Effect of Hyperbranched Polyester on Modification of Epoxy Resins Cured with Anhydride

The synthesis and characterization of hyperbranched polyester （HBP） with different molecular weight are studied. The effect of HBP on the modification of epoxy resins cured with anhydride is mainly discussed. The characteristics of HBP and the morphologies of cured system are determined by nuclear magnetic resonance spectroscopy （NMR）, gel permeation chromatography （GPC） and scanning electron microscope （SEM）. The impact strength of cured system is detected and Fourier transform infrared （FTIR） measurements were used to pursue the curing process. The investigation shows that HBP can improve the toughness by forming copolymer networks between epoxy resins, HBP and anhydride. Moreover, when the molecular weight of HBP is 1342g/mol the toughening effect is the best, and the changes of toughness are small with the increase of molecular weight of HBP to 3500 g/mol.

ULTRASONIC BEHAVIOR OF EPOXY RESINS/POLY (ETHYLENE OXIDE) BLENDS CURED WITH PHTHALIC ANHYDRIDE

By means of ultrasonic attenuation apparatus, the ultrasonic velocity and attenuation ofanhydride-cured epoxy resins (EP)/poly (ethylene oxide) (PEO) blends were measured on thebasis of pulse-echo method. It was found that the sonic velocity of the blends decreased as thetemperature increased, but attenuation coefficient increased and possessed a peak value. Largervelocity and smaller attenuation coefficient(α)can be obtained from perfect crosslinking networkstructures of pure DGEBA cured with phthalic anhydride(PA). As for cured DGEBA/PEO blendsystems,sonic velocity decreased as a function of PEO concentration,but attenuation coefficient(α) increased.

COMPARISON OF THE E44 EPOXY RESINS IN DIFFERENT CONTENTS OF CURING AGENT BY MICROWAVE AND THERMAL CURING METHODS

This paper discusses the fundamental principle of microwave heating, and based on the advantages of microwave heating, use maleic anhydride as curing agent. The technology of microwave curing E44 epoxy resins is investigated, the mechanical properties of cured epoxy resin samples in different contents of curing agent by microwave and thermal curing methods are measured respectively, and then some experimental results for which are obtained. At last, this paper analyses why microwave curing can improve mechanical property of epoxy resin.

Mechanical properties of short carbon/glass fiber reinforced high mechanical performance epoxy resins

To research the relationship between epoxy and fiber inherent property and mechanical properties of composite,we prepared a series of composites using three kinds of high mechanical performance epoxy resins as matrices and reinforced by the same volume fraction(5%)of short carbon and glass fiber.Their mechanical properties were investigated from the perspective of chemical structure and volume shrinkage ratio of epoxy.We analyzed their tensile strength and modulus based on the mixing rule and Halpin-Tsai eq...

MODIFICATION OF EPOXY RESINS WITH PHENOLIC HYDROXYL-TERMINATED POLYSILOXANE

Phenolic hydroxyl-terminated polysiloxanes were incorporated into epoxy resins to reduce the internal stress owing to the mismatch in coefficient of thermal expansion (CTE). Polysiloxane-epoxy resin block copolymers were made by a pre-reaction step prior to the curing. In the cured resin, the domain size of the polysiloxane phase depended on the structure of the phenolic hydroxyl-terminated polysiloxane. It was found that the modulus of the cured resin depended largely on the level of the modifier, while the CTE was affected greatly by the structure of the polysiloxane. By means of incorporating a few percent of methylphenylsiloxane unit into the polydimethylsiloxane chain, or by introducing; more compatible end-capping groups, the compounds of more effective low stress modifiers were synthesized.

Influence of Matrixes on Microstructure and Properties of CTBN Toughened Epoxy Resins

The influence of the type of epoxy resins(E-51, F-51)on themechanical properties and mi- crostructure of carboxyl-terminatedbutadiene nitrile rubber(CTBN)toughened epoxy resins investigated bydetermination of adhesive strength and toughness as well asobservation of scanning electron microstructure (SEM). The resultsindicate that the adhesive strength of CTBN toughened E-51 system issuperior to CTBN toughened F-51 system. However, CTBN toughened E-51system is inferior to CTBN toughened F-51 system in the toughness.

STUDIES ON EPOXY RESINS MODIFIED WITH POLY (BUTYLENE TEREPHTHALATE)-b-POLY (TETRAMETHYLENE GLYCOL)

Poly(butylene terephthalate)-b-poly(tetramethylene glycol) (PBT-b-PTMG) was used as rheology modifier for the epoxy resin. The segmental copolymer formed spherulites in the epoxy medium. This copolymer was very effective in endowing yield stresses to the liquid resin. The PTMG segment brought in a lowering of the dissolution temperature of the spherulites in the epoxy gel. The cured resin with PBT-b-PTMG as modifier was two-phase materials. The rheology modifier improved the mechanical properties of the cured resin as well. The flexible PTMG segments, however, were not in favour of the toughening effect of the modifier. This was attributed to the large domain size of the dispersed phase.

