亚临界水中聚碳酸酯解聚影响因素的研究
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摘要
本文在间歇式高压反应器中开展亚临界水中聚碳酸酯(PC)解聚的影响因素研究,采用气-质联谱(GC-MS)、气相色谱(GC)、傅立叶红外光谱(FT-IR)、扫描电子显微镜(SEM)对解聚产物进行定性定量分析,考察反应条件对聚碳酸酯解聚率、目标产物双酚A(BPA)、苯酚产率的影响。
在温度260~340℃、压力4.8~14.8 MPa、反应时间15~60 min、投料比(介质质量/ PC质量)8.0条件下,开展了聚碳酸酯在亚临界水中的解聚实验。结果表明亚临界水能有效降解PC;反应温度和反应时间是聚碳酸酯解聚及其产物双酚A(BPA)和苯酚产率的主要影响因素;随着温度的升高和时间的增加,双酚A产率先增加后下降,苯酚产率逐渐增加。较佳的反应条件是:反应温度为300℃,反应时间45 min,此时聚碳酸酯完全解聚,双酚A产率为36.88%,苯酚产率为31.16%;根据聚碳酸酯在亚临界水中解聚产物的GC-MS分析,结合聚碳酸酯的链节特点,提出亚临界水解聚聚碳酸酯反应过程是伴随着副反应的水解断裂过程;通过实验数据关联,解聚反应活化能为125.7 kJ·mol~(-1)。
在温度280~340℃、压力6.4~15.2 MPa、反应时间15~60 min、投料比8.0的条件下,开展了添加阻燃剂十溴联苯醚(DBDPO)或增塑剂邻苯二甲酸二正辛酯(DnOP)后聚碳酸酯在亚临界水中的解聚实验。发现温度和时间仍然是影响PC在亚临界水中解聚的主要影响因素,阻燃剂会促进PC的水解,而增塑剂则使PC不容易被水解,两者都使BPA的产率降低。添加阻燃剂的条件下,PC在反应温度为300℃、反应时间45min时完全解聚,实验条件范围内目标产物BPA的最高产率为30.9%;添加增塑剂的情况下,PC在反应温度为320℃、反应时间30min或300℃、反应时间60min时完全解聚,实验条件范围内目标产物BPA的最高产率为19.85%。根据PC添加上述两种助剂后在过热水中解聚产物的分析,并结合PC链结特点,提出了阻燃剂、增塑剂与PC在过热水中的水解机理。通过实验数据关联,添加阻燃剂十溴联苯醚后,反应活化能为116.48kJ·mol~(-1);添加增塑剂邻苯二甲酸二正辛酯后,反应活化能为147.17kJ·mol~(-1)。
The characteristics of depolymerization of polycarbonate(PC) in sub-critical water were investigated by using a high-pressure batch autoclave reactor. The products were qualitative and quantitative analyzed by Fourier-transform Infrared Spectroscopy (FT-IR), scanning electron microscope (SEM), Gas Chromatography/Mass Spectrometry (GC/MS) and Gas Chromatography (GC), respectively.
Depolymerization of PC in sub-critical water was studied under the conditions of temperature (260~340℃), pressure (4.8~14.8 MPa), reaction time(15~60min) and ratio of water/PC (8.0). It was found that PC can be effectively depolymerized in sub-critical water. The temperature and reaction time were main factors in the process of depolymerizaition. As the temperature and reaction time rised, the yield of bisphenol A increased at first and then reduced,while the yield of phenol increased throughout the process. The result showed that at reaction temperature 300℃, reaction pressure 8.7 MPa and reaction time 45 min, the PC could be depolymerized completely with the yield of BPA and phenol were 36.88% and 31.16%, respectively. Based on the qualitative and quantitative analyses of the products, the reaction mechanism, i.e. hydrolytic reaction and side reaction occurred simultaneously during the process of depolymerizaition of PC was proposed. The results of kinetic analysis indicated that the depolymerization followed a pseudo-first-order kinetics and the activation energy of PC depolymerizaition in sub-critical water obtained from Arrhenius equation was 125.7 kJ·mol~(-1).
Depolymerization of PC which added plastic additives was studied under the conditions of temperature (280~340℃), pressure (6.4~15.2 MPa), reaction time (15~60min) and ratio of water/PC (8.0). The plastic additives were flame retardants (Decabromodiphenyl ether , DBDPO) and plasticizer (Di-n-octyl Phthalate,DnOP). It was found that the flame retardants (DBDPO) would accelerate the hydrolysis of PC,while plasticizer (DnOP) has opposite effect. Both the additives would reduce the yield of BPA obviously, while the temperature and reaction time were still the main factors in this process. The result showed that the PC could be depolymerized completely and the yield of BPA was 30.9% with reaction temperature 300℃and reaction time 45 min when flame retardants had been added. The PC could be depolymerized completely and the yield of BPA was 19.85% with reaction temperature 320℃, reaction time 35 min or temperature 300℃, reaction time 60 min when plasticizer had been added.
