超分子构筑调控合成结构规整的梯形聚合物及其应用研究

综述了"超分子构筑调控的逐步偶联/聚合法",该方法将高分子化学与超分子化学相结合,利用多种类型的超分子弱键协同作用首先构筑预期的梯形超分子结构,再经聚合得到共价键梯形高分子.利用该方法合成了一系列结构规整的氧桥基和有机桥基梯形聚硅氧烷以及碳基梯形聚酯,并利用侧基间π-π叠加作用实现了对聚合物立体构型控制.扼要介绍了梯形聚合物在先进材料方面的应用,例如梯形聚硅氧烷液晶光致取向膜;由梯形聚硅氧烷合成的管状聚硅氧烷在高室温储存期微电子环氧塑封料方面的应用;以及基于梯形聚硅氧烷的拟筛板聚合物在二阶非线性光学材料方面的应用等.     

紫外光固化阳离子复合胶粘剂的制备与表征

以三芳基六氟磷酸硫鎓盐为引发剂,钛酸四异丙酯(TIP)为无机前驱体,3,4-环氧环己基甲基3,4-环氧环己基甲酸酯为单体,制备了含TiO2纳米结构的紫外光固化阳离子复合胶粘剂。通过原子力显微镜对复合胶粘剂形貌进行表征,研究了TIP含量对胶粘剂折射率和光透过率的影响。结果表明：TiO2无机相均匀地分散在胶粘剂的聚合物基体中,平均粒径约为20 nm;随着体系中TIP质量分数的变化,复合胶粘剂折射率为1.510 3~1.540 9可调;胶粘剂的光透过率随TIP质量分数增加略有减低,但当TIP含量高达40%时,光透过率维持在90%左右。     

Non-linear scission/recombination kinetics of living polymerization

Living polymers are formed by reversible association of primary units (unimers). Generally the chain statistical weight involves a factor σ < 1 suppressing short chains in comparison with free unimers. Living polymerization is a sharp thermodynamic transition for σ ≪ 1 which is typically the case. We show that this sharpness has an important effect on the kinetics of living polymerization (one-dimensional association). The kinetic model involves i) the unimer activation step (a transition to an assembly-competent state); ii) the scission/recombination processes providing growth of polymer chains and relaxation of their length distribution. Analyzing the polymerization with no chains but unimers at t = 0 , with initial concentration of unimers M ≳ M ^* (M^* is the critical polymerization concentration), we determine the time evolution of the chain length distribution and find that: 1) for M ^* ≪ M ≪ M ^*/σ the kinetics is characterized by 5 distinct time stages demarcated by 4 characteristic times t₁, t₂, t₃ and t^*; 2) there are transient regimes (t ₁ ≲ t ≲ t ₃) when the molecular-weight distribution is strongly non-exponential; 3) the chain scissions are negligible at times shorter than t₂. The chain growth is auto-accelerated for t ₁ ≲ t ≲ t ₂ : the cut-off chain length (= polymerization degree 〈n〉_w N ₁ ∝ t ² in this regime. 4) For t ₂ < t < t ₃ the length distribution is characterized by essentially 2 non-linear modes; the shorter cut-off length N₁ is decreasing with time in this regime, while the length scale N₂ of the second mode is increasing. (5) The terminal relaxation time of the polymer length distribution, t^*, shows a sharp maximum in the vicinity of M^*; the effective exponent is as high as ∼ σ^-1/3 just above M^*.     

稀土配合物-PAA-g-PE膜的荧光光谱

通过紫外光接枝聚合反应 ,将丙烯酸 (AA)接枝于PE膜表面 ,在一定 pH值条件下 ,使接枝膜与Eu3+、α 噻吩甲酰三氟丙酮 (TTA)的乙醇 水溶液或Tb3+、乙酰丙酮 (AcAc)的氯仿 水溶液作用 ,制得红色或绿色荧光膜。与相应的Eu(TTA) 3·(H2 O) 2 或Tb(AcAc) 3·(H2 O) 2 固态配合物相比 ,荧光膜的激发和发射光谱都发生了明显的变化 ,可以推测 ,稀土配合物与高分子材料之间发生了化学键结合。此外 ,还对荧光膜的红外光谱进行了观察。     

Ultrasound and Sonochemistry for Radical Polymerization: Sound Synthesis

The use of ultrasound as an external stimulus for promoting polymerization reactions has received increasing attention in recent years. In this Review article, the fundamental processes that can lead to either the homolytic cleavage of polymer chains, or the sonolysis of solvent (or other) small molecules, under the application of ultrasound are described. These reactions promote the production of reactive radicals, which can be utilized in chain-growth radical polymerizations under the right conditions. A full historical overview of the development of ultrasound-assisted radical polymerization is provided, with special attention given to the recently described systems that are “controlled” by methods of reversible (radical) deactivation. Perspectives are shared on what challenges still remain in polymer sonochemistry, as well as new areas that are yet to be explored.     

