Studied on mechanical, thermal and dielectric properties of BPh/PEN-OH copolymer

doi:10.1016/j.compositesb.2016.09.036

Composites Part B: Engineering

Volume 106, 1 December 2016, Pages 294-299

https://doi.org/10.1016/j.compositesb.2016.09.036 Get rights and content

Abstract

The thermosetting 4,4′-bis(3,4-dicyanophenoxy)biphenyl (BPh) was modified with the hydroxy-terminated poly(aryl ether nitrile) (PEN-OH). Two different crosslinking reactions including the polymerization of the nitrile groups and the formation of triazines were coexisted in the BPh/PEN-OH system, which depended on the different curing temperature. Moreover, along with the processing of crosslinking, the microstructure changed to plastic fracture first and then became brittle fracture (T > 320 °C), which was observed from SEM. The copolymer system showed good mechanical properties, outstanding thermal stability (over 520 °C) and high char yield (86.1% at 600 °C). Furthermore, they exhibited excellent dielectric properties. Both the dielectric constant and dielectric loss were found to be relatively stable over a wide range of frequencies ranging from 100 Hz to 200 kHz. Moreover, the dielectric stability was also found with respect to temperature.

Introduction

Matrix resins play an important role in the interfacial adhesion and transferring load stress in composite, which are a key factor to determine the performances of a composite [1], [2], [3], [4], [5]. Nowadays, BPh represents an important class of thermosetting resin and has been widely accepted as matrix resins in advanced composites for aerospace and electronic packaging applications [6], [7], [8], [9]. However, the BPh resins are brittle as a result of the high crosslink density, poor solubility and poor processability, limiting the applications to some extent [10].

The polymers based on thermoplastic/thermosetting blends or copolymers could exhibit synergistic properties to broaden the application [11], [12], [13], [14], [15]. Poly(aryl ether nitrile) is one of the high performance thermoplastic resins with outstanding properties, such as high thermal stability, excellent mechanical property and good radiation resistance, and the pendant nitrile groups probably promote adhesion of the polymer to many substrates by polar interaction with other functional groups [16], [17], [18]. In addition, the nitrile groups can also use as a potential site for polymer crosslinking [19], [20].

In this paper, the polymers based on BPh/PEN-OH copolymers were prepared. The terminal hydroxyl groups in PEN-OH could promote crosslinking reaction of BPh, and the pendant nitrile groups in PEN-OH could react with BPh to form a cross-linked polymer. The different polymer structure could be controlled by thermal crosslinking with different procedures and the mechanism of crosslinking reaction was described in detail. Moreover, the effect of crosslinking on the morphological, mechanical, thermal and dielectric properties was also studied.

Section snippets

Materials

BPh and PEN-OH were synthesized through our previous reports [21], [22]. Diphenyl diamine sulfoxide (DDS) was obtained from Yangzhou Tianchen Fine Chemical Co., Ltd., China. N-methyl-2-pyrrolidone (NMP) was supplied from Tianjin BODI Chemical Co., Ltd., China. Unless otherwise noted, all reagents were obtained from commercial suppliers and used without further purification.

Preparation of the BPh/PEN-OH prepolymers

A typical procedure for the preparation of the BPh/PEN-OH prepolymers was as follows: the required amount of BPh was

Curing characteristics of BPh/PEN-OH system

The curing reaction of BPh usually requires high cure temperatures and long cure durations. In the present study, the amine groups of DDS and hydroxyl groups of PEN-OH accelerate the polymerization of the nitrile groups, following a similar mechanism and resulting in similar cured products [23], [24]. The curing behaviors of BPh and BPh/PEN-OH are studied by DSC. From Fig. 1(a), an endothermic peak around 230 °C belongs to the melting temperature of the BPh. Meanwhile, the exothermic peak

Conclusion

In summary, BPh/PEN-OH copolymers were prepared by different heat-treatment temperatures and time. The curing behaviors and morphologies of BPh/PEN-OH systems were investigated. The possible crosslinking reactions including the polymerization of the nitrile groups and the formation of triazines were discussed at the different curing temperature. The copolymers showed good mechanical properties and superior thermal stability (T_5% > 520 °C). More importantly, the copolymers exhibited excellent

Acknowledgements

The authors wish to thank for financial support of this work from the National Natural Science Foundation (Nos. 51373028, 51403029) and “863” National Major Program of High Technology (2012AA03A212).

