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1.
A family of hydrophilic and flexible epoxy polymers was prepared from the reaction of poly(oxyalkylene)amines and diglycidyl ether of bisphenol‐A (DGEBA) at 1:1 molar ratio of N H to epoxide. The use of a high molecular weight (MW = 1000–6000) poly(oxyethylene–oxypropylene)amine and a low MW amine as curing agents provided epoxy materials with good properties in toughness and hydrophilicity. The hydrophilicity, probed by surface resistivity of these cured materials, was found to be affected by the nature and weight content of poly(oxyethylene) segment in the polymer backbone, and also by the degree of crystallinity. Specifically, in the presence of a water‐soluble poly(oxyethylene–oxypropylene)diamine of MW 2000 the cured epoxies can reach surface resistivity as low as 108.6–9.6 Ω/□. In comparison, the water‐insoluble poly(oxypropylene)diamine of MW 2000 afforded a higher surface resistivity of 1010.5 Ω/□ because of the difference in hydrophilicity between oxyethylene and oxypropylene functionalities. Poly(oxypropylene)diamine of MW 230 as the sole curing agent generated an epoxy with even higher surface resistivity of 1013 Ω/□ due to a highly crosslinking structure. With proper selection of mixed poly(oxyethylene–oxypropylene)diamine (25 wt%) and 2‐aminoethanol (9 wt%), the DGEBA cured polymer had an appropriate surface resistivity of 109.8 Ω/□ for antistatics. Moreover, this material was extremely ductile in appearance and showed over 500 % elongation at break during mechanical tests. The high flexibility is rationalized by the balanced chemical structure of poly(oxyalkylene) segments and bisphenol‐A distributed in a slightly crosslinked system. © 2000 Society of Chemical Industry  相似文献   

2.
By varying the cyanate/epoxy ratio, three polyetherimide(PEI)‐modified bisphenol A dicyanate–novolac epoxy resin blends with different epoxy contents were prepared. The effects of epoxy content on the dynamic mechanical behaviour of those blends were investigated by dynamic mechanical thermal analysis. The results showed that the glass transition temperature of the cyanate–epoxy network (Tg1) in the modified blend decreases with epoxy content. When the epoxy content increases, both the width of the glass transition of the cyanate–epoxy network and its peak density are depressed substantially. Although the tangent delta peak value of PEI is basically independent of epoxy content, the Tg of PEI (Tg2) decreases with epoxy content. Tg1 is independent of the PEI loading. When Tg1 is lower than Tg2, however, the Tg1 in the blend with revised phase structure is substantially lower than other blends. Copyright © 2004 Society of Chemical Industry  相似文献   

3.
Phenolic hydroxyl-terminated (HTPU) and aromatic amine-terminated (ATPU) PU modifiers were prepared by reacting two different macroglycols (PTMG, polytetramethylene glycol, Mn = 2000, and PBA, Polybutylene adpate, Mn = 2000) with 4,4′-diphenylmethane diisocyanate (MDI), then further coupling with two different coupling agents, bisphenol A or 4,4′-diaminodiphenyl sulfone (DDS). These four types of PU prepolymers were used to modify the epoxy resin with 4,4′-diamino-diphenyl sulfone as a curing agent. From the experimental results, it was shown that the values of fracture energy, GIC, for PU-modified epoxy were dependent on the macroglycols and the coupling agents. Scanning electron microscopy (SEM) revealed that the ether type (PTMG) of PU-modified epoxy showed the presence of an aggregated separated phase, which varied between 0.5 μm and 4 μm in the ATPU (PTMG) and between 1 μm and 1.5 μm in HTPU (PTMG) modified system. On the contrary, the ester type (PBA) PU-modified epoxy resin showed a homogeneous morphology and consequently a much smaller effect on toughening for its good compatibility with the epoxy network. In addition, it was found that the hydroxyl-terminated bisphenol A as a coupling agent improved fracture toughness more than the amine-terminated DDS because of effective molecular weight buildup by a chain extension reaction. The glass transition temperature (Tg) of modified epoxy resin as measured by dynamic mechanical analysis (DMA) was lower in PTMG-based PU than in a PBA-based PU series with the same weight of modifier.  相似文献   

