阻燃型生物质聚氨酯硬质泡沫的制备与性能研究
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摘要
聚氨酯硬质泡沫是目前世界上性能最佳的隔热保温材料，随着化石资源的大量使用和人类环保意识的增强，以生物质资源替代化石资源制备聚氨酯泡沫的研究受到了广泛的关注。利用价格便宜的腰果酚、蓖麻油等生物质资源替代苯酚等石化资源制备阻燃型聚氨酯硬泡对发挥生物质资源优势、改善生态环境，促进聚氨酯行业的发展均有明显的促进作用。
本论文以生物质资源腰果酚、蓖麻油为原料，通过Mannich反应、烷氧化反应、醇解、酯化等反应合成新型聚醚、聚酯多元醇，进一步制备性能良好的阻燃型聚氨酯硬质泡沫，研究生物质多元醇的结构对聚氨酯硬质泡沫性能的影响。主要研究内容和结论如下：
1.以腰果酚、苯酚、多聚甲醛、二乙醇胺、三聚氰胺等为原料，通过Mannich反应制备了不同结构和性能的腰果酚Mannich碱。对反应过程进行了分析和探索，采用FTIR、1H NMR、GPC、GC-MS、TG等对反应中间体和产物进行了结构表征和性能测试，证实了醛先与胺反应生成中间体的Mannich反应机理，讨论了影响腰果酚Mannich碱的产物组成、粘度、羟值、分子量等结构与性能指标的主要因素：反应温度、腰果酚用量、腰果酚对苯酚的替代量和三聚氰胺添加量等。
2.以不同结构的腰果酚Mannich碱为起始剂，和环氧丙烷发生烷氧基化反应合成腰果酚Mannich聚醚多元醇，产物具有粘度小、官能度可调﹑含有阻燃基团等优点。通过研究起始物结构、催化剂种类、环氧丙烷质量等因素对聚醚多元醇结构及性能的影响，确定了较优工艺条件，对聚醚多元醇进行羟值、粘度等性能测试和FT IR、TGA、GPC和1H NMR等结构表征。腰果酚用量越小，腰果酚对苯酚的替代量越低，三聚氰胺添加量越多，多元醇的粘度和羟值越大，热稳定性越高；筛选出适合制备阻燃型聚氨酯硬质泡沫的腰果酚Mannich聚醚多元醇。
3.以蓖麻油、小分子多元醇（乙二醇、甘油、季戊四醇）和苯酐为原料，发生醇解和酯化反应，制备与其它聚酯、聚醚多元醇相容性良好的蓖麻油聚酯多元醇，有利于组合多元醇体系的储存。考察了小分子醇种类和反应时间对蓖麻油基醇解产物羟值、粘度及分子量的影响；发现随着小分子醇官能度的增加，体系中单甘酯和二甘酯含量和转化率减少，羟值增加；蓖麻油聚酯多元醇中蓖麻油单酯和二酯的含量较醇解蓖麻油大幅减少，且伯羟基相对含量高于相应的醇解产物，蓖麻油聚酯多元醇的热稳定性高于工业苯酐聚酯多元醇PS-3152，主要由于蓖麻油脂肪酸链热稳定性高的原因。
4.将腰果酚Mannich聚醚多元醇、异氰酸酯、发泡剂、表面活性剂、阻燃剂等一起发泡制备了一系列复合阻燃型聚氨酯硬质泡沫；研究结果表明：不同腰果酚替代量的Mannich聚醚多元醇发泡活性较高且相差不大，腰果酚对苯酚替代量越高，多元醇和发泡剂环戊烷相容性越好，泡沫相对压缩强度和导热系数越小，热稳定性稍差、成炭率和临界氧指数越低，热释放量和烟释放量稍高，且燃烧后的炭层开孔和破裂较多。对不同三聚氰胺添加量的聚醚多元醇和无卤阻燃剂EG、聚磷酸铵（APP）和乙基膦酸二乙酯（DEEP）复配制备的聚氨酯泡沫样品性能进行了分析，结果发现无阻燃剂时三聚氰胺替代量越高，泡沫相对压缩强度、导热系数和临界氧指数越大，热稳定性和成炭率高；和EG复配制备的阻燃泡沫具有较好的力学性能、热稳定性和氧指数，锥形量热显示燃烧的热释放峰值、热释放总量烟释放参数明显降低，残炭率和炭层致密连续性明显增强；在提高氧指数、烟产生和释放方面EG优于APP和DEEP；和DEEP、APP和EG复配制备的阻燃型聚氨酯泡沫的固化时间和导热系数有所升高；添加相同阻燃剂的样品其阻燃性能随着添加量的增加而增加，固体阻燃剂APP和EG在增加力学性能、热稳定性及降低CO/CO2比值方面较液体阻燃剂DEEP效果好，含磷阻燃剂APP和DEEP在降低热释放速率方面优于EG，不同阻燃剂复配在炭层的致密性和连续性方面的效果优于单一阻燃剂。
5.蓖麻油基多元醇和异氰酸酯、发泡剂、表面活性剂和阻燃剂APP等发泡制备一系列阻燃型蓖麻油聚氨酯泡沫，并与PS-3152进行对比。研究结果发现：蓖麻油聚酯多元醇的发泡活性较醇解产物高，泡沫压缩强度、热稳定性高于醇解产物；但其发泡活性、氧指数和燃烧性能与PS-3152制备的泡沫性能相当，且热稳定性更高，导热系数更低；主要由于苯环刚性结构的引入提高了整个体系的硬段含量和成炭率；添加APP后的泡沫样品阻燃性能明显得到了提高，其中氧指数达到了25.9-26.8。
Rigid polyurethane foam (RPUF) is the best thermal insulation material with its optimalinsulating performance. However, with the increasing depletion of fossil resources and theimprovement in awareness of the environmental protection, researches on natural renewableresources replacing petrochemicals has attracted more and more attention. Cardanol and castoroil are important feedstock for the renewable production of flame-retardant polyurethane foamin biomass resources. Less expensive cardanol and castor oil can replace phenol fossilresources to formulate polyurethane foam thermal insulation material, which has significantpromotion to make biomass resource advantage, improve ecological environment and developpolyurethane material industry.
