Crystal structures of propanediamine complexed with L and DL- glutamic acid: effect of chirality on propanediamine.

The structures of complexes of 1,3-diaminopropane With L- and DL-glutamic acid have been determined. L-Glutamic acid complex: C3H12N22+.2C5H8NO4-, M(r) = 368.4, orthorhombic. P2(1)2(1)2(1), a = 5.199 (1), b = 16.832 (1). c = 20.076 (3) angstrom, V = 1756.6 (4) angstrom3, z = 4, D(x) = 1.39 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu = 1.1 cm-1, F(000) = 792. T = 296 K, R = 0.044 for 1276 observed reflections. DL-Glutamic acid complex: C3H12N22+.2C5H8NO4-, M(r) = 368.4, orthorhombic, Pna2(1), a = 15.219(2), b = 5.169 (1), c 22.457 (4) angstrom, V = 1766.6 (5) angstrom3 Z = 4, D(x) = 1.38 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu = 1.1 cm F(000) = 792, T = 296 K, R = 0.056 for 993 observed reflections. The conformation of diaminopropane is all-trans in the DL complex but trans-gauche in the L complex. The main packing feature in the L complex is the arrangement of diaminopropane around dimers of antiparallel L-glutamic acid molecules. The diaminopropane in the DL complex is sandwiched between two antiparallel glutamic acid molecules of the same chirality and this forms the basic packing unit. This might be the dominant form of interaction between L-glutamic acid and diaminopropane in solution. The structures reveal the adaptability of the polyamine backbone to different environments and the probable reasons for their choice as biological cations.

Structure of a monochloro bridged polymeric copper(II)-di-2-pyridylamine complex: [Cu(dipyam)Cl(NO3)].0.5H2O

Di-2-pyridylaminechloronitratocopper(II) hemihydrate, [CuCl(NO3)(C10H9N3)].0.5H2O, M(r) = 341.21, monoclinic, P2(1)/a, a = 7.382 (1), b = 21.494 (4), c = 8.032 (1) angstrom, beta = 94.26 (1)-degrees, V = 1270.9 angstrom 3, Z = 4, D(m) = 1.78, D(x) = 1.782 g cm-3, lambda(Mo K-alpha) = 0.7107 angstrom, mu(Mo K-alpha) = 19.47 cm-1, F(000) = 688. The structure was solved by the heavy-atom method and refined to a final R value of 0.034 for 2736 reflections collected at 294 K. The structure consists of polymeric [Cu(dipyam)Cl(NO3)] units bridged by a chloride ion.

X-ray studies on crystalline complexes involving amino acids and peptides. XXV. Structures of DL-proline hemisuccinic acid and glycyl-L-histidinium semisuccinate monohydrate and a comparative study of amino-acid and peptide complexes of succinic acid

DL-Proline hemisuccinic acid, C5H9NO2.1/2C4H6O4, M(r) = 174.2, P2(1/c) a = 5.254 (1), b = 17.480 (1), c = 10.230 (i) angstrom, beta = 119.60 (6)-degrees Z = 4, D(m) = 1.41 (4), D(x) = 1.42 g cm-3, R = 0.045 for 973 observed reflections. Glycyl-L-histidinium semisuccinate monohydrate, C8H13N4O3+.C4H5O4-.H2O, M(r) = 348.4, P2(1), a = 4.864 (1), b = 17.071 (2), c = 9.397 (1) angstrom, beta = 90.58-degrees, Z = 2, D(m) = 1.45 (1), D(x) = 1.48 g cm-3, R = 0.027 for 1610 observed reflections. Normal amino-acid and dipeptide aggregation patterns are preserved in the structures in spite of the presence of succinic acid/semisuccinate ions. In both the structures, the amino-acid/dipeptide layers stack in such a way that the succinic acid molecules/semisuccinate ions are enclosed in voids created during stacking. Substantial variability in the ionization state and the stoichiometry is observed in amino-acid and peptide complexes of succinic acid. Succinic acid molecules and succinate ions appear to prefer a planar centro-symmetric conformation with the two carboxyl (carboxylate) groups trans with respect to the central C=C bond. Considerable variation is seen in the departure from and modification of normal amino-acid aggregation patterns produced by the presence of succinic acid. Some of the complexes can be described as inclusion compounds with the amino acid/dipeptide as the 'host' and succinic acid/semisuccinate/succinate as the 'guest'. The effects of change in chirality, though very substantial, are not the same in different pairs of complexes involving DL and L isomers of the same amino acid.

