带液晶侧基的交联二阶非线性光学聚合物的合成和极化

对硝基氧化偶氮苯缩水甘油醚（４）经酸碱开环反应合成得对硝基氧化偶氮苯甘油单醚（５）．ＤＳＣ和偏光显微镜结果表明这两种低分子化合物都能形成液晶相。将（５）与六亚甲基二异氰酸酯的缩二脲进行电场极化交联反应，合成了交联型非线性光学聚合物，用交温ＦＴＩＲ和ＤＳＣ研究了交联反应过程。利用紫外可见吸收光谱研究了膜极化交联前后的取向及取向稳定性。     

增塑化学微交联聚氯乙烯中化学交联和物理交联的协同作用

由氯乙烯／ 邻苯二甲酸二烯丙基酯（ＶＣ／ＤＡＰ） 悬浮共聚合成了化学微交联聚氯乙烯（ＰＶＣ） 树脂,并进行增塑加工．共聚得到的化学交联ＰＶＣ 具有溶胶／ 凝胶分配特性,交联密度较低;化学交联ＰＶＣ 的溶胶和凝胶均存在分子链缠结作用,尤其当凝胶含量较高时,物理缠结对凝胶交联密度有较大贡献．化学交联对增塑ＰＶＣ 结晶性的影响较小,因此在增塑化学微交联ＰＶＣ 中同时存在化学交联网络和以分子链物理缠结点和微晶为交联点的物理交联网络,两者协同影响增塑ＰＶＣ 材料的性能．     

交联壳聚糖在锑形态分析中的应用

研究了交联壳聚糖（ＣＣＴＳ）对Ｓｂ（Ⅲ）－吡咯烷二硫代氨基甲酸铵（ＡＰＤＣ）和Ｓｂ（Ⅴ）－ＡＰＤＣ的吸附行为，并探讨了吸附机理。结果表明：在ｐＨ＝２时Ｓｂ（Ⅲ）－ＡＰＤＣ和Ｓｂ（Ⅴ）－ＡＰＤＣ的吸附率分别为９６％和９８％。吸附后，利用Ｓｂ（Ⅲ）和Ｓｂ（Ⅴ）形成氢化物的不同条件分别测定，建立了氢化物发生原子吸收（ＨＧＡＡＳ）测定水中痕量Ｓｂ（Ⅲ）和Ｓｂ（Ⅴ）的方法。该法的检出限为６０ｎｇ／Ｌ，回收率为９５％～１０７％，相对标准偏差为２１％～５６％。     

交联苯乙烯/丙烯酰胺共聚微球的制备及其C60功能化初探

以二乙烯基苯（ＤＶＢ）为交联剂,利用一次科料分散共聚合的方法合成了交联的苯乙烯（Ｓｔ）／丙烯酰胺（Ａｍ）共聚微球。实验发现,共聚单体Ａｍ的投料量和介质的极性对微球的形态有着显著的影响。在反应过程中并联ＰＳ链段和ＰＡｍ链段发生相分离,使粒子产生异形。随后,通过微球上的酰胺基团与Ｃ６０的反应,将Ｃ６０引入微球表面。初步的光电导性能测试表明,带有Ｃ６０的微球具有较好的光电导性能。     

镓皂石的合成和交联及其催化性能

用水热法合成了Ｇａ取代皂石（ＧａＳ，并用羟基铝低聚物与其交换制得了ＰＧａＳ。用ＸＲＤ，＾２７Ａｌ、＾２９Ｓｉ ＭＡＳ ＮＭＲ和ＮＨ３－ＴＰＤ表征了ＧａＳ，ＰＧａＳ和ＣＰＧａＳ。在１，２，４－三甲苯歧化反应中观察了ＰＳ（交联皂石）和ＰＧａＳ的催化性能。结果表明ＧａＳ的结晶度很高，Ｇａ确实进入了皂石的骨架，与ＰＳ相比，ＰＧａＳ的活性和活性衰减低，歧化选择性高。这可能与ＰＧａＳ表面Ｌ酸所占表面酸份额高有     

