聚氨酯废料化学回收综述
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摘要
针对聚氨酯废料(PUW)资源化利用程度低,易造成二次污染等问题,开展化学法回收聚氨酯废料的研究,探讨了PUW、醇解剂(ALC)和催化剂(CAT)的种类以及反应温度、反应时间、PUW/ALC质量比和ALC/CAT固定配比等关键因素的影响规律,研究表明,典型PUW的降解效率由高至低分别是弹性体>软质>硬质;甘油因其价格低,且有助于提升PUW再生产品性能,在ALC中得到了广泛的应用;同时,对比于传统胺类、亚锡类CAT,碱金属氢氧化物和碱金属盐类不仅表现出较高的催化效率(2～10倍)和降解效率(70%～80%)还能降低反应温度(20～30℃),尤其是碱金属盐类CAT还有助于增强再生产品的可塑性和降低副产物含量;最后,适宜的反应温度(160～200℃)和反应时间(2～3 h)以及一定的PUW/ALC质量比(1∶2～1∶3)和ALC/CAT固定配比(多元醇和胺类/碱金属氢氧化物化合物)能够有助于实现较高的PUW降解效率(70%～90%)。
Due to the low utilization of polyurethane waste(PUW) resources,causing secondary pollution and other issues,it has become increasingly important that polyurethane waste be chemically recovered.The key influence factors on the waste polyurethane alcoholysis process such as types of PUW,alcoholysis agent(ALC),catalyst(CAT),as well as the reaction temperature,reaction time,PUW/ALC and ALC/CAT ratio etc.Studies had shown that the degradation rate of typical PUW from high to low were elastomers > soft > hard;Because of its low price and help to improve the performance of PUW recycled products,glycerol has been widely used in ALC;Simultaneously,hydroxides and alkali metal salts not only showed higher catalytic efficiency(2 ～ 10 times) and degradation efficiency(70% ～ 80%) but also lower the reaction temperature(20 ～ 30 ℃).Especially the alkali metal salts ACT also contributed to the plasticity of the recycled product with less by-product.At last,the optimal reaction temperature(160 ～200 ℃) and reaction time(2 ～ 3 h) and the immobilization of ALC/CAT at a certain mass ratio of PUW/ALC(1∶ 2 ～ 1 ∶ 3) metal hydroxide compounds could help achieve higher PUW degradation efficiency(70% ～ 90%).
Due to the low utilization of polyurethane waste(PUW) resources,causing secondary pollution and other issues,it has become increasingly important that polyurethane waste be chemically recovered.The key influence factors on the waste polyurethane alcoholysis process such as types of PUW,alcoholysis agent(ALC),catalyst(CAT),as well as the reaction temperature,reaction time,PUW/ALC and ALC/CAT ratio etc.Studies had shown that the degradation rate of typical PUW from high to low were elastomers > soft > hard;Because of its low price and help to improve the performance of PUW recycled products,glycerol has been widely used in ALC;Simultaneously,hydroxides and alkali metal salts not only showed higher catalytic efficiency(2 ～ 10 times) and degradation efficiency(70% ～ 80%) but also lower the reaction temperature(20 ～ 30 ℃).Especially the alkali metal salts ACT also contributed to the plasticity of the recycled product with less by-product.At last,the optimal reaction temperature(160 ～200 ℃) and reaction time(2 ～ 3 h) and the immobilization of ALC/CAT at a certain mass ratio of PUW/ALC(1∶ 2 ～ 1 ∶ 3) metal hydroxide compounds could help achieve higher PUW degradation efficiency(70% ～ 90%).
引文
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[2]李迪,宋文生,魏稳涛,等.聚醚酯聚氨酯弹性体研究进展[J].化工新型材料,2015,43(9):24-26,29.
[3]李程,吴子刚,王晓彤,等.聚氨酯行业的现状及发展趋势[J].粘接,2016,37(11):63-67.
[4]Wager P A,Hischier R.Life cycle assessment of post-consumer plastics production from waste electrical and electronic equipment(WEEE)treatment residues in a Central European plastics recycling plant[J].Science of the Total Environment,2015,529(1):158-167.
[5]Park J S,Lim Y M,Nho Y C.Radiation-induced grafting with one-step process of waste polyurethane onto highdensity polyethylene[J].Materials,2015,9(1):13.
