酰亚胺二羧酸的合成研究

以偏苯三酸酐(TMA)为原料,分别与4,4'-二氨基二苯醚、4,4'-二氨基二苯甲烷、1,6-己二胺反应,得到三种含酰亚胺结构的二羧酸产物(DIDA-a、DIDA-b、DIDA-c)。利用傅里叶红外光谱(FT-IR)、核磁共振氢谱(1H NMR)对酰亚胺二羧酸的结构进行表征。通过单因素实验,考察溶剂用量、反应时间、反应温度和反应物摩尔比对二酸产物收率的影响,得出DIDA-a的优化合成条件:偏酐起始浓度1.11mol/L,酰亚胺化反应时间6h,酰亚胺化反应温度140℃,TMA和二胺摩尔比2.05;DIDA-b的优化合成条件:偏酐起始浓度1.05mol/L,酰亚胺化反应时间5.5h,酰亚胺化反应温度145℃,TMA和二胺摩尔比2.02;DIDA-c的优化合成条件:偏酐起始浓度0.95mol/L,酰亚胺化反应时间5h,酰亚胺化反应温度135℃,TMA和二胺摩尔比2.03。     

四取代全氟辛基金属酞菁的合成

以邻苯二甲酰亚胺为起始原料,在30%的发烟硫酸条件下经碘化得到3-碘邻苯二甲酰亚胺,氨解、脱水得到3-碘邻苯二甲腈,并与全氟辛基碘在铜粉催化作用下,生成3-全氟辛基邻苯二甲腈,选用DBU合成法得到了标题化合物。对3-碘邻苯二甲酰亚胺的合成条件进行考察,得到了最佳反应条件:反应温度为60℃,n(邻苯二甲酰亚胺)∶n(单质碘)=1∶1,反应时间为12 h。目标产物结构经1HNMR和HRMS确认。     

4-硝基邻苯二甲腈的合成

以邻苯二甲酸酐为原料,合成出邻苯二甲酰亚胺,经硝化,氨化、脱水反应合成了4-硝基邻苯二甲腈。还对邻苯二甲酰亚胺的硝化和4-硝基邻苯二甲酰胺的脱水反应条件进行了研究,获得较佳的工艺条件,从而高产率制备的4-硝基邻苯二甲腈。     

K2CO3催化合成N-丙炔基邻苯二甲酰亚脏

用邻苯二甲酰亚胺和3-氯丙炔反应制备N-丙炔基邻苯二甲酰亚胺.以正交实验设计的方法对N-丙炔基邻苯二甲酰亚胺的合成反应温度、反应时间、投料比以及相转移催化剂进行工艺条件优化,得出最佳工艺条件是反应温度60 ℃、反应时间6 h、n(邻苯二甲酰亚胺)∶n(碳酸钾)∶n(四丁基氯化铵)为1∶1.25∶0.05,收率91.7%.     

异构脱蜡孔口催化机理研究探针分子3-乙基-十一烷的合成

针对SAPO- 11的一维十元环直孔道结构,设计了具有特殊分子结构的长链烷烃3-乙基-十一烷.以3-戊酮和溴辛烷与镁反应生成的格氏试剂为原料,经加成、水解、脱水、催化加氢反应生成3-乙基-十一烷,红外和质谱分析确定合成产物正确.影响醇脱水反应的主要因素为温度和硫酸含量,适宜的脱水反应条件为温度50℃、时间90 min、...     

4-硝基-N-丁基邻苯二甲酰亚胺的制备

本文介绍了一种4-氨基-N-丁基邻苯二甲酰亚胺的合成方法。以苯酐和正丁胺为原料,合成了N-丁基邻苯二甲酰亚胺,然后采用混酸硝化一锅法工艺合成4-硝基-N-丁基邻苯二甲酰亚胺。考察了物料配比、反应温度、反应时间等因素对反应的影响。在最优条件下,4-硝基-N-丁基邻苯二甲酰亚胺的含量达到97%以上,总收率达到90%以上。     

