4-phenylethynylphthalic Anhydride Research Articles

Manufacturing of Thermoset Polyimide Composites by Laser Sintering

Selective Laser Sintering (SLS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the computer-aided design (CAD) model. SLS generally uses thermoplastic polymeric powders such as polyamides. The resultant 3D-printed objects are often weaker in their strength compared to traditionally processed materials, due to their higher porosity. This paper described the process development of using melt-processable imide oligomers terminated with reactive 4-phenylethynylphthalic anhydride (4-PEPA) to conduct laser sintering (LS). The first successful 3D-printing of high temperature RTM370 thermoset polyimide carbon fiber composite was further post-cured to promote additional crosslinking for achieving higher temperature (Tg = 370°C) capability. Another novel imide oligomer, RTM385-SLS, formulated with a complex melt viscosity [h*] of ~104-105 poise is also suitable for LS. RTM385-SLS resin powder was mixed with 20-25% of hexagonal boron nitride (h-BN) and subjected to LS to print out “Green” specimens which could be further post-cured to afford a thermally conductive but electrically insulating composites with high Tg of 385°C. The cured composite specimens were then subjected to mechanical testing, thermal conductivity and porosity evaluation as well as SEM characterization.

MD analysis on structure and property of thermosetting polyimides end-capped by phenylethynyl groups

Four phenylethynyl-containing thermosetting polyimide monomers, based on aromatic diamines with various molecular structure and 4-phenylethynylphthalic anhydride, were designed and synthesized to investigate their structure-properties relationships from a molecular dynamics perspective. The trifluoromethyl linkage in the diamine moiety of a polyimide gives the highest flexibility whereas the amide linkage imparts the lowest flexibility to the polymer chain. A more flexible polyimide has a lower melting temperature, lower cohesive energy density, lower mechanical properties, and larger the fraction free volume. Besides, intermolecular hydrogen bonding plays a critical role in the maintenance of physical properties. These simulated values show good agreement with experimental data. This project provided an important opportunity to advance the understanding of structure-property relationships of polyimides.

High performance imide oligomers and thermosets derived from 9,9-bis (3,4-dicarboxyphenyl)fluorene dianhydride

In this work, a new class of imide oligomers and thermosets with improved overall properties was developed by exploiting the steric effects of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF). First, a model compound was prepared from BPAF and aniline. This model compound possessed a twisted architecture, with two dihedral angles between fluorene ring and phthalimide segments of around 75°. Then, an array of phenylethynyl-endcapped imide oligomers was synthesized from BPAF, 4-phenylethynyl phthalic anhydride (4-PEPA), and aromatic diamines (4,4′-oxydianiline (4,4′-ODA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), m-phenylenediamine (m-PDA)). The BPAF-derived imide oligomers exhibited improved organic solvents solubility and higher melt viscosity compared to those based on 2,3,3′,4′-biphenyltetracarboxylic dianhydride (3,4′-BPDA), due to their bulky, twisted, and sterically hindered cardo architectures. The imide oligomers under pressure were converted into thermosets by the thermal crosslinking of phenylethynyl at 370 °C for 2 h. The BPAF-derived thermosets exhibited much higher glass transition temperature (Tg) (＞ 404 °C), 5% weight-loss temperature (T5%) (＞ 549 °C) in an air environment, and more excellent high-frequency dielectric properties from 30 to 45 GHz (dielectric constant as low as 2.85 and dielectric loss factor as low as 0.0037) while possessing comparable or even better mechanical properties relative to the 3,4′-BPDA-derived polymers. Therefore, these polymers based on BPAF may have potential applications as matrix resins for heat-resistant, structural and functional composites.