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[7]Chiu S H,Wu C L,Tsou C Y,et al.Study of the synthesis and properties of polyurethane containing pyridyl units for shape memory[J].Polymer Bulletin,2016,73(5):1303-1320.
[8]Herrero D S.Glycolysis process for polyurethane waste recycling[D].Castilla-La Mancha:Universidad de CastillaLa Mancha,2017.
[9]Mou S,Zhang G,Wei H,et al.Present situation of recycling technology of waste rigid polyurethane foam[J].Shandong Chemical Industry,2017,46(18):198-199.
[10]Garrido M A,Gerecke A C,Heeb N,et al.Isocyanate emissions from pyrolysis of mattresses containing polyurethane foam[J].Chemosphere,2017,168(1):667-675.
[11]Singsatit P,Pimpan V.Recycling of medical gown nonwoven fabric manufacturing waste as a filler for high density polyethylene[J].Journal of Metals,Materials and Minerals,2017,19(1):81-88.
[12]Aou K,Ge S,Mowery D M,et al.Two-domain morphology in viscoelastic polyurethane foams[J].Polymer,2015,56(1):37-45.
[13]Aou K,Schrock A K,Baugh III D,et al.Viscoelastic recovery behavior and imperfection in reactive polymer network of viscoelastic polyurethane memory foams[J].Polymer,2017,117(1):183-197.
[14]Wu H L,Chen F G,Wang J.Synthesis and properties of an alcoholysis lignin-based polyurethane film[J].Paper Science&Technology,2017,36(3):5-10.
[15]Paruzel A,Michaowski S,Hodan J,et al.Rigid polyurethane foam fabrication using medium chain glycerides of coconut oil and plastics from end-of-life vehicles[J].ACSSustainable Chemistry&Engineering,2017,5(7):6237-6246.
[16]Kim H Y,Choi J W,Chung Y C,et al.The grafting of recycled polyol from waste polyurethane foam onto new polyurethane and its impact on shape recovery and water vapor permeation[J].Fibers and Polymers,2017,18(5):842-851.
[17]夏峰,杨建军.防霉型水性聚氨酯涂料的功能设计与研究进展[J].化工新型材料,2017,45(7):220-222.
[18]Wang Y,Hou Y,Song H.Ring-closing depolymerization of polytetrahydrofuran to produce tetrahydrofuran using heteropolyacid as catalyst[J].Polymer Degradation and Stability,2017,144(1):17-23.
[19]向平,张成彬,张均,等.不同异氰酸酯型聚氨酯弹性体的合成与性能研究[J].化工新型材料,2017,45(4):70-72.
[20]张晓明,胡文峰,江燕妮,等.聚醚TSU-450L和聚醚H303复配制备硬质聚氨酯泡沫及性能研究[J].化工新型材料,2017,45(1):91-94.
[21]Yu C Y,Lee W J.Characteristics of glycolysis products of polyurethane foams made with polyhydric alcohol liquefied Cryptomeria japonica wood[J].Polymer Degradation and Stability,2014,101(1):60-64.
[22]Molero C,de Lucas A,Romero F,et al.Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst[J].Journal of Material Cycles and Waste Management,2009,11(2):130-132.
[23]赵潋景,顾晓华,杜星,等.聚氨酯废旧材料的降解回收再利用的研究[J].齐齐哈尔大学学报:自然科学版,2017,33(2):39-42.
[24]Park J S,Lim Y M,Nho Y C.Preparation of high density polyethylene/waste polyurethane blends compatibilized with polyethylene-graft-maleic anhydride by radiation[J].Materials,2015,8(4):1626-1635.
[25]刁青.废旧聚氨酯材料的醇解研究[D].上海:复旦大学,2012.
[26]Glowinska E,Wloch M.Rheology of glycolyzates produced by conversion of polyetherurethane wastes[J].Przemysl Chemiczny,2014,93(8):1308-1310.
[27]Nuraini L,Triwulandari E,Ghozali M,et al.Synthesis of polyurethane/silica modified epoxy polymer based on 1,3-propanediol for coating application[J].Indonesian Journal of Chemistry,2017,17(3):477-484.
