids as solvent and catalyst[J].Journal of Applied Polymer Science,2009,114(6):3561-3565.
[4]George N,Kurian T.Recent developments in the chemical recycling of postconsumer poly(ethylene terephthalate)waste[J].Industrial and Engineering Chemistry Research,2014,53(37):14185-14198.
[5]Jamdar V,Kathalewar M,Dubey K A,et al.Recycling of PET wastes using electron beam radiations and preparation of polyurethane coatings using recycled material[J].Progress in Organic Coatings,2017,107:54-63.
[6]Liu F,Chen J Y,Li Z L,et al.Alcoholysis of poly(ethylene terephthalate)to produce dioctyl terephthalate with sub-and supercritical isooctyl alcohol[J].Journal of Analytical and Applied Pyrolysis,2013,99:16-22.
[7]Campanelli J R,Kamal M R,Cooper D G.A kinetic-study of the hydrolytic degradation of polyethylene terephthalate at hightemperatures[J].Journal of Applied Polymer Science,1993,48(3):443-451.
[8]Grause G,Kaminsky W,Fahrbach G.Hydrolysis of poly(ethylene terephthalate)in a fluidised bed reactor[J].Polymer Degradation and Stability,2004,85(1):571-575.
[9]Kurokawa H,Ohshima M,Sugiyama K,et al.Methanolysis of polyethylene terephthalate(PET)in the presence of aluminium tiisopropoxide catalyst to form dimethyl terephthalate and ethylene glycol[J].Polymer Degradation and Stability,2003,79(3):529-533.
[10]Rusen E,Mocanu A,Rizea F,et al.Poly(ethylene terephtalate)recycled from post-consumer soft-drinks bottles:I.poly(ethylene terephtalate)depolymerization by glycolysis process[J].Material Plast,2013,50(2):130-133.
[11]Chen F F,Wang G H,Shi C,et al.Kinetics of glycolysis of poly(ethylene terephthalate)under microwave irradiation[J].Journal of Applied Polymer Science,2013,127(4):2809-2815.
[12]Wang H,Li Z X,Liu Y Q,et al.Degradation of poly(ethylene terephthalate)using ionic liquids[J].Green Chemistry,2009,11(10):1568-1575.
[13]Mittal A,Soni R K,Dutt K,et al.Scanning electron microscopic study of hazardous waste flakes of polyethylene terephthalate(PET)by aminolysis and ammonolysis[J].Journal of Hazardous Materials,2010,178(1/3):390-396.
[14]Shukla S R,Harad A M.Aminolysis of polyethylene terephthalate waste[J].Polymer Degradation and Stability,2006,91(8):1850-1854.
[15]Wang H,Liu Y Q,Li Z X,et al.Glycolysis of poly(ethylene terephthalate)catalyzed by ionic liquids[J].European Polymer Journal,2009,45(5):1535-1544.
[16]Lopez-Fonseca R,Duque-Ingunza I,De Rivas B,et al.Kinetics of catalytic glycolysis of pet wastes with sodium carbonate[J].Chemical Engineering Journal,2011,168(1):312-320.
[17]Wang Q,Yao X Q,Tang S F,et al.Urea as an efficient and reusable catalyst for the glycolysis of poly(ethylene terephthalate)wastes and the role of hydrogen bond in this process[J].Green Chemistry,2012,14(9):2559-2566.
[18]Zhu M L,Li S,Li Z X,et al.Investigation of solid catalysts for glycolysis of polyethylene terephthalate[J].Chemical Engineering Journal,2012,185:168-177.
[19]Wang Q,Lu X,Zhou X,et al.1-Allyl-3-methylimidazolium halometallate ionic liquids as efficient catalysts for the glycolysis of poly(ethylene terephthalate)[J].Journal of Applied Polymer Science,2013,129(6):3574-3581.
[20]Zhou X,Lu X,Wang Q,et al.Effective catalysis of poly(ethylene terephthalate)(PET)degradation by metallic acetate ionic liquids[J].Pure and Applied Chemistry,2012,84(3):789-801.
[21]Yue Q F,Yang H G,Zhang M L,et al.Metal-containing ionic liquids:highly effective catalysts for degradation of poly(ethylene terephthalate)[J].Advances in Materials Science and Engineering,2014,2014:1-6.
[22]Yue Q,Xiao L,Zhang M,et al.The glycolysis of poly(ethylene terephthalate)waste:Lewis acidic ionic liquids as high efficient catalysts[J].Polymers,2013,5(4):1258-1271.
[23]Paliwal N R,Mungray A K.Ultrasound assisted alkaline hydrolysis of poly(ethylene terephthalate)in presence of phase transfer catalyst[J].Polymer Degradation and Stability,2013,98(10):2094-2101.
[24]Zhang L,Gao J,Zou J,et al.Hydrolysis of poly(ethylene terephthalate)waste bottles in the presence of dual functional phase transfer catalysts[J].Journal of Applied Polymer Science,2013,130(4):2790-2795.
