含氟聚酰亚胺及其在微电子工业中的研究进展Ⅱ含氟聚酰亚胺在微电子工业中的应用

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从现代微电子工业对相关材料的性能要求、标准型聚酰亚胺材料所面临的挑战以及新型含氟聚酰亚胺在微电子工业中的应用等几个方面进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况。并指出为了推动我国微电子工业的发展，研制开发低成本、高技术含量的含氟聚酰亚胺材料具有十分重要的现实意义．     

可溶性含氟聚酰亚胺三元共聚物的合成

通过两步法实现了1,4双-(1,4二-氨基)苯氧基苯(TPEQ),4,4二-氨基二苯醚(ODA)和4,4′-六氟亚异丙基-邻苯二甲酸酐(6FDA)的三元共聚,所得共聚物(PAA)经高温法或化学法脱水环化得对应的可溶性含氟聚酰亚胺(PI)。通过粘度,DSC,TG和1H NMR等分析数据比较了其综合性能。对PI的研究结果表明,化学法的粘度一般高于高温法,所有的PI均具有良好的溶解性和耐热性;不仅溶于DMF,还能很好的溶于CHC l3和THF,有效地改善了其加工性能;Tg>227℃,热损失5%的温度多在488℃以上,m.p.>550℃。其中PI3具有最好的综合性能,粘度1.065 dL.g-1,Tg 241.7℃,热损失5%的温度488℃,m.p.557.9℃,拉伸强度108.81MPa。     

Synthesis and Properties of New Fluorinated Polyimides Derived from an Unsymmetrical and Noncoplanar Diamine

A new unsymmetrical and noncoplanar diamine containing trifluoromethyl and trimethyl groups, 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐2,3,5‐trimethylbenzene ( 2 ), was synthesized using 2,3,5‐trimethylhydroquinone and 2‐chloro‐5‐nitrobenzotrifluoride as starting materials. A series of fluorinated poly(ether imide)s (PEIs) ( 4a–4d ) were prepared from diamine 2 with four aromatic dianhydrides via a one‐step high‐temperature polycondensation procedure. The obtained PEIs were readily soluble in most organic solvents and could be solution‐cast into flexible and strong films. The resulting thin films exhibited light color and good optical transparency with a cutoff wavelength of 356–376 nm. They also displayed good thermal stability with glass transition temperatures (T_g) above 281°C, 10% weight loss temperatures in the range of 482–486°C, and the weight residue more than 55% at 800°C in nitrogen. Moreover, they revealed low dielectric constants (2.77–2.93 at 1 MHz) and low moisture absorptions (0.41%–0.57%).     

溶剂对聚酰亚胺电化学行为的影响

运用电化学循环伏安等方法研究了有机溶剂对可溶性聚酰亚胺(PI)电化学行为的影响.结果表明,PI在一些溶剂中能进行电化学反应.红外光谱研究表明溶剂对PI电化学行为的影响主要取决于不同结构的溶剂与PI之间的相互作用.     

可溶性聚酰亚胺的电化学行为

聚酚亚胺（PI）以其优良的热稳定性、化学稳定性和作为优良的绝缘材料而被广泛应用于电子工业'．Haushalt。了和Kra。l。e等Li发现I'I膜在一定条件下可进行电化学反应．PI由于在电沉积等方面有潜在的应用价值,现已有一些这方面的研究工作卜一'．但所用的材料都是不溶性的PI,且用不同的方法制备PI薄膜修饰电极,因此所报道的PI在水或非水溶液中的电化学行为各不相同［'－'j．另外,以往的研究大都用一种商品化的l'I,而没有系统地研究PI结构对电化学行为的影响．本文报道了由相同的二胺和不同的二欧经化学环化制备的5种可溶性PI…     

New Soluble Polyimides with High Optical Transparency and Light Color Containing Pendant Trifluoromethyl and Methyl Groups

A new aromatic diamine containing trifluoromethyl and methyl groups, namely α,α‐bis(4‐amino‐3‐methylphenyl)‐4‐(trifluoromethyl)phenylmethane ( 1 ), was synthesized from 2‐methylaniline and 4‐(trifluoromethyl)benzaldehyde. A series of fluorinated polyimides (PIs) were prepared from the diamine with four commercially available aromatic tetracarboxylic dianhydrides using a one‐step high‐temperature polycondensation procedure. These obtained PIs showed excellent solubility, with the dissolvability at a concentration of 10 wt% in most solvents, and they could afford flexible and strong films. Thin films of these PIs exhibited high optical transparency and light color, with the cutoff wavelength at 324–357 nm and transmittance higher than 74% at 450 nm. Moreover, these PIs possessed eminent thermal stability and good mechanical properties.     