[28]Wang J,Luo S,Haiping X U,et al.Effect of different catalysts on performance of glycolysis products of waste polyurethane fiber[J].Journal of Shanghai Second Polytechnic University,2016,33(1):15-19.
[29]Wang X,Chen H,Chen C,et al.Chemical degradation of thermoplastic polyurethane for recycling polyether polyol[J].Fibers and Polymers,2011,12(7):857-863.
[30]Troev K,Atanassov V,Tzevi R.Chemical degradation of polyurethanes.II.Degradation of microporous polyurethane elastomer by phosphoric acid esters[J].Journal of Applied Polymer Science,2000,76(6):886-893.
[31]Simón D,de Lucas A,Rodríguez J F,et al.Flexible polyurethane foams synthesized employing recovered polyols from glycolysis:Physical and structural properties[J].Journal of Applied Polymer Science,2017,134(32):1-9.
[32]Simón D,de Lucas A,Rodríguez J F,et al.Glycolysis of high resilience flexible polyurethane foams containing polyurethane dispersion polyol[J].Polymer Degradation and Stability,2016,133(1):119-130.
[33]Datta J,Kopczyńska P,Simón D,et al.Thermo-chemical decomposition study of polyurethane elastomer through glycerolysis route with using crude and refined glycerine as a transesterification agent[J].Journal of Polymers and the Environment,2018,26(1):166-174.
[34]Molero C,Lucas A D,Rodríguez J F.Recovery of polyols from flexible polyurethane foam by“split-phase”glycolysis:Study on the influence of reaction parameters[J].Polymer Degradation&Stability,2008,93(2):353-361.
[35]Lipshitz S D,Macosko C W.Kinetics and energetics of a fast polyurethane cure[J].Journal of Applied Polymer Science,2010,21(8):2029-2039.
[36]Kopczyńska P,Datta J.Rheological characteristics of oligomeric semiproducts gained via chemical degradation of polyurethane foam using crude glycerin in the presence of different catalysts[J].Polymer Engineering&Science,2017,57(8):891-900.
[37]Santos L M,Carone C L P,Dullius J,et al.Using different catalysts in the chemical recycling of waste from flexible polyurethane foams[J].Polímeros,2013,23(5):608-613.
[38]Simón D,Borreguero A M,De Lucas A,et al.Sustainable Polyurethanes:Chemical Recycling to Get It[M].Berlin:Springer International Publishing,2014:229-260.
[39]杨粉蓉.软质聚氨酯废料的回收与再利用研究[D].西安:西北大学,2011.
[40]Simón D,Borreguero A M,Lucas A D,et al.Novel polyol initiator from polyurethane recycling residue[J].Journal of Material Cycles&Waste Management,2014,16(3):1-8.
[41]Datta J.Effect of glycols used as glycolysis agents on chemical structure and thermal stability of the produced glycolysates[J].Journal of Thermal Analysis and Calorimetry,2012,109(2):517-520.
[42]Murai M,Sanou M,Fujimoto T,et al.Glycolysis of rigid polyurethane foam under various reaction conditions[J].Journal of Cellular Plastics,2003,39(1):15-27.
[43]Nikje M,Nikrah M,Haghshenas M.Microwave assisted“split-phase”glycolysis of polyurethane flexible foam wastes[J].Polymer Bulletin,2007,59(1):91-104.
[44]Gornicki A,Richter P,Polkowski W,et al.Anorectal and sexual functions after preoperative radiotherapy and fullthickness local excision of rectal cancer[J].European Journal of Surgical Oncology,2014,40(6):723-730.
[45]Wang Y,Wang F,Dong Q,et al.Core-shell expandable graphite@aluminum hydroxide as a flame-retardant for rigid polyurethane foams[J].Polymer Degradation and Stability,2017,146(1):267-276.
[2]李迪,宋文生,魏稳涛,等.聚醚酯聚氨酯弹性体研究进展[J].化工新型材料,2015,43(9):24-26,29.
[3]李程,吴子刚,王晓彤,等.聚氨酯行业的现状及发展趋势[J].粘接,2016,37(11):63-67.
[4]Wager P A,Hischier R.Life cycle assessment of post-consumer plastics production from waste electrical and electronic equipment(WEEE)treatment residues in a Central European plastics recycling plant[J].Science of the Total Environment,2015,529(1):158-167.