Study of the reaction between 1,2,3-trihydroxybenzene and 8-hydroxyquinoline in the solid state

1.2,3-Trihydroxybenzene (THB) reacts with 8-hydroxyquinoline (8HQ) in the solid state forming an orange-coloured charge transfer complex THB* (8HQ)(2). When the reaction was carried out in a petri dish, or when the vapours of 8HQ were allowed to react with solid THB (gravimetric study), the reaction product separated out as good quality, shiny single crystals. X-Ray diffraction studies on single crystals showed that they belong to the orthorhombic system with a = 15.408(1), b = 16.276(1), c = 7.825(1) Angstrom, Z = 4, D-x = 1.413 g cm(-3) and space group Pnaa. From the crystallographic evidence it has been found that the proton of the middle OH group of THB is transferred to the N atom of 8HQ. This accounts for the observed colour change. Kinetic studies on the solid state reaction showed that the 8HQ molecules diffuse towards THB, and the lateral diffusion occurs through surface migration, grain boundary diffusion and vapour phase diffusion. Gravimetric studies of the reaction between solid THB and 8HQ vapour showed that the diffusion of 8HQ molecules into the crystal lattice of THB has a higher energy of activation than that observed when the reactants are in contact. The nature of the crystal packing in the reaction product indicates diffusion of 8HQ molecules into the crystal lattice of THB along the c-axis, to occupy the cavities present between the THB molecules in the unit cell.

Structure of 4,6-Diacetylresorcinol

C10H10O4, M(r) = 194.19, monoclinic, P2(1)/c, a = 7.089 (1), b = 11.361 (1), c = 11.656 (1) angstrom, beta = 100.45 (3)-degrees, V = 922.92 (1) angstrom 3, Z = 4, D(m) = 1.410 (5), D(x) = 1.397 Mg m-3, lambda(Cu K-alpha) = 1.5418 angstrom, mu(Cu K-alpha) = 0.89 mm-1, T = 300 K, F(000) = 408, final R = 0.057 for 1701 observed reflections. The molecule is almost planar, with O(9) and O(12) of the acetyl groups deviating by 0.074 (1) and 0.071 (2) angstrom from the mean plane of the benzene ring. The bond lengths and bond angles of the benzene ring are normal. There are intramolecular hydrogen bonds between O(9) and H(14) and between O(12) and H(13); there are no intermolecular hydrogen bonds. The molecules are packed in layers parallel to the ac plane and are held together essentially by van der Waals interactions.

Structure of 9[alpha],19-dihydroxy-4-androstene-3,17-dione

C19H26O4, M(r) = 318.41, orthorhombic, P2(1)2(1)2(1), a = 10.591 (1), b = 11.133 (1), c = 13.657 (2) angstrom, V = 1610.29 angstrom 3, Z = 4, D(m) (flotation in KI) = 1.301, D(x) = 1.313 g cm-3, Mo K-alpha, lambda = 0.7107 angstrom, mu = 0.85 cm-1, F(000) = 688, T = 293 K, R = 0.057 for 1253 significant reflections. The A ring is disordered with atoms C(2) and O(19) occupying two possible sites. The molecules are held together by a hydrogen bond [O(9)...O(17) = 2.89 angstrom].

Non-existence of tight neighborly triangulated manifolds with beta(1)=2

All triangulated d-manifolds satisfy the inequality ((f0-d-1)(2)) >= ((d+2)(2))beta(1) for d >= 3. A triangulated d-manifold is called tight neighborly if it attains equality in this bound. For each d >= 3, a (2d + 3)-vertex tight neighborly triangulation of the Sd-1-bundle over S-1 with beta(1) = 1 was constructed by Kuhnel in 1986. In this paper, it is shown that there does not exist a tight neighborly triangulated manifold with beta(1) = 2. In other words, there is no tight neighborly triangulation of (Sd-1 x S-1)(#2) or (Sd-1 (sic) S-1)(#2) for d >= 3. A short proof of the uniqueness of K hnel's complexes for d >= 4 under the assumption beta(1) not equal 0 is also presented.

