用含螺环原碳酸酯的预聚物改性环氧树脂的研究

合成了一个新的螺环原碳酸酯单体，３，９ 二羟甲基 ３’，９’ 二苯基 １，５，７，１１ 四氧杂螺环［５，５］十一烷，它与二苯甲烷二异氰酸酯（ＭＤＩ）反应生成了低分子量预聚物，用该预聚物对环氧树脂进行改性，可以减少残留在树脂基体中的环氧基团，这说明该预聚物与环氧树脂之间发生了共聚固化反应．基体的Ｔｇ和热稳定性随预聚物加入量的增加而降低，但改性环氧树脂的粘接强度则随预聚物的加入量的增加而增加，螺环基团上的取代基对改性环氧树脂基体也有一定的影响，作者对上述试验观察到的现象进行了讨论．     

含螺环原碳酸酯的预聚物对环氧树脂的改性研究

Bailey发现螺环原酸酯和螺环原碳酸酯等单体在阳离子引发剂作用下进行双开环聚合反应时，伴随着体积膨胀［‘j．这一现象引起了高分子材料学家的极大兴趣，因为树脂固化时产生体积收缩，会使树脂材料内部产生收缩应力，是导致材料力学性能下降，使用寿命降低的主要原因之一．例如，用不饱和螺环原碳酸酯改性的某种补牙材料与牙的粘接力比不含螺环原碳酸酯的大一倍，并且改善了冲击强度而不改变模量．更为重要的是，由于体积稍微膨胀，补牙材料与牙齿间无缝隙，从而消除了在缝隙中繁殖细菌的可能性，达到既结实又卫生的目的【‘］．利用螺环…     

含螺环原碳酸酯齐聚物的合成表征及与环氧树脂的固化反应

合成了一种新的带羟基的螺环原碳酸酯，根据它与ＭＤＩ或ＨＤＩ的不同配比，制备了分子量不同的预聚物，其结构得到了核磁和红外数据的证实。用示差扫描量热仪和红外跟踪环氧树脂及其与预聚物混合后的固化反应过程。     

脂环族环氧树脂和螺环原碳酸酯的光引发正离子共聚合

<正> 无收缩单体-1,6,8,13-四氧螺[7,7]十三碳烷(SOC_7)和3,4-环氧基环己烷甲酸3',4'-环氧基环己烷甲酯(ERL-4221)的光引发正离子共聚合的研究结果表明,少量SOC_7加到ERL-4221体系中可抑制固化收缩没有明显降低热性能。ERL-4221对SOC_7的合适克分子比为4比1,由此得到T_g为203℃而聚合时体积收缩为4.4％的交联共聚物。     

螺环原酸酯改性环氧树脂的研究

合成了一个新的螺环原酸酯单体,即带有螺环原酸酯结构单元的环氧树脂（Ｅ ５４）．用该单体对环氧树脂进行改性,可以减少残留在树脂基体中的环氧基团,这说明该单体与环氧树脂之间发生了共聚固化反应．基体的Ｔｇ和热稳定性随预聚物加入量的增加而降低,但改性环氧树脂的粘接强度则随预聚物的加入量的增加而增加．对上述试验观察到的现象进行了讨论,并测试了改性环氧树脂基体的力学性能．     

聚丙撑碳酸酯增韧环氧树脂的研究

研究了聚丙撑碳酸酯（ＰＰＣ）对环氧树脂（ＥＰ）的改性作用、加入２０～３０Ｐｈｒ的ＰＰＣ，环氧树脂力学性能可以大幅度提高，粘接剪切强度为１２３３ＭＰａ，冲击强度为１６．７８ｋＪ／ｍ２；而纯环氧树脂固化物，其剪切强度为９．３６ＭＰａ，冲击强度为９．９９ｋＪ／ｍ２。ＳＥＭ和ＤＳＣ观测表明ＰＰＣ／ＥＰ体系呈两相结构。     

聚(碳酸丁二醇酯-co-异山梨醇碳酸酯-co-螺环碳酸酯)的制备与性能研究

通过两步熔融缩聚法合成了一系列基于碳酸二苯酯、1,4-丁二醇、异山梨醇和螺二醇的三元共聚碳酸酯（PBISC），其结构和组成经¹H NMR和¹³C NMR表征，并采用GPC、 TGA、 DSC、 WXRD和拉伸试验分别对PBISC的性能进行研究。结果表明：PBISC共聚物的玻璃化转变温度为63~72 ℃，T_d，max值接近350 ℃， PBISC共聚物具有较低的结晶性能。     

螺环原碳酸酯的单体合成及阳离子聚合

螺环原碳酸酯的单体合成及阳离子聚合袁金颖（合肥工业大学化工学院，合肥２３０００９）潘才元白如科（中国科学技术大学材料科学与工程系，合肥２３００２６）关键词合成螺环原碳酸酯阳离子聚合双开环聚合反应中图分类号Ｏ５２３．６２４Ｂａｉｌｅｙ于１９７２年发现，...     

