双（N,N′—亚烃基—2,2′—（芳亚甲基）二（3,4—二甲基吡咯— …

首次报道了新型Ｓｃｈｉｆｆ碱类配体双（Ｎ，Ｎ′－亚烃基－２，２′－（苯亚甲基）－二（３，４－二甲吡咯－５－醛缩亚胺）和双（Ｎ，Ｎ′－（１，２－亚乙基）－２，２′－（４－甲氧基苯亚甲基）二（３，４－二甲基吡咯－５－醛缩亚胺）及其双锰配合物的合成方法，光谱特征及用配合物催化ＰｈＩＯ单加氧化环己环反应的研究。     

含亚甲基链段苯并二嗯唑类聚合物的合成、表征及性能

通过溶液缩聚的方法合成了一系列含有不同长度亚甲基链段的聚苯并羟基酰胺（PHACx），然后在200～300℃下环化脱水制备了相应的聚多亚甲基苯并二嘿唑（PBOCx），并对其结构进行了表征，探讨了聚合物的溶解性、热性能和光物理性能。研究表明：在主链上引入亚甲基提高了苯并二嘿唑类聚合物在有机溶剂中的溶解性，其中PBOC3和PBOC4具有较好的溶解性能，但随着亚甲基数量的进一步增加，溶解性有下降趋势。此外，所有的PBOCx聚合物均表现出良好的耐热性，在空气中的热分解温度可达到450℃以上。对聚合物光物理性能的初步研究表明：随着柔性链段的增加，电子共轭作用逐渐减弱，紫外吸收发生了蓝移。     

聚对二亚甲基苯的激光离解质谱分析

聚对二亚甲基苯的激光离解质谱分析高文德，刘维铬，王守文，马洪，敖十庆，邓万卉，许建光（四川联合大学成都６１００６４）崔保顺，唐永建，马宏伟（中国工程物理研究院成都６１０００３）关键词激光，质谱，聚对二亚甲基苯聚对二亚甲基苯难溶于有机溶剂且加热时立即分...     

双[N,N'-亚烃基-2,2'-(芳亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]合双锰(Ⅱ)的合成、光谱特征及拟酶催化性能研究

首次报道了新型Schif碱类配体双[N,N-亚烃基-2,2-(苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]和双[N,N-(1,2-亚乙基)-2,2-(4-甲氧基苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]及其双锰配合物的合成方法、光谱特征及用配合物催化PhIO单加氧化环己烷反应的研究。     

亚胺膦钌配合物RuCl2P2N2的合成和催化性能

ＲｕＣｌ２（Ｐｈ３Ｐ）４或ＲｕＣｌ２（ＤＭＳＯ）４在甲苯中直接与等摩尔的亚胺膦配体Ｎ，Ｎ－双－［邻－（二苯基膦苯亚甲基）］乙二胺（Ｐ２Ｎ２）在甲苯中回流反应，高产率地合成了反式配位的双亚胺双膦钌配合物ｔｒａｎｓ－ＲｕＣｌ２Ｐ２Ｎ２．在温和条件下，该配合物作为新型催化剂有效地催化α，β－不饱和酸和几种功能团烯烃的选择加氢反应．讨论了可能的催化活性物种．     

聚偶氮乙烯及其异构体分子的稳定性差异和电子性质的量子化学研究

采用量子化学MNDO和CNDO/2-CO计算方法,对聚偶氮乙烯(C₂H₂N₂)₂3种异构体的稳定性进行了比较,指出聚偶氮乙烯和聚异亚甲基亚胺分子的稳定性比聚亚甲基亚胺高,分析了造成稳定性差异的原因。能带结构计算表明:三者中聚异亚甲基亚胺的导电性能最好,可望具有较高的本征和掺杂电导率。     

1,4—双（氯甲基）—2—甲氧基—5—壬氧基苯的均聚和共聚研究

以１，４－双（氯甲基）－２，５一二甲基苯（ＢＣＭＤＭＢ）和１，４－双氯甲基－２－甲氧基－５－壬氧基苯（ＢＣＭＭＯＮＯＢ）为单体，采用脱氯化氢法，合成了聚（２，５－二甲基）对亚苯基亚乙烯（ＰＤＭＰＶ）和聚（２－甲氧基－５－壬氧基）对亚苯基亚乙烯（ＰＭＯＮＯＰＶ）；并对ＢＣＭＤＭＢ和ＢＣＭＭＯＮＯＢ的共聚进行了研究。结果表明，适宜的反应条件为：碱与单体的摩尔比为２０∶１，在室温下聚合时间为３０ｈ，碱的ｐＨ＝１４时产率最高。用ＩＲ、１Ｈ－ＮＭＲ、ＵＶ—Ｖｉｓ对聚合物进行了表征。     

