亚砜还原法合成聚苯醚硫醚的结构与性能研究

以氟苯和氯化亚砜反应合成了4,4’-二氟二苯亚砜,并将其与4,4’二羟基二苯硫醚在N-甲基吡咯烷酮溶剂中进行亲核取代反应合成了聚苯醚硫醚醚亚砜,用乙二酰氯/四丁基碘化铵还原该亚砜聚合物制备了聚苯醚硫醚。用红外光谱和核磁共振谱对合成单体的结构进行了确认,同时对聚合物进行了红外光谱、核磁共振、元素分析、X射线光电子能谱、X射线衍射、DSC分析、TG/DTG以及溶解性测试。结果表明聚苯醚硫醚样品具有氧醚和硫醚交替的线性结构,特性粘度为0.55 dL/g的PPSE熔点达236℃,在氮气条件下,样品起始分解温度和最大分解速率处温度分别为359℃和514℃,在700℃时的重量保留率为43.3%,且在加热条件下能溶解于N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)等极性有机溶剂中。     

超高效液相色谱-质谱对动物源食品中氯丙嗪、异丙嗪及其代谢物的测定

建立了动物源食品中吩噻嗪类药物氯丙嗪、异丙嗪及其代谢物氯丙嗪亚砜和异丙嗪亚砜同时测定的固相萃取超高效液相色谱-电喷雾电离串联四极杆质谱(UPLC-ESI MS/MS)方法.样品用乙酸乙酯和氢氧化钠溶液提取,Oasis HLB柱富集净化,超高效液相色谱-电喷雾串联四极杆质谱仪检测,采用多反应监测正离子模式,可以一次性对动物源性食品中的吩噻嗪类药物氯丙嗪、异丙嗪及其代谢物氯丙嗪亚砜和异丙嗪亚砜进行定性和定量测定.方法在 1 ～100 μg/L范围具有良好的线性,回收率为76% ～96%,定量下限(S/N＞10)为异丙嗪5 μg/kg,氯丙嗪、氯丙嗪亚砜、异丙嗪亚砜1 μg/kg.检出限(S/N=3)为异丙嗪1.5 μg/kg,氯丙嗪、氯丙嗪亚砜、异丙嗪亚砜0.3 μg/kg.     

DEHSO萃取铊(Ⅲ)及其机理的研究

二(2-乙基已基)亚砜(DEHSO)是带支链的烷基亚砜,其溶解性能优于直链烷基亚砜,对铊(Ⅲ)的萃取化学尚来见报道。 本文研究了DEHSO-煤油溶液在盐酸介质中对铊(Ⅲ)的萃取行为。实验结果表明,该萃取反应速率快,萃取率随酸度增大而增大,随Cl~-离子浓度增大而降低;温度升高致使分配比下降,由logD与1/T×10~3对画图得斜率为1.95的直线,据此求得萃取反应的焓变     

高效液相色谱法测定羊体内的丙硫咪唑缓释弹代谢产物的血药浓度

用反相高效液相色谱法追踪分析不同时间内羊血清中药物浓度的变化,以供药物代谢动力学研究.药物为丙硫咪唑砜和丙硫咪唑亚砜(简称砜和亚砜),实验条件为ODS柱,流动相甲醇:水=7:3(v/v),紫外检测波长为290nm.在3h左右测定浓度达峰值,其最高浓度分别为4.01μg/mL和11.47μg/mL,五天左右下降为2.73μg/mL和1.32μg/mL附近.最小检出量为0.4ng/mL及0.7ng/mL.线性关系良好.丙硫咪唑砜和亚砜的回归相关系数分别为0.9994和0.9991.采用内标法测定回收率,平均为     

液相色谱-质谱联用分析土壤中的双(2-羟乙基)亚砜

建立了液相色谱 质谱联用技术测定土壤中双(2 羟乙基)亚砜的方法。对影响检测灵敏度的流动相组成、流速、探头温度等因素进行了优化,在优化实验条件下,方法线性范围在0.05～20mg L之间,最低检测质量浓度为0.025mg L(S N>3),对比了3种萃取剂对4种土壤中的双(2 羟乙基)亚砜的萃取率,结果表明,用水作萃取剂的萃取效果最佳,回收率在92%以上,RSD均小于4%。     

1-(2’-烷硫基乙氧基)甲基尿嘧啶及其氧化物的合成

采用 3 0 %H2 O2 /DEAD的试剂组合 ,用于将硫醚及亚砜的衍生物氧化成砜类物质的反应 ,合成了1 ( 2 烷硫基乙氧基 )甲基尿嘧啶及其氧化物 ,产物结构经元素分析、1HNMR和IR进行表征 ,并研究了其抗癌活性     

