Effect of Phenol/Formaldehyde Stoichiometry on the Modification of Epoxy Resin Using Epoxidized Novolacs

ABSTRACT

Unmodified epoxy resins based on bisphenol A exhibit brittleness and low elongation after cure. This article reports the results of a study for improving the properties of epoxy resin by blending with suitable thermosets. Hybrid polymer networks of diglycidyl ether of bisphenol A (DGEBA) resin with epoxidized phenolic novolac resins (EPN) containing phenol and formaldehyde in different stoichiometric ratios were prepared by physical blending. The modified epoxy resins were found to exhibit improved mechanical and thermal properties compared to the neat resin. DGEBA resins containing 2.5 to 20 wt% of epoxidized novolac resins (EPN) prepared in various stoichiometric ratios (1:0.6, 1:0.7, 1:08, and 1:0.9) between phenol and formaldehyde were cured using a room temperature amine hardener. The cured samples were tested for mechanical properties such as tensile strength, modulus, elongation, and energy absorption at break. All the EPNs are seen to improve tensile strength, elongation, and energy absorption at break of the resin. The blend of DGEBA with 10 wt% of EPN-3 (1:0.8) exhibits maximum improvement in strength, elongation, and energy absorption. EPN loading above 10 wt% is found to lower these properties in a manner similar to the behavior of any filler material. The property profiles of epoxy–EPN blends imply a toughening action by epoxidized novolac resins and the extent of modification is found to depend on the molar ratio between phenol and formaldehyde in the novolac.     

Hybrid Polymer Networks of Epoxy Resin and Substituted Phenolic Novolacs

Hybrid polymer networks of diglycidyl ether of bisphenol (DGEBA) resin and phenolic novolac resins were prepared and tested for mechanical properties, hardness, and water absorption. The novolacs employed were based on each of phenol and substituted phenols such as p-cresol, t-butyl phenol, and cardanol. Cardanol is the main constituent of cashew nut shell liquid (CNSL), a renewable resource. Blends containing 10–15 wt% of novolac resin show substantial improvement in properties. These properties show a declining trend with higher novolac loading. The stoichiometric ratio between phenol and formaldehyde in the novolacs was optimized (1:0.8) for maximum property enhancement. The property profiles of the epoxy/novolac networks show that novolacs are effective modifiers for commercial epoxy resin. Incorporation of novolacs of substituted phenols results in relatively greater improvement in energy absorption during failure.     

Novel flame retardant thermosets from nitrogen‐containing and phosphorus‐containing epoxy resins cured with dicyandiamide

A novel phosphorus‐containing epoxy resin (EPN‐D) was prepared by addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and epoxy phenol‐ formaldehyde novolac resin (EPN). The reaction was monitored by epoxide equivalent weight (EEW) titration, and its structure was confirmed by FTIR and NMR spectra. Halogen‐free epoxy resins containing EPN‐D resin and a nitrogen‐containing epoxy resin (XT resin) were cured with dicyandiamide (DICY) to give new halogen‐free epoxy thermosets. Thermal properties of these thermosets were studied by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), thermal mechanical analyzer (TMA) and thermal‐gravimetric analysis (TGA). They exhibited very high glass transition temperatures (T_gs, 139–175°C from DSC, 138–155°C from TMA and 159–193°C from DMA), high thermal stability with T_{d,5 wt %} over 300°C when the weight ratio of XT/EPN‐D is ≥1. The flame‐retardancy of these thermosets was evaluated by limiting oxygen index (LOI) and UL‐94 vertical test. The thermosets containing isocyanurate and DOPO moieties showed high LOI (32.7–43.7) and could achieve UL‐94 V‐0/V‐1 grade. Isocyanurate and DOPO moieties had an obvious synergistic effect on the improvement of the flame retardancy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes

Novel epoxy resin modifiers, DOPO–TMDS and DOPO–DMDP were synthesized by addition reaction of divinylsiloxane with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Halogen-free flame retardant epoxy resins were obtained through modification of o-cresol novolac epoxy resin cured by phenol novolac resin using DOPO–TMDS and DOPO–DMDP which were characterized by ¹H NMR, ¹³C NMR, ³¹P NMR and FT-IR measurements. Effects of the phosphorus-containing siloxanes on thermal stabilities, mechanical properties and flame retardant properties of the epoxy resins were investigated. The cured epoxy resins exhibited better mechanical properties and greatly improved flame retardant properties due to the presence of phosphorus-containing siloxanes. The cured epoxy resins with phosphorus loading of 2.0 wt% showed LOI values of 32–33 and achieved UL94V-0 ratings.     

Synthesis of aralkyl novolac epoxy resins and their modification with polysiloxane thermoplastic polyurethane for semiconductor encapsulation

A series of phenol‐based and naphthol‐based aralkyl epoxy resins were synthesized by the condensation of p‐xylylene glycol with phenol, o‐cresol, p‐cresol, or 2‐naphthol, respectively, followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The incorporation of stable dispersed polysiloxane thermoplastic polyurethane particles in the synthesized epoxy resin's matrix was achieved via epoxy ring‐opening with the isocyanate groups of urethane prepolymer to form an oxazolidone. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. A sea‐island structure was observed in all cured rubber‐modified epoxy networks via SEM. The results indicate that a naphthalene containing aralkyl epoxy resin has a low coefficient of thermal expansion, heat resistance, and low moisture absorption, whereas phenol aralkyl type epoxy resins are capable of imparting low elastic modulus result in a low stress matrix for encapsulation applications. Modification of the synthesized aralkyl epoxy resins with polysiloxane thermoplastic polyurethane have effectively reduced the stress of cured epoxy resins, whereas the glass transition temperature was increased because of the formation of the rigid oxazolidone structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1905–1916, 1999     

Epoxidized phenolic novolac: A novel modifier for unsaturated polyester resin

Unsaturated polyester resins (UPRs) are used widely in the fiber‐reinforced plastics (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, hybrid polymer networks (HPNs) based on UPR and epoxidized phenolic novolacs (EPNs) were prepared by reactive blending. A HPN is composed of a backbone polymer containing two types of reactive groups that can take part in crosslinking reactions via different mechanisms. EPNs were prepared by glycidylation of novolacs using epichlorohydrin. The novolacs had varying phenol: formaldehyde ratios. Blends of unsaturated polyester with EPN were then prepared. The physical properties of the cured blends were compared with those of the control resin. EPN shows good miscibility and compatibility with the resin and improves the toughness and impact resistance substantially. Considerable enhancement of tensile strength is also noticed at about 5% by weight of epoxidized novolac resin. TGA, DMA, and DSC were used to study the thermal properties of the toughened resin and the fracture behavior was studied using SEM. The blends are also found to have better thermal stability. Blending with EPN can be a useful and cost‐effective technique for modification of UPR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 457–465, 2006     

Synthesis of naphthalene containing aralkyl novolac epoxy resins for electronic application

Naphthalene containing aralkyl novolac epoxy resins were synthesized by the condensation of p‐xylylene glycol with 2,7‐dihydroxynaphthalene or 2‐naphthol followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. Comparisons of mono‐ and di‐functional naphthalene containing aralkyl novolac epoxy resins based on thermal and moisture absorption properties were also studied. The results indicate that a naphthalene containing aralkyl epoxy resin made from the difunctional naphthol has a low coefficient of thermal expansion, high heat resistance, and low moisture absorption.     

