Synthesis and characterization of imide ring and siloxane-containing cycloaliphatic epoxy resins

A novel imide ring and siloxane-containing cycloaliphatic epoxy compound 1,3-bis[3-(4,5-epoxy-1,2,3,6-tetrahydrophthalimido)propyl]tetramethyldisiloxane (BISE) was synthesized from 1,3-bis(3-aminopropyl)tetramethyldisiloxane and tetrahydrophthalic anhydride by a two-step procedure, which was then thermally cured with alicyclic anhydrides hexahydro-4-methylphthalic anhydride (HMPA) and hexahydrophthalic anhydride (HHPA), respectively. As comparison, a commercial available cycloaliphatic epoxy 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate (ERL-4221) cured with the same curing agents was also investigated. The experimental results indicated that the BISE gave the exothermic starting temperature higher than ERL-4221 no mater what kind of curing agents applied, implying the reactivity of the former is lower than the latter. The fully cured BISE epoxy resins have good thermal stability with thermal decomposition temperature at 5% weight loss of 346-348 °C in nitrogen, although they gave the relatively low glass transition temperatures due to the presence of flexible propyl and siloxane segments in the epoxy backbone. The BISE epoxy resins exhibited good mechanical and dielectric properties as well as low water absorption. The improved dielectric properties and the reduced water absorption of BISE epoxy resins are attributed to the low polarity as well as the hydrophobic nature of siloxane segment in the epoxy backbone.     

Synthesis and degradable property of novel sulfite-containing cycloaliphatic epoxy resins

Liquid cycloaliphatic diepoxide containing sulfite group (Epoxide-S) was designed and synthesized through the two-step reactions: the nucleophilic substitution between thionyl chloride and cyclohex-3-1-methanol, and the subsequent epoxidation. The chemical structures of the epoxidized product and its olefin precursor were confirmed by FTIR and ¹H NMR spectra. Different from conventional thermosetting epoxy resins, the cured Epoxide-S started to decompose at 185 °C. The apparently lower degradable temperature is desirable for reworkable electronic packaging materials because the dismantlement of waste electronic products or the replacement and repair of faulty chips become convenient. Moreover, after co-curing between Epoxide-S and the commercial cycloaliphatic diepoxide ERL-4221, the thermal degradation temperatures of the copolymers were tunable in the range from 185 to 323 °C by varying the ratio of two monomers. The unique degradation behaviors were investigated by means of computer calculation, thermogravimetric analysis, and FTIR spectra.     

Investigation of curing kinetics of various cycloaliphatic epoxy resins using dynamic thermal analysis

Curing reactions of three cycloaliphatic epoxy resins with methyltetrahydrophthalic anhydride (MTHPA) was investigated by differential scanning calorimetry at different heating rates. Activation energy was calculated based on Kissinger method and varied in the range of 67-72 kJ/mol depending on sample. The curing kinetic behavior was well described by Sestak-Berggren (SB) model and the order of the curing reaction is observed to be from 0.02 to 2.11 according to sample.     

Synthesis and characterization of novel multifunctional epoxy resin

A novel multifunctional epoxy resin was synthesized by polyphenol and epichlorohydrin.The structure and molecular weight ofthe multifunctional epoxy were characterized by FTIR and ESI-MS.DSC and DMTA were used to investigate the thermal propertyof multifunctional epoxy cured by DDS.The thermal resistance of the synthesized multifunctional epoxy was much better than astandard diglycidyl ether of bisphenol-A epoxy.     

新型三官能团脂环族环氧化合物的合成、表征及其阳离子引发光固化活性研究

以双环戊二烯等为原料合成一种新型三官能团液体脂环族环氧树脂. 通过红外光谱、 核磁共振氢谱及质谱等对其中间体及环氧树脂的结构进行了表征. 所得脂环族环氧树脂采用阳离子引发 剂二甲苯基碘鎓六氟磷酸盐引发进行紫外光固化, 对其光固化活性进行了研究, 同时讨论了氧化剂过氧化苯甲酰对该光固化体系的增感作用. 研究结果表明, 新合成的脂环族环氧树脂采用二甲苯基碘鎓六氟磷酸盐引发可以进行光固化, 过氧化苯甲酰明显地加快了其光固化速度, 固化膜具有较好的热稳定性.     

