Octahedral oligomeric silsesquioxane (OAPS and OG) - Polyimide hybrid nanocomposite films: Thermo-mechanical,dielectric and morphology properties

Abstract

The nano-sized SQS based polyimides have been successfully synthesized with different oxide groups such as phosphineoxide, sulfone and siloxane as in the backbone of polymer. The SQS-Polyimide nanocomposites prepared through the condensation process using amine and epoxy functionalized SQS as precursor. The presence of SQS in the resulting polyimide nanocomposites was confirmed by FTIR and XRD analyses. The presence of SQS and greatly enhances the char yield to an extent of 16% when compared to that of neat polyimide. The incorporation of SQS into polyimide lowered the value of dielectric constant from 3.31 to 2.09 at 1?MHz and the value of thermal expansion coefficient from 56.6 to 42.7?ppm/K. The composites sample prepared using 20?wt% SQS possess the lowest value of dielectric constant and CTE value. The hydrophobic nature of SQS contributes to lower the water uptake of composites from a value of 2.76 (neat polyimide) to 2.42 for POS-PI containing 20?wt% SQS. Further, the SQS polyimide composite systems possess the enhanced values of thermal stability and glass transition temperatures according their percentage weight. Data obtained from different studies, it is suggested that these hybrid composites can be used as an effective insulation materials for high performance microelectronics applications.     

Synthesis and characterization of fluorine functionalized graphene oxide dispersed quinoline-based polyimide composites having low-k and UV shielding properties

Polyimide nanocomposites having low-k and UV shielding properties have been developed using fluorine functionalized graphene oxide and bis(quinoline amine) based polyimide. The polyimide was synthesized using bis(quinoline amine) and pyromellitic dianhydride at appropriate experimental conditions, and its molecular structure was confirmed through various spectral analysis such as FTIR and NMR. The polyimide (PI) composites were prepared using bis(quinoline amine), pyromellitic dianhydride, and separately filled with 1, 5, 10 wt% of fluorinated graphene oxide (FGO) through in situ polymerization. The polymer composites were characterized using thermo gravimetric analysis (TGA), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM). In addition, the water contact angle, dielectric behavior, and UV–Vis shielding behavior of FGO/PI composites were evaluated. The value of the water contact angle of the polyimide was increased with increment of FGO in the polyimide matrix. The highest water contact angle of polyimide composites observed 108° was obtained for 15 wt% FGO reinforced polyimide composite. The value of the dielectric constant for neat, 1, 5, and 15 wt% FGO reinforced polyimide composites was obtained as 4.5, 3.7, 2.6, and 2.0, respectively. It is also observed from by UV–Vis spectroscopy analysis that the FGO reinforced polyimide composites have good UV shielding behavior.     

New poly(ether-imide)/MWCNT nanocomposite

New polyimide (PI) nanocomposites containing two different amounts of MWCNT (PI/MWCNT) were prepared via in situ polymerization technique. Transmission electron microscopy showed that MWCNT was exfoliated in the polymer matrix, resulting in well-dispersed morphologies at 1 and 3 mass% MWCNT contents. The effects of multiwalled carbon nanotubes (MWCNT) on the thermal and flammability properties of new PI derived from 1,3-bis[4,4′-aminophenoxy]propane and biphenyl dianhydride were investigated by thermogravimetric analysis (TG) in nitrogen and air atmosphere, differential scanning calorimetry, and microscale combustion calorimeter (MCC). The PI/MWCNT nanocomposites were electrically conductive with maximum conductivity obtained at 3 mass% MWCNT, which is favorable for many potential applications. TG results showed that the addition of MWCNT resulted in a substantial increase of the thermal stability and char yields of the nanocomposites compared to those of the neat PI. Flame retardancy of the nanocomposites was significantly improved in the presence of MWCNT.     

