生物基丁内酰胺及聚丁内酰胺的合成及性能
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摘要
以生物基来源的γ-氨基丁酸为原料,采用高温水解-减压精馏法制备了高纯度的生物基丁内酰胺(BBY);以BBY为原料,通过阴离子开环聚合,合成生物基聚丁内酰胺(BPBY)。采用傅里叶红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)、高效液相色谱(HPLC)、差示扫描量热分析(DSC)、生物质谱(BMS)、拉伸测试和老化降解实验等手段对BBY和BPBY的结构、纯度、热性能、力学性能和老化降解性能进行了研究,并与石油基聚丁内酰胺(PPBY)进行了比较。结果表明:精馏后BBY的纯度高达97.7%(质量分数),BPBY与PPBY具有相似的结构及相近的热学和力学性能,BPBY比PPBY降解得更快,30d内降解17.56%(质量分数)。
Highly purified bio-based butyrolactam(BBY)was prepared at about 97.7% purity from biologically derivedγ-aminobutyric acid(GABA)by high temperature hydrolysis and rectification under vacuum.The purified BBY was used as the monomer to prepare bio-based polybutylactam(BPBY)by anionic ring-opening polymerization.The structure of BBY and BPBY were characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance(NMR).High performance liquid chromatography(HPLC)was used to analyze the purity of BBY and bio-mass spectrometry(BMS)was used to measure the relative molecular mass of BPBY.In addition,differential scanning calorimetry(DSC)was used to compare the thermal properties between BPBY and petroleum-based polybutyrolactam(PPBY).Furthermore,tensile test and aging degradation test were carried out to find the differences between BPBY and PPBY.The results showed that BPBY was synthesized successfully from GABA by two main processes.The relative molecular mass of BPBY was lower than that of PPBY.The glass transition temperature and melting point of BPBY were 102.3℃ and 203.8℃,respectively.Tensile strength and elongation at break of BPBY film were 20.32 MPa and 8.78%,respectively.Although the relative molecular mass,thermal and mechanical properties of BPBY were not as good as PPBY,these properties were close between two materials,meaning that BPBY can replace PPBY in some conditions.In addition,the degradability of BPBY was 17.56%(mass fraction)in 30 d,which was faster than that of PPBY.BPBY is eco-friendly compared with PPBY and it could be used to solve the white pollution problem.
Highly purified bio-based butyrolactam(BBY)was prepared at about 97.7% purity from biologically derivedγ-aminobutyric acid(GABA)by high temperature hydrolysis and rectification under vacuum.The purified BBY was used as the monomer to prepare bio-based polybutylactam(BPBY)by anionic ring-opening polymerization.The structure of BBY and BPBY were characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance(NMR).High performance liquid chromatography(HPLC)was used to analyze the purity of BBY and bio-mass spectrometry(BMS)was used to measure the relative molecular mass of BPBY.In addition,differential scanning calorimetry(DSC)was used to compare the thermal properties between BPBY and petroleum-based polybutyrolactam(PPBY).Furthermore,tensile test and aging degradation test were carried out to find the differences between BPBY and PPBY.The results showed that BPBY was synthesized successfully from GABA by two main processes.The relative molecular mass of BPBY was lower than that of PPBY.The glass transition temperature and melting point of BPBY were 102.3℃ and 203.8℃,respectively.Tensile strength and elongation at break of BPBY film were 20.32 MPa and 8.78%,respectively.Although the relative molecular mass,thermal and mechanical properties of BPBY were not as good as PPBY,these properties were close between two materials,meaning that BPBY can replace PPBY in some conditions.In addition,the degradability of BPBY was 17.56%(mass fraction)in 30 d,which was faster than that of PPBY.BPBY is eco-friendly compared with PPBY and it could be used to solve the white pollution problem.
引文
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[2]HASHIMOTO K,HAMANO T,OKADA M.Degradation of several polyamides in soils[J].Applied Polymer Science,1994,54(10):1579-1583.
[3]张国胜,李勇进,颜德岳.新型尼龙214,414,614,814,1014和1214的合成与表征[J].化学学报,2002,36(11):60-68.
[4]KAWASAKI N,NAKAYAMA A,YAMANO N,et al.Synthesis,thermal and mechanical properties and biodegradation of branched polyamide 4[J].Polymer,2005,46(23):9987-9993.
[5]杨帆.微生物转化法产γ-氨基丁酸[D].江苏无锡:江南大学,2008.
[6]LEE J W,KIM H U,CHOI S,et al.Microbial production of building block chemicals and polymers[J].Current Opinion in Biotechnology,2011,22(62):758-767.
[7]KIM S H,SHIN B H,KIM Y H,et al.Cloning and expression of a full-length glutamate decarboxylase gene from Lactobacillus brevis BH2[J].Biotechnology and Bioprocess Engineering,2011,12(32):707-712.
[8]JANG G,KIM J,KIM D,et al.Degradation behavior of nylon 4in the presence of newly synthesized thermal stabilizers[J].Polymer Korea,2014,38(3):314-319.
[9]郑世昭,徐伟箭.树枝状尼龙6的合成与研究[J].功能高分子学报,2004,17(1):139-142.
[10]蒋光玉,刘洋,汪艳.4-丁内酰胺水解酶法制备γ-氨基丁酸[J].氨基酸和生物资源,2011,33(1):43-48.
[11]王群,邵正中.聚酰胺46的合成与结构研究:1.合成条件对产物分子量的影响[J].功能高分子学报,1997,10(1):72-78.
[12]黄虹云,李伟,费又庆.阴离子聚合制备PA6/12共聚物的研究[J].材料导报,2016,30(20):100-103.
[13]TACHIBANA K,HASHIMOTO K,TANSHO N,et al.Chemical modification of chain end in nylon 4and improvement of its thermal stability[J].Polymer Science:Part A.Polymer Chemistry,2011,49(11):2495-2503.
[14]CHO H H,JEON J W,LEE M H,et al.Structure and physical properties of variously drawn nylon 6-ran-nylon 4copolymer fibers[J].Textile Science&Engineering,2011,48(3):150-155.
[15]HASHIMOTO K,SUDO M,OHTA K,et al.Biodegradation of nylon4and its blend with nylon 6[J].Applied Polymer Science,2002,86(9):2307-2311.
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