VRLA高温电池用耐热阻燃ABS热降解行为分析

蓄电池Chinese labat manVRLA高温电池用耐热阻燃ABS热降解行为分析党志敏,刘桃松(浙江南都电源动力股份公司,浙江杭州311305)摘要:本文通过热重法(TG-DTG)比较高温VRLA蓄电池槽用的耐热阻燃ABS与普通ABS电池槽材料在热降解过程中的差异,并采用Flyn- Wall-Ozawa法求得其反应活化能。结果显示,耐热阻然ABS的初始热降解温度降低,但热降解速率降低且热降解温度范围扩大,炭化残重也有所増加。同时其活化能(E)随失重率(α)变化较复杂,α在0.2时耐热阻燃ABS的E相对较低,仅155.5kJ/mol,比纯ABS的低约50kJ/mol,在α大于0.3以后其Ea均比纯ABS的大,最大约243.6kJ/mol,比纯ABS的E3大52kJ/mol左右。关键词:ABS;阻燃;耐热;降解;活化能;高温ⅤRLA蓄电池中图分类号:TM912.1文献标识码:B文章编号:1006-0847(201501-06-04Analysis of thermal degradation behavior of heat resistant andfame retardant ABS resin for high temperature VRLa batteryDANG Zhi-min, LIU Tao-songNarada Power Source Co, Ltd, Hangzhou Zhejiang 311305, ChinaAbstract: The differences between heat resistant and flame retardant ABS resin for high temperatureVRla battery and pure abs resin in the thermal degradation process were studied by thethermogravimetry (TG-DTG), and their activation energy was calculated with Flynn-Wall-Ozawaequation in this paper. The results showed that the initial thermal degradation temperature of theheat resistant and flame retardant ABs dropped, meanwhile the degradation rate decreased, thermaldegradation temperature range expanded and residual weight also increased. At the same time, theactivation energy(Ea)changes with weight loss(a) were more complex, when a is 0. 2, Ea of the heatasistant and flame retardant abs was 155 kJ/mol, and 50 kJ/mol lower than that of pure abs. when ais greater than 0.3, Ea of heat resistant and flame retardant ABS was 243. 6 kJ/mol, and greater than thatof pure abs about 52 kJ/molKey words: ABS resin; flame retardant; heat resistant; degradation; activation energy; high temperatureVRLa battery0前言随着通信业的飞速发展及网络覆盖的全面性,三大通信运营商的移动通信其站总歉口经超过100收稿日期:2014-08-05万个,无人基站中国煤化前基站大都采用VRLA电CNMH制高点等015 No. 1 Vol5蓄电池试验研究Chinese labat manwww.batterychn.commvRA電j辮辗阻A的§热降解行为分析站,如果把基站空调设定温度由现在的25℃提高图1是耐热阻燃ABS和普通ABS在不同升温到35℃,温度提高10℃计算,整个机房的电耗率下的热重(TG)曲线。