聚氨酯硬泡用甲酸甲酯发泡剂简介
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- 英文论文题名：Brief Introduction of Methyl Formate Blowing Agent for Polyurethane Rigid Foam
- 论文作者：于剑昆
- 英文论文作者：YU Jiankun ; Liming Research & Design Institute of Chemical Industry Co.Ltd
- 年：2016
- 作者机构：黎明化工研究设计院有限责任公司;
- 论文关键词：聚氨酯硬泡 ; 发泡剂 ; 甲酸甲酯 ; HCF ; HFC ; HFO ; 戊烷类
- 英文论文关键词：polyurethane rigid foam ; blowing agent ; methyl formate ; HCFC ; HFC ; HFO ; pentanes
- 会议召开时间：2016-07-30
- 会议录名称：中国聚氨酯工业协会第十八次年会论文集
- 语种：中文
- 分类号：TQ314.24;TQ328.3
- 学会代码：JAZG
- 会议名称：中国聚氨酯工业协会第十八次年会
- 会议地点：中国上海
- 主办单位：中国聚氨酯工业协会
- 学会名称：中国聚氨酯工业协会
- 页数：12
- 文件大小：1151k
- 原文格式：D
- 会议级别：全国
摘要
介绍了以Ecomate~®为代表的甲酸甲酯发泡剂的性质。与传统发泡剂相比,甲酸甲酯发泡剂具有绿色环保、燃点较高、与组分相容性好、所得泡沫密度和导热系数较低等优点。详细介绍了甲酸甲酯单独作为发泡剂,以及它与HCFC、HFC、戊烷类、HFO等形成的组合发泡剂在聚氨酯硬质泡沫生产中的应用情况。
The properties of methyl formate blowing agent presented as Ecomate are introduced.Comparing with the traditional blowing agent,the methyl formate blowing agent possesses the advantages of green eco-friendly,high burning point,good compatibility with other components,low density and thermal conductivity coefficient of the foam prepared with it and so on.The application situation of methyl formate alone used as blowing agent and the combined blowing agents made from it with HCFCs,HFCs,pentanes,HFOs and so on in production of polyurethane rigid foam is introduced in detail.
The properties of methyl formate blowing agent presented as Ecomate are introduced.Comparing with the traditional blowing agent,the methyl formate blowing agent possesses the advantages of green eco-friendly,high burning point,good compatibility with other components,low density and thermal conductivity coefficient of the foam prepared with it and so on.The application situation of methyl formate alone used as blowing agent and the combined blowing agents made from it with HCFCs,HFCs,pentanes,HFOs and so on in production of polyurethane rigid foam is introduced in detail.
引文
[1]丁雪佳,薛海蛟,李洪波,等.硬质聚氨酯泡沫塑料研究进展[J].化工进展,2009,28(2):278-282.
[2]李同续.硬质聚氨酯泡沫CFC-11替代技术[J].聚氨酯工业,2005,20(5):5-8.
[3]李晓斌,曹宏斌,张懿.全水发泡硬质聚氨酯泡沫塑料技术研究进展[J].中国塑料,2014,18(7):1-4.
[4]MODESTI M,BALDOIN N,SIMIONI F.Formic acid as a co-blowing agent in rigid polyurethane foams[J].European Polymer Journal,1998,34(9):1 233-1 241.
[5]CHRISTMAN D L,REICHEL C J.Use of Formate Salts as Auxiliary Agents for Low Density Rigid Foams:US,5286758[P].1994-02-15.
[6]田中纯一,佐佐木隆夫,室野芳朗,等.断熱箱体の製造方法:JP昭63-059505[P].1988-03-15.
[7]郑宁来.环保型PU发泡剂[J].合成材料老化与应用,2014,43(2):79-80.
[8]世界最新型聚氨酯化学发泡剂在淄博问世[J].玻璃钢/复合材料,2014(11):124-124.
[9]毕戈华,毕玉遂,侯永正,等.聚氨酯化学发泡剂及其制备方法:中国,103146178A[P].2013-06-12.
[10]黄伟明,黄海龙,丁海波,等.聚氨酯发泡剂(PU-88)创新配方[C].南京:第十三次聚氨酯泡沫塑料科研、生产、技术交流会议文集,2013:292-294.
[11]苗军亮,刘保花.聚氨酯硬质泡沫用发泡剂的研究进展[J].辽宁化工,2015,44(11):1339-1340,1343.
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[14]RAPA A J.Methyl Formate as an Adjuvant in Phenolic Foam Formation:US,4033910[P].1977-07-05.
