2-亚甲基丁二酸酐和甲基丙烯酸甲酯的共聚反应研究

2—亚甲基—丁二酸酐(M_1,ITANH)和甲基丙烯酸甲酯(M_2,MMA)在四氢呋喃(THF)中以过氧化二苯甲酰(BPO)作引发剂进行自由基共聚合。由作图法衣得这两种单体在66℃的共聚竞聚率:表明它们趋于嵌均共聚。用粘度法和GPC测量了共聚物的分子量和分子量分布。共聚物在温和的条件下进行部分水解,得到一带有短的羧基侧链的聚电解质[11]。将[11]与无机盐LiClO_4混合后测得电导率δ-2.8272×10~(-4)S·cm~(-1),表明它具有较好的离子导电性。     

聚酰胺-聚ε-己内酯多嵌段共聚物合成、表征及反应动力学的研究

本文采用双羧基尼龙1010预聚物和双羟基聚δ-己内酯预聚物经熔融缩聚制得了不同嵌段链长度和不同软硬链段含量的尼龙1010-聚δ-己内酯多嵌段共聚物,并通过分子量(VPO)、核磁共振谱(~1H NMR)和热分析法(DSC)对该共聚物进行表征。同时,对尼龙1010和聚δ-已内酯熔融缩聚反应动力学作了研究。结果表明,该反应为二级反应,活化能为ΔΕ=58.2kcal/mol,反应常数K=1.36×10~(22)·e~(-2.93×10~4/T)。     

碳棒涂膜式离子选择电极的研究 Ⅱ.13,14-苯并-1,4,8,11-(15-冠硫醚-4)(TTX)-PVC膜银电极的研制

用合成的13,14-苯并-1,4,8,11-(15-冠硫醚-4)(TTX)为中性载体,溶于加有增塑剂邻苯二甲酸二辛酯(DOP)的聚氯乙烯(PVC)四氢呋喃(THF)溶液中制成涂膜溶液,将溶液涂布于石墨碳棒上制成银电极.其对银离子的线性响应范围为5×10~(-6)～1×10~(-1)mol·dm~(-3)检出下限为1×10~(-6)mol·dm~(-3),响应斜率为65mV,对Hg~(2+)、Cu~(2+)、Pb~(2+)、Cd~(2+)、Zn~(2+)的选择性系数分别为8×10~(-2)、5×10~(-3)、1×10~(-4)、5×10~(-4)、1×10~(-5),pH适用范围为1.0～5.5,内阻小于1MΩ.通过实验比较其主要性能与7601型商品银电极相近,在结构简单、制作方便及成本低廉等方面颇具特色.使用TTX作中性载体制成碳棒涂膜式银电极目前尚未见有报道.     

[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O配合物单晶的ESR研究

研究了咪唑桥联异三核配合物[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O与同构配合物[(NH_3)_5CoImZn(dien)ImCo(NH_3)_5]·4H_2O混合单晶在低温(100 K)下的ESR。应用适于求非同轴g张量和A张量的最小二乘法拟合技术,解出标题配合物的g张量和A张量主值分别为:g_1=2.246,g_2=2.093,g_3=2.048,A_1=1.63×10~(-2)cm~(-1),A_2=0.38×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)及g_1=2.245,g_2=2.090,g_3=2.051,A_1=1.64×10~(-2)cm~(-1),A_2=0.37×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)。配合物Cu~(2+)的4s、3d轨道上的电子自旋密度分别为0.018和0.557。Cu~(2+)与配体间的键有较强的共价性。     

聚甲基丙烯酸甲酯的苯溶液粘度对切变速度的依赖性 Ⅱ.用光散射法测定特性粘数分子量关系

在不同外加水压下作者等用毛细管粘度计测定了聚甲基丙烯酸甲酯五个分级试样的苯溶液粘度,并用光散射法在丙酮溶液中测定了重均分子量,得到下列特性粘数、分子量关系式(25°)。不加外压时:[η]=3.80×10~(-3)M~(0.79)毫升/克S_R=55达因/厘米~2:[η]_s=12.6×10~(-3)M~(0.70)D_R=5000秒~(-1):[η]_D=8.37×10~(-3)M~(0.73) 适用于分子量范围0.2—4.5×10~6。并指出用实验数据验证性粘数理论时,α值的切变速度依赖性有重要的影响。粘度数据中斜度系数 k′或β值,无论对 S_R 或 D_R 都没有显著的影响,与前人的结果有不同。对光散射测定所用仪器加以叙述并从光散射数据得到了试样的 A_2和<~2>_z 的数值。     