过硼酸钠在硫醚选择性氧化反应中的应用

过硼酸钠(NaBO_3·4H_2O)是一种可以使硫醚起选择性氧化反应生成相应亚砜的有效试剂,本文报道一系列苯硫醚化合物(1a-j)经氧化生成相应亚砜(2a-j),反应中烯键以及羟基、羰基、酯基、酰胺基、氰基等官能团未受影响。     

亚砜类非离子型表面活性剂在固/液界面上的吸附(III)碳黑/水溶液界面上的吸附

研究了癸基甲基亚砜在水溶液/炭黑界面上的吸附及温度、加盐(Nacl)、加酸(HCl)对吸附的影响.吸附等温线呈完整的双平台形式. 第一平台吸附量～6 μmol·m~(-2); 第二平台吸附量,即极限吸附量, 为42—48 μmol·m~(-2). 随着吸附增加, 炭黑/水溶液接触角下降, 润湿性, 悬浮性改善.应用两阶段吸附模型和吸附等温线通用公式可以对实验结果作定性和定量的解释. 提供了吸附热力学数据. 指示吸附第二阶段是与体相中表面活性剂胶团化作用相似的熵驱动过程。     

Al(Ⅲ)盐水解聚合过程中Al5和Al9的制备及初步表征

采用铝粉、水合氯化铝和水为原料,通过调整反应温度、原料配比及溶液碱化度,经蒸发、结晶制备了铝盐水解聚合产物中的2种中间产物,即水合氯化五聚铝AlCl3·4Al(OH)3·7.5H2O和水合氯化九聚铝2AlCl3·7Al(OH)3·18H2O分别采用粉末XRD物相分析、化学分析和IR光谱对其进行了表征. 以化学分析为主要监测手段,对AlCl3·4Al(OH)3·7.5H2O和2AlCl3·7Al(OH)3·18H2O的形成过程进行了研究. 结果表明,随温度的变化反应基本上是一个可逆的过程,75 ℃是AlCl3·4Al(OH)3·7.5H2O和2AlCl3·7Al(OH)3·18H2O析出的最佳温度,该温度下产物的结晶状态良好,其纯度分别可达99.57%和88.68%.     

含氮试剂对p-DCC/AlCl_3引发异丁烯正离子聚合的影响

以对-二枯基氯(DCC)/AlCl3体系引发异丁烯在二氯甲烷(CH2Cl2)正己烷(Hex)(40/60,V/V)混合溶剂中进行正离子聚合,探讨了DCC用量、含氮试剂2,6-二叔丁基吡啶(DtBP)和三苯胺(TPA)对异丁烯正离子聚合转化率、产物分子量及其分布的影响.结果表明,DCC和体系中微量水均可与AlCl3产生竞争络合,形成两种活性中心并引起相继的竞争引发,聚合产物的GPC谱图呈双峰分布,分子量分布宽;增加DCC用量有利于DCC与AlCl3的络合,致使链增长反应主要通过DCC与AlCl3络合形成的活性中心引发,但聚合产物分子量相对较低,分子量分布较宽;使用DtBP,可有效地抑制微量水引发及活性链向单体的转移反应,使分子量分布明显变窄,基本实现DCC的控制引发;采用DtBP与TPA共同调节聚合反应,可使聚合产物分子量分布变窄的同时,进一步提高分子量,从而得到相对较高分子量(Mw=103200)和单峰分子量分布(Mw/Mn=2.09)的聚异丁烯产物.     

主链含酰亚胺结构的聚醚醚酮的合成及其性能

以1,4-二苯氧基苯为单体分别与N,N′-(4,4′-二苯甲烷)-双-(3,4-二甲酰亚胺基苯甲酰氯)和N,N′-(4,4′-二苯砜)-双-(3,4-二甲酰亚胺基苯甲酰氯),采用低温溶液缩聚合成了2种主链含酰亚胺结构的聚醚醚酮树脂,聚合物的比浓对数粘度分别为0.98和0.61 dL/g。 用FT-IR、¹H NMR和WAXD进行了结构表征,用DSC和TGA测试了热性能。 结果表明,聚合物有较高的玻璃化转变温度(T_g分别为236和263 ℃),N₂气气氛中热分解温度(5%T_d)分别为529和512 ℃,能溶于N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、氯仿和间甲酚等常见的有机溶剂中。     