Properties of epoxy resin cured by phenol novolac/4-hydroxyphenylmaleimide polymer blend hardeners

Phenol novolac/4-hydroxyphenylmaleimide (HPMI) homopolymer (PHPMI) blends or phenol novolac/HPMI-styrene copolymer (HPMI-St) blends were used as the hardener of epoxy resins. Curing behaviour of the above systems and thermal and mechanical properties of the cured epoxy resins were studied. It was not necessary to use a curing accelerator for this system because PHPMI or HPMI-St had an accelerating effect on the curing reaction. Curing behaviour was investigated by measurement of gelation time(JIS K 6910) and differential scanning calorimetry thermogram (JIS K 7122). Test pieces made from neat resins and from reinforced resins with glass fibre or fused silica were evaluated in terms of thermal and mechanical properties, respectively. It was found that the heat resistance and the mechanical properties improved with increase of PHPMI or HPMI-St content in the hardener.     

Synthesis of a bifunctional epoxy monomer containing anthracene moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing anthracene moiety in the backbone was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. Thermal properties of its cured polymer with phenol novolac were examined by thermomechanical, dynamic mechanical, and thermogravimetric analyses. The cured polymer with phenol novolac showed higher glass transition temperature (T_g), lower thermal expansion, lower moisture absorption, and higher anaerobic char yield at 700°C than a cured polymer having a phenylene group in place of anthracene moiety. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 953–959, 1999     

Phenol novolac/poly(4- hydroxyphenylmaleimide) blend hardeners for DGEBA-type epoxy resin

Phenol novolac/poly (4-hydroxyphenylmaleimide) (PHPMI) blends were used as an epoxy resin hardener. The curing behavior of the above system and the thermal and mechanical properties of the cured epoxy resin were studied. It was not necessary to use a curing accelerator for this system, because PHPMI caused acceleration of the curing reaction. The curing mechanism of this system was investigated by using model compounds. Test pieces from the neat resins and the glass fiber reinforced resins were evaluated in terms of thermal and mechanical properties, respectively. It was found that heat resistance and mechanical properties were improved by increasing the amount of PHPMI in the hardener.     

New type of phenolic resin: Curing reaction of phenol‐novolac based benzoxazine with bisoxazoline or epoxy resin using latent curing agent and the properties of the cured resin

In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

一种含磷酚醛/环氧树脂阻燃性的研究

以双酚S、甲醛和三聚氰胺为原料合成含氮线性酚醛树脂,并用其作为固化剂,结合阻燃剂甲基膦酸酐对环氧树脂进行阻燃改性。利用TGA对环氧/酚醛树脂与环氧/酚醛树脂/膦酸酐两种浇铸体系的热稳定性能进行了比较研究。结果表明甲基膦酸酐为阻燃剂,酚醛树脂固化环氧树脂能得到效果较好的阻燃材料,垂直燃烧试验结果为UL-94V-0级。     

Enhanced Thermal Conductivity of Epoxy Composites with MWCNTs/AlN Hybrid Filler

To further improve the thermal conductivity of epoxy resin, the multi-walled carbon nanotube/aluminum nitride (MWCNTs/AlN) hybrid filler was employed to prepare thermal conductivity MWCNTs/AlN/epoxy composite by casting process, and the silane coupling reagent of γ-glycidoxy propyl trimethoxy silane(KH-560) was also used to functionalize the surface of MWCNTs and/or AlN. Results revealed that, the thermal conductivity of epoxy resin was improved remarkably with the addition of MWCNTs/AlN hybrid filler, a higher thermal conductivity of 1.04 W/mK could be achieved with 29 wt% MWCNTs/AlN hybrid filler (4 wt% MWCNTs +25 wt% AlN), about 5 times higher than that of native epoxy resin. And the epoxy composite with 29 wt% MWCNTs/AlN hybrid filler possessed better thermal conductivity and mechanical properties than those of single 5 wt% MWCNTs or 40 wt% AlN. The thermal decomposition temperature of MWCNTs/AlN/epoxy composite was increased with the addition of MWCNTs/AlN hybrid filler. For given filler loading, surface treatment of MWCNTs and/or AlN by KH-560 exhibited a positive effect on the thermal conductivity of epoxy composite.     

