基于原子转移自由基聚合技术的偶氮苯星形液晶聚合物的合成与表征

利用原子转移自由基聚合(ATRP)技术合成了含不同端基取代基的偶氮苯三臂星形侧链液晶聚合物. 均苯三酚与2-溴异丁酰溴通过酯化反应制备三官能团引发剂, 引发偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)或6-[4-(4-乙氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(EMAzo)的ATRP反应. 利用核磁共振氢谱(¹H NMR)、凝胶色谱(GPC)、差示扫描量热法(DSC)和偏光显微镜(POM)等手段对星形聚合物进行表征. 星形聚合物的液晶性与相应均聚物相似, 但偶氮苯端基取代基的不同导致星形聚合物的液晶性差别显著. 在紫外/可见光照射下星形聚合物呈现明显的异构化转变.     

苯乙烯的单电子转移活性自由基聚合

以2,2-二溴甲基-1,3-二溴丙烷（PEBr4）为引发剂,Cu0粉/三（2-二甲氨基乙基）胺（Me6-TREN）为催化体系,在二甲亚砜（DMSO）和H2O的混合溶剂中实现了苯乙烯（St）的单电子转移活性自由基聚合（SET-LRP）。 通过1H NMR和GPC分析表明,所得聚合物为星形结构并具有较窄的分子量分布Mw/Mn=1.20（MGPCn=25.3×103,转化率为42.6%）,且聚合物的链端保留了-Br端基。 考察了溶剂、反应温度及相转移催化剂对聚合的影响,结果表明,混合溶剂中H2O的体积分数由10%增加至20%导致了聚合速率的降低,表观聚合速率常数（kappp）由0.026 4 h-1减小至0.019 7 h-1;升高反应温度、增加催化剂用量以及相转移催化剂的加入分别导致聚合体系的kappp增加,同时,催化剂用量的增加和相转移催化剂的加入使聚合物的分子量分布系数降低。     

Application of Linear and Branched Poly(Ethylene Glycol)‐Poly(Lactide) Block Copolymers for the Preparation of Films and Solution Electrospun Meshes

Poly(ethylene glycol)‐poly(lactide) (PEG‐PLA) block copolymers are processed to solvent cast films and solution electrospun meshes. The effect of polymer composition, architecture, and number of anchoring points for the plasticizer on swelling, degradation, and mechanical properties of these films and meshes is investigated as potential barrier device for the prevention of peritoneal adhesions. As a result, adequate properties are achieved for the massive films with a longer retention of the plasticizer PEG for star‐shaped block copolymers than for the linear triblock copolymers and consequently more endurable mechanical properties during degradation. For electrospun meshes fabricated using the same polymers, similar trends are observed, but with an earlier start of fragmentation and lower tensile strengths. To overcome the poor mechanical strengths and an occurring shrinkage during incubation, which may impair the coverage of the wound, further adaptions of the meshes and the fabrication process are necessary.

     

阵列波导光栅梳状带通滤波器的传输效率

在光波导模场分布高斯近似条件下,根据星形光波导耦合器的耦合特性,推导出了基于累加运算和卷积运算近似表达的阵列波导光栅梳状带通滤波器光谱响应效率的函数表达式。给出了阵列波导光栅梳状带通滤波器光谱响应效率曲线的半最大值全宽度和阵列波导光栅梳状带通滤波器的通道中心波长的光谱响应度与器件参数的关系。在输入信号光谱分布高斯近似条件下,给出了阵列波导光栅梳状带通滤波器信号通道传输效率的计算表达式和输入信号光谱宽度对阵列波导光栅梳状带通滤波器信号通道输出特性的影响。给出了物理意义明确的函数表达式,它们可为快速分析阵列波导光栅梳状带通滤波器的特性提供理论基础。     

Molecular dynamics simulation of brushes formed by star polyelectrolytes under theta solvent conditions

Using molecular dynamics simulations, we have studied polyelectrolyte brushes formed by partially or fully charged star polymers tethered on a planar surface under theta solvent conditions. The diagram of states for salt‐free solutions differs in the location of osmotic regime (OB) compared with the respective diagram reported by Borisov and Zhulina. In contrast, simulation results dictate that the OB regime appears for values of the ratio F /α ^?1/2 l_B ^?1 much larger than unity, which is the threshold of counterion localization, with F denoting the branch functionality, α the charged units fraction and l_B the Bjerrum length. The simulation results support that the brush height scaling laws H ～ α ² l_B F ^1.049S ³s ^?1 and H ～ α^0.302 F ^0.23S for the charged Pincus Brush (PB) and osmotic (OB) regimes, respectively, where S is the spacer length and s is the grafted area per star chain. The respective theoretical scaling laws are H ～ α ² l_B F ^1.88S ³s ^?1 and H ～ α ^1/2 F ^0.44S . © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1110–1117     

Impact of chain architecture (branching) on the thermal and mechanical behavior of polystyrene thin films

