BMI／BCE树脂体系反应固化动力学研究

第17卷 第2期化学物理学报VoI.17，No.22004年4月CHINESE JOURNAL OF CHEMICAL PHYSICSApr.20041003-7713/2004/02-219-6＊Corresponding author ，TeI ：+86-451-8641-4323，E-maiI ：guowinboy@ or zsguo@碳纤维/双马树脂预浸料体系的固化动力学郭战胜＊， 杜善义， 张博明（哈尔滨工业大学复合材料研究所，哈尔滨 150001）张宝艳， 陈祥宝（北京航空材料研究院，北京 100095）摘 要： 给出了以等温固化航空航天工业用预浸料和纯树脂的固化动力学模型的研究.树脂基体是改性的BMI 树脂，增强相是碳纤维（T700-12S ）.用n 级反应模型分析了一系列差示扫描量热法（DSC ）的试验数据.无论是纯树脂或是预浸料，固化温度越高，固化速率就越大.达到峰值以后，固化速率降低比较快，导致预浸料体系的总反应热低.纤维的存在明显影响树脂的固化反应，预浸料体系固化动力学参数和纯树脂的参数有显著差异.增强纤维约束了树脂基体固化过程中的分子运动能力，降低了体系的固化程度，但没有改变树脂的固化机理.关键词： 固化动力学；纯双马树脂；预浸料；DSC 中图分类号：O631 文献标识码：ACure Kinetics of Carbon Fiber /Bismaleimide PrepregGuo Zhansheng ＊， Du Shanyi ， Zhang Boming（Center for Composite Materials ，Harbin Institute of Technology ，Harbin 150001）Zhang Baoyan ，Chen Xiangbao（Beijing Institute of Aeronautical Materials ，Beijing 100095）Abstract A new isothermaIIy based cure kinetic modeI for the prepreg was presented using an industriaIIy sup-pIied prepreg rather than neat resin.The matrix resin was bismaIeimide （BMI ）resin ，and the reinforcement was carbon fiber T700-12S.A series of isothermaI DifferentiaI Scanning CaIorimetry （DSC ）tests were performed and anaIyzed by the proposed n th-order reaction modeI.An increase in the cure rate was observed at the higher temper-ature in both neat and prepreg.After reaching the peak vaIue ，the cure rate of resin dropped off faster in prepreg ，resuIting in a Iower average vaIue of the uItimate heat of reaction.The presence of carbon fiber was found to signifi-cantIy impact the curing behavior of the resin ，Ieading to significant changes from the neat resin kinetic parameters.The carbon fibers imposed restrictions on the moIecuIar mobiIity of reactive species ，reduced the extent of poIymeri-zation within the system and did not change the cure mechanism of resin.Keywords Cure kinetics ，Neat BMI ，Prepreg ，DSC1 IntroductionInformation on the kinetics of cure aIIows a proper design of the cure and post-cure cycIes ，which pIay acruciaI roIe in the optimization of processing parameters and the guaIity of the finaI product.There are manyIiteratures for studying the cure kinetic of resin ［1-18］.As it is known ，the resin usuaIIy fIows through the fiber reinforcements when used in aeronauticaI or other in-dustries.These fibers may be sized，and they may change the kinetics.There is no consensus，however，with respect to the influence of fillers or reinforced ma-terials on the cure kinetics［10-16］.For example，Dutta and Ryan studied the kinetic effects of carbon black and silica fillers on the cure of an epoxy-amine sys-tem［10］，concluding that the heat of reaction is inde-pendent of the filler content but dependent on the type of filler.Han et al.found that the curing rate of a res-in is greatly influenced by the presence of fibers and the type of fibers employed［11］.The cure rate of prepreg system can be very different from that of neat resin，after a10min cure.Mijovic and Wang found that the presence of graphite fiber in a tetraglycidyl4，4 -diaminodiphenylmethane（TGDDM）/diaminodiphenyl sulfone（DDS）composite caused a slight increase in the cure rate but had no effect on the degree of cure［12］.Kaelble et al.found that differing surface treatments of a graphite fiber did not substantially alter the cure kinetic or degree of cure of an epoxy resin［13］. Grenier-Loustalot