利用脂肪酶催化乙二醇与丁二酸二甲酯进行酯交换反应,合成了聚丁二酸乙二醇酯(PES)并探究其疏水性能。通过单因素实验得到较优的反应条件:反应温度55℃、底物摩尔比1∶2、脂肪酶体积分数30%、反应时间24h,此条件下产物平均聚合度达3.06,单体转化率显著提升。通过傅里叶变换红外光谱仪、基质辅助激光解析电离串联飞行时间质谱仪、接触角测量仪、扫描电子显微镜对产物进行了表征和分析测试。结果表明:产物为低聚物,其中酯-醇端基结构(nae)占主导;在棉织物表面原位合成PES后,基材表面由亲水转变为疏水,接触角超过90°;原位合成的PES沉积在棉织物表面,使得棉织物表面均涂覆了颗粒状的涂层,进而达到疏水效果。
Using lipase to catalyze the ester exchange reaction between ethylene glycol and dimethyl succinate,polyethylene succinate was synthesized,and its hydrophobic properties were investigated.The optimal reaction conditions were obtained through one-way experiments:reaction temperature of 55 ℃,substrate molar ratio of 1∶2,lipase volume fraction of 30%,and reaction time of 24h.The average polymerization degree of the products under these conditions reached 3.06,and the conversion rate of monomers was significantly improved.The products were characterized and analyzed by Fourier transform infrared spectroscopy,matrix-assisted laser resolved ionization tandem time-of-flight mass spectrometry,contact angle measurement instrument,and scanning electron microscope.The results showed that the products were oligomers,in which the ester-alcohol end-group structure (nae) was dominant.After in situ synthesis of polyethylene succinate on the surface of cotton fabric,the surface of the substrate was transformed from hydrophilic to hydrophobic,with a contact angle of more than 90°.The in situ-synthesized PES deposited on the surface of cotton fabric and formed a uniformly granular coating on the surface of cotton fabric,achieving a hydrophobic effect.
[1] 刘涛,程刊,牛昉昉,等.生物可降解聚酯酰胺的合成、结构性能及其纺织材料在医疗卫生领域的应用[J].产业用纺织品,2024,42(3):1-11.
[2] 李振超,魏东,苗庆,等.乙酸氧钛催化酯化缩聚法合成聚丁二酸乙二醇酯及其性能研究[J].低碳化学与化工,2024,49(2):60-66.
[3] Bouyahya C,Klonos P A,Zamboulis A,et al.Preparation and structural-thermodynamical investigation of renewable copolyesters based on poly (ethylene succinate) and polyisosorbide[J].Polymers,2024,16(15):2173.
[4] 张馨文.聚丁二酸乙二醇酯共聚物的结晶与性能研究[D].北京:中国石油大学(北京),2023.
[5] 王翼嵩,王松林,姜冰雪,等.聚酯合成催化技术的研究进展[J].高校化学工程学报,2024,38(1):1-13.
[6] 潘祖仁.高分子化学[M].5版.北京:化学工业出版社,2011:145-147.
[7] Khoon Poh A,Choy Sin L,Sit Foon C,et al.Polyurethane wood adhesive from palm oil-based polyester polyol[J].Journal of Adhesion Science and Technology,2014,28(11):1020-1033.
[8] Moghadam P N,Yarmohamadi M,Hasanzadeh R,et al.Preparation of polyurethane wood adhesives by polyols formulated with polyester polyols based on castor oil[J].International Journal of Adhesion and Adhesives,2016,68:273-282.
[9] Wang X,Guo W,Song L,et al.Intrinsically flame retardant bio-based epoxy thermosets:a review[J].Composites Part B:Engineering,2019,179:107487.
[10] 郑梦迪,辛嘉英,崔添玉,等.机械酶催化及其在食品领域的应用研究进展[J].食品工业科技,2025,46(11):403-410.
[11] 周游,李攀登,贺雷雨,等.酶法催化高酸值米糠油脱臭馏出物甲酯化[J].山东大学学报(理学版),2024,59(11):85-92.
[12] 季骁彦,许蕊,王飞,等.VKT多肽介导的固定化疏棉状嗜热丝孢菌脂肪酶催化制备生物柴油[J].化工进展,2024,43(6):3285-3292.
[13] Zhang Y,Nie H,Zhang F,et al.Construction of an aspergillus oryzae ΔnptB ΔpyrG host for homologous expression of lipase and catalytic property characterization of recombinant lipase[J].Applied Biochemistry and Biotechnology,2025,197:873-890.
[14] Perin G B,Felisberti M I.Phosphorylated polyesters inspired by phospholipids:synthesis,characterization,and potential applications[J].Biomacromolecules,2023,24(11):5207-5218.
[15] Wang Y,Xia M,Kong X,et al.Tailoring chain structures of l-lactide and ε-caprolactone copolyester macromonomers using rac-binaphthyl-diyl hydrogen phosphate-catalyzed ring-opening copolymerization with monomer addition strategy[J].RSC Advances,2017,7(46):28661-28669.
[16] Petrović Z S,Javni I.The effect of soft-segment length and concentration on phase separation in segmented polyurethanes[J].Journal of Polymer Science Part B:Polymer Physics,1989,27(3):545-560.
[17] Cui S,Liu Z,Li Y.Bio-polyols synthesized from crude glycerol and applications on polyurethane wood adhesives[J].Industrial Crops and Products,2017,108:798-805.
[18] 赵晓曼.棉织物表面酯酶催化原位聚合疏水化改性研究[D].无锡:江南大学,2019.
[19] 杨俊,崔佳琦,于鹏飞,等.脂肪酶酶活力检测方法研究进展[J].食品与生物技术学报,2024,43(12):29-36.
[20] Tomke P D,Zhao X,Chiplunkar P P,et al.Lipase-ultrasound assisted synthesis of polyesters[J].Ultrasonics Sonochemistry,2017,38:496-502.
[21] Zhao X,Bansode S R,Ribeiro A,et al.Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)[J].Ultrasonics sonochemistry,2016,31:506-511.
[22] 苏静.漆酶修饰及其催化芳香类化合物聚合影响机制研究[D].无锡:江南大学,2019.
[23] 常海波.缩聚反应中体系反应程度与数均聚合度关系的推导[J].化学教育,2015,36(14):13-15.
[24] 黄成毅,温萍,唐旭东,等.羟基硅油改性SiO2制备复合粒子及超疏水涂层的制备与性能[J].化工新型材料,2023,51(S1):122-126.
[25] 孟凡杰,黄贺东,梁新月,等.纳米纤维素修饰的碳纳米纤维制备及其疏水性研究[J].化工新型材料,2023,51(6):98-102;108.
基金资助
江苏省政策引导类计划(BZ2020010);塔里木大学校长基金(TDZKCX202512)
PDF