Fluorinated Aromatic Polyimides as High‐Performance Electret Materials

In view of the increasing significance of technology‐driven devices such as microelectromechanical systems, energy‐harvesting devices, and organic field effect transistors, polymer electret materials with durable electret performance at elevated temperatures become more and more important. However, typical polymer electret materials lose their performance at elevated temperatures. To provide polymer materials with improved electret performance over a broad temperature range, a series of aromatic polyimides with different degree of fluorosubstitution is presented. Isothermal surface potential decay measurements at elevated temperatures reveal that minor differences in the chemical structure have a major influence on the electret behavior. The best performance is found for the polyimide containing a hexafluoroisopropylidene moiety in both the bisanhydride‐ and the diamine‐based unit. Excellent long‐term charge storage stability at 120 °C is observed. From the initial surface charge 94% remains after 24 h. This polyimide even tolerates short‐term exposure of 30 s at 300 °C with almost no loss of performance. These findings demonstrate that this particular polyimide is suitable for device applications at elevated temperatures during fabrication and use.

     

Soluble and Colorless Polyimides from Alicyclic Diamines

Abstract

A series of novel polyimides was synthesized from alicyclic diamines and various aromatic dianhydrides by one-step polymerization in m-cresol without a catalyst. The polymerization was conducted for 4 hours with refluxing, which was enough to obtain the polymers with high molecular weight. The inherent viscosities of the resulting polyimides were in the range of 0.30 ～1.29 dL/g. The prepared polyimides showed excellent thermal stabilities and good solubility. All the polymers were readily soluble in common organic solvents such as chloroform, tetrachloroethane (TCE), dimethylacetamide (DMAc), etc and the glass transition temperatures were observed at 199 to 311°C. UV-visible spectra were obtained to measure the transparency of polymer films. All the polymers showed high transmission above 90% in the wavelength of 400 ～700 nm.     

含氟聚酰亚胺的研究进展

综述了含氟聚酰亚胺研究的新进展,介绍了含氟单体,聚合物合成方法及主要性质。着重介绍了含氟聚酰亚胺的物理化学性质,光学和电学性能以及气体选择透过性。同时简述全氟代聚酰亚胺的合成,性能及应用前景。     

Molecular Dynamics Simulations of Helium Permeation in Polyimides with a Bulky Dianhydride and a Fluorinated Diamine

Fully‐atomistic molecular dynamics (MD) simulations have been carried out to model helium transport through four different glassy polyimides. While the polymer matrices had been pre‐validated, specific parameters and combination rules were used here in order to describe helium‐helium and helium‐polymer interactions. Gas permeabilities are in very good agreement with experimental evidence. Two ways to decrease chain cohesion and improve gas transport were considered – the replacement of an ODPA by a bulky BCDA dianhydride, and the substitution of a site on an ODA diamine by a CF₃. The fluorinated polyimide appears to be the most promising material with more heterogeneity in the void‐space distribution, the highest model permeability and fewer constraints from an experimental point of view.

     

超支化聚酰亚胺的研究进展

近年来,由超支化大分子和线性聚酰亚胺结合而形成了一类新型超支化聚合物———超支化聚酰亚胺(HBPIs),这类聚合物具有独特的理化特性。本文综述了HBPIs最新的研究进展,重点介绍了HBPIs的合成方法,并对其表征及应用进行了描述。     

超支化聚酰亚胺的研究进展

近年来,由超支化大分子和线性聚酰亚胺结合而形成了一类新型超支化聚合物--超支化聚酰亚胺(HBPIs),这类聚合物具有独特的理化特性.本文综述了HBPIs最新的研究进展,重点介绍了HBPIs的合成方法,并对其表征及应用进行了描述.     

