醇解废弃聚酯制备聚氨酯泡沫
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摘要
聚酯纤维作为一种高分子材料在各个行业中被广泛应用,同时,废弃聚酯的数量也在日渐增多,若不对废弃聚酯进行回收处理利用,不仅会造成资源浪费,而且还会给环境带来大量的污染,因此,废弃聚酯的回收利用成为了当前聚酯工业发展的重大研究课题。另外,近年来我国建筑能耗持续快速提升,建筑节能成为全社会关注的热点问题,而硬质聚氨酯泡沫是一种非常优秀的保温隔热材料,主要应用于外墙保温等工业用途,这可以增加建筑物内部的可用面积,对地价越来越昂贵的城市有特别的吸引力。因此将聚酯回收和聚氨酯泡沫二者有机地结合起来,不仅可以解决废弃聚酯的处理问题,而且得到的发泡材料强度高,质量轻,且成本低廉。
本课题研究了乙二醇醇解废弃聚酯纤维的工艺条件,分析了反应温度、反应时间、催化剂含量等各种参数对醇解工艺的影响,采用扫描量热法DSC、热重法TGA、红外光谱IR等测试手段对醇解产物进行表征,并测试和分析了醇解产物的羟值和酸值,综合各种结果推断出醇解产物为对苯二甲酸乙二醇酯。确定了醇解率可达到97.08%的醇解工艺条件为:温度为196℃,催化剂Zn(AC)_2?2H_2O含量为0.2%,反应时间2.5h。分析表明:醇解的主要产物是聚酯纤维的单体对苯二甲酸乙二醇酯(BHET),经结晶提纯后,BHET纯度可达96%。
研究BHET的化学结构得知:在BHET的对位上有两个-OH,-OH可以与多异氰酸酯(PAPI)中的-NCO基发生反应,经过一系列的链增长、气体发生以及交联反应等制备聚氨酯泡沫材料。研究分析了泡沫催化剂和发泡剂等辅助原料对硬质聚氨酯泡沫压缩性能和密度的影响,并采用傅立叶变换红外光谱仪、DSC、TGA和光镜等测试仪器对产物进行定性分析,确定产物结构为聚氨酯结构,产物熔点为156℃,分解温度为240℃,并了解了泡沫体的胞体结构,这种网络骨架和泡孔结构增强了泡沫体的支撑力,提高了压缩性能。结果表明当原料配比一定,催化剂0.32g、发泡剂0.8g时,得到聚氨酯泡沫有较高的压缩强度724kpa和较低的密度99 kg·m-3。
With the development of the PET, the amount of the PET is increasing, there will be a result in wastage of resources and a lot of white pollution, if we don’t recycle waste PET. So, the reseaech of resolving this problem has been a big object. The waste PET includes Waste PET fiber, waste PET bottle scrap, waste PET film, and so on. In this thesis, we use glycolysis to recycle the waste PET, and reuse it in to polyurethane foam.
In addition, China's building energy consumption is sustained and rapid upgrading in recent years. Building energy efficiency become to all the hot issues of social concern.The rigid polyurethane foam is a very good insulation material, it mainly used in external wall insulation, This can increase the usable area inside the building, more and more expensive cities on the land have special appeal. So we will organically combine the recovery polyester and polyurethane foam , it not only solve the disposal of waste polyester ,But also the foam material has high strength, light weight and low cost.
This paper studied the glycol alcoholysis craft for waste PET fiber, analyzed the influence of reaction temperature, the reaction time and the catalyst density to the alcoholysis craft, The best glocoholysis craft is: at 196～198℃, ethylene glycol and waste polyester fiber weight ratio was 1:4, the glycolysis time was 2h,and 0.5% zinc acetate was used as catalyst. PET was thoroughly glycolysed and the glycolysis conversion rate is 97.08%. The glycolysis products were analyzed by hydroxyland acid values and identified by different techniques, such as DSC, IR. The glycolysis predominant glycolysis product was BHET monomer, its purity reached 96% after crystallization depuration.
The chemical structure of BHET that: In BHET the right position on the two-OH, -OH can react with more isocyanate, after a series of chain growth, vapor, crosslinking reaction and preparation of polyurethane foam.This article discussed the influence of auxiliary materials,such as foam catalyst and foaming agent,on the compression performance and density of rigid polyurethane. The products were characterized by IR, DSC, optical microscope. determine the product structure of polyurethane, product of the melting point of 156℃, and to understand the cellular structure of foam, this network skeleton and the cell structure of foam support increased power, improves the compression performance.When a fixed proportion of raw materials, catalyst is 0.32g and foam is 0.8g, the result shows that polyurethane foam has higher compressive strenger and lower density.
