新型热塑性聚酰亚胺改性环氧胶粘剂的研制

采用含羧基聚酰亚胺粉末,对环氧树脂胶粘剂进行改性,制得新型环氧胶粘剂,其拉伸剪切强度可达30.0MPa以上,初始分解温度大于368.5℃。随着聚酰亚胺量的增加,其耐热性也相应提高。此外,环氧胶粘剂体系的疏水性也有一定程度的提高。     

热塑性聚酰亚胺增韧环氧树脂胶粘剂的研制

利用热塑性聚酰亚胺粉末增韧改性环氧树脂,得到了综合性能优异的胶粘剂体系,并对其凝胶化时间、接触角、表面能、疏水性、耐热性等各项性能进行了研究。     

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。     

聚酰亚胺齐聚物改性胶粘剂的制备及性能研究

利用2,2-双[4-（4-氨基苯氧基）苯1丙烷及偏苯三酸酐合成聚酰亚胺齐聚物,并用此齐聚物改性环氧树脂胶粘剂。使用红外光谱、凝胶化时间、接触角和拉伸剪切强度对改性胶粘剂性能进行表征。结果表明,齐聚物的加入对环氧树脂固化反应具有促进作用;当100质量份环氧中加入16份齐聚物时,胶粘剂力学性能最佳;当齐聚物用量为20份时;胶粘剂表面能最高。     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

单组分环氧树脂胶粘剂用潜伏性固化剂

对单组分环氧树脂胶粘剂用潜伏性固化荆的研发进展进行了扼要的综述.     

电位滴定法在聚酰亚胺合成中的应用

未完全环化的酰胺酸对聚酰亚胺的性能有重要影响,用电位滴定法可直接测定其含量。对常规的电位滴定装置进行了改进,用VB语言编写了上位机操作软件,实现了滴定控制、数据采集和处理等功能,建立了一套自动电位滴定测试系统,可用于测定二步法合成聚酰亚胺过程中剩余聚酰胺酸的含量。测定结果表明:数据的重现性好、灵敏度高,且操作方便,为进一步开展聚酰亚胺合成及其亚胺化动力学研究提供了可行的途径。     

聚酰亚胺胶粘剂的改性研究

介绍了聚酰亚胺(PI)胶粘剂改性的研究进展,详细讨论了缩合型PI胶粘剂、热塑性PI胶粘剂和加成型PI胶粘剂的发展现状、最新进展、性能(物理机械性能、耐热性、耐化学性和成型加工性)及其在各领域中的应用。总结了PI胶粘剂存在的具体问题和未来的发展趋势。     

Improvement of adhesion of Kevlar fiber to epoxy by chemical modification

Kevlar 149 fibers were surface-modified by chlorosulfonation and subsequent reaction of -SO₂O with some reagents (e.g. glycine, water, ethylenediamine, and 2-butanol) to improve the adhesion to epoxy resin. The mechanical properties and surface topography of the modified fibers were investigated at different reaction times and reagent concentrations. The surface functional groups introduced into the surface of the fibers were identified by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS). The interfacial shear strength (IFSS) between the fibers and epoxy resin was measured by the microbond test. The results showed that the IFSS was markedly improved (by a factor of 2.25) by the chlorosulfonation/glycine treatment and that the fiber strength was not affected. Scanning electron microscopy (SEM) was also used to study the surface topography of fibers pulled from the epoxy resin. Furthermore, energy dispersive X-ray (EDX) spectroscopy was used to qualitatively examine the amount of sulfur in the fiber surfaces and in the fracture surfaces of fibers from microbond pull-out specimens. The results of EDX examination were consistent with a change of the fracture mode from the interface between the fiber and the epoxy resin to a location within the fiber and/or epoxy resin as observed by SEM.     

