Dynamic mechanical and thermal characterization of high-performance polybenzoxazines

Two polybenzoxazines are cured in an autoclave from the polyfunctional benzoxazine monomers, 8,8′-bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6′-bis(2,3-dihydro-3-phenyl-4H-1,3-benzoxazinyl) ketone. The density and tensile properties of these polybenzoxazines are measured at room temperature. Dynamic mechanical tests are performed to determine the T_g, crosslink density, and the activation enthalpy of the glass-transition process for these two polybenzoxazines. The effect of postcure temperature on the T_g of the polymers is investigated and discussed in terms of crosslink density. Fourier transform infrared (FTIR) spectroscopy is also applied for the molecular characterization of the curing systems. Thermal properties of these polybenzoxazines are studied in terms of isothermal aging and decomposition temperature via thermogravimetric analysis. These two polybenzoxazines show mechanical and thermal properties similar to or better than bismaleimides and some polyimides. They also show very high char yield after being carbonized in a nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3257–3268, 1999     

Synthesis and characterization of novel bisphthalonitrile resins linked by different molecular weight main-chain polybenzoxazines

A series of novel type bisphthalonitriles with different molecular weight main-chain polybenzoxazines as linkages have been successfully synthesized using 4, 4′-diaminodiphenyl methane, paraformaldehyde, bisphenol A and 4-nitrophthalonitrile as initial materials. The structures were characterized by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (¹H-NMR). The formation of benzoxazine and the existence of nitrile groups were confirmed by the absorbance at 950cm^?1 of benzene attached with oxazine ring and 2231 cm^?1 of nitrile groups. The characteristic resonance peaks observed at about 4.52 (C-CH₂-N) and 5.28 ppm (N-CH₂-O) also determined the structure of benzoxazine ring. The curing behaviors were monitored by differential scanning calorimetry (DSC) and FT-IR. Two-stage polymerization mechanisms were observed according to the ring-opening of benzoxazine and the polymerization of nitrile groups catalyzed by phenolic hydroxyl groups, which generated during the curing reaction of benzoxazine. The polymerization of these bisphthalonitriles exhibited self-promoted curing behaviors. The completion of polymerization was proved by the disappearance of the band located at 950 cm^?1 in FT-IR. Thermogravimetric analysis (TGA) was used to investigate the thermal stability, and the results showed that the cured polymers achieved extremely high char yield from 61.1% up to 74.2% at 800°C under nitrogen and exhibited increasing decomposition temperature as the contents of phthalonitrile groups increased, which indicated that the polymerization of phthalonitriles could improve the thermal stability.     

Improved thermal and mechanical properties of polybenzoxazines based on alkyl‐substituted aromatic amines

The thermal and mechanical properties of polybenzoxazine thermoset networks containing varying amounts of phenolic Mannich bridges, arylamine Mannich bridges, and methylene bridges have been investigated. In materials based on m‐toluidine and 3,5‐xylidine, the onset of thermal degradation is delayed until around 350 °C with no significant effect on the final char yield. The first of the three weight‐loss events usually seen in aromatic amine‐based polybenzoxazines is absent in these two materials. Materials with additional amounts of arylamine Mannich bridges and methylene bridges show improved mechanical properties, including higher crosslink densities and rubbery plateau moduli. Correlations between the observed mechanical properties and network structures are established. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3289–3301, 2000     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Studies on the mesophase formation mechanism of polybenzoxazines: polymerisation induction