Photosensitive fluorinated polyimides with a low dielectric constant based on reaction development patterning

The fluorinated polyimide PI(6FDA/HFBAPP) was prepared by the reaction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (HFBAPP) in 1‐methyl‐2‐pyrrolidone/toluene. A multiblock copolyimide with both fluorinated and rigid‐rod segments, PI(6FDA/HFBAPP)(BPDA/2‐DMB), was prepared by the addition of a second dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and a second diamine, 2,2′‐dimethylbenzidine (2‐DMB), to the polyimide main chain. The potential lithographic performance of photosensitive polyimides composed of nonphotosensitive fluorine‐containing polyimides and photosensitive diazonaphthoquinone (DNQ) was studied on the basis of a new imaging principle recently proposed by our laboratory, that is, reaction development patterning. Neat PI(6FDA/HFBAPP) showed a low dielectric constant (?) of 2.41 and a low dissipation factor (tan δ) of 0.0027 at 20 GHz, and a 10‐μm resolution of the fluorinated polyimide/DNQ system was demonstrated with reactive development with a solution including ethanolamine after ultraviolet exposure. Although slight changes in the dielectric properties were observed in the presence of DNQ residues, these values (? = 2.63 and tan δ = 0.0033 at 20 GHz) were low enough for use in microelectronic applications. However, PI(6FDA/HFBAPP)(BPDA/2‐DMB), having a lower coefficient of thermal expansion (CTE; 33 ppm/°C) than PI(6FDA/HFBAPP) (49 ppm/°C), exhibited good positive photosensitivity, whereas the relatively low‐CTE multiblock copolyimide displayed a much higher ? value (3.48 at 1 MHz) than the highly fluorinated polyimide (2.88 at 1 MHz). A film consisting of PI(6FDA/HFBAPP)(BPDA/2‐DMB) and the remaining DNQ derivatives showed a CTE value comparable to that of the neat polyimide film. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 861–871, 2003     

A simple approach toward low‐dielectric polyimide nanocomposites: Blending the polyimide precursor with a fluorinated polyhedral oligomeric silsesquioxane

This article describes a new and simple method for preparing polyimide nanocomposites that have very low dielectric constants and good thermal properties: simply through blending the polyimide precursor with a fluorinated polyhedral oligomeric silsesquioxane derivative, octakis(dimethylsiloxyhexafluoropropyl) silsesquioxane (OF). The low polarizability of OF is compatible with polyimide matrices, such that it can improve the dispersion and free volume of the resulting composites. Together, the higher free volume and lower polarizability of OF are responsible for the lower dielectric constants of the PI‐OF nanocomposites. This simple method for enhancing the properties of polyimides might have potential applicability in the electronics industry. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6296–6304, 2008     

基于氟碳表面活性剂插层水滑石的聚酰亚胺纳米复合材料的制备与性能

以氟碳表面活性剂全氟辛基磺酸钾为插层剂, 通过离子交换制备插层水滑石, 并以其为填料, 通过原位插层聚合方法, 制备了水滑石/氟碳表面活性剂/聚酰亚胺纳米复合材料. 用X射线衍射、 红外光谱和热失重等方法分析插层水滑石结构. 结果表明, 全氟辛基磺酸钾插层水滑石后, 水滑石的层间距由0.76 nm增加到2.52 nm, 在水滑石层间构建了氟碳链的微环境. 这种氟化水滑石可剥离分散于聚酰亚胺基体中, 改善了纳米复合材料的气体阻隔性能、 介电性能和机械性能. 这种影响不仅体现无机纳米片层的杂化效果, 而且展示出氟碳链的特点.     

Preparation of Meldrum's acid-functionalized polyimides exhibiting organo-soluble,reactive, self-crosslinkable,and colorless features

Functional polyimides (PIs) having some desired properties, for example, organo-solubility, chemical reactivity, crosslinkable feature, and high transparency in visible region, are attractive for specific applications. This work reports an effort to integrate the above-mentioned properties in one polyimide through introduction of Meldrum's acid (MA) moieties to polyimide chains with using a MA-containing diamine (MADA) as a monomer. The polyimide prepared with MADA and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) (PI[MADA-6FDA]) has a number-averaged molecular weight of 56,800 g mol⁻¹, shows good solubility in tetrahydrofuran and aprotic high polar solvents, and exhibits post-reactivity/crosslinkability through MA-mediated ketene chemistry. Crosslinked PI(MADA-6FDA) film shows a glass transition temperature of 289°C, a dielectric constant of about 2.78, and high flexibility bearing a near-180° bending. The MA-mediated ketene chemistry contributes to in situ building up covalent linkages between PI chains and silica nanoparticles (SNPs) in preparation of PI/SNPs nanocomposite films (NCF). Formation of the PI/SNPs NCFs enhances the thermal and mechanical properties, reduces the dielectric constants, and increases the transparency. The properties of the MA-functionalized PI are attractive for further studies on their applications.     