聚丙撑碳酸酯／环氧树脂体系的力学性能

研究了聚丙撑碳酸酯／环氧树酯固化产物的动态力学性能和力学性能，考察了ＰＰＣ的分子量、含量对力学谱和力学性能的影响．结果表明，随ＰＰＣ含量增加，ｔａｎδ半峰宽增加，ＰＰＣ含量在２０～３０份时力学性能达最佳值，ＰＰＣ的分子量对力学性能的影响不大，但对动态力学和相区尺寸稍有影响。     

环碳酸酯开环聚合物制备、性能和应用研究进展

综述了近年来环碳酸酯开环均聚与共聚产物的制备、性能与应用研究进展     

3，9－二羟乙基－3＇，9＇－二苯甲基－1，5，7，11－四氧杂螺环［5，5］十一烷的合成和聚合反应

从两二酸二乙酯、氯乙酸乙酯和氯苄出发，经ＬｉＡｌＨ４还原，合成新的二元醇，进而合成新的螺环化合物：３，９－二羟乙基－３＇，９＇－二苯甲基－１，５，７，１１－四氧杂螺［５，５］十一烷．该化合物的结构由它的氢和碳－１３核磁共振谱、红外光谱和元素分析得到证明．该单体在三氟化硼乙醚络合物的作用下进行开环聚合反应．由于环上四个取代基的稳定作用，聚合物的收率比较低（产率１０％左右）．通过对聚合物的结构分析，提出了这一单体的阳离子开环聚合反应机理．对随聚合温度升高，聚合物中酯基／苯基的克分子比降低，以及本体聚合时得到交联聚合物等一系列现象作了探讨．     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Keggin Polyoxometalate [CuI(2,2''-bipy)2]3[PWⅥ12O40]

A Keggin-type tungstohosphate compound [CuI(2,2'-bipy)2]3[PWVI12O40] 1 (bipy = bipyridine) was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C60H48Cu3N12O40PW12) crystallizes in the monoclinic system, space group P21/c with a = 16.9837(10), b = 17.9732(13) c = 27.8701(13)(A), β = 96.1039(10)°, V = 8459.2(9)(A)3, Mr = 4004.89, Z = 4, Dc = 3.145 g/cm3, μ = 17.089 mm-1, F(000) = 7208, S = 1.005, the final R = 0.0469 and wR = 0.0827 for 10807 observed reflections (I > 2σ(I)). Compound 1 consists of one discrete normal Keggin polyanion [PWVI12O40]3- and three isolated coordinated cat- ions [CuI(2,2'-bipy)2]+. Significantly, there exist three crystallographically independent asymmetric reduced copper (I) centers in 1. Furthermore, the compound shows strong photoluminescence property in solid state at room temperature.     

Synthesis,Crystal Structure and Luminescent Property of a 2-D Hybrid Constructed from [Pb_2I_4] Subunits

A novel organic-inorganic hybrid compound, [Pb2I4（bipy）], （bipy = 4,4′-bipyridine）, was synthesized by self-assembly and its structure was determined by X-ray crystallography method The crystal belongs to the monoclinic system, space group P2 1/c with α = 4.4691（9）, b = 15.385（3）, c = 14.136（3） A, β = 93.75（3）°, V= 969.9（3） A^3, Mr = 1078.16, Dc= 3.692 g/cm^3, F（000） = 916, μ = 23.688 mm^-1, Z = 2, the final R = 0.0395 and wR = 0.0887 for 1557 observed reflections with I 〉 2σ（I）. The title compound presents a two-dimensional layer-like structure constructed from [PbI5N] octahedron and bis-bridging ligand 4,4′-bipyridine. The fluorescence of the title compound is also discussed in this communication.     

四-α-(2，2，4-三甲基-3-戊氧基)酞菁金属配合物(M=Co，Ni，Cu，Zn)的合成与光谱性质(英)

A series of [tetra-α-(2,2,4-tirmethyl-3-pentoxy) phthalocyaninato] metal complexes(M=Co, Ni, Cu, Zn)were prepared by cyclotetramerization of 3-(2,2,4-tirmethyl-3-pentoxy)phthalonitrile with corresponding anhydrous metal salts， using 1.8-diazabicyclo[5.4.0] undec-7-ene (DBU) as the catalyst. HPLC analysis shows that one isomer predominates in the product of nickel complex, while at least two main constitutional isomers exist in the product of other metal complexes. The complexes (in the form of mixture of constitutional isomers) were characterized by elemental analyses, MS, IR and UV-Vis spectroscopy.     