According to the distribution of depolymerization products and the energy of carbon chain, the main mechanism of depolymerization of PC with plastic additives in sub-critical water was proposed. The result of kinetic analysis showed that the activation energy of PC depolymerized in sub-critical water was 116.48 kJ·mol~(-1) when flame retardants had been added, and the activation energy was 147.17 kJ·mol~(-1) when plasticizer had been added.
在温度260~340℃、压力4.8~14.8 MPa、反应时间15~60 min、投料比(介质质量/ PC质量)8.0条件下,开展了聚碳酸酯在亚临界水中的解聚实验。结果表明亚临界水能有效降解PC;反应温度和反应时间是聚碳酸酯解聚及其产物双酚A(BPA)和苯酚产率的主要影响因素;随着温度的升高和时间的增加,双酚A产率先增加后下降,苯酚产率逐渐增加。较佳的反应条件是:反应温度为300℃,反应时间45 min,此时聚碳酸酯完全解聚,双酚A产率为36.88%,苯酚产率为31.16%;根据聚碳酸酯在亚临界水中解聚产物的GC-MS分析,结合聚碳酸酯的链节特点,提出亚临界水解聚聚碳酸酯反应过程是伴随着副反应的水解断裂过程;通过实验数据关联,解聚反应活化能为125.7 kJ·mol~(-1)。
在温度280~340℃、压力6.4~15.2 MPa、反应时间15~60 min、投料比8.0的条件下,开展了添加阻燃剂十溴联苯醚(DBDPO)或增塑剂邻苯二甲酸二正辛酯(DnOP)后聚碳酸酯在亚临界水中的解聚实验。发现温度和时间仍然是影响PC在亚临界水中解聚的主要影响因素,阻燃剂会促进PC的水解,而增塑剂则使PC不容易被水解,两者都使BPA的产率降低。添加阻燃剂的条件下,PC在反应温度为300℃、反应时间45min时完全解聚,实验条件范围内目标产物BPA的最高产率为30.9%;添加增塑剂的情况下,PC在反应温度为320℃、反应时间30min或300℃、反应时间60min时完全解聚,实验条件范围内目标产物BPA的最高产率为19.85%。根据PC添加上述两种助剂后在过热水中解聚产物的分析,并结合PC链结特点,提出了阻燃剂、增塑剂与PC在过热水中的水解机理。通过实验数据关联,添加阻燃剂十溴联苯醚后,反应活化能为116.48kJ·mol~(-1);添加增塑剂邻苯二甲酸二正辛酯后,反应活化能为147.17kJ·mol~(-1)。
The characteristics of depolymerization of polycarbonate(PC) in sub-critical water were investigated by using a high-pressure batch autoclave reactor. The products were qualitative and quantitative analyzed by Fourier-transform Infrared Spectroscopy (FT-IR), scanning electron microscope (SEM), Gas Chromatography/Mass Spectrometry (GC/MS) and Gas Chromatography (GC), respectively.
Depolymerization of PC in sub-critical water was studied under the conditions of temperature (260~340℃), pressure (4.8~14.8 MPa), reaction time(15~60min) and ratio of water/PC (8.0). It was found that PC can be effectively depolymerized in sub-critical water. The temperature and reaction time were main factors in the process of depolymerizaition. As the temperature and reaction time rised, the yield of bisphenol A increased at first and then reduced,while the yield of phenol increased throughout the process. The result showed that at reaction temperature 300℃, reaction pressure 8.7 MPa and reaction time 45 min, the PC could be depolymerized completely with the yield of BPA and phenol were 36.88% and 31.16%, respectively. Based on the qualitative and quantitative analyses of the products, the reaction mechanism, i.e. hydrolytic reaction and side reaction occurred simultaneously during the process of depolymerizaition of PC was proposed. The results of kinetic analysis indicated that the depolymerization followed a pseudo-first-order kinetics and the activation energy of PC depolymerizaition in sub-critical water obtained from Arrhenius equation was 125.7 kJ·mol~(-1).
Depolymerization of PC which added plastic additives was studied under the conditions of temperature (280~340℃), pressure (6.4~15.2 MPa), reaction time (15~60min) and ratio of water/PC (8.0). The plastic additives were flame retardants (Decabromodiphenyl ether , DBDPO) and plasticizer (Di-n-octyl Phthalate,DnOP). It was found that the flame retardants (DBDPO) would accelerate the hydrolysis of PC,while plasticizer (DnOP) has opposite effect. Both the additives would reduce the yield of BPA obviously, while the temperature and reaction time were still the main factors in this process. The result showed that the PC could be depolymerized completely and the yield of BPA was 30.9% with reaction temperature 300℃and reaction time 45 min when flame retardants had been added. The PC could be depolymerized completely and the yield of BPA was 19.85% with reaction temperature 320℃, reaction time 35 min or temperature 300℃, reaction time 60 min when plasticizer had been added.
According to the distribution of depolymerization products and the energy of carbon chain, the main mechanism of depolymerization of PC with plastic additives in sub-critical water was proposed. The result of kinetic analysis showed that the activation energy of PC depolymerized in sub-critical water was 116.48 kJ·mol~(-1) when flame retardants had been added, and the activation energy was 147.17 kJ·mol~(-1) when plasticizer had been added.
引文
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