References (35)

Y.J. Lei et al.
Preparation process and properties of exfoliated graphite nanoplatelets filled Bisphthalonitrile nanocomposites
J Phys Chem Solids
(2012)
R. Du et al.
Synthesis and thermal properties of bisphthalonitriles containing aromatic ether nitrile linkages
Polym Degrad Stab
(2009)
X. Liu et al.
Phase morphology and mechanical properties of a poly(ether sulfone)-modified bismaleimide resin
J Polym Sci
(2007)
D. Augustine et al.
Hydroxyl terminated PEEK-toughened epoxy-amino novolac phthalonitrile blends-Synthesis, cure studies and adhesive properties
Polymer
(2014)
Y.X. He et al.
Micro-crack behavior of carbon fiber reinforced thermoplastic modified epoxy composites for cryogenic applications
Compos Part B
(2013)
P. Motamedi et al.
Modification of nanostructure and improvement of mechanical properties of polypropylene/polyamide 6/layered silicate ternary nanocomposites through variation of processing route
Compos Part B
(2016)
C.W. Lee et al.
Synthesis of cyanato-functional polymaleimides and their application in negative-tone photoimaging by post-crosslinking
React Funct Polym
(2009)
H. Tang et al.
An effective approach to enhance temperature independence of dielectric properties for polyarylene ether nitrile films
Mater Lett
(2012)
D.J. Hourston et al.
The toughening of epoxy-resins with thermoplastics: 1. Trifunctional epoxy-resin polyetherimide blends
Polymer
(1992)
J.Y. Shieh et al.
Synthesis of novel flame retardant epoxy hardeners and properties of cured products
Polymer
(2001)

H. Tang et al.

Synthesis and dielectric properties of polyarylene ether nitriles with high thermal stability and high mechanical strength

Mater Lett

(2011)

G.Y. Nam et al.

Toughening of carbon fiber/epoxy composite by inserting polysulfone film to form morphology spectrum

Polymer

(2004)

M. Fanica et al.

Thermal behavior of some organic/inorganic composites based on epoxy resin and calcium carbonate obtained from conch shell of Rapana thomasiana

Compos Part B

(2012)

S.J. Park et al.

Cure behaviors and thermal stabilities of tetrafunctional epoxy resin toughened by polyamideimide

Macromol Res

(2015)

G. Aijuan

High performance bismaleimide/cyanate ester hybrid polymer networks with excellent dielectric properties

Compos Sci Technol

(2006)

D.N. Mao et al.

Enhanced mechanical and thermal properties of recycled ABS/nitrile rubber/nanofil N15 nanocomposites

Compos Part B

(2016)

H. Zhou et al.

Preparation and property comparison of ortho, meta, and para autocatalytic phthalonitrile compounds with amino group

Polym Adv Technol

(2011)

Cited by (36)