N-(芳亚甲基)芳胺Schiff碱汞化反应区域选择性研究

本文用量子化学的MNDO方法对N-(苯亚甲基)苯胺、N-(苯亚甲基)-2-甲苯胺与N-(4-硝基苯亚甲基)-2-甲氧基苯胺Schiff碱汞化反应区域选择性进行了研究,结果表明,在其稳定构象下,芳胺环上的电荷密度大于苯基亚甲基环, 故汞化反应发生在芳胺环上；分子中亚胺氮原子的电荷密度最大, 在汞化反应过程中, 亚胺氮原子首先与醋酸汞配位,然后再进行邻位亲电进攻,生成邻位汞化产物；而在N-(苯亚甲基)-2-甲苯胺分子中, 邻位甲基阻碍了亚胺氮原子与汞原子的配位作用,故无邻位汞化产物生成。计算结果与实验结果一致, 并进一步支持了已经提出的反应机理。     

含异亚丙基聚亚胺醚酮空心微球的制备

以1,4-双-（4’-溴苯酰基）苯和2,2-双-[4-（4-氨基苯氧基）苯基]丙烷为单体,以三（二亚苄基丙酮）二钯为催化剂,1,1’-联萘-2,2’-二苯膦（BINAP）为配体,由钯催化的胺基化反应缩聚合成了含异亚丙基的聚亚胺醚酮（pr—PIEK）,并通过微封装法制备了pr—PIEK空心微球．     

螺二邻二亚甲基噻吩和环二邻二亚甲基噻吩的合成

Errede等曾利用氢氧化邻甲基苄基三甲基铵的热解制得螺二邻二亚甲基苯、环二邻二亚甲基苯和聚邻二亚甲基苯。Winberg等人对噻吩的季铵碱的热解有所研究,但未能触及活泼的中间体2,3-二亚甲基-2,3-二氢化噻吩Ⅷ及其二聚体螺环化合物和环状化合物。     

改性PPO的溶解性能研究

研究了 PPO、羧化 PPO(C-PPO)、苯酰化 PPO(BA-PPO)、苯磺酰化 PPO(BS-PPO)和磺化 PPO(S-PPO)在不同溶剂中的溶解能力,分别讨论了各种取代基以及取代度对溶解性能的影响,测定了各种改性 PPO 在溶剂中的特性粘数,估计了它们的溶度参数。发现,在 PPO 的溶解过程中,色散力起重要作用,S-PPO 样品的溶解过程则是极性力和氢键起主导作用,而 BA-PPO 和 BS-PPO 的溶解过程则是三种力相互作用的结果。对于不同取代度的 C-PPO,随取代度增加,在极性和形成氢键的溶剂中的溶解能力增加。     

Thermotropic copolyesters containing the 1,4-cyclohexylenedimethylene spacer

Poly[oxy(2-methyl-1,4-phenylene)oxyterephthaloyl-co-oxy(2-methyl-1,4-phenylene)oxy-1,4-cyclohexanediacetoyl] (I), poly[oxy(2-chloro-1,4-phenylene)oxyterephthaloyl-co-oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl] ( II ), and poly[oxy(2-methyl-1,4-phenylene)oxyterephthaloyl-co-oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl] ( III ) were synthesized and shown to form birefringent fluid states in the melt.     

聚苯醚羧酸盐的聚集态结构

本文用热学、力学和散射方法研完了聚苯醚羧酸盐的链结构、羧化聚苯醚(C-PPO)在二氧六环溶液中用0.5 NaOH或CsOH的醇水溶液中和成钠型或铯型的C-PPO离聚体,用DSC测定一系列羧酸盐含量的C-PPO离聚体的玻璃化转变温度得到形成离子微区的临界阳离子浓度约为5mol％;动态力学谱中在高于玻璃化转变温度域出现的α松弛峰亦证明了微相结构的存在;SAXS结果表明其离子微区的尺寸约为30(?),其尺寸大小和离聚体中阳离子浓度无     

取代基对PPC/聚苯醚羧酸酯共混体系相容性的影响

由二氧化碳活化并与环氧丙烷共聚而成的脂肪族聚碳酸酯(PPC)是一类有发展前途的新型高分子弹性体。研究它与其它高聚物的混容性及混容机制对于开拓这一新材料的应用领域具有十分重要的意义。本文合成了一系列不同取代度和不同链长酯基的聚苯醚羧酸酯[E(x)-C^yPPO]^[3],探索了PPC与各聚苯醚狡酸醋的混容性,讨论了聚苯醚梭酸酷的取代度及侧基链长对PPC/E(x)-C^yPPO共混体系混容性的影响。     

Unperturbed dimensions of poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly(2,6-diphenyl-1,4-phenylene oxide) chains

The unperturbed chain dimensions of unfractionated poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly-(2,6-diphenyl-1,4-phenylene oxide) have been measured by combining molecular weight data from light scattering with intrinsic viscosity data in chloroform. The unperturbed chain dimensions of the former polymer were also measured directly by light scattering dissymmetry in a critical consolute solvent mixture (methyl cyclohexane: 1,4-dioxane 50:50 by volume). The results of these measurements and of measurements reported by other investigators are satisfactorily explained by postulating no dimension-expanding prejudice in azimuthal angle in chain conformers of the 2,6-substituted-1,4-phenylene oxide polymers. This corresponds to equal population of the two chain rotation energy minima at azimuthal angles 90° and 270°. Accepting this postulate, one calculates from the observed chain dimensions that the C? O? C bond angle is 118–120° in these aromatic polyethers in solution.     

