Relationships in a bismaleimide resin system. Part I: Cure mechanisms

A series of bismaleimide resin systems has been examined in order to identify the molecular features responsible for the mechanical response of these materials. A range of network structures was produced both by formulation of resins with different ratios of N,N′-bismaleimido-4,4′-diphenylmethane (BMI) and methylene dianiline (MDA), and by the use of different thermal processing cycles. Spectrographic and chromatographic techniques were used to study the reactions that occurred during the cure. Two principal reactions were confirmed: a Michael addition reaction which provides linear chain growth, and an addition reaction which produces crosslinking through the double bonds of the maleimide group. In general, curing at a lower temperature or increasing the MDA content served to favor chain extension over crosslinking, which might be expected to increase molecular mobility in the resin.     

Glass transition temperatures in bismaleimide-based resin systems

The glass transition temperatures in bismaleimide-based resins were investigated using different stoichiometric ratios of 1, 1′-(methylenedi-4, 1-phenylene)bismaleimide (BMI) and 4, 4′-methylenedianiline (MDA). The resin cure involves a low temperature primary amine addition to the maleimide double bonds and a high temperature homopolymerization of the maleimide double bonds. The network topology and the glass transition temperature changes with resin composition and curing conditions were determined using differential scanning calorimetry (DSC). An empirical model was used to relate the glass transition temperature to the extents of the amine addition and the homopolymerization reactions in 1:1 and 2:1 BMI:MDA resins. The changes in thermal properties with resin post-cure were also examined.     

Photocrosslinking of a maleimide functionalized polymethacrylate

A polymethacrylate bearing pendent maleimide (MI) groups has been crosslinked by UV irradiation of the photoinitiator‐free functionalized polymer. The reaction was followed in situ by real‐time IR spectroscopy and shown to proceed with an initial quantum yield of two maleimide double bonds polymerized per photon absorbed, the value expected for a photocycloaddition mechanism. A twofold increase of the reaction rate was achieved by performing the UV irradiation in the presence of a thioxanthone photosensitizer (1 wt%). Insolubilization of the photoresist requires the reaction of at least 18 MI double bonds per polymer chain, thus implying the occurrence of an intramolecular coupling process between neighbouring MI groups located on the same polymer chain. In the presence of an electron donor monomer, like the divinylether of triethyleneglycol used, the cycloaddition reaction gives way to a radical‐induced copolymerization of maleimide and vinyl ether double bonds, which becomes the only crosslinking process in a stoichiometric mixture of the two components. Copyright © 2003 Society of Chemical Industry     

Diethynyl terminated siloxane bases (bisazomethine Schiff base)

Summary Bis-4 ethynylbenziminopropyl-hexamethyldisiloxane was prepared and characterized. The flexible central unit of this product allows an easy and thorough polymerization of the ethynyl groups at a moderate temperature.After thermal polymerization of the ethynyl groups, another reaction takes placeupon curing, leading to a product presenting no detectable Tg.This increase in crosslinking could be related to a diene synthesis involving both olefinic and imine double bonds.     

Dual crosslinking of carboxylated nitrile butadiene rubber latex employing the thiol‐ene photoreaction

At present, the most common used crosslinking process for carboxylated nitrile butadiene rubber (XNBR) latex is an accelerated sulfur curing system with zinc oxide. To avoid allergenic reactions related to residual accelerator levels in dipped XNBR latex articles such as medical gloves, a dual curing process has been developed combining thermal and photochemical crosslinking reactions. The two‐step procedure involves the formation of covalent and ionic bonds to ensure good mechanical properties of the final products. The photochemical thiol‐ene reaction is used to generate covalent crosslinks between the remaining C?C double bonds of the butadiene units whereas the carboxylic moieties are conventionally cured with divalent metal oxides (ZnO) under elevated temperature (formation of ionic crosslinks). The photochemical curing step is carried out both in the latex phase using a falling film photoreactor (prevulcanization) as well as in the solid phase by UV irradiation of dried XNBR films (postvulcanization). The mechanical properties and crosslink densities of the cured XNBR films are determined and the influence of selected curing parameters is assessed. The results give evidence that a combined approach of thermal prevulcanization and photochemical postvulcanization makes the production of latex articles (e.g., gloves) with tailored properties and good skin compatibility feasible. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

