双酚A型二胺和二酐合成可溶性聚酰亚胺的研究

采用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)为单体,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,并分别经热亚胺化和化学亚胺化过程合成了双酚A型聚酰亚胺(PI).用FTIR、DSC、TGA等对聚合物的结构和性能进行了表征.F...     

BAPP-PBAP-ODPA共聚聚酰亚胺的合成

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4-苯基-2,6-双(4-氨基苯基)吡啶(PBAP)作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化合成了3种聚酰亚胺。用傅里叶变换红外光谱和核磁共振氢谱表征聚合物的结构,结果表明在1 780,1 720,725 cm~(-1)附近出现了聚酰亚胺的特征吸收峰。采用热重分析,溶解性、拉伸性能和吸水率测试表征了产物性能。所合成的聚酰亚胺溶解性和热稳定性良好,在N_2气氛中,起始降解温度超过500℃;800℃质量保持率为46.2%～64.5%(化学亚胺化)和52.6%～64.8%(热亚胺化)。聚酰亚胺膜的拉伸强度、拉伸断裂应变、拉伸模量分别为107.2～109.6 MPa,7.8%～10.5%,2.13～2.28 GPa。膜的吸水率为0.68%～0.75%。     

DABA-BAPP-BPADA共聚聚酰亚胺的合成与性能

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)及3,5-二氨基苯甲酸(DABA)作为二胺,2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化过程合成了可溶性共聚聚酰亚胺。用FT-IR对聚合物的结构进行了表征,性能测试采用了溶解性测试、DSC、TGA、拉伸测试和吸水率测试。FT-IR图谱表明,在1 780cm~(-1)、1720 cm~(-1)和740 cm~(-1)左右出现了聚酰亚胺的特征吸收峰。共聚聚酰亚胺在常见有机溶剂中可溶,并且有很好的热稳定性,玻璃化转变温度T_g为226.5℃,在氮气氛中降解起始温度508.5℃,800℃质量保持率为46.5%。共聚聚酰亚胺膜的拉伸强度、拉伸模量、断裂伸长率分别为109.7MPa、2.25GPa和15.2%。     

新型含吡啶环芳香二胺及其可溶性聚酰亚胺的合成与表征

以苯甲醛和3-(4-硝基苯氧基)苯乙酮(NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-苯基-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(PNPP),再用Pd/C和水合肼将PNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-苯基-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(PAPP)。以PAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.59 dL/g和0.56 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(T_g)为230.8℃,氮气氛中10%失重温度为552.0℃,同时,膜还有较好的力学性能,拉伸强度为88.6 MPa,拉伸模量为1.04 GPa,断裂伸长率为8.7%,膜的吸水率为0.89%。     

氟化聚吡啶酰亚胺的合成

用4-苯基-2,6-双[3-(4-氨基-2-三氟甲基苯氧基)苯基]吡啶作为二胺,均苯四甲酸二酐及2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐作为二酐,以N,N-二甲基甲酰胺为溶剂,通过常规的两步法,合成了可溶性氟化聚吡啶酰亚胺.傅里叶变换红外光谱显示在1 780,1 720,1 380 cm-1附近出现了聚酰...     

新型含吡啶环二胺及其可溶透明性氟化聚酰亚胺的合成与表征

以4-三氟甲基苯甲醛和3-(4-硝基苯氧基)苯乙酮(m,p-NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-(4-三氟甲基苯基)-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(m,p-3FPNPP),再用Pd/C和水合肼将m,p-3FPNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)。以m,p-3FPAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.78 dL/g和0.65 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(Tg)为234.4℃,氮气氛中10%失重温度为575.3℃,膜有很好的光学透明性,截止波长为369 nm,同时,膜还有较好的力学性能,拉伸强度为96.4 MPa,拉伸模量为1.63 GPa,断裂伸长率为9.2%,膜的吸水率为0.68%。     

含三(4-氨基苯基)苯的超支化聚酰亚胺的合成及表征

合成了三胺单体1,3,5-三(4-氨基苯基)苯(TAPB),将其与3,3′,4,4′-二苯酮四酸二酐(BTDA)缩合,采用化学亚胺化和热亚胺化两种方法合成了一种新型超支化聚酰亚胺(HBPIs).经红外光谱和核磁共振确认产物结构.对聚合物的性能进行分析,结果表明,聚合物的溶解性得到很好的改善.     