Embriogenesis somatica en reproduccion in vitro del cultivo de piña (Ananas comosus L. Merr) cultivar MD-2

La piña es reconocida como una de las frutas más finas de las re giones tropicales y se denomina la reina de todas las frutas. En Nicaragua se consume principalmente como frut a fresca, refresco y otros productos derivados de la industrialización de la piña. Para el estudio de embriogénesis somática en piña cultivar MD - 2 se realizaron diferentes variantes de medios de cultivo en las fases de inducción, multiplicación, formación de plantas , enraizamiento y aclimatación de plantas. En la fase de inducción de callo s con el empleo de explante s de hojas no se produjo iniciación de callos, pero con explantes de ápices meristemáticos se obtuvieron los mejores resultados en los medios qu e contenían 1 mg/l de 2,4 - D y 0 y 0.2 mg/l 6 - B encil - amino - purina . La multiplicación de callos fue mejor en los medios de cultivos que se le suministraron 2 mg/l de Ácido Indolacético y 1.8 mg/l de A cido - naftaleno - acético con agua de coco al 1 5% y 400 mg/ l de carbón activado . La formaci ón de pla n tas se favoreció en el medio de cultivo que contenía 0.38 mg/l de Ácido Indolbutírico y dos mg/l de 6 - Bencil - Amino - Purina. En l a fase de enraizamiento de las plantas resultó ser mejor el medio de cultivo que con tenía 0.5 mg/l de Ácido Indolacé tico y 40 g/l de sacarosa . En la fase de aclimat iz ación de plantas los medios que previamente se desarrollaron en las cinco variantes de medios en la fase de en raizamiento presentaron los mejores resultados con respecto al po rcen taje de sobrevivencia.

Produção de carotenoides em culturas in vitro de Cleome rosea Vahl ex DC (Capparaceae) e avaliação de sua toxicidade e potencial antioxidante

A produção e a otimização de substâncias de valor medicinal têm sido alcançadas pelo uso das técnicas de cultura de tecidos vegetais, que têm apresentado grande relevância quando se considera o status de conservação de uma espécie ou sua ocorrência em ambientes ameaçados. No presente trabalho foi avaliada a produção de carotenoides em culturas de calos e células em suspensão de Cleome rosea Vahl ex DC, espécie nativa encontrada em áreas de restinga nos estados do Rio de Janeiro e de São Paulo. Plantas micropropagadas obtidas a partir de raízes produzidas in vitro foram usadas como fonte de explantes para o início das culturas de calos. A produção de massa calogênica foi avaliada em meio MS suplementado com diferentes concentrações das auxinas ácido 2,4-diclorofenoxiacético e ácido 4-amino- 3,5,6-tricloropicolínico, na presença de luz ou no escuro. O uso de diferentes meios básicos de cultura (B5, Nitsch, White) também foi avaliado. A calogênese foi induzida em todos os tratamentos, entretanto a maior produção de biomassa foi alcançada pelas culturas mantidas na presença de luz. A maior produção de massa calogênica foi obtida em culturas iniciadas no meio MS suplementado com 0,2 mg.L-1 de 2,4-D. A exposição das culturas à luz foi um fator essencial para a produção de carotenoides, que só ocorreu nas culturas mantidas nessa condição. Culturas de calos foram submetidas a tratamentos com substâncias elicitoras (extrato de levedura, metil jasmonato, quitosana) em diferentes concentrações e por um período de exposição de sete ou 14 dias visando otimizar a produção do pigmento. A maior produção de carotenoides nas culturas elicitadas foi alcançada com o tratamento com metil jasmonato (MJ) na concentração de 300 μM, independentemente do tempo de exposição ao elicitor. Análises cromatográficas mostraram que o processo de elicitação com MJ induziu ao aumento na produção de β-caroteno. Calos elicitados nessa condição foram usados para iniciar culturas de células em suspensão (CCS). Estas culturas foram acompanhadas por três subculturas realizadas a cada 20 dias, durante a fase exponencial de crescimento. Embora as CCS tenham mantido uma produção de biomassa constante ao longo das subculturas, os valores de produção de carotenoides foram inferiores àqueles alcançados pelas culturas de calos e não houve diferenças estatísticas significativas quando comparadas às CCS iniciadas a partir de calos não elicitados. Extratos de calos produzidos em meio MS suplementado com 0,2 mg.L-1 de 2,4-D foram avaliados quanto à sua capacidade antioxidante por meio da incubação dos extratos com DNA plasmidial em presença de cloreto estanoso (SnCl2), um potente agente redutor capaz de produzir quebras na molécula de DNA. Os extratos foram avaliados em concentrações crescentes (25 - 500 μg.mL-1) e apresentaram uma proteção dose dependente à ação do SnCl2. Estudos de toxicidade com o modelo de Artemia salina demonstraram que os extratos não apresentaram toxicidade nas concentrações avaliadas. Os resultados alcançados mostram que a elicitação foi eficiente para a otimização da produção de β-caroteno nas culturas in vitro e que os extratos obtidos a partir desses materiais apresentaram atividade antioxidante, indicando o êxito das técnicas de cultura de tecidos para a produção deste metabólito sob condição in vitro.