磷酸钙骨水泥水化过程的XRD实时分析

采用ＸＲＤ实时分析方法,研究了磷酸钼骨水泥水化过程中反应物磷酸四钙（ＴｅｔｃＰ）和二水磷权氢钙（ＤＣＰＤ）的消失过程,以及生成物羟基磷灰石（ＯＨＡｐ）的形成过程。结果表明,ＤＣＰＤ比ＴｅｔＣＰ溶解速度快而先耗尽,水化反应的速度受ＴｅｔＣＰ控制,水化产物的主晶相为结晶ＯＨＡＰ。方法简单易行,合理可靠,能够准确实时体现水化反应的动态过程。     

粘度法研究胶态分散凝胶交联过程

通过粘度测定方法,研究了部分水解聚丙烯酰胺（ＨＰＡＭ）／ 柠檬酸铝（ＡｌＣｉｔ） 交联过程中粘度变化的特性．聚合物浓度高的ＨＰＡＭ／ＡｌＣｉｔ 体系粘度随反应时间的延长而上升,其体系粘度最终高于相同聚合物浓度的ＨＰＡＭ 溶液粘度．聚合物浓度低的ＨＰＡＭ／ＡｌＣｉｔ 体系粘度随反应时间的延长而下降,其体系粘度低于相同聚合物浓度的ＨＰＡＭ 溶液粘度．ＨＰＡＭ／ＡｌＣｉｔ 交联体系的聚合物浓度低于临界浓度时,交联反应后形成稀胶态分散凝胶（ＴＣＤＧ） ．在实验条件下,临界浓度在１５０ ～３００ｍｇ／Ｌ 之间．当聚合物浓度于临界浓度和７００ｍｇ／Ｌ之间时,形成浓胶态分散凝胶（ＣＣＤＧ） ;当聚合物浓度高于７００ｍｇ／Ｌ 时,ＨＰＡＭ／ＡｌＣｉｔ 交联体系形成整体凝胶．     

一种非晶硅膜改性弹性玻璃毛细管交联中等极性固定相色谱柱的制备

研究了非晶硅膜改性的弹性玻璃毛细管交联ＯＶ－１７０１中等极性固定相色谱柱。在适当温度下，采用过氧化二异丙苯（ＤＣＵＰ）游离基引发交联ＯＶ－１７０１固定液，成功地制备了交联ＯＶ－１７０１柱，该柱具有柱效高、惰性好、耐溶剂、抗腐蚀和耐高温等性能，是一种新型高性能的中等极性交联柱。     

交联XE－60和PEG－20M极性固定相非晶硅膜改性弹性玻璃毛细管柱研究

研究了交联ＸＥ－６０和ＰＥＧ－２０Ｍ极性固定相非晶硅膜改性弹性玻璃毛细管柱，在适当的温度下，用过氧化二异丙苯（ＤＣＵＰ）游离基引发交联，成功地制备了ＸＥ－６０和ＰＥＧ－２０Ｍ极性柱，它们均具有柱效高、惰性好、化学稳定性好和耐溶剂、抗腐蚀、耐高温等性能，是一种新型的极性交联柱。     

PVC／PE交联共混体系的动态学力学研究

在ＰＶＣ／ＰＥ共混体系中加入交联剂和引发剂能产生ＰＶＣ－ＣＯ－ＰＥ共聚物，这种共聚物在共混物中可起到增容剂的作用，通过动态力学分析和扫描电镜研究了ＰＶＣ／ＰＥ交联混体系的相容性，发现引发剂，交联剂，稳定剂和增塑剂等对共混和的中的交联反应均有较大的影响。     

丙烯酸乙酯/烯丙基缩水甘油醚共聚物的热可逆共价交联

研究了双环戊二烯基二羧酸及其铵盐对丙烯酸乙酯 /烯丙基缩水甘油醚共聚物的交联反应 ,对比了二者的交联速度 .用DSC评价了它们的热可逆转化行为 .制得了热可逆部分达 79 7%的共价交联环氧型丙烯酸酯橡胶     

聚氯乙烯的热可逆共价交联

利用环戊二烯 (CPD)在常温下自动二聚形成双环戊二烯 (DCPD)、在高温下DCPD又可解聚成CDD的热可逆Diels Alder反应 ,合成了DCPD二羧酸衍生物 ,并将其引作聚氯乙烯 (PVC)的共价交联 ,研究了交联剂种类和用量对交联程度、力学性能和流动特性的影响及交联产物的热可逆转化行为 ,制得了力学性能和耐热性均有所提高的热可逆共价交联PVC     