NR硫化返原过程的动力学研究

采用依据ＮＲ硫黄硫化返原机理建立起来的硫化返原动力学模型,对普通硫黄硫化体系和半有效硫化体系的ＮＲ在不同温度下的硫化曲线进行了计算机非线性拟合,从而求出了各步反庆的速率常数,并进上步得到多硫键、双硫键和单硫键密度之和及交联密度随硫化时间变化的关系。结果表明：不同温度下两种体系采用该模型得到的模拟曲线与实际数据相吻合,求出的同一体系速率常数与硫化温度的关系符合Ａｒｒｈｅｎｉｕｓ方程。两种体系多硫键的     

The effect of curing history on the residual stress behavior of polyimide thin films

The effect of curing history on the residual stress behaviors in semiflexible structure poly(4,4′‐oxydiphenylene pyromellitimide) (PMDA–ODA) and rigid structure poly(p‐phenylene biphenyltetracarboximide) (BPDA–PDA) polyimide was investigated. Depending upon the curing history and different structures of polyimide, the residual stress behaviors and the morphology of polyimide thin films were detected in situ by using a wafer bending technique and wide angle X‐ray diffraction (WAXD), respectively. For the rigid structure BPDA–PDA polyimide, the residual stress and the slope decreased from 11.7 MPa and 0.058 MPa/°C to 4.2 MPa and 0.007 MPa/°C as the curing temperature increased, and the annealing process is done. However, for the semiflexible structure PMDA–ODA, the change of the residual stress and the slope was relatively not significant. In addition, it was found that the cured polyimide prepared at a higher temperature with a multistep curing process showed a higher order of chain in‐plain orientation and packing order than does the polyimide film prepared at a lower temperature with a one‐step curing process. These residual stress behaviors of polyimide thin films show good agreement with WAXD results, such as polyimide chain order, orientation, and intermolecular packing order, due to curing history. Specifically, it shows that the effect of curing history on residual stress as well as morphological change was significant in rigid BPDA–PDA polyimide but, not in semiflexible PMDA–ODA polyimide. Therefore, it suggests that the morphological structure depends upon curing history, and the polyimide backbone structure might be one of important factors to lead the low residual stress in polyimide thin films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3287–3298, 1999     

Surface improvement on water and oil affinities and absorption rate of PVA/Tung oil-coated paperboard and fiberboard

A novel coating material on paperboard and fiberboard from poly(vinyl alcohol) (PVA) modified with Tung oil was developed. The PVA/Tung oil coating was cured at several conditions: 25, 40, 50, and 60°C, in the presence of two types of catalysts, i.e., thermal catalyst using potassium persulfate (KPS) and redox catalyst using KPS and sodium thiosulfate. The chemical crosslinked structure of PVA/Tung oil-coating films was confirmed by FTIR. The result indicated the decrease in the double bonds of Tung oil by crosslinking reaction, especially at 60°C. In comparison with the same curing temperature, the films with redox catalyst showed more reduction in the number of double bonds of Tung oil. DMA results of the PVA/Tung oil-coating materials with redox catalyst showed the lowering of the heights of both β transition peak of Tung oil and α transition peak of PVA. FTIR and DMA results confirmed the more efficient crosslinking reaction of redox catalytic system than that of the thermal catalytic system. The water resistance and mechanical properties of these coating materials exhibited better values as projected to higher curing temperature and redox catalyst. SEM images showed the smooth surface of PVA/Tung oil covered on the paperboards with ~72 µm in thickness. The contact angle of water or oil drop and dynamic change in contact angle on the surfaces of PVA/Tung oil-coated paperboards and fiberboards were investigated. The results show the contact angles for both water and oil were lower than those of the uncoated ones, indicating the improvement of water and oil affinities of the PVA/Tung oil-coating materials. The dynamic changes in contact angle of the coated ones also decreased, suggesting the reduction in water and oil absorption rates of these coated substrates.     

