Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Synergism and multiple mechanical relaxations observed in ternary systems based on benzoxazine,epoxy, and phenolic resins

The synergism in the glass‐transition temperature (T_g) of ternary systems based on benzoxazine (B), epoxy (E), and phenolic (P) resins is reported. The systems show the maximum T_g up to about 180 °C in BEP541 (B/E/P = 5/4/1). Adding a small fraction of phenolic resin enhances the crosslink density and, therefore, the T_g in the copolymers of benzoxazine and epoxy resins. To obtain the ultimate T_g in the ternary systems, 6–10 wt % phenolic resin is needed. The molecular rigidity from benzoxazine and the improved crosslink density from epoxy contribute to the synergistic behavior. The mechanical relaxation spectra of the fully cured ternary systems in a temperature range of −140 to 350 °C show four types of relaxation transitions: γ transition at −80 to −60 °C, β transition at 60–80 °C, α₁ transition at 135–190 °C, and α₂ transition at 290–300 °C. The partially cured specimens show an additional loss peak that is frequency‐independent as a result of the further curing process of the materials. The ternary systems have a potential use as electronic packaging molding compounds as well as other highly filled systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1687–1698, 2000     

Synthesis and characterization of an adipic acid–derived epoxy resin

Adipic acid, a highly abundant chemical that can be produced from biomass, was used to prepare an aromatic‐free epoxy resin. Synthesis of the diglycidyl adipate was performed by a one‐step process using epichlorohydrin and by a two‐step process comprising allylation and epoxidation. The viscosity of diglycidyl adipate is 25 mPa·s, which is 99% lower than the diglycidyl ether of bisphenol A (DGEBA). The storage modulus at 25 °C for cured diglycidyl adipate and DGEBA is 2000 and 3200 MPa, respectively. The alpha transition temperature through peak of the loss modulus and the peak of tan(δ), are 77 °C and 90 °C, respectively. Low‐viscosity epoxy applications are discussed herein. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2625–2631     

Preparation and properties of biocomposites composed of bio‐based epoxy resin,tannic acid,and microfibrillated cellulose

As new bio‐based epoxy resin systems, glycerol polyglycidyl ether (GPE) and sorbitol polyglycidyl ether (SPE) were cured with tannic acid (TA) at various conditions. When the curing conditions were optimized for the improvement of thermal and mechanical properties, the most balanced properties were obtained for the GPE/TA and SPE/TA cured at 160 °C for 2–3 h at the epoxy/hydroxyl ratio of 1/1. The cured SPE/TA had a higher glass transition temperature (T_g) and tensile strength than the cured GPE/TA. Next, biocomposites of GPE/TA and SPE/TA with microfibrillated cellulose (MFC) were prepared by mixing aqueous solution of the epoxy/curing reagent with MFC, and subsequent drying and curing at the optimized condition. For both the GPE/TA/MFC and SPE/TA/MFC biocomposites, T_g and the storage modulus at rubbery plateau region increased with increasing MFC content over the studied range of 3–15 wt %. The tensile strength at 25 °C for GPE/TA/MFC biocomposite with MFC content 10 wt % was 76% higher than that of control GPE/TA, while the tensile modulus was little improved. On the other hand, the tensile strength and modulus of SPE/TA/MFC biocomposite with MFC content 10 wt % were 30 and 55% higher than those of control SPE/TA, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 425–433, 2010     

Degradable and chemically recyclable epoxy resins containing acetal linkages: Synthesis,properties, and application for carbon fiber‐reinforced plastics

Four sorts of epoxy resins containing degradable acetal linkages were synthesized by the reaction of bisphenol A (BA) or cresol novolak (CN) resin with vinyl ethers containing a glycidyl group [4‐vinlyoxybutyl glycidyl ether (VBGE) and cyclohexane dimethanol vinyl glycidyl ether (CHDMVG)] and cured with known typical amine‐curing agents. The thermal and mechanical properties of the cured resins were investigated. Among the four cured epoxy resins, the CN‐CHDMVG resin (derived from CN and CHDMVE) exhibited relatively high glass transition temperature (T_g = ca. 110 °C). The treatment of these cured epoxy resins with aqueous HCl in tetrahydrofuran (THF) at room temperature for 12 h generated BA and CN as degradation main products in high yield. Carbon fiber‐reinforced plastics (CFRPs) were prepared by heating the laminated prepreg sheets with BA‐CHDMVG (derived from BA and CHDMVE) and CN‐CHDMVG, in which strands of carbon fibers are impregnated with the epoxy resins containing conventional curing agents and curing accelerators. The obtained CFRPs showed good appearance and underwent smooth breakdown with the aqueous acid treatment in THF at room temperature for 24 h to produce strands of carbon fiber without damaging their surface conditions and tensile strength. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of a deuterated phenolic resin