ABSTRACT

To study the mesophase formation mechanism of polybenzoxazine, a novel linear benzoxazine oligomer bearing cholesteryl side groups [poly(PC-AC)] was designed and synthesised through thermally activated ring-opening polymerisation of a monofunctional benzoxazine monomer (PC-AC). The PC-AC was obtained by Mannich condensation reaction using mesomorphic amine of cholesteryl 4-aminobenzoate, p-cresol and paraformaldehyde as starting materials. During the isothermal polymerisation of PC-AC monomer, the phase evolution from a crystal phase to an isotropic molten phase and then to a liquid crystal (LC) phase was observed. Since it is PC-AC oligomers that form the LC phase, ‘polymerisation-induced LC’ mechanism is put forward. We believe that the structure factors including the confined formation of intramolecular hydrogen bonding and the side chain position of mesogenic units also play an important role in the formation of the LC phase. Furthermore, poly(PC-AC) exhibits a smectic mesophase. This work provides new insight into the LC phase formation mechanism of polybenzoxazines. This is very helpful to guide the rational design and synthesis of polymers with high thermal conductivity and high-temperature resistance.     

Preparation of conductive polybenzoxazines by oxidative polymerization

Soluble and thermally curable conducting high molecular weight polybenzoxazine precursors were prepared by oxidative polymerization 3‐phenyl‐3,4‐dihydro‐2H‐benzo[e][1,3] oxazine (P‐a) alone and in the presence of thiophene (Th) with ceric ammonium nitrate in acetonitrile. The structure of the precursors was confirmed by FTIR, ¹H NMR, and DSC measurements, indicating the presence of a cyclic benzoxazine structure, together with small but varying amount of a ring opened phenolic structure. The resulting polymers exhibit conductivities around 10^?2 S cm^?1 and undergo thermal curing at various temperatures. Attempts to copolymerize P‐a with another electroactive monomer, pyrrole (Py), by a similar redox process were unsuccessful, which was attributed to the unfavourable oxidation potential of Py. The cured products exhibited high thermal stability but lower conductivity, than those of the precursors. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 999–1006, 2007     

Synthesis and Characterization of Thermally Curable Benzoxazine‐Functionalized Polystyrene Macromonomers

Summary: Thermally curable benzoxazine ring‐containing polystyrene macromonomers were synthesized and characterized. 1,4‐Dibromo‐2,5‐bis(bromomethyl)benzene and 1,4‐dibromo‐2‐(bromomethyl)benzene were used as initiators in the atom transfer radical polymerization of styrene. The resulting polymers were used in combination with 3‐aminophenylboronic acid hemisulfate, for a Suzuki coupling. The obtained polymers, with amino groups in the middle or end of the chains, were reacted with formaldehyde and phenol to yield benzoxazine ring‐containing macromonomers. In addition to the glass transition temperature of the polystyrene segment observed at ca. 105 °C, differential scanning calorimetry thermograms exhibit an exotherm at ca. 276 °C corresponding to the oxazine thermal polymerization. Both macromonomers undergo thermal curing with the formation of thermosets having polystyrene segments.

Structure of the benzoxazine‐functionalized polystyrene.     

An investigation of the thermal and thermo‐oxidative degradation of polybenzoxazines with a reactive functional group

The thermal behavior of a series of polybenzoxazines based on 3‐aminophenylacetylene has been investigated. The effect of reactive amine on the thermal cleavage of the Mannich base is examined under both inert and oxidative environments. It has been shown that the thermal stability of polybenzoxazines is substantially improved by the reactive amine. Various biphenols are found to have insignificant effect on the thermal stability of this series of polybenzoxazines. These nitrogen containing phenolic resins are nonflammable polymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 647–659, 1999     

Greatly enhanced thermo‐oxidative stability of polybenzoxazine thermoset by incorporation of m‐carborane

Novel polybenzoxazine precursor containing m‐carborane unit in the main‐chain has been firstly synthesized through click reaction of diazidomethyl m‐carborane (DAMC) and diacetylene bisbenzoxazine (DABB). Meanwhlie, the traditional polybenzoxazine precursor was also prepared through click reaction of diazidomethyl p‐benzene (DAPB) and DABB as a control. 1H NMR was used to confirm the structures of the monomers and the resulting polymers. FT‐IR and differential scanning calorimetry (DSC) were used to study the curing behavior of carborane‐containing benzoxazine polymer (CCBP). Dynamic mechanical analysis (DMA) study demonstrated that the cured CCBP had high storage moduli and high Tg. Thermogravimetric analysis (TGA) and ablation test showed that the cured CCBP had outstanding thermo‐oxidative stability. During thermal ablation of cured CCBP, organic material was degraded, and a passivation layer with oxidized m‐carboranes was formed, which prevented the underlying polymer from further degradation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 973–980     

