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.     

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。     

由苯-1,2,4-三羧酸-1,2-酐和二乙醇胺合成结构非对称超支化聚(酰胺-酯)

通过准发散法和一步法由苯 1 ,2 ,4 三羧酸 1 ,2 酐 (BTAA)和二乙醇胺 (DEA)合成了新型水溶性结构非对称超支化聚 (酰胺 酯 ) .聚合物的端基可通过BTAA与DEA的加料比来调节 .产物结构经FTIR ,1 H NMR和TGA进行了表征 .在一步法中 ,当BTAA于DEA的加料比大于 2 0 4时 ,反应体系不易凝胶 ,当加料比小于 2时 ,体系容易发生交联 .在准发散法中 ,不用中间分离过程 ,采用合成树状大分子发散法相同的加料方式 ,可得到大分子产物     

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.     

交联聚合物P(MMA-MAh)-PEG1500基凝胶电解质锂离子键合极性基团作用FTIR研究

用聚乙二醇(PEG1500)和甲醇先后与共聚物(P(MMA-MAh))发生酯化反应,合成得到交联聚合物P(MMA-MAh)-PEG1500.以该交联聚合物P(MMA-MAh)-PEG1500、碳酸丙烯酯(PC)和锂盐(LiClO4)为三种组分制备凝胶聚合物电解质,电解质性能必会受到这些组分间存在的微观相互作用的影响.采用FTIR来研究PC和P(MMA-MAh)-PEG1500中存在的极性基团(C=O和C—O—C)与Li+的相互作用.对于PC/LiClO4和polymer/LiClO4体系,FTIR定量分析显示,极性基团对Li+的吸收系数分别为0.113和0.267,说明在红外光谱中Li+键合C=O和C—O—C极性基团比自由极性基团吸收灵敏度高;另外,计算该二体系中Li+键合极性基团(C=O和C—O—C)的当量百分数极限值分别为94%和45%,表明极性基团与Li+间存在的相互作用是可逆的,并且体系PC/LiClO4中相互作用强度大于体系polymer/LiClO4.     

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...     

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.     

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。     

部分水解聚丙烯酰胺柠檬酸铝体系临界交联浓度的研究

采用落球粘度计、核孔膜过滤、动态光散射 (DLS)和2 7Al NMR法 ,研究了高分子量、低浓度的部分水解聚丙烯酰胺 (HPAM)与柠檬酸铝 (AlCit)体系形成交联聚合物溶液 (LPS)的临界交联浓度 .研究结果表明 ,HPAM AlCit体系在聚合物浓度较低时 ,溶液中主要发生形成交联聚合物线团 (LPC)的交联反应 ,此时形成的是LPS ,聚合物浓度增加到某一临界值后 ,体系中形成线团后 ,存在线团间的交联 ,此时形成的是弱凝胶 .不同方法所测得的HPAM AlCit体系的临界交联浓度基本相同 ,对于粘均相对分子质量为 1 4× 10 7的HPAM ,在NaCl浓度为 2 0 0 0mg L ,交联比 2 0∶1时形成的交联体系 ,其临界交联浓度在 2 0 0～ 30 0mg L间 .     

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     

Molecular composite. II. Novel block copolymer and semi-interpenetrating polymer network of rigid polyamide and flexible polyimide

2,2'-Dimethyl-4,4'-diamino-biphenyl was used to prepare a lyotropic amine-terminated polyamide (PBTA) prepolymer with terephthaloyl dichloride, and an amide oligomer with reactive endcaps of maleimide, respectively. The former was employed in an attempt to increase the solubility of PA/PI block copolymers, and the latter to produce a three-dimensional (isotropic) reinforced molecular composite through the technology of a semiinterpenetrating polymer network (semi-IPN). PBTA prepolymer was copolymerized with an amine-terminated polyimide via a coupling reaction using terephthaloyl dichloride. The resultant block copolymers were characterized by IR, NMR, η_inh and GPC to confirm that the copolymerization reaction was precisely accomplished, as well as to determine their composition and molecular weight. Thermal analysis and lyotropic behavior were also studied for these copolymers. Rigid-rod amide oligomer was crosslinked in the presence of another flexible polyimide. Five sets of semi-IPN films were prepared under varying compositions. The curing conditions were investigated by DSC; in addition, the cured semi-IPNs exhibited a single phase (1 T_g) according to examination by an instrument for thermally stimulated current (TSC). No large-scale phase separation was observed in SEM images of the fractured surfaces. © 1994 John Wiley & Sons, Inc.