Synthesis and properties of a second‐order,nonlinear‐optical,addition‐type polyimide with high thermal and temporal stability

A highly thermally and temporally stable, second‐order, nonlinear‐optical polyimide with an X‐type chromophore (2‐{4‐[4,5‐di(4‐nitrophenyl)imidazolyl]phenyl}‐4,5‐di(4‐aminophenyl)imidazole) was synthesized by the Michael addition reaction. The structure of the prepolymer was characterized with Fourier transform infrared (FTIR). Its thermal stability and curing behavior were studied with differential scanning calorimetry, thermogravimetric analysis, and FTIR. After the curing, the glass‐transition temperature of the polyimide greatly increased. The FTIR results suggested that addition and/or crosslinking reactions were carried out during the thermal curing of the prepolymer. A poling polyimide film was achieved, and the thermal and temporal stability of the poling‐induced orientation were evaluated with a multistep corona‐poling technique at an elevated temperature and with in situ second harmonic generation (SHG) measurements. The temporal orientation of the poled polyimide film was over 1000 h at 150°C; it retained 85% of the initial second‐order, nonlinear‐optical coefficient. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dual-curing behavior and scratch characteristics of hydroxyl functionalized urethane methacrylate oligomer for automotive clearcoats

UV–thermal dual-curable, hydroxyl- and methacrylate-functionalized urethane oligomers with different contents of unsaturated double bonds and hydroxyl groups have been synthesized and incorporated into automotive clearcoats to investigate their curing and scratch behaviors. Dynamic mechanical analyses (DMA) and FT-IR analyses were performed to observe the variation of the crosslinking networks that resulted from the chemical reactions by UV and thermal dual-curing operations with varying curing conditions, such as UV dose, thermal curing time, thermal curing temperature, and curing sequence. The scratch behaviors of dual-cured automotive clearcoats were analyzed via nano-scratch tests, accompanied with scratch images simultaneously visualized using scanning electron microscopy (SEM). The mechanical and chemical properties, such as impact resistance, pencil hardness, acid-etch resistance, and stone-chip resistance, of dual-curable clearcoats were also compared with those of UV mono-cure and 1 K thermal-cure clearcoats. The results clearly showed that the dual-curing process induced a considerably higher degree of crosslinking for the cured clearcoats prepared from the dual-curable oligomers, melamine crosslinkers, and photoinitiators. Their mechanical properties including scratch resistance were also noticeably improved via the UV–thermal curing sequence, which led to an increased conversion rate of double bonds compared with clearcoats produced using the thermal–UV curing sequence. The best conditions for high crosslinking density as well as high hardness and modulus were 2400 mJ/cm² at 150 °C for 10 min in the UV–thermal curing process. This result was corroborated from the reaction kinetics and surface images of the scratched clearcoats captured by SEM.     

热固性聚酰亚胺的研究进展及其在印制电路板上的应用

热固性聚酰亚胺作为一类先进的基体树脂,在航空航天、印制电路板、高温绝缘材料等领域的应用不断扩大.相对于热塑性聚酰亚胺来说,热固性聚酰亚胺具有更好的可加工性能.而且,其加工窗口温度可通过变换不同反应性端基来实现.若选用合适的反应性端基,其在固化时无小分子挥发物放出.对热固性聚酰亚胺的研究现状分类作了综述,对降冰片烯、烯丙基降冰片烯、乙炔基、苯乙炔基、马来酰亚胺、苯基马来酰亚胺、苯并环丁烯等封端型热固性聚酰亚胺的研究进展进行了重点阐述,对它们结构与性能的关系、齐聚物的固化机理等进行了讨论,并对其在印制电路板上的应用和发展趋势作了概述和展望.     