and Grenier investigated the curing mechanism of similar TGDDM/DDS systems in the presence of glass and carbon fibers［14］.They conclu-ded that the presence of fibers did not change the reac-tion mechanism or network structure，but did lead to notable differences in the cure rate，especially at low temperature.Michaud et al.studied the cure kinetic of resin transfer molding（RTM）resin［15］，and found that the fiber impacted the cure behavior significant，and reduced the extent of polymerization within the system. Wang et al.studied the isothermal cure of the commer-cial epoxy prepreg SPX8800［16］，containing diglycidyl ether of bisphenol A，dicyanodiamide，diuron，and re-inforcing glass fibers，under two conditions by near-in-frared spectroscopy（NIR）.There are several experimental technigues to char-acterization of thermosetting resin and prepreg，such as differential scanning calorimetry（DSC）［1-19］，NIR［16，20］，and Fourier Transform Infra-Red（FT-IR）［13，21-24］.DSC is the widest utilized experimental technigue to obtain the degree and cure rate of cure of thermosetting resins.program in the area of processing-structure-property-cost relationship in neat thermoset resin and compos-ites，we have undertaken a study of cure kinetics of neat BMI resins［2］.In this study，cure kinetic model is established for a benchmark prepreg system：T700/ bismaleimide（BMI），a carbon fiber reinforced BMI resin.2 Experimental2.1 MaterialsThe material used in this study was carbon fiber/ bismaleimide（T700/BMI）prepreg，which is com-monly used as the polymeric matrix in high-perform-ance composites employed in the aircraft，spacecraft and other industries.The BMI matrix resins consisted of4，4*-bismaleimidodiphenylmethane（BMIM，BMPM）and0，0*-diallyl bisphenol A（DABPA，DA-BA）.BMIM was well mixed with both87phr of bis-phenol A and other materials at130C，where the unit phr was an abbreviation of“part per one hundred mass base resin”，and here BMIM was a base resin.The re-inforcement material was carbon fiber（T700-12S）. The prepreg was prepared at the room temperature by the wet impregnated method.Reactions during mixing were negligible，as confirmed by4h isothermal （60C）DSC thermogram.The prepreg was then either tested immediately or stored in the refrigerator.If prepreg isn*t used in one month，it should be discar-ded and a fresh one prepared.2.2 ProcedureSamples were removed from the refrigerator and allowed to warm to25C.Small sample guantities（15 ~30mg）were then placed in sealed aluminum pans. The calorimetric measurements were made with Perkin Elmer Pyris1DSC.An inter-cooler was used to stabi-lize the system.Nitrogen with a flow rate of20~ 30mL/min was used as a purge gas to minimize oxida-tion of the sample during the measurements.Before the measurements on the BMI，two standard materials，in-dium（99.999%pure）and zinc（99.999%pure），were used to calibrate the temperature and energy axis of the Pyris1DSC following the manufacturer*s manu-022化学物理学报第17卷after sampie insertion and the exothermic reaction was considered compiete when the recorder signai ieveied off to the baseiine.The heat of reaction was determined by carrying the reaction isothermaiiy to compietion at the foiiowing temperatures ：170，180，190，200，210，220C.The totai area under the exotherm curve ，based on the extrapoiated baseiine at the end of the re-action ，was used to caicuiate