聚酰亚胺胶粘剂改性技术研究进展

介绍了近年来聚酰亚胺(PI)胶粘剂的常见改性方法。重点分析和总结了PI胶膜表面化学改性方法(包括等离子体改性、离子束改性、化学试剂改性和表面接枝聚合改性等)和PI胶粘剂材料化学改性方法,并对PI胶粘剂改性技术的未来发展趋势进行了展望。     

Characteristics of polyimide ultrafine fibers prepared through electrospinning

A novel route for making polyimide sub‐micron fibers is described. The ultrafine fibers are prepared by electrospinning a poly(amic acid) solution, a precursor of polyimide, followed by thermal imidization. The fiber diameters, which are much smaller than conventionally spun fibers, range from a few tens of nanometers to several micrometers. A rectangular cross‐section is observed in the case of sub‐micron fibers with a cross‐sectional dimension below ～500 nm. © 2003 Society of Chemical Industry     

聚酰亚胺的合成及其膜的制备

先在四氢呋喃/甲醇(质量比为4:1)混合溶剂体系中合成聚酰胺酸(PAA),后在真空烘箱中(200℃/h)形成聚酰亚胺(PI)膜,并通过IR和TG/DTG对产物进行了表征,结果表明能得到耐高温的Pl膜。     

Improved polyimide/metal adhesion by chemical modification approaches

To increase their adhesion to silver, polyimide (PI) surfaces were modified by sulfonation reactions by means of different experimental procedures. The results of these modification reactions were analyzed in terms of the variation of the surface chemical composition examined by X‐ray photoelectron spectroscopy. Long‐time reactions were also followed by monitoring the increase in weight of the PI films. Changes in the total surface free energy were evaluated by contact angle measurements with the sessil drop method. The influence of the modification reactions on silver/PI adhesion was estimated by means of a 180° peeling test according to ASTM standards. Finally, the effect of chemical modification on film roughness was investigated by means of atomic force microscopy. The results obtained showed that a net improvement, that is, over the maximum rate according to the reference ASTM test, was attained via both the gaseous SO₃ and concentrated H₂SO₄ procedures, with the latter procedure more effective in the presence of silver sulfate as a catalyst. However, the former was judged more convenient because of the low amount of reagents used and the simplicity of cleaning operations. Interestingly, optimum adhesion levels were attained after only very low contact times with all sulfonating agents, that is, after about 30 s. These results were compared with the effects on PI/silver adhesion of traditional etching procedures with KOH aqueous solutions at different temperatures. In this case, good adhesion was observed only after longer reaction times, that is, on the order of 1–2 min in the case of 1M KOH and 1 h in the case of 0.1M KOH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1971–1985, 2001     

单组分环氧胶固化剂及促进剂的改性研究

采用间甲苯胺对固化剂双氰胺进行改性,红外表明双氰胺的—C≡N与间甲苯胺的—NH2发生反应,提高了固化剂的反应活性;XRD也证实了改性反应的进行。采用硫酸铜改性咪唑,XRD表明了有新的物质生成。经改性的双氰胺具有较好的活性和贮存稳定性。但单独使用改性双氰胺作固化剂,用量一般较大(为环氧树脂的25%),影响体系的流动性;而复合使用改性双氰胺和咪唑,在保证性能和固化时间的前提下,双氰胺的用量可减少至15%。改性双氰胺与环氧树脂具有较好的相容性,使环氧树脂固化体系的力学性能具有较大幅度的提高。     

纳米颗粒对环氧树脂胶粘剂／钢铁附着强度的影响

采用纳米Al2O3、纳米CaCO3、纳米SiO2三种纳米颗粒,机械混合对环氧树脂胶粘剂进行改性,并对纳米颗粒改性的环氧树脂胶粘试样进行了附着强度的检测。结果发现,通过改变纳米颗粒的种类和含量,环氧胶粘剂／钢铁基体之间的附着强度得到不同程度的提高,其中添加2％纳米Al2O3颗粒的环氧胶粘剂与钢铁基体的附着强度提高了4倍左右。通过断面形貌特征和不同基体粗糙度下对添加纳米颗粒环氧胶与钢铁基体之间附着强度的检测,对此现象产生的原因进行了分析和讨论。     

