共查询到19条相似文献,搜索用时 15 毫秒
1.
Tadatomi Nishikubo Eiji Takehara Atsushi Kameyama 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3013-3020
Photochemical reactions of various blocked polyfunctional amines such as bis(4-formylaminophenyl)methane (FAPM), bis(4-acetylaminophenyl)methane (AAPM), bis(4-benzoylaminophenyl)methane (BAPM), 2,4-diformylaminotoluene (DFAT), m-xylene diformamide, and bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1.6-diamine were carried out to give the corresponding free amines in THF solution, in epoxy resin, or in polyurethane oligomer with terminal isocyanate groups. Photolysis of FAPM and DFAT to produce the corresponding polyfunctional amines such as 4,4'-methylenedianiline and 2,4-diaminotoluene proceeded with 80 and 75% conversions, respectively, in THF solution under UV irradiation at 5 h. AAPM and BAPM also produced the corresponding photo-Fries rearrangement products with 32 and 38% conversions, respectively, under the same irradiation conditions. The photolysis of those compounds also occurred with similar conversions in the epoxy resin and in the polyurethane oligomer under UV irradiation; and the thermal curing reactions of the epoxy resin and the polyurethane oligomer with photogenerated polyfunctional amines proceeded smoothly after heating at 140°C for 2 hrs. © 1993 John Wiley & Sons, Inc. 相似文献
2.
Transformation
of dynamic DSC results into isothermal data for the curing kinetics study
of the resol resins 总被引:1,自引:0,他引:1
M. V. Alonso M. Oliet J. García F. Rodríguez J. Echeverría 《Journal of Thermal Analysis and Calorimetry》2006,86(3):797-802
Kinetics of thermosetting polymers curing is difficult to study by isothermal
methods based on the differential scanning calorimetry (DSC) technique. The
difficulty is due to the low sensitivity of the equipment for total reaction
heat measurements during high temperature process. The aim of this paper is
to display the equivalence between a dynamic model, the Ozawa method, and
an isothermal isoconversional fit, which allows predicting the isothermal
behavior of the resol resins cure through dynamic runs by DSC. In this work,
lignin–phenol–formaldehyde and commercial phenol–formaldehyde
resol resins were employed. In addition, the isothermal kinetic parameters
for both resins were performed by means of transformation of the data obtained
from the dynamic Ozawa method. 相似文献
3.
Imidazole‐type thermal latent curing agents with high miscibility for one‐component epoxy thermosetting resins
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Kenji Kudo Sawako Fuse Masahiro Furutani Koji Arimitsu 《Journal of polymer science. Part A, Polymer chemistry》2016,54(17):2680-2688
Epoxy resins are important thermosetting resins widely employed in industrial fields. Although the epoxy–imidazole curing system has attracted attention because of its reactivity, solidification of a liquid epoxy resin containing imidazoles proceeds gradually even at room temperature. This makes it difficult to use them for one‐component epoxy resin materials. Though powder‐type latent curing agents have been used for one‐component epoxy resin materials, they are difficult to apply for fabrication of fine industrial products due to their poor miscibility. To overcome this situation and to improve the shelf life of epoxy–imidazole compositions, we have developed a liquid‐type thermal latent curing agent 1 , generating an imidazole with a thermal trigger via a retro‐Michael addition reaction. The latent curing agent 1 has superior miscibility toward epoxy resins; in addition, it was confirmed that the epoxy resin composition has both high reactivity at 150 °C, and long‐term storage stability at room temperature. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2680–2688 相似文献
4.