Soluble imide oligomers containing benzoxazole structures

A series of soluble thermosetting polyimide resins containing benzoxazole structure were synthesized by two-step polymerization using 4-phenylethynylphthalic anhydride (4-PEPA) as the end-capping reagent, 2-(4-aminophenyl)-5-aminobenzoxazole (BOA) and 3,4′-diaminodiphenyl ether (3,4′-ODA) as the aromatic diamines, and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as the aromatic dianhydride. The imide oligomers were characterized by employing Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), solubility tests and rheological measurements. Thermosetting polyimides derived from the imide oligomers were then produced via a thermal cross-linking reaction of the phenylethynyl group. The thermal and mechanical properties of the thermosets were studied using thermogravimetric analysis (TGA), dynamic mechanical thermal analysis (DMA), and mechanical property measurements. The effects of chemical architectures and molecular weights of the imide oligomers on processability, thermostability and mechanical properties were systematically investigated. The results showed that all the copolymerized imide oligomers possessed good solubility in organic and low melt viscosity, and the corresponding thermosets exhibited high glass transition temperature (up to 401°C) and 5% weight-loss temperature (up to 533°C) in an air atmosphere while excellent mechanical properties (flexural strength up to 217 MPa and elongation at break up to 11.2%). With the increase of the concentration of the benzoxazole group, the imide oligomers of PI-X-2 (-O-, -BO-, -B-) exhibited less solubility and higher minimum melt viscosity but improved glass transition temperature after curing and mechanical properties of their thermosets.

Development of High-Performance Composites with Molecular Weight Controlled Polyimide Oligomers End-Capped with Phenylethynyl Groups

A series of molecular weight controlled polyimide oligomer (Oligo-PI) resins were developed via the polymerization of 4,4′-(1,3-phenylenedioxy)dianiline (TPE-R), 2,3′,3,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4-phenylethynyl phthalic anhydride (PEPA). PEPA was served as the molecular weight controlling and reactive end-capping agent. Oligo-PI resins have an asymmetric and amorphous structure, which could make better processability to fabricate composites. To investigate the effect of molecular weight (MW) and chain extension structures of phenylethynyl groups by thermal curing on thermal and mechanical properties, carbon fabric reinforced Oligo-PIs (Oligo-PI/CFs) were prepared via hot press technique. Morphology, mechanical and thermal properties of Oligo-PI/CFs were measured by SEM, TGA, IZOD impact tester, and UTM (three-point bending test). As MW got higher and the ordered network structures were formed, the composite exhibited excellent thermal stability. Flexural strengths also increased by building the crosslinked structures. On the other hand, impact strengths were less influenced. Among Oligo-PI/CFs, Oligo-PI/CF-3 showed comparatively good performance. The mechanical properties of Oligo-PI/CF-3 (5 ply) was evaluated at both 25 °C and 200 °C. The composite maintained high strengths even at high temperatures, demonstrating the durability of Oligo-PI/CFs in harsh conditions utilized for the aerospace and military applications.

Effect of Blending Modifications for Phenylethynyl-terminated Polyimides

A reactive diluent (ODA-PEPA) and a flexible phenylethynyl-terminated imide oligomer (PEI-PEPA) were designed and synthesized based on the 2,3,3’,4’-diphenyl ether tetracarboxylic acid dianhydride (a-ODPA), 3,4’-oxydianiline (3,4’-ODA), and 4-phenylethynylphthalic anhydride (PEPA). Solution blended systems with the addition of 5, 10, and 15 wt% ODA-PEPA to PEI-PEPA oligomer and their cured resin systems were prepared. Results showed that ODA-PEPA is semi-crystalline in nature. The Tg values of cured resins were improved from 273 °C to 280 °C by the addition of ODA-PEPA, due to the higher crosslink densities. In addition, rheological properties of blends showed lower melt viscosity and wider processing window, revealing improved melt processabilities for potential application in making advanced composites. The isothermal viscosity in 280 °C of PEI-PEPA containing 15 wt% ODA-PEPA reactive diluent decreased by two thirds, due to the low molecular weight of ODA-PEPA. The cured blends demonstrated high thermal stability and heat resistance. 5 wt% thermal decomposition temperatures (Td5) of the cured blends were above 549 °C and 547 °C in N2 and air atmosphere, respectively. The char yield reported at 800 °C in N2 atmosphere increased from 58.8% to 63.7 % with the addition of ODAPEPA. Meanwhile, the cured polyimides blends possessed good bond strength (> 9.3 MPa).

Highly Soluble Phenylethynyl-terminated Imide Oligomers and Thermosetting Polyimides Based on 2,2′,3,3′-Biphenyltetracarboxylic Dianhydride

The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step method using 2,2′,3,3′-biphenyltetracarboxylic dianhydride(3,3′-BPDA) and aromatic diamines as the monomers, and 4-phenylethynyl phthalic anhydride(PEPA) as the end-capping agent. The imide oligomers based on 3,3′-BPDA showed excellent solubility in low boiling point solvents and low melt viscosity, which were attributed to their unique bent architectures. High-performance thermosetting polyimides were produced from these oligomers via thermal crosslinking of the phenylethynyl groups. The mechanical and thermal properties of the thermosets were studied using tensile testing, dynamic mechanical thermal analysis(DMTA), and thermogravimetric analysis(TGA). The 3,3′-BPDA-based thermosets exhibited excellent thermal properties, with glass transition temperatures of up to 455 °C, and 5% mass loss temperatures of up to 569 °C in air. The thermosets based on 3,3′-BPDA showed superior thermal properties compared to those derived from TriA-X series oligomers.