聚酰亚胺改性环氧树脂/酸酐体系固化动力学研究

采用非等温差示扫描量热(DSC)法研究了聚酰亚胺(PI)改性环氧树脂(EP)/酸酐体系的固化反应动力学及其固化工艺。通过Kissinger法、Ozawa法和Crane法计算出该体系的动力学参数。结果表明:该固化体系具有较高的活性,其固化工艺条件为"80℃/2 h→120℃/2 h",后处理工艺为150℃/2 h;采用Kissinger法和Ozawa法计算出该体系的平均表观活化能为8.24 kJ/mol;结合Crane方程计算出该体系的反应级数为0.95,近似一级反应。     

共缩聚聚酰胺酸和聚酰亚胺的微波辐射合成研究

在N,N′-二甲基甲酰胺(DMF)溶剂中,选用3,3,′4,4′-二苯酮四羧酸二酐(BTDA)、均苯四甲酸酐(PMDA)和4,4′-二氨基二苯醚(ODA)为单体,微波辐射低温溶液缩聚合成一种共缩聚聚酰亚胺的前驱体聚酰胺酸(PAA),然后亚胺化脱水环化生成共缩聚聚酰亚胺(PI)。通过特性黏数([η])、红外光谱(FT-IR)和热重分析(TGA)对聚合物进行了结构表征和性能测试。结果表明,微波辐射溶液聚合能够提高PAA的特性黏数及产率,微波的引入大大缩短了反应时间;IR表明,在1778 cm-1和1723 cm-1处观察到聚酰亚胺特征峰;TG表明,PI在氮气中535℃左右开始降解,10%热失重温度(Td10%)为587℃。     

微波辐射合成聚酰胺酸和聚酰亚胺的研究

在N,N’-二甲基甲酰胺溶剂中,以均苯四甲酸酐和3,3’,4,4’-二苯酮四羧酸二酐为二酐单体,4,4’-二氨基二苯醚和4,4’-二氨基二苯甲烷为二胺单体,采用微波辐射低温溶液共缩聚,合成了聚酰胺酸(PAA)预聚体,然后亚胺化脱水、环化,生成共缩聚聚酰亚胺(PI)。通过红外光谱(FT-IR)、特性粘度[η]和热重分析(TG)等对聚合物进行了一系列的结构表征和性能测试。结果表明,微波辐射溶液聚合能够提高PAA的特性粘数及产率,微波的引入大大缩短了反应时间;FT-IR表明,在1 775 cm-1和1 724 cm-1处观察到聚酰亚胺特征峰;TG表明,PI的5%热失重温度(Td5%)为477℃,10%热失重温度(Td10%)为553℃。     

Improvement in the adhesion between copper metal and polyimide substrate by plasma polymer deposition of cyano compounds onto polyimide

The surface modification of Kapton film by means of plasma polymer deposition is discussed from the viewpoint of improving the adhesion between copper metal and Kapton film substrate. Plasma polymers of AN (acrylonitrile) and FN (fumaronitrile) were used for the surface modification, and the adhesion between the copper metal and the plasma polymer-coated Kapton film was evaluated by the T-peel strength measurement. The surfaces of peeled layers were analyzed by X-ray photoelectron spectroscopy (XPS) and the failure mode is discussed. The plasma polymer deposition of AN and FN shows an effective improvement in the adhesion between the copper metal and Kapton film; in particular, the AN plasma polymer deposition increased the peel strength 4.3 times. Failure occurred mainly in the Kapton film, and the adhesion between the AN plasma polymer and the Kapton film and that between the copper metal and the AN plasma polymer were found to be quite strong.     

低温固化铅酸蓄电池用防腐耐酸无溶剂环氧胶粘剂的研制

选用环氧树脂、T -3 1固化剂、低分子聚酰胺类固化剂、促进剂、活性稀释剂及各种填料等原料制备了低温固化防腐耐酸无溶剂胶粘剂 ,测试了胶粘剂的粘接强度及耐酸性能。