Agrobacterium-mediated transformation of Kentucky bluegrass

Embryogenic calli of Kentucky bluegrass, named Md, were induced from mature seeds and embryos, and proliferated on medium K3 containing 2,4-dichlorophenoxyacetic acid (2,4-D, 10.0 mumol/L), 6-benzylaminopurine (BAR, 0.5 mumol/L) and K5 which was the K3 medium supplemented with cupric sulfa (0.5 mumol/L) under dim-light condition (20-30 mumol.m(-2).s-1, 16 h light) at 24 degreesC. Embryogenic calli were transformed with plasmids pDM805 Carring bar and gus genes, Which was mediated by an Agrobacterium strain AGL1, four transgenic lines were obtained. The important factors that affect the transformation efficiency and obtain desirable number of transgenic plants included: (1) the quality of embryogenic calli; (2) light condition and time of co-cultivation; (3) concentration of antibiotics used for suppressing the overgrowth of Agrobacterium in the course of transformed plant regeneration; (4) selection pressure, etc. The micro nutrient of cupric had significant influence on the quality of embryogenic calli. This presentation is the first successful protocol of Kentucky bluegrass transformation mediated by Agrobacterium.

杯[4]芳烃配位和超分子化学的研究

本论文依据主客体作用原理，从分子工程出发，主要利用各式杯芳烃主体与不同客体分子和金属离子进行组装，研究这类超分子的合成条件及规律，探讨主客体之间的相互影响及其自组装原理。 在第二章中，首先研究了银氨离子可诱导杯[4]芳烃(L1)形成超分子胶囊，接下来的工作中，我们对杯[4]芳烃进行修饰，合成了两种杯芳烃羧酸配体25, 26, 27, 28-tetrakis(carboxy methoxy)-calix[4]arene (L2) 和25, 26, 27, 28-tetrakis(carboxy methoxy)-p-t-butylcalix[4]arene (L3)；并分别以六次甲基四胺和三苯基膦为中性配体，构筑了一个由胶囊构筑的三维网络结构和一个四核银的簇合物。 在第三章中，用六次甲基四胺作为中性配体与银离子和对磺酸杯[4]芳烃进行组装，得到了一个纳米孔材料，在该结构中，银与六次甲基四胺形成的配位多聚体作为模板，诱导对磺酸杯芳烃排列形成孔道。由于模板的作用，拉大了杯芳烃之间的距离。 在第四章中，用pnno (pyrazine-N,N’-dioxide)作为客体分子，在稀土离子存在的情况下与杯芳烃进行超分子组装。不同的实验方法分别得到了由超分子胶囊构筑的三维网络结构和A-B-A 的双层结构。稀土Nd与 5,11,17,23- tetrasulfonato- 25,26,27,28-tetra- ethoxycarbonylmethoxyl-calix[4]arene (L4)组装时，得到了一个由氢键连接的层状化合物。 在第五章中，在水溶液条件下，[M(bpdo)22H2O]2+ (M=Zn, Cu; bpdo=2, 2’- bipyridine-N, N’-dioxide )诱导对磺酸基杯[4]芳烃形成超分子胶囊；并且该胶囊通过电荷辅助的π•••π作用与[M(bpdo)3]2+组装成纳米孔材料，气体吸附的测试表明该纳米孔对甲醇有一定气体吸附能力。当用稀土离子代替金属离子时，形成了类似的超分子胶囊和孔状结构。结果表明稀土孔材料比过渡金属孔材料具有更好的热稳定性。