ABC型pH响应含氟三亲性嵌段共聚物的合成与自组装
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摘要
以甲基丙烯酸叔丁酯(tBMA)、甲基丙烯酸异辛酯(EHMA)及丙烯酸全氟辛基乙基酯(FA)作为单体,采用可逆加成-断裂链转移聚合法(RAFT)及一步酸性水解反应,得到ABC型pH响应含氟三亲性嵌段共聚物PMAA_(30)-b-PEHMA_(51)-b-PFA_6。通过核磁共振氢谱(~1H-NMR)、红外光谱(IR)、凝胶渗透色谱(GPC)及氟元素分析法(F-EA)表征了其分子结构,并利用透射电镜(TEM)及动态激光光散射法(DLS)研究了共聚物在二甲基甲酰胺(DMF)/H_2O溶液中的自组装行为。结果表明,随着溶液中水含量的增加,胶束形貌会由棒状变为尺寸较大的树枝状结构;在溶液中加入酸(HCl)或碱(NaOH)后,胶束形貌会由棒状结构转变为具有多隔室核结构或核-壳-冠结构的球形聚集体,胶束尺寸也产生相应的变化。
A novel ABC-type pH-responsive fluorinated triphilic block copolymer PMAA_(30)-b-PEHMA_(51)-b-PFA_6 was synthesized by three-step successive reversible addition fragmentation chain transfer(RAFT) polymerization and one-step acidolysis reaction, incorporating with methylmethacrylate(MAA), 2-ethylhexyl methacrylate(EHMA), and 1 H,1 H,2 H,2 H-perfluorodecyl acrylate(FA) as hydrophilic, lipophilic, and fluorophilic units, respectively. The internal structure of the as-prepared triphilic block copolymer was characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR), infrared spectrum(IR), gel permeation chromatography(GPC) and fluoroelement analysis(F-EA). Otherwise, the self-assembly behaviors of the copolymer PMAA_(30)-b-PEHMA_(51)-b-PFA_6 in dimethylformamide/water(DMF/H_2O) solution were investigated by the turbidity measurement(OD), transmission electron microscope(TEM) and dynamic light scattering(DLS). The results indicated that the triphilic block copolymer exhibited an interesting morphology evolution from rod-like structure to the larger size tree-branch structure, along with water volume fraction increasing from 20% to 60%. The morphology formation mechanism was explained according to the comprehensive effect of multiple forces including that the crystallization of the side chains of the fluorinated blocks, the strong incompatibility between the lipophilic and fluorophilic blocks, the balance between the core-chain stretching and the shell-chain tension. Furthermore, the morphology transitions from rod-like micelles to multi-compartment spherical structures or to core-shell-corona spheres, as well as the corresponding changes of the diameters of the micelles, were obtained by adding acid(HCl) or alkali(NaOH) into the system. The micellar structure transformation was derived from the effect of protonation or deprotonation effect of the carboxyl, which was based on the ionization equilibrium of weak-acid PMAA polyelectrolyte in aqueous solution. This study amplified the self-assemble behavior of linear triphilic block copolymers, and contributed to the design of functional fluoropolymer.