4.
An epoxy resin system based on a triglycidyl p‐amino phenol (MY0510) was crosslinked using stoichiometric amounts of 4,4′‐diaminodiphenyl sulfone. The epoxy was modified with random copolymers, polyethersulfone‐poly(ether‐ethersulfone) (PES:PEES), with either amine or chlorine end groups, at 10 and 20 wt %. The reaction kinetics for both unmodified and modified epoxy systems were studied using differential scanning calorimetry in isothermal and dynamic conditions. The results show that the degree of conversion in thermoplastic‐modified epoxies at any reaction time is smaller compared with the unmodified resin. Gel point (GP) determination was done from rheological measurements. The modified system containing 20% of the PES:PEES additive showed considerable increase in the GP. The reaction rate shows the characteristic of an autocatalytic reaction where the product acts as catalyst. The activation energy, Ea calculated from the isothermal reaction depends on the extent of conversion and increases with increasing PES:PEES content. For unmodified epoxy system, the average Ea is 67.8 ± 4.1 kJ mol?1 but for systems modified with 20 wt % of amine and chlorine PES:PEES, the value increased to 74.1 ± 3.3 and 77.9 ± 4.4 kJ mol?1, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

5.
The thermal degradation of two epoxy systems diglycidyl ether of bisphenol A (DGEBA n = 0)/1,2‐diamine cyclohexane (DCH) containing different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD), was studied by thermogravimetric analysis to determine the reaction mechanism of the degradation process for these two systems. Values of the activation energy, necessary for this study, were calculated by using various integral and differential methods. Values obtained by using the different methods were compared to the value obtained by Kissinger's method, which does not require a knowledge of the reaction mechanism. All the experimental results were compared to master curves in the range of Doyle's approximation (20–35% of conversion). Analysis of the results suggests that the two reaction mechanisms are Rn and Fn deceleratory type in contrast with the sigmoidal A2 type of the system with filler and the sigmoidal A4 type of the system without additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1199–1207, 2004  相似文献   

6.
Different crown ethers (4‐aminobenzo‐15‐crown‐5 (4‐aminobenzo‐15‐C5), 1,4,10,13‐tetraoxa‐7,16‐diazacyclooctadecane (diaza‐18‐crown‐6), tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (H4DOTA) and tetraazacyclododecane‐1,4,7,10‐tetraacetamide (H2ODDA)) were used as curing agent for bisphenol A diglycidyl ether (BADGE, n = 0). The maximum enthalpy change for all systems except that formed by the epoxy resin with H4DOTA corresponds to a stoichiometric ratio, since from this value the reaction enthalpies decrease when the proportion of epoxy increases. Heteropolymerization reaction occurs in all the crown ethers. Etherification reactions occur at temperatures much lower (30 °C less) than for the porphyrin systems studied in which a second signal appears at 300 °C. The etherification is evidenced by a slight shoulder in the thermograms for H4DOTA and H2ODDA. The systems BADGE (n = 0)/4‐aminobenzo‐15‐C5 and BADGE (n = 0)/diaza‐18‐crown‐6 improve the thermal stability of the epoxy resin by 30 °C approximately while the improvement for BADGE (n = 0)/H4DOTA and BADGE (n = 0)/H2ODDA is about 60 °C. © 2017 Society of Chemical Industry  相似文献   

7.
A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between GIC and plateau modulus (above the resin Tg), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999  相似文献   

8.
Modification of existing polymers leads to enhancement of many desirable properties. So, a hyperbranched polyurethane (HBPU) of monoglyceride of Mesua ferrea L. seed oil, poly(ε‐caprolactone)diol (Mn = 3000 g mol?1), 2,4‐toluene diisocyanate, and glycerol with 30% hard segment (NCO/OH = 0.96) has been modified with different amounts of bisphenol‐A based epoxy resin. The system is cured by poly(amido amine) hardener at 120°C for specified period of time. Improvement of thermostability, scratch hardness, and impact strength are observed by this modification of HBPU. The differential scanning calorimetry (DSC) results show improvement of melting temperature of the modified systems. The enhancement of tensile strength is about 2.4 times compared with that of the unmodified one. The morphology and structural changes due to variation of epoxy content was studied by scanning electron microscopy (SEM) analysis and Fourier transform infrared (FTIR) spectroscopy. The rheological properties of the epoxy‐modified HBPU show the dependence on the amount of epoxy resin. Shape memory study of the crosslinked HBPUs shows 90–98% thermoresponsive shape recovery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

