Investigation of Bimetallic Nickel Catalysts in Catalyst‐Transfer Polymerization of π‐Conjugated Polymers

A comparative study involving bimetallic nickel catalysts designed from disubstituted N,N,N′,N′‐tetra(diphenylphosphanylmethyl)benzene diamine bridging ligands is reported. Catalyst behavior is explored in the Kumada catalyst‐transfer polymerization (KCTP) using poly(3‐hexylthiophene) (P3HT) as the model system. The success of a controlled polymerization is monitored by analyzing monomer conversion, degree of polymerization, end‐group identity, and molecular weight distribution. The characterization of P3HT obtained from KCTP initiated with the bimetallic catalysts shows chain‐growth behavior; however, the presence of Br/Br end‐groups and broader molecular weight distribution reveals a reduced controlled polymerization compared to the commonly employed Ni(dppp)Cl₂. The observed increase in intermolecular chain transfer and termination processes in KCTP initiation with the bimetallic catalysts can be attributed to a weaker Ni(0)‐π‐aryl complex interaction, which is caused by increased steric crowding of the coordination sphere.     

低分子量聚合物电解质的合成与性能

研究了低分子量梳状聚合物电解质的合成方法及结构，性能。首先合成了不同分子量的甲基丙烯酸聚乙二醇单甲醚酯，并进一步合成了分子量一万左右的梳状聚合物电解质，结果表明：反应严格按照反应方程进行，精制产物是非晶的梳状聚合物，本聚合物体系均存在两个玻璃化转变温度，一个在100℃左右，归属为梳状聚合物主链的玻璃化转变，另一个在－20摄氏度以下，归属于侧链玻璃化转变，在室温下侧链可以运动，有利于电活性物质的迁移和扩散，并用超微电极研究了该电解质的行为。     

芳香族聚酯的相转移催化合成及其介晶态行为的研究——Ⅰ.聚酯的合成及介晶态行为

本文用相转移催化方法合成了四种新颖的芳香族聚酯。对所得聚合物进行了红外光谱、热重分析、偏光显微镜、示差扫描量热仪和解偏振光强等测试,以研究它们的结构和性能。它们的热分解温度都在330℃以上。其中的聚对,对′-1,4,7-三氧杂庚撐基二苯甲酸对苯二酚酯和聚对苯二甲酸对,对′-1,8-二氧杂辛撐基二苯酚酯,呈现向列型相转变,它们的清晰点分别为237℃和327℃。其它两种含双酚A或酚酞基团的聚酯则不存在液晶行为。对实验结果进行了讨论。     

Color Stability of Dry Earth Pigmented Maxillofacial Silicone A-2186 Subjected to Microwave Energy Exposure

PURPOSE: The purpose of this study was to measure spectrophotometrically the color stability of pigmented A-2186 silicone maxillofacial elastomer with 10% by volume of titanium white dry earth opacifier before and after exposure to microwave energy over a simulated 1.5-year period of microwave sterilization. Materials AND METHODS: A-2186 silicone elastomer opacified with titanium white dry earth pigment, pigmented with 5 cosmetic dry earth pigment colors [no pigment (control) group (Pc), red (Pr), yellow ochre (Py), burnt sienna (Po), and a mixture of Pr + Py + Po color group (P3)], was used in this study. Each of the 5 experimental groups consisted of 5 specimens. All specimens were placed in a 250 ml glass beaker filled with 150 ml of water (replenished for each microwave exposure). An exposure of 6 minutes was used 18 times (simulating 1.5 years of microwave sterilization with one 6 minute exposure monthly). Reflectance values were measured by spectrophotometer. Three- and two-way analyses of variance with repeated measures were performed for the color difference (DeltaE*) with the factors of group/color/months, and group/months, respectively. Means were compared by Tukey Honest Significant Difference (HSD) multiple range test calculated at the 0.05 level of significance using SPSS. RESULTS: The trained human eye can detect color changes (DeltaE*) greater than 1.0. Most DeltaE* values of the red pigment group at all intervals and the mixed pigment group at 15- and 18- month intervals increased significantly greater than 1.0 (p < 0.001) compared with the control group. Yellow and burnt sienna groups remained the most color stable over time with DeltaE* values below 0.35. CONCLUSIONS: Lack of color stability of red dry earth pigmented A-2186 silicone maxillofacial elastomers was clinically significant after 12-month exposure to microwave energy as compared with yellow, burnt sienna, and opacified A-2186 dry earth pigments.     