In the present work, a series of novel polyether, polyester polyols were explored from thebiomass resources cardanol and castor oil by Mannich reaction, alkyl oxidation reaction,alcoholysis, esterification reaction and so on. Further, flame-retardant RPUFs with goodphysical and thermal performance were obtained. The main purpose of the thesis was to revealeffect of structure of biomass-based polyols on properties of rigid RPUF. The main researchcontents and conclusions were summarized as follows.
1. Cardanol-based Mannich bases with different structures and properties weresynthesized from cardanol, paraformaldehyde, diethanolamine and melamine by Mannichreaction. The intermediate and products were characterized and tested using FT IR,1H NMR,GPC, GC-MS and TG. The mechanism of first step aldehyde and amine adduct was confirmedin Mannich reaction. The main factors affecting the structure and properties of productcomposition, viscosity, hydroxyl value and molecular weight of cardanol-based Mannichpolyether polyols were discussed, such as reaction temperature, amount of cardanol, cardanolalternative of phenol, melamine and so on.
2. Cardanol-based Mannich polyether polyols were synthesized by initiator cardanol-based Mannich bases and propylene oxide through alkoxylation reaction, which havesome advantages such as low viscosity, adjustable functionality and containing flame retardantgroups.The structure and properties of Mannich polyether polyol were determined by studyingthe initiator structure, catalyst type, quality of propylene oxide and other factors. The optimumprocess conditions for cardanol-based Mannich polyether polyols were obtained throughtesting hydroxyl value, viscosity and characterizing FT IR, TG, GPC and1H NMR The smallerthe amount of cardanol, the lower the amount of phenol substitution, the more the amount ofmelamine added, the viscosity and hydroxyl value of the polyol larger and the thermal stabilityhigher. The cardanol-based Mannich polyether polyols suitable for preparing flame-retardantRPUF were chosen.
3Castor oil-based polyether polyols were synthesized using small molecule polyols(ethylene glycol, glycerol and pentaerythritol), castor oil and phthalic anhydride as rawmaterial by alcoholysis and esterification reaction, which have good compatibility with otherpolyester and polyether polyols and in favor of combination polyols system of long-termstorage. The effects of small molecule polyol species and reaction time on hydroxyl value,viscosity and molecular weight of castor oil-based alcoholysis products were investigated. Themonoglyceride and diglyceride content and conversion rate significantly reduced, the hydroxylvalue increased with increasing functionality of small molecule polyols. Compared to thealcoholysis of castor oil, the monoester and diester content of castor oil-based polyester polyolssubstantially reduced, and the primary hydroxyl groups relatively content of was higher. Thethermal stability of castor oil-based polyester polyols were higher than the commercialpolyester polyol PS-3152because of the high thermal stability of castor oil fatty acid chain.