《先进技术聚合物》2018,29(7):1922-1929
The effects of inorganic particles such as Al2O3 and B4C on the solidification kinetics and heat resistance of phthalonitrile resin were investigated. The properties of the blends and the cured products were tested by rheometer, differential scanning calorimetry, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The results revealed that B4C and Al2O3 inorganic particles could prolong the gel time of phthalonitrile resin and broaden the processing window. The curing kinetic analysis showed that the presence of the particles could significantly reduce the curing activation energy of phthalonitrile resins by 72.38 kJ/mol down to 43.03 kJ/mol. Meanwhile, the heat resistance of the phthalonitrile resin was improved. Among them, the blend system combined with 30% B4C showed prominent thermoresistance. And while the Td5% weight loss temperature was 600°C, char yield at 1000°C was higher than 86% under nitrogen atmosphere; while the Td5% weight loss temperature was 581°C, char yield at 1000°C was higher than 80% under air atmosphere. Hence, the resulting resins were good candidate matrix of high‐temperature structural composites. 相似文献
5.
Caiyuan Pan Longwu Qi Ruke Bai 《Journal of polymer science. Part A, Polymer chemistry》1995,33(13):2151-2155
Prepolymers were prepared by the reaction of 3,9-dihydroxyethyl-3′9′-dibenzyl-1,5,7,11-tetraoxaspiro(5,5)undecane with 4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexa-methylene diisocyanate (HDI). The number-average molecular weights of the prepolymers can be controlled by changing the mole ratios of spiro compound and diisocyanates. Kinetic studies of the cure reaction for the epoxy resin system modified with or without prepolymers were followed by a HLX-1 dynamic torsional vibration apparatus. The results indicated that gel time (tg) and activation energy (Ea) increased as the content of prepolymers in the epoxy resin system increased. A difference with the cure reaction of the pure epoxy resin, the second-order reaction for the epoxy resin modified with the prepolymers, was obtained. Rate constants (k) of the cure reaction are 0.231 min?1 for the epoxy resin, and 0.312 min?1 for the modified epoxy resin. The mechanism of the cure reaction was discussed. © 1995 John Wiley & Sons, Inc. 相似文献
6.
Several phenol‐urea‐formaldehyde (PUF) cocondensed resol resins were synthesized by different procedures. The curing kinetics and network properties of these PUF resins were examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). A kinetic study indicated that the activation energy values of PUF resins are generally higher than those of phenol‐formaldehyde (PF) resins during curing processes, but the curing rates of PUF resins are faster than those of PF resins. The pH values of PUF systems have a significant influence on the rate constants, although they affect the activation energy very slightly. Moreover, the dependence of activation energy on the conversion showed that there are more individual reactions with different activation energies occurring during the curing processes in PUF resins than in PF resins. The decomposition of methylene ether bridges to form methylene bridges probably occurs at high temperature in PUF resins. DMTA data indicated that the network rigidity of PUF resins is slightly lower than that of PF resin. The gel point and Ttan δ2 transition measured by DMTA were consistent with the kinetic results obtained from the DSC data, but they were also related to the physical and mechanical properties of the network, especially with regard to the Ttan δ2 transition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1929–1938, 2003 相似文献
7.
Wei Wei Xin Sun Weitao Ye Bowen Zhang Xiaoma Fei Xiaojie Li Xiaoya Liu 《先进技术聚合物》2020,31(7):1553-1561
A novel thermal latent curing agent, 2MZS, was obtained through the reaction of 2‐methylimidazole (2MZ) and a symmetrically carboxyl‐functionalized star‐shaped molecule based on cyclotriphosphazene (N3P3‐COOH). In the complex, the resonance of N3P3‐COOH reduced the activity of lone electron pairs on the pyridine‐type nitrogen atom of imidazole ring, suppressing the nucleophilic attack and crosslinking reaction between 2MZ and epoxy resin. As a result, the storage stability was improved distinctly for the one‐pot epoxy compound, which could be steadily stored at room temperature for nearly 1 month. Nonisothermal DSC revealed a delayed initiation curing mechanism of the prepared one‐pot system, and which could undergo rapid curing reaction upon raising the temperature. Moreover, the introduction of terminally polyfunctional star‐shaped phosphazene derivative could promote the curing process at elevated temperature, as well as improve the chain rigidity of the cured resin by chemical incorporation into the cross‐linked network, thus endowing the cured resin with enhanced glassy storage modulus. The epoxy thermoset exhibited the highest glass transition temperature and thermal degradation temperature when 20 wt% of 2MZS was used. It is suggested that the novel latent curing agent is potential for high‐performance one‐pot epoxy compound, particularly recommended for application in electronic packaging fields. 相似文献
8.