Novel three-dimensional wintersweet-like BaTiO<inf>3</inf>-decorated halloysite nanotube nanohybrids/polyarylene ether nitrile nanocomposites for flexible thermal-resistant dielectrics
2024, Applied Surface Science
The development of high-performance polymer-based nanocomposites in the field of organic film capacitors in high-temperature environments needs to address two key issues: the controllable construction of nanofillers and the enhancement of the temperature resistance characteristics within the polymer matrix. In this study, an effective method was proposed to prepare functional nanohybrids consisting of three-dimensional “wintersweet-like” barium titanate (BT) attached to halloysite nanotubes (HNTs) though polydopamine and polyethyleneimine co-modification (H-B@PP). These nano-hybrids are subsequently incorporated into polyarylene ether nitrile (PEN) matrix, resulting in the fabrication of functional nanocomposite films (PEN/H-B@PP). Ultimately, the highly thermally stable PEN-based nanocomposite films were obtained via a solid-phase crosslinking reaction (CPEN/H-B@PP). The microstructure, surface morphology of nano-hybrids and the mechanical, thermal and dielectric properties of nanocomposite films were investigated comprehensively. The results reveal that when the content of H-B@PP is 10 wt%, the tensile strength and modulus of the nanocomposite film reach 107.7 MPa and 2230.4 MPa, which are 5.28 % and 10.08 % higher than those of the pure PEN film, respectively. Additionally, the dielectric constant of nanocomposites containing 40 wt% nanofillers is 3.82 times that of pure PEN, while the dielectric loss is only below 0.04 at 1 kHz. Furthermore, the thermal stability of all nanocomposite films is further enhanced after the crosslinking reaction. Moreover, the dielectric constant-temperature coefficient of CPEN nanocomposites remains below 5 × 10⁻⁴ °C⁻¹ within the temperature range of 25–220 °C. All in all, this work presents a fabrication strategy for novel high-temperature resistant nanocomposite films, thereby expanding the potential applications of dielectric films in harsh environments.
Core-shell structure polydopamine and polyethylenimine co-assisted MoS<inf>2</inf>-BaTiO<inf>3</inf>/polyarylene ether nitrile nanocomposites for high-temperature resistant organic dielectrics
2024, Journal of Alloys and Compounds
In this work, a novel nanoparticle ((MoS_2-BT)@ (PDA+PEI)) was constructed through two-dimensional molybdenum disulfide (MoS₂) and zero-dimensional barium titanate (BT) via in-situ polymerization and co-modification of polydopamine (PDA) and polyethylenimine (PEI). Then the nanofillers were dispersed in the Polyarylene ether nitrile (PEN) matrix by film casting to obtain PEN/(MoS₂-BT)@ (PDA+PEI) nanocomposite dielectric films. Subsequently, the latter were subjected to chemical crosslinking at high temperature to obtain CPEN/(MoS₂-BT)@ (PDA+PEI) nanocomposites. The effects of filler content on the properties of PEN matrix composite films were investigated. The results indicate excellent compatibility between (MoS₂-BT)@ (PDA+PEI) and the PEN matrix due to the introduction of an organic modification layer, resulting in overall good performance of nanocomposite films, including good thermal stability with a glass transition temperature (T_g) exceeding 240 °C after chemical crosslinking. The dielectric constant of CPEN nanocomposites containing 40 wt% of the hybrid nanoparticles is 20.2 and the dielectric loss is 0.032 at 1 kHz, the dielectric constant-temperature coefficient of all CPEN nanocomposites is less than 6 × 10⁻⁴ °C⁻¹ at the temperature range of 25–220 °C. In short, the incorporation of (MoS₂-BT)@ (PDA+PEI) effectively enhances the thermal, mechanical, and dielectric properties of PEN-based nanocomposites.
Modification on phthalonitrile containing benzoxazine with cyaniding diamine-type benzoxazine: Curing reaction and properties of their glass fiber-reinforced composites
2023, Polymer
Phthalonitrile resin is a kind of high-performance thermosetting resins. Decreasing the curing temperature and accelerating the curing reaction rate have become the focus of research on phthalonitrile modification. Based on the reactivity, thermal and mechanical properties of diamine-type benzoxazine, a monocyano-functionalized diamine-type benzoxazine (MD-cn) was synthesized and applied to modify bisphthalonitrile resin containing bisphenol-type benzoxazine/nitrile phenylenediamine (BA-ph/BAB). Curing reaction properties and curing mechanism of BA-ph/BAB/MD-cn were studied by gelation time, DSC, DRA and in-situ IR. Results showed that MD-cn could significantly boost the curing reaction rate and reduce its curing temperature of BA-ph/BAB. Meanwhile, glass fiber reinforced composites (BA-ph/BAB/MD-cn/GF) was prepared and their properties were studied. Results showed that MD-cn improved the crosslinking density and curing degree of BA-ph/BAB could make the BA-ph/BAB/MD-cn resin matrix possess higher stiffness. Therefore, BA-ph/BAB/MD-cn/GF composites exhibited higher flexural strength (494 MPa, increased 40%) and flexural modulus (26 GPa, increased 13%) as well as good dimensional stability. Compatibility between MD-cn and BA-ph/BAB was investigated by DMA and SEM. Moreover, with the increase of MD-cn content, the good thermal stabilities (T_5%>404.5 °C, Y_{c, 800} _°C>66%) of cured BA-ph/BAB/MD-cn were obtained. Besides, interfacial adhesion properties of BA-ph/BAB/MD-cn/GF composite laminates were also studied.
Polyarylene ether nitrile composites film with self-reinforcing effect by cross-linking and crystallization synergy
2022, Polymer
Polymer dielectrics with outstanding temperature resistance and mechanical properties are expected to be used in 5G communication systems. Here, self-reinforced cross-linked polyarylene ether nitrile (CPEN) films were rationally designed and fabricated by introducing polyarylene ether nitrile terminated with hydroxyl (PEN-OH) into phthalonitrile end-capped polyarylene ether nitrile (PEN-Ph) and applying post-solid phase chemical reaction. For the catalytic effect on cross-linking reaction and crystallization enhancement of PEN-OH, the comprehensive performance of composite had been greatly improved, which showed a synergistic effect of crosslinking-crystallization. Intriguingly, properties of CPEN films can be finely tuned with the increase of PEN-OH crystallinity. The results show that CPEN films have excellent overall performance with a T_g of 390 °C, a long service life at 300 °C (4.05 × 10² min, 95 wt% residual weight), and low dielectric constant of 2.9. More commendably, CPEN film possessed a higher tensile modulus (3.6 GPa) of over 194% compared to the untreated film due to the crystals immobilized by chemical crosslinking reaction. Tuning the properties of composites by modulating the crosslinking-crystallization behavior opens up a new way to design high-performance polymeric dielectric materials.
Toughening effect of self-assembled thermoplastic particles on phthalonitrile containing benzoxazine and improved mechanical properties in the presence of fibers reinforcement
2022, Polymer
Citation Excerpt :
At present, researchers have designed a series of phthalonitrile resins with different structures and superior performance were designed by the thoughtful researchers, such as bisphenol A, poly (aryl ether) and imide [2,20,21], which are collectively referred to as traditional nitrile-based resin. Nevertheless, traditional nitrile-based resin was difficult to process (long curing period, high curing temperature) [22–24]. Hence, phthalonitrile containing benzoxazine (BA-ph) as a novel kind of high-performance resin which could polymerize at low temperature but applied at high temperature gradually replaced the traditional nitrile-based resin.
Phthalonitrile containing benzoxazine resin (BA-ph) was a new type of high-performance resin which could be used at high temperature by autocatalytic molding at low temperature. However, its brittleness after polymerization and weak interaction with fibers when it as the matrix of fiber reinforced composites (FRC) were obstacles to its wide application. In this study, Poly (arylene ether nitrile) containing phenolphthalein (PP-PEN) was introduced by solution blending to toughen BA-ph and its glass fiber (GF) FRC. The effects of PP-PEN on the crosslinking behavior and processability of BA-ph were studied by differential scanning calorimetry (DSC) and dynamic rheology analysis (DRA). The effect of PP-PEN on the structural strength and thermal stability of BA-ph/GF was further studied by other characterization methods. The non-notchable impact strength of BA-ph/PP-PEN/GF FRC formed at lower temperature (200 °C) could reach 148 kJ/m², which was 91.4% higher than that of BA-ph/GF FRC. Furthermore, the fracture morphology showed that PP-PEN significantly enhanced the interfacial strength between BA-ph and GF. It has potential applications in aerospace, rail transportation and the fields requiring high-performance polymer matrix FRC.
Investigation of the controllable thermal curing reaction for ultrahigh T<inf>g</inf> polyarylene ether nitrile compositions
2022, Polymer
High-performance polymer plays critical roles in 5G communication and electronic applications. Hence, special engineering plastic polyarylene ether nitrile (PEN) suitable for use in a harsh environment (T_g ＞ 400 °C,T_5% ＞ 500 °C, and tensile strength 100 MPa) has been developed. Bisphthalonitrile (BPh) units form a flexible bridge between the nitrile of PEN. In the preparation, DDS acts as a catalyst and ZnCl₂ functions as both a catalyst and a reinforcing phase, to enhance the degree of crosslinking and mechanical properties of the resulting compositions. Therefore, the structure of a linear polymer is converted into a 3D network, resulting in greatly enhanced performance. The mode of action for DDS/ZnCl₂ and the transformation of nitrile groups has been described. These insights provide an understanding of the impact of crosslinking factors in structure formation and supply a feasible design strategy for the preparation of high-performance polymer films.

