環(huán)氧樹脂固化劑固化條件及配方

1、精心整理精心整理精心整理精心整理環(huán)氧樹脂固化劑固化條件及配方（一）表1-1多胺固化劑的性質(zhì)？?類別名稱略稱密度/gml-1室溫狀態(tài)黏度/Pas熔點(diǎn)/c脂肪胺二乙烯三胺DETA0.954液態(tài)0.005三乙烯四胺TETA0.98液態(tài)0.019四乙烯五胺TEPA1.00液態(tài)0.001二乙氨基丙胺DEPA液態(tài)乙二胺EDA液態(tài)聚酰胺-多胺基于胺值不同，可由半固態(tài)至液態(tài)半固態(tài)（胺值90）液態(tài)1.02.5（胺值600）脂環(huán)族孟烷二胺MDA液態(tài)0.019異佛爾酮二胺IPDA0.924液態(tài)0.018N-氨乙基哌嗪N-AEP液態(tài)3,9-雙（3-胺丙基）-2,4,8,10-四氧雜螺十烷加合物ATU加合物液態(tài)脂肪族雙

2、（4-胺基-3-甲基環(huán)己基）甲烷0.945液態(tài)因加合物種類而異雙（4-胺基環(huán)己基）甲烷0.95固態(tài)0.0640芳香族間苯二甲胺m-XDA1.05結(jié)晶體液體二氨基二苯基甲烷DDM1.05固體89二氨基二苯基砜DDS1.33固體175間苯二胺m-PDA0.95固體62其他雙氰胺DICY固體207210己二酸二酰肼AADH固體180?表1-2BA樹脂與多胺固化劑的固化條件、性能及應(yīng)用類別名稱胺當(dāng)量個(gè)化劑）（%）適用期標(biāo)準(zhǔn)固化條件HDT/C特點(diǎn)用途優(yōu)點(diǎn)缺點(diǎn)粘層澆涂接壓鑄料脂DETA20.6510820min常溫X4天90低黏適用期OOOO肪胺+100CX30min125度、室溫速固短、白化現(xiàn)象TETA

3、24.461292030min常溫X4天+100CX30min98124各種機(jī)械性能均衡毒性（分子質(zhì)量愈小毒性愈大）OOOOTEPA27.1714122040min常溫X7天+100CX30min115室溫固化、長(zhǎng)的適用期低溫性能、電性能耐熱性低，耐藥品性毒性O(shè)OOODEPA65粘接8澆注4層壓614h65CX4h+115CXlh85OOOX聚酰胺-多胺906000.54h因胺值而不同常溫X7天+60CX2h55113配比范圍寬，機(jī)械性能均衡，粘接性、耐水性耐熱性，耐藥品性O(shè)XXO脂環(huán)胺MDA42.5226h80CX2h+130CX30min148158低黏度、耐熱性、耐穩(wěn)定性因吸收CO2而發(fā)

4、泡OOOXIPDA41241h80CX4h+150CXlh與MDA同與MDA同在室溫下只固化至B-階段與DE-TA、TETA同XOOXN-AEP4320222030min常溫X3天+200CX30min110120與DETA、TETA同沖擊性與MDA同在室溫下只固化至B-階段與DE-TA、TETA同XOOXATU加合物4513312h常溫X7天+60CX2h5581適用長(zhǎng)期、速耐熱性O(shè)XOO固，配比寬，可撓性、粘接性、透明無色固化物603h80CX2h+150CX2h155160耐熱性、高溫機(jī)械性，高溫電性能XOOO5360CX3h+150CX2h150耐熱性、高溫機(jī)械性，高溫電性能XOOO芳

5、香胺m-XDA34.1161820min常溫X7天+60CXlh130150常溫固化，使用期長(zhǎng)、耐熱性因吸收CO2而發(fā)泡OXXXDDM49.625308h80CX2h+150CX4h150耐熱性、電性能、耐藥品性混合操作，固化物著色OOOOm-PDA3414166h80CX2h+150CX4h150類似DDM類似DDMOOOXDDS62.13035約1年110CX2h+200CX4h180190適用期長(zhǎng)，耐熱性混合操作，混合物咼黏OOOX其他DICY20.9612月160CXlh+180CX20min125潛伏性，半固化物貯存穩(wěn)定混合操作，高溫固化OOOXAADH潛伏性，可撓性混合操作OOXO