本课题研究了乙二醇醇解废弃聚酯纤维的工艺条件,分析了反应温度、反应时间、催化剂含量等各种参数对醇解工艺的影响,采用扫描量热法DSC、热重法TGA、红外光谱IR等测试手段对醇解产物进行表征,并测试和分析了醇解产物的羟值和酸值,综合各种结果推断出醇解产物为对苯二甲酸乙二醇酯。确定了醇解率可达到97.08%的醇解工艺条件为:温度为196℃,催化剂Zn(AC)_2?2H_2O含量为0.2%,反应时间2.5h。分析表明:醇解的主要产物是聚酯纤维的单体对苯二甲酸乙二醇酯(BHET),经结晶提纯后,BHET纯度可达96%。
研究BHET的化学结构得知:在BHET的对位上有两个-OH,-OH可以与多异氰酸酯(PAPI)中的-NCO基发生反应,经过一系列的链增长、气体发生以及交联反应等制备聚氨酯泡沫材料。研究分析了泡沫催化剂和发泡剂等辅助原料对硬质聚氨酯泡沫压缩性能和密度的影响,并采用傅立叶变换红外光谱仪、DSC、TGA和光镜等测试仪器对产物进行定性分析,确定产物结构为聚氨酯结构,产物熔点为156℃,分解温度为240℃,并了解了泡沫体的胞体结构,这种网络骨架和泡孔结构增强了泡沫体的支撑力,提高了压缩性能。结果表明当原料配比一定,催化剂0.32g、发泡剂0.8g时,得到聚氨酯泡沫有较高的压缩强度724kpa和较低的密度99 kg·m-3。
With the development of the PET, the amount of the PET is increasing, there will be a result in wastage of resources and a lot of white pollution, if we don’t recycle waste PET. So, the reseaech of resolving this problem has been a big object. The waste PET includes Waste PET fiber, waste PET bottle scrap, waste PET film, and so on. In this thesis, we use glycolysis to recycle the waste PET, and reuse it in to polyurethane foam.
In addition, China's building energy consumption is sustained and rapid upgrading in recent years. Building energy efficiency become to all the hot issues of social concern.The rigid polyurethane foam is a very good insulation material, it mainly used in external wall insulation, This can increase the usable area inside the building, more and more expensive cities on the land have special appeal. So we will organically combine the recovery polyester and polyurethane foam , it not only solve the disposal of waste polyester ,But also the foam material has high strength, light weight and low cost.
This paper studied the glycol alcoholysis craft for waste PET fiber, analyzed the influence of reaction temperature, the reaction time and the catalyst density to the alcoholysis craft, The best glocoholysis craft is: at 196～198℃, ethylene glycol and waste polyester fiber weight ratio was 1:4, the glycolysis time was 2h,and 0.5% zinc acetate was used as catalyst. PET was thoroughly glycolysed and the glycolysis conversion rate is 97.08%. The glycolysis products were analyzed by hydroxyland acid values and identified by different techniques, such as DSC, IR. The glycolysis predominant glycolysis product was BHET monomer, its purity reached 96% after crystallization depuration.
The chemical structure of BHET that: In BHET the right position on the two-OH, -OH can react with more isocyanate, after a series of chain growth, vapor, crosslinking reaction and preparation of polyurethane foam.This article discussed the influence of auxiliary materials,such as foam catalyst and foaming agent,on the compression performance and density of rigid polyurethane. The products were characterized by IR, DSC, optical microscope. determine the product structure of polyurethane, product of the melting point of 156℃, and to understand the cellular structure of foam, this network skeleton and the cell structure of foam support increased power, improves the compression performance.When a fixed proportion of raw materials, catalyst is 0.32g and foam is 0.8g, the result shows that polyurethane foam has higher compressive strenger and lower density.