View all citing articles on Scopus

¹: Yumin Huang and Yusi Luo contribute equally to this work.

View full text

Studied on mechanical, thermal and dielectric properties of BPh/PEN-OH copolymer

Abstract

Introduction

Section snippets

Materials

Preparation of the BPh/PEN-OH prepolymers

Curing characteristics of BPh/PEN-OH system

Conclusion

Acknowledgements

J Phys Chem Solids

Polym Degrad Stab

J Polym Sci

Polymer

Compos Part B

Compos Part B

React Funct Polym

Mater Lett

Polymer

Polymer

Mater Lett

Toughening of carbon fiber/epoxy composite by inserting polysulfone film to form morphology spectrum

Polymer

Thermal behavior of some organic/inorganic composites based on epoxy resin and calcium carbonate obtained from conch shell of Rapana thomasiana

Compos Part B

Cure behaviors and thermal stabilities of tetrafunctional epoxy resin toughened by polyamideimide

Macromol Res

High performance bismaleimide/cyanate ester hybrid polymer networks with excellent dielectric properties

Compos Sci Technol

Enhanced mechanical and thermal properties of recycled ABS/nitrile rubber/nanofil N15 nanocomposites

Compos Part B

Preparation and property comparison of ortho, meta, and para autocatalytic phthalonitrile compounds with amino group

Polym Adv Technol