RHEOLOGICAL MODIFICATION OF EPOXY RESINS WITH NANO SILICA PREPARED BY THE SOL-GEL PROCESS

Nano silica-modified epoxy resins were synthesized by the sol-gel process, The materials have the morphological structure of nano particales dispersed in the epoxy matrix. The dispersed phase formed a physical network in the resin and thus influenced the rheological behavior greatly. However, the nano silica did not show a significant influence on the mechanical properties of the cured resins.

PROMOTION EFFECT OF MELAMINE ON FLAME RETARDANCY OF EPOXY RESINS CONTAINING CAGED BICYCLIC PHOSPHATE

Caged bicyclic phosphate （CBP） and its dimelamine salt （PDS） were synthesized and added to epoxy resins to obtain the flame retarded epoxy resin composites. The flammability of the composites was characterized by the limiting oxygen index （LOI） and cone calorimeter tests. The LOI values of flame retarded composites increase consistently with the increase of flame retardant amounts, and they are almost the same when the loading of CBP is the same as that of PDS, although the phosphorus content of PDS is much lower than that of CBP. The total heat release increases in the order of CBP30/ER 〈 PDS30/ER 〈 PDS15/ER 〈 CBPI5/ER, whereas that of specific extinction area is CBP15/ER 〉 CBP30/ER 〉 PDS30/ER ≌ PDS15/ER. PDS exhibits more effective inhibition of oxidation of combustible gases. In the tests of thermogravimetric analyses （TG） and Fourier transform infrared spectroscopy （FT-IR）, it is found that the degradation of the composites is influenced greatly by the addition of flame retardants. By scanning electron microscopy （SEM）, a thick and tight char-layer is observed for PDS30/ER, resulting from the interaction of nitrogen species with phosphorus species. Therefore, the combination of CBP with melamine in the flame retarded system can improve the flame retardancy greatly.

MECHANICAL RELAXATION AND INTERMOLECULAR INTERACTION IN EPOXY RESINS/POLY (ETHYLENE OXIDE) BLENDS CURED WITH PHTHALIC ANHYDRIDE

The miscibility of the blend,composed of a bisphenol A epoxy resins (Diglycidyl ether of bisphenol A) (DGEBA) and poly(ethylene oxide) (PEG) and crosslinked by phthalic anhydride (PA) was studied using dynamic mechanical method. Single glass transition temperatures intermediate between the two pure components were observed for all blend levels. The secondary relaxation mechanism should relate to not only diester linkage, but also hydroxyether structural unit in the system. Fourier transform infrared spectroscopy (FTIR) is applied to study the curing reaction and intermolecular specific interaction of the system. The results indicate the PEO participates the crosslinking reaction, accelerates the curing reaction and make the reaction more perfect. The shifts of the hydroxyl band and carbonyl band demonstrate the presence of the intermolecular interaction in the cured blend. Moreover, the molecular interaction between the side hydroxyl in the hydroxyether units and the ether bond in PEO macromolecules is stronger.

Influence of aliphatic epoxy monomer on the blowing-out effect in the flame retardant epoxy resins

An aliphatic epoxy monomer＂polypropyleneglycol-diglycidylether（PPGDGE,YF878）＂is loaded in the epoxy resins（EP）to evaluate the influence of epoxy structure on the blowing-out effect,which is caused by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide（DOPO）and octaphenyl silsesquioxane（OPS）.The flame retarding properties of these EP composites were tested using the LOI and UL-94 procedures.The pyrolytic gases produced and the thermal stability of the EP composites with different flame retardants were detected by TGA-FTIR in air.The negative effect of YF878 was detected from the TTI,HRR,and p-HRR results after the cone calorimeter test.The char produced by the EP composites after the cone calorimeter test was investigated by FTIR.It is proposed that the aliphatic chain of the YF878 is easy to break down and produce combustible gases,so it does not easily form a crosslinked structure in the condensed phase.These results are very helpful for investigation of the conditions under which the blowing-out effect in epoxy resins can be caused by synergy of phosphorous and silicon.