Model reactions for preparing poly(imino-tetrafluoro-1,4-phenylene)

2,3,4,5,6-Pentafluoroformanilide was prepared giving, in addition, two new compounds 4,5,6,7-tetrafluoro-1-pentafluorophenyl-benzimidazole and 2,3,4,5-tetrafluoro-6-[(pentafluorophenyl)amino]formanilide. Sodium 2,3,4,5,6-pentafluoro-formanilide was reacted with hexafluorobenzene in a molar ratio of 1:4 to give oligomers of α-pentafluorophenyl-ω-fluoro-poly(imino-tetrafluoro-1,4-phenylene). Some of the oligomers were isolated. The results indicate that poly(imino-tetrafluoro-1,4-phenylene) could be formed. Model reaction on hexafluorobenzene with sodium acetanilide, molar ratio 1:2, gave a low yield of N,N′-diacetyl-diphenyl-tetrafluoro-1,4-phenylenediamine.     

改性PPO的溶解性能和溶度参数的初步估计

研究了聚苯醚PPO、羧化PPO、苯酰化PPO、苯磺酰化PPO和磺化PPO在不同溶剂中的溶解能力,分别讨论了各种取代基以及取代度对聚合物溶解性能的影响,由PPO衍生物的特性粘数估算了它们的溶度参数。     

Reaction of zinc enolates derived from 1-aryl-2,2-dibromoalkan-1-ones with tetramethyl 2,2′-(1,4-phenylenedimethylidene)dimalonate,dimethyl 3,3′-(1,4-phenylene)bis(2-cyanoacrylate), and 2,2′-(1,4-phenylenedimethylidene)-bis(malononitrile)

Zinc enolates derived from 1-aryl-2,2-dibromoalkanones reacted with tetramethyl 2,2′-(1,4-phenylenedimethylidene)dimalonate, dimethyl 3,3′-(1,4-phenylene)bis(2-cyanoacrylate), and 2,2′-(1,4-phenylenedimethylidene)bis(malononitrile) to give, respectively, tetramethyl 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroylcyclopropane-1,1-dicarboxylates), dimethyl 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroyl-1-cyanocyclopropane-1-carboxylates), and 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroylcyclopropane-1,1-dicarbonitriles) as a single stereoisomer.     

THERMOPLASTIC ELASTOMERS. II. POLY(ETHER-ESTER-IMIDE)S BASED ON 1,4-DIAMINOBUTANE,TRIMELLITIC ANHYDRIDE, 1,4-DIHYDROXYBUTANE,AND POLY(ETHYLENE OXIDE)S

A series of new poly(ether-ester-imide)s, PEEIs, was prepared from an imide dicarboxylic acid based on 1,4-diaminobutane and trimellitic anhydride. This imide dicarboxylic acid polycondensed with 1,4-dihydroxybutane formed the hard segments and poly(ethylene oxide), PEO-1000, or mixtures of PEO-1000 and poly(tetramethylene oxide), PTMO-1000, were used as soft segments. Whenever PTMO-1000 was used as comonomer, macrophase separation was observed at the end of the polycondensation. However, this macrophase separation had little influence on the mechanical properties. A poly(ether-esterimide), PEEI, containing neat PEO-1000 was characterized by dynamic mechanical thermoanalysis, stress-strain and hysteresis measurements, and by melt rheology. The mechanical properties were compared with those of an analogous PEEI containing neat PTMO-1000 and with those of a poly(ether-ester), PEE, based on poly(butylene terephthalate) hard segments and PTMO-1000.     

Polymerization by oxidative coupling. II. Co-redistribution of poly(2,6-diphenyl-1,4-phenylene ether) with phenols

Poly(2,6-diphenyl-1,4-phenylene ether) reacts with phenols in the presence of an initiator to form a mixture of low molecular weight hydroxyarylene ethers. Although the reaction is similar to the equilibration of poly(2,6-dimethyl-1,4-phenylene ether) with phenols, higher reaction temperatures and larger initiator concentrations are required. Compounds as 3,3′,5,5′-tetraphenyl-4,4′-diphenoquinone, tert-butyl perbenzoate, and benzoyl peroxide are active initiators. The structure of the polymer affects the extent to which the polymer equilibrates.