Synthesis and properties of phosphorus-containing bio-based epoxy resin from itaconic acid

A phosphorus-containing bio-based epoxy resin (EADI) was synthesized from itaconic acid (IA) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO). As a matrix, its cured epoxy network with methyl hexahydrophthalic anhydride (MHHPA) as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A (DGEBA) system as well as good flame retardancy with UL94 V-0 grade during a vertical burning test. As a reactive flame retardant, its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were investigated. Results showed that after the introduction of EADI, not only were the flame retardancy determined by vertical burning test, LOI measurement, and thermogravimetric analysis significantly improved, but also the curing reactivity, glass transition temperature (T _g), initial degradation temperature for 5% weight loss (T _d(5%)), and flexural modulus of the cured system improved as well. EADI has great potential to be used as a green flame retardant in epoxy resin systems.     

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

A new epoxy resin (Bis-ENA) containing naphthalene structure linked with a 1,4-bis(isopropylidene)phenylene was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. To estimate the effect of naphthalene moiety on the cured polymer, an epoxy resin (Bis-EP) having phenyl moiety was synthesized, and curing behaviors of Bis-ENA and Bis-EP with phenol novolac were evaluated by differential scanning calorimetry. The incorporation of naphthalene structure into the resin backbone increased the curing temperature and reduced the curing reactivity. Thermal properties of the cured polymers obtained from Bis-ENA and Bis-EP with phenol novolac were examined by thermomechanical analysis and dynamic mechanical analysis. Mechanical properties and moisture resistance were evaluated by flexural strength, flexural modulus, and moisture absorption measurements. The cured polymer obtained from Bis-ENA showed higher glass transition temperature, higher flexural modulus, lower thermal expansion, and lower moisture absorption than that from Bis-EP. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3063–3069, 1999     

Synthesis of a novel DPPA‐containing benzoxazine to flame‐retard epoxy resin with maintained thermal properties

The flame‐retarded epoxy resin with improved thermal properties based on environmentally friendly flame retardants is vital for industrial application. Hereby, a novel reactive‐type halogen‐free flame retardant, 10‐(3‐(4‐hydroxy phenyl)‐3,4‐dihydro‐2H‐benzo[e] [1,3] oxazin‐4‐yl)‐5H‐phenophosphazinine 10‐oxide (DHA‐B) was synthesized via a two‐step reaction route. Its structure was characterized using ¹H, ¹³C, and ³¹P NMR and HRMS spectra. For 4,4′‐diaminodipheny ethane (DDM) and diglycidyl ether of bisphenol A (DGEBA)‐cured systems, the epoxy resin with only 2 wt% loading of DHA‐B passed V‐0 rating of UL‐94 test. Significantly, its glass transition temperature (T_g) and initial decomposition temperature (T_5%) were as high as 169.6°C and 359.6°C, respectively, which were even higher than those of the corresponding original epoxy resin. Besides, DHA‐B decreased the combustion intensity during combustion. The analysis of residues after combustion suggested that DHA‐B played an important role in the condensed phase.     

液晶环氧p-PEPB的合成及改性双酚-A环氧树脂的研究

本文以对羟基苯甲酸乙酯、丙烯溴、对苯二酚等为原料合成了双4-环氧丙基醚苯甲酸对苯二酚酯液晶环氧树脂(p-PEPB).用IR、1HNMR、DSC、POM和XRD的对其进行了表征,结果表明该化合物为向列型液晶,其熔点为180℃,清晰点为250 ℃.研究了 p-PEPB/双酚-A环氧(BPAER)/4,4,-二氨基二苯醚(DDE)体系的非等温固化过程,得到了固化温度参数、表观活化能Ea及p-PEPB含量对Tg的影响,结果表明p-PEPB为5%可使BPAER的Tg提高14 ℃,固化过程服从Ozawa模型.     

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

A new type of epoxy resin containing 4,4′-diphenylether moiety in the backbone (2) was synthesized, and was confirmed by gel permeation chromatography, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. In addition, in order to evaluate the influence of 4,4′-diphenylether moiety in the structure, epoxy resins having 4,4′-biphenylene moiety (4) and having 1,4-phenylene moiety (6) in place of 4,4′-diphenylether moiety were synthesized. The cured polymer obtained through the curing reaction between the new diphenylether-containing epoxy resin and phenol novolac was used for making a comparison of its thermal and physical properties with those obtained from 4, 6, and bisphenol-A (4,4′-isopropylidenediphenol) type epoxy resin. The cured polymer obtained from 2 showed markedly higher anaerobic char yield at 700°C of 44.0 wt %, higher fracture toughness, and higher mechanical strength and modulus. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3687–3693, 1999     

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     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.     