3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3′-甲基氧杂环丁烷的合成及其共聚体研究

以三羟甲基乙烷为原料,通过脱水反应首先制得3-羟甲基-3′-甲基氧杂环丁烷(HMO).HMO再分别与丙烯腈和二缩三乙二醇单甲醚反应得到两个取代氧杂环丁烷单体3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3′-甲基氧杂环丁烷(HMOAN和HMOPEO).再用阳离子开环聚合方法,以BF3.乙醚作催化剂,丁二醇为引发剂,将两类单体共聚即可得到一系列不同组成的共聚物(PAP).利用1H NMR谱图计算了该共聚物中两种不同结构单元的比,结果表明,其与投料比基本吻合.GPC测得该共聚物的数均分子量范围为2 756~5 342,分子量分布为1.26~1.83.DSC测试结果发现,除在225~246 K之间有一个玻璃化转变温度之外,在305~348 K之间还存在一个热转变温度.TGA测得共聚物的分解温度为573 K,远高于目前广泛使用的液体电解质.电导率测试结果表明,AN20的室温电导率可达到1.07×10-5S/cm,353 K时电导率可达到2.79×10-4S/cm,接近实用要求.     

酮型烃型双(4′-苯并-12-冠-4)钠电极的研究

利用合成的亚辛基、亚壬基、亚癸基、辛二酰、壬二酰和癸二酞双(4＇-苯并-12-冠-4)制成了PVC膜钠离子选择电极,研究了各种增塑剂,载体结构,膜组分和不同浓度内充液与电极性能的关系。邻硝基苯辛醚增塑的亚辛基双冠醚钠电极有较好的选择性,选择系数对Li~+、K~+、NH_4~+分别为1.3×10~(-3),8×10~(-2)和6×10~(-3)。对Ca~(2+),Mg~(2+),Sr~(2+),Ba~(2+)均小于2×10~(-4)。线性范围:2×10~(-5)～10~(-1)mol/L(NaCl)。     

高分子量聚α-乙烯呲啶的特性粘数与分子量的关系

在浓硫酸或稀硫酸中聚合得到了高分子量P2VP,~(13)C-NMR谱确定其为无规聚合物。特性粘数(切变速度D=0)与分子量之间的关系为[η]_(D=0)=1.27×10~(-2)(?)_W~(0.70)(在DMF中,25℃,(?)_W=2.66×10~6—10.0×10~6)。在DMF中,25℃,不依赖于切变速度的最大特性粘数为260毫升·克~(-1),相应的分子量M_η=1.74×10~6左右。无扰尺寸(_0/M)=6.08×10~(-18)厘米~2·克~(-1),在DMF 中B参数为1.91×10~(-27)厘米~3。     

聚碳酸酯的裂解色谱分析

聚碳酸酯(简称PC)是一种综合性能优良的热塑性工程塑料。可用酯交换法或光气法生产。本文用裂解色谱(简称PGC)分析了PC在600℃时热降解产物,用PGC法测定了不同来源PC样品的分子量,其结果与粘度法测定的一致。每次分析时间约30min。微量水份对定量精度有影响。从末端基团降解碎片可以鉴别PC聚合工艺中所用的分子量调节剂。 1.PC样品经沉淀分级法获得的级分,用粘度法测定其分子量,分别为:1.25×10~4;1.79×10~4;2.57×10~4;3.56×10~4。     