[5]Park J S,Lim Y M,Nho Y C.Radiation-induced grafting with one-step process of waste polyurethane onto highdensity polyethylene[J].Materials,2015,9(1):13.
[6]Ross P,Escobar G,Sevilla G,et al.Micro and nanocomposites of polybutadienebased polyurethane liners with mineral fillers and nanoclay:thermal and mechanical properties[J].Open Chemistry,2017,15(1):46-52.
[7]Chiu S H,Wu C L,Tsou C Y,et al.Study of the synthesis and properties of polyurethane containing pyridyl units for shape memory[J].Polymer Bulletin,2016,73(5):1303-1320.
[8]Herrero D S.Glycolysis process for polyurethane waste recycling[D].Castilla-La Mancha:Universidad de CastillaLa Mancha,2017.
[9]Mou S,Zhang G,Wei H,et al.Present situation of recycling technology of waste rigid polyurethane foam[J].Shandong Chemical Industry,2017,46(18):198-199.
[10]Garrido M A,Gerecke A C,Heeb N,et al.Isocyanate emissions from pyrolysis of mattresses containing polyurethane foam[J].Chemosphere,2017,168(1):667-675.
[11]Singsatit P,Pimpan V.Recycling of medical gown nonwoven fabric manufacturing waste as a filler for high density polyethylene[J].Journal of Metals,Materials and Minerals,2017,19(1):81-88.
[12]Aou K,Ge S,Mowery D M,et al.Two-domain morphology in viscoelastic polyurethane foams[J].Polymer,2015,56(1):37-45.
[13]Aou K,Schrock A K,Baugh III D,et al.Viscoelastic recovery behavior and imperfection in reactive polymer network of viscoelastic polyurethane memory foams[J].Polymer,2017,117(1):183-197.
[14]Wu H L,Chen F G,Wang J.Synthesis and properties of an alcoholysis lignin-based polyurethane film[J].Paper Science&Technology,2017,36(3):5-10.
[15]Paruzel A,Michaowski S,Hodan J,et al.Rigid polyurethane foam fabrication using medium chain glycerides of coconut oil and plastics from end-of-life vehicles[J].ACSSustainable Chemistry&Engineering,2017,5(7):6237-6246.
[16]Kim H Y,Choi J W,Chung Y C,et al.The grafting of recycled polyol from waste polyurethane foam onto new polyurethane and its impact on shape recovery and water vapor permeation[J].Fibers and Polymers,2017,18(5):842-851.
[17]夏峰,杨建军.防霉型水性聚氨酯涂料的功能设计与研究进展[J].化工新型材料,2017,45(7):220-222.
[18]Wang Y,Hou Y,Song H.Ring-closing depolymerization of polytetrahydrofuran to produce tetrahydrofuran using heteropolyacid as catalyst[J].Polymer Degradation and Stability,2017,144(1):17-23.
[19]向平,张成彬,张均,等.不同异氰酸酯型聚氨酯弹性体的合成与性能研究[J].化工新型材料,2017,45(4):70-72.
[20]张晓明,胡文峰,江燕妮,等.聚醚TSU-450L和聚醚H303复配制备硬质聚氨酯泡沫及性能研究[J].化工新型材料,2017,45(1):91-94.
[21]Yu C Y,Lee W J.Characteristics of glycolysis products of polyurethane foams made with polyhydric alcohol liquefied Cryptomeria japonica wood[J].Polymer Degradation and Stability,2014,101(1):60-64.
[22]Molero C,de Lucas A,Romero F,et al.Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst[J].Journal of Material Cycles and Waste Management,2009,11(2):130-132.
[23]赵潋景,顾晓华,杜星,等.聚氨酯废旧材料的降解回收再利用的研究[J].齐齐哈尔大学学报:自然科学版,2017,33(2):39-42.
[24]Park J S,Lim Y M,Nho Y C.Preparation of high density polyethylene/waste polyurethane blends compatibilized with polyethylene-graft-maleic anhydride by radiation[J].Materials,2015,8(4):1626-1635.
[25]刁青.废旧聚氨酯材料的醇解研究[D].上海:复旦大学,2012.