Fourier transform infrared and high-resolution solid-state carbon-13 NMR spectroscopic characterization of cured polystyrylpyridine resins

Interesting crosslinked materials possessing good mechanical and thermal properties are obtained by condensation of 2,4,6-trimethylpyridine (collidine) with terephthalic aldehyde in the presence of an acidic catalyst. Fourier transform infrared spectroscopy has been used to follow the kinetics of the chemical reactions involved in the formation of the tridimensional network using aldehyde and ethylene absorption bands. The first steps of the reaction consist in the addition of aldehyde groups on the methyl groups of collidine followed by a dehydration reaction which leads to the formation of ethylenic functions. Crosslinking is obtained by an addition reaction of the methyl groups of collidine on the double bonds created in the first processes. These reactions are strongly dependent on the reaction temperature. Cured resins prepared with different acidic catalysts have been studied by carbon-13 NMR. p-Toluene sulfonic acid leads to residual aldehyde groups in the cured resins whereas no residual aldehyde groups are observed after a relatively short curing time when sulfuric acid is used as the catalyst. The networks created in the two cases are not equivalent and present different mechanical properties.     

Physicochemical characterization of alloy of polyimide with varying degree of crosslinking through diisocyanates

Polyimide alloys are prepared by blending the crosslinked and uncrosslinked polyamic acid components and followed by thermal imidization. The blend components can be synthesized by the reaction of polyamic acid with the varying concentration of crosslinker [here methylene bis (4-phenyl isocyanate or MDI)] from 1.54 × 10^?2 mol/L (i.e. hypothetically calculated critical crosslinker concentration or CCC) to 1.54 × 10^?6 mol/L. This communication discusses the synthesis and characterization of polyimide (PI) blends and alloys prepared by varying degrees of crosslinking introduced via isocyanate-amic acid reaction. The polyimides were prepared by thermally imidizing the polyamic acid blends at different curing temperatures from 50°C to 350°C. The degree of imidization and residual solvent content for blends having varying mole fractions of crosslinked (or branched) and uncrosslinked components and two extreme conditions and at specified temperature-time profiles have been studied. The resultant PI-MDI blends have exhibited synergism on mechanical properties. The improvement in mechanical properties, however, was significantly higher at the lower imidization temperature (i.e. 50°C to 150°C). The feasibility of preparing polyimide alloys with synergistic combinations of crosslinked and uncrosslinked polyimide components was inferred.     

Effect of network heterogeneities on the physical properties of nitrile rubbers cured with dicumyl peroxide

The scope of this study is to continue our earlier studies on the peroxide curing of diene elastomers. The effect of peroxide content and temperature on the curing and mechanical properties of NBR and H‐NBR rubbers with different acrilonitrile content was evaluated. Experimental evidence indicates that saturated rubbers behave as expected whereas in unsaturated nitrile rubbers abstraction of allylic hydrogen and addition to the double bonds can act as mechanism of crosslinking, the weight of each mechanism is dependent of DCP content and curing temperature. The addition mechanism produces densely crosslinked zones or clusters, generating a heterogeneous network with effect on the vulcanizate properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3377–3382, 2007     

酚醛树脂高性能化改性研究进展

介绍了酚醛树脂增韧、耐热改性研究及改性后的高性能酚醛树脂作为摩擦材料的应用。增韧改性方法包括 :橡胶改性 ,腰果壳油改性 ,热塑性树脂改性 ,桐油改性 ,新型固化剂改性 ,马来酰亚胺改性及腰果壳油 /双马来酰亚胺复合改性 ;而耐热改性方法包括 :胺类改性 ,硼酸改性 ,芳烃改性 ,钼改性 ,聚酰亚胺改性 ,磷改性 ,苯并嗪化合物改性及氰酸酯化改性     

不同硫化体系天然橡胶阻尼减震材料的硫化动力学及其性能研究

研究硫黄和促进剂用量对高阻尼天然橡胶胶料硫化特性的影响,并通过非线性拟合探讨硫化体系对硫化胶力学性能的影响。结果表明:随着硫黄用量的减小,硫化前驱体形成交联键的反应活性和交联键降解速率均是先增大后减小,力学强度下降,阻尼性能提高;随着促进剂/硫黄用量比的增大,硫化前驱体形成交联键的反应活性提高,交联键降解速率减小,力学强度提高,阻尼性能下降。     