A highly deuterated novolac‐type phenolic resin was prepared by polycondensation of deuterated phenol and formaldehyde using oxalic acid as an acid catalyst. The polycondensation of deuterated monomers and the formation of the highly deuterated phenolic resin were confirmed by the gel permeation chromatography, IR, and ¹H NMR analyses. With the exception of hydroxyl groups, the degree of deuteration was estimated to be more than 98%. The polymer conformation in THF solution was evaluated by the scaling exponent of the Mark–Houwink–Sakurada equation. The exponent of the deuterated phenolic resin is 0.26 in THF at 40 °C and is close to that of a nondeuterated phenolic resin, which suggests that phenolic resins behave like a compact sphere irrespective of deuteration. The curing behavior of the deuterated phenolic resin with hexamethylenetetramine was confirmed by differential scanning calorimetry analysis. The cured highly deuterated phenolic resin exhibits a lower incoherent neutron scattering background than that of the nondeuterated phenolic resin, which suggests that the former is suitable for matrix resins with low incoherent backgrounds for small‐angle neutron scattering studies of thermosetting resins. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Contributions of side groups to the water diffusion in cured epoxy resins (2) study on physical aging

Novolac epoxy resins cured with novolac resin, novolac acetate resin, novolac butyrate resin, and novolac phenylacetate resin named as EP, EPA, EPB, and EPP, respectively, were prepared. Their physical aging behavior at a T_g‐30 °C (30 °C below glass‐transition temperature) was examined by positron annihilation lifetime spectroscopy and differential scanning calorimetry. The ortho‐positronium annihilation lifetime τ₃ variation extent of EP is less apparent than that of the other three esterified samples during physical aging. The time dependence of ops intensity I₃ agreed with the Kohlrausch‐Williams‐Watts (KWW) equation. The relaxation time (τ₀) and nonexponential parameter were calculated. The free volume and enthalpy relaxation rate characterized by the reciprocal of τ₀ and ?ΔH/?logt, respectively, exhibit the same order—EPP > EPB > EPA > EP. These results suggest that the extend and rate of relaxation are not only related to the frozen free volume produced by quenching but also significantly influenced by segmental mobility of the network that attributed to the side‐group flexibility and their interaction with networks. This work also supports the fact that side‐group flexibility and the free‐volume fraction and distribution act in concert to control the water‐diffusion behavior in epoxy networks. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1135–1142, 2003     

Syntheses of conductive adhesives based on epoxy resin and polyanilines by using N‐tert‐butyl‐5‐methylisoxazolium perchlorate as a thermally latent curing reagent

Conductive composites consisted of epoxy resin and polyanilines (PANIs) doped with dodecylbenzenesulfonic acid ( 1 ), dodecylsulfonic acid (2), di(2‐ethylhexyl)sulfosuccinic acid (3), and HCl were synthesized by use of N‐tert‐butyl‐5‐methylisoxazolium perchlorate (5) under various reaction conditions. It was found that the composites with PANI doped with acid 2 (PANI‐2) prepared by curing with 10 mol % of reagent 5 at 80 °C for 12 h showed high electroconductivity along with the low conducting percolation threshold (3 wt % of PANI‐2). Furthermore, the composite with even ?10 wt % of PANI‐2 exhibited ?10^?1 S/cm of electroconductivity. The UV–vis and IR measurements indicated that the conductive emeraldine salt form of PANI‐2 in the composite was maintained after the curing reaction. The thermal stability was studied by TGA and DSC measurements, and then, the T_d10 and T_g of the composite with 5 and 10 wt % of PANI‐2 were found to be similar to those with the cured epoxy resin itself. In addition, the similar investigation with an oxetane resin instead of the epoxy resin was also carried out. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 718–726, 2006     