[15]SCOTT R J.Methyl Formate E-Trichlorofluoromethane Blowing Agent for Polystyrene:US,3914191[P].1975-10-21.
[16]HANDA Y P,FRANELS G A,CASTNER G C,et al.Reduced-VOC and Non-VOC Blowing Agents for Making Expanded and Extruded Thermoplastic Foams:US,8598244[P].2013-12-03.
[17]HANDA Y P.Expanded and Extruded Bio-Degradable and Reduced Emission Foams Made with Methyl Formate-Based Blowing Agents:US,7846987[P].2010-12-07.
[18]CHEUNG Y W,DOBRESKI D V,TURNER R,et al.Polymer Blends of Bio-Degradable or Bio-Based and Synthetic Polymers and Foams Thereof:US,7872056[P].2011-01-18.
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[20]KALINOWSKI T T,KESKE D G,MATIMBA V,et al.Rigid Foam Compositions and Method Employing Methyl Formate as a Blowing Agent:US,7635723[P].2009-12-22.
[21]杨水清,蒋文俊,王荣华,等.一种无氟环保型聚氨酯硬泡板材组合料:中国,103709369A[P].2014-04-09.
[22]杨水清,蒋文俊,王荣华,等.一种含发泡剂的硬泡用聚醚多元醇的制备方法:中国,103724651A[P].2014-04-16.
[23]DOERGE H P,SPITLER K G,MORTIMER C E.Rigid Foams Using Blends of Chlorofluorocarbons and Hydrocarbons as Blowing Agent:EP,0450422A2[P].1991-10-09.
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[25]CHEN Wen-pin.Blowing Agents for Foaming Polyurethane Having No Ozone Depletion Potential and Uses and Preparations Thereof:US,5283003[P].1994-02-01.
[26]ASHIDA K.Halogen-Free Blowing Agents that Include Cyclo-aliphatic Hydrocarbons and Are Suitable for Isocyanate-Based Polymeric Foams:US,5336696[P].1994-08-09.
[27]山柏芳,傅东海,毕升,等.一种用于保温聚氨酯塑料的发泡剂组合物:中国,103351476A[P].2013-10-16.
[28]关志强,冯运成,麦景恒,等.用于保温聚氨酯塑料的发泡剂:中国,102675679A[P].2012-09-19.
[29]ZHU Z,WILLIAMS D J,BOGDAN M C.Process for Making Polyurethane and Polyisocyanurate Foams Using Mixtures of a Hydrofluorocarbon and Methyl Formate as a Blowing Agent:US,2005-027770A1[P].2005-12-15.
[30]ZHU Z,WILLIAMS D J,BOGDAN M C.Process for Making Polyurethane and Polyisocyanurate Foams Using Mixtures of a Hydrofluorocarbon and Methyl Formate as a Blowing Agent:US,2006-0160911Al[P].2006-07-20.
[31]贾雪芹,倪军,邵静,等.电热水器用组合聚醚及原料组合物及其制备方法:中国,104017154A[P].2014-09-03.
[32]HIBINOH Y,HESAKA T,TAKADA N.Blowing Agent,Premix and Process for Preparing Rigid Polyurethane Foam or Polyisocyanurate Foam:US,7326362[P].2008-02-05.
[33]朱霞林,王林,华卫琦,等.一种聚氨酯硬质泡沫及其制备方法:中国,102443134A[P].2012-05-09.
[34]ROBIN ML,BARTELT J E.Azeotropic and Azeotrope-Like Compositions of Z-1,1,1,4,4,4-Hexafluoro-2-Butene,Trans-1,2-Dichloroethylene,and Cyclo-Pentane:US,2011-0147638Al[P].2011-06-23.
[35]ROBIN ML,BARTELT J E.Azeotropic and Azeotrope-Like Compositions of Z-1,1,1,4,4,4-Hexafluoro-2-Butene,Trans-1,2-Dichloroethylene,and a Third Component:US,2015-0001433A1[P].2015-01-01.
[36]LOH G,ROBIN M L,GREAZZO J A.Foam-forming Compositions Containing Azetropic or Azetrope-Like Mixtures Containing Z-1,1,1,4,4,4-Hexafluoro-2-Butene and Methyl Formate and Their Uses in the Preparation of Polyisocyanurate-Based Foams:US,8658708[P].2014-02-25.
[37]ROBIN ML.Azeotropic and Azeotrope-Like Compositions of E-1,1,1,4,4,4-Hexafluoro-2-Butene:US,7972525[P].2011-07-05.
[38]ROBIN ML.Azeotropic and Azeotrope-Like Compositions of E-1,1,1,4,4,4-Hexafluoro-2-Butene:US,8262924[P].2012-09-11.