4A series of composite flame-retardant RPUFs were prepared with cardanol-basedMannich polyether polyols, blowing agent, surfactant, flame retardants and isocyanate. Theresults showed that the higher foaming behavior of cardanol-based Mannich polyether polyolwith different amount of cardanol were almost same. The higher cardanol amount of phenolsubstitution, the better miscible with blowing agent cyclopentane, the smaller compressive strength and thermal conductivity, the lower thermal stability, residue char yield and limitiedoxygen index, the higher heat release and smoke emission of the RPUFs, and the moreopenings and cracking carbon layer after combustion. The properties of flame retardant RPUFsamples from different amounts of melamine-based Mannich polyether polyols addinghalogen-free flame retardants expanded graphite (EG), ammonium polyphosphate (APP) andDiethyl ethylphosphonate (DEEP) were analyzed. It was found that the higher the amount ofmelamine replacement foam, the greater the relative compressive strength, thermalconductivity, and the limitied oxygen index, the higher thermal stability and residue char yield.For EG filled RPUFs, the heat release peak, the total heat release and amount of smoke releaseparameters were significantly decreased, the mechanical properties, thermal stability, limitiedoxygen index, the yield and dense continuity of the char layer after combustion significantlyenhanced. EG was better in improving limited oxygen index, smoke production and releaseareas than DEEP and APP. Compared to non-flame retardant PUF, the curing times and thermalconductivities of RPUFs adding flame retardants DEEP, APP and EG were slightly increased.The flame retardant properties of the RPUF samples increased with the amount of the sameflame retardant. The solid flame retardants APP and EG were better in increasing themechanical properties, thermal stability and lowering ratio of CO/CO2than the liquid flameretardant DEEP. And, the phosphorus flame retardants APP and DEEP were better in reducingheat release rate than EG, the different flame retardants compound in the density and continuityof the carbon layer better than single flame.
5A series of castor oil-based flame retardant RPUFs were prepared from castor oil-basedpolyols, isocyanate, blowing agent, surfactant and flame retardant APP, and commercialpolyester polyol PS-3152were compared. The results showed that the foaming activities ofcastor oil-based polyester polyols were higher than alcoholysis products, the correspondingfoam compressive strength and thermal stability better. Compared to PS-3152based PUF, thefoaming activity of the oxygen index and the combustion performance of PUFs prepared fromcastor oil-based polyester polyol were quite, and higher thermal stability and lower thermal conductivity. This is mainly due to the introduction of benzene ring, improving the hardsegment content and residue char yield. The flame retardant properties of APP-filled PUFssignificantly improved with the limited oxygen index25.9-26.8.
本论文以生物质资源腰果酚、蓖麻油为原料，通过Mannich反应、烷氧化反应、醇解、酯化等反应合成新型聚醚、聚酯多元醇，进一步制备性能良好的阻燃型聚氨酯硬质泡沫，研究生物质多元醇的结构对聚氨酯硬质泡沫性能的影响。主要研究内容和结论如下：
1.以腰果酚、苯酚、多聚甲醛、二乙醇胺、三聚氰胺等为原料，通过Mannich反应制备了不同结构和性能的腰果酚Mannich碱。对反应过程进行了分析和探索，采用FTIR、1H NMR、GPC、GC-MS、TG等对反应中间体和产物进行了结构表征和性能测试，证实了醛先与胺反应生成中间体的Mannich反应机理，讨论了影响腰果酚Mannich碱的产物组成、粘度、羟值、分子量等结构与性能指标的主要因素：反应温度、腰果酚用量、腰果酚对苯酚的替代量和三聚氰胺添加量等。