Nonaqueous synthesis of nanosilica in epoxy resin matrix and thermal properties of their cured nanocomposites

Nonaqueous synthesis of nanosilica in diglycidyl ether of bisphenol‐A epoxy (DGEBA) resin has been successfully achieved in this study by reacting tetraethoxysilane (TEOS) directly with DGEBA epoxy matrix, at 80 °C for 4 h under the catalysis of boron trifluoride monoethylamine (BF₃MEA). BF₃MEA was proved to be an effective catalyst for the formation of nanosilica in DGEBA epoxy under thermal heating process. FTIR and ²⁹Si NMR spectra have been used to characterize the structures of nanosilica obtained from this direct thermal synthetic process. The morphology of the nanosilica synthesized in epoxy matrix has also been analyzed by TEM and SEM studies. The effects of both the concentration of BF₃MEA catalyst and amount of TEOS on the diameters of nanosilica in the DGEBA epoxy resin have been discussed in this study. From the DSC analysis, it was found that the nanosilica containing epoxy exhibited the same curing profile as pure epoxy resin, during the curing reaction with 4,4′‐diaminodiphenysulfone (DDS). The thermal‐cured epoxy–nanosilica composites from 40% of TEOS exhibited high glass transition temperature of 221 °C, which was almost 50 °C higher than that of pure DGEBA–DDS–BF₃MEA‐cured resin network. Almost 60 °C increase in thermal degradation temperature has been observed during the TGA of the DDS‐cured epoxy–nanosilica composites containing 40% of TEOS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 757–768, 2006     

Polyethersulfone‐epoxy terminated materials as thermosetting resins for microelectronic devices

A totally aromatic polyether/sulfone resin (PES‐E) was synthesized and tested as an insulating glue in the construction of a Chip‐on‐Chip (CoC) device. PES‐E, essentially constituted of open‐chain macromolecules of low molecular mass (M _n of about 3000 Da) with hydroxy and/or epoxy end‐groups, has a glass transition temperature of about 150 °C and is subject to crosslinking at temperatures higher than 320 °C. A CoC device was assembled using a five‐step process by interposing a layer of PES‐E between two chips. After curing, SEM cross section images showed a homogeneous crosslinked resin layer well stuck (flick and shear tests) to both chips. The chemical structure of the chains and the hydroxy/epoxy end‐groups ratio were optimized to obtain a crosslinked material with good adhesion and sufficient flexibility to avoid cracking during assembly and use. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5682–5689, 2009     

Flame‐retardant epoxy resins from o‐cresol novolac epoxy cured with a phosphorus‐containing aralkyl novolac

A novel phosphorus‐containing aralkyl novolac (Ar‐DOPO‐N) was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) first with terephthaldicarboxaldehyde and subsequently with phenol. The chemical structures of the synthesized compounds were characterized with Fourier transform infrared, ¹H and ³¹P NMR, and elemental analysis. Ar‐DOPO‐N blended with phenol formaldehyde novolac was used as a curing agent for o‐cresol formaldehyde novolac epoxy, resulting in cured epoxy resins with various phosphorus contents. The epoxy resins exhibited high glass‐transition temperatures (159–177 °C), good thermal stability (>320 °C), and retardation on thermal degradation rates. High char yields and high limited oxygen indices (26–32.5) were observed, indicating the resins' good flame retardance. Using a melamine‐modified phenol formaldehyde novolac to replace phenol formaldehyde novolac in the curing composition further enhanced the cured epoxy resins' glass‐transition temperatures (160–186 °C) and limited oxygen index values (28–33.5). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2329–2339, 2002     