进一步研究通过改变配体bpdo为tpdo (tpdo=terpyridine-1, 1’, 1’-trisoxide)得到了一个层状化合物。 在第六章中，将新型的有机配体与丙基焦杯芳烃或甲基间苯二酚杯芳烃进行自组装得到新奇的杯芳烃超分子结构。这些新型的有机配体含有N-O或C=O 官能团的有机分子4,4'-dipyridyl N, N'-dioxide (L5), tetra-2-pyridinyl-N, N', N", N"'-tetraoxide- pyrazine (L6) and 1, 10-phenanthroline-5, 6-dione (L7)。它们是具有特殊的氢键受体和空间构型的有机分子，由于氢键等弱相互作用在形成超分子结构中的重要作用，三种不同的有机配体与杯芳烃自组装得到了三种不同的杯芳烃超分子结构。

反式1，4-聚丁二烯的形态和结构研究

高分子材料一般都具有某种特定的结构，这种结构将直接决定着材料的性能。当高聚物从一种结构变为另一种结构时，其材料的性能将发生改变。近来，M.Hikosaka根据聚乙烯结晶的特点，提出了“链滑移扩散理论”，认为对聚合物热处理时，其晶体片层增厚快慢与分子链的滑移扩散能力有关。反式1,4-聚丁二烯(TPBD)在常压下能以六方相稳定存在，是少有的几种具有六方相结构的聚合物。因为其六方相分子链具有较高的构象数，而各个构象之间由于能垒相差不大，构象之间很容易发生转变；因而分子链运动时相对容易，决定了六方相分子链之间的滑移扩散能力较强。为了验证M.Hikosaka的理论，特对样品在六方相温度范围进行热处理。另外由于TPBD在不同的温度下能以两种晶型稳定存在，这两种晶型之间是怎样转变的也是我们关心的问题，而且通过电镜第一次摄得了单斜相和六方相共存的电子衍射。针对上述问题我们进行了下列研究。(1)以三氯化钒体系，稀土催化剂体系合成了两种分子量的反式1,4-聚丁二烯，用IR，NMR分析高分子量样品的反式1,4结构含量为96.2%，低分子量样品反式l,4结构含量为91.2%。对两种分子量样品进行DSC研究，结果表明低分子量样品的转变温度。熔融温度均比高分子量样品低；用Thomoson-Gibbs方程计算了该样品的片层厚度，并与样品的SAXS实验结果对照，认为这种转变温度和熔点的差异除了与1,2-结构的含量有关外，也与不同分子量具有不同的片层厚度有很大关系。(2)对不同分子量的TPBD进行WAXD实验，研究了其在不同温度下的相行为及单斜相向六方相的相转变过程。以PLM为手段跟踪观察了低分子量样品的相态转变，发现许多晶粒在相转变时从视场中消失。用电镜观察到了单斜相电子衍射，六方相电子衍射及单斜相和六方相共存的电子衍射， 并发现两相结构的形貌没有大的差别。(3)用Cerius~2软件模拟了单斜相结构和六方相结构的分子链堆砌，认为单斜相向六方相发生转变时，六方相分子链构象与单斜相分子链构象相比，有序度较低，从而使其堆砌结构变得松散。同时也模拟了单斜相和六方相在晶带轴为[001]方向的电子衍射，实验观察只能得到计算机模拟所得的单斜相和六方相内层的几个电子衍射点。(4)对低分子量样品在64 ℃热处理1小时后进行的DSC，WAXD，SAXS研究表明，样品的片层厚度显著增大，结晶度也相应提高。(5)研究了高分子量样品在85 ℃和低分子量样品在53 ℃热处理不同时间后，所得的DSC曲线。结果表明随时间增加，TPBD的转变峰温度值明显增加；而且发现在前5分钟内处理样品时，结晶度都有明显增加，处理样品5分钟以后结晶度增长缓慢。对高分子量样品四次升降温时，发现降温曲线有肩峰出现，但升温曲线没有肩峰出现，把肩峰的出现归结于有小尺寸亚稳定晶体的形成。(6)对高分子量样品的六方相等温结晶数据及对由熔体快速冷却到一定温度生成单斜相的等温结晶数据进行处理，得到平衡熔点为476K，比文献值高。并利用Thomoson-Gibbs方程，得到了单斜相和六方相的温度对尺寸倒数的相图，确定了在一定尺寸下单斜相和六方相稳定存在的温度范围。(7)用电镜观察了在70 ℃热处理不同时间后所得形貌图，并讨论了样品在六方相中热处理时，样品聚集体的聚集方式。(8)研究了两种分子量样品溶液结晶时所得的球晶形貌，发现其结晶形貌与分子量有关，而且发现摄得的电子衍射是六方相电子衍射，而不是室温下稳定存在的单斜相电子衍射，认为是由于电子辐照使样品升温而发生了晶型转变。(9)用修饰后的Avrami方程，Ozawa，方程分别处理了TPBD非等温结晶数据，由Jeziorny修饰的Avrami方程分析显示TPBD的非等温结晶明显地分为一次结晶和二次结晶两个阶段，指数值n意味着一次结晶和二次结晶的成核种类，Ozawa方程分析不能很好地适用于TPBD的六方相非等温结晶数据，主要是由于Ozawa理论的不精确假定，如二次结晶，结晶温度对片层厚度相关性及整个结晶过程中恒定的冷却函数等。并由Kissinger方程得到六方相的结晶活化能为167.9kJ/mol。