Ferrocene Containing Polyimides as a Route to Low-κ Dielectric Materials

Polyimides incorporating the ferrocene unit were prepared by in situ curing of poly (amic acid) macromolecules with ferrocene, for the molecular-level design of low dielectric constant (low-κ) materials. The effects of ferrocene on dielectric properties of polyimide are investigated in detail in this study. Ferrocene containing polyimides exhibit a number of desirable properties including low-water absorption and admirable thermal stability. Systematic studies demonstrate that proper insertion of ferrocene into a polyimide backbone can give rise to a reduction in the material's dielectric constant. All composites were subjected to DSC measurements for the purpose of examining Tg from all composition. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and the other conventional techniques were used for structural characterization.     

Fully aromatic macrocycle‐terminated polyimide: synthesis and cross‐linking

This study reported a method to prepare fully aromatic macrocycle‐terminated polyimides (MC‐PI). The macrocycle of aryl ether ketones was prepared from (4‐amino)phenylhydroquinone and a di‐fluoro monomer under pseudo high dilution condition. Novel aromatic fully MC‐PI oligomers were successfully prepared by the reaction of 2,3,3′,4′‐biphenyltetracarboxylic diandhydride with 2,5‐bis(4′‐aminophenoxy)‐biphenyl and sulfur‐containing macrocycle of aryl ether ketone. The MC‐PI oligomers were cross‐linkable in the heating, and the glass transition temperatures of the polyimides increased after thermally cured. The cross‐linking reaction of MC‐PI could form fully aromatic thermosetting polyimide by ring‐opening reaction. After cross‐linking, these polyimides showed higher glass transition temperatures and excellent thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermal behaviors of polyimide with plasma-modified carbon nanotubes

A series of plasma-modified carbon nanotubes with maleic anhydride (mCNT) based on polyimide (mCNT/PI) nanocomposites were prepared by a two-step method. The mCNT/PI nanocomposites exhibit excellent thermal properties owing to mCNT and its good dispersion in the polyimide matrix. The TEM patterns were proved to show dispersed behavior of mCNT in the PI matrix. By using thermogravimetric analysis (TGA), thermogravimetric with infrared spectra (TGA-IR), we discuss the kinetic behavior during the degradation of nanocomposites. Then Ozawa and Kissinger's theorems were calculated based on the relationship between activation energy and mCNT content.     

A study of atmospheric-pressure CHF3/Ar plasma treatment on dielectric characteristics of polyimide films

In this work, the influence of atmospheric-pressure CHF(3)/Ar plasma treatment on surface dielectric properties of polyimide films was investigated using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements. The dielectric characteristics of the films were studied using a dielectric spectrometer. From the results, it was found that the plasma treatment introduced fluorine functional groups onto the polyimide surfaces. F 1s/C 1s ratios of the polyimides were enhanced with the increase of plasma treatment time. Consequently, the fluorine groups led to a decrease of the surface free energy and dielectric constant of the polyimide films, which can largely be attributed to the decrease of the deformation polarizability or London dispersive component of surface free energy of the solid surface studied.     

Photoimageable polyimides derived from α,α‐(4‐amino‐3,5‐dimethylphenyl)phenylmethane and aromatic dianhydride

Soluble and inherent photoimageable polyimides with improved photopatterning features were prepared from α,α‐(4‐amino‐3,5‐dimethylphenyl)phenylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. The polyimides possessed good combined chemical and physical properties: thermal stability was observed, with an initial thermal decomposition temperature of 565 °C and a high glass‐transition temperature of 318 °C. Homogeneous polyimide solutions in common organic solvents with solid contents as high as 20 wt % were prepared. These solutions had a shelf life greater than 3 months. The polyimides had high electric insulating properties and low dielectric constants and dissipation factors. Fine patterns were processed by direct exposure of the polyimide coatings to UV i‐line, followed by development with an organic developer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3012–3020, 2002     

Polyimides with alicyclic diamines. II. Hydrogen abstraction and photocrosslinking reactions of benzophenone-type polyimides