Novel quaternary ammonium borates as latent catalysts for epoxy–phenolic resins

Novel tetrabutylammonium tetrakis(substituted benzoyloxy)borate salts ( 1a – 1d ) were synthesized by the reaction of tetrabutylammonium tetraphenylborate and corresponding substituted benzoic acids. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with the ammonium borates in diglyme at 150 °C for 6 h proceeded up to 84–94% conversions and gave polymers with number‐average molecular weights of 3750–5750, whereas the polyaddition at 80 °C for 6 h gave less than 9% conversions. The catalytic activity of ammonium borates 1a – 1d depended on the substituent of the phenyl group of the borates, and the order of activity was 1b (p‐OMe) > 1a (? H) > 1c (p‐NO₂) > 1d [3,5‐(NO₂)₂]. The ammonium borate catalyst with the substituent that yielded lower acidity of the corresponding substituted benzoic acid tended to reveal higher activity. In comparison with tetrabutylammonium bromide (TBAB) as a conventional ammonium salt, 1a – 1d revealed better thermal latency. The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts in bulk at 40 °C was better than that with TBAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2689–2701, 2002     

Novel high performance RTM bismaleimide resin with low cure temperature for advanced composites

A novel performance matrix, coded as LCRTM, with low cure and post‐cure temperature (≤ 200°C) for fabricating advanced polymer composites via resin transfer molding (RTM), was successfully developed, made up of 4,4′‐bismaleimidodiphenylmethane (BDM) and N‐allyl diaminodiphenylether (ADDE). Investigations show that the stoichiometry of BDM and ADDE has great effect on the processing and performance parameters of the resultant resins. In the case of the optimum formulation (the mole ratio of BDM and ADDE is 1:0.55), the injection temperature range is between 70–82°C, and the pot life at 80°C is 300 min, moreover, the cured resin has desirable thermal and mechanical properties after being cured at 200°C for 6 hr, reflecting a great potential as high performance matrices for fabricating advanced composites via the RTM technique. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and properties of two novel silicon‐containing cycloaliphatic epoxy resins for electronic packaging application

In this paper, two silicon‐containing cycloaliphatic olefins were synthesized through the nucleophilic substitution reactions of cyclohex‐3‐enyl‐1‐methanol with di‐ or tri‐chlorosilane compounds. Then, after epoxidation, two new cycloaliphatic epoxy resins with different epoxy groups were successfully prepared. Their chemical structures were confirmed by ²⁹Si NMR, ¹H NMR, and Fourier‐transform infrared spectra (FTIR). The properties of cured products, including viscoelasticity, glass transition temperature (T_g), coefficient of thermal expansion, thermal stability and water absorption, were investigated. Compared to the difunctional epoxy resin, the trifunctional one exhibited a remarkably increased cross‐linking density from 0.82 to 4.08 × 10^?3 mol/cm³ and T_g from 157 to 228°C. More importantly, prior to curing, they had viscosities of only 240–290 mPa sec at 25°C, which were much lower than that of ERL‐4221 (409 mPa sec), providing the possibility of easy processing. The high glass transition temperatures, good thermal stabilities, and mechanical properties as well as excellent flowability endow the silicon‐containing epoxy resins with promising potential in microelectronic packaging application. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and characterization of liquid‐crystalline epoxy and its blend with conventional epoxy

Terephthaloyl chloride was reacted with 4‐hydroxy benzoic acid to get terephthaloylbis(4‐oxybenzoic) acid, which was characterized and further reacted with epoxy resin [diglycidyl ether of bisphenol A (DGEBA)] to get a liquid‐crystalline epoxy resin (LCEP). This LCEP was characterized by Fourier transform infrared spectrometry, ¹H and ¹³C NMR spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). LCEP was then blended in various compositions with DGEBA and cured with a room temperature curing hardener. The cured blends were characterized by DSC and dynamic mechanical analysis (DMA) for their thermal and viscoelastic properties. The cured blends exhibited higher storage moduli and lower glass‐transition temperatures (tan δ_max, from DMA) as compared with that of the pure DGEBA network. The formation of a smectic liquid‐crystalline phase was observed by POM during the curing of LCEP and DGEBA/LCEP blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3375–3383, 2003     

The POSS side chain epoxy nanocomposite: Synthesis and thermal properties

The IPI‐POSS‐modified epoxy resin (IPEP) was prepared from isocyanato‐propyldinethylsilyl‐isobutyl‐POSS (IPI‐POSS) and diglycidyl ether of bisphenol A epoxy resin. The steric hindrance of the IPEP bulky POSS side chain improved the curing activation energies. The POSS particles sizes were about 2–3 nm and dispersed uniformly. At lower IPEP concentration (POSS < 12 wt %), the glass transition temperatures (T_gs) of the IPEP nanocomposites increased from 118 to 170 °C. The char yield increased from 15 to 20 wt %, and the LOI values increased from 22 to 28. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 643–652, 2010     