Masayuki Oba 《Journal of polymer science. Part A, Polymer chemistry》1996,34(4):651-658
The effect of new additives on the thermal conversion of a range of polyamic acids to polyimides at temperatures lower than 100°C was investigated using infrared spectroscopy. Additives such as m-hydroxybenzoic acid, p-hydroxyphenylacetic acid, and p-hydroxybenzenesulfonic acid were found to be highly effective as curing catalysts or accelerators. The degree of imidization of polyamic acids in the presence of additives increased with an increase in the reaction temperature, and complete imidization was achieved at 140–200°C. The reaction was characterized by a rapid rate that slowed with time. © 1996 John Wiley & Sons, Inc. 相似文献
9.
Synthesis of a novel phosphorus‐containing curing agent and its effects on the flame retardancy,thermal degradation and moisture resistance of epoxy resins
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A novel phosphorus‐containing compound diphenyl‐(1, 2‐dicarboxylethyl)‐phosphine oxide defined as DPDCEPO was synthesized and used as a flame retardant curing agent for epoxy resins (EP). The chemical structure of the prepared DPDCEPO was well characterized by Fourier transform infrared spectroscopy, and 1H, 13C and 31P nuclear magnetic resonance. The DPDCEPO was mixed with curing agent of phthalic anhydride (PA) with various weight ratios into epoxy resins to prepare flame retardant EP thermosets. The flame retardant properties, combustion behavior and thermal analysis of the EP thermosets were respectively investigated by limiting oxygen index (LOI), vertical burning tests (UL‐94), cone calorimeter measurement, dynamic mechanical thermal analysis and thermogravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of the char residues for EP thermosets were respectively investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS). The water resistant properties of the cured EP were evaluated by putting the samples into distilled water at 70°C for 168 hr. The results revealed that the EP/20 wt% DPDCEPO/80 wt% PA thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.2%. The cone test results revealed that the incorporation of DPDCEPO effectively reduced the combustion parameters of the epoxy resin thermosets, such as heat release rate and total heat release. The dynamic mechanical thermal analysis test demonstrated that the glass transition temperature (Tg) decreased with the increase of DPDCEPO content. The TGA results indicated that the incorporation of DPDCEPO promoted the decomposition of epoxy resin matrix ahead of time and led to a higher char yield and thermal stability at high temperatures. The surface morphological structures and analysis of the XPS of the char residues of EP thermosets revealed that the introduction of DPDCEPO benefited the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resin material surface during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After water resistance tests, the EP/20 wt% DPDCEPO/80 wt% PA thermosets retained excellent flame retardancy, and the moisture adsorption of the EP thermosets decreased with the increase of DPDCEPO content in EP thermosets because of the existence of the P–C bonds and the rigid aromatic hydrophobic structure in DPDCEPO. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
10.
Hiroto Kudo Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(5):709-726
This paper reports new addition reactions of oxetanes with certain protonic reagents such as carboxylic acid, phenol, and thiol, and with certain aprotic reagents such as acyl chloride, thioester, phosphonyl dichloride, silyl chloride, and chloroformate using quaternary onium salts as catalysts. The kinetic study of the addition reactions of oxetanes was also investigated. These new addition reactions were applicable to the synthesis of new polymers. These polyaddition systems could also construct both polymer main chains and reactive side chains. The alternating copolymerization of oxetanes with carboxylic anhydride was performed. Furthermore, it was found that anionic ring‐opening polymerization of oxetanes containing hydroxy groups proceeded to afford the hyperbranched polymer (HBP) with an oxetanyl group and many hydroxy groups at the ends of the polymer chains. Alkali developable photofunctional HBPs were synthesized by the polyaddition of bis(oxetane)s or tris(oxetane)s, and their patterning properties were examined, too. The photo‐induced cationic polymerization of the polymers with pendant oxetanyl groups and the thermal curing reactions of polyfunctional oxetanes (oxetane resins) were also examined to give the crosslinking materials quantitatively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 709–726, 2007 相似文献
11.