从图1可见,随着升将降低60%~80%,在能源息敏箱傻份公4和耐热阻燃ABS的热降解为了响应国家号召和市场发展,都向高温方向偏移,使热降果,提高蓄电池的使用温度从而降低空调能耗显得解开始的温度和热降解结束温度都升高。纯ABS尤为必摘要但ξR澒疱滟斬梼命檨火地依赖賁锉衤温Ⅴ眄热降解衅缆臾栒础艭煇$艿鸲」,而温度,幽溘增痂府热痂柲糇的锤稱失汞采Fly耐热燃B§酌魚窿夯两卒渀段能-笮躉裡280池鼓胀示容鲑苄降然券也孴蟾雉降管漒黾滟佻,但苾弜蚜徳,斈獎董然溫麂酧能寔配芳啷阻燃法长期酶变嵩瘟所蒿温电澠技棊怣笙〕喃為甏羍(α剂的,另←翱征温粳挝睡3θ~α,电池技錾毹是研发奣無畦燃Bs材料ABS的低约5尖重舉为8%大读温度范慟焉缍A的热腳解特本毁针对新妍變的耐热姐燃AB樂用鵝重大征煴虔相,冇它是ABS对应的热降解温度。经过法比较龚铐罾通^A⑧S黾沲槽糖料熟憐解过倒鑾高禤θ篙溘岩氿纯ABS炭化残重接近于2%,而耐异,并粜得舍殺动丹學摻数,从而棘鄄热热盛纛炭化董约8295101.604稳定性。目前测定反应动力学参数的方法主要有热图2是以10℃C/min升温速率为例做的热失重重法(ha付清mFqe积aon亮曲线iFt到n什H在高动力学数〃公高整88r析法(口Ah评2沿fer只经历℃时DANG Zhi-min0羈大先速率达167%,但耐热阻燃ABS经1实验Narada power source co,Lld,H的溻麼范赛。1#,为h应的最大失重速率为10%/min,也就是说一方面其热降解速率降低,另釆風弸q'帕毳贠誕仪ea在氚ntan鼒而其最志热隆解速焘癍的峰混应亮温高向偏气氛下ⅴ氖旐为卲9d佃巴is升溻速往ther酪趑觀热寀帏宪兩撮高u很园时也而见耐为10、tgm3g科钿;栟員质譟约 h19rastivation限AS陷解团始的暈度降倆alb糨热降解温度范μ5ρorⅰ下较耐赭阳蝾s師譜诵ath梮前ia有颸诒认凝而晶阻燃剂徳梳粗提前伈解成ABS电訑槽挞榖的热鯈解衎沩羲喦da迸利脶郈ρεd,m嶶αw林逦釅热區氤a限屿挞粬虣α解秈橪煷waHa翛解凤动学方程忒縐同妹重審 Resid的郝作机耦餡俠枧t表朋所用的砠燃体下的活ε能at該方法的佻畾丕霙要知道誚细的s(α)系丕是通过媞杖料氽解温廚逦主斅通i綴氧化应过程 resistant and flame retardant abs was155kJ/mol,a速率达到阻的的 that of pure ABS, when ais greater than 0.3, Ea of heat resistant and flame retardant ABS was 243.6 kJ/mol, and greater than thatof pure ABS about 52 kJ/molKey words; ABS resin; fame retardant; heat resistant: degradation; activation energy; high temperatureLAbatter060040前言随着通信业的飞速发展及网络覆盖的全面性收稿日期:2014080300+960o大通信运营商的移动信基話点教已经超过100万个,无人基中国煤化工目前基站大都图1不同升温速率用《E电CNMH民房制高点等062015No.Vol.522015NoVo152071蓄电池Chinese labat man温度,K;B—加热速率。00000()+()2350由表1和表2两种材料TG曲线读取的不同升温速率下失重率和温度的相应值,用 Flynn-WallOzawa方程对两种材料分别在升温速率B为10、20、30和40℃C/min,失重率即转化率a为0.1~0.8下做图3,经线性拟合发现,其线性相关系数均大于08(见表1和表2),lgB对1T呈良好的温度/℃线性关系。按表1和表2所列拟合直线的斜率,通图2不同材料在10Cmn下的DTG曲线过式(1)中直线斜率等于(,求得不同失重率下采用Fψ nn -Wall-Ozawa法计算材料的热降解动的活化能,并做活化能与失重率曲线如图4所示力学参数,见式(1),式中:E。