聚辛烯-1Mark-Houwink常数的确定及其分子量分布研究

本文用GPC结合特性粘度的方法,对聚辛烯-1四氢呋喃体系的Mark-Houmink常数进行订定。数据处理采用了Weiss法和流体力学平均分子量(?)_x两种方法,α值分别为0.701和0.625,相对误差10％左右,所得Mark-Hon-Wink方程Weiss法为:[η]_(THF)~(25℃)=3.89×10~(-4)[M]~(0.701)(?)_x法为[η]_(THF)~(℃25)=4.14×10~(-4)M~(0'625)。本文还研完了聚合反应条件对聚辛烯-1分子量及分子量分布的影响。发现三种TiCl_3为主催化剂,三乙基铝为助催化剂时,其GPC谱图均为双峰型,两个峰的比例随聚合反应条件不同而变化。表明聚合体系至少有两种不同性质的活性中心,有着不同的形成和增长速率。     

聚氯乙烯-马来酸二乙酯分子量与特性粘数关系的研究

<正> 氯乙烯-马来酸二乙酯共聚树脂(氯-马树脂)是一种聚氯乙烯改性树脂。其特点为:可以用廉价的氯化石蜡代替增塑剂DBP,而树脂仍具有好的使用性能。本工作是先将氯-马树脂样品进行童沉淀分级,取得分子量较均一的各个级场,然后用快速动态渗透压和静态渗透压法测走其数均分子量;用光散射法测定其重均分子量;用粘度法测     

INVESTIGATION ON THE RELATIONSHIP BETWEEN INTRINSIC VISCOSITY AND MOLECULAR WEIGHT OF POLY (VINYL CHLORIDE-DIETHYL MALEATE)

A poly (vinyichloride-diethyl maleate) copolymer has been fractionated by repeated precipitation method. All fractions and the unfractionated sample have been characterized by viscometry, dynamic osmometry, Zimm static osmometry, light scattering and gel permeation chromatography. After correction for polydispersity, a [η]～M relationship for monodisperse polymer solutions has been obtained:[η]=1.99×10~(-3)M~(0.87) (ml/g, at 25℃, in cyclohcxanone)For the copolymer solution in THF, the second virial coefficient A_2 decreases as the molecular weight increases. The relationship isA_2=2 slope ((?)_n RT)~(-1/2).     

Bis(allyl)gallium cation, tris(allyl)gallium, and tetrakis(allyl)gallate: synthesis, characterization, and reactivity

A series of cationic, neutral, and anionic allylgallium complexes has been isolated and fully characterized. It includes neutral [Ga(η(1)-C(3)H(5))(3)(L)] (1, L = THF; 2, L = OPPh(3)), cationic [Ga(η(1)-C(3)H(5))(2)(THF)(2)](+)[A](-) (3, [A](-) = [B(C(6)F(5))(4)](-); 4, [A](-) = [B(C(6)H(3)Cl(2))(4)](-)), as well as anionic [Cat](+)[Ga(η(1)-C(3)H(5))(4)](-) (5, [Cat](+) = K(+); 6, [Cat](+) = [K(dibenzo-18-c-6](+); 7, [Cat](+) = [PPh(4)](+)). Binding modes of the allyl ligand in solution and in the solid state have been studied comparatively. Single crystal X-ray analyses revealed a four-coordinate neutral gallium center in 2, a five-coordinate cationic gallium center in 4 and [4·THF], and a four-coordinate anionic gallium center with a bridging μ(2)-η(1):η(2) coordination mode of the allyl ligand in 6. The reactivity of this series of allylgallium complexes toward benzophenone and N-heteroaromatics has been investigated. Counterion effects have also been studied. Reactions of 1 and 5 with isoquinoline revealed the first examples of organogallium complexes reacting under 1,2-insertion with pyridine derivatives.     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应

RE(CH2SiMe3)3(THF)2和1.5 equiv.(C4H3NHCH2)2NCH3(1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η1∶η1∶η1-(C4H3NCH2)2NCH3]RE{μ-η5∶η5∶η1-(C4H3NCH2)2NCH3}RE[η1∶η1∶η1-(C4H3NCH2)2NCH3](THF)[RE=Y(2),Er(3),Yb(4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