The epoxy resins containing imine bonding were prepared from hydroxyl substituted Schiff base monomers in two steps. At the first step, hydroxyl substituted Schiff base monomers were synthesized via condensation reaction. At the second step, epoxy resins were synthesized from the reaction between Schiff base monomers and epichlorohydrine (EPC). Then curing processes of epoxy resins were achieved by p-phenylenediamine compound. The structures of resulting compounds were confirmed by FT-IR, UV-Vis and 1H-NMR. TG-DTA and DSC measurements were performed for thermal characterizations of the compounds. Chemical resistances of the cured epoxy-amine systems were determined for coating applications in acidic, alkaline and organic solvents. HCl (10%, aqueous solution), NaOH (10%, aqueous solution), DMSO, DMF, N-methylpyrrolidone, ethanol, THF and acetone were used for corrosion tests. Chemical resistance data of the synthesized epoxy resins demonstrated that they have good chemical resistance against various acid, alkaline and common organic solvents. Surface morphologies of epoxy resin and the cured epoxy resin were determined with scanning electron microscopy (SEM) measurements. Also, optical band gap (Eg) values of Schiff base monomers and epoxy resins were calculated from UV-Vis measurements. 相似文献
12.
Seung Han Ho Gyu Yoon Kwang S. Suh Whan Gun Kim Tak Jin Moon 《Journal of polymer science. Part A, Polymer chemistry》1999,37(6):713-720
The effects of the concentration of triphenylphosphine as a catalyst on the cure reaction of the biphenyl epoxy/phenol novolac resin system were studied. The kinetic study was carried out by means of the analysis of isothermal experiments using a differential scanning calorimeter. All kinetic parameters including the reaction orders, activation energy and kinetic rate constants were evaluated. To describe the cure reaction with the catalyst concentration, the normalized kinetic model was developed. The suggested kinetic model with a diffusion term was successfully able to describe and predict the cure reaction of epoxy resin compositions as functions of the catalyst content and temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 713–720, 1999 相似文献
13.
A novel low‐temperature curing polytriazole resin was prepared from a triazide and a tetraalkyne and characterized. The resin can be cured at 70°C. The glass transition temperature Tg and thermal decomposition temperature Td5 of the cured resin with the molar ratio of azide to alkyne group [A]/[B] = 1.0:1.0 reached 324 and 355°C, respectively. The study on the curing kinetics of the resin shows that the apparent activation energy of the curing reaction is 93 kJ mol?1. The flexural strength of the cured resin reached 137.6 MPa at room temperature and 102.6 MPa at 185°C. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
14.
用傅里叶红外光谱、差示扫描量热仪和热重分析测试技术研究了双酚A甲醛酚醛环氧树脂(bis-ANER)与二氨基二苯醚(DDE)的固化反应及其固化产物的热降解性能。在等温固化反应中环氧基团红外光谱吸收强度随固化时间延长而逐渐减弱,羟基吸收强度逐渐增强,固化反应后期出现羰基红外吸收,其强度随固化时间的延长而增强。用Kissinger法和Ozawa-Flynn-Wall法计算出的bis-ANER/DDE非等温固化反应活化能分别为57.6和61.5kJ/mol。固化产物的热降解首先是醚键的断裂,在N2气和O2气气氛下起始阶段的热降解反应均符合g(α)=[-ln(1-α)]2/3的核增长反应机理,2种气氛下高温阶段的热降解机理不同,O2气在降解过程中产生氧化作用。 相似文献
15.
C. Martín J. C. Ronda V. Cdiz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(5):1701-1710
Boron‐containing novolac resins were synthesized by the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl)oxide. These novolac resins were crosslinked with diglycidyl ether of bisphenol A (DGEBA), and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. The boron‐containing novolac resins were less thermally stable than the unmodified novolac resin. Their modification degree and DGEBA content were related to the crosslinking density of the materials. The boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed down the degradation and prevented it from being total. They also showed good flame‐retardant properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1701–1710, 2006 相似文献
16.