9.
A new hyperbranched polymer (HBP) with a flexible aromatic skeleton and terminal epoxy groups was synthesized to improve the toughness of diglycidyl ether of bisphenol A. The HBP was characterized using nuclear magnetic resonance, Fourier transfer infrared spectroscopy and gel permeation chromatography. The effect of HBP on the thermomechanical and mechanical properties of modified epoxy systems was studied. For evaluating the efficiency of the modified epoxy systems, composite samples using glass fiber cloth were molded and tested. Using dynamic mechanical analysis, a slight reduction in glass transition temperature (Tg) with increasing HBP content was observed. Analysis of fracture surfaces revealed a possible effect of HBP as a toughener and showed no phase separation in the modified resin systems. The results showed that the addition of 15 phr HBP maximized the toughness of the modified resin systems with 215 and 40% increases in impact and flexural strengths, respectively. Tg and heat resistance of cured modified resin systems decreased slightly with an increase in HBP content and, at 15 phr HBP, only a 2.6% decrease in thermomechanical properties was observed. Meanwhile, a molded composite with HBP showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin. © 2015 Society of Chemical Industry  相似文献   

10.
A series of intercrosslinked networks formed by diglycidyl ether of bisphenol A epoxy resin (DGEBA) and novel bismaleimide containing phthalide cardo structure (BMIPP), with 4,4′‐diamino diphenyl sulfone (DDS) as hardener, have been investigated in detail. The curing behavior, thermal, mechanical and physical properties and compatibility of the blends were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), notched Izod impact test, scanning electron microscopy (SEM) and water absorption test. DSC investigations showed that the exothermic transition temperature (Tp) of the blend systems shifted slightly to the higher temperature with increasing BMIPP content and there appeared a shoulder on the high‐temperature side of the exothermic peak when BMIPP content was above 15 wt %. TGA and DMA results indicated that the introduction of BMIPP into epoxy resin improved the thermal stability and the storage modulus (G′) in the glassy region while glass transition temperature (Tg) decreased. Compared with the unmodified epoxy resin, there was a moderate increase in the fracture toughness for modified resins and the blend containing 5 wt % of BMIPP had the maximum of impact strength. SEM suggested the formation of homogeneous networks and rougher fracture surface with an increase in BMIPP content. In addition, the equilibrium water uptake of the modified resins was reduced as BMIPP content increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
Epoxy-terminated poly(aryl ether sulfone)s (PSE) were prepared by the reaction of epichlorohydrin with hydroxyethyl-terminated polysulfones, which were synthesized from chloro-terminated polysulfones (PSC) and diethanolamine. Both PSE and PSC were used as modifiers for toughening of bisphenol A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulfone. The mechanical, thermal, and dynamic viscoelastic properties of the modified resins were examined and compared to the parent epoxy resin. The effectiveness of PSC was larger than that of PSE. The fracture toughness, KIC, for the modified resin increased 45% at slight expense of its mechanical properties on 20 wt % addition of PSC (Mw 5300). These results were discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system.  相似文献   

12.
The mechanical properties, thermomechanical properties, and fracture mechanic properties of block-copolymer (BCP), core–shell rubber (CSR) particles, and their hybrids in bulk epoxy/anhydride system were investigated at 23 °C. The results show that fracture toughness was increased by more than 268% for 10 wt % BCP, 200% for 12 wt % of CSR particles, and 100% for hybrid systems containing 3 wt % of each, BCP and CSR. The volume content of nanoparticles influences the final morphology and thus influences the tensile properties and fracture toughness of the modified systems. The toughening mechanisms induced by the BCP and CSR particles were identified as (1) localized plastic shear-band yielding around the particles and (2) cavitation of the particles followed by plastic void growth in the epoxy polymer. These mechanisms were modeled using the Hsieh et al. approach and the values of GIc of the different modified systems were calculated. Excellent agreement was found between the predicted and the experimentally measured fracture energies. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48471.  相似文献   