活化能,kJ/mo由图4可见,耐热阻燃ABS的E随失重率A—指前因子,s;F(a)一转化率函数;厂一反应变化较复杂,失重率在0.2以下时耐热阻燃ABS表1耐热阻燃ABS活化能及相关系数B/℃·min)斜率相关系数E2/(kU·mo")40338.55350.3536087365.18-8.54109926155484721523713938526390.528.20730.9687149.4099403.15412.04421.1342591-12.167098682214943422.29432.134407444612.52609928228.0297433.77444.57453.6545987-11.86209982159444382454.13465.134708711.5209847209716452.7546609474.748091-11.70309997213.04740846535476.614852249048-133810.9974243.5946表2ABS活化能及相关系数B/(C·mn)10斜率相关系数E/(kJ·mo)405.3341443422.5243041-1143709768208.2050.2417.16427.8443605444.3-11.05909847201.32370.342398435.57445.63452.58-10.55909915192.22142.78452.39460.8209886189.10850.5436.26448.9745972467.5310.0609918183.137406442.63455.6746704475779.688409889176.37260744946463.4475.5484.029457309914172.165508460.37472.68483954922710.5030.9872191.20216乘2,4曾1013140145150155160165132135/s1000K中国煤化工图3经 Flynn-Wall-Ozawa法处理后的lgB~(1/门CNMHG015 No. 1 Vol5蓄电池试验研究Chinese labat manwww.batterychn.com的E相对较低,仅155.5kJ/mo,比纯ABS低约3瓮K;B-加热速率。50kJ004567E.1AE体系在由热重分析发现:耐热剂和燃剂的加入使分解锑ABS皓祩瞞擀槲料阚掣陬在气00j通腽黦蟹蕰燄輝有加n过化与凤应动力学猾凘两槲馔徳殊圃璋形助2时但失]1率皈化能和·率车颡荆作下E4040k/率的纯趴见教話和桊在材炭弛前罡謝孖在0温度/℃于陇闌塨帝辮眯巒辭寗镪08时,鳳增棡辑歐A俪比之怖食犁(当破坏到稠齑樺下,鎯鄉5舶棘滌鎯z癫朱甄潾帱料啷瀞眷鄯拙黻誌腫擦曲线坳盥4藺遢电调腌嫠勢,慼頲倗于撚旿荘衎亻怣熏瘠κσ池所用甡鹔阻惦A胭蚋热頵諠提髜泆重率08加是因材料樂太了—反应变化较复杂,失重率在02以下时耐热阻燃ABS表1耐热阻燃ABS參佬关系数B/℃C·min")斜率相关系数E/(kJ·mo|)20耐热惠ABS38.55350.3536087锪元俊g等热重弸定聚合势絷骖解反应动力02~361523713938526390.学参数鸦辱工觀料应用49q956):7073203403.15A85412044211342號引等2睚然PcA8s的热降解力学[高分04·4222943213,440.740.54337744157453654595材料样第工楼号923912306438245413465134:鹏A姐燃饿態试中教财倦重一红外光0745275466094747480.塘技术的用[]雅程塑料痤翔4203,31(2):0.8465.354261435224906442138109942435946表2ABS活雠掣袄叠阻燃ABS的制备性能及热降解机理研图不同失重下的话化Cm30U太廉北大学款3E/,my140533414434225243041-114370.9768208.205(上接第5页)02417.16427.8443605423.98435.574456-11.05909847201323710.55909915192.22145结论0.443081442.784523946082103880.9886189.108505436264489745972[便種长清,本文通过研究得03456743704密铅酸电泄树醒分析[肌电463.4475548492000类,914172.1655(1)采用整体铸煣0.亚流揶亶胶封舶缃5[冲翱志刚,効玉茠健〕繳η正板棚鈣合金的异构,能够满足:"“,"“,"↓峙八奸中14n:115-118用户的使用寿1·用阀控铅酸(2)通19-124显著提高板棚与:金13。程优化及节(3)合廷的结合强度,电池制造工(4)控纬.217-227达到了最适值,。s1161s1113135,等.阀控式提高活性物质n:19K中国煤化北京:机循环寿命明显提高。图3经 Flynn-Wall-Ozawa法处理后山出CNMHG08|2015No.Vol.522015 NoI Vol. 52