the isothermai heat of cure ，H T at a given temperature.After the isothermai cure was compieted ，the sam-pie was cooied down to 50C rapidiy in the DSC.It was then heated at 10C /min from 50to 350C in order to determine the residuai heat of reaction ，H res .The sum of the isothermai heat （H T ）and the residuai heat （H res ）were taken to represent the uitimate heat of cure （H u ）.Finaiiy ，the sampies were weighted again and compared to the initiai weight.Weight iosses were neg-iigibie in aii cases.3 Results and discussionA series of isothermai DSC thermograms of prepreg systems are obtained and shown in Fig.1.The cure rate ，which is proportionai to the rate of heat gen-eration ，passes through a maximum and then decreases as a function of curing time.Aiso ，with a decrease of the cure temperature ，the cure reaction shifts to a ion-ger curing time.The maximum cure rate （peak vaiue ）curves appearing at about t =0mean that the cure re-action foiiows an n th-order reaction.Such behavior is typicai of the n th-order reactions and is anaiogous tothat observed and reported in the neat resin ［2］.Afterreaching the peak vaiue ，the cure rate faiis off to the baseiine guickiy.The cure rate eguation used to de-scribe the cure kinetics is ：d !d t =k （T ）f （!）=A exp -E ()RT（1-!）n（1）where d !/d t is the cure rate ，and !is the degree of cure ；k （T ）is the rate constant ，defined by an Arrhe-nius type of reiationship ，and f （!）is the function of cure mechanism ，usuaiiy determined by experimentaiconstant ，A is the freguency factor or pre-exponentiai constant ，E is the activation energy ，and T is the pro-cessing temperature expressed in Keivin.The cure rate is determined from the DSC trace ，the expression as foiiow ：d !d t =1H u d Hd t（2）where H u ，the uitimate heat of cure ，is the sum of the isothermai heat of cure （H T ）and the residuai heat （H res ）obtained in the subseguentiy dynamic DSC run.To caicuiate the degree of cure ，the DSC curves are in-tegrated and normaiized with respect to H u and sampie weight.We aiso note that the caicuiations of heats of reaction （H T and H res ）in reinforced systems are nor-maiized with respect to the mass ofBMI.Time /minFig.1 Cure rate as a function of time at different temperatures 回170C ，O 180C ，A 200C ，7210C ，＊220C.Vaiues of the uitimate heat of cure ，for both neat resin and prepreg system cured at different tempera-tures ，are summarized in Tabie 1.The average vaiue of H u is higher for neat resin than that for reinforced res-in.It appears then that the presence of carbon fiber contributes to a decrease in the overaii number of chemicai reactions and hence a iower vaiue of H u .Piot of the degree of cure as a function of time for prepreg is shown in Fig.2.The degree of cure increa-ses with increasing temperatures.At a given time ，the higher cure temperature ，the higher degree of cure.The degree of cure increases guickiy at the beginning of the cure stage ，and becomes iow in the iatter cure122第2期郭战胜等：碳纤维/双马树脂预浸料体系的固化动力学by chemicaI reaction but by diffusion.TabIe1 The uItimate heat of cure as a function of cure temperature Temperature/C Neat BMI resin/（J/g）Prepreg（J/g）17086.5371.22180161.5135.71190180.2149.83200212.4184.45210264.6206.43220288.44221.93Time/minFig.2 Degree of cure as a function of time at different temperatures 回170C，O180C，＊190C，7200C，＊210C，O220C.A direct