超支化聚缩水甘油的合成及性能
|
摘要
以三羟甲基丙烷为引发剂、缩水甘油(2,3-环氧-1-丙醇)为单体、无水N-甲基吡咯烷酮(NMP)为溶剂,采用阴离子开环聚合、一步法制备了超支化聚缩水甘油(hPG)。通过调控单体与引发剂的物质的量之比,成功合成了3种不同数均分子量的hPG;通过核磁共振氢谱、凝胶渗透色谱、傅里叶红外光谱等表征了hPG的支化结构、分子量及分布、化学官能团;采用差示扫描量热仪、热重分析仪、粒径-电位分析仪等分析了hPG的玻璃化转变温度(T_g)、热降解温度(T_d)及热稳定性和溶液性质等参数。结果表明,溶剂NMP的引入有利于hPG数均分子量的快速增加和单分散性的提升;hPG的T_g和T_d随着数均分子量的增加略有增加。
Hyperbranched polyglycerol(hPG) with controlled molecular weight and narrow polydispersity has been synthesized by one-step anionic ring-opening polymerization(ROP) reaction, in which monomer glycidol(2,3-epoxy-1-propanol) was added dropwise to the mixture solution of timethylolpropane(TMP) initiator, potassium tert-butoxide(K-tOBu) base, and anhydrous N-methylpyrrolidone solvent, for the prevention of cyclized byproduct. hPGs with three different molecular weights were synthesized through tailoring the molar ratio of initiator to monomer. Various techniques including1 H-NMR, inverse gated(IG) NMR spectroscopy, gel permeation chromatography(GPC) and Fourier transform infrared spectroscopy(FT-IR), were employed to characterize the chemical structure, degree of branching(DB), molecular weight and polydispersity of the synthesized hPG. Differential scanning calorimetry(DSC), thermogravimetric(TG), analyzer particle size and Zeta analyzer were used to analyze their glass transition temperature(Tg), thermal stability and solution properties,respectively. Results demonstrate that three hPGs were synthesized with targeted molecular mass(1.5×10~3, 4.6×10~3,11.2×10~3) and polydispersities in the range of 1.82 —2.05. Importantly, the solvent N-methylpyrrolidone could rapidly increase the molecular weight of hPG during the reaction and improve its mono-dispersity compared to the non-solvent system. Moreover, the glass transition temperature(T_g) and thermal degradation temperature(T_d) of hPG were increased slightly with the increasing molecular weight from 1.5×10~3 to 11.2×10~3.
Hyperbranched polyglycerol(hPG) with controlled molecular weight and narrow polydispersity has been synthesized by one-step anionic ring-opening polymerization(ROP) reaction, in which monomer glycidol(2,3-epoxy-1-propanol) was added dropwise to the mixture solution of timethylolpropane(TMP) initiator, potassium tert-butoxide(K-tOBu) base, and anhydrous N-methylpyrrolidone solvent, for the prevention of cyclized byproduct. hPGs with three different molecular weights were synthesized through tailoring the molar ratio of initiator to monomer. Various techniques including1 H-NMR, inverse gated(IG) NMR spectroscopy, gel permeation chromatography(GPC) and Fourier transform infrared spectroscopy(FT-IR), were employed to characterize the chemical structure, degree of branching(DB), molecular weight and polydispersity of the synthesized hPG. Differential scanning calorimetry(DSC), thermogravimetric(TG), analyzer particle size and Zeta analyzer were used to analyze their glass transition temperature(Tg), thermal stability and solution properties,respectively. Results demonstrate that three hPGs were synthesized with targeted molecular mass(1.5×10~3, 4.6×10~3,11.2×10~3) and polydispersities in the range of 1.82 —2.05. Importantly, the solvent N-methylpyrrolidone could rapidly increase the molecular weight of hPG during the reaction and improve its mono-dispersity compared to the non-solvent system. Moreover, the glass transition temperature(T_g) and thermal degradation temperature(T_d) of hPG were increased slightly with the increasing molecular weight from 1.5×10~3 to 11.2×10~3.
引文
[1]ZHENG Y,LI S,WENG Z,et al.Advances from synthesis to applications[J].Chemical Society Reviews,2015,44(12):4091-4130.
[2]刘兴亮,罗静,李小杰,等.新型双功能性超支化聚合物的制备及表征[J].功能高分子学报,2018,31(2):147-152.
[3]HUANG H,LIU M,JIANG R,et al.Fabrication and characterization of hyperbranched polyglycerol modified carbon nanotubes through the host-guest interactions[J].Materials for Biological Applications,2018,91:458-465.
[4]WEI Q,BECHERER T,NOESKE P L M,et al.A universal approach to cross linked hierarchical polymer multi layers as stable and highly effective antifouling coatings[J].Advanced Materials,2014,26(17):2688-2693.
[5]SONG Y,DUAN Y,ZHOU L.Multi-carboxylic magnetic gel from hyperbranched polyglycerol for efficient and selective adsorption of methylene blue and methyl violet dyes[J].Journal of Colloid and Interface Science,2018,529:139-149.
