不同磺化度对磺化聚醚醚酮气体调节膜渗透性的影响
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摘要
以磺化聚醚醚酮(SPEEK)为原材料,制备自发式气体调节膜。利用红外光谱、扫描电镜等手段表征PEEK分子改性前后结构的变化。通过一系列测试手段研究磺化度(DS)对气体调节膜溶解性、吸水性和透气透湿性的影响规律。结果表明:磺酸基团成功接入PEEK分子主链,提高了材料的溶解性和吸水性,极大地降低了膜的生产成本。通过控制SPEEK的磺化度,可以制备对CO_2/O_2具有不同分离系数的气体调节膜;随着磺化度的增大,膜对CO_2的透气性增大,对O_2的透气性减小。不同磺化度的SPEEK膜对纯CO_2的透过系数范围为1.48×10~(-15)～1.16×10~(-14)(cm~3·cm/(cm~2·s·Pa)),对纯O_2的透过系数范围为1.54×10~(-15)～3.00×10~(-15)(cm~3·cm/(cm~2·s·Pa)),对分离系数α_(CO_2/O_2)调节范围为0.49～7.53。SPEEK膜的透湿性不受磺化度大小的控制,高磺化度或低磺化度均可以制备出高透湿性的气体调节膜。
Sulfonated poly ether ether ketone(SPEEK) was used to prepare self-breathing gas adjustable membranes, and their structure was analyzed by FT-IR and SEM. The effects of the degree of sulfonation for the solubility, water absorption and permeability of membranes were analyzed by a series of test. The results show that-HSO_3 is successfully connected to the main chains of PEEK, which greatly reduces the cost of membrane production and improves the solubility and water absorption. Different gas permeability membranes for CO_2/O_2 can be prepared by changing the degree of sulfonation of SPEEK. As the degree of sulfonation increases, the gas permeability of the membrane for CO_2 increases, and the permeability for O_2 decreases. The permeability of membranes with different degrees of sulfonation of SPEEK for pure CO_2, O_2 and separation coefficient of CO_2/O_2 is in the range of 1.48×10~(-15)～1.16×10~(-14)(cm~3·cm·cm~(-2)·s~(-1)·Pa~(-1)), 1.54×10~(-15)～3.00×10~(-15)(cm~3·cm·cm~(-2)·s~(-1)·Pa~(-1)) and 0.49～7.53, respectively. The moisture permeability of the SPEEK membrane is not controlled by the degree of sulfonation, and a high moisture permeability gas adjustable membrane can be prepared at a high sulfonation degree or low sulfonation degree.
Sulfonated poly ether ether ketone(SPEEK) was used to prepare self-breathing gas adjustable membranes, and their structure was analyzed by FT-IR and SEM. The effects of the degree of sulfonation for the solubility, water absorption and permeability of membranes were analyzed by a series of test. The results show that-HSO_3 is successfully connected to the main chains of PEEK, which greatly reduces the cost of membrane production and improves the solubility and water absorption. Different gas permeability membranes for CO_2/O_2 can be prepared by changing the degree of sulfonation of SPEEK. As the degree of sulfonation increases, the gas permeability of the membrane for CO_2 increases, and the permeability for O_2 decreases. The permeability of membranes with different degrees of sulfonation of SPEEK for pure CO_2, O_2 and separation coefficient of CO_2/O_2 is in the range of 1.48×10~(-15)～1.16×10~(-14)(cm~3·cm·cm~(-2)·s~(-1)·Pa~(-1)), 1.54×10~(-15)～3.00×10~(-15)(cm~3·cm·cm~(-2)·s~(-1)·Pa~(-1)) and 0.49～7.53, respectively. The moisture permeability of the SPEEK membrane is not controlled by the degree of sulfonation, and a high moisture permeability gas adjustable membrane can be prepared at a high sulfonation degree or low sulfonation degree.
引文
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[3] An J S,Zhang M,Zhan Z G.Effect of Packaging film on the quality of ‘Chaoyang’ honey peach fruit in modified atmosphere packaging[J].Packag.Technol.,2007,20:71-76.
[4] Mistriotis A,Briassoulis D,Giannoulis A,et al.Design of biodegradable bio-based equilibrium modified atmosphere packaging (EMAP) for fresh fruits and vegetables by using micro-perforated poly-lactic acid (PLA) films[J].Postharvest Biol.Technol.,2016,111:380-389.
[5] Sandhya.Modified atmosphere packaging of fresh produce:current status and future needs[J].LWT-Food Sci.Technol.,2010,43:381-392.
[6] Mangaraj S,Goswami T K,Giri S K,et al.Perm-selective MA packaging of litchi for preserving quality and extension of shelf-life[J].Postharvest Biol.Technol.,2012,71:1-12.
[7] 郭圆圆,鲁晓翔,李江阔.自发气调包装对青皮核桃采后生理及品质的影响[J].食品科学,2014,35(4):205-209.Guo Y Y,Lu X X,Li J K.Effect in postharvest physiology and quality of pellicle with modified atmosphere package [J].Food Science,2014,35(4):205-209.
[8] Xiao G N,Zhang M,Shan L,et al.Extending shelf-life of fresh oyster mushrooms (Pleurotus ostreatus) by modified atmosphere packaging with chemical treatments[J].Afr.J.Biotechnol.,2011,10:509-9517.
[9] Tin P S,Chung T S,Liu Y,et al.Effects of cross-linking modification on gas separation performance of Matrimid membranes[J].J.Membr.Sci.,2003,25:77-90.
[10] AmmarA A,Lzatahry E,Al-Maadeed M,et al.Nanoclay compatibilization of phase separated polysulfone/polyimide films for oxygen barrier[J].Appl.Clay Sci.,2017,137:123-134.
[11] Guillen G R,PanY J,Li M H,et al.Preparation and characterization of membranes formed by nonsolvent induced phase separation:a review [J].Ind.Eng.Chem.Res.,2011,50:3798-3817.
[12] Devesh S,Yuvraj S N,Jugmendra S U,et al.Synthesis and modification of poly (ether ether ketone) and their properties:a review[J].Polym.Rev.,2012,52:189-228.
[13] Wang M,Wang Z,Zhao S,et al.Recent advances on mixed matrix membranes for CO2 separation [J].Chin.J.Chem.Eng.,2017,25:1581-1597.
[14] Asim L K,Li X F.Mixed gas CO2/CH4 and CO2/N2 separation with sulfonated PEEK membranes[J].J.Membr.Sci.,2011,372:87-96.
[15] 吕健飞.醚醚酮改性膜的制备及CO2分离性能研究[D].石河子:石河子大学,2015.Lü J F.Preparation of modified polyether ether ketone and application for CO2 capture [D].Shihezi:Shihezi University,2015.
[16] 黄雪红,林娟,郑榕学,等.原子转移自由基聚合法制备侧链型磺化聚醚醚酮阳离子交换膜[J].应用化学,2014,31(8):878-884.Huang X H,Lin J,Zheng R X,et al.Preparation of side-chain sulfonated poly ether ether ketone cation exchange membranes by atom transfer radical polymerization[J].Chinese Journal of Applied Chemistry,2014,31(8):878-884.
[17] Xu Liu,Meng,X Y,Wu J T,et al.Microstructure and properties of novel SPEEK/PVDF-g-PSSA blends for proton exchange membrane with improved compatibility[J].RSC Adv.,2015,5:69621-69628.
[18] Kanehashi S,Kishida M,Kidesaki T,et al.CO2 separation properties of a glassy aromatic polyimide composite membranes containing high-content 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid[J].J.Membr.Sci.,2013,430:211-222.