Photopolymerization of enzymatically synthesized methacrylated poly(caprolactone) with poly(ethylene glycol) macromonomer

Polycaprolactone (PCL) based α,ω-methacrylated macromonomer (DMPCL) was synthesized via enzymatic ring-opening polymerization (eROP) by using Novozyme 435 as the enzyme immobilized catalyst. DMPCL was further photopolymerized with monofunctional poly(ethylene glycol) methyl ether methacrylate (PEGMA-950) macromonomer and trimethylolpropane triacrylate (TMPTA) as tri-functionalized crosslinking agent in glass vials when CHCl₃ was the solvent and Irgacure 819 was the photoinitiator. Ultraviolet (UV) Light Emitting Diode (LED) bulbs enabled photoinduced reactions at room temperature with low heat generation and high reaction efficiency. The obtained gels were characterized with Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC). DMPCL participated as an effective crosslinking agent in the photopolymerization of PEGMA-950. Combined usage of DMPCL and PEGMA-950 resulted in significantly more effective polymerization than the separate photopolymerizations of these macromonomers.     

Condensed Mode Cooling of Ethylene Polymerization in Fluidized Bed Reactors

This review gives an overview of the evolution of the technology of condensed mode cooling, primarily for the case of ethylene polymerization on supported catalysts in fluidized bed reactors. It is well known that this mode of heat removal is quite effective in allowing polyolefin manufacturers to increase significantly production rates. What is perhaps less well understood are all of the issues that, in addition to the effect of the latent heat of vaporization of injected liquid components, also have an impact on the rate of production and behavior of the reactor. However, the liquid components injected into the reactor can vaporize rapidly under full‐scale conditions, leaving behind several heavy components (with respect to ethylene) that have numerous effects on how the particles behave, on the reaction rate, and on fluidization, fouling, and other parameters related to reactor and process performance.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.     

Rare-earth metal derivatives supported by aminophenoxy ligand: Synthesis,characterization and catalytic performance in lactide polymerization

A library of rare-earth metal derivatives supported by an aminophenoxy ligand was prepared and their catalytic performance in lactide polymerization was investigated. It was found that the synthetic strategy had a profound effect on the formation of aminophenoxy rare-earth metal complexes. Amine elimination between Ln[N(SiMe₃)₂]₃(μ-Cl)Li(THF)₃ (Ln = Yb, Y) and 1 equiv. of the aminophenol [HONH] ([HONH] = ο-OCH₃-C₆H₄NHCH₂(3,5-^tBu₂-C₆H₂-2-OH)) in toluene gave the unexpected heterobimetallic bis(aminophenoxy) rare-earth metal complexes [ON]₂LnLi(THF)₂ (Ln = Yb ( 1 ), Y ( 2 )). When the reactions were carried out in THF and TMEDA, amine elimination produced the aminophenoxy rare-earth metal amide complexes {[ON]LnN(SiMe₃)₂}₂ (Ln = Yb ( 5 ), Y ( 6 )) in ca 85% isolated yields. Complexes 5 and 6 could also be obtained from salt metathesis reaction of {[ON]LnCl(THF)}₂ (Ln = Yb ( 3 ), Y ( 4 )) with NaN(SiMe₃)₂ in a 1:2 molar ratio. In addition, treatment of complexes 3 and 4 with NaOAr (Ar = &bond;C₆H₄-4-^tBu) and (SiMe₃)₂NC(NPrⁱ)₂Na in 1:4 and 1:2 molar ratios provided the corresponding aminophenoxy rare-earth metal derivatives {[ON](μ-OAr)Ln(μ-OAr)Na(THF)₂}₂ (Ln = Yb ( 7 ), Y ( 8 )) and {[ON]Ln[(ⁱPrN)₂CN(SiMe₃)₂]}₂ (Ln = Yb ( 9 ), Y ( 10 )), respectively. These complexes were fully characterized, and their molecular structures were determined using single-crystal X-ray diffraction. Polymerization experiments showed that complexes 1 , 2 , 5 , 6 , 9 and 10 were highly active for the ring-opening polymerization of l -lactide in toluene, and complex 1 promoted l -lactide polymerization in a controlled fashion. The polymerization of rac-lactide initiated by the neutral aminophenoxy rare-earth metal complexes 5 , 6 , 9 and 10 in THF afforded heterotactic polymers.     

Photoinitiated polymerization of methacrylates comprising phenyl moieties

Investigation of photopolymerization kinetics of 4-(4-methacryloyloxyphenyl)-butan-2-one (1) in comparison with 2-phenoxyethyl methacrylate (2) and phenyl methacrylate (3) using a UV-LED emitting at 395 nm shows significantly faster polymerization of 1 compared to both 2 and 3 at 40°C. Vitrification affects photopolymerization kinetics of all methacrylates under investigation. Interestingly, quantitative final conversion is observed during photoinitiated polymerization of 1 and 2 whereas 3 shows limited conversion at about 80%. Furthermore, higher degree of polymerization is obtained by photoinitiated polymerization of 1 compared to 2 and 3. This shows that the 3-oxobutyl substituent at the phenyl ring of 1 significantly affects both polymerization kinetics and final conversion of the photoinitiated polymerization. Moreover, an additional higher molecular weight fraction is observed in case of polymerization of 1 at 85°C that is above the glass transition temperature of the polymer formed during photoinitiated polymerization. As a thermal polymerization at 85°C in the absence of light results in a high molecular weight polymer as well, an additional thermal process may be discussed as reason for the higher molecular weight polymer fraction in case of the photopolymer made at 85°C.