可溶性PBAP-ODPA-BPADA共聚聚酰亚胺的合成与性能

用4-苯基-2,6-双(4-氨基苯基)吡啶作为二胺,3,3′,4,4′-二苯醚四羧酸二酐和双酚A型二酐作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化过程合成了3种聚酰亚胺。用傅里叶变换红外光谱对聚合物的结构进行表征,表明在1 780,1 720,725cm-1附近出现了聚酰亚胺的特征吸收峰。采用溶解性测试、X射线衍射、热重分析、拉伸测试和吸水率测试表征了产物性能。所合成的共聚聚酰亚胺溶解性较好,溶于常见有机溶剂。所合成的聚酰亚胺膜热稳定性良好,在氮气氛中,起始降解温度超过500℃,10%失重温度为547.1～601.5℃,800℃质量保持率为64.8%～67.2%。聚酰亚胺膜的拉伸强度、拉伸模量、断裂伸长率分别为105.8～112.6 MPa,2.24～2.32 GPa,9.5%～10.2%。膜的吸水率为0.96%～0.98%。     

可溶性BAPP-MDA-ODPA共聚聚酰亚胺的合成与性能

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4,4′-二氨基二苯甲烷(MDA)作为二胺,3,3,′4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化过程合成了可溶性共聚聚酰亚胺。用FT-IR对聚合物的结构进行了表征,FT-IR测试结果表明在1 780 cm-1、1 720 cm-1和725 cm-1左右出现了聚酰亚胺的特征吸收峰。采用溶解性测试、DSC、TGA、拉伸测试和吸水率测试对产物的性能进行了测试。共聚聚酰亚胺在常见有机溶剂中可溶,并且有很好的热稳定性,在氮气氛中,起始降解温度超过500℃,800℃质量保持率为58.2%。共聚聚酰亚胺膜的拉伸强度、拉伸模量、断裂伸长率分别为103.5 MPa,2.36 GPa和11.7%。同时共聚聚酰亚胺膜还有很低的吸水率,为0.87%。     

含羟基聚酰亚胺改性环氧胶的制备及性能研究

将3,3'-二氨基-4,4'-二羟基联苯(DADHBP)、2,2-双(3-氨基-4-羟基苯基)六氟丙烷(BAH-PFP)和3,3',4,4'-四羧酸二苯醚二酐(ODPA)、3,3',4,4'-四羧酸二苯甲酮二酐(BTDA)单体聚合,再经亚胺化得到含羟基聚酰亚胺(HPI)粉末,采用傅里叶红外光谱对其进行了表征。由HPI、烯丙基双酚A、双马来酰亚胺、2-乙基-4-甲基咪唑与N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯甲烷(TGDDM)共聚反应制得胶粘剂,并对胶粘剂的热性能、力学性能及吸水性进行了研究,结果表明:该胶拉伸剪切强度为21.1 MPa,固化后吸水率为0.49%。通过凝胶化时间法计算胶粘剂的表观活化能为64.5 kJ/mol。     

Polypropylene nanocomposite using maleated PP and diamine

The insertion of the aliphatic diamine inside the organoclay will help the dispersion of the clay platelets in the PP/clay nanocomposite due to the reaction between the maleated PP and the diamine. Cloisite®20A was just simply mixed with hexamethylene diamine (HMDA) under shearing condition in Brabender mixer. HMDA group was successfully penetrated into silicate layers. As a result of penetration, d‐spacing of organoclay was increased. Polypropylene/clay nanocomposites were prepared by compounding with maleated PP and amine‐treated clay. From the FTIR spectra, reaction between amine group and maleic‐anhydride group was confirmed. The effect of the organoclay on the properties of the nanocomposite such as the morphology, dynamic mechanical properties, crystal structure and crystallization behavior, glass transition temperature, thermal stability, and tensile properties were investigated and analyzed. Nanocomposites with amine‐treated clays show enhanced properties compared with those with non–amine‐treated clay (Cloisite®20A). From the TEM analysis, nanocomposites with amine‐treated clays shows better dispersibility compared with those with Cloisite®20A alone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

乙撑胺的市场分析及生产工艺技术比较

对乙撑胺系列产品的国内外市场进行了分析,并对不同生产工艺技术进行了比较。认为应引进国外先进生产技术,优化产品结构,开拓新的应用领域     

N-酰基乙二胺三乙酸类表面活性剂的结构特点与物化性能

重点介绍了螯合性表面活性剂-N-酰基乙二胺三乙酸钠的制备与性能，该类表面活性剂同时具备表面活性和螯合性，对人体和环境温和，与其他表面活性剂的配伍性好，与酶，漂白剂的相容性好，对金属具有防腐和钝化作用。具有广泛的应用领域。     

Polymers with reactive p-phenylene diamine groups

Suspension copolymers of N-ethyl-N-(2-methacroylethyl)-p-phenylenediamine (AMBD) and 2-hydroxyethyl-methacrylate (HEMA) were prepared and the copolymerization conditions were determined. The reactive copolymers contain a theoretical number of reactive groups capable of reacting with low-moleculare weight compounds. A change in the porous character of the copolymer has no influence on its reactivity.     