(N2)3- radical chemistry via trivalent lanthanide salt/alkali metal reduction of dinitrogen: new syntheses and examples of (N2)2- and (N2)3- complexes and density functional theory comparisons of closed shell Sc3+, Y3+, and Lu3+ versus 4f(9) Dy3+

New syntheses of complexes containing the recently discovered (N(2))(3-) radical trianion have been developed by examining variations on the LnA(3)/M reductive system that delivers "LnA(2)" reactivity when Ln = scandium, yttrium, or a lanthanide, M = an alkali metal, and A = N(SiMe(3))(2) and C(5)R(5). The first examples of LnA(3)/M reduction of dinitrogen with aryloxide ligands (A = OC(6)R(5)) are reported: the combination of Dy(OAr)(3) (OAr = OC(6)H(3)(t)Bu(2)-2,6) with KC(8) under dinitrogen was found to produce both (N(2))(2-) and (N(2))(3-) products, [(ArO)(2)Dy(THF)(2)](2)(μ-η(2):η(2)-N(2)), 1, and [(ArO)(2)Dy(THF)](2)(μ-η(2):η(2)-N(2))[K(THF)(6)], 2a, respectively. The range of metals that form (N(2))(3-) complexes with [N(SiMe(3))(2)](-) ancillary ligands has been expanded from Y to Lu, Er, and La. Ln[N(SiMe(3))(2)](3)/M reactions with M = Na as well as KC(8) are reported. Reduction of the isolated (N(2))(2-) complex {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2)), 3, with KC(8) forms the (N(2))(3-) complex, {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)], 4a, in high yield. The reverse transformation, the conversion of 4a to 3 can be accomplished cleanly with elemental Hg. The crown ether derivative {[(Me(3)Si)(2)N](2)Y(THF)}(2)(μ-η(2):η(2)-N(2))[K(18-crown-6)(THF)(2)] was isolated from reduction of 3 with KC(8) in the presence of 18-crown-6 and found to be much less soluble in tetrahydrofuran (THF) than the [K(THF)(6)](+) salt, which facilitates its separation from 3. Evidence for ligand metalation in the Y[N(SiMe(3))(2)](3)/KC(8) reaction was obtained through the crystal structure of the metallacyclic complex {[(Me(3)Si)(2)N](2)Y[CH(2)Si(Me(2))NSiMe(3)]}[K(18-crown-6)(THF)(toluene)]. Density functional theory previously used only with reduced dinitrogen complexes of closed shell Sc(3+) and Y(3+) was extended to Lu(3+) as well as to open shell 4f(9) Dy(3+) complexes to allow the first comparison of bonding between these four metals.     

MOLECULAR STRUCTURE OF ORGANOLANTHANIDE COMPLEX [Li(THF)_4]_2[{ (η~5-CH_3C_5H_4)NdCl(μ_2-Cl)NdCl_2(η~5-CH_3C_5H_4)}_2(μ_4-O)]

<正> The crystal structure of the complex [Li(THF)4]2[{(η5-CH3C5H4)Nd-Cl(μ2-Cl)NdCl2(η5-CH3C5H4)}2(μ4-O)] has been determined by X-ray diffraction technique. The crystal is monoclinic of space group C2/c with a = 22. 740(7) ,b= 18. 319 (6),c=18. 330(6) A,β=93. 04(3)°,V = 7624. 93A3,Dc= 1. 55g/cm3,Z = 4,F(000) = 2800,μ=15. 02cm-1. The complex is consisted of two [Li(THF)4]+cations and one [{(η5-CH3C5H4)NdCl(μ2-Cl)NdCl2(η5-CH3C5H4)}2(μ4-O)]2-dianion. The two units [Cη5-CH3C5H4)NdCl(μ2-Cl)NdCl2(η5-CH3C5H4)] in the tetra nnclear-neodymium dianion are connected by a μ4-O bridge with the average Nd -μ4-O 2. 36(1) A ,Nd -C(ring) 2. 76(3)A,Nd-Cl 2. 823(7)A and Nd-μ2-Cl 2. 798(7)A.     