Synthesis, characterization, thermal properties and flame retardancy of a novel nonflammable phosphazene-based epoxy resin

Hexakis(4-hydroxyphenoxy)-cyclotriphosphazene (PN-OH) was synthesized through nucleophilic substitution of the chloride atoms of hexachlorocyclotriphosphazene and reduction of the aldehyde groups, and its chemical structure was characterized by elemental analysis, ¹H and ³¹P NMR, and Fourier transform infrared (FTIR) spectroscopy. A new phosphazene-based epoxy resin (PN-EP) was successfully synthesized through the reaction between diglycidyl ether of bisphenol-A (DGEBA) and PN-OH, and its chemical structure was confirmed by FTIR and gel permeation chromatography. Four PN-EP thermosets were obtained by curing with 4,4′-diaminodiphenylmethane (DDM), dicyandiamide (DICY), novolak and pyromellitic dianhydride (PMDA). The reactivity of PN-EP with the four curing agents presents an increase in the order of DDM, PMDA, novolak and DICY. An investigation on their thermal properties shows that the PN-EP thermosets achieve higher glass-transition and decomposition temperatures in comparison with the corresponding DGEBA ones while their char yields increase significantly. The PN-EP thermosets also exhibit excellent flame retardancy. The thermosets with novolak, DICY and PMDA achieve the LOI values above 30 and flammability rating of UL94 V-0, whereas the one with DDM reaches the V-1 rating. The nonflammable halogen-free epoxy resin synthesized in this study has potential applications in electric and electronic fields in consideration of the environment and human health.     

Enthalpy relaxation in a partially cured epoxy resin

The enthalpy relaxation of a partially cured (70%) epoxy resin, derived from diglycidyl ether of bisphenol-A cured by methyl-tetrahydrophthalic anhydride with accelerator, has been investigated. The key parameters of the structural relaxation (the apparent activation energy Δh*, the nonlinearity parameter x, and the nonexponentiality parameter β) are compared with those of the fully cured epoxy resin. The aging rates, characterized by the dependences of the enthalpy loss and peak temperature on log(annealing time), are greater in the partially cured epoxy than they are in the fully cured resin at an equivalent aging temperature (T_a = T_g − 20°C). There is a significant reduction in Δh*, from 1100 kJ mol⁻¹ for the fully cured system to 615 kJ mol⁻¹, as the degree of cure is reduced. The parameter x determined by the peak-shift method appears essentially independent of the degree of cure (x = 0.41 ± 0.03 for the partially cured resin compared with 0.42 ± 0.03 obtained previously for the fully cured resin), and does not follow the usually observed correlation of increasing x as Δh* decreases. This invariability of the parameter x seems to indicate that it is determined essentially by the local chemical structure of the backbone chain, and rather little by the supramolecular structure. On the other hand, the estimated nonexponentiality parameter β lies between 0.3 and 0.456, which is significantly lower than in the fully cured epoxy (β ≅ 0.5), indicative of a broadening of the distribution of relaxation times as the degree of cross-linking is reduced. Like the parameter x, this also does not follow the usual correlation with Δh*. These results are discussed in the framework of strong and fragile behavior of glass-forming systems, but it is difficult to reconcile these results in any simple way with the concept of strength and fragility. © 1996 John Wiley & Sons, Inc.     

A novel intumescent flame retardant imparts high flame retardancy to epoxy resin

Intumescent flame retardant (IFR) has received the considerable attention ascribed to the inherent advantages including non‐halogen, low toxicity, low smoke release and environmentally friendly. In this work, a novel charring agent poly (piperazine phenylaminophosphamide) named as PPTA was successfully synthesized and characterized by Fourier transform infrared spectra (FTIR) and X‐ray photoelectron spectroscopy (XPS). Then, a series of flame‐retardant EP samples were prepared by blending with ammonium polyphosphate (APP) and PPTA. Combustion tests include oxygen Index (LOI), vertical Burning Test (UL‐94) and cone calorimeter testing,these test results showed that PPTA greatly enhances the flame retardancy of EP/APP. According to detailed results, EP containing 10 wt% APP had a LOI value of 30.2%,but had no enhancement on UL‐94 rating. However, after both 7.5 wt% APP and 2.5 wt% PPTA were added, EP‐7 passed UL‐94 V‐0 rating with a LOI value of 33.0%. Moreover, the peak heat release rate (PHRR) and peak of smoke product rate (PSPR) of EP‐7 were greatly decreased. Meanwhile, the flame‐retardant mechanism of EP‐7 was investigated by scanning electron microscopy (SEM), thermogravimetric analysis/infrared spectrometry (TG‐IR) and X‐ray photoelectron spectroscopy (XPS). The corresponding results presented PPTA significantly increased the density of char layer, resulting in the good flame retardancy.     