A novel ABC-type pH-responsive fluorinated triphilic block copolymer PMAA_(30)-b-PEHMA_(51)-b-PFA_6 was synthesized by three-step successive reversible addition fragmentation chain transfer(RAFT) polymerization and one-step acidolysis reaction, incorporating with methylmethacrylate(MAA), 2-ethylhexyl methacrylate(EHMA), and 1 H,1 H,2 H,2 H-perfluorodecyl acrylate(FA) as hydrophilic, lipophilic, and fluorophilic units, respectively. The internal structure of the as-prepared triphilic block copolymer was characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR), infrared spectrum(IR), gel permeation chromatography(GPC) and fluoroelement analysis(F-EA). Otherwise, the self-assembly behaviors of the copolymer PMAA_(30)-b-PEHMA_(51)-b-PFA_6 in dimethylformamide/water(DMF/H_2O) solution were investigated by the turbidity measurement(OD), transmission electron microscope(TEM) and dynamic light scattering(DLS). The results indicated that the triphilic block copolymer exhibited an interesting morphology evolution from rod-like structure to the larger size tree-branch structure, along with water volume fraction increasing from 20% to 60%. The morphology formation mechanism was explained according to the comprehensive effect of multiple forces including that the crystallization of the side chains of the fluorinated blocks, the strong incompatibility between the lipophilic and fluorophilic blocks, the balance between the core-chain stretching and the shell-chain tension. Furthermore, the morphology transitions from rod-like micelles to multi-compartment spherical structures or to core-shell-corona spheres, as well as the corresponding changes of the diameters of the micelles, were obtained by adding acid(HCl) or alkali(NaOH) into the system. The micellar structure transformation was derived from the effect of protonation or deprotonation effect of the carboxyl, which was based on the ionization equilibrium of weak-acid PMAA polyelectrolyte in aqueous solution. This study amplified the self-assemble behavior of linear triphilic block copolymers, and contributed to the design of functional fluoropolymer.
引文
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[13] TAN J Q, LIU W Q, Wang Z F. Preparation and self-assembly of pH-sensitive amphiphilic comb-shaped copolymer containing long fluorinated side chains [J]. Journal of Macromolecular Science: Part A. Chemistry, 2016, 53(11): 716-724.
[14] LI X X, HUO, X, HAN H J, et al. Synthesis, self-assembly and pH sensitivity of a novel fluorinated triphilic block copolymer [J]. Chinese Journal of Polymer Science, 2017, 33(11): 1363-1372.
[15] 刘雅琨, 李欣欣, 霍晓, 等. pH敏感含氟三亲性嵌段共聚物的合成及自组装 [J]. 上海理工大学学报(自然科学版), 2016, 37(5): 504-510.
[16] LI S, He J L, Zhang, M Z, et al. Multicompartment morphologies self-assembled from fluorinated ABC triblock terpolymers: The effects of flexible and rigid hydrophobic moieties [J]. Polymer Chemistry, 2016, 7(9): 1773-1781.
[17] SKRABANIA K, VON BERLEPSCH H, BOTTCHER C, et al. Synthesis of ternary, hydrophilic-lipophilic-fluorophilic block copolymers by consecutive RAFT polymerizations and their self-assembly into multicompartment micelles [J]. Macromolecules, 2010, 43(1): 271-281.
[18] LI X X, YANG Y H, LI G J, et al. Synthesis and self-assembly of a novel fluorinated triphilic block copolymer [J]. Polymer Chemistry, 2014, 5(15): 4553-4560.
[19] LAI J T, FILLA D, SHEA R. Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents [J]. Macromolecules, 2002, 35(18): 6754-6756.
[20] 李欣欣, 房冰, 林珊, 等. 丙烯酸全氟烷基乙基酯嵌段共聚物的组成结构表征 [J]. 高分子学报, 2003(6): 910-913.
[21] SHEN H W, EISENBERG A. Morphological phase diagram for a ternary system of block copolymer PS310-b-PAA52/dioxane/H2O [J]. Journal of Physical Chemistry B, 1999, 103(44): 9473-9487.
[2] 韩克, 张国颖. 双重响应两亲性聚前药的合成及其在药物控释方面的应用[J]. 功能高分子学报, 2018, 31(2): 98-107.
[3] 张震, 谭连江, 龚兵, 等. 基于“分子胶”的新型两亲性嵌段共聚物β-CD-PLA的合成及其胶束化[J]. 功能高分子学报, 2017, 30(3): 321-326.
[4] 谢亚珍, 刘敬成, 胡琼, 等. 双亲性共聚物P(St/VBT-co-MA)自组装胶束的制备及其乳化性能[J]. 功能高分子学报, 2016, 29(2): 200-206.
