甲基取代的聚芳醚酮酮酰亚胺树脂的合成与性能

N,N′-(4,4′-二苯甲烷)-二偏苯三甲酰亚胺酰氯(DIDC-M)与4,4′-二(2-甲基-苯氧基)三苯二酮(o-Me-DPOTPDK) 进行低温溶液共缩聚,制备了甲基侧基取代的聚芳醚酮酮酰亚胺(o-Me-PEKKI)聚合物.用FT-IR,1H-NMR,DSC,TG 和WAXD对聚合物的结构和性能进行了表征.研究表明:聚合物为非晶态结构;具有较高的玻璃化转变温度(Tg:241 ℃)和较好的耐热性能(Td:487 ℃);能溶解于间甲酚、NMP、氯仿、四氯乙烷等有机溶剂中.     

基于5-羟甲基-1.3-苯二酸的两个四连接锌配合物的合成、结构和性质

在辅助配体4,4′-二(1H-咪唑-1-基)-1,1′-双苯（4,4′-DIB）的帮助下,5-羟甲基-1.3-苯二甲酸(H₂HIA)与Zn(BF₄)₂通过溶剂热或者水热反应构建出了两个具有sql网络的三维超分子配合物,即{[Zn₂(HIA)₂(4,4′-DIB)₂]·xGuest}_n (1, CCDC: 1989855 )和[Zn₂(HIA)₂(4,4′-DIB)₂]_n(2, CCDC: 1989856)。并对配合物的PXRD, IR, TGA和荧光等特性进行了表征。     

均相时间分辨免疫分析铕穴状螯合剂的合成

以2,6-二（溴甲基）吡啶-3,5-二甲酸二乙酯为起始原料,经溴化、取代、加成及酸化反应合成了两种铕穴状荧光螯合剂Eu³⁺ 2,6-{N,N′,N,N′-[二（2,2′-联吡啶-6,6′-二甲基）]二（氨甲基）}-吡啶-二羧酸[Eu³⁺ bpy.bpy.py(CO₂H)₂, 1]和Eu³⁺2,6-{N,N′,N,N′-[二（2,2′ 联吡啶-6,6′-二甲基）]二（氨甲基）}-吡啶-二[N-(2-氨基乙基)酰胺]{Eu³⁺bpy.bpy.py[CONH(CH₂)₂NH₂]₂, 2},其结构和性能经¹H NMR, MS(ESI)和荧光光谱表征。结果表明：1的最佳激发波长为312 nm,发射特征峰位于598和615 nm,荧光寿命为1 064 μs,量子产量为10%。 2的最佳激发波长为311 nm,发射特征峰位于597和616 nm,荧光寿命为398 μs,量子产率为12.1%。     

双邻位甲基取代聚芳醚酮酰亚胺的合成与性能研究

N,N′-(4,4′-二苯甲烷)-二偏苯三甲酰亚胺酰氯(DIDC-M)分别与4,4′-二(2,6-二甲基-苯氧基)二苯酮(o-Me2-DPOBP)和4,4′-二(2,6-二甲基-苯氧基)三苯二酮(o-Me2-DPOTPDK)进行低温溶液共缩聚,合成了两种含双邻位甲基侧基和主链含亚胺结构的聚醚酮醚酮酰亚胺(o-Me2-PEKEKI-Pa)及聚醚酮酮醚酮酰亚胺(o-Me2-PEKKEKI-Pb)共聚物.用FT-IR,1H-NMR,DSC,TGA和WAXD对共聚物的结构和性能进行了表征.研究表明Pa和Pb均为非晶态结构;具有较高的玻璃化转变温度(Pa为240℃,Pb为237℃);能溶解于DMF、DMAc、NMP、二氯甲烷、氯仿等普通有机溶剂中,溶剂挥发后成膜性良好,可制成透明薄膜.共聚物Pa,Pb的拉伸强度分别为80.0MPa,51.8MPa,断裂伸长率6.9%,4.6%,杨氏模量2.0GPa,1.8GPa.     

