含9-丁基咔唑基二炔/聚炔汞及二炔金配合物的合成与性质

合成了9-丁基咔唑基聚炔汞聚合物[—HgC≡CRC≡C—]n及其二聚体[MeHgC≡CRC≡CHgMe]和金的二聚体[(PPh3)AuC≡CRC≡CAu(PPh3)](R=9-丁基咔唑基). 用 1H NMR, 13C NMR, 31P NMR, FTIR, FAB-MS, UV-Vis, Fluorescence及Phosphorescence 光谱对其进行了表征. 结果表明, 体系中金和汞产生的重原子效应可以促进单线激发态S1与三线激发态T1的系间跃迁, 使标题化合物产生有机三线态发光.     

铜催化的多组分反应合成二芳基炔丙胺类衍生物

以醛、苯乙炔和二芳胺为原料, 三组分一锅法合成了一系列二芳基炔丙胺类化合物. 产物的结构通过1H NMR, 13C NMR和HRMS证实.     

改性甲基二苯乙炔基硅烷的固化及其复合材料

制备了双（N-间乙炔基苯基邻苯二甲酰亚胺）醚（BE）改性甲基二苯乙炔基硅烷（MDPES）（BE／MDPES）。研究表明,选择BE／MDPES的固化温度时,必须同时考虑网络的形成反应和BE中醚键的断裂反应。当最终固化温度控制在300℃时,mBE／mMDPES=4／5的玻璃纤维复合材料的弯曲强度高达275MPa,235℃时的高温弯曲强度为241MPa,保留率达88．5％,且优异的耐热性能与介电性能保持不变。     

含碳硼烷半夹心型钴硫16电子化合物与二炔烃的反应性研究

含双硫取代碳硼烷二齿配体的半夹心型钴16电子化合物CpCo[S2C2(B10H10)](Co16e)分别与1,4-二乙炔基苯(L1)、(S)-2,2′-二乙酰氧基-6,6′-二乙炔基-1,1′-联萘(L2)、2-溴-5-乙炔基噻吩(L3)和2,5-二乙炔基噻吩(L4)反应,分别得到18电子单核化合物CpCo(S2C2B10H9)(H2CCPhC≡CH)(1),CpCo(S2C2B10H9)[H2CC(C24H16O4)C≡CH](2),CpCo(S2C2B10H9)[H2CC(C4H2S)Br](3),和CpCo(S2C2B10H9)[H2CC(C4H2S)C≡CH](4)。化合物1～4的结构中都发生了金属诱导B-H键活化并生成了新的C-B键。在Co16e与L4的反应中,还得到了两分子炔烃以头对头二聚插入到金属中心的18电子化合物CpCo(S2C2B10H9)[HC≡C(C4H2S)C=CH-CH=C(C4H2S)C≡CH](5)。上述化合物通过NMR、IR、MS、元素分析等方法进行表征。     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

1,1,3,3-四甲基胍基衍生物的合成及其与二酸的分子识别性能研究

四甲基胍分别与间苯二甲酰氯和间苯二磺酰氯反应合成了间苯二甲酰四甲基胍和间苯二磺酰四甲基胍,其结构经元素分析,IR,1H NMR和EI-MS表征.核磁滴定研究表明,上述化合物可与二酸形成1 ∶1化学计量络合物,其络合常数在5.33×105～3.68×105.     

含咔唑和偶氮苯的乙炔衍生物的合成

采用Sonagashira偶联反应和N-烷基化反应合成了含有咔唑和偶氮苯的乙炔衍生物:3-乙炔基-9-(4-[4-(硝基)苯基偶氮苯]氧)亚丁基咔唑3.其结构通过IR,1H NMR,13C NMR,元素分析和X-射线单晶衍射法测定.标题化合物属单斜晶系,P21/c空间群;a=9.238(3),b=28.240(8),c...     