Isobaric cure shrinkage behaviors of epoxy molding compound in isothermal state

The warpage of plastic‐encapsulated IC packages after molding is believed to be induced by thermal and cure shrinkage of epoxy molding compound (EMC). To study the warpage behaviors of EMC, the amount of cure‐induced shrinkage needs to be understood. Volume shrinkage behaviors induced by cure reaction of EMC in isothermal and isobaric states were studied with a differential scanning calorimeter (DSC) and a pressure–temperature‐controlled dilatometer. The results show that higher pressure induce more volume shrinkage under fixed temperature but the difference of volume shrinkage under different pressure levels doesn't obey the principle of linearity. It is observed that the amount of chemical volume shrinkage at 145 °C is higher than those under three other temperatures: 160, 175, and 190 °C. The chemical volume shrinkage of EMC is found to be very process dependent. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2392–2398, 2005     

Benzoxazine containing polyester thermosets with improved adhesion and flexibility

High molecular weight polyesters containing thermally curable benzoxazine units in the main chain have been synthesized. For this purpose, first the diol functional monomer is synthesized through the Mannich and subsequent ring closure reactions of bisphenol‐A, paraformaldehyde, and 5‐amino‐1‐pentanol. Polycondensation of the resulting benzoxazine and pyromellitic dianhydride or 4‐4′‐(hexafluoroisopropylidene) diphatalic anhydride with or without dibutyltin laurate yielded the corresponding polyesters with the molecular weights between 5800 and 7000 Da. The structures of the precursor diol monomer and the resulting polyesters are confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy analysis. Curing behavior of both the monomer and polymers has also been studied by differential scanning calorimetry. Flexible films of the polyesters were obtained by solvent casting on tin plates and crosslinked by heating in the absence of any catalyst. The cured films exhibited high flexibility and adhesion on the tin plates as determined by ASTM and DIN tests. Thermal properties of the cured polymers were also investigated by thermogravimetric analysis (TGA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4279–4284, 2010     

Thermal shrinkage of electrospun PVP nanofibers

This paper outlines the shrinkage of electrospun polyvinylpyrrolidone (PVP) fiber mats during thermal treatment. The thermal behavior and phase changes within the fibers were investigated by DSC and TGA/DTA. Five precursors with different PVP loading in ethanol were electrospun. The mats shrinkage as function of temperature was measured in the RT–200 °C range. Shrinkage rate drastically increased above the polymer glass transition point, T_g (150–180 °C), due to increase in polymer chain mobility. Mats shrinkage at 200 °C as function of PVP concentration showed a minimum at ∼10%wt. Below 10% PVP the mats morphology is non‐uniform, consisting of beads and fibers. Above 10% PVP, only flat and uniform fibers were observed. This paper outlines the dominant mechanism governing the mats shrinkage during heating. In addition, the effect of PVP concentration on the expansion of fibers diameter was investigated and found to be consistent with the linear shrinkage observing a minimum at ∼10% PVP. The effect of applied voltage on mat shrinkage was investigated, and showed a minimum at 12 kV. Understanding the interplay between fibers morphology and thermal shrinkage allows precursor composition and system optimization needed for minimizing shrinkage negative effects on the structure and properties of electrospun fiber mats. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 248–254     

Synthesis and characterization of novel epoxy monomers and liquid crystal thermosets