~(27)AINMR对碱式氯化铝的研究

实验室制得的碱式氯化铝,用~(27)Al NMR进行分析,发现在众多聚合体中存在[AlO_4Al_(12)(OH)_(24)(H_2O)_(12)]~(7+)离子,其化学位移相对于六水合铝离子[Al(H_2O)_6]~(3+)的零位移为δ=63ppm,试铁灵定时比色法对其存在进行了验证。研究了反应条件如酸浓度、铝酸当量比和陈化时间对产物组成及质量的影响,得出最佳条件为盐酸浓度16%,铝酸当量比为1:0.5,陈化时间为50h左右。     

有机-无机复合型聚合物电解质的研究进展

聚合物电解质是现在锂离子电池研究领域的热点，有机－无机复合型聚合物电解质（CSPE）是现在聚合物电解质的研究主流。在聚合物电解质中添加无机添末，特别是纳米材料，大大改善了聚合物电解质的机械性能、离子导电性能以及界面稳定性能。对CSPE性能进行了评价，对在CSPE中添加无机粉末性能改善机理作了概括和探讨，并对CSPE的前景作了展望。     

聚醋酸乙烯酯与铜（Ⅱ）离子的配位反应及其催化作用

以ＥＳＲ、ＵＶ和ＩＲ表征Ｃｕ（２＋）离子与ＰＶＡＣ的配位反应。根据ＣＵＣｌ２·２Ｈ２Ｏ乙醇溶液与ＰＶＡｃ－ＣｕＣｌ２·２Ｈ２Ｏ乙醇溶液的电导率差值随Ｃｕ（２＋）离子摩尔浓度变化的明显转析点得知，１个Ｃｕ（２＋）离子大约能与ＰＶＡｃ４个链节单元配位。证实ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系的聚合体是无规ＰＭＭＡ，得率为７０％。讨论了ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系络合催化引发下的游离基反应历程。     

一种含胆甾醇介晶基团的侧链液晶高分子的合成

以２，４－二异氰酸甲苯酯（２，４—ＴＤＩ）、胆甾醇、丙烯酸β－羟丙酯为原料，合成了含胆甾醇介品基团的侧链液晶高分子、并用ＮＭＲ、ＩＲ和元素分析方法对其结构进行了鉴定。聚合物的相转变温度和形态织构用ＤＳＣ、Ｘ－射线衍射和偏光显微镜进行了测定和观察。     

5-FU多聚缓释体植入技术治疗脑胶质瘤

目的观察5-氟尿嘧啶(5-FU)多聚缓释体植入胶质瘤内化疗的临床效果,探索化疗药物的新剂型和新途径。方法在60例胶质瘤病人在开颅术中或以立体定向方式植入5-FU多聚缓释体,5-FU含量100～150mg。随访5～24周,通过影像学检查,计算肿瘤平均径。比较手术前及各随访时间段肿瘤平均径的变化,并观察瘤周水肿情况。结果38例病人术后病情稳定。无化疗不良反应。肿瘤平均径在术后5、12和24周以上均有显著缩小。其中第12周随访病例肿瘤平均径缩小最显著。肿瘤周边水肿带在开颅手术的病人比较宽,而在立体定向手术病人无明显加重表现。结论低剂量5-FU瘤内缓释体植入术治疗脑胶质瘤安全有效,无明显不良反应。     

丙帕锗的制备及分析

目的 探索合成条件，制备体内活性和稳定性好的高聚物丙帕锗．并分析其结构确定目的物的正确性。方法 以GeO2为起始原料，磷酸二氢钠为还原剂,制备3-氧锗丙烯酸低分子量聚合物和高分子量3-氧锗丙烯酸(丙帕锗)，并进行元素、红外光谱、核磁共振和X-射线的分析。结果 高分子量聚合物生成，在320℃以下不分解，终产率为72．9％。结论 所采用的方法可行，合成的产品结构正确。