Simultaneous Chiral Fixation and Chiral Regulation Endowed by Dynamic Covalent Bonds

The construction of chiral superstructures through the self-assembly of non-chiral polymers usually relies on the interplay of multiple non-covalent bonds, which is significantly limited by the memory ability of induced chirality. Although the introduction of covalent crosslinking can undoubtedly enhance the stability of chiral superstructures, the concurrent strong constraining effect hinders the application of chirality-smart materials. To address this issue, we have made a first attempt at the reversible fixation of supramolecular chirality by introducing dynamic covalent crosslinking into the chiral self-assembly of side-chain polymers. After chiral induction, the reversible [2+2] cycloaddition reaction of the cinnamate group in the polymer chains can be further controlled by light to manipulate inter-chain crosslinking and decrosslinking. Based on this photo-programmable and dynamic chiral fixation strategy, a novel pattern-embedded storage mechanism of chiral polymeric materials was established for the first time.     

Thermally reversible linking of halide-containing polymers by potassium dicyclopentadienedicarboxylate

A novel crosslinker for thermally reversible covalent (TRC) linking of halide-containing polymers is suggested. Chlorine-containing polymers such as chloromethylstyrene copolymers, chlorinated polypropylene, polyvinylchloride, chlorinated polyisoprene, and polyepichlorohydrin were crosslinked with potassium dicyclopentadienedicarboxylate (KDCPDCA). The crosslinker was prepared by reacting potassium ethoxide with dicyclopentadienedicarboxylic acid. Because of the low solubility of KDCPDCA in organic solvents, a phase transfer catalyst, benzyltrimethyl-ammonium bromide, was employed for the crosslinking reaction. The crosslinking reaction occurred at a higher rate in a polar solvent, such as dimethylformamide, than in a nonpolar one, such as toluene, and was affected by the nature of the chlorine-containing polymer. Some of the polymers crosslinked even at room temperature. The chain-extending reaction between KDCPDCA and a α,ω-dihalide compound such as α,α′-dichloro-p-xylene, 1,4-dichlorobutane, or 1,4-dibromobutane also was carried out to obtain linear oligomers. The IR spectra indicated that the crosslinking and chain-extending reactions were based on the esterification between the halide carbon bonds of the polymer and the COOK groups of KDCPDCA. The flowability at 195 °C and solubility on heating in a dichlorobenzen-maleic compound mixture of the crosslinked polymers indicated that the TRC crosslinking occurred via the reversible Diels–Alder cyclopentadiene/dicyclopentadiene conversion as long as the polymer was thermally stable and did not contain olefinic CC bonds. The TRC linking also was confirmed by the rapid decrease of the specific viscosity of the obtained linear oligomers on heating. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4390–4401, 1999     

Comparison of irreversible and reversible cluster formation

Covalent and reversible cluster molecules were synthesized by an A₃B₂ type gelation. Crosslinking of three-arm hydroxyl-terminated star polymers with 2,4-toluenediisocyanate gave branched polymers, while the reversible analogue was made by crosslinking of tertiary amine-terminated star polymers with bis(4-hydroxy-3,5-dinitrophenyl) adipate. Gelation process was followed by static and dynamic light scattering. The extent of reacted groups was measured with UV spectroscopy. Growth of the covalent clusters could be described in terms of percolation scaling laws. The experimental gel point (P_{OH, cr} = 0.70) was shifted significantly from the theoretical predicted gel point (P_{OH, cr} = 0.50), indicating extensive ring formation during the gelation. The reversible endlinking reaction gave no macroscopic gelation, though increase of the cluster dimensions was observed. Ring formation proved to be an important side reaction in both cases; however, the ring formation ability seems to change in a different manner during the course of a gelation.     