引文
1.张师民.聚酯的生产及应用[M].北京:中国石化出版社,1997.295-296
2.钱伯章.聚酯回收利用及技术进展[J].橡塑资源利用,2008(4):30-35
3.陈士宏,杨惠娣,张玉霞.PET瓶回收技术进展[J].中国塑料,2005,19(12):79-82
4. Viksne A, Rence L, Berzina R, et al.Unsaturated polyester resins on the base of chemical degradation products of PET varnishes[J].Polymer Recycling,1997,3(3):227-237
5.王晓春,张建飞.PET降解研究[J].合成纤维,2002,6(31):5-8
6.马玉刚,杨勇,徐元源,相宏伟.PET聚酯化学解聚进展[J].化工进展,2000(1):32-35
7. Xi Guoxi,Lu Maixi,Sun Chen.Study on depolymerization of waste polyethylene terephtha -late into monomer of bis(2-hydroxyethyl terephthalate)[J].Polymer Degradation and Stab -ility,2005(8):117-120
8. Chen C H,Chen C Y,Lo YW,et al.Studies of glycolysis of poly(ethyene terephalate)recycle from postconsumer soft-drink bottles[J].J ApplPolym Sci,2001(8):943-948
9. Chen J Y.Pressure glycolysis of PET waste[J].J Appl Polym Sci ,2001(4):11-17
10. Viksne A,Kalnins M,Rence L,et al.Unsaturated polyester resins based on the PET waste glycolysis products by ethylene,propylene,diethyene glycols and their mixtures[J].Polyme Recycling,2000(1):15-22
11. Gamze G,Tuncer Y,Saadet O,et al.Simultaneous glycolysis and hydrolysis of polyethylene terephthalate and characterization of the products by differential scanning calorimetry [J]. Polymer,2003(6):7609-7616
12.张从容,安林红.聚对苯二甲酸乙二醇酯回收技术进展及前景[J].中国塑料,2001,10 (15):79-82
13. Mans our S H,Ikladious N E.Depolymerizati of poly (ethyleneterephthalate) wastes using
1,4-butanediol and triethylene glycol[J].Polymer Testing,2002(21):497-505
14. Gamze G, Tuncer Y,Saadet O, et al.Simultanous glycolysis and hydrolysis of polyethylene terephthalate and characterization of products by differential scanning calori-metry[J].polyer,2003(44):7609-7616
15. Mans our S H,Ikladious N E.Depolymerizati of poly ( ethyleneterephthalate) wastes using
1,4-butanediol and triethylene glycol[J].Polymer Testing,2002(21):497-505
16.逯德木,许忠斌,佟立芳,方征平胡立勤.废聚对苯二甲酸乙二醇酯的复合解聚条件[J].高分子材料科学与工程,2008,7(24):154-178
17.赵明耀.非纤维用热塑性聚酯工艺与应用[M].北京:化学工业出版社,2002.342-345
18.刘建平,郑玉斌.高分子科学与材料工程[M].北京:化学工业出版社,2005.31
19.钱伯章.废弃聚酯转产PTA将在意大利实施[J].聚酯工业,2005,18(4):25-29
20.程俊,丁文,于洁.用聚酯废料合成气干性不饱和树脂[J].高分子材料与工程,2002,22(12) :23-30
21.刘建树,邹黎明,王依民.国外尼龙及PET聚酯制品的回收再生状况[J].上海化工,2002, 27(1):24-26
22.朱吕民,刘益军.聚氨酯泡沫塑料[M].第三版.北京:化学工业出版社,2005.1-13.
23.聚氨酯发泡材料在汽车上应用的新技术[J].工程塑料.2008,26(10):53-54
24. Mobanty A K,MisraM,DrzalL T.Sustainable biocomposites from renewable resource-s opportunities challenges in the green materials world[J].Journal of Polymersand the Environment.2002,10(1-2):19-26
25.雄卫,黄洪,赵守佳.聚氨酯系列产品在外墙保温体系中的应用[J].新型建筑材料.2007 (5):69-73
26.钱伯章,朱建芳.建筑节能保温材料技术进展[J].建筑节能.2009.37(2):56-60
27.朱吕民,刘益军.聚氨酯泡沫塑料[M].第三版.北京:化学工业出版社,2005.31-33.