[39]邢益辉,芮益华,姚志洪,等.一种聚氨酯反应组合物及采用该组合物制备的硬质泡沫的方法:中国,102675579A[P].2012-09-19.
[40]CHEN B B,BONNE P.Azeotrope-Like Composition of 3,3,3-Trifluoro-1-Chloropropene and Methyl Formate:US,7479238[P].2009-01-20.
[41]BOGDAN M C,WILLIAMS D J,LING YK.Foams and Articles Made from Foams Containing 1-Chloro-3,3,3-Trifluoropropene(1233zd):US,2013-0149452Al[P].2013-06-13.(CN104271650A)
[42]WILLIAMS D J,LING Y K,QIN S L,et al.Foams and Articles Made from Foams Containing HCFO or HFO Blowing Agents:US,2014-0312261A1[P].2014-10-23.
[43]SINGH R R.Monochlorotrifluoropropene Compounds and Compositions and Methods Using Same:US,8962707[P].2015-02-24.
[2]李同续.硬质聚氨酯泡沫CFC-11替代技术[J].聚氨酯工业,2005,20(5):5-8.
[3]李晓斌,曹宏斌,张懿.全水发泡硬质聚氨酯泡沫塑料技术研究进展[J].中国塑料,2014,18(7):1-4.
[4]MODESTI M,BALDOIN N,SIMIONI F.Formic acid as a co-blowing agent in rigid polyurethane foams[J].European Polymer Journal,1998,34(9):1 233-1 241.
[5]CHRISTMAN D L,REICHEL C J.Use of Formate Salts as Auxiliary Agents for Low Density Rigid Foams:US,5286758[P].1994-02-15.
[6]田中纯一,佐佐木隆夫,室野芳朗,等.断熱箱体の製造方法:JP昭63-059505[P].1988-03-15.
[7]郑宁来.环保型PU发泡剂[J].合成材料老化与应用,2014,43(2):79-80.
[8]世界最新型聚氨酯化学发泡剂在淄博问世[J].玻璃钢/复合材料,2014(11):124-124.
[9]毕戈华,毕玉遂,侯永正,等.聚氨酯化学发泡剂及其制备方法:中国,103146178A[P].2013-06-12.
[10]黄伟明,黄海龙,丁海波,等.聚氨酯发泡剂(PU-88)创新配方[C].南京:第十三次聚氨酯泡沫塑料科研、生产、技术交流会议文集,2013:292-294.
[11]苗军亮,刘保花.聚氨酯硬质泡沫用发泡剂的研究进展[J].辽宁化工,2015,44(11):1339-1340,1343.
[12]WAGNER G.Integral SkinFoams:US,5922348[P].1999-07-13.
[13]WATKINSON J,ELRICH R R.Process for the Preparation of Flexible Polyurethane Foams in the Presence of Alkyl Alkanoate Blowing Agents:US,3879315[P].1975-04-22.
[14]RAPA A J.Methyl Formate as an Adjuvant in Phenolic Foam Formation:US,4033910[P].1977-07-05.
[15]SCOTT R J.Methyl Formate E-Trichlorofluoromethane Blowing Agent for Polystyrene:US,3914191[P].1975-10-21.
[16]HANDA Y P,FRANELS G A,CASTNER G C,et al.Reduced-VOC and Non-VOC Blowing Agents for Making Expanded and Extruded Thermoplastic Foams:US,8598244[P].2013-12-03.
[17]HANDA Y P.Expanded and Extruded Bio-Degradable and Reduced Emission Foams Made with Methyl Formate-Based Blowing Agents:US,7846987[P].2010-12-07.
[18]CHEUNG Y W,DOBRESKI D V,TURNER R,et al.Polymer Blends of Bio-Degradable or Bio-Based and Synthetic Polymers and Foams Thereof:US,7872056[P].2011-01-18.
[19]KALINOWSKI T T,KESKE D G,MATIMBA V,et al.Rigid Foam Compositions and Method Employing Methyl Formate as a Blowing Agent:US,6753357[P].2004-06-22.
[20]KALINOWSKI T T,KESKE D G,MATIMBA V,et al.Rigid Foam Compositions and Method Employing Methyl Formate as a Blowing Agent:US,7635723[P].2009-12-22.
[21]杨水清,蒋文俊,王荣华,等.一种无氟环保型聚氨酯硬泡板材组合料:中国,103709369A[P].2014-04-09.
[22]杨水清,蒋文俊,王荣华,等.一种含发泡剂的硬泡用聚醚多元醇的制备方法:中国,103724651A[P].2014-04-16.