双酚F型聚酰亚胺薄膜的制备与性能

以4-氯代酞酰亚胺和双酚F为原料,在N,N′-二甲基乙酰胺溶剂中,经水解、酸化、脱水,合成了一种新型的双酚F型二酐(BPFDA)单体,并用1H NMR和IR测试方法确认了其结构。 采用传统的一步法,用N,N′-二甲基乙酰胺作溶剂,BPFDA分别与4,4′-二氨基二苯醚（ODA）和4,4′-二氨基二苯甲烷（MDA）聚合,得到聚酰胺酸,并进一步热亚胺化得到聚酰亚胺薄膜,并对其进行了表征。 结果表明,BPFDA/ODA薄膜和BPFDA/MDA薄膜的玻璃化转变温度分别为200和204 ℃; 热失重分析表明,质量损失5%的温度分别为506.50和459.10 ℃;其拉伸强度分别为110和100 MPa。     

新型的4,4′-二甲基二苯酮分子间的夺氢固相光化学反应

本文报道了新型的4,4′-二甲基二苯酮分子间夺氢的固相光化学反应。4,4′-二甲基二苯酮晶体分子间的晶格排列,适合于分子间夺氢的要求,得到与液相不同的新产物,4-(对-甲基苯甲酰)苄基-双-(对-甲基)苯基甲醇。初步探讨了4,4′-二甲基二苯酮的固相光化学反应机理。     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

噻唑的研究Ⅳ.4,4''''-二-氯代甲基-2,2''''-雙噻唑的化學.六烷基2,2''''-雙噻唑-4,4''''-二甲基-二銨鹽的合成

1.二硫代乙二酰胺和1,3-二-氯代丙酮在丙酮中和在沉淀碳酸钙存在时缩合得4,4'-二-氯代甲基-2,2'-双噻唑。 2.4,4'-二-氯代甲基-2,2'-双噻唑的两个氯原子反应性能和一级烷基氯相同,能被(1)碘原子:(2)CH_3COO—基团:(3)C_6H_4(CO)_2N—基团:(4)(CH_3)_2N—基团,(5)基团,(6)C_6H_5O—基团,(7)ρ-CH_3C_6H_4O-基团,(8)(C_2H_5)_2N—基团所取代。 3.2,2'-双噻唑-4,4'-二甲基异硫脲二盐酸盐和氫氧化钾溶液共沸得2,2'-双噻唑-4,4'-二甲基二硫醇。 4.其季铵盐可由二法制得:(1)4,4'-二-氯代甲基-2,2'-双噻唑和三甲胺缩合产生二氯化六甲基2,2'-双噻唑-二甲基二铵。(2)4,4'-(N-四甲基-二-氨甲基)-2,2'-双噻唑和碘代甲烷生成二碘化六甲甚2,2'-双噻唑-4,4'-二甲基二铵;相似地-4,4'-(N-四乙基-二-氦甲基)-2,2'-双噻唑和碘代乙烷生成二碘化六乙基2,2'-双噻唑-4,4'-二甲基二铵。     

一种三聚季铵盐表面活性剂的合成

以N,N′-二甲基十八烷胺和1,6-二溴己烷为原料制得单头季铵盐(1);以1-溴十八烷和N,N,N′,N′-四甲基-1,6-己二氨己烷为原料制得单头季铵盐(2); 1和2反应合成了一种三聚季铵盐表面活性剂(3),其结构经1H NMR和IR确证。采用电导法和吊环法研究了3的表面性能。结果表明：25 ℃下,3的cmc为0.01 mmol·L^-1; γ_cmc为14.904 mN·m^-1; C₂₀为0.003 mmol·L^-1。     

有机可溶性高折射率聚酰胺酰亚胺的合成与性能

采用含硫二胺1,4-双(4-氨基苯硫基)苯(2SPDA)与偏苯三酸酐反应制备了一种含硫二酸化合物1,4-双(4-三甲酰亚胺基苯硫基)苯(BTPB).以此二酸为原料与两种高硫含量二胺单体,4,4′-双(4-氨基苯硫基)二苯硫醚(3SDA)以及2,7-双(4-氨基苯硫基)噻蒽(APTT)通过高温缩聚法制备了两种聚酰胺酰亚胺(PAI).制备的PAI在室温下可溶解于N-甲基-2-吡咯烷酮(NMP)中.PAI薄膜的起始热分解温度(T5%)超过440℃,玻璃化转变温度(Tg)大于190℃.PAI薄膜在波长大于500nm的可见光区具有良好的透明性.此外,PAI薄膜的折射率大于1.73,双折射小于0.04.     