Phenylethynyl-terminated oligoimides with ultra-low melt viscosity derived from 1,4-bis(3,4-dicarboxy phenoxy)benzene dianhydride

Most of the existing polyimide oligomers for resin transfer molding (RTM) processing exhibited high melt viscosity, which can only maintain below 1 Pa·s at 280°C for 2 h, leading to very high process temperatures. So novel RTM-type oligomers with lower and stable melt viscosities are more desirable. Three series of thermoset oligoimides derived from 1,4-bis(3,4-dicarboxy phenoxy)benzene dianhydride and three different aromatic diamines were prepared herein. The diamines included 4,4′-oxydianiline, 2,2′-bis(trifluoromethyl)benzidine (TFDB), and 2-phenyl-4,4′-diaminodiphenyl ether ( p-ODA). 4-Phenylethynylphthalic anhydride was used as an endcapping reagent. Effects of the chemical structures and molecular weights of the oligoimides on their aggregated structures, melt processability, and the thermal and mechanical properties of the cured films were then systematically investigated. X-Ray diffraction results indicated that ODA series oligoimides and TFDB series oligoimides showed crystallinity in various degrees. However, the asymmetric p-ODA enables the p-ODA series oligoimides to exhibit amorphous forms. It was found that the p-ODA-based oligoimide with a molecular weight of 750 g mol−1 showed very low melt viscosity of 1 Pa·s even at 210°C, and the melt viscosity could maintain below 1 Pa·s after isothermal aging for 2 h at any temperature in the range of 200–280°C by rheological measurements. The cured film also showed a high glass transition temperature of 355°C by dynamic mechanical analysis, very good thermal stability by thermogravimetric analysis, and good mechanical properties. It might be more suitable for RTM processes in the future.

High Tg and Thermo-Oxidatively Stable Thermosetting Polyimides Derived from a Carborane-Containing Diamine.

To provide high-temperature polyimide matrix resins, novel carborane-containing thermosetting polyimides are presented. First, the low-viscosity carborane-containing imide oligomers are synthesized using newly designed 1-(3-amino-4-tolyl)-2-(4-aminophenyl)-o-carborane and aromatic dianhydride as monomers, 4-phenylethynyl phthalic anhydride as the end-capping reagent. Followed by thermal curing, the resulting polyimides show high Tg (≥500°C) and above 92.1% char yield at 800°C both in nitrogen and air atmosphere due to the incorporation of the bulky carborane cages. Aging studies, performed at 400 and 500°C for 5 h in air on a carborane-containing polyimide and a carborane-free polyimide, show that the polyimide with carborane groups possesses excellent thermo-oxidative stability. Moreover, the novel polyimides exhibit constant and relatively low coefficient of thermal expansion values over a wide range of temperature, indicative of a remarkable dimensional stability. Thus, this study clearly demonstrates the viability of the incorporation of carborane cages to access polyimide thermosets with ultrahigh Tg and thermo-oxidative stability.

Thermal oxidation of PEPA-terminated polyimide

The thermal oxidative stability of a 4-phenylethynyl phthalic anhydride (PEPA) endcapped polyimide (PI) was investigated. A surface reaction layer formed due to oxidization during thermal aging and grew in thickness with increasing aging time. Analysis of the surface layer revealed a partial loss of aromatic ring, ether linkage, and imide linkage in the aged polymer. The partial loss of the imide linkage and ether linkage in the surface layer was corroborated by the observed release of carbon monoxide and carbon dioxide reaction products. The oxidized layer exhibited discoloration and an increase in glass transition temperature. The surface discoloration was attributed to the formation of the conjugated unsaturated or aromatic carbonyl groups and/or the charge transfer complex. Interior regions of the oxidized samples were largely unaffected, except for a more compact molecular configuration. Compared with aging at high temperatures (288°C, 316°C), aging at 204°C produced similar chemical changes in the cured polymer, albeit with a low degradation rate. The oxidative stability of the imide polymer surpassed that of conventional nadic-endcapped PIs due to the greater intrinsic thermal stability of the PEPA endcap. The unusual oxidative stability of the PI, combined with superior mechanical properties, warrant consideration as a composite matrix for future applications in high-temperature service conditions.