Four new epoxy monomers have been synthesized and characterized as part of a program to prepare novel liquid crystal thermoset (LCT) materials. Three of the new epoxy monomers contained a biphenyl mesogen and were not liquid crystalline (LC). The remaining epoxy monomer, which contained a 1,4-dibenzoyloxybenzene mesogen, was synthesized in an overall yield of 30% and displayed a broad (83°C) nematic liquid crystalline phase. The new liquid crystalline epoxy monomer was cured at 120°C and postcured at 175°C with a stoichiometric amount of 1,4-phenylenediamine. The thermal transitions of the resulting LCT were studied by differential scanning calorimetry (DSC), polarized light optical microscopy (POM), thermomechanical analysis (TMA), and wide angle x-ray diffraction (WAXD) as a function of cure time and temperature. A process characterization diagram was constructed which shows that LCTs based on this new LC monomer can be processed in the liquid crystalline phase over a broad range of times and temperatures. Qualitative agreement with previous epoxy LCT results was found, as LCT's with smectic phases and without clearing temperatures were observed at long cure times (high crosslink densities), whereas nematic phases with clearing temperatures predominated in networks at short cure times (low crosslink densities). © 1993 John Wiley & Sons, Inc.     

Effect of methoxy position on dynamic mechanical and shape memory properties of methoxyphenol-based polybenzoxazines

Abstract

Two series of benzoxazines were synthesized from o-, m-, and p-methoxyphenols, two polyetheramines with different molecular weights, and formaldehyde. The glass transition temperatures (T _gs) of m-methoxyphenol-based polybenzoxazines are respectively higher than those of o- and p-methoxyphenol-based counterparts. The polybenzoxazines exhibit thermally induced one-way dual-shape memory behavior based on T _g, and the o- and p-methoxyphenol-based polybenzoxazines exhibit higher shape memory performance than m-methoxyphenol-based counterparts under motion constraints.     

Synthesis and characterization of nanomagnetite thermosets based on benzoxazines

Nanomagnetite thermosets were obtained by thermally activated ring opening copolymerization of benzoxazine groups coated on the surface of the nanomagnetite with bare benzoxazine. For this purpose, carboxylic acid containing 1,3‐benzoxazine was synthesized and covalently bonded on magnetite nanoparticles by postcoating method. The average size of benzoxazine coated nanoparticles was 40–100 nm as determined by Dynamic Light Scattering (DLS), Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM) measurements. The crystal structure of benzoxazine coated nanoparticles was shown to be magnetite by X‐ray diffraction (XRD) analysis. Thermally activated curing behavior of nanomagnetite‐benzoxazines has also been studied by differential scanning calorimetry (DSC). Magnetic and thermal properties of the cured samples were investigated. It was shown that the precursor nanomagnetite benzoxazine and cured samples exhibited typical ferromagnetic character with low coercivities between 1.5 and 2.5 Oe. The cured samples showed high thermal stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6780–6788, 2008     

Effect of fiber length and composition on mechanical properties of carbon fiber‐reinforced polybenzoxazine

The mechanical strength and modulus of chopped carbon fiber (CF)‐reinforced polybenzoxazine composites were investigated by changing the length of CFs. Tensile, compressive, and flexural properties were investigated. The void content was found to be higher for the short fiber composites. With increase in fiber length, tensile strength increased and optimized at around 17 mm fiber length whereas compressive strength exhibited a continuous diminution. The flexural strength too increased with fiber length and optimized at around 17 mm fiber length. The increase in strength of composites with fiber length is attributed to the enhancement in effective contact area of fibers with the matrix. The experimental results showed that there was about 350% increase in flexural strength and 470% increase in tensile strength of the composites with respect to the neat polybenzoxazine, while, compressive properties were adversely affected. The composites exhibited an optimum increase of about 800% in flexural modulus and 200% in tensile modulus. Enhancing the fiber length, leads to fiber entanglement in the composites, resulted in increased plastic deformation at higher strain. Multiple branch matrix shear, debonded fibers and voids were the failures visualized in the microscopic analyses. Defibrillation has been exhibited by all composites irrespective of fiber length. Fiber debonding and breaking were associated with short fibers whereas clustering and defibrillation were the major failure modes in long fiber composites. Increasing fiber loading improved the tensile and flexural properties until 50–60 wt% of fiber whereas the compressive property consistently decreased on fiber loading. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and characterization of sulfone containing main chain oligobenzoxazine precursors