Photosensitive polyimides with alicyclic diamines and benzophenone moiety were prepared by reactions of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with diamines in aprotic solvents, followed by thermal or chemical imidizations. Among them the polyimide from BTDA and bis(4-amino-3-methylcyclohexyl) methane (DMDHM) can be dissolved in several organic solvents such as dichloromethane, tetrachloroethane, and N-methyl-2-pyrrolidone (NMP). In order to compare properties of the polyimides with alicyclic diamines with those of corresponding aromatic polyimides, the UV absorption spectra and fluorescence spectra of these polyimides and their model compounds were investigated. No occurrence of charge transfer at photoexcited states was ascertained for the polyimides with alicyclic diamines. The hydrogen abstraction and crosslinking during photoirradiation have been studied to learn the influence of the elimination of charge transfer process in these photosensitive polyimides. The quantum yield of hydrogen abstraction for the model compound of alicyclic polyimides is 0.56 in THF measured with HPLC. The quantum yield for the photocrosslinking reaction of the solvent-soluble polyimide with alicyclic diamine, PI(BTDA/DMDHM), was determined to be 0.004 in air from gel permeation chromatography (GPC) measurement, which is four times higher than that for photosensitive polyimides with aromatic diamines. © 1994 John Wiley & Sons, Inc.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.     

Poly(ether‐imide) and related sepiolite nanocomposites: investigation of physical,thermal, and mechanical properties

Novel poly(ether‐imide) and sepiolite nanocomposites were synthesized based on a unique diamine monomer with the aim of improving physical and mechanical properties of final polyimide films. The diamine was polycondensed with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride to produce related poly(ether amic acid) prepolymer. Pure poly(ether‐imide) and nanocomposite films were prepared via thermal imidization process of poly(ether amic acid). Coexistence of ether, pyridine, and phenylene functional groups in the diamine chemical structure resulted in flexible polyimide films with significant thermal, physical, and mechanical properties. Thermal stability, glass‐transition temperature, dimensional stability, and tensile properties of polymer and nanocomposites were studied and compared. Morphology of nanocomposites was also investigated using scanning and transmission electron microscopic methods to study the distribution and dispersion behavior of sepiolite nanofibers in the polyimide matrix. By introduction of sepiolite nanoparticles, overall improvement of properties was observed in respect to pure polyimides. Copyright © 2015 John Wiley & Sons, Ltd.     

Simultaneous Preparation of PI/POSS Semi‐IPN Nanocomposites

Summary: This investigation presents a simultaneous and convenient approach to produce a high‐performance polyimide with a low dielectric constant by introducing the octa‐acrylated polyhedral oligomeric silsesquioxane (methacrylated‐POSS) into a polyimide matrix to form polyimide semi‐interpenetrating polymer network (semi‐IPN) nanocomposites. The differential scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) results indicate that the self‐curing of methacrylated‐POSS and the imidization of polyamic acid (PAA) occurs simultaneously. The morphology of a semi‐IPN structure of polyimide/POSS‐PI/POSS nanocomposites with POSS nanoparticles embedded inside the matrix is elucidated. The POSS particles are uniform and are aggregated to a size of approximately 50–60 nm inside the polyimide matrix. The interconnected POSS particles are observed at high POSS content. The structure is highly cross‐linked, so the PI/POSS nanocomposites have an enhanced glass transition temperature. The high porosity of the PI/POSS nanocomposites markedly reduces the dielectric constant of PI because of the nanometer‐scale porous structure of POSS.

FT‐IR spectra of the various compounds of A) methacrylate‐POSS before curing, B) methacrylate‐POSS after curing, C) PAA containing 15 wt.‐% POSS, and D) PI/POSS containing 15 wt.‐% POSS.     

Preparation and properties of thermally stable polyimides derived from asymmetric trifluoromethylated aromatic diamines and various dianhydrides

A novel method for the preparation of an asymmetric fluorinated aromatic diamine, 3,4′-bis(4-amino-2-trifluoromethylphenoxy)-benzophenone was investigated. This new diamine containing trifluoromethyl side group was synthesized from the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 3,4′-dihydroxybenzo phenone in the presence of potassium carbonate, followed by catalytic reduction with SnCl₂·6H₂O and concentrated hydrochloric acid. This novel diamine was used to react with different commercially available aromatic tetracarboxylic dianhydrides to prepare polyimides via thermal or chemical imidization. The polyimide properties such as inherent viscosity, solubility, thermal and surface properties were investigated to illustrate the contribution of the trifluoromethyl group and the asymmetry structure of the polyimide. The polyimides obtained had good thermal stability and the glass transition temperature values ranged from 225 to 267 °C. All of these novel polyimides held 10% weight loss at the temperature above 543 °C in air and left more than 47% residue even at 800 °C in nitrogen. The inherent viscosities of the obtained polyimides were above 0.73 dL/g and were easily dissolved in both polar, aprotic solvents and some low-boiling-point solvents. Moreover, these PI films had dielectric constants of 2.94-3.53 (1 kHz), with moisture absorption in the range of 0.07-0.34 wt%. In comparison of the PIs (5) series with the analogous symmetric PIs (6) series based on 4,4′-bis(4-amino-2-trifluoromethylphenoxy)-benzophenone, the (5) series revealed better solubility, low dielectric constant and moisture absorption.     