Highly soluble phenylethynyl terminated oligoimides derived from 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane, 4,4′-oxydianiline and mixed thioetherdiphthalic anhydride isomers

Novel highly soluble phenylethynyl-endcapped oligoimides derived from mixed thioetherdiphthalic anhydride isomers (m-TDPA) and 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI), 4,4′-oxydianiline (4,4’-ODA) with 4-phenylethynylphthalic anhydride (PEPA) as a reactive endcapping agent were synthesized. The calculated molecular weights of all the oligoimides were 2500 g·mol−1.The effect of the mole ratio of DAPI/4,4’-ODA on solubility and melt viscosity of oligoimides as well as the thermal and mechanical properties of cured polyimide films was investigated. Experimental results indicated that DAPI greatly improved the solubility (>30 wt.%) of the oligoimides in low boiling points solvents when the content of DAPI was more than 10 mol% per total diamine. All the oligoimides exhibited very good processability with minimum melt viscosity lower than 60 Pa·s at about 330 °C. Tough and brown films were obtained after thermally cured at 370 °C for 1 h and dynamic mechanical analysis (DMA) showed that glass transition temperatures of the cured films increased up to 340 °C with the increasing content of DAPI. However, the thermal stability and mechanical properties decreased with the increase of DAPI content. The temperature of 5% weight loss was higher than 470 °C in both air and N2 atmosphere obtained by thermogravimetric analysis (TGA). And the tensile strengths of the cured films were about 60 MPa.

Process development for phenylethynyl-terminated PMDA-type asymmetric polyimide composites

A new type of polyimide, designated TriA X, has been developed for high-temperature composite applications. TriA X is a polymerized monomeric reactant (PMR)-type polyimide derived from 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 2-phenyl-4,4′-diaminodiphenyl ether (p-ODA), and phenylethynyl phthalic anhydride (PEPA). The polymer has an asymmetric, nonplanar backbone, resulting in an amorphous structure and high toughness. In this work, a TriA X resin (with degree of polymerization n = 7 in the imide oligomer) was investigated for processability and performance in carbon fiber composites. Rheological measurements were performed on an oligomer with a low degree of imidization to understand the chemo-rheology of the resin system and determine a suitable B-staging temperature. A composite molding cycle was designed, which yielded fully consolidated woven carbon fiber laminates. Void contents in panels produced with this molding cycle were <0.1% as measured by image analysis (IA) of polished sections, and <0.2% as measured by X-ray micro-computed tomography (micro-CT). Matrix-dominated mechanical properties of composites fabricated with the TriA X polymer exceeded those of PMR-15 and AFR-PE-4 composites. These mechanical properties and a measured glass transition temperature of 367°C indicate potential for use of this resin system in high-temperature composites.

2,3,3′,4′-Oxydiphthalic dianhydride-based phenylethynyl-terminated imide oligomers for low-temperature resin transfer molding applications

A series of imide resins were prepared using 2,3,3′,4′-oxydiphthalic dianhydride, 4-phenylethynylphthalic anhydride, and aromatic diamines (1, 3-bis(3-aminophenoxy), 3,4′-oxyaniline, 2,2′-bis (trifluoromethyl) benzidine, and m-phenylenediamine) as starting materials. These imide oligomers were characterized by means of Fourier transform infrared spectroscopy, differential scanning calorimetry, intrinsic viscosity measurements, and rheological measurements. Some of these oligomers exhibited low (<1 Pa·s at 250°C) and stable (>2 h at 250°C) melt viscosity, which was highly desirable for resin transfer molding process. Thermosetting polyimides (PIs) were then produced from these oligomers via thermal cross-linking reaction of phenylethynyl group. The properties of the thermosets were studied using tensile and flexural testing, dynamic mechanical thermal analysis, and thermogravimetric analysis. The cured PIs exhibited a good combination of thermal and mechanical properties, with a tensile strength of 31–76 MPa, flexural strength of 38–142 MPa, glass transition temperatures of 233–358°C, and 5% weight loss temperatures of 540–545°C under nitrogen atmosphere.

