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丙烯腈和(甲基)丙烯酸酯基团转移共聚合的竞聚率 总被引:4,自引:0,他引:4
研究了丙烯腈(AN)和甲基丙烯酸甲酯(MMA)、乙酯(EMA)、丁酯(BMA)、丙烯酸丁酯(BA)和顺丁烯二酸二丁酯(DBM)等5种酯类单体的基团转移无规共聚.用Kelen Tudus法测定了二元共聚体系的竞聚率,分别为rAN=1022、rMMA=077、rAN=568、rEMA=016、rAN=859、rBMA=009、rAN=408、rBA=006;rAN=138,rDBM=006.发现竞聚率,单体组分对聚合速率的影响等都和阴离子共聚类似. 相似文献
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丙烯酸-β-羟乙酯和甲基丙烯酸正丁酯共聚合参数的测定与研究 总被引:1,自引:0,他引:1
用^1H-NMR分析法测定了丙烯酸-β-羟乙酯(M1)和甲基丙烯酸正丁酯(M2)的共聚物组成,用Mayo-Lewis模型的误差变量法计算出不同温度下该体系的溶液聚合的竞聚率,分别为r1=0.63,r2=1.17(60℃);r1=0.61,r2=1.01(80℃);r1=0.61,r2=0.97(100℃);r1=0.70,r2=1.03(120℃);r1=0.68,r2=0.88(140℃)和r1=0.66,r2=0.86(160℃)。根据Arrhenius方程计算获得了体系均聚、共聚反应频率因子之比Aii/Aij和活化能之差Eii-Eij,并讨论了溶剂、氢键对共聚合单体活性的影响。 相似文献
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异戊二烯/甲基丙烯酸甲酯嵌段共聚物的合成与微结构研究 总被引:2,自引:0,他引:2
用稀土催化剂RE(P204)3 (i Bu)3Al BrCH2CH2Br(RE=Nd,Pr,Y等)合成嵌段共聚物P(IP b MMA).系统考察了共聚合反应特征,以DSC,1H NMR,13C NMR技术研究了该嵌段共聚物的微结构.发现以二溴乙烷为添加剂的稀土催化体系是制备P(IP b MMA)的良好催化剂,共聚物含2个玻璃化转变温度,分别为-756℃和129℃,嵌段共聚物的结构规整,(IP)m段以cis 1,4结构为主,其含量为97%左右,3,4 结构为3%左右,链节间以头 尾方式连接.(MMA)n段以间同立构为主,其含量达74%. 相似文献
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丙烯酸酯和甲基丙烯酸酯基团转移共聚研究 总被引:1,自引:0,他引:1
研究了三种丙烯酸酯分别和四种甲基丙烯酸酯的基团转移共聚,用1H NMR法测定共聚物组成,扩展的Kelen Tudos法测定竞聚率,结果为γMA=923、γMMA=006;γEA=1415、γMMA=001;γBA=751、γMMA=002;γMA=1441、γEMA=001;γMA=1396、γBMA=023;γMA=866、γi BMA=008,表明基团转移聚合同阴离子聚合有明显的相似之处. 相似文献
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本文比较了Mo(Ⅵ)-1-(2-吡啶基偶氮)-2-萘酚(PAN)与Mo(Ⅵ)-4(2-吡啶基偶氮)间苯二酚(PAR)的极谱性质,讨论它们在作为吸附波试剂时的优缺点,以求得在选择络合剂时的感性和理性认识.本文还报道了Mo(Ⅵ)-PAN-KBrO3吸附催化波体系,最佳实验条件,0.1mol/LHAc--NaAc,pH=4.6,0.01mol/LKBrO3,2.5×10-5mol/LPAN.峰电位为-0.71V(vs.SCE),检出限1×10-9mol/L,线性范围0~6×10-7mol/L 相似文献
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尼龙6/多单体接枝聚丙烯共混物的形态结构及力学性能的研究 总被引:14,自引:4,他引:10
用多组分熔融接枝的方法将甲基丙烯酸缩水甘油酯( G M A) 和苯乙烯( St) 共同接枝于聚丙烯( P P) 上,制得多单体接枝聚丙烯 P P g ( G M A co St) .该接枝物具有高的 G M A 接枝率.本研究利用 F T I R、 S E M、 T E M、 D S C 和力学性能测试等分析方法,研究了多组分熔融接枝聚丙烯( P P g ( G M A co St)) 对尼龙6/ P P 共混物的形态结构, Tg 和力学性能的影响.结果表明, P P g ( G M A co St) 中的环氧基团与尼龙6( P A6) 末端的胺基发生化学反应,原位形成的 P P P A6 共聚物能有效的改善 P A6 与 P P 的相容性,可以使 P P 均匀的分散在 P A6 基体中,相区尺寸明显减小,提高了拉伸强度.由于两相的相容性较好,从而共混物的 Tg 有明显的变化.此外,通过透射电镜观察,发现 P A6/ P P g ( G M A co St)(70/30) 合金中存在着特殊的微相分离结构. 相似文献
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鬼灯擎素的结构分析 总被引:3,自引:0,他引:3
本文报道了从鬼灯擎(Rodgersid aesculifolia Batal)中提取的鬼灯擎素(Bergenin)晶体的结构研究。鬼灯擎素晶体为正交晶系,C_(14)H_(18)O_(10),M_r=346.28,其晶胞参数a=7.468(9),b=13.899(4),c=14.228(0)A;空间群为P2_12_12_1;晶胞内分子数Z=4,D_c=1.5560g/cm~3,结构模型由SHELXTL程序解出;经Fourier合成和最小二乘修正,最后的偏离因子R=0.028。此外,利用晶体结构分析所得分子中各原子的坐标,以半经验分子轨道法CNDO/2程序计算了分子总能量、净电荷分布以及Wiberg键级等,并以此讨论了分子的反应活性中心。 相似文献
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Ritch JS Chivers T Eisler DJ Tuononen HM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(16):4643-4653