[23]DOERGE H P,SPITLER K G,MORTIMER C E.Rigid Foams Using Blends of Chlorofluorocarbons and Hydrocarbons as Blowing Agent:EP,0450422A2[P].1991-10-09.
[24]LEE B P,ANTHONY C J.Binary Azeotropes of Hydrogen-Containing Halocarbons with Methyl Formate:W0,91-13966A1[P].1991-09-19.
[25]CHEN Wen-pin.Blowing Agents for Foaming Polyurethane Having No Ozone Depletion Potential and Uses and Preparations Thereof:US,5283003[P].1994-02-01.
[26]ASHIDA K.Halogen-Free Blowing Agents that Include Cyclo-aliphatic Hydrocarbons and Are Suitable for Isocyanate-Based Polymeric Foams:US,5336696[P].1994-08-09.
[27]山柏芳,傅东海,毕升,等.一种用于保温聚氨酯塑料的发泡剂组合物:中国,103351476A[P].2013-10-16.
[28]关志强,冯运成,麦景恒,等.用于保温聚氨酯塑料的发泡剂:中国,102675679A[P].2012-09-19.
[29]ZHU Z,WILLIAMS D J,BOGDAN M C.Process for Making Polyurethane and Polyisocyanurate Foams Using Mixtures of a Hydrofluorocarbon and Methyl Formate as a Blowing Agent:US,2005-027770A1[P].2005-12-15.
[30]ZHU Z,WILLIAMS D J,BOGDAN M C.Process for Making Polyurethane and Polyisocyanurate Foams Using Mixtures of a Hydrofluorocarbon and Methyl Formate as a Blowing Agent:US,2006-0160911Al[P].2006-07-20.
[31]贾雪芹,倪军,邵静,等.电热水器用组合聚醚及原料组合物及其制备方法:中国,104017154A[P].2014-09-03.
[32]HIBINOH Y,HESAKA T,TAKADA N.Blowing Agent,Premix and Process for Preparing Rigid Polyurethane Foam or Polyisocyanurate Foam:US,7326362[P].2008-02-05.
[33]朱霞林,王林,华卫琦,等.一种聚氨酯硬质泡沫及其制备方法:中国,102443134A[P].2012-05-09.
[34]ROBIN ML,BARTELT J E.Azeotropic and Azeotrope-Like Compositions of Z-1,1,1,4,4,4-Hexafluoro-2-Butene,Trans-1,2-Dichloroethylene,and Cyclo-Pentane:US,2011-0147638Al[P].2011-06-23.
[35]ROBIN ML,BARTELT J E.Azeotropic and Azeotrope-Like Compositions of Z-1,1,1,4,4,4-Hexafluoro-2-Butene,Trans-1,2-Dichloroethylene,and a Third Component:US,2015-0001433A1[P].2015-01-01.
[36]LOH G,ROBIN M L,GREAZZO J A.Foam-forming Compositions Containing Azetropic or Azetrope-Like Mixtures Containing Z-1,1,1,4,4,4-Hexafluoro-2-Butene and Methyl Formate and Their Uses in the Preparation of Polyisocyanurate-Based Foams:US,8658708[P].2014-02-25.
[37]ROBIN ML.Azeotropic and Azeotrope-Like Compositions of E-1,1,1,4,4,4-Hexafluoro-2-Butene:US,7972525[P].2011-07-05.
[38]ROBIN ML.Azeotropic and Azeotrope-Like Compositions of E-1,1,1,4,4,4-Hexafluoro-2-Butene:US,8262924[P].2012-09-11.
[39]邢益辉,芮益华,姚志洪,等.一种聚氨酯反应组合物及采用该组合物制备的硬质泡沫的方法:中国,102675579A[P].2012-09-19.
[40]CHEN B B,BONNE P.Azeotrope-Like Composition of 3,3,3-Trifluoro-1-Chloropropene and Methyl Formate:US,7479238[P].2009-01-20.
[41]BOGDAN M C,WILLIAMS D J,LING YK.Foams and Articles Made from Foams Containing 1-Chloro-3,3,3-Trifluoropropene(1233zd):US,2013-0149452Al[P].2013-06-13.(CN104271650A)
[42]WILLIAMS D J,LING Y K,QIN S L,et al.Foams and Articles Made from Foams Containing HCFO or HFO Blowing Agents:US,2014-0312261A1[P].2014-10-23.
[43]SINGH R R.Monochlorotrifluoropropene Compounds and Compositions and Methods Using Same:US,8962707[P].2015-02-24.