About the phase transitions in aqueous solutions of thermoresponsive copolymers and hydrogels based on 2-(2-methoxyethoxy)ethyl methacrylate and oligo(ethylene glycol) methacrylate

About the phase transitions in aqueous solutions of thermoresponsive copolymers and hydrogels based on 2-(2-methoxyethoxy)ethyl methacrylate and oligo(ethylene glycol) methacrylate
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DOI:
10.1021/ma062925q
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发表时间:
2007-04-03
期刊:
影响因子:
5.5
通讯作者:
Hoth, Ann
Hoth, Ann
中科院分区:
化学1区
文献类型:
--
作者:
Lutz, Jean-Francois;Weichenhan, Katja;Hoth, Ann

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用1H NMR、动态光散射和比浊法研究了甲基丙烯酸2-(2-甲氧基乙氧基)乙酯(MEO(2)MA)和低聚乙二醇甲基丙烯酸酯(OEGMA,Mn = 475 gmol(-1))共聚物在水中的相变。这些共聚物是通过原子转移自由基聚合(ATRP)合成的,以获得具有均匀的链-链共聚单体组成的大分子,因此具有窄的相变。如前所述,每个链含有10摩尔%OEGMA的共聚物(M-n = 20 × 100 g mol(-1 ;)M-w/M-n = 1.35)在40 ℃左右的水中表现出急剧的LCST,而每条链具有20 mol %OEGMA的共聚物在40 ℃左右的水中表现出急剧的LCST,(M-n = 19 500 g mol(-1); M-w/M-n = 1.32)在略高于50 ℃时沉淀。DLS表明,这些相变很可能是由于可逆的线圈到球的转变。此外,在交联剂二甲基丙烯酸乙二醇酯的存在下,通过ATRP合成了MEO(2)MA和OEGMA的共价交联网络。这些水凝胶是温敏性的,并表现出与其单链类似物(例如,在网络内含有20摩尔%OEGMA的水凝胶在约51-53 ℃下经历相变)。
The phase transitions in water of well-defined copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO(2)MA) and oligo(ethylene glycol) methacrylate (OEGMA, M-n = 475 g mol(-1)) were studied by means of H-1 NMR, dynamic light scattering (DLS) and turbidimetry. These copolymers were synthesized by atom transfer radical polymerization (ATRP) in order to obtain macromolecules with a homogeneous chain-to-chain comonomer composition and therefore with a narrow phase transition. As previously reported, copolymers containing 10 mol % of OEGMA per chain (M-n = 20 100 g mol(-1 ;) M-w/M-n = 1.35) exhibited a sharp LCST in water around 40 degrees C, whereas copolymers having 20 mol % of OEGMA per chain (M-n = 19 500 g mol(-1); M-w/M-n = 1.32) precipitated slightly above 50 degrees C. DLS indicated that these phase transitions are most likely due to a reversible coil-to-globule transition. Moreover covalently cross-linked networks of MEO(2)MA and OEGMA were synthesized by ATRP in the presence of the cross-linker ethylene glycol dimethacrylate. These hydrogels were thermoresponsive and exhibited LCST values comparable to those measured for their single-chains analogues (e.g., hydrogels containing 20 mol % of OEGMA within the network underwent phase transitions at approximately 51-53 degrees C).