带有不同端炔保护基团的新型苯乙炔树枝状化合物的合成

以1,3,5-三溴苯为原料,通过Sonogashira反应,设计并合成了两种带有不同端炔保护基团的1,3,5-取代的苯乙炔树枝状化合物:1,3,5-三[3-(3-甲基-3-羟基-1-丁炔基)-5-(三异丙基硅乙炔基)苯基乙炔基]苯(B1)和1,3,5-三[3-(三甲基硅乙炔基)-5-(三异丙基硅乙炔基)苯基乙炔基]苯(B2),并对合成路线的选择进行了比较和讨论.用1H NMR,13C NMR,质谱,元素分析等表征手段确认了中间体及最终产物的结构.这两种苯乙炔树枝状化合物各自带有两类不同的周边端炔保护基团,可根据其脱保护条件的不同引入不同的周边功能基团.     

苯乙炔悬挂取代的热致交联型芴-三苯胺交替聚合物的合成与表征

通过Suzuki偶合反应合成出由苯乙炔悬挂取代的芴-三苯胺类交替共轭聚合物聚(9,9-二辛基-2,7-芴-共-N-4-苯乙炔-4,4'-三苯胺)(PFT-PE),并通过NMR和FT-IR对其化学结构进行了表征。结果表明:该聚合物易溶于常用的有机溶剂,可通过溶液旋涂的方式进行薄膜制备。由PFT-PE薄膜的吸收起始波长可知其光学带宽为2.82 eV。其薄膜较溶液态的荧光光谱发生了显著的红移并且变宽,说明在固态下聚合物分子链间发生了一定的堆积。由其电化学起始氧化电位可知PFT-PE的最高能量占有轨道能级(HOMO)为-5.39 eV,其氧化过程具有高度的可逆性,说明该聚合物具有良好的电化学稳定性。悬挂炔键功能团的存在使得该聚合物无需外加引发剂即可在一定温度下发生分子间的交联反应。     

1,7-二芳基-1,6-庚二炔化合物的合成

1,6-庚二炔是有机合成的重要中间体,我们以Pd Cl2/Cu I为催化剂,NEt3为碱,在四氢呋喃溶剂中实现了二炔与卤代芳烃Sonogashira偶联反应,合成了10个1,7-二芳基-1,6-庚二炔化合物,该方法也适用于二卤芳烃如1,8-二碘萘与末端炔偶联合成1,8-二苯乙炔基萘.所有合成的目标化合物结构经1H NMR,13C NMR,IR和MS表征.     

Characterisation and effect of polymer network deformation in reverse-mode polymer-stabilised cholesteric texture

In reverse-mode polymer-stabilised cholesteric texture (PSCT), the dynamic response is derived from local director reorientation governed by dielectric coupling effect/self-assembly and polymer network deformation. A double exponential rise/decay model is proposed to investigate the underlying physical mechanisms. Through simulation of the transient rise and decay processes, the polymer network deformation in PSCT can be quantitatively evaluated. Less deformation and faster restoration speed of the polymer network can suppress hysteresis. These results provide useful guidelines for future PSCT fabrication and performance optimisation.     

漆酚醛缩聚物/丙烯酸树脂IPN涂料的制备及性能

漆酚醛缩聚物/丙烯酸树脂IPN涂料的制备及性能;漆酚甲醛缩聚物;丙烯酸树脂;互穿聚合物网络;涂料     

Electrical response characterisation of poly(ethylene glycol) macromer (PEGM)/chitosan hydrogels in NaCl solution

Interpenetrating polymer network hydrogels composed of poly(ethylene glycol) macromer (PEGM) and chitosan were synthesised by UV irradiation of solutions in a mild aqueous media. The IPN hydrogels exhibited the equilibrium water content (EWC) in the range of 86-94%. The hydrogels were characterised using FT-IR, FT-Raman spectroscopy and differential scanning calorimetry (DSC). The results from DSC measurements indicate that the melting endotherms of PEGM, within the hydrogels, decreased in intensities and shifted to lower temperatures comparing with a linear PEGM. This was due to the decrease of the crystallinity in the IPN hydrogels with higher contents of PEGM. The electrical response of the IPN hydrogels was also investigated by applying electrical current to the hydrogels immersed in a NaCl solution. The extent of a bending degree of the IPN hydrogel depends on the IPN hydrogel composition and applied electric field strength.     