2.以不同结构的腰果酚Mannich碱为起始剂，和环氧丙烷发生烷氧基化反应合成腰果酚Mannich聚醚多元醇，产物具有粘度小、官能度可调﹑含有阻燃基团等优点。通过研究起始物结构、催化剂种类、环氧丙烷质量等因素对聚醚多元醇结构及性能的影响，确定了较优工艺条件，对聚醚多元醇进行羟值、粘度等性能测试和FT IR、TGA、GPC和1H NMR等结构表征。腰果酚用量越小，腰果酚对苯酚的替代量越低，三聚氰胺添加量越多，多元醇的粘度和羟值越大，热稳定性越高；筛选出适合制备阻燃型聚氨酯硬质泡沫的腰果酚Mannich聚醚多元醇。
3.以蓖麻油、小分子多元醇（乙二醇、甘油、季戊四醇）和苯酐为原料，发生醇解和酯化反应，制备与其它聚酯、聚醚多元醇相容性良好的蓖麻油聚酯多元醇，有利于组合多元醇体系的储存。考察了小分子醇种类和反应时间对蓖麻油基醇解产物羟值、粘度及分子量的影响；发现随着小分子醇官能度的增加，体系中单甘酯和二甘酯含量和转化率减少，羟值增加；蓖麻油聚酯多元醇中蓖麻油单酯和二酯的含量较醇解蓖麻油大幅减少，且伯羟基相对含量高于相应的醇解产物，蓖麻油聚酯多元醇的热稳定性高于工业苯酐聚酯多元醇PS-3152，主要由于蓖麻油脂肪酸链热稳定性高的原因。
4.将腰果酚Mannich聚醚多元醇、异氰酸酯、发泡剂、表面活性剂、阻燃剂等一起发泡制备了一系列复合阻燃型聚氨酯硬质泡沫；研究结果表明：不同腰果酚替代量的Mannich聚醚多元醇发泡活性较高且相差不大，腰果酚对苯酚替代量越高，多元醇和发泡剂环戊烷相容性越好，泡沫相对压缩强度和导热系数越小，热稳定性稍差、成炭率和临界氧指数越低，热释放量和烟释放量稍高，且燃烧后的炭层开孔和破裂较多。对不同三聚氰胺添加量的聚醚多元醇和无卤阻燃剂EG、聚磷酸铵（APP）和乙基膦酸二乙酯（DEEP）复配制备的聚氨酯泡沫样品性能进行了分析，结果发现无阻燃剂时三聚氰胺替代量越高，泡沫相对压缩强度、导热系数和临界氧指数越大，热稳定性和成炭率高；和EG复配制备的阻燃泡沫具有较好的力学性能、热稳定性和氧指数，锥形量热显示燃烧的热释放峰值、热释放总量烟释放参数明显降低，残炭率和炭层致密连续性明显增强；在提高氧指数、烟产生和释放方面EG优于APP和DEEP；和DEEP、APP和EG复配制备的阻燃型聚氨酯泡沫的固化时间和导热系数有所升高；添加相同阻燃剂的样品其阻燃性能随着添加量的增加而增加，固体阻燃剂APP和EG在增加力学性能、热稳定性及降低CO/CO2比值方面较液体阻燃剂DEEP效果好，含磷阻燃剂APP和DEEP在降低热释放速率方面优于EG，不同阻燃剂复配在炭层的致密性和连续性方面的效果优于单一阻燃剂。
5.蓖麻油基多元醇和异氰酸酯、发泡剂、表面活性剂和阻燃剂APP等发泡制备一系列阻燃型蓖麻油聚氨酯泡沫，并与PS-3152进行对比。研究结果发现：蓖麻油聚酯多元醇的发泡活性较醇解产物高，泡沫压缩强度、热稳定性高于醇解产物；但其发泡活性、氧指数和燃烧性能与PS-3152制备的泡沫性能相当，且热稳定性更高，导热系数更低；主要由于苯环刚性结构的引入提高了整个体系的硬段含量和成炭率；添加APP后的泡沫样品阻燃性能明显得到了提高，其中氧指数达到了25.9-26.8。
Rigid polyurethane foam (RPUF) is the best thermal insulation material with its optimalinsulating performance. However, with the increasing depletion of fossil resources and theimprovement in awareness of the environmental protection, researches on natural renewableresources replacing petrochemicals has attracted more and more attention. Cardanol and castoroil are important feedstock for the renewable production of flame-retardant polyurethane foamin biomass resources. Less expensive cardanol and castor oil can replace phenol fossilresources to formulate polyurethane foam thermal insulation material, which has significantpromotion to make biomass resource advantage, improve ecological environment and developpolyurethane material industry.
In the present work, a series of novel polyether, polyester polyols were explored from thebiomass resources cardanol and castor oil by Mannich reaction, alkyl oxidation reaction,alcoholysis, esterification reaction and so on. Further, flame-retardant RPUFs with goodphysical and thermal performance were obtained. The main purpose of the thesis was to revealeffect of structure of biomass-based polyols on properties of rigid RPUF. The main researchcontents and conclusions were summarized as follows.
1. Cardanol-based Mannich bases with different structures and properties weresynthesized from cardanol, paraformaldehyde, diethanolamine and melamine by Mannichreaction. The intermediate and products were characterized and tested using FT IR,1H NMR,GPC, GC-MS and TG. The mechanism of first step aldehyde and amine adduct was confirmedin Mannich reaction. The main factors affecting the structure and properties of productcomposition, viscosity, hydroxyl value and molecular weight of cardanol-based Mannichpolyether polyols were discussed, such as reaction temperature, amount of cardanol, cardanolalternative of phenol, melamine and so on.