Synthesis and Characterization of Soluble Polyimides Derived from 4,4′‐Diamino‐3,3′‐dimethyldiphenylmethane and Their Pervaporation Performances

Two kinds of soluble polyimides were synthesized from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane (DMMDA) and two dianhydrides (including BTDA, ODPA) via a two‐step method, low temperature solution polycondensation and next chemical imidization. All polyimides were readily soluble in common polar solvent, such as DMF, DMAc and NMP. The polyimides were characterized by FT‐IR, NMR, DSC, XRD and EA. The results showed that all of the polyimides revealed an amorphous nature and their inherent viscosities were 0.68–0.96 dlg^?1. The glass transition and melt temperature of these polyimides were determined by DSC and ranged from 224–283°C and 372–384°C, respectively. Thermogravimetric analysis indicated that these polyimides remained fairly stable up to a temperature around or below 400°C. Moreover, 10% mass losses were recorded at approximately 525°C in nitrogen atmosphere. They had a tensile strength in the range 89–137 MPa, and elongations breaking at around 10%. The pervaporation properties of the prepared polyimide dense membranes for ethanol/water mixtures were investigated at a different temperature and the average value of the separation factor and total permeation flux were 46–108 and 660–1380 g/m²h, respectively.     

含氟聚酰亚胺及其在微电子工业中的研究进展Ⅰ含氟单体及聚酰亚胺的合成

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况.主要从含氟二胺单体、二酐单体及含氟聚酰亚胺在合成方面的研究进展情况进行了详细的综述.重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况,并指出为了推动含氟聚酰亚胺这类具有优良综合性能的功能材料在工业上的广泛应用,就必须首先解决含氟单体种类较少这个制约含氟聚酰亚胺发展的瓶颈问题.     

光敏聚酰亚胺的最新进展

综述光敏聚酰亚胺作为感光高分子的最新进展，着重叙述了有机硅改性光敏聚酰亚胺，自增感光敏聚酰亚胺和含氟光敏聚酰亚胺的制备方法和性能研究。     

Polyimides for electronics applications

A variety of options exists for lithographically defining polyimides for microelectronics applications. The two investigated here, photosensitive polyimide and wet etching of low-stress polyimides, offer lower cost, higher throughput solutions compared with dry etch processes. Via sizes of less than 25 μm and film thicknesses of greater than 14 μm are difficult to process using these techniques: however, for applications such as interlayer dielectrics for high-density packaging or solder masks for flip chip die attachment, these limitations may not be insurmountable. Photosensitive polyimide can be patterned with fewer steps, but the overall quality of the film in terms of surface planarity and residual stress is not as good as wet etching of conventional polyimide.     

Synthesis and Characterization of Novel Polyimides Based on Pyridine-containing Diamine

A new aromatic diamine monomer containing pyridine unit, 2,6-bis （4-aminophenoxy- 4＇-benzoyl）pyridine（BABP）, was synthesized in three steps, starting from 2,6-pyridinedicarboxyl chloride. A series of novel pyridine-containing polyimides were prepared v/a the polycondensation of BABP with various aromatic dianhydrides through poly（amic acid） precursors, and thermal or chemical imidization of the precursors. The polyimides exhibit desirable properties, e.g., good solubility in N-methyl-2-pyrrolidone and m-cresol, excellent thermal stability and film-forming capability, as well as high inherent viscosity, indicating high molecular weight.     

聚酰亚胺研究新进展

聚酰亚胺（PI）是一类重要的高性能聚合物,广泛应用在航空航天、微电子、汽车、石油等高科技领域。由于其结构上的可设计性,世界上越来越多的研究者投入到这类高技术材料的研究开发中。本文分别从可溶性PI的分子设计与合成、功能性PI的合成与用途、PI绿色合成方法、PI纳米复合材料的制备4个方面综述了近年来PI的研究热点和新进展,为了解聚酰亚胺的研究提供了有价值的信息。     

Soluble Polyamides and Polyimides Functionalized with Benzo‐15‐Crown‐5‐Pendant Groups

Summary: A new diamine monomer containing a crown ether was made to react with commercial diacid chlorides and dianhydrides to yield new aromatic polyamides and polyimides. The crown ether moiety was introduced as a pendant group so that the polymers showed enhanced solubility in organic solvents, good thermal properties (high transition temperatures and high thermal stability), and good film‐forming ability.

The new aromatic polyamides and polyimides bearing a benzo‐15‐crown‐5‐pendant group synthesized here.