Copolymerization of caprolactam with polyoxybutylene diamine

Nylon 6-polyoxybutylene block copolymers were prepared by reacting polyoxybutylene diamine with caprolactam in the presence of phosphoric acid. The copolymerization was carried out in a Helicone-type reactor and the effect of time, temperature, and caprolactam concentration on the properties of the products was recorded. Differential Scanning Calorimetry studies of the products suggest the presence of both the ABA and AB types of sequences, where A and B represent nylon 6 and polyether blocks, respectively. Dynamic mechanical measurements of typical copolymers revealed the presence of at least two different nylon moieties. The melt rheology data reflect a general increase in the pseudoplasticity of the copolymer with the increase of the polyether content. Increases of the polyether content in the copolymer result in an increased elongation and a decreased tensile strength and modulus.     

Curing kinetics and properties of epoxy resin-fluorenyl diamine systems

Diglycidyl ether of bisphenol fluorene (DGEBF), 9,9-bis-(4-aminophenyl)-fluorene (BPF) and 9,9-bis-(3-methyl-4-aminophenyl)-fluorene (BMAPF) were synthesized to introduce more aromatic structures into the epoxy systems, and their chemical structures were characterized with FTIR, NMR and MS analyses. The curing kinetics of fluorenyl diamines with different epoxy resins including DGEBF, cycloaliphatic epoxy resin (TDE-85) and diglycidyl ether of bisphenol A (DGEBA) was investigated using non-isothermal differential scanning calorimetry (DSC), and determined by Kissinger, Ozawa and Crane methods. The thermal properties of obtained polymers were evaluated with dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The results show that the values of activation energy (E_a) are strongly dependent on the structures of epoxy resin and curing agent. The curing reactivity of epoxy system is restrained by the introduction of rigid fluorene into chain backbone and flexible methyl into side groups. The cured DGEBF/fluorenyl diamine systems exhibit remarkably higher glass transition temperature, better thermal stability and lower moisture absorption compared to those of DGEBA/fluorenyl diamine systems, and display approximate heat resistance and much better moisture resistance relative to those of TDE-85/fluorenyl diamine systems.     

甲苯二胺装置扩产改造的目标与瓶颈分析

对甲苯二胺(TDA)生产装置扩建改造的目标与瓶颈进行了分析,阐述了目标与瓶颈在TDA装置扩建改造中相辅相成的关系。根据制定目标和发现瓶颈的一般原则,先消除拓朴信息瓶颈,再考虑强度瓶颈,最后再考虑容积瓶颈。根据目标与瓶颈分析结果制定改造方案,在投资很少的情况下,TDA装置生产能力可提高100%,且改造后蒸汽、循环水单位产品消耗量降低30%以上,原料与催化剂消耗都有所下降,具有好的社会效益和经济效益。     

间苯二甲胺的生产技术与应用进展

综述了间苯二甲胺(MXDA)的生产技术与应用进展。工业上以间二甲苯为原料,经气相氨氧化制得间苯二腈(IPN),再通过催化加氢制得MXDA,该合成路线第一步间二甲苯氨氧化制备IPN的技术已经趋于成熟,第二步IPN催化加氢制备MXDA可采用釜式间歇加氢或固定床连续加氢工艺。日本三菱瓦斯化学公司是目前全球最大的MXDA生产商,采用固定床连续加氢工艺,合计生产能力50 kt/a,国内IPN合计生产能力32 kt/a左右,MXDA生产能力6.5kt/a。MXDA除部分用于合成环氧树脂固化剂、间二甲苯二氰酸酯外,主要用于生产尼龙MXD6,具有广阔的市场前景,是国内亟待发展的重要的精细化工中间体。我国应重点围绕加氢催化剂,固定床连续工艺流程和分离工艺开展研究,形成具有自主知识产权的MXDA生产工艺,提高产品市场竞争力。     

Functionalization of carbon nanofibers with diamine and polyimide oligmer

This paper discusses the functionalization of oxidized carbon nanofibers (OCNF) with monomer and oligmer that mimic the structure of repeat unit of a polyimide (2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride-phenylene diamine). The goal was to covalently bind groups to the surface of OCNF that would both improve compatibility with the polyimide and potentially in case of the oligmer allow for chain entanglement in composite format. The reactions were carried out with or without initial activation by thionyl chloride (SOCl₂). Functionalization following each reaction step was characterized using thermal gravimetric analysis (TGA), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). While quantitative analyzes indicated that the concentration of surface reactive oxygen groups was fairly low, the OCNFs were successfully functionalized with the aromatic diamine, dianhydride and the polyimide oligmer.