Synthesis and properties of phosphorus containing advanced epoxy resins

A series of advanced epoxy resins with various epoxy equivalent weights were synthesized from a reactive phosphorus‐containing diol, 2‐(6‐oxido‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6‐yl)‐1,4‐dihydroxy phenylene and diglycidyl ether of bisphenol A and then cured with 4,4′‐diaminodiphenyl sulfone, phenol novolac, or dicyandiamide. The parameters of the polymerization reaction (such as reaction time, catalyst) are discussed in this article. Thermal properties of cured epoxy resins were studied using differential scanning calorimetry, dynamic mechanical analysis, and thermal gravimetric analysis. The flame retardancy of cured epoxy resins was tested by limiting oxygen index. The relations between thermal properties, flame retardancy, and epoxy equivalent weights were also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 429–436, 2000     

Synthesis of tetrafunctional epoxy resins and their modification with polydimethylsiloxane for electronic application

High-performance tetrafunctional epoxy resins were synthesized by reacting a suitable tetraphenols which were obtained by the condensation of appropriate dialdehyde with phenol followed by epoxidation with a halohydrin. The structure of the synthesized tetraphenols was confirmed by infrared (IR), mass spectra (MS), and nuclear magnetic resonance (NMR) spectroscopy. Dispersed silicone rubbers were used to reduce the stress of the synthesized tetrafunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation application. The dynamic viscoelastic properties and morphologies of neat rubber-modified epoxy networks were investigated. The thermal mechanical properties and moisture absorption of encapsulants formulated from the synthesized tetrafunctional epoxy resins were also studied. The results indicate that a low-stress, high glass transition temperature (T_g), and low-moisture-absorbing epoxy resin system was obtained for semiconductor encapsulation application. © 1996 John Wiley & Sons, Inc.     

Synthesis of a novel epoxy resin containing pyrene moiety and thermal properties of its cured polymer with phenol novolac

A new epoxy resin containing the pyrene moiety in the backbone (3) was synthesized and confirmed by gel permeation chromatography and field‐desorption mass spectroscopy and infrared spectroscopy. In addition, to evaluate the influence of the pyrene moiety on the structure, epoxy resins having an anthrylene moiety (5) and having a phenylene moiety (7) were synthesized. The cured polymer obtained through the curing reaction between 3 and phenol novolac was used for making a comparison of its thermal properties with those obtained from 5, 7, and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from 3 showed a higher glass transition temperature, lower coefficient of linear thermal expansion, lower moisture absorption, and markedly higher anaerobic char yield at 700°C of 37.6 wt %, which might be attributed to the higher aromaticity of 3 containing the pyrene moiety. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 528–535, 2000     

Low dielectric thermoset. I. Synthesis and properties of novel 2,6‐dimethyl phenol‐dicyclopentadiene epoxy

A 2,6‐dimethyl phenol‐dicyclopentadiene novolac was synthesized from dicyclopentadiene and 2,6‐dimethyl phenol, and the resultant 2,6‐dimethyl phenol‐dicyclopentadiene novolac was epoxidized to 2,6‐dimethyl phenol‐dicyclopentadiene epoxy. The structures of novolac and epoxy were confirmed by Fourier transform infrared spectroscopy (FTIR), elemental analysis, mass spectroscopy (MS), nuclear magnetic resonance spectroscopy (NMR), and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol‐dicyclopentadiene epoxy was then cured with 4,4‐diaminodiphenyl methane (DDM), phenol novolac (PN), 4,4‐diaminodiphenyl sulfone (DDS), and 4,4‐diaminodiphenyl ether (DDE). Thermal properties of cured epoxy resins were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric analysis (DEA), and thermal gravimetric analysis (TGA). These data were compared with those of the commercial bisphenol A epoxy system. Compared with the bisphenol A epoxy system, the cured 2,6‐dimethyl phenol‐ dicyclopentadiene epoxy resins exhibited lower dielectric constants (～3.0 at 1 MHz and 2.8 at 1 GHz), dissipation factors (～0.007 at 1 MHz and 0.004 at 1 GHz), glass transition temperatures (140–188°C), thermal stability (5% degradation temperature at 382–404°C), thermal expansion coefficients [50–60 ppm/°C before glass‐transition temperature (T_g)], and moisture absorption (0.9–1.1%), but higher modulus (～2 Gpa at 60°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2607–2613, 2003     