A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda){(EPtBu(2))(2)N}] (3 a, E=S; 3 b, E=Se; 3 c, E=Te) has been developed. The one-electron oxidation of the sodium complexes [Na(tmeda){(EPR(2))(2)N}] with iodine produces a series of neutral dimers (EPR(2)NPR(2)E--)(2) (4 b, E=Se, R=iPr; 4 c, E=Te, R=iPr; 5 a, E=S, R=tBu; 5 b, E=Se, R=tBu; 5 c, E=Te, R=tBu). Attempts to prepare 4 a (E=S, R=iPr) in a similar manner produced a mixture including HN(SPiPr(2)). Compounds 4 b, 4 c and 5 a-c were characterised by multinuclear NMR spectra and by X-ray crystallography, which revealed two alternative structures for these dimeric molecules. The derivatives 4 b, 4 c, 5 a and 5 b exhibit acyclic structures with a central chalcogen-chalcogen linkage that is elongated by approximately 2 % (E=S), 6 % (E=Se) and 8 % (E=Te) compared to typical single-bond values. By contrast, 5 c adopts an unique spirocyclic contact ion-pair structure in which a [(TePtBu(2))(2)N](-) ion is Te,Te' chelated to an incipient [(TePtBu(2))(2)N](+) cyclic ion. DFT calculations of the relative energies of the two structural isomers indicate a trend towards increasing stability for the contact ion pair relative to the corresponding dichalcogenide on going from S to Se to Te for both the isopropyl and tert-butyl series. The two-electron oxidation of [Na(tmeda){(EPtBu(2))(2)N}] (E=S, Se, Te) with iodine produced the salts [(EPtBu(2))(2)N](+)X(-) (7 a, E=S, X=I(3); 7 b, E=Se, X=I; 7 c, E=Te, X=I), which were characterised by X-ray crystallography. Compound 7 a exists as a monomeric, ion-separated complex with [d(S--S)=2.084(2) A]; 7 b and 7 c are dimeric [d(Se--Se)=2.502(1) A; d(Te--Te)=2.884(1) A]. 相似文献
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苯乙烯和丙烯酸 β 羟乙酯不同温度的竞聚率测定吴平平吴玉芳陆琛杨全兴韩哲文(华东理工大学材料科学研究所上海200237)陈顺喜朱清仁(中科院中国科技大学结构分析开放实验室合肥230026)关键词苯乙烯,丙烯酸 β 羟乙酯,共聚合,竞聚率丙烯酸 β?.. 相似文献
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Phthalocyanines of Cobalt and Rhodium with O, S, and Se Donor Ligands Di(phenolato)-, -(benzenethiolato)- and -(benzeneselenonato)phthalocyaninatocobaltate(III) and -rhodate(III) are prepared by the reaction of di(hydroxo)phthalocyaninatometalate with phenol resp. benzenethiol or benzeneselenol and isolated as poorly soluble tetra(n-butyl)ammonium salts of the formula (nBu4N)[M(EPh)2Pc2?] (M = Co, Rh; E = O, S, Se). In the Uv-vis spectra π–π* transitions in the Pc2?-typical B, Q, N and L regions are observed. For the Rh-complexes with E = S, Se there is a further band at 18.0 kK due to excitonic π(Ph)–π(Pc) interactions. The (E→Rh-charge-transfer(CT)) transition is observed for E = Se at 26.0 kK, being obscured by the Q, N region for E = O, S. The strong, broad (E → Co? CT) transition (E = O, S, Se) absorbs at ~20.5 kK. A second CT-transition is detected within the Q, N region for E = S, Se. Molecular vibrations (in cm?1) are examined by m.i.r., f.i.r, FT-Raman and dispersive resonance-Raman(RR) spectra. The C? E stretching mode (v7a) of the axial EPh ligands is observed for E = O at 1256/1262, 1269 (Co, m.i.r./RR), 1246/1265 (Rh), for E = S at 1085 (Co, Rh; RR) and for E = Se at 1069 (Co, Rh; RR). The C? C? E deformation mode (v6a) is assigned for E = O at 554/557 (Co, RR), 568 (Rh, RR) and for E = S at 420 (Co, Rh; RR). The following vibrational modes of the trans-ME2N4 skeleton are assigned: vs(ME) for Co: 381 (O)/271 (S)/139 (Se); for Rh: 408/297/156; vas(ME) for Co: 352/277/235; for Rh: 391/278/225; vas(MN) absorbs nearly independent of M and E at ~325 (f.i.r.) M? E? C deformation modes are observed between 246 and 200 (f.i.r.) resp. 217 and 186 (RR). 相似文献