comparison between neat resin and prepreg system is shown in Fig.3.The behavior differ-ence is sIight at Iower cure temperatures，but signifi-cant at higher cure temperatures.The curves for prepreg are somewhat beIow the corresponding iso-therms for neat resin.At the same temperature，the cure time for neat resin is shorter than that for the prepreg system.This may be caused by the fibers and viscosity increasing which impose restrictions on the moIecuIar mobiIity of reactive species.Cure rate as a function of degree of cure，with the temperature as a parameter，is shown in Fig.4.Once again，the observed dependence is very simiIar to that reported for the neat resin［2］.It is seen in the Fig.4 that the maximum cure rate occurs between0~0.04% degree of cure.The!th-order reaction is generaIIy characterized by the maximum rate at zeroconver-Time/minFig.3 Degree of cure vs.time for neat resin and prepregsystem at different temperatures回BMI-170C，A BMI-180C，＠BMI-190C，O BMI-200C，＊BMI-210C，古Prepreg-210C，O Prepreg-200C，O Prepreg-190C，A Prepreg-180C，回Prepreg-170C.Degree of cure/%Fig.4 Cure rate as a function of degree of cureat various temperatures回170C，＠180C，A200C，甲210C，古220C.DSC curves，it is found that the time reguired to reach the maximum cure rate is approximateIy identicaI to ze-ro.It is the same as neat resin.Now we wiII determine the function of cure mech-anism by the reduced time method，which is aIso caIIed Sharp method［25］.For this prepreg system，Fig. 5is the resuIt when experimentaI data are compared with theoreticaI data where"（!）=In（1-!）.It is cIear that they agree very weII.This means that the conversion function#（!）is eguaI to（1-!）.222化学物理学报第17卷Degree of cureFig.5 The comparison experimentaI data andtheoreticaI data for BMI resin回Sharp et al.theoreticaI curve，＠l70C，甲l90C，令200C，A l80C，O2l0C，＊220C.（tp）is found to decrease with increasing temperatures，in a Iinear fashion，as shown in Fig. 6.It is interest-ing to note，however，that the curves for the prepreg Iie above those of neat resin.Hence at a given temper-ature，it takes a IittIe Ionger to reach the maximum ratepeak（tp）in the presence ofreinforcement.T-l/l03K-lFig.6 Time to reach peak vs.cure temperaturefor neat resin and prepreg回BMI resin，O Prepreg.The kinetic rate constant k is read off the originaI DSC trace and normaIized with respect to the sampIe weight.The temperature dependence of cure rate con-stant k for both neat resin and prepreg can be presented by the Arrhenius eguation.But the k vaIues are sIightIy summary of the corresponding kinetic parameters is giv-en in TabIe2.TabIe2 Summary of kinetic parameters（n=l）Neat resin PrepregA/min-l 4.95X l08 4.ll X l05E/（kJ/moI）83.359.35AIthough the effect of the reinforcement on cure kinetics is not onIy very pronounced，there are severaI points that shouId be emphasized.As one wouId ex-pect，a higher cure temperature resuIts in an increase in the cure rate in both neat and prepreg.The Iower vaIue of Huin prepreg suggests the roIe of carbon fiber in restricting the moIecuIar mobiIity of reactive species. As the diffusion controI becomes progressiveIy more im-portant，the moIecuIes in the vicinity of reinforcement are“shieIded”（by carbon fiber）and hence increas-ingIy Iess IikeIy to encounter reactive species than the moIecuIes in the buIk.That couId be the reason why the cure rate，after going