Rheological cure characterization of phosphazene–triazine polymers

Cyclomatrix phosphazene–triazine network polymers were synthesized by co‐curing a blend of tris(2‐allylphenoxy), triphenoxy cyclotriphosphazene (TAP), and tris(2‐allylphenoxy) s‐triazine (TAT) with bis(4‐maleimido phenyl) methane (BMM). The co‐curing of the three‐component resin was investigated by dynamic mechanical analysis using rheometry. The cure kinetics of the Diels–Alder step was studied by examining the evolution of the rheological parameters, such as storage modulus (G′), loss modulus (G″), and complex viscosity (η*), for resins of varying compositions at different temperatures. The curing conformed to an overall second‐order phenomenological equation, taking into account a self‐acceleration effect. The kinetic parameters were evaluated by multiple‐regression analysis. The absence of a definite trend in the cure process with blend composition ratio was attributed to the occurrence of a multitude of competitive reactions whose relative rates depend on the reactant ratio and the concentration of the products formed from the initial phase of reaction. The cure was accelerated by temperature for a given composition, whereas the self‐acceleration became less prominent at higher temperature. Gelation was accelerated by temperature. The gel conversion decreased with increase in maleimide concentration and, for a given composition, it was independent of the cure temperature. The activation energy for the initial reaction and the crosslinking process were estimated for a composition with a maleimide‐to‐allyl ratio of 2 : 1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 908–914, 2003     

Synthesis and characterization of thermosetting polyacetylene-terminated silicone resins

A novel polyacetylene-terminated silicone (PTS) resins possessing low curing temperature and high heat resistance has been prepared by Grignard reaction using m-diacetylenylbenzene (DEB), 1,3,5-triacetylenylbenzene(TEB), and dichlorosilane as original materials. The reaction of the functional groups was characterized by in situ Fourier transform infrared spectrometer. The experimental results indicated that Si─H and C≡CH bonds are almost exclusively involved in the crosslinking reaction, while ─C≡C─ bonds only partially react. Further, Si─H and C≡CH bonds can participate in the curing reaction at relatively low temperatures, but ─C≡C─ bonds require higher temperature, indicating the higher activity of Si─H and C≡CH bonds than ─C≡C─ bonds. As determined by differential scanning calorimetry, PTS resins have low peak exothermic temperature at 184.5 °C, which is lower than MSP resin (~ 210 °C); in addition, rheological test showed that PTS resins have a very wide processing window from 40 to 163.3 °C, indicating that the PTS resins have excellent processability with a low curing temperature and wide processing window. What is more, TGA results of thermal-cured PTS resins revealed that T_d5 (5% weight loss temperature) of PTS-H10 reached the highest of 684.4 °C. Compared with PTS-H0 resin, there is an increase of 124.2 °C and the remarkably increased heat resistance correlated with a higher m-DEB input ratio. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48783.     

不饱和聚酯树脂的常温固化

综述了不饱和聚酯树脂的固化特征、固化反应,固化机理和交联固化反应活性。介绍了4种固化反应过程、引发剂和固化反应链增长过程,同时介绍了其交联固化反应活性及影响因素。     

Cure reaction for modified diallylbisphenol A/diaminodiphenylsulfone/bismaleimide

The glass‐transition temperature as a function of curing conversion for a modified diallylbisphenol A/diaminodiphenylsulfone/bismaleimide (BMI) resin was investigated at different temperature regimes and modeled using a modified Di Benedetto equation. Although the relationship between the glass‐transition temperature and conversion of the BMI system conforms to the Di Benedetto equation for α < 0.6 and at lower cure temperatures, at higher cure temperatures the results deviated significantly from the equation; thus, it was an inadequate model for the system. Fourier transform IR analysis showed that the major crosslinking reactions did not occur during cure for the modified BMI at and below 150°C. However, as the cure temperature was increased, the crosslinking reactions responsible for 3‐dimensional network structures became more dominant. At 190°C the C? N? C_stretch vibration of the uncured maleimide ring converted into succinimide rings in the curing process. Simultaneously, a decrease was observed for the absorbance bands of ? C? H_bending (maleimide). The higher cure temperatures induced a significantly faster initial crosslinking rate and also resulted in a shorter period of time after which further crosslinking was retarded, because the increase in the crosslinks also physically slowed further crosslinking activity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 227–235, 2002