Epoxy resin curing reaction studied by proton multiple‐quantum NMR

This study demonstrates that the curing reaction of thermosetting polymers, in particular, epoxy resins cured with aliphatic amines, can be characterized by different multiple‐quantum (MQ) NMR experiments performed in low‐field spectrometers. Measurements of the curing reaction at 40 °C, 70 °C, and 100 °C are carried out to obtain the kinetic parameters like induction time, vitrification time, polymerization rate, and activation energy being consistent with data obtained by other traditional and complementary techniques. Besides, it is demonstrated that ¹H MQ‐NMR spectroscopy is a successful approach to overcome the experimental challenge arising from the characterization of high dipolar‐coupled polymers to study the network structure and segmental dynamics of thermosetting polymer networks. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1324–1332     

Synthesis and curing of liquid crystalline epoxy resin based on naphthalene mesogen

Aromatic liquid crystalline epoxy resin (LCE) based on naphthalene mesogen was synthesized and cured with aromatic diamines to prepare heat‐resistant LCE networks. Diaminodiphenylester (DDE) and diaminodiphenylsulfone (DDS) were used as curing agents. The curing reaction and liquid crystalline phase of LCE were monitored, and mechanical and thermal properties of cured LCE network were also investigated. Curing and postcuring peaks were observed in dynamic DSC thermogram. LCE network cured with DDE displayed liquid crystalline phase in the curing temperature range between 183 and 260°C, while that cured with DDS formed one between 182 and 230°C. Glass transition temperature of cured LCE network was above 240°C, and crosslinked network was thermally stable up to 330°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 419–425, 1999     

Influence of carboxyl‐terminated (butadiene‐co‐acrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends

A mixture of epoxy with liquid nitrile rubber, carboxyl‐terminated (butadiene‐co‐acrylonitrile) (CTBN) was cured under various temperatures. The cured resin was a two‐phase system, where spherical rubber domains were dispersed in the matrix of epoxy. The morphology development during cure was investigated by scanning electron microscope (SEM). There was slight reduction in the glass transition temperature of the epoxy matrix (T_g) on the addition of CTBN. It was observed that, for a particular CTBN content, T_g was found to be unaffected by the cure temperature. Bimodal distribution of particles was noted by SEM analysis. The increase in the size of rubber domains with CTBN content is due probably to the coalescence of the rubber particles. The mechanical properties of the cured resin were thoroughly investigated. Although there was a slight reduction in tensile strength and young's modulus, appreciable improvements in impact strength, fracture energy, and fracture toughness were observed. Addition of nitrile rubber above 20 parts per hundred parts of resin (phr) made the epoxy network more flexible. The volume fraction of dispersed rubbery phase and interfacial area were increased with the addition of more CTBN. A two‐phase morphology was further established by dynamic mechanical analysis (DMA). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2531–2544, 2004     

Curing reaction of biphenyl epoxy resin with different phenolic functional hardeners

The investigation of cure kinetics and relationships between glass transition temperature and conversion of biphenyl epoxy resin (4,4′-diglycidyloxy-3,3′,5,5′-tetramethyl biphenyl) with different phenolic hardeners was performed by differential scanning calorimeter using an isothermal approach over the temperature range 120–150°C. All kinetic parameters of the curing reaction including the reaction order, activation energy, and rate constant were calculated and reported. The results indicate that the curing reaction of formulations using xylok and dicyclopentadiene type phenolic resins (DCPDP) as hardeners proceeds through a first-order kinetic mechanism, whereas the curing reaction of formulations using phenol novolac as a hardener goes through an autocatalytic kinetic mechanism. The differences of curing reaction with the change of hardener in biphenyl epoxy resin systems were explained with the relationships between T_g and reaction conversion using the DiBenedetto equation. A detailed cure mechanism in biphenyl-type epoxy resin with the different hardeners has been suggested. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 773–783, 1998