13.
A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, 1H NMR and 13C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: Mn = 9600 g mol?1, Mw = 9800 g mol?1, Mw/Mn = 1.1 for poly(ETCA); Mn = 14 300 g mol?1, Mw = 16 200 g mol?1, Mw/Mn = 1.2 for poly(ETCA‐co‐AA); Mn = 17 900 g mol?1, Mw = 18 300 g mol?1, Mw/Mn = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry  相似文献   

14.
Fracture toughness of epoxy was determined by quantitative fractography, one of the techniques for brittle materials based on fracture mechanics. Two different epoxy systems, an anhydride‐cured and an amine‐cured epoxy based upon diglycidyl ether of bisphenol A (DGEBA) were studied. Epoxies with different average molar mass between crosslinks (Mc) or crosslink density were prepared by varying the cure profiles. The materials were characterized using differential scanning calorimetry (DSC), dynamic mechanical spectroscopy (DMS), and density measurements. Optical microscopy was used to measure the dimensions of the different regions on the fracture surfaces of unnotched samples that were tested to failure under tension. The fracture toughness values were calculated from the relationship between the measured sizes and fracture stress. Epoxies with lower Mc values or higher crosslink densities have lower fracture toughness values. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 257–268, 1999  相似文献   

15.
A low viscosity tetrafunctional epoxy resin was synthesized by reacting amino-terminated polydimethylsiloxane with epichlorohydrin followed by dehydrohalogenation. The synthesized tetrafunctional aliphatic epoxy resin had an epoxy equivalent weight of 382, Mn of 1492, Mw of 2296, and a viscosity of 4.2 poise at 25°C. The chemical structure of the tetrafunctional aliphatic epoxy resin was studied by gel permeation chromatography (GPC), Fourier transform infrared spectra (FTIR), and 1H-NMR spectra. Results showed the tetrafunctional aliphatic epoxy-blended aromatic epoxy resin possessed high impact strength and flexural strength. SEM photographs were investigated to study the compatibility of the blended epoxy system. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 51–58, 1998  相似文献   

16.
This paper reports on the use of an epoxidized hyperbranched polymer (HBP) as an additive to an epoxy anhydride resin system. The hyperbranched polymer used was an aliphatic polyester with a molecular weight of around 10 500 g mol?1. The epoxy resin mixture used was a combination of a difunctional diglycidyl ether of bisphenol A (DGEBA) epoxy and an epoxy novolac, and was cured with a catalysed anhydride curing agent. It has been shown that, at a concentration range of 0 to 20 wt% addition, the HBP is able to almost double the fracture toughness, with little evidence of any deleterious effects upon processing and the durability of the cured resin system. The flexural modulus and stress, however, were found to both decrease by about 30% as a result of HBP addition while the Tg was found to decrease by about 10%. The processability of the uncured resin systems has been investigated by using rheological and calorimetric techniques and it was found that the processability window, as determined by the gel time and viscosity changes, was relatively unaffected by HBP addition. The fracture surfaces were evaluated by using scanning electron microscopy which showed that the unique structure of the HBP facilitates an enhanced interaction with the polymer matrix to achieve excellent toughness enhancement of the polymer matrix. The durability of the epoxy network has been investigated via thermogravimetric analysis (TGA) and solvent uptake, and the HBP has been shown to have little systematic deleterious effect upon the degradation temperatures and the total amount of solvent absorbed. Copyright © 2003 Society of Chemical Industry  相似文献   