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。     

Synthesis and properties of aromatic poly (ether sulfone)s and poly (ether ketone)s based on methyl-substituted biphenyl-4,4′-diols

Novel methyl-substituted aromatic poly (ether sulfone)s and poly (ether ketone)s were synthesized from combinations of 3,3′,5,5′-tetramethylbipheny-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol, and 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorobenzo-phenone by nucleophilic aromatic substitution polycondensation. The polycondensations proceeded quantitatively in a N-methyl-2-pyrrolidone-toluene solvent system in the presence of anhydrous potassium carbonate to afford the polymers with inherent viscosities between 0.86 and 1.55 dL/g. The methyl-substituted poly (ether sulfone)s and poly (ether ketone)s showed good solubility in common organic solvents such as chloroform, tetrahydrofuran, pyridine, m-cresol, and N,N-dimethylacetamide. The tetramethyl- and hexamethyl-substituted aromatic polyethers had higher glass transition temperatures than the corresponding unsubstituted polymers, and did not decompose below 350°C in both air and nitrogen atmospheres. The films of the methyl-substituted poly (ether ketone)s became insoluble in chloroform by the irradiation of ultraviolet light, indicating the occurrence of photochemical crosslinking reactions. © 1994 John Wiley & Sons, Inc.     

含苯乙炔的可自交联高温高性能聚芳醚酮的合成与性能

将可交联的苯乙炔结构引入到热塑性聚芳醚酮链中, 并对其交联前后的性能进行了深入研究.     

4,4’-二氯二苯酮合成二氮杂萘联苯酮结构聚醚砜酮的研究

以4-(4-羟基苯基)*2,3-二氮杂萘-1-酮(DHPZ)、4,4’-二氯二苯砜(DCS)和4,4’-二氯二苯酮(DCK)为原料,采用分步加料的方法,合成了系列高分子量的聚芳醚砜酮共聚物(PPESKs),其特性黏度在0.40 ～0.61dL/g之间,解决了由于DCK活性低不适合用于聚芳醚合成的问题.采用FTIR、示差...     

Synthesis and Characterization of Novel Organosoluble Methyl Substituted Poly(aryl Ether Ketone)s Containing Sulfone Linkage

Several new methyl substituted poly(aryl ether ketone)s containing sulfone linkage with inherent viscosities of 0.62–0.84 dL/g have been prepared from 4,4′‐bis(2‐methylphenoxy)diphenylsulfone and 4,4′‐bis(3‐methylphenoxy)diphenylsulfone with terephthaloyl chloride and isophthaloyl chloride by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl₃ as a catalyst in 1,2‐dichloroethane, respectively. These polymers having weight‐average molecular weight in the range of 71,000–49,000 are all amorphous and show high glass transition temperatures ranging from 167 °C to 191 °C, excellent thermal stability at temperatures over 400 °C in air or nitrogen, high char yields of 51–58% in nitrogen and good solubility in CHCl₃ and polar solvents such as DMF, DMSO and NMP at room temperature.     