2,3'-联吡啶还原合成毒藜碱、安那他品和异毒藜碱

本论文从2，3'-联吡啶出发，利用两个吡啶环上氮的反应活性差异，选择性合成了单烷基盐1-甲基-2，3，-联吡啶盐、1-甲基-1，一氧-2，3，-联吡啶盐和1'-甲基／节基2，3气联吡啶盐，还原单烷基盐合成了天然生物碱毒黎碱、安那他品和异毒黎碱及其衍生物：对异毒黎碱的合成由还原N，-节基盐后脱节基简化为一步实现还原和脱节基直接得到异毒黎碱。通过用（R）-BINOL和（S）-BINOL对N，-节基异毒黎碱拆分得到了旋光纯的N，-节基异毒黎碱和异毒黎碱，-N，-节基异毒黎碱的旋光度［a］D20：-61．50（c＝2．0，乙醇），卜异毒黎碱的旋光度fa］D20：-14．4"（c-1．0，乙醇）；将C关异毒黎碱用（RMTPA和（s）MT队衍生为Mosher酞胺，应用Mosllel方法确定了C）异毒黎碱手性中心的绝对构型为R型，即（R）-C）异毒黎碱，同时发现，由（R）一MTPA合成的Mosller酞胺中顺式旋转异构体占优。而通常在环胺的Mosller酞胺中，是反式旋转异构体占优。这一例外被MollteCarlo模型模拟计算结果解释：稀溶液中C卜异毒黎碱的Moshel－酞胺，顺式构型能量上比反式更有利。不对称合成天然生物碱更具有挑战性。对异毒黎碱还原合成中的呱l淀烯类中间体，用BINAP-灿催化体系进行了催化不对称还原的合成研究，氢化N'-节基-1，，4，，5，，6，-四氢一2，3，一联吡陡时得到了最高为21．5％的对映体选择性，而对N'-节基一1，，2'，5'，6，-四氢-2，3'一联吡陡的氢化则只得到了不超过10．0％的对映体选择性。