The modulus and glass transition temperature (T_g) of ultrathin films of polystyrene (PS) with different branching architectures are examined via surface wrinkling and the discontinuity in the thermal expansion as determined from spectroscopic ellipsometry, respectively. Branching of the PS is systematically varied using multifunctional monomers to create comb, centipede, and star architectures with similar molecular masses. The bulk‐like (thick film) T_g for these polymers is 103 ± 2 °C and independent of branching and all films thinner than 40 nm exhibit reductions in T_g. There are subtle differences between the architectures with reductions in T_g for linear (25 °C), centipede (40 °C), comb (9 °C), and 4 armed star (9 °C) PS for ≈ 5 nm films. Interestingly, the room temperature modulus of the thick films is dependent upon the chain architecture with the star and comb polymers being the most compliant (≈2 GPa) whereas the centipede PS is most rigid (≈4 GPa). The comb PS exhibits no thickness dependence in moduli, whereas all other PS architectures examined show a decrease in modulus as the film thickness is decreased below ～40 nm. We hypothesize that the chain conformation leads to the apparent susceptibility of the polymer to reductions in moduli in thin films. These results provide insight into potential origins for thickness dependent properties of polymer thin films. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of mikto‐topology star polymer containing one cyclic arm

Well‐defined mikto‐topology star polystyrene composed of one cyclic arm and four linear arms was synthesized by a combination of atom transfer radical polymerization (ATRP) and Cu‐catalyzed azide‐alkyne cycloaddition (CuAAC) click reaction. First, the bromine‐alkyne α,ω‐linear polystyrenes containing four hydroxyl groups protected with acetone‐based ketal groups were synthesized by ATRP of styrene using a designed initiator. Then, the bromine end‐group was converted to the azide and the linear polystyrene was cyclized intra‐molecularly by the CuAAC reaction. The four hydroxyl groups were released by deprotection and then esterified with 2‐bromoisobutyryl bromide to produce a cyclic polymer bearing four ATRP initiating units. By subsequent ATRP of styrene to grow linear polymers with the cyclic polystyrene as a macroinitiator, the mikto‐topology star polymers were prepared. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Fluorinated star‐shaped block copolymers: Synthesis and optical properties

Tetrakis(4‐(1‐bromoethyl)phenyl)silane is synthesized and utilized to initiate the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to generate bromo‐terminated four‐armed PMMA macroinitiators, which further initiate the ATRP of methylacryloyloxyl‐2‐hydroxypropyl perfluorooctanoate (FGOA) to create fluorinated star‐shaped block copolymers PMMA‐b‐poly(FGOA)s with fluorine content ranging from 0 to 31.7 wt %. The polymerizations are well controlled with the polydispersity indices <1.30. The polymers readily dissolve in common organic solvents and show good film‐formation. Compared with the nonfluorinated sample, the fluorinated films exhibit significantly increased water contact angles owing to the enrichment of fluorine on the surface. The enhanced hydrophobicity is advantageous for the optical stability when the devices work under a moist environment. Moreover, the films possess high thermo‐optic coefficients, tunable refractive indices, and extremely low birefringence coefficients because of the presence of bulky and rigid tetraphenylsilane core and star‐shaped topological structure, showing potential application in optical waveguide devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1969–1977     

Synthesis of 4μ‐PS2PEO2, 4μ‐PS2PCL2, 4μ‐PI2PEO2, and 4μ‐PI2PCL2 star‐shaped copolymers by the combination of glaser coupling with living anionic polymerization and ring‐opening polymerization

4μ‐A₂B₂ star‐shaped copolymers contained polystyrene (PS), poly(isoprene) (PI), poly(ethylene oxide) (PEO) or poly(ε‐caprolactone) (PCL) arms were synthesized by a combination of Glaser coupling with living anionic polymerization (LAP) and ring‐opening polymerization (ROP). Firstly, the functionalized PS or PI with an alkyne group and a protected hydroxyl group at the same end were synthesized by LAP and then modified by propargyl bromide. Subsequently, the macro‐initiator PS or PI with two active hydroxyl groups at the junction point were synthesized by Glaser coupling in the presence of pyridine/CuBr/N,N,N ′,N ″,N ″‐penta‐methyl diethylenetri‐amine (PMDETA) system and followed by hydrolysis of protected hydroxyl groups. Finally, the ROP of EO and ε‐CL monomers was carried out using diphenylmethyl potassium (DPMK) and tin(II)‐bis(2‐ethylhexanoate) (Sn(Oct)₂) as catalyst for target star‐shaped copolymers, respectively. These copolymers and their intermediates were well characterized by SEC, ¹H NMR, MALDI‐TOF mass spectra and FT‐IR in details. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Hyperbolicity of C~1 -star invariant sets for C~1 -class dynamical systems

In this paper, we simply prove, in the framework of Liao, the hyperbolicity of C 1 -star invariant sets of C 1 -class differential systems on a closed manifold of dimension≤ 4, without using the C 1 -connecting lemma and even the ergodic closing lemma.