Synthesis and characterization of halogen‐containing poly(ether ketone ketone)s

A series of novel poly(ether ketone ketone)s (PEKKs) were synthesized from diphenyl ether and isophthaloyl chloride derivatives such as 5‐halo‐ and 5‐tert‐butyl‐isophthaloyl chloride. The aromatic electrophilic substitution route to polyketones was a convenient route for the preparation of the polymers in high yields via precipitation polycondensation at a low temperature with aluminum trichloride as a catalyst. High molecular weight PEKKs were achieved with number‐average molecular weights of 15,000–100,000 g/mol for polymers that showed good solubility in organic solvents. The presence of substituents greatly modified the spectroscopic features in comparison with those of unsubstituted isophthaloyl poly(ether ketone ketone)s, particularly for the series containing halogens, for which significant variations of the chemical shifts in both ¹H and ¹³C NMR spectra were observed; these shifts could be related to the nature of the halogen. Thermal properties were also affected by the presence of pendent substituents, with clear enhancements of the glass‐transition temperatures, which could be ascribed to the nature and bulkiness of the substituents. Thermogravimetric analyses showed that the new polymers had good thermal resistance, although an important drop in thermal resistance was observed for polymers bearing large halogen atoms, such as bromine and iodine. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2601–2608, 2002     

Synthesis of aromatic poly(ether amide amide ether ketone ketone)s by electrophilic Friedel–Crafts solution polycondensation

A new monomer, N,N′‐bis(4‐phenoxybenzoyl)‐p‐phenylenediamine (BPBPPD), was prepared by the condensation of p‐phenylenediamine with 4‐phenoxybenzoyl chloride in N,N‐dimethylacetamide (DMAc). Novel aromatic poly(ether amide amide ether ketone ketone)s (PEAAEKKs) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of BPBPPD with a mixture of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC), over a wide range of TPC/IPC molar ratios, in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The influences of reaction conditions on the preparation of polymers were examined. The polymers obtained were characterized by different physico–chemical techniques such as FT‐IR, Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and wide angle X‐ray diffraction (WAXD). The polymers with 70–100 mol% IPC are semicrystalline and have remarkably increased T_gs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) due to the incorporation of amide groups in the main chain. The polymers with 70–80 mol% IPC had not only high T_gs of 209–213°C, but also moderate T_ms of 339–348°C, which are suitable for melt processing. The polymers with 70–80 mol% IPC had tensile strengths of 107.5–109.8 MPa, Young's moduli of 2.53–2.69 GPa, and elongations at break of 9–11% and exhibited high thermal stability and good resistance to organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Novel Organosoluble Polychloro Substituted Aromatic Poly(Ether Ketone)s

A novel monomer of tetrachloroterephthaloyl chloride (TCTPC) was prepared by the chlorination of terephthaloyl chloride catalyzed by ferric chloride at 175‐180 °C for 10 h, and confirmed by FTIR, MS and elemental analysis. A series of new polychloro substituted poly(aryl ether ketone)s with inherent viscosities of 0.58‐0.65 dL/g have been prepared from TCTPC with aromatic ether monomers by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl₃ as a catalyst in 1,2‐dichloroethane. Glass‐transition temperatures of these polychlorinated polymers ranged from 267 to 280 °C by DSC. The degradation temperature at 5% weight loss by TGA in nitrogen for these polymers ranged from 486 to 534 °C, and the char yields at 700 °C were 54‐65%. The polymers having a weight‐average molecular weight in the range of 65,900‐79,300 are all amorphous and readily soluble in polar solvents such as DMF, DMSO and NMP at room temperature. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 86.1‐99.7 MPa, Young's moduli of 2.32‐3.35 GPa, and elongations at break of 10‐15%.     

含芳酯侧基聚芳醚酮的合成与性能

以偏苯三甲酸酐酰氯(TMAc),对苯二甲酰氯(TPC),1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)为单体,采用亲电溶液共缩聚,通过改变TMAc、TPC的摩尔比,制备了系列含羧基侧基的聚芳醚酮树脂(PEK-A).在对甲苯磺酸催化下与苯酚进行酯化反应合成了系列主链带芳酯侧基的聚芳醚酮树脂(PEK-COO-Ar).用...     

低温溶液缩聚合成聚芳醚酮酮的研究

低温溶液缩聚合成聚芳醚酮酮的研究宋才生，蔡明中，周丽云（江西师范大学化学系南昌３３００２７）关键词低温溶液缩聚，付一克或化反应，聚芳醚酮酮，二苯醚聚芳醚酮酮（ＰＥＫＫ）是一种新型的热塑性耐热高分子材料，具有优异的机械力学性能，耐溶剂抗化学腐蚀性能，抗...     