The preparation of soluble and processable polybenzoxazine precursors capable of forming high performance networks is an important field of research with a broad spectrum of application. This study demonstrates an approach that utilizes aromatic sulfonediamine, bisphenol‐A, and formaldehyde in Mannich‐type polycondesation to prepare polybenzoxazine precursor. The structure of the oligomeric precursor (M_n = 2600) was confirmed by FTIR and ¹H NMR spectral analysis. The precursor contained both sulfone and benzoxazine ring structures in the backbone. It was shown that small amount of ring‐opened phenolic groups were also present. Thermally activated self‐curing behavior of precursor in the absence of catalyst was studied by differential scanning calorimetry. Thermal properties of the cured polymers were also investigated by thermo gravimetric analysis. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Flood control and shrinkage in the Haihe River Mouth

Because of overusing water resources in the upper and middle reaches of the Haihe Basin, less and less water flows to the river mouth. The Haihe River flow is cut off in most time of the seasons, sediment deposited in the river mouth channel is rarely scoured away, and many of the river mouth channels have been shrinking quickly. The discharge capacity of the channel is consequently reduced greatly, which results in more and more serious flood hazard. Many tide gates have been built for storing fresh water and preventing the salty and turbid water. The channel downstream of the gate is silting up and people have to dredge the channel every year before the flood season. This paper studies the laws of the siltation and strategies controlling channel shrinkage. The strategies are digger dredging, trailer dredging, scouring with pumping water or storing tidal water, building double guiding dikes and building a new gate. Comparison of various strategies is performed, suggesting the most effective strategy con     

The mechanical and magnetic alignment of liquid crystalline epoxy thermosets

The processing of a new series of liquid crystalline (LC) epoxy networks was evaluated. Above the glass transition temperature, the low crosslink density networks could be mechanically aligned. The mechanically oriented networks readily lost orientation upon heating. Highly anisotropic liquid crystalline (LC) epoxy networks were also prepared by aligning the mesophase of the prepolymer during the curing process under the influence of a magnetic field. Orientation parameters (f) of 0.13 to 0.57 were achieved by these processes as determined by x-ray diffraction analysis. The ability of the magnetically aligned networks to retain their orientation above the glass transition temperature was determined by time-resolved x-ray diffraction. The stability of the alignment of these networks was found to depend on crosslink density. The effect of the anisotropy of these networks was investigated by measuring the coefficient of thermal expansion (CTE). In the aligned networks, there was a substantial reduction in CTE parallel to the direction of the applied field compared to the randomly oriented networks. © 1992 John Wiley & Sons, Inc.     

Anisotropy in the thermal shrinkage of polyimide film

Anisotropy in a polyimide film was investigated in a quantitative manner by a nonlinear regression of the thermal shrinkage data obtained from thermomechanical analysis. The thermally induced shrinkage of this pyromellitic dianhydride–oxydianiline polyimide film at 573 K was directionally anisotropic in the film plane by as much as about 0.4%. The direction of maximum thermal shrinkage was inclined by about π/6 rad from the machine direction of the film. The thermal shrinkage behavior of the polyimide films in the vicinity of the glass‐transition temperature (T_g) showed an unusual anisotropic response. On the basis of a correlation between the anisotropy in the thermal shrinkage of the films and the molecular orientation of the polyimide, this characteristic thermal shrinkage behavior around T_g is suggested to be due to a recovery of the free volume lost by a physical aging process. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3222–3229, 2000