Phosphorylated Salicylic Acid as Flame Retardant in Epoxy Resins and Composites

A novel,versatile flame retardant substructure based on phosphorylated salicylic acid(SCP)is described and used in the synthesis of new flame retardants for HexFlow
RTM6,a high-performance epoxy resin used in resin transfer molding processes as composite matrix.The starting material salicylic acid can be obtained from natural sources.SCP as reactive phosphorus chloride is converted with a novolak,a novolak containing 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide(DOPO)substituents or DOPO-hydroquinone to flame retardants with sufficient thermal stability and high char yield.Additionally,these flame retardants are soluble in the resin as well as react into the epoxy network.The determined thermal stability and glass transition temperatures of flame retarded neat resin samples as well as the interlaminar shear strength of corresponding carbon fiber reinforced composite materials showed the applicability of these flame retardants.Neat resin samples and composites were tested for their flammability by UL94 and/or flame-retardant performance by cone calorimetry.All tested flame retardants decrease the peak of heat release rate by up to 54%for neat resin samples.A combination of DOPO and SCP in one flame retardant shows synergistic effects in char formation and the mode of action adapts to neat resin or fiber-reinforced samples,so there is efficient flame retardancy in both cases.Therefore,a tailoring of SCP based flame retardants is possible.Additionally,these flame retardants efficiently reduce fiber degradation during combustion of carbon fiber-reinforced epoxy resins as observed by scanning electron microscopy and energy dispersive X-ray spectroscopy.

Synthesis and Characterization of Modified Epoxy Resins by Silicic Acid Tetraethyl Ester and Nano-SiO_2

A kind of modified epoxy resins was obtained by condensation of epoxy resin with silicic acid tetraethyl ester（TEOS） and nano-SiO2. The reactions were performed with hydrochloric acid as a catalyst at 63 ℃. The structure, thermal stability and morphological characteristics of the modified epoxy resins were studied through infrared spectra（FT-IR） analysis, thermogravimetric（TG） analysis and scanning electron microscopy respectively. It has been found from the IR and TG study that modified epoxy resins have greater thermal stability than epoxy resins, and its thermal stability has been improved by the formation of inter-crosslinked network structure. The modified epoxy resins exhibit heterogeneous morphology and heterogeneity increases with more TEOS feeding, which in turn confirms the formation of inter-crosslinked network structure in modified epoxy resins.

Synthesis, Characterization and Flame-retardant Properties of Epoxy Resins and AACHH Composites

Flame retardant epoxy resins were prepared by a simple mixed method using ammonium aluminum carbonate hydroxy hydrate （AACHH） as a halogen-free flame retardant. The prepared samples were characterized by X-ray diffraction, thermogravimetric and differential scanning calorimetry, scanning electron microscope and limiting oxygen index（LOI） experiments. Effects of AACHH content on LOI of epoxy resins/AACHH composite and flame retardant mechanism were investigated and discussed. Results show that AACHH exhibites excellent flame-retardant properties in epoxy resin（EP）. When the content of AACHH was 47.4%, the LOI of EP reached 32.2%. Moreover, the initial and terminal decomposition temperature of EP increased by 48 ℃ and 40 ℃, respectively. The flame retarded mechanism of AACHH is due to the synergic flame retardant effects of diluting, cooling, decomposition resisting and obstructing.

CTBN-TOUGHENED EPOXY RESINS——EFFECT OF CURING MECHANISM ON NETWORK STRUCTURE OF THE RUBBER PHASE

Epoxy resins toughened with carboxyl-terminated butadieneacrylonitrile copolymers (CTBN) are two-phase thermosets. The network of the in situ formed rubber particles depends upon the curing mechanism of the resin. When a primary polyamine such as triethylene tetramine was used as curing agent, the network of the rubber phase was quite incomplete, whereas a perfect rubber network was formed with 2-ethyl-4-methyl imidazole as the curing agent.

A Study on a Magnesium-Based Layered Composite Used as a Flame Retardant for Phenolic Epoxy Resins

The effects of a magnesium-based layered composite on the flammability of a phenolic epoxy resin(EP)are studied.In order to produce the required composite material,first,magnesium hydroxide,aluminum salt and deionized water are mixed into a reactor according to a certain proportion to induce a hydrothermal reaction;then,the feed liquid is filtered out using a solid-liquid separation procedure;finally,the material is dried and crushed.In order to evaluate its effects on the flammability of the EP,first,m-phenylenediamine is added to EP and vacuum defoamation is performed;then,EP is poured into a polytetrafluoroethylene mold,cooled to room temperature and demoulded;finally,the magnesium-based layered composite is added to EP,and its flame retardance is characterized by thermogravimetric analysis,limiting oxygen index and cone calorimetry.The X-ray diffraction patterns show that the baseline of magnesium-based layered composite is stable and the front shape is sharp and symmetrical when the molar ratio of magnesium to aluminium is 3.2:1;with the addition of magnesium-based layered composite,the initial pyrolysis temperature of EP of 10%,15%and 30%magnesium-based layered composite decreases to 318.2°C,317.9°C and 357.1°C,respectively.After the reaction,the amount of residual carbon increases to 0.1%,3.45%and 8.3%,and the limiting oxygen index increases by 28.3%,29.1%and 29.6%,respectively.The maximum heat release rate of cone calorimeter decreases gradually.The optimum molar ratio of Mg:Al for green synthesis is 3.2:1,and the NO_(3)-intercalated magnesium-based layered composite has the best flame retardance properties.