Preparation and properties of polyhedral oligomeric silsesquioxane/epoxy hybrid resins

Octaaminophenyl polyhedral oligomeric silsesquioxane (OAPS) was synthesized using three‐step method and used to modify o‐cresol‐novolac epoxy resin (ECN) for printed circuit board. The influence of OAPS on the reactivity and the final properties of the hybrid networks were evaluated. The intercrosslinking reaction between ECN and OAPS was confirmed by Fourier transform infrared spectra. The ECN/OAPS hybrids have better impact strength, higher electrical resistivity and thermal stability, lower water absorption than the unmodified ECN. The volume resistivity and surface resistivity of the hybrids increase by an order of magnitude or more compared to the neat epoxy. The thermal stability of the hybrids improves by the incorporation of OAPS; the initial decomposition temperature and char yield show an increasing tendency up to 4 wt% loading of OAPS. The hybrids exhibit higher storage modulus and glass transition temperature (T_g) than the neat epoxy. The T_g of the hybrids greatly improves up to 153.3°C at 3 wt% content, much higher than 119.4°C of the neat epoxy. POLYM. COMPOS., 34:1753–1760, 2013. © 2013 Society of Plastics Engineers     

Effect of Hyperbranched Poly (Trimellitic Anhydride Ethylene Glycol) Epoxy (HTME) on Thermal Degradation Activation Energies of HTME/Diglycidyl Ether of Bisphenol-A Epoxy Hybrid Resin by Kissinger and Flynn–Wall–Ozawa Method

The thermal degradation behavior and kinetics of hyperbranched poly (trimellitic anhydride ethylene glycol) epoxy (HTME)/diglycidyl ether of bisphenol-A epoxy (DGEBA) hybrid resin was investigated with thermogravimetric analysis (TGA) by using Kissinger method and Flynn–Wall–Ozawa method. The results show that the thermal degradation activation energies of DGEBA, 9 wt% HTME-1/91wt% DGEBA, 3 wt% HTME-2/97 wt% DGEBA, 9 wt% HTME-2/91 wt% DGEBA, 15 wt% HTME-2/85 wt% DGEBA, and 9 wt% HTME-3/91wt% DGEBA are 152.5, 144.4, 135.4, 133.2, 121.8 and 143.0 kJmol^?1, respectively, by Kissinger method. and the activation energies are 173.3, 165.0, 163.2, 151.7, 137.7 and 159.7 kJmol^?1, respectively by Flynn–Wall–Ozawa method. With the increase of HTME content, the activation energies of HTME/DGEBA hybrid resin decrease. Although molecular weight or generation of hyperbranched epoxy resins (HTME) has little effect on the thermal degradation activation energies and other kinetics data.     

Synthesis,characterization, and properties of a novel epoxy resin containing both binaphthyl and biphenyl moieties

A new epoxy resin containing both binaphthyl and biphenyl moieties in the skeleton (BLBPE) was synthesized and confirmed by electrospray ionization mass spectroscopy, ¹H‐nuclear magnetic resonance spectroscopy, and infrared spectroscopy. To evaluate the combined influence of two moieties, one epoxy resin containing binaphthyl moiety and another containing biphenyl moiety were also synthesized, and a commercial biphenyl‐type epoxy resin (CER3000L) was introduced. Thermal properties of their cured polymers with phenol p‐xylene resins were characterized by differential scanning calorimetry, dynamic mechanical, and thermogravimetric analyses. The cured polymer obtained from BLBPE showed remarkably higher glass transition temperature and lower moisture absorption, as well as comprehensively excellent thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009