3,3＇,4,4＇-二苯醚二酐的合成工艺研究

以N-甲基-4-硝基邻苯二甲酰亚胺为起始原料,二甲基亚砜为溶剂,亚硝酸钾为催化剂进行偶联反应,所得偶联产物经水解、酸析、无水化合成3,3＇,4,4＇二苯醚二酐。对影响偶联反应的因素反应温度和反应时间进行了考察,通过优化反应条件,确定了最佳反应温度为165℃,最佳反应时间为11h,偶联产物的质量收率最高为43%。     

氨基化单甲氧基聚乙二醇的合成研究

首先合成了单甲氧基聚乙二醇对甲苯磺酸酯(mPEG-OTs),然后根据盖布瑞尔合成法原理,以邻苯二甲酰亚胺钾盐(PPI)为亲核试剂与mPEG-OTs反应,生成单甲氧基聚乙二醇的邻苯二甲酰亚胺衍生物(mPEG-PI),mPEG-PI与水合肼反应肼解生成伯胺,合成了一端为氨基的单甲氧基聚乙二醇(mPEG-NH2)。讨论了缚酸剂、溶剂、反应条件对反应的影响。通过红外、液质联用、核磁共振谱图证实了产物与目标分子的结构相吻合。     

SAPO-11/HZSM-5对乙醇脱水制乙烯反应的催化性能

测定HZSM-5与SAPO-11复合催化剂(SAPO-11/HZSM-5)对乙醇脱水制乙烯反应的催化性能,考察反应工艺条件;对比HZSM-5、SAPO-11和SAPO-11/HZSM-5催化乙醇脱水制乙烯反应性能;分析三种催化剂表面酸量及酸强度,以及对反应产物组成的影响。结果表明:SAPO-11/HZSM-5催化乙醇脱水制乙烯反应的适宜条件为:压力0.1 MPa,温度240℃,空速1.2 h-1,乙醇浓度99.7%;乙醇转化率、乙烯选择性分别为99.19%和98.77%;气相产物中乙烯含量达到98.92%,C3、C4组分含量分别为0.37%和0.40%,未检测到C5以上组分。SAPO-11/HZSM-5催化乙醇脱水制乙烯反应温度比HZSM-5、SAPO-11低60℃。适度增加催化剂表面弱酸量及强度,并使其具有相当比例的强酸量,有利于提高乙醇脱水制乙烯反应活性和乙烯选择性。     

双酰亚胺类蛋白质荧光探针的合成

以6种N 取代 4 氨基 邻苯二甲酰亚胺及马来酸酐为起始原料合成了相应的6种N (N 取代 邻苯二甲酰亚胺 4 基) 马来酰亚胺(Ⅱ)。丙酮为溶剂,氮气保护,室温下N 取代 4 氨基 邻苯二甲酰亚胺及马来酸酐反应2 5h得到N (N 取代 邻苯二甲酰亚胺 4 基) 氨基马来酰酸(Ⅰ),收率均>90%。Ⅰ在三乙胺与乙酐作用下,脱水环合生成N (N 取代 邻苯二甲酰亚胺 4 基) 马来酰亚胺(Ⅱ),反应收率达69%～85%。各步产物经1HNMR、IR确定结构。在研究脱水环合反应的过程中,分离得到其中一种产物的反应中间体:N (N 丁基 邻苯二甲酰亚胺 4 基) 氨基马来酰酸乙酸酐(Ⅲ),由此推测该反应为五元环过渡态的SN2亲核取代机理。     

轶纶~聚酰亚胺短纤维耐化学性研究

用不同浓度硝酸、硫酸和氢氧化钠溶液在不同温度下处理不同的时间,分别对轶纶聚酰亚胺短纤维、进口聚酰亚胺短纤维及聚酰胺酰亚胺短纤维抗断裂强度保持情况、水蒸汽中处理24 h短纤维的抗断裂强度保持情况和滤料的收缩情况进行耐化学性试验。结果表明,轶纶短纤维耐氢氧化钠性能要明显好于进口聚酰亚胺短纤维和聚酰胺酰亚胺短纤维,长期耐硫酸性能及耐硝酸性能略好于进口聚酰亚胺短纤维,并且都好于聚酰胺酰亚胺短纤维,特别是轶纶短纤维耐受高浓度的硫酸及硝酸的性能要好于其它两种短纤维,轶纶短纤维及滤料耐水蒸汽性能要好于其它几种短纤维及滤料。同时,对轶纶短纤维进行了红外分析,测试结果表明它的结构在酸碱处理前后并没有变化。     