Preparation, characterization and dielectric properties of 4,4-diphenylmethane diisocyanate (MDI) based cross-linked polyimide films

Four different types of cross-linked polyimides based on 4,4-diphenylmethane diisocyanate (MDI) were prepared by the reaction of different types of conventional poly(amic acid) intermediates with MDI as a cross-linking agent. Subsequently, they were thermally imidized in order to obtain corresponding cross-linked polyimide structure. The results of FTIR-ATR showed that MDI can effectively react with carboxylic acid groups of PAA to form cross-linked polyimide films. TGA, FTIR-ATR and SEM analyses were carried out for characterization of cross-linked polyimide (CPI) films. Moreover, the electrical properties such as dielectric breakdown strength, dielectric constant, I-V characteristics and loss factor of MDI based cross-linked polyimides have been checked. In addition, some physical properties such as water uptake, adhesion, hardness and solubility properties of the films were investigated.The results showed that all CPI films have good insulating properties such as high dielectric breakdown voltage, low loss factor (tan δ), leakage density and excellent physical properties.     

Novel fluorinated polyimides derived from an unsymmetrical diamine containing trifluoromethyl and methyl pendant groups

Novel fluorinated polyimides were prepared from an unsymmetrical diamine, 3‐methyl‐4‐(4‐amino‐2‐trifluoromethylphenoxy)‐4'‐aminobenzophenone ( 3 ), with four aromatic dianhydrides via a one‐step high‐temperature polycondensation procedure. All the obtained polyimides were soluble in some polar solvents such as NMP, DMAc, and DMF. Flexible and tough films were prepared by casting from polymer solution. These polyimide films exhibited high optical transparency, good mechanical and thermal properties. Moreover, they possessed low dielectric constants and low‐moisture absorption. Due to their properties, these fluorinated polyimides could be considered as photoelectric and microelectronic materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and properties of polyimides derived from bis-(Aminophenoxy) containing naphthalene, [Phenyl] propane and [Methyl] cyclohexane segment and 4, 4′-carbonyldiphthalic anhydride

ABSTRACT

Three wholly, semi aromatic and aliphatic-aromatic polyimides containing bis(phenoxy) naphthalene, bis[(phenoxy) phenyl] propane and bis(phenoxy-methyl) cyclohexane segments by the two-step procedure from 2, 7-bis(4-aminophenoxy) naphthalene (BAPON), 2, 2-bis[4-(4-aminophenoxy)phenyl]propane (BAPOP), 1, 4-bis (4-aminophenoxy methyl) cyclohexane (BAPMC) as a diamine and 4,4′-carbonyldiphthalic anhydride (CDPA) were prepared. The first step of this procedure including ring-opening polyaddition in a polar solvent to give poly(amic-acid)s, second step containing cyclodehydration reaction to form polyimides. Synthesized monomer and polyimides were characterized by FT-IR, ¹H NMR spectroscopy and elemental analyses (CHN) that obtained results gave the most powerful evidence. The polyimide synthesized from BAPON was characterized as semi-crystalline, whereas the other polyimides showed amorphous patterns by the x-ray diffraction studies. The inherent viscosity was ranging between 0.87–1.01 dL/g. Tensile strength, initial moduli, and elongation at break of the polyimide films ranged from 88–117 MPa, 1.98–2.32 GPa, and 5–8%, respectively. Thermogravimetric analysis in nitrogen atmosphere shows that these polymers having good stability, so 10% weight will be lost in the range of 500–630°C. The point of polyimide with BAPMC segment, is “adding of good thermal stability and processability” lower moisture absorption and dielectric constant (0.75% and 2.90).