[25]Bartolome L,Imran M,Lee K G,et al.Superparamagneticγ-Fe2O3nanoparticles as an easily recoverable catalyst for the chemical recycling of PET[J].Green Chemistry,2014,16(1):279-286.
[26]Zhu M,Li Z,Wang Q,et al.Characterization of solid acid catalysts and their reactivity in the glycolysis of poly(ethylene terephthalate)[J].Industrial and Engineering Chemistry Research,2012,51(36):11659-11666.
[27]Aouissi A,Al-Deyab S S,Al-Shahri H.The cationic ring-opening polymerization of tetrahydrofuran with 12-tungstophosphoric acid[J].Molecules,2010,15(3):1398-1407.
[28]Vu T H T,Au H T,Nguyen T M T,et al.Esterification of 2-keto-lgulonic acid catalyzed by a solid heteropoly acid[J].Catalysis Science&Technology,2013,3(3):699-705.
[29]Mokbel H,Xiao P,Simonnet-Jégat C,et al.Iodoniumpolyoxometalate and thianthrenium-polyoxometalate as new onecomponent UV photoinitiators for radical and cationic polymerization[J].Journal of Applied Polymer Science Part A:Polymer Chemistry,2015,53(8):981-989.
[30]Wang X H,Li F,Chen Y G.Polyoxometalates supporting cyclopendienylzirconium CPZrXW11O39n-:a new kind of olefin polymerization catalyst[J].Inorganic Chemistry Communications,2005,8(1):70-71.
[31]Geng Y R,Dong T,Fang P T,et al.Fast and effective glycolysis of poly(ethylene terephthalate)catalyzed by polyoxometalate[J].Polymer Degradation and Stability,2015,117:30-36.
[32]Shi L X,Zhang X W,Wu C D.The synergistic effect of[WZn(VO)2(ZnW9O34)2]12-cores and peripheral metal sites in catalytic oxidative cyclization of acetylacetone[J].Dalton Transactions,2011,40(4):779-781.
[33]Imran M,Kim D H,Al-MasrY W A,et al.Manganese-,cobalt-,and zinc-based mixed-oxide spinels as novel catalysts for the chemical recycling of poly(ethylene terephthalate)via glycolysis[J].Polymer Degradation and Stability,2013,98(4):904-915.
[34]Qiu G,Huang Z X,Tang Z L.Simulation of the dual meiting endotherms of PET[J].Polymeric Materials Science and Engineering,1998,14:9-14.
[2]Sharma V,Parashar P,Srivastava P,et al.Recycling of waste petbottles using dimethyl sulfoxide and hydrotalcite catalyst[J].Journal of Applied Polymer Science,2013,129(3):1513-1519.
[3]Liu F S,Cui X,Yu S T,et al.Hydrolysis reaction of poly(ethylene terephthalate)using ionic liquids as solvent and catalyst[J].Journal of Applied Polymer Science,2009,114(6):3561-3565.
[4]George N,Kurian T.Recent developments in the chemical recycling of postconsumer poly(ethylene terephthalate)waste[J].Industrial and Engineering Chemistry Research,2014,53(37):14185-14198.
[5]Jamdar V,Kathalewar M,Dubey K A,et al.Recycling of PET wastes using electron beam radiations and preparation of polyurethane coatings using recycled material[J].Progress in Organic Coatings,2017,107:54-63.
[6]Liu F,Chen J Y,Li Z L,et al.Alcoholysis of poly(ethylene terephthalate)to produce dioctyl terephthalate with sub-and supercritical isooctyl alcohol[J].Journal of Analytical and Applied Pyrolysis,2013,99:16-22.
[7]Campanelli J R,Kamal M R,Cooper D G.A kinetic-study of the hydrolytic degradation of polyethylene terephthalate at hightemperatures[J].Journal of Applied Polymer Science,1993,48(3):443-451.
[8]Grause G,Kaminsky W,Fahrbach G.Hydrolysis of poly(ethylene terephthalate)in a fluidised bed reactor[J].Polymer Degradation and Stability,2004,85(1):571-575.
[9]Kurokawa H,Ohshima M,Sugiyama K,et al.Methanolysis of polyethylene terephthalate(PET)in the presence of aluminium tiisopropoxide catalyst to form dimethyl terephthalate and ethylene glycol[J].Polymer Degradation and Stability,2003,79(3):529-533.
[10]Rusen E,Mocanu A,Rizea F,et al.Poly(ethylene terephtalate)recycled from post-consumer soft-drinks bottles:I.poly(ethylene terephtalate)depolymerization by glycolysis process[J].Material Plast,2013,50(2):130-133.
[11]Chen F F,Wang G H,Shi C,et al.Kinetics of glycolysis of poly(ethylene terephthalate)under microwave irradiation[J].Journal of Applied Polymer Science,2013,127(4):2809-2815.
[12]Wang H,Li Z X,Liu Y Q,et al.Degradation of poly(ethylene terephthalate)using ionic liquids[J].Green Chemistry,2009,11(10):1568-1575.
[13]Mittal A,Soni R K,Dutt K,et al.Scanning electron microscopic study of hazardous waste flakes of polyethylene terephthalate(PET)by aminolysis and ammonolysis[J].Journal of Hazardous Materials,2010,178(1/3):390-396.