苯乙炔封端的可交联含氟聚芳醚的合成及性能

从光电集成器件对于材料性能的需要出发 ,我们相继合成了一系列可溶性的含氟聚芳醚和聚芳醚酮[1～ 5] .为了满足器件的多层化制备过程以及使器件成型后具有优异的性能 ,本文在间三氟甲基苯取代的聚芳醚 (1 1 F- PAE)中引进可交联的苯乙炔端基 ,合成了可热交联的高含氟量聚芳醚 ,并对其性能进行了初步研究 .1　实验部分1 .1　试剂与仪器　 4-苯乙炔苯酚 (PEP)按文献 [6 ]方法制备 ;3 -氟甲基苯代对苯二酚 (3 F- PH)按文献[2 ]方法制备 ;十氟联苯 ,Aldrich公司 ,99%;无水碳酸钾 ,A.R.级 ,天津化学试剂厂 ;甲苯 ,A.R.级 ,北京化工厂 ;N-…     

含二氮杂萘酮结构聚芳醚腈酮酮的合成及表征

以5种含杂萘联苯结构的单体与2,6-二氯苯腈、1,4-二(4-氟代苯甲酰基)苯为原料进行亲核缩聚反应,制备了一系列含有杂萘联苯结构的新型聚芳醚腈酮酮树脂.其特性粘度在0.51~1.15 dL.g-1之间.采用FT-IR,示差扫描量热仪(DSC),热重分析仪(TGA)对聚合物的结构和性能进行了表征,结果表明,聚芳醚腈酮酮的玻璃化转变温度(Tg)在252~294℃之间,10%热失重温度(Td)在457℃以上,具有优异的耐热性能.聚芳醚腈酮酮均可溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、和氯仿等极性非质子型有机溶剂中,聚合物均可溶解于NMP后浇铸得到透明的、韧性好的薄膜.     

Polycarbazoles via C?N coupling reactions of phthaloyl bis‐9H‐carbazoles with activated difluorides

1,3‐Phthaloyl bis‐9H‐carbazole (MPC) and 1,4‐phthaloyl bis‐9H‐carbazole (PPC) were synthesized by a Friedel‐Crafts reaction of carbazole with terephthaloyl chloride or isophthaloyl chloride. Homopolymers were obtained by a C? N coupling reaction with activated difluorides and copolymers were synthesized with 4,4′‐biphenol as a comonomer by a nucleophilic substitution reaction between these NH‐ and OH‐containing monomers and the activated difluoro monomers. The inherent viscosities of the polymers ranged from 0.35 to 1.03 dL/g. These polymers exhibited glass‐transition temperatures greater than 238 °C with the PPC‐containing homopolymer showing the highest value, 326.4 °C. The thermal stabilities indicated no significant weight loss below 450 °C and the temperatures of 5% weight loss ranged from 514.0 to 546.3 °C. The polymers showed reasonable solubility in organic solvents such as DMAC, DMSO, and NMP. UV absorption and fluorescence emission properties are presented. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4326–4331, 2009     

含冠醚环的席夫碱型液晶高分子的合成与表征

以 4 ,4′ (α ,ω 烷亚甲基二酰氧 )二苯甲醛和二氨基二苯并 14 冠 4为单体 ,采用溶液缩聚方法 ,首次合成了一类新的含冠醚环的席夫碱型液晶高分子 .一种单体采用脂族二酰氯和对羟基苯甲醛反应制备 ,另一种新的单体采用二硝基二苯并 14 冠 4 ,在钯 碳催化剂存在下 ,水合肼还原制备 .通过1H NMR、13 C NMR和分子力学计算方法研究了二氨基二苯并 14 冠 4的两种异构体的空间立体结构 ,发现能从1H NMR谱图上区分它们的立体结构 .它们的立体结构近似属于Cs 和C2 群 .聚合物的分子量不高 ,Mn 在 130 0 0～ 2 4 0 0 0之间 .单体的结构通过元素分析、IR、1H NMR和MS等方法确证 .聚合物的性质采用GPC、DSC、TG和POM等方法进行了研究 .发现所有的聚合物加热到各自的熔融温度 (Tm)以上都能形成液晶态 ,在液晶态可以观察到向列相的丝状织构和纹影织构 .聚合物的玻璃化转变温度 (Tg)、熔融温度和各向同性温度 (Ti)随聚合物分子中柔性间隔基的变化而变化 ,它们有较高的清亮点温度和宽的液晶态温度范围 .WAXD的研究进一步证实了聚合物的液晶性