酰亚胺基锂电池有机聚合物负极材料的制备及电化学性能研究

设计合成了一系列聚酰亚胺基的共轭骨架材料用于锂电池负极.首先,选用具有不同共轭体系的二酐分子用作共聚物构建单元,随后通过亚胺化反应与三聚氰胺共缩聚.最后,通过进一步热处理提高材料的交联程度和稳定性.将该材料用于锂离子电池负极表现出稳定的电化学性能.聚合物的倍率性能测试结果表明:在150 mA·g~(-1)的电流密度下,循环150次后,放电比容量达到471 mAh·g~(-1)以上,在2 A·g~(-1)的较大电流密度下,放电比容量达122.1 mAh·g~(-1),当电流密度返回至100 mA·g~(-1)时,其放电比容量又上升至532.3 mAh·g~(-1)左右,材料具有较好的倍率性能,聚合物材料在充放电过程中,避免了有机小分子材料在与锂离子结合后,易溶于电解液造成的容量损失.同时,共聚物骨架的共轭结构单元和极性基团,可在保证材料的导电性的同时增加材料结合锂离子的能力,因此表现出了优异的倍率性能.     

氯化聚乙烯的热可逆共价交联

采用新型热可逆共价交联剂 ,以溶液反应法使氯化聚乙烯 (CPE)交联制得了凝胶量在 80 %左右的共价交联CPE ,研究了不同牌号CPE、催化剂及其用量、反应温度、反应时间及交联剂用量对CPE交联程度的影响 ,并测定了共价交联CPE的热可逆转化特性     

The Crosslinking of Ethylene-Vinyl Acetate Copolymers with Sodium Alcoholates

When reacting ethylene-vinyl acetate copolymers (EVA) with sodium alcoholates in alcohol, the alcoholysis of EVA is accompanied by crosslinking reactions. Crosslinking can be detected by the increase in torque in a plastograph. This paper reports on investigations on the mechanism of the crosslinking reaction. Both crosslinking via C?C bonds and formation of a thermally reversible network via polymer alcoholate structures can be found. If an ethylene-vinyl alcohol copolymer is obtained by complete saponification of EVA, however, only thermally reversible crosslinking can be demonstrated. This leads to the conclusion that irreversible crosslinking is established through a reaction of the acetate side chains. The reaction products of the low-molecular weight model substances, pentanol-3-acetate and sodium isopropylate in isopropanol, are analyzed by means of gas chromatography. These results suggest a partial Claisen condensation as a mechanism of the irreversible crosslinking process.     

Investigation of thermo-reversibility of polymer crosslinked by reversible covalent bonds through torque measurement

Brominated butyl rubber (BIIR) was crosslinked through an esterification reaction using the sodium salt of dicyclopentadiene dicarboxylic acid (DCPDCA) as crosslinking agent. The crosslinked BIIR could de-crosslink upon heating and re-crosslink upon cooling due to Diels-Alder type reversible de-dimerization/re-dimerization of dicyclopentadiene moieties in the rubber networks. Torque measurement of the crosslinked rubber was conducted at various temperatures using a typical curemeter to investigate the thermo-reversibility. It was revealed that proper temperature for thermal processing of the crosslinked BIIR would be around 174 °C, at which the crosslinked polymer exhibits good flowability and is not too high to induce unexpected side reactions. The torque measurement was also carried out to investigate the efficiency of antioxidant on retarding the loss of the thermo-reversibility of the crosslinked polymer during heating-cooling cycles. It was found that addition of antioxidant 2246 [2,2′-methylenebis(6-tert-butyl-4-methylphenol)] into BIIR could significantly improve the thermo-reversibility of DCPDCA crosslinked BIIR. Torque measurement provides a convenient and sensitive method to understand the thermal behavior of reversible covalent crosslinked polymer.     

环氧氯丙烷橡胶的热可逆共价交联

以环戊二烯二羧酸钾 [DCPD(COOK) 2 ]为交联剂 ,采用溶液反应法使环氧氯丙烷橡胶 (环氧氯丙烷均聚物 ,CER)交联 ,制得了凝胶含量达 88 75 %的交联CER ,研究了溶剂种类、反应温度、催化剂及交联剂用量对凝胶形成量的影响 .IR谱证明 ,DCPD(COOK) 2 与CER发生双端酯化而交联 ;反应溶解性试验表明 ,该共价交联聚合物具有热可逆转化特性 ,热可逆转化百分率随反应温度的提高、交联剂用量的增多而下降