6、?方括號(hào)中為標(biāo)準(zhǔn)用量精心整理?室溫，樣品量100g?0=良好乂=差?表1-3不同類型固化劑-環(huán)氧樹脂固化物性能比較固化劑W個(gè)化劑)(%)凝膠時(shí)間/min固化周期熱變形溫度/C抗壓強(qiáng)度/MPa抗壓模量/GPa壓縮形變(%)DETA123025C凝膠+100CX2h122115.353.57薄荷烷二胺(或MDA)22480100CX2h+200CX3h151133.862.688.0N-AEP20203025C凝膠+150CX2h11094.131.9210.5聚酰胺樹脂10018025C凝膠+120CX3h5849.431.4113.0固化劑抗拉強(qiáng)度/MPa抗拉模量/GPa斷裂伸長(zhǎng)率/%介電強(qiáng)度

7、/kVmm-i介電常數(shù)23C,60HztanO耐化學(xué)性，質(zhì)量增量(%)60Hz103Hz沸丙酮3h沸水24hDETA74.832.81(5.318.324.10.0150.0200.630.51薄荷烷二胺(或MDA)61.783.02:2.918.125.30.0050.0181.701.51N-AEP65.902.7513.815.763.00.0180.025破壞2.80聚酰胺樹脂37.761.68才02.763.20.0350.033破壞3.60?所用原料樹脂：環(huán)氧當(dāng)量=180195的雙酚A型環(huán)氧樹脂；凝膠時(shí)間在23C用藥1.1L舞料測(cè)定。?表1-4二乙烯三胺的質(zhì)量分?jǐn)?shù)對(duì)固化物的硬度及耐

8、化學(xué)腐蝕性能的影響W(二乙烯三胺)不同溫度下的巴科爾硬度沸水中3h沸丙酮中3h后25C60C80C100C120C巴科爾硬度增重(%)巴科爾硬度增重(%)6330250.8207.44734180270.7003.6683526120310.48121.66938251610310.45250.8010372618100320.44310.5211382621100330.49350.541236272280310.46350.201334271650300.48350.26?所用樹脂為環(huán)氧當(dāng)量為190的雙酚A型環(huán)氧樹脂，室溫凝膠后在110C固化4h。理論計(jì)算二乙烯三胺質(zhì)量分?jǐn)?shù)=10.8%。?

9、表1-5分別用三乙烯四胺、低分子聚酰胺樹脂固化東都化成YD型環(huán)氧樹脂的性能對(duì)比精心整理樹脂型號(hào)W(三乙烯四胺)/%W(低分子聚酰胺)/%使用期/min抗彎強(qiáng)度/MPa抗拉強(qiáng)度/MPa抗壓強(qiáng)度/MPa粘結(jié)力/MPa硬度(洛氏)熱變形溫度/C沖擊韌性/(kJm-2)M級(jí)P級(jí)YD-115105061.7835.30100.030.6137461.65013040.2137.2750.997.5572392.3YD-127105044.1322.56109.343.9260541.15013056.8836.2862.966.0877422.0YD-12810546.1924.52113.764.12

10、61551.25013076.4939.2362.376.3780432.1?固化測(cè)試條件：100g樹脂配料，20C固化7d后測(cè)定強(qiáng)度。熱變形溫度為負(fù)荷2.5kgl4d后測(cè)定,低分子聚酰胺胺值為350。表1-6在24C下環(huán)氧樹脂的環(huán)氧基殘留量固化時(shí)間/h環(huán)氧基殘留量/(%)固化時(shí)間/h環(huán)氧基殘留量/(%)0100.09541.7292.512441.226.545.512540.83143.9表1-7固化溫度與剪切強(qiáng)度的關(guān)系固化溫度/C固化時(shí)間/h抗剪強(qiáng)度/MPa固化溫度/C固化時(shí)間/h抗剪強(qiáng)度/MPa202560.012.3950.540.0360.020.01450.542.0表1-8芳胺