[6]SMITH C E,LEE J,SEO Y,et al.Worm-like superparamagnetic nanoparticle clusters for enhanced adhesion and magnetic resonance relaxivity[J].Acs Applied Materials and Interfaces,2017,9(2):1219-1225.
[7]LIU Z,AN X,DONG C,et al.Modification of thin film composite polyamide membranes with 3D hyperbranched polyglycerol for simultaneous improvement in their antifouling properties[J].Journal of Materials Chemistry A,2017,5(44):23190-23197.
[8]UTRATA WESOLEK A,WALACH W,BOCHENEK M,et al.Branched polyglycidol and its derivatives grafted-from poly(ethylene terephthalate)and silica as surfaces that reduce protein fouling[J].European Polymer Journal,2018,105:313-322.
[9]MOHAMMADIFAR E,BODAGHI A,DADKHAHTEHRANI A,et al.Green synthesis of hyperbranched polyglycerol at room temperature[J].Acs Macro Letters,2017,6(1):35-40.
[10]ROSSOW T,HEYMAN J A,EHRLICHER A J,et al.Controlled synthesis of cell-laden microgels by radical-free gelation in droplet microfluidics[J].Journal of the American Chemical Society,2012,134(10):4983-4989.
[11]葛娟,卢丹,周权,宋宁,等.乙炔基封端氢化超支化聚碳硅烷的合成、表征及性能[J].功能高分子学报,2018,31(4):374-380.
[12]WILMS D,WURM F,NIEBERLE J,et al.Hyperbranched polyglycerols with elevated molecular weights[J].Macromolecules,2009,42(9):3230-3236.
[13]YAN D,GAO C,FREY H.Promising Dendritic Materials:An Introduction to Hyperbranched Polymers[M].Inc:John Wiley&Sons,2011,8:847-861.
[14]朱贤平,林珩,郑柏存.EAA-g-MPEG的合成及其对HDPE的亲水改性[J].功能高分子学报,2016,29(3):352-358.
[2]刘兴亮,罗静,李小杰,等.新型双功能性超支化聚合物的制备及表征[J].功能高分子学报,2018,31(2):147-152.
[3]HUANG H,LIU M,JIANG R,et al.Fabrication and characterization of hyperbranched polyglycerol modified carbon nanotubes through the host-guest interactions[J].Materials for Biological Applications,2018,91:458-465.
[4]WEI Q,BECHERER T,NOESKE P L M,et al.A universal approach to cross linked hierarchical polymer multi layers as stable and highly effective antifouling coatings[J].Advanced Materials,2014,26(17):2688-2693.
[5]SONG Y,DUAN Y,ZHOU L.Multi-carboxylic magnetic gel from hyperbranched polyglycerol for efficient and selective adsorption of methylene blue and methyl violet dyes[J].Journal of Colloid and Interface Science,2018,529:139-149.
[6]SMITH C E,LEE J,SEO Y,et al.Worm-like superparamagnetic nanoparticle clusters for enhanced adhesion and magnetic resonance relaxivity[J].Acs Applied Materials and Interfaces,2017,9(2):1219-1225.
[7]LIU Z,AN X,DONG C,et al.Modification of thin film composite polyamide membranes with 3D hyperbranched polyglycerol for simultaneous improvement in their antifouling properties[J].Journal of Materials Chemistry A,2017,5(44):23190-23197.
[8]UTRATA WESOLEK A,WALACH W,BOCHENEK M,et al.Branched polyglycidol and its derivatives grafted-from poly(ethylene terephthalate)and silica as surfaces that reduce protein fouling[J].European Polymer Journal,2018,105:313-322.
[9]MOHAMMADIFAR E,BODAGHI A,DADKHAHTEHRANI A,et al.Green synthesis of hyperbranched polyglycerol at room temperature[J].Acs Macro Letters,2017,6(1):35-40.
[10]ROSSOW T,HEYMAN J A,EHRLICHER A J,et al.Controlled synthesis of cell-laden microgels by radical-free gelation in droplet microfluidics[J].Journal of the American Chemical Society,2012,134(10):4983-4989.
[11]葛娟,卢丹,周权,宋宁,等.乙炔基封端氢化超支化聚碳硅烷的合成、表征及性能[J].功能高分子学报,2018,31(4):374-380.
[12]WILMS D,WURM F,NIEBERLE J,et al.Hyperbranched polyglycerols with elevated molecular weights[J].Macromolecules,2009,42(9):3230-3236.
[13]YAN D,GAO C,FREY H.Promising Dendritic Materials:An Introduction to Hyperbranched Polymers[M].Inc:John Wiley&Sons,2011,8:847-861.
[14]朱贤平,林珩,郑柏存.EAA-g-MPEG的合成及其对HDPE的亲水改性[J].功能高分子学报,2016,29(3):352-358.