含反-1,4聚丁二烯链段的顺-1,4聚丁二烯橡胶的合成、（金+监）认和性能

顺-1,4聚丁二烯橡胶是合成橡胶中的第二大品种，具有耐磨、生热低等的优点，一贯是轮胎胎面胶的重要组成部分。但随着子午线轮胎的出现和大量使用，对母胶强度和轮胎的耐湿滑性提出了更高的要求，而利用应力下结晶有可能提高母胶强度，为此我们开展了合成含少量反-1，4聚丁二烯链烯链段的顺-1，4-聚丁二烯橡胶的研究。本文报导了它的合成、（金+监）认及生胶、母胶和硫化胶的性能。合成中我们试探了既能使丁二烯反-1，4聚合和顺-1，4聚合，又能使内双键打开的钒和钴的络合催化体系，采用以钒催化剂先使丁二烯反-1，4聚合，在达到转化率10-20%时，以钴催化剂将剩余的丁二烯进行顺-1，4聚合的步骤，再寄于同时发生催化接枝的想法来实现反-1，4-聚丁二烯链段和顺-1，4聚丁二烯链段的共聚合。实验中考查了合成的条件，对得到的产物用溶解度法、扭摆测定动态力学行为，X射线衍射分析、电镜分析以及线膨胀等手段和以等量的反-1，4聚丁二烯和顺-1，4聚丁二烯的共混胶进行了对比，证明我们得到的产物是反-1，4聚丁二烯链段和顺-1，4聚丁二烯的接枝共聚物，不是无规共聚物，也不是两种均聚物的共混胶。文中讨论了聚合反应机理。对含有不同反-1，4链段和分子量的共聚胶的生胶性能，混炼胶性能进行了初步考察，结果表明，特性粘数（[η]）_(甲苯）~（30℃）在2（分升/克）左右，含反-1，4链段9-20%的顺丁共聚胶，不含凝胶，其生胶强度和混炼胶强度较镍顺丁橡胶高一倍以上，挤出行为特好。看来这种共聚胶将为子午线轮胎所欢迎的新顺丁品种。对这种胶的硫化配方和硫化条件条件尚待进一步研究。初步结果表明，可与一般顺丁橡胶接近，而抗撕性能又比一般顺丁高。利用本工作的实验方法制备不同结构链段的共聚胶还不多见。因此，除了工作本身研制成了一种新的顺丁品种外，对利用本方法，改善其他橡胶品种，设计研制新的高分子和研究反应机理走出了一条新路。

