液相色谱-电喷雾质谱法分析脂肪醇聚氧乙烯醚硫酸钠

采用电喷雾质谱(ESI/MS)技术建立了脂肪醇聚氧乙烯醚硫酸钠(AES)的烷基碳链分布、乙氧基分布及平均EO数、平均相对分子质量的测定方法;采用液相色谱-电喷雾质谱(LC-ESI/MS)测定了AES中的游离十二烷基硫酸钠(SDS)的含量。将本方法应用于实际样品的测定,并与核磁共振法测得的平均EO数进行比较,二者的测定结果相当吻合,从而验证了本法的可靠性。     

Hybird Membrane with High Proton Conductivity and Selectivity Based on SPEEK for Direct Methanol Fuel Cells

Composite membranes based on sulfonated silica/sulfonated poly(ether ether ketone)(SPEEK) were prepared by means of sol-gel method so as to gain a high conductivity and reasonable methanol permeability.The sulfonated silica is generated in situ via the hydrolysis of sulfonated 3-anminopropyl triethoxysilane(KH550) synthesized newly from 3-aminopropyl triethoxysilane and 1,4-butane sultone.The membrane with a silica mass fraction of 5% exhibits a conductivity of 0.187 S/cm at 80 °C and a methanol coefficient with 9.72×10-7 cm2/s.The composite membranes show improved condutive ability and better selectivity that can be promisingly used in direct methanol fuel cell.     

芴-氮杂萘酮-聚芳醚酮离聚物的合成与性能

以双酚芴、双酚A型二氮杂萘酮、二氟二苯酮和二氟二苯酮磺酸钠为原料, 通过调整4种单体的比例以及加料顺序控制缩聚反应, 制备了一系列具有不同离子交换容量的含芴和二氮杂萘酮联苯单元的嵌段聚芳醚酮, 简称芴-氮杂萘酮-聚芳醚酮离聚物. 采用黏度测试、傅里叶衰减全反射红外光谱(FTIR-ATR)、氢谱(1H NMR)和热失重(TGA)等分析方法, 对不同结构的芴-氮杂萘酮-聚芳醚酮离聚物的分子量、结构及热稳定性进行了表征. 实验结果表明, 采用控制缩聚法能够制备出不同离子交换容量的高分子量芴-氮杂萘酮-聚芳醚酮离聚物, 该系列离聚物具有良好的热稳定性. 对该系列离聚物膜进行了抗氧化性、水解稳定性、吸水率、耐醇性、离子交换容量和质子传导率测试. 测试结果表明, 该系列离聚物具有良好的抗氧化性、水解稳定性、耐醇性、质子传导率和适当的吸水率.     

一维链状冠醚配合物[K(B18-C-6)]_2[M(SCN)_4](M=Pd,Pt)的合成与结构

合成了苯并18-冠-6（B18-C-6）与K_2[Pd(SCN)_4]生成的配合物[K（B18-C-6 ）]_(12) [Pd(SCN)_4] (1), [K(B18-C-6)]_2[Pt(SCN)_4] (2)和[K(B18-C-6)]_2 [Pt(SCN)_4]·C_2H_4Cl_2 (3),并通过元素分析、红外光谱、单晶X射线衍射进行 了表征。1和2为单斜晶系,空间群P2_l/n,晶体学数据：1, a = 1.00970(17) nm, b = 1.3157(2) nm, c = 1.7303(3) nm, β = 94.841(2)°, V = 2.2852(7) nm~3, Z = 2, F(000) = 1136, R_1 = 0.0257。3为三斜晶系,空间群P1,晶体学 数据：a = 0.95914(18) nm, b = 1.2137(2) nm, c = 2313(2) nm, α = 63.693 (2)°, β = 76.293(2)°, γ-1.2406(4) n~3, Z = 1 F(000)618,R_1 = 0.0366 。在固态,三个配合物相邻的两个[K（B18-C-6）]~+基团通过冠醚氧化原子与钾的 子的相边接而形成一维链状结构。     

弱相互作用构筑的二维、三维冠醚配合物{[K(18-C-6)2(C2H4Cl2)}[Ni(dmit)2]2和[K(18-C-6)][Ni(dmit)2]的合成与结构