In the present study, a novel aryl‐boron‐containing phenolic resin named as PBPR has been synthesized from phenol and formaldehyde in the presence of phenylboronic acid. The chemical structure of the PBPR was confirmed by Fourier transform infrared, nuclear magnetic resonance and X‐ray photoelectron spectroscopy. The molecular weight, viscosity and curing behavior were examined to demonstrate that PBPRs have better processability than common boric acid‐modified phenolic resin. The thermal stability and fracture toughness of the cured PBPRs were greatly enhanced, where the char yield at 1000°C (nitrogen atmosphere) and the glass transition temperature reached 70.0% and 218°C, respectively. The excellent mechanical and ablative properties of the PBPR composites may have benefited from the good interfacial adhesion between the resin matrix and the reinforced fiber. The flexural strength and the linear ablative rate are 436.8 ± 5.2 MPa and 0.010 mm/sec, respectively. This study opens a new window for the preparation of high‐performance ablative composites by designing a resin matrix containing an aryl‐boron backbone. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
17.
Zhi‐Qi Cai Jianzhong Sun Daodeng Wang Qiyun Zhou 《Journal of polymer science. Part A, Polymer chemistry》2007,45(17):3922-3928
The curing kinetics of a novel liquid crystalline epoxy resin with combining biphenyl and aromatic ester‐type mesogenic unit, diglycidyl ether of 4,4′‐bis(4‐hydroxybenzoyloxy)‐3,3′,5,5′‐tetramethyl biphenyl (DGE‐BHBTMBP), and the curing agent diaminodiphenylsulfone (DDS) was studied using the advanced isoconvensional method (AICM). DGE‐BHBTMBP/DDS curing system was investigated the curing behavior by means of differential scanning calorimetry (DSC) during isothermal and nonisothermal processes. Only one exothermal peak appeared in isothermal DSC curves. A variation of the effective activation energy with the extent of conversion was obtained by AICM. Three different curing stages were confirmed. In the initial curing stage, the value of Ea is dramatically decreased from ~90 to ~20 kJ/mol in the conversion region 0–0.2 for the formation of LC phase. In the middle stage, the value of Ea keeps about ~80 kJ/mol for cooperative effect of reaction mechanism and diffusion control. In the final stage, a significant increase of Ea from 84 to 136 kJ/mol could be caused by the mobility of longer polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3922–3928, 2007 相似文献
18.
Moon G. Kim Yimin Wu Larry W. Amos 《Journal of polymer science. Part A, Polymer chemistry》1997,35(15):3275-3285
A wood adhesive-type phenol–formaldehyde (PF) resol resin synthesized with a typical formaldehyde to phenol mol ratio of 2.10 was thoroughly cured and studied by the solid-state crosspolarization/magic angle spinning 13C nuclear magnetic resonance (CP/MAS NMR) spectroscopy. The methylene group/phenol mol ratio values found were between 1.35 and 1.46, close to the value of a completely cured PF polymer structure. The amount of formaldehyde emitted during resin curing was very small. Other formaldehyde-derived groups determined from CP/MAS NMR spectra and relatively high levels of oxidation products of formaldehyde determined from water extracts of cured resin raised the total formaldehyde-derived groups/phenol mol ratio value to close to that of the synthesis mol ratio. Technological implications of these findings are discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3275–3285, 1997 相似文献
19.
Ken Motokura 《Tetrahedron letters》2005,46(33):5507-5510
α-Alkylation of various nitriles with carbonyl compounds successfully proceeded using a hydrotalcite-supported palladium nanoparticle as a multifunctional catalyst. The alkylated nitriles were formed through aldol reaction at base sites on the hydrotalcite surface followed by hydrogenation by molecular hydrogen on the palladium nanoparticle. 相似文献