28. Darwin P R,Martinez De,et al.Poly(ethylenetere phthalate)copolymers containing Nitroter phthalic units.Methanolytic Degradation[J].Applied Polymer Science,2002(40):227-228
29.秦梅,刘大强,陈天舒.PET废料降解制不饱和聚酯树脂的研究[J].化学工程师,1997,60 (3):11-13
30. Menger F M,Keiper J S.Gemini surfactants[J].AngewChem.Int Ed,2000,39(11):906-920
31. Kim S,Lu M. Unsaturated polyester resins based on recycled PET.preparation and curing behavior[J].J Appl Polym Sci,2001(80):1052-1057(缺卷的)
32.席国喜,邢新艳,孙晨.废聚酯醇解条件的研究[J].环境科学研究,2004(5):38-39
33.聚酯多元醇中羟值的测定HG/T2709-95.中华人民共和国化学工业部.11-12
34.聚酯多元醇中羟值的测定HG/T2708-95.中华人民共和国化学工业部.8-9
35.秦梅.PET醇解物制取聚酯双组分涂料合成研究[J].哈尔滨工业大学学报,1999,4(5): 21-24
36. Menger F M,Migulin V A.Synthesis and Properties of the Multiarmed Geminis[J].J-OrgChem,1999,64(24):8916-8921
37. Guclu G,Kasgoz A,Ozbudak S,et al.Glycolysis of poly(ethylene terephthalate) wastes in xylene[J].Journal of Applied Polymer Science,1998,69(12):2311-2319
38.姜志国,刘红梅,李效玉.植物油多元醇改性硬质聚氨酯泡沫性能的研究[J].聚氨酯工业.2007,22(6):22-25
39. Zlatanie A, Lava C, ZhangW, et al. Effect of structure on p roperties of polyols and poly- urethanes based on different vegetable oils [J].Journal of polymer science. 2004,42(5): 809-819
40.朱传勇,孟令辉,王陆虹.环戊烷发泡硬质聚氨酯泡沫塑料及性能表征[J].哈尔滨师范大学自然科学学报,2008,24(5):38-40
41. Chalivendar. V. B. Processing and Mechanical Characterization of Lightweight Poly-urethane Composites[J].Journal ofMaterials Science,2003,38(8):1631-1643.
42. Zlatanic A,Lava C,Zhang W,et al.Effect of structure on properties of polyols and p-olyurethanes based on different vegetable oils[J].Journal of Polymer Science:Part B:Polymer Physics,2004,42(5):809-819
43.朱吕民,刘益军.聚氨酯泡沫塑料[M] .第三版.北京:化学工业出版社,2005.408.
44.夏凡,吴晓青.增强聚氨酯硬质泡沫塑料压缩性能研究[J].玻璃钢/复合材料,2009,(3): 53-55
45.朱吕民,刘益军.聚氨酯泡沫塑料[M].第三版.北京:化学工业出版社,2005.31-36.
2.钱伯章.聚酯回收利用及技术进展[J].橡塑资源利用,2008(4):30-35
3.陈士宏,杨惠娣,张玉霞.PET瓶回收技术进展[J].中国塑料,2005,19(12):79-82
4. Viksne A, Rence L, Berzina R, et al.Unsaturated polyester resins on the base of chemical degradation products of PET varnishes[J].Polymer Recycling,1997,3(3):227-237
5.王晓春,张建飞.PET降解研究[J].合成纤维,2002,6(31):5-8
6.马玉刚,杨勇,徐元源,相宏伟.PET聚酯化学解聚进展[J].化工进展,2000(1):32-35
7. Xi Guoxi,Lu Maixi,Sun Chen.Study on depolymerization of waste polyethylene terephtha -late into monomer of bis(2-hydroxyethyl terephthalate)[J].Polymer Degradation and Stab -ility,2005(8):117-120
8. Chen C H,Chen C Y,Lo YW,et al.Studies of glycolysis of poly(ethyene terephalate)recycle from postconsumer soft-drink bottles[J].J ApplPolym Sci,2001(8):943-948
9. Chen J Y.Pressure glycolysis of PET waste[J].J Appl Polym Sci ,2001(4):11-17
10. Viksne A,Kalnins M,Rence L,et al.Unsaturated polyester resins based on the PET waste glycolysis products by ethylene,propylene,diethyene glycols and their mixtures[J].Polyme Recycling,2000(1):15-22
11. Gamze G,Tuncer Y,Saadet O,et al.Simultaneous glycolysis and hydrolysis of polyethylene terephthalate and characterization of the products by differential scanning calorimetry [J]. Polymer,2003(6):7609-7616
12.张从容,安林红.聚对苯二甲酸乙二醇酯回收技术进展及前景[J].中国塑料,2001,10 (15):79-82
13. Mans our S H,Ikladious N E.Depolymerizati of poly (ethyleneterephthalate) wastes using
1,4-butanediol and triethylene glycol[J].Polymer Testing,2002(21):497-505
14. Gamze G, Tuncer Y,Saadet O, et al.Simultanous glycolysis and hydrolysis of polyethylene terephthalate and characterization of products by differential scanning calori-metry[J].polyer,2003(44):7609-7616
15. Mans our S H,Ikladious N E.Depolymerizati of poly ( ethyleneterephthalate) wastes using
1,4-butanediol and triethylene glycol[J].Polymer Testing,2002(21):497-505
16.逯德木,许忠斌,佟立芳,方征平胡立勤.废聚对苯二甲酸乙二醇酯的复合解聚条件[J].高分子材料科学与工程,2008,7(24):154-178
17.赵明耀.非纤维用热塑性聚酯工艺与应用[M].北京:化学工业出版社,2002.342-345
18.刘建平,郑玉斌.高分子科学与材料工程[M].北京:化学工业出版社,2005.31
19.钱伯章.废弃聚酯转产PTA将在意大利实施[J].聚酯工业,2005,18(4):25-29
20.程俊,丁文,于洁.用聚酯废料合成气干性不饱和树脂[J].高分子材料与工程,2002,22(12) :23-30
21.刘建树,邹黎明,王依民.国外尼龙及PET聚酯制品的回收再生状况[J].上海化工,2002, 27(1):24-26
22.朱吕民,刘益军.聚氨酯泡沫塑料[M].第三版.北京:化学工业出版社,2005.1-13.