through the maximum，faIIs off to the baseIine noticeabIy faster in the prepreg.4 ConslusionA new isothermaIIy-based，cure kinetic modeI for the carbon fiber/BMI prepreg is presented using an in-dustriaIIy suppIied prepreg rather than neat BMI resin. The DSC measurement of BMI prepreg is very usefuI in eIucidating the curing process and in determining the kinetic parameters for the modeI.Its resuIts can be used to optimize the curing process of BMI prepreg in its appIications to aircraft and aerospace structures. The BMI prepreg is measured isothermaIIy from l70to 220C.The isothermaI cure reaction heat increases with the increment of cure temperature.The maximum reaction heat of isothermaI cure can be achieved at 220C.The degree of cure at isothermaI cure tempera-tures beIow220C is Iess than l.In the earIier stage of isothermaI cure reaction where the cure rate at the higher temperatures is faster than that at the Iower tem-peratures，the cure reaction is controIIed by chemicaI reaction，whereas in the Iatter cure stage，the cure re-322第2期郭战胜等：碳纤维/双马树脂预浸料体系的固化动力学ExperimentaI resuIts are described weII by an n th-order reaction modeI.In aII cases，higher cure temper-ature Ieads to an increase in cure rate.The degree of cure at the maximum rate of reaction is independent of temperature but takes a Ionger time to attain in prepreg.VaIues of the cure rate constant，I，are sIightIy Iower for the prepreg.AIso，the vaIues of Hu are Iower for prepreg.An expIanation is offered in terms of the restrictions to moIecuIar mobiIity imposed by the carbon fiber.The fibers act as heat sinks，re-ducing the peak exotherm，reducing the degree of cure within the system，and unchanging the cure mecha-nism.References［1］Turi E A.ThermaI Characterization of PoIymeric MateriaIs （2nd Ed.），Academic Press，New York，1998.1388［2］Guo Z S，Du S，Zhang B，et al.35th SAMPE TechnicaI Conference，Dayton，USA，2003［3］Ng S J，BosweII R，CIaus S J，et al. .Advanced Mater.，2002，34：33［4］Zeng Wenru，Li Shufen，Chow W K.Chin. .Chem.Phys.，2003，16：64［5］Guo Z S，Du S，Zhang B，et al.Acta Materiae Compositae Sinica，2004，21：121［6］PappaIardo L T. .Appl.Polym.Sci.，1977，22：809［7］Yang L F，Yao K D，Koh W. .Appl.Polym.Sci.，1999，73：1501［8］Shin D D，Hahn H posites：Part A，2000，31：991［9］Lee K，Biney P0，Zhong Y.46th InternationaI SAMPE Symposium and Exhibition（Proceedings），2001，II：2217［10］Dutta A，Ryan M E. .Appl.Polym.Sci.，1979，24：635［11］Han C D，Lee D S，Chin H B.Polym.Eng.Sci.，1986，26：393［12］Mijovic J，Wang H T.SAMPE .，1988，24：42［13］KaeIbIe D H，Dynes P J，CirIin E H. .Adhes.，1974，6：23［14］Grenier-LoustaIot M F，Grenier P.Polymer，1992，33：1187［15］Michaud D J，Beris A N，Dhurjati P S. .Compos.Ma-ter.，2002，36（10）：1175［16］Wang O，Storm B K，HoumoIIer L P. .Appl.Polym.Sci.，2003，87（14）：2295［17］Kim J，Moon T J，HoweII J R. .Compos.Mater.，2002，36：2479［18］Gao Jungang，Li Yanfang.Acta Physico Chimica Sinica，2000，16：405［19］Sun L，Pang S，SterIing A M.et al. .Appl.Polym.Sci.，2002，86：1911［20］Mijovic J，AndjeIic S.Macromolecules，1996，19：239［21］PheIan J C，Sung C S P.Macromolecules1997，30：6845［22］George G A，Cash G A，RintouI L.Polymer International 1996，41：169［23］Farguharson S，Smith W，Rigas E，et al.Proc.SPIE，2001，4201：103［24］Liu Weichang，Liu Deshan，Shen Shengjun，et el. .Functional Polymers，1999，12：307［25］Hu Rongzu，Shi Oizhen.ThermaI AnaIysis Kinetics，Bei-jing：Academic PubIisher，2001.196422化学物理学报第17卷。