White phosphorus activation at a metal-phosphorus triple bond: a new route to cyclo-triphosphorus or cyclo-pentaphosphorus complexes of niobium

The Nb-P triple bond in [P≡Nb(N[Np]Ar)(3)](-) (Np = CH(2)(t)Bu; Ar = 3,5-Me(2)C(6)H(3)) has produced the first case of P(4) activation by a metal-ligand multiple bond. Treatment of P(4) with the sodium salt of the niobium phosphide complex in weakly coordinating solvents led to formation of the cyclo-P(3) anion [(P(3))Nb(N[Np]Ar)(3)](-). Treatment in tetrahydrofuran (THF) led to the formation of a cyclo-P(5) anion [(Ar[Np]N)(η(4)-P(5))Nb(N[Np]Ar)(2)](-), which represents a rare example of a substituted pentaphosphacyclopentadienyl ligand. The P(4) activation pathway was shown to depend on the dimer-monomer equilibrium of the niobium phosphide reagent, which, in turn, depends on the solvent used for the reaction. The pathway leading to the cyclo-P(3) product was shown to require a 2:1 ratio of the phosphide anion to P(4), while the cyclo-P(5) formation requires a 1:1 ratio. The cyclo-P(3) salt has been isolated in 56% yield as orange crystals of the [Na(THF)](2)[(P(3))Nb(N[Np]Ar)(3)](2) dimer or in 83% yield as an orange powder of [Na(12-crown-4)(2)][(P(3))Nb(N[Np]Ar)(3)]. A solid-state X-ray diffraction experiment on the former salt revealed that each Nb-P(3) unit exhibits pseudo-C(3) symmetry, while (31)P NMR spectroscopy showed a sharp signal at -223 ppm that splits into a doublet-triplet pair below -50 °C. It was demonstrated that this salt can serve as a P(3)(3-) source upon treatment with AsCl(3), albeit with modest yield of AsP(3). The cyclo-P(5) salt was isolated in 71% yield and structurally characterized from red crystals of [Na(THF)(6)][(Ar[Np]N)(η(4)-P(5))Nb(N[Np]Ar)(2)]. The anion in this salt can be interpreted as the product of trapping of an intermediate pentaphosphacycplopentadienyl structure through migration of one anilide ligand onto the P(5) ring. The W(CO)(5)-capped cyclo-P(3) salt was also isolated in 60% yield as [Na(THF)][(OC)(5)W(P(3))Nb(N[Np]Ar)(3)] from the activation of 0.5 equiv of P(4) with the sodium salt of the tungsten pentacarbonyl adduct of the niobium phosphide anion.     

Synthesis and structural characterization of alkaline-earth-metal bis(amido)silane and lithium oxobis(aminolato)silane complexes

Several of alkaline-earth-metal complexes [(η(2):η(2):μ(N):μ(N)-Li)(+)](2)[{η(2)-Me(2)Si(DippN)(2)}(2)Mg](2-) (4), [η(2)(N,N)-Me(2)Si(DippN)(2)Ca·3THF] (5), [η(2)(N,N)-Me(2)Si(DippN)(2)Sr·THF] (6), and [η(2)(N,N)-Me(2)Si(DippN)(2)Ba·4THF] (7) of a bulky bis(amido)silane ligand were readily prepared by the metathesis reaction of alkali-metal bis(amido)silane [Me(2)Si(DippNLi)(2)] (Dipp = 2,6-i-Pr(2)C(6)H(3)) and alkaline-earth-metal halides MX(2) (M = Mg, X = Br; M = Ca, Sr, Ba, X = I). Alternatively, compounds 5-7 were synthesized either by transamination of M[N(SiMe(3))(2)](2)·2THF (M = Ca, Sr, Ba) and [Me(2)Si(DippNH)(2)] or by transmetalation of Sn[N(SiMe(3))(2)](2), [Me(2)Si(DippNH)(2)], and metallic calcium, strontium, and barium in situ. The metathesis reaction of dilithium bis(amido)silane [Me(2)Si(DippNLi)(2)] and magnesium bromide in the presence of oxygen afforded, however, an unusual lithium oxo polyhedral complex {[(DippN(Me(2)Si)(2))(μ-O)(Me(2)Si)](2)(μ-Br)(2)[(μ(3)-Li)·THF](4)(μ(4)-O)(4)(μ(3)-Li)(2)} (8) with a square-basket-shaped core Li(6)Br(2)O(4) bearing a bis(aminolato)silane ligand. All complexes were characterized using (1)H, (13)C, and (7)Li NMR and IR spectroscopy, in addition to X-ray crystallography.     