2. Cardanol-based Mannich polyether polyols were synthesized by initiator cardanol-based Mannich bases and propylene oxide through alkoxylation reaction, which havesome advantages such as low viscosity, adjustable functionality and containing flame retardantgroups.The structure and properties of Mannich polyether polyol were determined by studyingthe initiator structure, catalyst type, quality of propylene oxide and other factors. The optimumprocess conditions for cardanol-based Mannich polyether polyols were obtained throughtesting hydroxyl value, viscosity and characterizing FT IR, TG, GPC and1H NMR The smallerthe amount of cardanol, the lower the amount of phenol substitution, the more the amount ofmelamine added, the viscosity and hydroxyl value of the polyol larger and the thermal stabilityhigher. The cardanol-based Mannich polyether polyols suitable for preparing flame-retardantRPUF were chosen.
3Castor oil-based polyether polyols were synthesized using small molecule polyols(ethylene glycol, glycerol and pentaerythritol), castor oil and phthalic anhydride as rawmaterial by alcoholysis and esterification reaction, which have good compatibility with otherpolyester and polyether polyols and in favor of combination polyols system of long-termstorage. The effects of small molecule polyol species and reaction time on hydroxyl value,viscosity and molecular weight of castor oil-based alcoholysis products were investigated. Themonoglyceride and diglyceride content and conversion rate significantly reduced, the hydroxylvalue increased with increasing functionality of small molecule polyols. Compared to thealcoholysis of castor oil, the monoester and diester content of castor oil-based polyester polyolssubstantially reduced, and the primary hydroxyl groups relatively content of was higher. Thethermal stability of castor oil-based polyester polyols were higher than the commercialpolyester polyol PS-3152because of the high thermal stability of castor oil fatty acid chain.
4A series of composite flame-retardant RPUFs were prepared with cardanol-basedMannich polyether polyols, blowing agent, surfactant, flame retardants and isocyanate. Theresults showed that the higher foaming behavior of cardanol-based Mannich polyether polyolwith different amount of cardanol were almost same. The higher cardanol amount of phenolsubstitution, the better miscible with blowing agent cyclopentane, the smaller compressive strength and thermal conductivity, the lower thermal stability, residue char yield and limitiedoxygen index, the higher heat release and smoke emission of the RPUFs, and the moreopenings and cracking carbon layer after combustion. The properties of flame retardant RPUFsamples from different amounts of melamine-based Mannich polyether polyols addinghalogen-free flame retardants expanded graphite (EG), ammonium polyphosphate (APP) andDiethyl ethylphosphonate (DEEP) were analyzed. It was found that the higher the amount ofmelamine replacement foam, the greater the relative compressive strength, thermalconductivity, and the limitied oxygen index, the higher thermal stability and residue char yield.For EG filled RPUFs, the heat release peak, the total heat release and amount of smoke releaseparameters were significantly decreased, the mechanical properties, thermal stability, limitiedoxygen index, the yield and dense continuity of the char layer after combustion significantlyenhanced. EG was better in improving limited oxygen index, smoke production and releaseareas than DEEP and APP. Compared to non-flame retardant PUF, the curing times and thermalconductivities of RPUFs adding flame retardants DEEP, APP and EG were slightly increased.The flame retardant properties of the RPUF samples increased with the amount of the sameflame retardant. The solid flame retardants APP and EG were better in increasing themechanical properties, thermal stability and lowering ratio of CO/CO2than the liquid flameretardant DEEP. And, the phosphorus flame retardants APP and DEEP were better in reducingheat release rate than EG, the different flame retardants compound in the density and continuityof the carbon layer better than single flame.
5A series of castor oil-based flame retardant RPUFs were prepared from castor oil-basedpolyols, isocyanate, blowing agent, surfactant and flame retardant APP, and commercialpolyester polyol PS-3152were compared. The results showed that the foaming activities ofcastor oil-based polyester polyols were higher than alcoholysis products, the correspondingfoam compressive strength and thermal stability better. Compared to PS-3152based PUF, thefoaming activity of the oxygen index and the combustion performance of PUFs prepared fromcastor oil-based polyester polyol were quite, and higher thermal stability and lower thermal conductivity. This is mainly due to the introduction of benzene ring, improving the hardsegment content and residue char yield. The flame retardant properties of APP-filled PUFssignificantly improved with the limited oxygen index25.9-26.8.
引文
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