23.聚氨酯发泡材料在汽车上应用的新技术[J].工程塑料.2008,26(10):53-54
24. Mobanty A K,MisraM,DrzalL T.Sustainable biocomposites from renewable resource-s opportunities challenges in the green materials world[J].Journal of Polymersand the Environment.2002,10(1-2):19-26
25.雄卫,黄洪,赵守佳.聚氨酯系列产品在外墙保温体系中的应用[J].新型建筑材料.2007 (5):69-73
26.钱伯章,朱建芳.建筑节能保温材料技术进展[J].建筑节能.2009.37(2):56-60
27.朱吕民,刘益军.聚氨酯泡沫塑料[M].第三版.北京:化学工业出版社,2005.31-33.
28. Darwin P R,Martinez De,et al.Poly(ethylenetere phthalate)copolymers containing Nitroter phthalic units.Methanolytic Degradation[J].Applied Polymer Science,2002(40):227-228
29.秦梅,刘大强,陈天舒.PET废料降解制不饱和聚酯树脂的研究[J].化学工程师,1997,60 (3):11-13
30. Menger F M,Keiper J S.Gemini surfactants[J].AngewChem.Int Ed,2000,39(11):906-920
31. Kim S,Lu M. Unsaturated polyester resins based on recycled PET.preparation and curing behavior[J].J Appl Polym Sci,2001(80):1052-1057(缺卷的)
32.席国喜,邢新艳,孙晨.废聚酯醇解条件的研究[J].环境科学研究,2004(5):38-39
33.聚酯多元醇中羟值的测定HG/T2709-95.中华人民共和国化学工业部.11-12
34.聚酯多元醇中羟值的测定HG/T2708-95.中华人民共和国化学工业部.8-9
35.秦梅.PET醇解物制取聚酯双组分涂料合成研究[J].哈尔滨工业大学学报,1999,4(5): 21-24
36. Menger F M,Migulin V A.Synthesis and Properties of the Multiarmed Geminis[J].J-OrgChem,1999,64(24):8916-8921
37. Guclu G,Kasgoz A,Ozbudak S,et al.Glycolysis of poly(ethylene terephthalate) wastes in xylene[J].Journal of Applied Polymer Science,1998,69(12):2311-2319
38.姜志国,刘红梅,李效玉.植物油多元醇改性硬质聚氨酯泡沫性能的研究[J].聚氨酯工业.2007,22(6):22-25
39. Zlatanie A, Lava C, ZhangW, et al. Effect of structure on p roperties of polyols and poly- urethanes based on different vegetable oils [J].Journal of polymer science. 2004,42(5): 809-819
40.朱传勇,孟令辉,王陆虹.环戊烷发泡硬质聚氨酯泡沫塑料及性能表征[J].哈尔滨师范大学自然科学学报,2008,24(5):38-40
41. Chalivendar. V. B. Processing and Mechanical Characterization of Lightweight Poly-urethane Composites[J].Journal ofMaterials Science,2003,38(8):1631-1643.
42. Zlatanic A,Lava C,Zhang W,et al.Effect of structure on properties of polyols and p-olyurethanes based on different vegetable oils[J].Journal of Polymer Science:Part B:Polymer Physics,2004,42(5):809-819
43.朱吕民,刘益军.聚氨酯泡沫塑料[M] .第三版.北京:化学工业出版社,2005.408.
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