两种端乙炔基芳醚砜单体的核磁研究双端乙炔基芳醚砜溶液聚合反应和催化剂的研究非等温DSC法测双[4－（4－乙炔基苯氧基）苯基]砜（酮）的本体聚合反应动力学

本工作对下面两种端乙炔基芳醚砜单体的核磁共振谱进行了研究。通过加入位移试剂Eu（fod）_3引起共振吸收峰化学位移值的变化趋热及同核去偶，'H选择质子去偶的方法分别对其'H谱和~(13)C谱（COM）做了归属。在确认对化合物＜I＞'H谱和~(13)C谱（COM）归属的基础上，演绎出三种苯环上取代基团的'H和~(13)C化学位移取代参数。这些基团的取代参数目前在文献中尚未见报导，用这些参数来计算化的＜II＞的'H和~(13)C谱（COM）化学位移值时，与观测值有较好的吻合。本工作对双[4－（4－乙炔基苯氧基）苯基]砜的溶液聚合反就（DMSO）作溶剂、PdCl_2·2DMSO作催化剂）进行了研究。采用高压液体色谱和旋转薄层色谱分离反应的各种中间产物，通过中间产物的红外和'HNMR谱变化，演绎聚合反应的历程，还在'H核磁谱仪样品管内做了短时间反应，跟踪记录反应信息。聚合产物自始至终可分为溶于二氯甲烷和不溶于二氯甲烷两部分。在整个反应过程中，可溶性产物逐渐转变成不溶性产物，色谱分析表明可溶性产物是由未反应的单体、线型及环状低聚物、聚合度在9－10的齐聚物和少量聚合度更高的组分构成的。从称重测量不溶性产物所占比重和可溶性产物的高压液体色谱诸吸收峰峰高的变化，推算出聚合反应过程中单体、主要中间产物的变化趋势。可溶性产物的红外光谱中2920、1665－25、960－930、890，760－730 cm~(-1)吸收峰和'HNMR谱中的5.3, 3.5ppm吸收表明产物具有共轭多烯结构。'HNMR谱在芳核质子区出现7.7ppm吸收峰表明反应初期已有环化现象，这点与本体聚合反应是不同的。不溶性产物除聚合度或交联度高以外，与可溶性产物在结构上也有差异，其芳化程度高很多。从不同反应时间中间产物的红外和'HNMR谱（可溶部分）变化，显示了溶液聚合反应历程十分复杂，同时存在着几种反应。主反应是氯化钯络合物引发的配位络合聚合反应，钯络合物与单体的端乙炔基络合生成活性中心，三键在顺式位打开，生成共轭多烯增长链。链增长过程中伴随着热引起的多烯链顺－反异构化，部分反式多烯分子内环化，继而脱质于芳化生成三取代苯形式的环交联，芳化过程中可发生链的局部断裂。最终产物是共轭多烯链间通过芳环，炔烯桥交联成的体型聚合物。多烯和端乙炔基之间，多烯－多烯之间可发生Diels-Alder反应，因此溶液聚合产物再经短时间热处理，芳化程度增高，玻璃化温度大幅度提高。另外还研究了反应的溶剂效应和增加因含量对反应产率的影响，发现用氯仿和二氯甲烷作溶剂有利于共轭多烯链的顺－反异构化，固含量在2.25－11.25％范围，聚合产率变化不大。本文还对适用于双端炔基聚合反应的催化剂作了广泛的试探，首先考察了若干钯络合物，发现除PdCl_2·2DMSO外，PdCl_2·2MeCN、PdCl_2·2PhCN络合物也可作为双端炔基芳醚砜溶液聚合的催化剂。钴、镍的膦络合物[Co(PPh_3)_2]Cl_2、[Ni(PPh_3)_2]Cl_2可使双端炔基芳醚砜环化生成环状低聚物。极性溶剂四氢呋，二氧六环。氯仿和三氯甲烷可以用作Ziegler-Natta催化剂聚合双端炔基芳醚砜的溶剂。用AlEt_3-Ti(OBu)_4催化得到的聚合物以顺式多烯为主，玻璃化浊度高于250℃，热形变稳定性好。Al/Ti比在6－8时催化活性较高。用稀土体系的Ziegler-Natta催化剂AlEt_3-NdCl_3·2THF、AlEt_3－（CF_3COO）_3Nd也可得到类似的催化效果。制备了以双氰为配位基的高分子－钯络合物，在催化双端炔基单体聚合时具有与类似的低分子钯络合物PdCl_2·2MeCN相近的效果。改变高分子催化剂的N／Pd比未出现明显的活性高峰。这部分工作还有待深入，予期在进一步深入研究之后，该高分子催化剂可用于制备双端乙炔基芒醚砜增强复合材料的连续化浸渍工序，让单体的氯仿溶液流经高分子－钯络合物填充的柱子形成齐聚物后，再浸渍涂层，可缩短成型的热固化时间，具有较大的经济意义。用非等温DSC法测定了双[4-(4-乙炔基苯氧（基)苯基]砜和双[4-(4-乙炔基苯氧基)苯基]酮的本体热聚合及有PdCl_2·2DMSO存在下的催化聚合的反劝力学参数，并与文献报导的（3－乙炔基苯氧基）苯模型物和双[4－（3－乙炔基苯氧基）苯基]砜的本体热聚合反应动力学参数进行比较。经电子计算机最小二乘曲线拟合程序汞得的结果表明表现反就活化能Eap，指数前因子A均与DSC的升温速率和转化率无关。讨论了模型物端乙炔基的位置和链上砜基，羰基的存在对聚合反应的影响，还通过对DSC升温过程中试样的红外光谱跟踪，解释了DSC峰表征的化学反应。