11、的影響芳胺名稱方胺用量(m)/g熱變形溫度/C無080間苯二胺3.81044,4-二氨基二苯甲烷6.593表1-9KH-514膠粘劑的耐老化性能老化項(xiàng)目室溫抗剪強(qiáng)度/MPa60C抗剪強(qiáng)度/MPa不均勻扯離強(qiáng)度/kNmT老化前225.0220.025360C,30天25.225.460C,相對(duì)濕度98%,3026.722.0天廣州地區(qū)，3年大氣老化23.416.331海水，30天22.422.2煤油，135天22.621.6丙酮，135天19.617.4酒精，135天17.217.6表1-10低分子聚酰胺固化物性能固化劑熱變形溫度/C抗彎強(qiáng)度/MPa抗彎模量/GPa抗拉強(qiáng)度/MPa斷裂伸長(zhǎng)率/%

12、沖擊韌度/(kjm-2)巴氏強(qiáng)度VT1545771.64285060V-1257085911051.82.25686575V-140110115982.2561.12.76971V115：n(二聚酸):n(DTA)=2：3；胺值238V-125：m(二聚酸):n(DTA)=l：2；胺值345V-140：m(二聚酸):n(DTA)=l：2；胺值375表1-11脂環(huán)族多元胺的固化物性能固化劑W(%)熱變形溫度/C抗彎強(qiáng)度/MPa抗彎模量/GPa抗拉強(qiáng)度/MPa斷裂伸長(zhǎng)率(%)沖擊韌度/kJm2硬度(洛氏M)介質(zhì)常數(shù)50Hz,23C功率因數(shù)50Hz,23C體積電阻率/QcmC260331301501

13、072.64774.00.0052X1016MDA622148158109123642.91.62.2105IPDA241491254.30733.63.80.0021X1016HM30150100501083.11X1016NAEP20100120100648.85.46.595105mXDA16181301501243.07756.74.00.0052X1016表1-12芳香胺二胺的固化物性能固化劑W(%)熱變形溫度抗彎強(qiáng)度/MPa抗彎模量/GPa抗壓強(qiáng)度/MPa抗拉強(qiáng)度/MPa斷裂伸長(zhǎng)率沖擊韌度/kJm2硬度(洛氏M)介質(zhì)常數(shù)50Hz,23C功率因數(shù)50Hz,23C體積電阻率/Qcm/C

14、(%)m-PD274563.01.11.61083.30.007DDM27301551232.774574.41.62.71064.40.0041X1015DDS35401751263.0603.3110m(PDA):m(DDM)=6:4201501153.174564.82.71051104.50.0061X1016m(DDM)m(IPDA)=4:6251551163.40.012表1-13芳香胺固化環(huán)氧樹脂的耐化學(xué)腐蝕性能?化學(xué)藥品用間苯二胺固化用二氨基二苯基砜固化試樣外觀變化抗彎強(qiáng)度/MPa試樣外觀變化抗彎強(qiáng)度/MPa初始180天后初始180天后25%HCl(5

15、4C浸泡)稍綠135.92111.89稍有發(fā)黑122.8862.4725%CHCOOH3無變化135.92126.34無變化122.88105.03100%三氯乙烯無變化135.92105.03無變化122.8891.996%NaOCl嚴(yán)重粉化135.92135.23嚴(yán)重粉化122.88127.38蒸餾水無變化135.92127.68無變化122.88127.0050%Na0H(82C浸泡)表面稍發(fā)暗135.92143.47稍發(fā)暗122.88118.7625%HSO24表面稍發(fā)暗135.92102.97邊緣稍有發(fā)黑122.88111.8925%HCl表面發(fā)黑135.92107.09相當(dāng)?shù)陌l(fā)黑八