Synthesis and thermal characterization of phosphorus containing siliconized epoxy resins

Siliconized epoxy matrix resin was developed by reacting diglycidyl ethers of bisphenol A (DGEBA) type epoxy resin with hydroxyl terminated polydimethylsiloxane (silicone) modifier, using γ-aminopropyltriethoxysilane crosslinker and dibutyltindilaurate catalyst. The siliconized epoxy resin was cured with 4, 4-diaminodiphenylmethane (DDM), 1,6-hexanediamine (HDA), and bis (4-aminophenyl) phenylphosphate (BAPP). The BAPP cured epoxy and siliconized epoxy resins exhibit better flame-retardant behaviour than DDM and HDA cured resins. The thermal stability and flame-retardant property of the cured epoxy resins were studied by thermal gravimetric analysis (TGA) and limiting oxygen index (LOI). The glass transition temperatures (T_g) were measured by differential scanning calorimetry (DSC) and the surface morphology was studied by scanning electron microscopy (SEM). The heat deflection temperature (HDT) and moisture absorption studies were carried out as per standard testing procedure. The thermal stability and flame-retardant properties of the cured epoxy resins were improved by the incorporation of both silicone and phosphorus moieties. The synergistic effect of silicone and phosphorus enhanced the limiting oxygen index values, which was observed for siliconized epoxy resins cured with phosphorus containing diamine compound.     

Preparation and characterization of microencapsulated LDHs with melamine‐formaldehyde resin and its flame retardant application in epoxy resin

Layered double hydroxides (LDHs) are emerging as a new and green high‐efficient flame retardant. But LDHs aggregate seriously because of their hydrophilicity, which affect deeply the mechanical and flame retardant properties of their composites. For the first time in this paper, microencapsulated LDHs (MCLDHs) with melamine‐formaldehyde (MF) resin were prepared by microencapsulation technology to enhance their compatibility and dispersion within epoxy resin (EP). The mechanical and flame retardant performances of EP/MCLDH composite were studied by comparing with EP/LDH composite. Results showed that the water contact angle of MCLDHs increased from 8.9° to 122.1°, which indicated good compatibility. The particle size of MCLDHs decreased sharply, and more than one‐third were up to submicron scale, which can be conducive to dispersion. Moreover, the tensile strength and elongation at break of EP/MCLDHs with different flame retardant contents were higher than those of EP/LDHs. And the addition of MCLDHs increased the glass transition temperature (Tg) of EP/MCLDHs, which meant a strong interfacial interaction. Besides, compared with EP/LDHs, the limiting oxygen index values of EP/MCLDHs were higher, and its peak of heat release rate and total heat release decreased by 16.3% and 5.5% respectively. EP/MCLDHs achieved from V‐1 to V‐0 rate with the increasing content of MCLDHs from 20% to 30%, while LDHs/EP never passed tests. In the process of heating, H₂O, CO₂, and NH₃ released from MCLDHs formed gaseous phase, and the remaining dense char layers and oxides produced condensed phase, which played an important role in inhibiting combustion.     

Synthesis,characterization of novel interacting blends of acrylated poly(ester-amide)s containing epoxy residues with vinyl ester resin

Unsaturated bisamic acids were prepared by reaction between maleic anhydride and different aromatic diamines. Unsaturated poly(ester-amide) resin (UPEAs) was prepared by reaction of diglycidylether of bisphenol-A (DGEBA) with unsaturated bisamic acids. Acrylation of Unsaturated poly(ester-amide)s (UPEAs) was carried out to afford acrylated UPEAs resin (i.e., AUPEAs). Interacting blends of Acrylated unsaturated poly(ester-amide)s (AUPEAs) with vinyl ester epoxy (VE) resin were prepared. APEAs and AUPEAs were characterized by elemental analysis, molecular weight determined by vapor pressure osmometer and by IR spectral study and by thermogravimetry. The curing of interacting blends was monitored on differential scanning calorimeter (DSC). Based on DSC data in situ glass reinforced composites of the resultant blends have been prepared and characterized for mechanical, electrical and chemical properties. Unreinforced blends were characterized thermo-gravimetrically (TGA).     

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.