[5] FAN X H, ZHAO, Y L, XU W, et al. Linear-dendritic block copolymer for drug and gene delivery [J]. Materials Science & Engineering C, 2016, 62: 943-959.
[6] MAI Y Y, EISENBERG A. Self-assembly of block copolymers [J]. Chemical Society Reviews, 2012, 41(18): 5969-5985.
[7] ULRICH K, GALVOSAS P, KARGER J, et al. Self-assembly and diffusion of block copolymer templates in SBA-15 nanochannels [J]. Journal of Physical Chemistry B, 2010, 114(12): 4223-4229.
[8] KRAFFT M P, RIESS J G. Highly fluorinated amphiphiles and colloidal systems, and their applications in the biomedical field. A contribution [J]. Biochimie, 1998, 80(5/6): 489-514.
[9] JENA S S, ROY S G, AZMEERA V, et al. Solvent-dependent self-assembly behaviour of block copolymers having side-chain amino acid and fatty acid block segments [J]. Reactive & Functional Polymers, 2016, 99: 26-34.
[10] ANDREEA S V, KEVIN M, NISA V S, et al. Synthesis and self-assembly behaviour of poly(Nα-Boc-L-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-L-tryptophan)[J].RSC Advances, 2016, 6(29): 24142-24153.
[11] URADE V N, BOLLMANN L, KOWALSKI J D, et al. Controlling interfacial curvature in nanoporous silica films formed by evaporation-induced self-assembly from nonionic surfactants: Ⅱ. Effect of processing parameters on film structure [J]. Langmuir the ACS Journal of Surfaces & Colloids, 23(8): 4268-4278.
[12] PEDRONI V I, SCHULZ P C, GSCHAIDER M E, et al. Chitosan structure in aqueous solution [J]. Colloid & Polymer Science, 2003, 288(1): 100-102.
[13] TAN J Q, LIU W Q, Wang Z F. Preparation and self-assembly of pH-sensitive amphiphilic comb-shaped copolymer containing long fluorinated side chains [J]. Journal of Macromolecular Science: Part A. Chemistry, 2016, 53(11): 716-724.
[14] LI X X, HUO, X, HAN H J, et al. Synthesis, self-assembly and pH sensitivity of a novel fluorinated triphilic block copolymer [J]. Chinese Journal of Polymer Science, 2017, 33(11): 1363-1372.
[15] 刘雅琨, 李欣欣, 霍晓, 等. pH敏感含氟三亲性嵌段共聚物的合成及自组装 [J]. 上海理工大学学报(自然科学版), 2016, 37(5): 504-510.
[16] LI S, He J L, Zhang, M Z, et al. Multicompartment morphologies self-assembled from fluorinated ABC triblock terpolymers: The effects of flexible and rigid hydrophobic moieties [J]. Polymer Chemistry, 2016, 7(9): 1773-1781.
[17] SKRABANIA K, VON BERLEPSCH H, BOTTCHER C, et al. Synthesis of ternary, hydrophilic-lipophilic-fluorophilic block copolymers by consecutive RAFT polymerizations and their self-assembly into multicompartment micelles [J]. Macromolecules, 2010, 43(1): 271-281.
[18] LI X X, YANG Y H, LI G J, et al. Synthesis and self-assembly of a novel fluorinated triphilic block copolymer [J]. Polymer Chemistry, 2014, 5(15): 4553-4560.
[19] LAI J T, FILLA D, SHEA R. Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents [J]. Macromolecules, 2002, 35(18): 6754-6756.
[20] 李欣欣, 房冰, 林珊, 等. 丙烯酸全氟烷基乙基酯嵌段共聚物的组成结构表征 [J]. 高分子学报, 2003(6): 910-913.
[21] SHEN H W, EISENBERG A. Morphological phase diagram for a ternary system of block copolymer PS310-b-PAA52/dioxane/H2O [J]. Journal of Physical Chemistry B, 1999, 103(44): 9473-9487.
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