[26]Glowinska E,Wloch M.Rheology of glycolyzates produced by conversion of polyetherurethane wastes[J].Przemysl Chemiczny,2014,93(8):1308-1310.
[27]Nuraini L,Triwulandari E,Ghozali M,et al.Synthesis of polyurethane/silica modified epoxy polymer based on 1,3-propanediol for coating application[J].Indonesian Journal of Chemistry,2017,17(3):477-484.
[28]Wang J,Luo S,Haiping X U,et al.Effect of different catalysts on performance of glycolysis products of waste polyurethane fiber[J].Journal of Shanghai Second Polytechnic University,2016,33(1):15-19.
[29]Wang X,Chen H,Chen C,et al.Chemical degradation of thermoplastic polyurethane for recycling polyether polyol[J].Fibers and Polymers,2011,12(7):857-863.
[30]Troev K,Atanassov V,Tzevi R.Chemical degradation of polyurethanes.II.Degradation of microporous polyurethane elastomer by phosphoric acid esters[J].Journal of Applied Polymer Science,2000,76(6):886-893.
[31]Simón D,de Lucas A,Rodríguez J F,et al.Flexible polyurethane foams synthesized employing recovered polyols from glycolysis:Physical and structural properties[J].Journal of Applied Polymer Science,2017,134(32):1-9.
[32]Simón D,de Lucas A,Rodríguez J F,et al.Glycolysis of high resilience flexible polyurethane foams containing polyurethane dispersion polyol[J].Polymer Degradation and Stability,2016,133(1):119-130.
[33]Datta J,Kopczyńska P,Simón D,et al.Thermo-chemical decomposition study of polyurethane elastomer through glycerolysis route with using crude and refined glycerine as a transesterification agent[J].Journal of Polymers and the Environment,2018,26(1):166-174.
[34]Molero C,Lucas A D,Rodríguez J F.Recovery of polyols from flexible polyurethane foam by“split-phase”glycolysis:Study on the influence of reaction parameters[J].Polymer Degradation&Stability,2008,93(2):353-361.
[35]Lipshitz S D,Macosko C W.Kinetics and energetics of a fast polyurethane cure[J].Journal of Applied Polymer Science,2010,21(8):2029-2039.
[36]Kopczyńska P,Datta J.Rheological characteristics of oligomeric semiproducts gained via chemical degradation of polyurethane foam using crude glycerin in the presence of different catalysts[J].Polymer Engineering&Science,2017,57(8):891-900.
[37]Santos L M,Carone C L P,Dullius J,et al.Using different catalysts in the chemical recycling of waste from flexible polyurethane foams[J].Polímeros,2013,23(5):608-613.
[38]Simón D,Borreguero A M,De Lucas A,et al.Sustainable Polyurethanes:Chemical Recycling to Get It[M].Berlin:Springer International Publishing,2014:229-260.
[39]杨粉蓉.软质聚氨酯废料的回收与再利用研究[D].西安:西北大学,2011.
[40]Simón D,Borreguero A M,Lucas A D,et al.Novel polyol initiator from polyurethane recycling residue[J].Journal of Material Cycles&Waste Management,2014,16(3):1-8.
[41]Datta J.Effect of glycols used as glycolysis agents on chemical structure and thermal stability of the produced glycolysates[J].Journal of Thermal Analysis and Calorimetry,2012,109(2):517-520.
[42]Murai M,Sanou M,Fujimoto T,et al.Glycolysis of rigid polyurethane foam under various reaction conditions[J].Journal of Cellular Plastics,2003,39(1):15-27.
[43]Nikje M,Nikrah M,Haghshenas M.Microwave assisted“split-phase”glycolysis of polyurethane flexible foam wastes[J].Polymer Bulletin,2007,59(1):91-104.
[44]Gornicki A,Richter P,Polkowski W,et al.Anorectal and sexual functions after preoperative radiotherapy and fullthickness local excision of rectal cancer[J].European Journal of Surgical Oncology,2014,40(6):723-730.
[45]Wang Y,Wang F,Dong Q,et al.Core-shell expandable graphite@aluminum hydroxide as a flame-retardant for rigid polyurethane foams[J].Polymer Degradation and Stability,2017,146(1):267-276.