不同环氧树脂改性BMI／CE树脂体系的非等温固化行为研究吴广磊;寇开昌;晁敏;卓龙海;蒋洋【摘要】采用差示扫描量热仪研究了不同牌号环氧树脂对双马来酰亚胺／氰酸酯（BMI／CE）树脂体系在不同升温速率下的固化反应。

在保持BMI和CE质量比为1：2的前提下，加入同等质量不同牌号环氧树脂，运用Kissinger法、Ozawa 法和Crane法求得活化能和反应级数等动力学参数。

结果表明，用环氧树脂（AG80）改性BMI／CE树脂体系的活化能平均值为81．55kJ／mol，反应级数为0．93；环氧树脂（TDE-85）改性的树脂体系的活化能平均值为69．25kJ／mol，反应级数为0．92；环氧树脂（TDE-85）改性BMI／CE树脂体系更有利于固化工艺的实现。

%The cure kinetics of epoxy resin （AG--80 and TDE-85）modified bismaleimide/cyanate ester （BMI/CE） system was investigated at different heating rates, using non-isothermal differential scanning calorimetry （DSC）. The curing kinetics parameters of the system were obtained by Kissinger, Ozawa equation, and Crane＇s theory. For epoxy resin（AG-80） modified System, the average activation energy was 81. 55 kJ/mol, and the reaction order was 0. 93. For epoxy resin （TDE-85）modified system, the average activation energy was 69.25 kJ/mol, and the reaction order was 0. 92. Compared to epoxy resin （AG-80） modified system, the results indicated that the addition of epoxy resin （TDE-85）could lower the activation energy of the modified system and the curing reaction could occur at a relative low temperature.【期刊名称】《中国塑料》【年(卷),期】2011(025)012【总页数】4页(P47-50)【关键词】环氧树脂;双马来酰亚胺;氰酸酯树脂;固化动力学【作者】吴广磊;寇开昌;晁敏;卓龙海;蒋洋【作者单位】西北工业大学理学院应用化学系,陕西西安710129;西北工业大学理学院应用化学系,陕西西安710129;西北工业大学理学院应用化学系,陕西西安710129;西北工业大学理学院应用化学系,陕西西安710129;西北工业大学理学院应用化学系,陕西西安710129【正文语种】中文【中图分类】TQ323.5CE是20世纪60年代研制开发的一种新型高性能热固性树脂［1］，其主要用作高性能印刷电路板和先进战斗机雷达罩树脂基体，另外还可作为高性能电子封装材料的树脂基体。

双马来酰亚胺（BMI）树脂的改性研究进展张杨;冯浩;杨海东;王海民【摘要】Bismaleimide(BMI)resins have excellent properties,such as high temperature resistance,chemical resistance, wet and heat ageing resistance,and excellent mechanical properties and so on. However,BMI resins are hard to process for their high mold temperature,and the cured products are brittle because of the high crosslinking densities. So,lots of works have been performed to achieve good fracture toughness of the BMI resins. In this paper,methods of modification of BMI resins were summarized. Modifiers,such as aromaticdiamine,allylphenols,thermoplastic resins,elastomer and inorganic nanoparticles are used to modify BMI. Some new BMI resins are synthesized.%双马来酰亚胺（BMI）树脂具有优异的综合性能，如耐高温、耐化学品、耐湿热以及优良的力学性能等。

然而BMI 成型温度高、固化物的交联密度大导致固化物的脆性大。

研究人员针对 BMI 树脂的增韧改性做了大量的工作。

综述了 BMI 树脂的改性方法，如芳香族二元胺扩链改性、烯丙基化合物改性、热塑性树脂改性、弹性体改性、新型 BMI 单体的合成和无机纳米材料改性。

双马来酰亚胺树脂固化技术及反应机理研究进展任荣;熊需海;刘思扬;陈平【摘要】双马来酰亚胺树脂是一种高性能热固性树脂，在尖端技术领域有着广泛的应用。

本文综述了双马来酰亚胺树脂（ BMI）在热、微波辐射、电子束辐射和紫外光等作用下固化成型技术及固化机理等方面的研究进展。

%Bismaleimide is a class of high-performance thermosetting resin and widely applied in high-tech fields.This paper discusses the progress in curing technology and reaction mechanism of bismaleimide resin under the conditions of thermal activation,microwave radiation,electron beam and UV-irradiation.【期刊名称】《纤维复合材料》【年(卷),期】2014(000)002【总页数】5页(P10-14)【关键词】双马来酰亚胺( BMI);固化成型技术;固化机理【作者】任荣;熊需海;刘思扬;陈平【作者单位】沈阳航空航天大学航空航天工程学院辽宁省高性能聚合物基复合材料重点实验室，沈阳110136;沈阳航空航天大学航空航天工程学院辽宁省高性能聚合物基复合材料重点实验室，沈阳110136;沈阳航空航天大学航空航天工程学院辽宁省高性能聚合物基复合材料重点实验室，沈阳110136;沈阳航空航天大学航空航天工程学院辽宁省高性能聚合物基复合材料重点实验室，沈阳110136; 大连理工大学化工学院精细化工国家重点实验室，辽宁大连116024【正文语种】中文双马来酰亚胺树脂(下称双马或BMI)是一种典型的耐热型热固性树脂。

其优越性能如加工性能、粘结性、电绝缘性、耐疲劳性、高强度以及耐湿热能力使之作为基体树脂或粘胶剂广泛应用于先进复合材料领域、多层印刷电路板以及电绝缘器件等电子电器行业[1]。