Influence of Material Properties on the Damage-Reporting and Self-Healing Performance of a Mechanically Active Dynamic Network Polymer in Coating Applications

We conducted a detailed investigation of the influence of the material properties of dynamic polymer network coatings on their self-healing and damage-reporting performance. A series of reversible polyacrylate urethane networks containing the damage-reporting diarylbibenzofuranone unit were synthesized, and their material properties (e.g., indentation modulus, hardness modulus, and glass-transition temperature) were measured conducting nanoindentation and differential scanning calorimetry experiments. The damage-reporting and self-healing performances of the dynamic polymer network coatings exhibited opposite tendencies with respect to the material properties of the polymer network coatings. Soft polymer network coatings with low glass-transition temperature (~10 °C) and indentation hardness (20 MPa) exhibited better self-healing performance (almost 100%) but two times worse damage-reporting properties than hard polymer network coatings with high glass-transition temperature (35~50 °C) and indentation hardness (150~200 MPa). These features of the dynamic polymer network coatings are unique; they are not observed in elastomers, films, and hydrogels, whereby the polymer networks are bound to the substrate surface. Evidence indicates that controlling the polymer’s physical properties is a key factor in designing high-performance self-healing and damage-reporting polymer coatings based on mechanophores.     

Perfectly‐alternating linear (AB)n multiblock copolymers: Effect of molecular design on morphology and properties

Perfectly‐alternating linear (AB)_n multiblock copolymers consist of n AB block pairs covalently linked in an alternating sequence. Although these copolymers can microphase‐order in the same fashion as their lower‐order (n = 1) diblock analogs, the 2(n ? 1) biconformational midblocks comprising each copolymer molecule have a considerable impact on microstructural characteristics and bulk properties. We have applied transmission electron microscopy, differential scanning calorimetry (DSC), and extensional rheometry to examine and compare the morphologies and properties of two series of compositionally symmetric (lamellar) poly(styrene‐b‐isoprene)_n (SI)_n (1 ≤ n ≤ 4) multiblock copolymers. In one series, chain length was held constant allowing block mass (M_b) to decrease with increasing n. In the second copolymer series, M_b remained relatively invariant. Increasing n in these two series generally promoted reductions in both the lamellar period and upper (styrenic) glass‐transition temperature, but noticeable increases in tensile modulus and yield strength. These observed trends are more pronounced in the copolymer series with constant chain length due to the coupled relationship between n and M_b. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 947–955, 2001     

Carbenoid polycondensation with telechelic polyethers having dichloroacetic acid ester groups

Poly(ethylene oxide) [poly(EO)], with number-average molecular weights (M_ns) of 1000 and 2000, and poly(tetrahydrofuran) [poly(THF)] with M_ns of 1000 and 2000, possessing dichloroacetic acid ester end groups ( 1 , and 2 , respectively) were prepared from precursor diols by esterification with dichloroacetyl chloride in the presence of pyridine. 1 and 2 were subjected to the reaction with copper metal in DMSO to produce the corresponding segmented polyethers containing fumarate/maleate groups within the main chain ( 3 and 4 , respectively), through a polycondensation of carbalkoxy carbenoid intermedlates generated via α, α-dichloro elimination from the end groups of 1 and 2 . The radical polymerization of styrene in the presence of 3 and 4 produced network copolymers consisting of poly (EO) or poly(THF) and polystyrene segments. © 1994 John Wiley & Sons, Inc.     

聚碳酸酯型聚氨酯互穿网络聚合物的研究概况

简述了聚磷酸酯型聚氨酯（PCU）互穿网络聚合物（IPN）的发展及最新研究动态。介绍了其制备、表征、结构与性能的关系。预示了聚碳酸酯型聚氨酯互穿网络聚合物材料的开发前景。     

互穿网络聚合物的某些进展

综述近年来热塑性互穿网络聚合物及以蓖麻油为原料合成的互穿网络聚合物的进展。     

二阶非线性光学聚合物材料的最新研究进展

随着激光技术与光纤通信技术的蓬勃发展 ,迫切要求提高非线性光学极化聚合物的性能 ,以满足器件化的要求 ,这就需要从分子设计和极化方法等方面进行研究和优化。本文以聚合物主链结构为线索 ,以非线性光学性能为依据 ,介绍了二阶非线性光学聚合物的最新研究进展 ,并展望了该类聚合物在光通信领域的应用前景     

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry （TG） of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.