Synthesis and characterization of phenylethynyl-terminated polyimide/carboxylated multiwalled carbon nanotube composite film

Phenylethynyl-terminated polyimide (PI)/carboxylated multiwalled carbon nanotube (MWCNT) composite films were synthesized from 4,4′-oxydianiline, carboxylated MWCNTs, and 3,3′,4,4′-biphenyl tetracarboxylic dianhydride and capped by 4-phenylethynylphthalic anhydride through in situ polymerization under sonication. The results of scanning electron microscopy indicated that the carboxylated MWCNTs were uniformly dispersed in the phenylethynyl-terminated PI matrix. Thermal gravimetric analysis indicated that the initial thermal decomposition temperatures of the films were up to 500°C, and the addition of carboxylic MWCNT have advantage of thermal properties of the phenylethynyl-terminated PI. The dynamic mechanical thermal analysis results clearly indicated that the glass transition temperature increases with increasing carboxylated MWCNT content. In addition, the mechanical properties of the composite films were improved by the carboxylated MWCNTs. The electrical properties were greatly enhanced due to the good conductivity of the carboxylated MWCNTs.

Phenylethynyl-terminated imide oligomers derived from thioetherdiphthalic anhydride isomers with decreased melt viscosities

A series of oligomers based on the mixture of thioetherdiphthalic anhydride isomers and 4,4′-oxydianiline with 4-phenylethynylphthalic anhydride as reactive endcapping reagent were prepared. The calculated molecular weights were in the range of 1150–5070 g mol−1 with different degrees of polymerization ( n = 1, 3, 5, 7, and 9). The effect of molecular weight of the aromatic oligomers on their processability and solubility as well as the thermal and mechanical properties of the thermal-cured polyimides (PIs) was systematically investigated. The typical oligomer (Oligo-1) could be melted at temperatures of 289–334°C to yield stable molten fluid with melt viscosity below 1.0 Pa s. The melt viscosity of the oligomers increased with the increasing molecular weight. After thermally curing at 370°C, the thermoset PIs exhibited good thermal properties. The glass transition temperatures of oligomers measured by differential scanning calorimetry were in the range of 286–326°C, and the temperature of 5% weight loss was higher than 524°C. The cured films also showed good mechanical properties with tensile strength above 72 MPa and modulus more than 2.5 GPa.

High thermal stable polyimide resins derived from phenylethynyl-endcapped fluorenyl oligoimides with low melt viscosities

To improve the processability and thermal stability of polyimide, a series of novel phenylethynyl-endcapped oligoimides (PEPA-oligoimides) with calculated molecular weights (MnC) were successfully prepared from thermal imidization of 4,4’-(9-fluorenylidene) dianiline (BAFL) as fluorenyl diamine, 4,4′-oxy-diphthalic anhydride (ODPA) as aromatic dianhydride and 4-phenylethynylphthalic anhydride (4-PEPA) acted as reactive end-capping reagent at elevated temperatures. Experiment results indicated that the oligoimides were the mixtures of PEPA-endcapped oligomers with different degrees of polymerization characterized by MALDI-TOF mass spectra. The influence of chemical structures on the melt processabilities of the oligoimides, the thermal, dielectric and mechanical properties of the thermoset resins was studied. The typical oligoimide resin owned minimum melt viscosity of 0.2 Pa·s at around 310 °C and wide melting processing window, suitable for resin transfer molding (RTM). Besides, its corresponding thermal-cured polyimide resin possessed glass transition temperature (Tg) as high as 514 °C. The dielectric constants of polyimide resins decreased from 3.15 to 2.80 by reducing the MnC. The mechanical properties of the polyimide neat resins were improved gradually with increasing MnC. Finally, the carbon fiber/polyimide (Cf/PI) composite laminates showed excellent mechanical strength retention rate at 350 °C, might be long-term served at extremely high temperature in aerospace and aviation field.