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Ivanov SV Miller SM Anderson OP Solntsev KA Strauss SH 《Journal of the American Chemical Society》2003,125(16):4694-4695
The synthesis and characterization of several salts of the B(12)F(12)(2-) anion are reported. The potassium salt was prepared in 72% recrystallized yield by treating K(2)B(12)H(12) with liquid HF at 70 degrees C for 14 h and 20% F(2)/N(2) in liquid HF at 25 degrees C for 72 h. The CPh(3)(+), N(n-Bu)(4)(+), NH(n-C(12)H(25))(3)(+), NH(4)(+), and Li(+) salts were prepared by metathesis reactions. The [NH(n-C(12)H(25))(3)](2)[B(12)F(12)] salt is soluble in aromatic hydrocarbon solvents. The B(12)F(12)(2-) anion is remarkably stable. The salts Li(2)B(12)F(12) and [NH(4)](2)[B(12)F(12)] were stable when heated to 450 and 480 degrees C, respectively. The B(12)F(12)(2-) anion did not react with 98% H(2)SO(4), 70% HNO(3), 3 M KOH, a 10-fold excess of Ce(NH(4))(2)(NO(3))(6) in aqueous solution, or metallic sodium in THF. In addition, B(12)F(12)(2-) did not react with metallic lithium in a mixture of ethylene carbonate and dimethyl carbonate, was not reduced at 0 V versus Li(+/0) in that solvent, and underwent a quasi-reversible oxidation at 4.9 V versus Li(+/0). The structure of [CPh(3)](2)[B(12)F(12)] was determined by single-crystal X-ray diffraction: tetragonal, space group I4(1)/acd, a = 19.102(2), b = 19.102(2), c = 20.535(3) A, V = 7492.2(2) A(3), Z = 8, T = 173(2) K, R(1) = 0.064. The B(12)F(12)(2-) anion weakly interacts with the two symmetry related CPh(3)(+) cations via F.C contacts of 3.087(2) A, which are very close to the 3.17 A sum of van der Waals radii for these two atoms. Taken together, the data suggest that B(12)F(12)(2-) may be useful as a very robust weakly coordinating anion. 相似文献
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采用弹性竿模型 (Elasticrodmodel) ,用MonteCarlo方法对DNA分子的构象进行研究 .通过计算发现 ,DNA分子的能量是由弯曲势能EB 和扭转势能ET 两部分组成 ,通常EB 比ET 大一至两个数量级 .同时给出了均方回转半径与链长之间的关系为〈R2g〉 =1 1 69 5 -3 5×n +0 0 2 5×n2 ,它体现了DNA分子结构的特点 .验证了公式Lk=Wr+Tw ,得出Lk与Wr比较接近的结论 ,考虑DNA分子的构型 ,意味着DNA分子容易被弯曲而不易被扭转 ,但随着连接系数的增加 ,DNA被扭转的几率也在增加 .这为分析DNA分子的结构特征提供了一种新方法 相似文献
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Sproules S Banerjee P Weyhermüller T Yan Y Donahue JP Wieghardt K 《Inorganic chemistry》2011,50(15):7106-7122
Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-?))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-?))](1-) ? [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-?))](1-) complexes highlights tungsten's preference for higher oxidation states. 相似文献
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研究了与偏二溴乙烯(VDBr,M_1)共聚的不同单体(M_2)——丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)和苯乙烯(St)的性质和共聚物的序列分布对记录材料紫外光敏性的影响。结果表明,含St的紫外光敏性最高,含MA的较差。对同一类共聚物记录材料而言,光敏性与共聚物的序列分布,主要是P_2(M_1M_2)有对应关系。本文还报道了VDBr与MA、MMA及St在55±0.2℃以偶氮二异丁腈为引发剂的自由基共聚反应竞聚率(r)分别为,VDBr-MA:r_1=0.72±0.05,r_1=0.72±0.05;VDBr-MMA:r_1=0.50±0.04,r_2=1.74±0.04;VDBr-St:r_1=0.40±0.04,r_2=1.12±0.04。 相似文献