研究了18－冠－6与NiCl·6H2O,K2dmit(dmit=4,5-dimercapto-1,3-dithiole- 2-thione,C3S5^2－）在不同溶剂中反应生成的两个标题配合物{[K(18-C-6)]2 (C2H4Cl2)}[Ni(dmit)2]2（1）和[K(18-C-6)][Ni(dmit)2](2)。通过元素分析、红 外光谱、单晶X射线衍射进行了表征。1和2均属三斜晶系,空间群P1^-.1的晶体学 数据：a=1.0272(2)nm,b=1.2282(3)nm,c=1.4205(3)nm,α=113.473(3)°,β=90. 609(3)°,γ=91.439(3)°,V=1.6430(6)nm^3,Z=2,F（000)=876,R1=0.0503。2的 晶体学数据：a=0.8502(2)nm,b=1.2178(4)nm,c=1.5118(4)nm,α=86.454(5)°,β =77.734(5)°,γ=85.364(5)°,V=1.5228(8)nm^3,Z=2,F(000)=774,R1=0.0565。配 合物1,2分别通过K…S,K…Cl,S…S和K…S,S…S弱相互作用形成二维、三维网状 结构。     

诺卜醇衍生物的合成及其13C化学位移分析

诺卜基醚;诺卜基酯;诺卜醇衍生物的合成及其13C化学位移分析     

新型苯基取代杂萘联苯型聚芳醚的合成与性能

二氮杂萘酮;耐热性;溶解性;新型苯基取代杂萘联苯型聚芳醚的合成与性能     

4,4＇-二苯氧基二苯砜、4,4＇-二苯氧基二苯酮、对苯二甲酰氯三元共聚物的合成

聚醚酮醚酮酮;4;4＇-二苯氧基二苯砜、4;4＇-二苯氧基二苯酮、对苯二甲酰氯三元共聚物的合成;聚醚砜醚酮酮;低温溶液浓缩聚     

Synthesis and photoinduced deprotection of calixarene derivatives containing certain protective groups

Calixarene derivatives 1a , 1b , and 1c containing pendant tert‐butoxycarbonyl (t‐BOC) groups were synthesized in 81, 93, and 83% yields, respectively, by the reaction of C‐methylcalix[4]resorcinarene (CRA), p‐methylcalix[6]arene (MCA), and p‐tert‐butylcalix[8]arene (BCA) with di‐tert‐butyl dicarbonate using triethylamine as a base in pyridine. Calixarene derivatives 2a , 2b , and 2c containing pendant trimethylsilyl ether (TMSE) groups were obtained in 58, 50, and 82% yields, respectively, by the reaction of CRA, MCA, and BCA with 1,1,1,3,3,3‐hexamethyldisilazane using chlorotrimethylsilane as an accelerator in tetrahydrofuran. Calixarene derivatives 3a , 3b , and 3c containing pendant cyclohexenyl ether (CHE) groups were also prepared in 65, 78, and 84% yields, respectively, by the reaction of CRA, MCA, and BCA with 3‐bromocyclohexene using potassium hydroxide as a base as well as tetrabutylammonium bromide as a phase‐transfer catalyst in N‐methyl‐2‐pyrolidone. The photoinduced deprotection of calixarene derivatives 1a – c was examined with bis‐[4‐(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) as a photoacid generator on UV irradiation followed by heating in the film state, and it was found that the deprotection of the t‐BOC groups of 1a proceeded smoothly in high conversion. The deprotection rates of the t‐BOC groups of 1b and 1c were much lower than that of 1a under the same irradiation conditions. The photoinduced deprotection of calixarenes 2b – c containing tetramethylsilane groups as well as 3a – c containing CHE groups were also examined under similar reaction conditions in the film state, and it was found that the deprotection rates of calixarenes 2b – c and 3a – c were lower than those of the corresponding 1a – c calixarenes. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1481–1494, 2001     

Application of novel polymers with S‐alkylsulfonium salt moieties as alkylating agents and thermal latent cationic initiators

Sulfonium‐containing polymers prepared from dibenzothiophene and diphenyl sulfide were applied as both alkylating agents and latent initiators for the cationic polymerization of glycidyl phenyl ether. The alkylation of acetonitrile proceeded smoothly with poly(S‐n‐octyl‐2‐vinyldibenzothiophenium tetrafluoroborate) ( 4 ; 64 mol % octyldibenzothiophenium tetrafluoroborate unit) to give N‐(n‐octyl)acetamide in an excellent yield on the basis of the starting octyldibenzothiophenium tetrafluoroborate unit in 4 . The cationic polymerization of glycidyl phenyl ether was also carried out in the presence of poly(S‐methyl‐2‐vinyldibenzothiophenium tetrafluoroborate) or poly(S‐n‐octyl‐4‐vinyldiphenylsulfonium tetrafluoroborate) to confirm their moderate thermal latent activity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3928–3933, 2001