Synthesis,Crystal Structure and Magnetic Property of Sanwich‐Type Heteropolyoxometalate Na9[(Na(H2O),}3{Cu(H20)}3(BiW9O33)2] 42H2O

The heteropolytungstate Na₉[{Na(H₂O)₂}₃{Cu(H₂O)}₃(BiW₉O₃₃) 42H₂O is obtained by the reaction of Na₂WO₄·2H₂O, Bi(NO₃)₃ · 5H₂O with CuCl₂ · 2H₂O at pH≠6. The structure and chemical composition are determined by X‐ray diffraction analysis and elemental analysis. The crystal data and main structure refinement are: a = 1.410(3) nm, b=2.338(5) nm, c=3.173(6) nm, β=98.06(4)°. V= 10.354(35) nm³. monoclinic crystal system, space group: C2/c, Z = 4, R₁= 0.0471. wR₂ = 0.0642 I>2σ(I)]. R₁= 0.1371, wR₂ = 0.0868 (all data). [(Na(H₂O)₂}₃{Cu(H₂O)}₃W₉O₃₃)₂]^9– has D₃₄ symmetry. IR, UV‐vis spectra, TG curve and magnetic property of the complex were also discussed. The compound exhibits an antiferromagnetic coupling with J= ‐8.08 cm^?1 and g =2.21.     

Single-Stage Extraction and Separation of Co2+ from Ni2+ Using Ionic Liquid of [C4H9NH3][Cyanex 272]

The purpose of this study was to optimize the extraction conditions for separating Co²⁺ from Ni²⁺ using N-butylamine phosphinate ionic liquid of [C₄H₉NH₃][Cyanex 272]. A Box–Behnken design of response surface methodology was used to analyze the effects of the initial pH, extraction time, and extraction temperature on the separation factor of Co²⁺ from sulfuric acid solution containing Ni²⁺. The concentrations of Co²⁺ and Ni²⁺ in an aqueous solution were determined using inductively coupled plasma-optical emission spectrometry. The optimized extraction conditions were as follows: an initial pH of 3.7, an extraction time of 55.8 min, and an extraction temperature of 330.4 K. The separation factor of Co²⁺ from Ni²⁺ under optimized extraction conditions was 66.1, which was very close to the predicted value of 67.2, and the error was 1.7%. The equation for single-stage extraction with high reliability can be used for optimizing the multi-stage extraction process of Co²⁺ from Ni²⁺. The stoichiometry of chemical reaction for ion-exchange extraction was also investigated using the slope method.     

一种含[Ni(CN)4]2-和[Cu(pn)]2+构筑元组成的超分子配合物的合成、单晶结构和磁学性质

A cyano-bridged heterometallic supramolecular complex {[Cu(pn)]₃[Ni(CN)₄]₃}_n (1) has been synthesized and structurally characterized by single crystal X-ray diffraction. 1 displays an interesting 3D structure formed by μ₄, μ₃-[Ni(CN)₄]^2- tectons bridging five-coordinated and six-coordinated Cu(II) ions. The magnetic property shows that 1 behaves as weakly ferromagnetic interactions between the adjacent Cu(II) ions through the diamagnetic spacer NC-Ni-CN. CCDC: 624387.     

一维链状氰根桥联配合物[Pr(bet)_2(H_2O)_3Fe(CN)_6]_n的合成、晶体结构和磁性

以K3Fe(CN) 6 ,甜菜碱和Pr(NO3) 3·6H2 O合成了一维链状氰根桥联配合物 [Pr(bet) 2 (H2 O) 3Fe(CN) 6 ] n,并通过元素分析、红外光谱进行了表征。利用单晶X射线四圆衍射测定了配合物的晶体结构 ,晶体属正交晶系 ,P2 1 2 1 2 1 空间群 ,晶胞参数a =0 9634 ( 2 )nm ,b =1 45 5 6( 3)nm ,c =1 7798( 9)nm ,V =2 495 9( 9)nm3,Dc=1 70 6Mg·m3,Z =4,GOF =0 970 ,F( 0 0 0 ) =12 84,R1 =0 0 30 7。变温磁化率 ( 1 8～ 30 0K)表明在Pr3 和Fe3 离子间存在弱的反铁磁相互作用。     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Property of a Novel Coordination Polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4''-bpy)

A novel coordination polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4’-bpy) (Mr = 928.51) was synthesized by the hydrothermal reaction of EuCl3·6H2O, adipic acid and 4,4’-bpy, and determined by elemental analysis, IR spectroscopy, thermal gravimetric analysis, single-crystal diffraction and fluorescence property. X-ray analysis reveals that a three-dimensional network has been formed between Eu3+ by carboxyl of adipic acid. The crystal is of orthorhombic, space group Pbcn with a = 21.870(7), b = 7.652(2), c = 19.624(6) (A), V = 3284.1(17)(A)3, Z = 4, Dc = 1.878 g/cm3, μ = 3.854 mm-1, F(000) = 1824, R = 0.0345 and wR = 0.0565. The coordination polymer exhibits intensive red light under UV excitation at room temperature, which is attributed to the 5D0→7F2 transition of Eu(Ⅲ) ions.