聚芳醚亚砜的合成与表征

以二苯醚和二氯亚砜为主要单体 ,在无水AlCl3/CH2 ClCH2 Cl/NMP催化剂溶剂体系中进行低温溶液共聚 ,合成聚芳醚亚砜 (PPOS) ,研究了AlCl3/NMP用量及单体摩尔比对聚合反应的影响 .用IR、DSC、TG和X ray等对PPOS进行结构和性能的分析与表征 ,研究结果表明 :PPOS属无定形聚合物 ,具有较高的玻璃化转变温度 (Tg) ,软化温度在 2 6 0℃左右 ,在加热过程中出现二个热分解温度     

SYNTHESIS AND CHARACTERISTICS OF POLY(ARYLENE ETHER DIKETONE)S

Poly(arylene ether diketone)s were prepared by the aromatic nucleophilicdisplacement reaction of 4,4'-difluorobenzil with different bisphenols in the presence of an-hydrous potassium carbonate in diphenylsulfone at elevated temperature. The polymersobtained had inherent viscosity of 0.51 ～ 0.63 dL/g, and exhibited glass transition temper-ature ranging from 136 ～217℃ mainly depending on the bisphenols used in the polymersynthesis. Thermogravimetry of these polymers showed excellent thermal stability, indi-cating that 10% weight losses of the polymers were observed in the range above 428℃ and438℃ in air and nitrogen, respectively. The mechanical properties of these polymers werealso described and the permeability of five polymers for H_2, O_2 and N_2 was determined at30℃.     

Poly(ether imide)s derived from phthalazinone‐containing dianhydrides

An unsymmetrical and noncoplanar heterocyclic dianhydride was synthesized from a bisphenol‐like phthalazinone, 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, and a series of novel poly(ether imide)s based on it, with intrinsic viscosities of 0.67–1.42 dL/g, were obtained by one‐step solution polymerization in m‐cresol at 200 °C for 20 h. The polymers were readily soluble in N‐methyl‐2‐pyrrolidinone and m‐cresol. The poly(ether imide)s derived from 4,4′‐oxydianiline and 4,4′‐methylenedianiline were also very soluble in chloroform, 1,1′,2,2′‐tetrachloroethane, and N,N‐dimethylacetamide. The glass‐transition temperatures were 289–326 °C, as determined by differential scanning calorimetry. All the degradation temperatures for 5% weight loss occurred above 482 °C in nitrogen. The tensile strength of thin films of some of the polymers varied from 103.1 to 121.4 MPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6089–6097, 2004     

含3,5-二甲基二氮杂萘酮联苯结构聚醚酰亚胺的合成与性能

由4-[(3,5-二甲基-4-羟基)苯基]-2,3-杂萘-1-酮与4-氯-N-苯基邻苯酰亚胺通过亲核取代反应、水解反应和脱水反应合成了一种新型不对称含二氮杂萘联苯结构的二酐单体,并对其进行结构表征.由新型二酐单体与市售的二胺单体通过“一步法”溶液聚合反应合成了5种含二氮杂萘酮联苯结构的聚醚酰亚胺.通过FTIR和¹HNMR方法研究了聚合物的结构及性能.结果表明,该类聚合物既具有较高的耐热性能,又可以在室温下溶解于非质子极性溶剂,如N-甲基吡咯烷酮和间甲酚等.     

Synthesis and characterization of aromatic poly(ether sulfone)s containing pendant sodium sulfonate groups

Poly(ether sulfone)s containing pendant sodium sulfonate groups were prepared by the aromatic nucleophilic substitution reaction of 4,4′-dichlorodiphenylsulfone ( 1 ) and sodium 5,5′-sulfonylbis (2-chlorobenzenesulfonate) ( 2 ) with bisphenols ( 3 ) in the presence of potassium carbonate in N,N-dimethylacetamide. A new monomer 2 containing the sodium sulfonate groups was synthesized by the sulfonation of 1 with fuming sulfuric acid. The polycondensation proceeded smoothly at 170°C and produced the desired poly(ether sulfone)s containing the sodium sulfonate with inherent viscosities up to 1.2 dL/g. The polymers were quite soluble in strong acid, dipolar aprotic solvents, m-cresol, and dichloromethane. The thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 460°C in nitrogen atmosphere. Both the glass transition temperatures and hydrophilicity of the polymers increased with increasing their concentrations of sodium sulfonate groups. © 1993 John Wiley & Sons, Inc.