Novel composite nanofibers based on polyamide 66/graphene oxide- grafted aliphatic- aromatic polyamide: preparation and characterization

New polyamide 66/graphene oxide (GO)-grafted aliphatic-aromatic polyamide (polyamide-imide) (PAI) (PA66/GOF) composites nanofibers were successfully prepared via electrospinning method for the first time. An polyamide imide (PAI) was synthesized using polycondensation reaction from a dicarboxylic acid and a diamine based on 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy) dianiline, and characterized by ¹HNMR and FTIR. Morphological, structural, thermal and mechanical characteristics of the nanocomposite fibers were investigated by means of SEM, TEM, WAXD, DMTA and TGA techniques. Composites nanofibers of PA66/GO, PA66/PAI and PA66/GOF with smooth surface, uniform structure as well as with diameter ranging from 195 to 784 nm were obtained. The GO incorporation caused a reduction in the nanofibers diameters. The TEM images showed that the GO was well dispersed in the PA66 nanofibers without significant aggregation. An approximately 10 °C temperature increase in the glass transition temperature of PA66 was achieved by addition of 0.5 wt% of PAI, resulting from aliphatic-aromatic structure of PAI. By the TGA results, an increase about 40 °C was observed in the thermal stability of PA66/PAI composite nanofibers in comparison with that of pure PA66 nanofibers.     

芳香性聚酰亚胺的阻燃改性研究进展

综述了芳香性聚酰亚胺(PI)在共混、共缩聚以及结构改性方面的研究进展,其中共聚改性按引入基团的不同又分为聚酰胺酰亚胺(PAI)、聚酯酰亚胺共聚物、引入含氮杂环等,结构改性包括在主链中引入杂元素、功能性侧基的引入、引入扭曲或非共平面结构,并提出PI在阻燃领域的发展方向。     

含噁唑环支链的苯氧型共聚聚酰亚胺的合成与表征

以3,5-二硝基苯甲酰氯和邻氨基苯酚为原料合成了含苯并噁唑基团的二胺,然后将其与二氨基二苯醚(ODA)和二苯醚四甲酸二酐(ODPA)进行常温共聚合成聚酰胺酸,最后采用两步法合成了含苯并噁唑支链的可溶性聚酰亚胺(PI)。采用红外光谱(FT-IR)、差示扫描量热法(DSC)和热重分析(TGA)等测试手段分析了该PI的结构、热性能和在各溶剂中的溶解性能。实验结果表明,经300℃热处理1h后,聚酰胺酸转化为酰亚胺化比较完全;引入苯并噁唑支链基团可以提高PI的耐热性,其玻璃化转变温度(Tg)在300℃左右,初始热分解温度为552.5℃;该PI在强极性溶剂中溶解性能良好,但不溶于一般的极性溶剂中,说明其在提高加工性能的同时仍能保持耐一般溶剂的性能。     

Studies on the preparation and properties of conductive polymers. IV. Novel method to prepare metallized plastics from metal chelates of polymides–imides

A new type of polyamide–imides (PAI) was synthesized by direct polycondensation. A series of polyamide–imide metal chelate films was prepared by the transition-metal salts (AgNO₃, CuCl₂, and CoCl₂) mixed with the polyamide–imides in NMP solution. These polyamide–imide metal chelate films were reduced by various reducing agents, and the reduced films exhibited low surface resistivity around 10⁰?10¹ Ω/cm². The surfaces of these conductive films were proved to be metallized by means of X-ray analysis. The metal adhered on the film was believed to be responsible for the improvement of electrical conductivity. The effects of kinds and concentrations of metal salts, kinds and concentrations of reducing agents, and reduction time on the conductivity of metallized films were investigated. The IR spectra and SEM observations of unreduced and reduced polymer chelate films were also studied.     

