柔性链段的引入对聚甲基丙烯酸三苯基甲酯性能的影响
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摘要
为了改善聚甲基丙烯酸三苯基甲酯(PTrMA)的热稳定性和加工性,采用热聚合法引入甲基丙烯酸甲酯(MMA)的柔性链段,合成了三种不同比例的共聚物(PTrMA-co-MMA),通过红外光谱和核磁共振氢谱对所制备的单体、均聚物和共聚物进行了结构表征,并利用差示扫描量热仪、热重分析仪及X射线衍射仪对均聚物和共聚物进行了性能测试.结果表明:通过引入1∶5,1∶15和1∶25三个比例的MMA后,PTrMA的DSC曲线中玻璃化转变峰发生了左移现象,玻璃化转变温度由150℃分别降低至140℃、138℃和132℃,使分解温度得到了很大的提高,即引入MMA可以使聚合物的玻璃化转变温度减小,热稳定性提高;PTrMA在2θ=12.6°,30.2°和42.3°存在三个特殊衍射峰,不同比例的PTrMA-co-MMA也出现了与均聚物类似的三个衍射峰,即2θ=12.5°,31.1°和42.2°;随着MMA引入量的增大,衍射峰的面积有递减趋势,说明MMA的引入并不影响共聚物的结晶行为,但可使结晶度逐渐降低,大大提高了PTrMA材料的柔性.
In order to improve the thermal stability and fabricability of polytriphenylmethyl methacrylate,copolymers of three different proportions were synthesized by introducing flexible methyl methacrylate segment by thermal polymerization method.The structures of the monomer,homopolymer and copolymer were characterized by FTIR and 1 H-NMR.The properties of the homopolymer and copolymer were tested by a differential scanning calorimeter,a thermal gravimetric analyzer and an X-ray diffractometer.The results show that the glass transition peak of PTrMA was shifted to the left introduced MMA at 1∶5,1∶15,1∶25 in the DSC curve.The glass transition temperature was reducedfrom 150℃to 140℃,138℃and 132℃,and the decomposition temperature had been greatly improved.The result shows that the glass transition temperatures decrease and the thermal stability increases.X-ray diffraction peaks emerge at 2θ =12.6°,30.2°and 42.3°.Copolymers of three proportions have similar diffraction peaks at 2θ =12.5°,31.1°,and 42.2°.With the increase in the amount of methyl methacrylate,the diffraction peak areas show a diminishing trend,which means that the addition of methyl methacrylate has no effect on the crystalline structure,but leads to a gradual decrease in the degree of crystallinity.
In order to improve the thermal stability and fabricability of polytriphenylmethyl methacrylate,copolymers of three different proportions were synthesized by introducing flexible methyl methacrylate segment by thermal polymerization method.The structures of the monomer,homopolymer and copolymer were characterized by FTIR and 1 H-NMR.The properties of the homopolymer and copolymer were tested by a differential scanning calorimeter,a thermal gravimetric analyzer and an X-ray diffractometer.The results show that the glass transition peak of PTrMA was shifted to the left introduced MMA at 1∶5,1∶15,1∶25 in the DSC curve.The glass transition temperature was reducedfrom 150℃to 140℃,138℃and 132℃,and the decomposition temperature had been greatly improved.The result shows that the glass transition temperatures decrease and the thermal stability increases.X-ray diffraction peaks emerge at 2θ =12.6°,30.2°and 42.3°.Copolymers of three proportions have similar diffraction peaks at 2θ =12.5°,31.1°,and 42.2°.With the increase in the amount of methyl methacrylate,the diffraction peak areas show a diminishing trend,which means that the addition of methyl methacrylate has no effect on the crystalline structure,but leads to a gradual decrease in the degree of crystallinity.
引文
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[2]叶辉,席涛,姚路路,等.甲基丙烯酸甲酯共聚改性水性聚氨酯膜制备及膜性能[J].高分子材料科学与工程,2017,33(7):144.YE Hui,XI Tao,YAO Lulu,et al.Preparation and Properties of Methyl Methacrylate Modified Waterborne Polyurethane Membrane[J].Polymer Materials Science and Engineering,2017,33(7):144.(in Chinese)
[3]虞斌,林雪春,丁孟贤,等.甲基丙烯酸三苯甲酯不对称聚合过程中的立体化学[J].高分子学报,1992(22):2051.YU Bin,LIN Xuechun,DING Mengxian,et al.Stereochemistry in Asymmetric Polymerization of Triphenyl Methyl Methacrylate[J].Acta Polymerica Sinica,1992(22):2051.(in Chinese)
[4]崔小明.国内外甲基丙烯酸甲酯的供需现状及发展前景分析[J].石油化工技术与经济,2016,32(4):27.CUI Xiaoming.Supply and Demand Status of Methyl Methacrylate at Home and Abroad and Its Development Prospect[J].Technology&Economics in Petrochemicals,2016,32(4):27.(in Chinese)
[5]KO K Y,HWANG S H.Monomer composition Effects on Thermal Properties of Transparent Poly(Methyl Methacrylate-co-isobornly Methacrylate-co-cyclohexyl Maleimide)Terpolymers[J].Journal of Industrial and Engineering Chemistry,2018,59:50.
[6]HARILALl A,DASIREDDY V D B C,FRIEDRCHH B.Effect of Water and Methanol in the Production of Methyl Methacrylate Over Iron Phosphate Catalysts[J].Reaction Kinetics,Mechanisms and Catalysis,2018,124(1):265.
[7]YOO H Y,JU M,BRCKESTEIN S.Increasing QCMSensitivity Based on High Molecular Weight Porous Polymers[J].Sensors and Actuators B:Chemical,2018,254:573.
[8]TOPOUS M,KONTONASAKI E,BIKIANAS D,et al.Reinforcement of a PMMA Resin for Interim Fixed Prostheses with Silica Nanoparticles[J].Journal of the Mechanical Behavior of Biomedical Materials,2017,69:213.
[9]HANEET M,SALEEM H,HABIB A.Use of Graphene Nanosheets and Barium Titanate as Fillers in PMMA for Dielectric Applications[J].Synthetic Metals,2017,223:101.
[10]RESHETENOK T V,ST-PIERRE J.Effects of Propylene,Methyl Methacrylate and Isopropanol Poisoning on Spatial Performance of a Proton Exchange Membrance Fuel Cell[J].Journal of Power Sources,2018,378:216.
[11]HANDAYANIi A S,CHALID M,BUDIANTO E,et al.Grafting of Amylopectin With Various Alkyl Methacrylate by Atom Transfer Radical Polymerization for Engineering Application[J].Macromolecular Symposia,2017,371:58.
[12]WU D X,DING W D,KOUBAA A,et al.Robust DEA to Assess the Reliability of Methyl Methacrylate-hardened Hybrid Poplar Wood[J].Annals of Operations Research,2016,248(1/2):515.
[13]WU M C,CHAN S H,LIN T F,et al.Detection of Volatile Organic Compounds Using Electrospun P3HT/PMMA Fibrous Film[J].Journal of the Taiwan Institute of Chemical Engineers,2017(78):552.
[14]ALBERTINI R J.The Lower Alkyl Methacrylates:Genotoxic Profile of Non-carcinogenic Compounds[J].Regulatory Toxicology and Pharmacology,2017,84:77.
[15]ZHONG X P,HUANG Y,CAO H J,et al.Polyhedral Oligomeric Silsesquioxane-modified Gel Polymer Electrolyte Based on Matrix of Poly(Methyl Methacrylate-maleic Anhydride)[J].Journal of Solid State Electrochemistry,2016,21(3):849.