[14]Shukla S R,Harad A M.Aminolysis of polyethylene terephthalate waste[J].Polymer Degradation and Stability,2006,91(8):1850-1854.
[15]Wang H,Liu Y Q,Li Z X,et al.Glycolysis of poly(ethylene terephthalate)catalyzed by ionic liquids[J].European Polymer Journal,2009,45(5):1535-1544.
[16]Lopez-Fonseca R,Duque-Ingunza I,De Rivas B,et al.Kinetics of catalytic glycolysis of pet wastes with sodium carbonate[J].Chemical Engineering Journal,2011,168(1):312-320.
[17]Wang Q,Yao X Q,Tang S F,et al.Urea as an efficient and reusable catalyst for the glycolysis of poly(ethylene terephthalate)wastes and the role of hydrogen bond in this process[J].Green Chemistry,2012,14(9):2559-2566.
[18]Zhu M L,Li S,Li Z X,et al.Investigation of solid catalysts for glycolysis of polyethylene terephthalate[J].Chemical Engineering Journal,2012,185:168-177.
[19]Wang Q,Lu X,Zhou X,et al.1-Allyl-3-methylimidazolium halometallate ionic liquids as efficient catalysts for the glycolysis of poly(ethylene terephthalate)[J].Journal of Applied Polymer Science,2013,129(6):3574-3581.
[20]Zhou X,Lu X,Wang Q,et al.Effective catalysis of poly(ethylene terephthalate)(PET)degradation by metallic acetate ionic liquids[J].Pure and Applied Chemistry,2012,84(3):789-801.
[21]Yue Q F,Yang H G,Zhang M L,et al.Metal-containing ionic liquids:highly effective catalysts for degradation of poly(ethylene terephthalate)[J].Advances in Materials Science and Engineering,2014,2014:1-6.
[22]Yue Q,Xiao L,Zhang M,et al.The glycolysis of poly(ethylene terephthalate)waste:Lewis acidic ionic liquids as high efficient catalysts[J].Polymers,2013,5(4):1258-1271.
[23]Paliwal N R,Mungray A K.Ultrasound assisted alkaline hydrolysis of poly(ethylene terephthalate)in presence of phase transfer catalyst[J].Polymer Degradation and Stability,2013,98(10):2094-2101.
[24]Zhang L,Gao J,Zou J,et al.Hydrolysis of poly(ethylene terephthalate)waste bottles in the presence of dual functional phase transfer catalysts[J].Journal of Applied Polymer Science,2013,130(4):2790-2795.
[25]Bartolome L,Imran M,Lee K G,et al.Superparamagneticγ-Fe2O3nanoparticles as an easily recoverable catalyst for the chemical recycling of PET[J].Green Chemistry,2014,16(1):279-286.
[26]Zhu M,Li Z,Wang Q,et al.Characterization of solid acid catalysts and their reactivity in the glycolysis of poly(ethylene terephthalate)[J].Industrial and Engineering Chemistry Research,2012,51(36):11659-11666.
[27]Aouissi A,Al-Deyab S S,Al-Shahri H.The cationic ring-opening polymerization of tetrahydrofuran with 12-tungstophosphoric acid[J].Molecules,2010,15(3):1398-1407.
[28]Vu T H T,Au H T,Nguyen T M T,et al.Esterification of 2-keto-lgulonic acid catalyzed by a solid heteropoly acid[J].Catalysis Science&Technology,2013,3(3):699-705.
[29]Mokbel H,Xiao P,Simonnet-Jégat C,et al.Iodoniumpolyoxometalate and thianthrenium-polyoxometalate as new onecomponent UV photoinitiators for radical and cationic polymerization[J].Journal of Applied Polymer Science Part A:Polymer Chemistry,2015,53(8):981-989.
[30]Wang X H,Li F,Chen Y G.Polyoxometalates supporting cyclopendienylzirconium CPZrXW11O39n-:a new kind of olefin polymerization catalyst[J].Inorganic Chemistry Communications,2005,8(1):70-71.
[31]Geng Y R,Dong T,Fang P T,et al.Fast and effective glycolysis of poly(ethylene terephthalate)catalyzed by polyoxometalate[J].Polymer Degradation and Stability,2015,117:30-36.
[32]Shi L X,Zhang X W,Wu C D.The synergistic effect of[WZn(VO)2(ZnW9O34)2]12-cores and peripheral metal sites in catalytic oxidative cyclization of acetylacetone[J].Dalton Transactions,2011,40(4):779-781.
[33]Imran M,Kim D H,Al-MasrY W A,et al.Manganese-,cobalt-,and zinc-based mixed-oxide spinels as novel catalysts for the chemical recycling of poly(ethylene terephthalate)via glycolysis[J].Polymer Degradation and Stability,2013,98(4):904-915.
[34]Qiu G,Huang Z X,Tang Z L.Simulation of the dual meiting endotherms of PET[J].Polymeric Materials Science and Engineering,1998,14:9-14.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |