Synthesis of Poly(aryl amide imide)s Derived from o-diphenyltrimellitic Anhydride

The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o diphenyltrimellitic anhydride are described.The poly(aryl amide imide)s having inherent viscosities of 0.39-1.43dL/g in N methyl 2 pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.

Synthesis of Novel Poly(aryl ether amide)s Containing the Phthalazinone Moiety

Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.

Synthesis of Methyl-substituted Phthalazinone-based Aromatic Poly(amide imide)s

A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36~0.65 dL/g. These polymers had high glass transition temperatures above 300C and they lost 10% weight between 426~475C in N2. The structure of diamine 1 and the polymers was confirmed by IR, 1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP, m-cresol etc. and easily cast into tough, flexible films. The X-ray indicated that they are all amorphous.

SYNTHESIS OF NEW AROMATIC POLY(AMIDE IMIDE)S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N- dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Tg) are in the range of 301-327°C, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 'C.

Synthesis of a Poly(amide-imide)from 5,6-Diphenyl-1-chloroformyl3,4-benzenedicarboxylic Anhydride and Bis (4-aminophenyl)ether

A novel poly (amide-imide) was prepared from a novel monomer: 5,6-diphenyl-chloroformyl-3,4-benzenedicarboxylic anhydride and bis (4-aminophenyl) ether. The polymer was characterized by FTIR. (HNMR)-H-1. DSC and TGA.

New optically active poly(amide-imide)s derived from N,N'-(4,4-diphthaloyl)-bis-L-leucine and hydantoin derivatives:Synthesis and properties

Six new optically active poly（amide-imide）s （5a-f） were synthesized through the direct polycondensation reaction of N,N′-（4,4′- diphthaloyl）-bis-L-leucine （3） with six hydantoin derivatives （4a-f）. Tripbenyl phosphite （TPP）/pyridine in the presence of calcium chloride （CaCl2） and N-methyl-2-pyrrolidone （NMP） were successfully applied for direct polycondensation. The polycondensation reactions produce a series of new poly（amide-imide）s （5a-f） in high yields, and inherent viscosity between 0.42 and 0,55 dL/g. The resulting poly（amide-imide）s （5a-f） were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis （TGA and DTG）, solubility test and FT-IR spectroscopy.

新型含氟聚酰胺酰亚胺的合成与性能

由于芳香族聚酰胺酰亚胺(PAI)的溶解性较低,限制了其在溶液加工方法中的应用。为了提高PAI的溶液加工性、降低溶剂使用成本并提高热性能,研究了三苯环结构和氟取代对PAI的性能影响,以苯甲醛和对三氟甲基苯甲醛与2,6-二甲基苯胺为原料,合成了新的二胺化合物4-[(4-氨基-3,5-二甲基苯基)苯基甲基]-2,6-二甲基苯胺(ADPD)、4-[(4-氨基-3,5-二甲基苯基)[4-(三氟甲基)苯基]甲基]-2,6-二甲基苯胺(ADFPD),再与偏苯三酸酐酰氯合成了含新结构的PAI。通过傅里叶变换红外光谱、核磁共振氢谱等对单体和聚合物进行表征,通过分析证明成功合成新型PAI;采用差示扫描量热分析、热重分析、水接触角、溶解性能测试对PAI性能进行了表征。结果表明,制备的聚合物均具有良好的热稳定性能和溶解性,玻璃化转变温度大于300℃,在氮气的环境下5%热失重温度在430℃及以上,最大热失重温度在600℃以上;在类似化学结构上,对比未引入—CF_(3)的PAI-1和引入—CF_(3)的PAI-2的测试结果,发现PAI-2在溶解性和热性能上均优于PAI-1,并且能够明显降低聚合物的表面能,表明—CF_(3)能够有效提高PAI的部分性能。

热重分析法测定聚酰胺-酰亚胺分解反应的活化能

聚酰胺-酰亚胺(PAI)是分子中酰胺键和酰亚胺键交替存在的一类非晶热塑型聚合物,PAI材料的热稳定性决定其在加工使用过程中的可靠性,但目前关于PAI热分解动力学研究相对较少。通过对市售PAI样品和研究院自产PAI样品分别在不同升温速率5,10,15℃/min条件下进行热重分析实验,根据Ozawa-Flynn-Wall法求算热分解反应的活化能:市售PAI颗粒状样品活化能Ea=343.70 J·mol^(-1),研究院自产颗粒样品Ea=318.29 J·mol^(-1)、粉末样品Ea=233.92 J·mol^(-1)。结果表明研究院自产PAI样品的热分解稳定性与市售样品基本一致,同时样品加工方式对热分解温度有重要影响,市售颗粒样品堆积密度1.3845 g/cm^(3)大于研究院自产样品堆积密度1.226 g/cm^(3),热分解温度略高,活化能稍大。

POLYMERIZATION OF N,N'-(PYROMELLITOYL)-BIS-L-LEUCINE DIACID CHLORIDE WITH HYDANTOIN DERIVATIVES BY MICROWAVE IRRADIATION

Facile and rapid polycondensation reactions of N,N'-(pyromellitoyl)-bis-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h were developed by using a domestic microwave oven in the presence of a small amount of polar organic medium such as o-cresol. The polycondensation reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7-10 min, producing a series of novel optically active poly(amide-imide)s 3a-h with high yield and inherent viscosity of 0.35-0.65 dL/g. All of the above polymers were fully characterized by FT-IR, elemental analyses, inherent viscosity (η inh ), solubility test and specific rotation. Some structural characterization and physical properties of these optically active poly(amide-imide)s are reported.

含酰胺单元聚酰亚胺薄膜的结构设计与制备

设计合成了一种含酰胺-酰亚胺结构和三氟甲基侧基的二酸,将其与4种含不同取代基的二胺单体通过一步缩聚法制备成一系列聚酰胺-酰亚胺(PAI)薄膜,研究分子链结构对PAI薄膜光学性能、尺寸稳定性、热稳定性、力学性能等的影响。结果表明:随着PAI结构中氟和酰胺单元含量的增加,PAI薄膜的透光率和尺寸稳定性得到提高,波长450 nm处的透光率均在79%以上,测试温度为50~300℃内的热膨胀系数为(22.99~33.79)×10^(-6)K^(-1);同时,分子链的刚性特征及酰胺单元的存在使PAI薄膜具有优异的力学性能,经过上万次弯折后,薄膜的拉伸强度平均值仍保持在77.1~93.6 MPa,弹性模量平均值为2.83~3.31 GPa,保持较高的力学性能。因此,通过引入三氟甲基和酰胺单元可制备出光学性能、尺寸稳定性、耐热稳定性及力学性能优异的PAI薄膜,该薄膜在柔性有机发光二极管、挠性覆铜板等领域具有广泛的应用潜力。

聚酰亚胺类聚合物合成及其在涂层中应用研究进展

随着科技的发展,涂层领域对高性能聚合物的兴趣和需求增加。聚酰亚胺类聚合物作为高分子金字塔顶端的材料,理应在涂层领域发挥作用。聚酰亚胺类高分子涂层由于其结构的特殊性,常常用作热防护层、防水耐湿层、耐辐射层等隔离层,在航空航天、电子、机械制造以及建筑等行业具有广泛的应用。本文介绍了聚酰亚胺类聚合物(PI,PAI,PEI)的合成方法,着重阐述了高性能聚合物(PI,PAI,PEI)近几年在涂层方面的研究与发展,最后对聚酰亚胺类高性能涂层材料现阶段面临的问题与挑战以及未来的发展方向提出了看法。

SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(AMIDE-IMIDE)S CONTAINING PHOTOSENSITIVE CHALCONE UNITS IN THE MAIN CHAIN

A series of new optically active poly（amide-imide）s were synthesized by direct polycondensation reaction of 4,4＇-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride （TsCl）, pyridine （Py） and dimethylformamide （DMF） system as condensing agent. The resulting thermally stable poly（amide-imide）s were obtained in good to high yields and inherent viscosities ranging between 0.35 dL/g and 0.58 dL/g and were characterized with FTIR, IH-NMR, CHN, Ultraviolet, TGA and DTG techniques.

Synthesis and characterization of optically active and organosoluble poly(amide-imide)s containing imidazole rings as pendent groups by direct polycondensation

Six new optically active poly(amide-imide)s(PAIs) 6a-f were prepared by direct polycondensation reaction of N-trimelli-tylimido-L-histidine 4 as a chiral diacid with various aromatic diamines 5a-f.Triphenyl phosphite(TPP)/pyridine(Py) in the presence of calcium chloride(CaCl2) and N-methyl-2-pyrrolidone(NMP) were successfully applied to direct polycondensation reaction.The resulting new polymers were in good yields,and had inherent viscosities ranging between 0.29 and 0.41 dL g-1 and were detected with elemental analysis,FTIR,1H-NMR spectroscopy,specific rotation and differential scanning calorimeter(DSC),thermogravimetric analysis(TGA),and derivative of thermaogravimetry(DTG).Imidazole pendent groups of the polymer chains disturb interchain and intrachain interactions and make these PAIs readily soluble in polar aprotic solvents such as N,N-dimethylacetamide(DMAc),N,N-dimethylformamide(DMF),dimethylsulfoxide(DMSO),NMP and solvents such as sulfuric acid.Thermogravimetric analysis indicated that the residual weight percents of polymers at 600 °C were between 56.47% and 68.76%,which show their thermal stability.

OPTICALLY ACTIVE AND FLAME-RETARDANT POLY(AMIDE-IMIDE)S BASED ON PHOSPHINE OXIDE MOIETY AND N,N′-(PYROMELLITOYL)BIS-L-AMINO ACID IN THE MAIN CHAIN:SYNTHESIS AND CHARACTERIZATION

Six new optically active and flame-retardant poly（amide-imide）s PAls 5a-5f containing phosphine oxide moiety as a flame-retardant unit in the main chain were synthesized from direct polycondensation reaction of six chiral N,N＇-（pyromellitoyl）-bis-L-amino acid 3a-3f with bis（3-aminophenyl）phenyl phosphine oxide 4 in a medium consisting of N-methyl-2-pyrrolidone （NMP）, triphenyl phosphite （TPP）, calcium chloride （CaCl2） and pyridine. The polymerization reactions produced a series of optically active poly（amide-imide）s with good yield and good inherent viscosity of 0.34-0.70 dLg^-1. The resulted polymers were fully characterized by means of FTIR and ^1H-NMR spectroscopy, gel permeation chromatography （GPC）, elemental analyses, inherent viscosity and solubility tests. Thermal properties and flameretardant behavior of the PAIs 5a-5f were investigated using thermal gravimetric analysis （TGA and DTG） and limiting oxygen index （LOI）. Data obtained by thermal analysis （TGA and DTG） revealed that these polymers showed good thermal stability. Furthermore, high char yield in TGA and good LOI values indicated that the resulting polymers were capable of exhibiting good flame retardant properties. N,N＇-（pyromellitoyl）-bis-L-amino acids 3a-3f were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride （1,2,4,5-benzenetetracarboxylicacid-1,2,4,5-dianhydride） 1 with L-alanine 2a, L-valine 2b, L-leucine 2c, L-isoleucine 2d, L-phenyl alanine 2e and L-2-aminobutyric acid 2f in acetic acid solution.

SYNTHESIS OF ORGANO SOLUBLE AROMATIC POLY(AMIDE-IMIDE)S BASED ON 2-(5-(3,5-DINITROPHENYL)-1,3,4-OXADIAZOLE-2-YL)PYRIDINE IN AN IONIC LIQUID

In this work, the syntheses of new thermally stable poly（amide-imide）s with pendant 2-pyridyl-l,3,4-oxadiazole units in n-butyl methyl imidazolium bromide as reaction media have been reported. A new dicarboxylic acid has been derived from the reaction of diamine, 2-（5-（3,5-diaminophenyl）-1,3,4-oxadiazole-2-yl）pyridine （POBD）, and trimellitic acid anhydride. Polymers were prepared from the reaction of the diimide-diacid （DIDA） and different aromatic diamines in butyl methyl imidazolium bromide, [bmim] [Br], in the presence of triphenyl phosphite （TPP） as condensing agent without needing any extra components. The prepared poly（amide-imide）s were characterized by FTIR, elemental analysis, and through the synthesis of a model compound. The prepared polymers were soluble in polar and aprotic solvents, such as DMF, DMSO, NMP and DMAc. The inherent viscosity of the polymer solutions was in the range of 0.52-1.33 dL/g measured in concentrated H2SO4 at a concentration of 0.125 g/dL at （25 ± 0.5）℃. The results are compared with the results obtained from common direct polycondensation with NMP as solvent. Polymers obtained in ionic liquid showed higher inherent viscosity than that of polymers obtained via classical method in NMP. Thermal properties of the polymers were studied with DSC and TGA methods.

SYNTHESIS AND CHARACTERIZATION OF ORGANO-SOLUBLE POLY(AMIDE-IMIDE)S BASED ON 1,2-BIS[4-(TRIMELLITIMIDO)PHENOXY]ETHANE AND AROMATIC DIAMINES

New organo-soluble poly（amide-imide）s（PAIs） 8a-8f were prepared from newly synthesized 1,2-bis[4,4＇-（trimellitimido） phenoxy]ethane 6 via direct polycondensation with various aromatic diamines.The diacid 6 was synthesized by the condensation reaction of 12-bis[4-atninophenoxy]ethane 4 with trimellitic anhydride 5 in acetic acid.All polymers were obtained in quantitative high yields with inherent viscosities of 0.48-0.61 dL/g.All of these polymers were highly soluble in organic solvents such as,N-methyl-2-pyrrolidone（NMP）,dimethylformamide（DMF）,N,N＇-dimethylacetamide （DMAc） and dimethylsulfoxide（DMSO） at room temperature and were fully characterized by means of NMR spectroscopy, FTIR spectroscopy,elemental analyses,inherent viscosity,solubility test,specific rotation,differential scanning calorimetry （DSC） and thermogravimetric analysis（TGA）.

NEW COHORT OF OPTICALLY ACTIVE NANOSTRUCTURE POLY(AMIDEIMIDE)S:PRODUCTION AND PROPERTIES

Novel aromatic-aliphatic poly（amide-imide）s containing chiral units in the main chain and hydroxyl benzamide units in the side chain have been obtained from the step-growth polymerization of 3,5-diamino-N-（4-hydroxyphenyl） benzamide （2） with different chiral diacid chlorides （la-le）. Theoretical calculations were done by means of computational chemistry methods to narrate the stable conformation and orientation of each diacid chloride monomers under reaction conditions. These polymers were characterized by conventional techniques. The resulting polymers show good thermal stability. Other physical properties of polymers including crystallinity, inherent viscosity and morphological characteristics were also studied.

Preparation and Characterization of Poly(amide-imide)/ZnO Nanocomposites Containing Pendent Benzoxazole and Benzimidazole Segments

In the present investigation, novel poly（amid-imide）/zinc oxide nanocomposites（PAI/Zn O NCs） containing benzoxazole and benzimidazole pendent groups with different amounts of modified zinc oxide nanoparticles（Zn O NPs） were successfully prepared via the ex situ method. Poly（amid-imide）（PAI） was prepared by direct polycondensation of 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole（DCA） with 5-（2-benzimidazole）-1,3-phenylenediamine（DAMI） and provided the polymeric matrix with well-designed groups. The surface of Zn O NPs was functionalized with 3-aminopropyltriethoxysilane（APS） coupling agent to have a better dispersion and enhancing possible interactions of NPs with functional groups of polymer matrix. The amount of APS bonded to the Zn O surface was determined by thermogravimetric analysis. PAI/Zn O nanocomposites were characterized by Fourier transform infrared spectroscopy（FTIR）, X-ray diffraction（XRD）, and scanning electron microscopy（SEM）. SEM analysis showed that the modified Zn O nanoparticles were homogeneously dispersed in polymer matrix. In addition, TGA data indicated an enhancement of thermal stability of the nanocomposite compared with the neat polymer.

Synthesis of novel poly(aryl ether amide)s containing the phthalazinone moiety

Two novel heterocylic diamine monomers: l,2-dihydro-2-(4-aminophenyl)-4-4-(4-aminophenoxy) phenyl]-(2H)-phthalazin-l-one and 1,2-Dihydro-2-( 4-aminophenyl )-4-[4-(4-aminophenoxy-3, 5-dimethylphenyl]-(2H)-phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16–1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N,N -dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide ( DMSO ), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition temperatures ( Tg) in the 291–329°C range.

含联苯二氮杂萘酮结构聚芳酰胺的合成与表征

用类双酚单体4[4(4羟基苯基)苯基]2H二氮杂萘1酮(DHPZpP)与对氯苯腈进行亲核取代反应后碱性水解合成一种扭曲、非共平面杂环芳香二酸,4{4[4(4羧基苯氧基)苯基]苯基}2(4羧基苯基)二氮杂萘1酮(2).由二酸2和各种芳香二胺进行膦酰化缩聚反应制得了一系列的含联苯二氮杂萘酮结构聚芳酰胺,其特性粘数在0.42～0.72dLg之间.该类聚芳酰胺均可溶解于NMP、DMAc和DMSO等极性有机溶剂中,并且可用DMAc为溶剂制成具有良好机械性能的透明聚合物薄膜,聚合物薄膜的拉伸强度为80～89MPa.该类聚芳酰胺具有优异的耐热性,玻璃化转变温度Tg在298～328℃之间,10%的热失重温度(Td)在470℃以上.