Titanocene-phosphine derivatives as precursors to cytotoxic heterometallic TiAu2 and TiM (M = Pd, Pt) compounds. Studies of their interactions with DNA

A series of tri- and bimetallic titanium-gold, titanium-palladium, and titanium-platinum derivatives of the general formulas [Ti{η(5)-C(5)H(4)(CH(2))(n)PPh(2)(AuCl)}(2)]·2THF [n = 0 (1); n = 2 (2); n = 3 (3)] and [TiCl(2){η(5)-C(5)H(4)κ-(CH(2))(n)PPh(2)}(2)(MCl(2))]·2THF [M = Pd, n = 0 (4); n = 2 (5); n = 3 (6) ; M = Pt, n = 0 (7); n = 2 (8); n = 3 (9)] have been synthesized and characterized by different spectroscopic techniques and mass spectrometry. The molecular structures of compounds 1-9 have been investigated by means of density functional theory calculations. The calculated IR spectra of the optimized structures fit well with the experimental IR data obtained for 1-9. The stability of the heterometallic compounds in deuterated solvents [CDCl(3), dimethyl sulfoxide (DMSO)-d(6), and mixtures 50:50 DMSO-d(6)/D(2)O and 1:99 DMSO-d(6)/D(2)O at acidic and neutral pH] has been evaluated by (31)P and (1)H NMR spectroscopy showing a higher stability for these compounds than for Cp(2)TiCl(2) or precursors [Ti{η(5)-C(5)H(4)(CH(2))(n)PPh(2)}(2)]. The new compounds display a lower acidity (1-2 units) than Cp(2)TiCl(2). The decomposition products have been identified over time. Complexes 1-9 have been tested as potential anticancer agents, and their cytotoxicity properties were evaluated in vitro against HeLa human cervical carcinoma and DU-145 human prostate cancer cells. TiAu(2) and TiPd compounds were highly cytotoxic for these two cell lines. The interactions of the compounds with calf thymus DNA have been evaluated by thermal denaturation (1-9) and by circular dichroism (1, 3, 4, and 7) spectroscopic methods. All of these complexes show a stronger interaction with DNA than that displayed by Cp(2)TiCl(2) at neutral pH. The data are consistent with electrostatic interactions with DNA for TiAu(2) compounds and for a covalent binding mode for TiM (M = Pd, Pt) complexes.     

[(C_5H_4CH_3)_2HoN_4CPh]_2·[(C_5H_4CH_3)(C_5H_5)HoN_4CPh]_2的合成和晶体结构

（C5H4CH3）3Ho和（C5H4CH3）2Ho（C5H5）与5-苯基四唑（HN4CPh）在THF中反应，得到复合产物[（C5H4CH3）2HoN4CPh]2·[（C5H4CH3）（C5H5）HoN4CPh]2，该晶体属三斜晶系，P1空间群，晶胞参数为a=9．386（3），b=13．071（3），c=16.571（2）A，a=86．90（1），β=74．61（2），γ=77.30（2）°，V=1912．2（8）A3，Z=1，Dc=1.602g／cm3，Mr=922．61，μ=41．92cm－1，F（000）=896，最终偏离因子R=0．041，Rw=0．056．晶体数据显示，在同一个晶胞里有两个组成不同的分子，每一个分子都是具有对称中心的四唑基桥二聚体结构，其桥环单元-HoN3HoN3-是平面型的。每个钬原子分别被两个茂基和3个四唑基氮原子配位，形成1个边桥变形四面体构型。