17.
This study has evaluated three low‐viscosity epoxy additives as potential tougheners for two epoxy resin systems. The systems used were a lower‐reactive resin based upon the diglycidyl ether of bisphenol A (DGEBA) and the amine hardener diethyltoluene diamine, while the second epoxy resin was based upon tetraglycidyl methylene dianiline (TGDDM) and a cycloaliphatic diamine hardener. The additives evaluated as potential tougheners were an epoxy‐terminated aliphatic polyester hyperbranched polymer, a carboxy‐terminated butadiene rubber and an aminopropyl‐terminated siloxane. This work has shown that epoxy‐terminated hyperbranched polyesters can be used effectively to toughen the lower cross‐linked epoxy resins, i.e. the DGEBA‐based systems, with the main advantage being that they have minimal effect upon processing parameters such as viscosity and the gel time, while improving the fracture properties by about 54 % at a level of 15 wt% of additive and little effect upon the Tg. This result was attributed to the phase‐separation process producing a multi‐phase particulate morphology able to initiate particle cavitation with little residual epoxy resin dissolved in the continuous epoxy matrix remaining after cure. The rubber additive was found to impart similar levels of toughness improvement but was achieved with a 10–20 °C decrease in the Tg and a 30 % increase in initial viscosity. The siloxane additive was found not to improve toughness at all for the DGEBA‐based resin system due to the poor dispersion within the epoxy matrix. The TGDDM‐based resin systems were found not to be toughened by any of the additives due to the lack of plastic deformation of the highly cross‐linked epoxy network Copyright © 2003 Society of Chemical Industry  相似文献   

18.
Hygrothermally decomposed polyurethane (HD‐PUR) of a polyester type was used as an impact modifier in tri‐ and tetrafunctional epoxy (EP) resins. Between 5 and 80 wt % of the PUR modifier was added to the EP prior to its crosslinking with a diamine compound (diaminodiphenyl sulfone, DDS). The mean molecular weight between crosslinks (Mc ) was determined from the rubbery plateau modulus of the dynamic mechanical thermal analysis (DMTA) spectra. The fracture toughness (Kc) and energy (Gc) of the modified resins were determined on static‐loaded compact tension (CT) specimens at ambient temperature. The change in the Kc and Gc as a function of Mc followed the prediction of the rubber elasticity theory. The efficiency of the HD‐PUR modifier was compared with that of a carboxyl‐terminated liquid nitrile rubber (CTBN). Attempts were also made to improve the functionality of the modifier by hygrothermal decomposition of PUR in the presence of glycine and ε‐caprolactam, respectively. DMTA and fractographic results showed that HD‐PUR functions as an active diluent and a phase‐separating additive at the same time. As HD‐PUR can be regarded as an amine‐functionalized rubber, it was used as the hardener (by replacing DDS) in some EP formulations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1139–1151, 2000  相似文献   

19.
N-Phenylmaleimide–styrene copolymers (PMS) and reactive N-phenylmaleimide–styrene–p-hydroxystyrene (HSt) terpolymers (PMSH) containing p-hydroxyphenyl groups were used to improve the toughness of bisphenol A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. PMS and PMSH were effective modifiers for epoxies. The morphologies of the modified resins depended on modifier structure and content. The most effective modification for the cured resins was attained because of the co-continuous structure of the modified resins in both PMS and PMSH modification systems. When using 15wt% of PMS (M¯w 125000), the fracture toughness, KIC, for the modified resin increased by 230%, with retention of flexural modulus and glass transition temperature, but with a loss of flexural strength, compared with the values for the unmodified epoxy resin. When using PMSH as the reactive modifier, the efficiency decreased with increase in HSt content, because of the increasing extent of dispersion of the PMSH-rich continuous phases. In the modification with 10wt% PMSH (1·0mol% HSt unit, M¯w 294000), the modified resin had balanced physical properties. © of SCI.  相似文献   

20.
Epoxy–melamine hybrid resins were obtained from in situ polymerization of siliconized (SE500) and phosphorylated (PE690) epoxy resins with hexakis(methoxymethyl)melamine (HMMM). The hybrid resins having HMMM contents less than 15 wt % exhibited high transparency and homogeneity. The compatibilities between SE500 and melamine as well as that between PE690 and melamine were poor than the compatibility between general bisphenol‐A epoxy and melamine. Incorporation of HMMM altered the degradation mechanisms and enhanced the thermal stability of the epoxy resins, especially for PE690 based resins. Excellent flame retardant property was observed with the hybrid resins because of the Si? N and P? N synergisms of flame retardation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1071–1077, 2006  相似文献   

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