Ordered copolyamide-imides and copolyester-imides

A group of copolyamide-imides and copolyester-imides completely ordered has been obtained by the reaction of aliphatic and aromatic diamines with symmetrical monomers possessing reactive imide group. The aromatic diimide-amide and diimide-ester monomers were prepared by means of the reaction of acidolysis between trimellitic acid imide and acetoxy derivative of aromatic diamines and diphenols. The diimide-ester monomers with aliphatic substitutes were obtained by ester interchange between glycols and the methyl ester of trimellitimide. The polymerization reactions were carried out in a solution of polar solvents and the solated polymers were characterized with the object of estabilishing a relation between the properties and the structure of each one.     

Melt Rheology of Low-Density Polyethylene/Polyamide 6 using Ionomer as a Compatibilizer

Rheology of blends of polyamide 6 with low-density polyethylene compatibilized with sodium-, zinc-, and lithium-neutralized ethylene-methacrylic acid ionomers were investigated at 11, 33 and 55% neutralization of ionomer. Blends of polyamide 6 with low-density polyethylene without compatibilizer had lower shear viscosities than a mixing rule would predict. After adding compatibilizer, the shear viscosity of the blend is increased, presumably due to the formation of graft copolymer from the reaction of the primary amine with free acid groups. The increase of shear and elongational viscosity properties is less with EMAA than with the ionomers; which is consistent with mechanical property and dispersed phase size results presented in an earlier publication. For high polyamide 6 content blends, zinc-neutralized compatibilizers yielded the highest shear and elongational viscosities; while for low polyamide 6 contents, lithium-neutralized compatibilizers yielded the highest viscosities.     

Chemical stability of some poly(amide imide) type polymers

The stability of some heterocyclic poly(amide imide)s in acidic and alkaline medium was compared to the structurally related polyimide and poly(amide imide)s without other heterocyclic groups. All the polymers have high stability in acidic medium. The introduction of additional heterocycles such as 1,3,4-0xadiazole or phenylquinoxaline into the macromolecular chain of a poly(amide imide) increases substantially the resistance to alkaline medium. Polyamides containing imide rings only in the side chain are more stable to hydrolysis than related polyamide having imide units in the main chain.     

Miscibility in binary blends of aromatic and alicyclic polyamides

Miscibility was studied for four polyamide blends of 6I/6T [copolymer consisting of 1,6‐hexamethylene diamine and isophthalic acid (6I) (70 wt %) and terephthalic acid (6T) (30 wt %)] with MXD6 (polyamide of m‐xylenediamine and adipic acid), BAC6 (polyamide of 1,3‐bis(aminomethyl)cyclohexane and adipic acid), TR55 (copolymer consisting of nylon 11 (30 wt %), and polyamide of bis(3‐methyl, 4‐aminocyclohexyl)methane (30 wt %) and isophthalic acid (70 wt %), and CX7323 (polyamide of bis(4‐aminocyclohexyl)methane and dodecanedicarboxylic acid), using differential scanning calorimetry, X‐ray diffraction method, and electronmicroscopic observation. In quenched MXD6/(6I/6T) and BAC6/(6I/6T) blends, MXD6 and BAC6 components were miscible to 6I/6T, but TR55 and CX7323 components were completely phase‐separated from 6I/6T. Interestingly on electronmicroscopic observations, TR55 and CX7323 components were seen as droplets in 6I/6T medium when the content is low, but when 50 wt %, a layered structure was constructed with 6I/6T, reminiscent of morphological structure in block copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3971–3978, 2006     

Characterization of low molecular weight carboxyl-terminated polyamides obtained by reactive extrusion of polyamide 6 with trimellitic anhydride

Reactive extrusion has been applied as a very effective and fast process for controlled chemical degradation of a commercial polyamide 6 with trimellitic anhydride in the melt. A reaction mechanism based mainly on the amide/anhydride reaction has been discussed and confirmed by measurements of the solution viscosity, end group analysis, SEC, NMR, and IR spectroscopy. The systematic loss of molecular weight of the polyamides resulting from PA chain repture and the formation of imide linkages and carboxyl end groups were investigated. The theoretical values of molecular weight and end group concentration of the obtained oligoamides predicted by the reaction mechanism are in good agreement with the experimental ones. © 1996 John Wiley & Sons, Inc.