Statistical deduction and experimental verification on kinetic equations for the curing reactions of epoxy resins/amines

Based on three typical mechanisms (second-order, third-order and competitive mechanisms) for the curing reactions of the epoxy resins with amines, a pair of the kinetic equations (for primary and secondary aminations) was presented to explain the uniformity and relationship among the three different kinetic mechanisms of the reactions. The presented macro-equations were deduced from the kinetic micro-equations by the statistics method. And the constitutive equations were verified by experimental data at different reaction times and temperatures (95°C, 60°C and 39°C), taking diglycidyl ether of bisphenol A (DGEBA) /ethyleneamine (EA) as a model.

Study on effect of crosslink structure on decomposition of epoxy resins in nitric acid

One chemical approach using nitric acid as the solvent to decompose thermosetting epoxy resin was discussed. The samples were prepared by using different kinds of curing agents, namely polyamide (PA651), isophorone diamine (IPDA), 4,4'-diaminodiphenylmethane (DDM) and 2-ethyl-4-methy-imidazole (EMI-2,4) and different kinds of epoxy resins, namely bisphenol-A epoxy resin(E-44), bisphenol-A epoxy resin(E-51), N,N,N',N' teraglycidy 4,4' diaminodiphenyl methane (AG-80) and diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate (TDE-85). Their effects on decomposition rate were investigated and the decomposition products were analyzed by Infra-red (IR) spectra, and Gas Chromatography-Mass Spectrometry (GC-MS). Based on conclusions drawn from experiments, the mechanism of degrading thermosetting epoxy resin with nitric acid was envisaged tentatively.

Nucleophilic amino acids as a renewable alternative to petrochemically-derived amines in glycerol epoxy resins

The standard epoxy resin curing agents revealed are from unsustainable petroleum-based sources,which produce poisonous exhaust when cured.Amino acids,a bio-based epoxy curing agent with amino and carboxyl groups,are another potential curing agent.Water-soluble epoxy resins cured with lysine(Lys),glutamic acid(Glu),leucine(Leu),and serine(Ser)as amino acids were inves-tigated.The results showed that the water-soluble epoxy resin(glycerol epoxy resins,GER)was cured with Lys and Glu after reacting.Fourier transform infrared(FT-IR)spectroscopic analysis of the GER-Lys showed that the amino and carboxyl groups of Lys primarily reacted with the epoxy groups of GER.The elongation at break of Lys-cured GER(GER-Lys)cured at 70℃ with a molar ratio of 1꞉0.75 was 75.32%.The fact that elongations at break of GER-Lys(79.43%)were higher than those of GER-Glu(17.33%),respectively supports the decrease of crosslinking density by the amino acid-cured GER reaction.The potential of Lys and Glu alternatives for petrochemical amines is demonstrated and provides promising opportunities for industrial application.

Low dielectric constant and highly intrinsic thermal conductivity fluorine-containing epoxy resins with ordered liquid crystal structures

Epoxy resins with a high dielectric constant and low intrinsic thermal conductivity coefficient cannot meet the current application requirements of advanced electronic and electrical equipment.Therefore,novel fluorine-containing liquid crystal epoxy compounds(TFSAEy)with fluorinated groups,biphenyl units,and flexible alkyl chains are first synthesized via amidation and esterification reactions.Then,4,4′-diaminodiphenylmethane(DDM)is used as a curing agent to prepare the corresponding fluorine-containing liquid crystal epoxy resins.The obtained dielectric constant(ε)and dielectric loss(tanδ)values of TFSAEy/DDM at 1 MHz are 2.54 and 0.025,respectively,which are significantly lower than those of conventional epoxy resins(E-51/DDM,3.52 and 0.038).Additionally,the intrinsic thermal conductivity coefficient(λ)of TFSAEy/DDM is 0.36 W/(m⋅K),71.4%higher than that of E-51/DDM(0.21 W/(m⋅K)).Meanwhile,the corresponding elastic modulus,hardness,glass transition temperature,and heat resistance index of TFSAEy/DDM are 5.73 GPa,0.35 GPa,213.5◦C,and 188.7℃,respectively,all superior to those of E-51/DDM(3.68 GPa,0.27 GPa,107.2℃,and 174.8℃),presenting potential application in high-heating electronic component packaging and printed circuit boards.