Highly soluble phenylethynyl-endcapped imide oligomers derived from thioetherdiphthalic anhydride isomers

Novel imide oligomers (calculated molecular weights: 1250–5000 g mol−1) based on the mixture of thioetherdiphthalic anhydride isomers ( m-TDPA) with 2-phenyl-4,4′-diaminodiphenyl ether ( p-ODA) in the presence of 4-phenylethynylphthalic anhydride (PEPA) as reactive endcapping agent were prepared. Then pyromellitic dianhydride (PMDA) was introduced to the polymerization of m-TDPA/ p-ODA (mole m-TDPA:molePMDA = 1:1). The effect of molecular weights and polymer chemical structures of the aromatic oligomers on their processability and solubility as well as the thermal and mechanical properties of the thermal-cured polyimides (PIs) was systematically investigated. All the oligomers showed good solubility (more than 30 wt%) in N-methyl-2-pyrrolidone and very low melt viscosities. The minimum melt viscosities of Oligo-5 was 61.5 Pa s at 321°C. The melt viscosity of the oligomers increased with the increase of molecular weight. After thermally curing at 370°C for 1 h, the thermoset PIs exhibited good thermal properties. The glass transition temperatures of oligomers measured by differential scanning calorimetry were in the range of 264–337°C, and the temperature of 5% weight loss was higher than 505°C. The cured films also demonstrated good mechanical properties with tensile strength and modulus greater than 52 MPa and 2.9 GPa, respectively.

Phenylethynyl-Terminated Polyimide Oligomers with Low Viscosity and Good Thermal Properties

A series of addition-type imide oligomer (degree of polymerization: n=1-9) derived from 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride (a-ODPA), 3,4'-oxydianiline (3,4'-ODA) and 4-phenylethynylphthalic anhydride (PEPA) was synthesized by thermal imidization. The resultant oligomers were characterized for their chemical architecture, thermal property, and processability. The experimental results showed that oligomers PI-1 and PI-2 had somewhat crystalline phase. PI-4, PI-6 and PI-9 exihibited high solubility in solvents. These imide oligomers have a very low melt viscosity, and thus provide wide processing window by the rheological behaviors. Furthermore, the cured polyimides exhibited excellent thermal stability under N2 atmosphere. The temperatures of 5% weight loss in N2 atmosphere were all above 524°C.

Synthesis and characterization of phenylethynyl-terminated polyimide oligomers derived from 2,3,3′,4′-diphenyl ether tetracarboxylic acid dianhydride and 3,4′-oxydianiline

With the goal of improving processability of imide oligomers and achieving high toughness of thermosetting polyimides, a series of 4-phenylethynylphthalic anhydride (PEPA)-terminated imide oligomers prepared by the reaction of 2,3,3′,4′-diphenyl ether tetracarboxylic acid dianhydride (a-ODPA) and 3,4′-oxydianiline (3,4′-ODA) with different molecular weights (degree of polymerization: n = 1–9) were formed. The resultant oligomers with different molecular weights were characterized for their chemical architecture, cure behavior, thermal properties, solubility in organic solvents and rheological characteristics. Besides, the thermal properties and tensile test of cured polyimide films were also evaluated. The imide oligomer (degree of polymerization: n = 1) has some somewhat crystalline phase, and imide oligomers (degree of polymerization: n = 2–9) showed excellent solubility (40 wt%) in N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) at room temperature. Furthermore, the rheological properties of imide oligomers showed very low melt viscosity and wider processing window. The cured films exhibited good thermal properties with the glass transition temperatures of 282–373 °C and 5 wt% thermal decomposition temperatures higher than 551 °C in nitrogen atmosphere. The elongation at break of the prepared films was found to be high (almost > 9.3%).

Phenylethynyl- and naphthylethynyl-terminated hyperbranched polyimides with low melt viscosity

In the past decades, 4-phenylethynyl phthalic anhydride has been the most commonly used endcapper for polyimide (PI). A series of different groups of terminated hyperbranched PIs (HBPIs) were synthesized from 1,3,5-tris(2-trifluoromethyl-4-aminophenoxy)benzene, bis[4-(3,4-dicarboxyphenoxy)phenyl]ether dianhydride, and 4-phenylethynylphthalic anhydride or 4-(1-naphthylethynyl)phthalic anhydride. The glass transition temperatures ( Tgs) of the polymers varied from 166°C to 193°C. The 5% weight loss temperatures of polymers were in the range of 548 to 571°C and those of the endcapped HBPIs increased to the range of 600 to 601°C after curing. The PIs exhibited rather low melt viscosity at processing temperature and the complex viscosity increased continuously with the temperature increase. Because there is a large temperature difference between the Tg and cross-linking exothermic temperature, HBPIs provided a wide processing window.