16、、122.8858.3540%甲醛邊緣稍有溶脹135.9298.85邊緣稍有溶脹122.88108.4625%锘酸鋁稍有粉化135.92125.62表面稍有痕跡122.88107.7828.5%硫酸鋁稍有發(fā)黑135.92129.74無變化122.88118.07表1-14?；翌惔龠M(jìn)劑固化性能促進(jìn)劑固化時(shí)間/min抗剪強(qiáng)度/MPa促進(jìn)劑固化時(shí)間/min抗剪強(qiáng)度/MPa乙酰胍1031.8乙酰胍1016.12038.52031.14040.64040.1表1-15酰肼的熔點(diǎn)、使用期及固化物差熱分析酰肼固化劑熔點(diǎn)/c使用期/天差熱分析起始溫度/c放熱峰/c琥珀酸酰肼(SuADH)1631201611

17、65己二酸酰肼(AADH)180120161167間苯二酸酰肼(IPADH)212120150154160對(duì)一羥基安息香酸酰肼(POBH)248120153161水楊酸酰肼(SaAH)151152496130苯基氨基酸酰肼(PAPAH)93952115150DICY207208300178182表1-16有機(jī)酸酰肼固化環(huán)氧樹脂鐵-鐵粘接的剪切強(qiáng)度固化劑固化條件150CX0.5h150CXlh150CX2h170CX0.5hSuADH16.514.4AADH凝膠25.0IPADH凝膠20.0POBH凝膠23.5PAPAH凝膠27.5DICY液態(tài)液態(tài)16.422.6表1-17國(guó)產(chǎn)的某些改性胺固化劑

18、的質(zhì)量指標(biāo)商品牌號(hào)色澤胺值/(mgK0Hg-1)黏度(40C)/(Pas)TY200W182155100800TY203W142002020100TY300183151520100TY3051W17350200.210TY650152002010100TY65115400200.210TY60016650200.1TG011105AH1黃一黃棕色6006506080AH2黃一黃棕色4805208090AH3黃棕色400450140T314604801113表1-18烷基、芳基聚酰胺樹脂的典型性能?商品牌號(hào)胺值/mgKOHg-i黏度/Pas色澤（加德納法）活潑氫摩爾質(zhì)量/gmol-i相對(duì)密度推薦

19、使用量/g對(duì)環(huán)氧當(dāng)量為190的樹脂對(duì)環(huán)氧當(dāng)量為500的樹脂L-9085-110(60C)10.020.0125301.00250275-L-130130-15020.0123901.0020024080120L-130A85-95(25C)2.5-6000.84-140160L-190180-220(60C)10.020.0121751.00851004060L-220210-23010.0-20.0121501.0060906090L-220A147-161(25C)0.71.0-2100.96-6080L-250245-285(40C)14.025.0121200.9860803040L-

20、275265-295(20C)2.03.0121100.9855702535L-375355-395(20C)4.06.0121000.985060-L-410390-430(20C)1.02.012900.974050-L-425400-440(20C)10.020.0100n（丙烯腈）：n（DTA）=2:l50588609506307701.522.127896表1-21胺加合物（由環(huán)氧乙烷、環(huán)氧丙烷制）的固化物性能固化劑使用期/min(50g料,25C)熱變形溫度/C抗壓強(qiáng)度/MPa抗拉強(qiáng)度/MPa抗彎強(qiáng)度/MPa抗彎模量/GPaN,N-雙（羥乙基）DTA（I）2458316841023

21、.5N,N雙(羥丙基)DTA(II)2968291951163.7N,N雙(羥乙基)TTA(III)2876291911092.8N-(羥乙基)DTA(IV)1996288105982.9m(IV):m(I)=85:15923021051093.0m(IV):m(I):m(雙酚A)=85:15:15842461031193.3N-（羥丙基）DTA27942571051093.0N（3苯氧基,2-羥丙基）DTA5790246981233.2N（2-苯基,2-羥乙基）DTA1893274105883.7N-(羥丙基)m-PAD2501163161341554.0表1-22典型的酸酐固化劑的性質(zhì)類別

22、名稱略稱狀態(tài)黏度/Pas熔點(diǎn)/C單官能團(tuán)型鄰苯二甲酸酐PA粉末128四氫鄰苯二甲酸酐THPA固體100六氫鄰苯二甲酸酐HHPA固體34甲基四氫鄰二甲酸酐MeTHPA液體0.0350.06甲基六氫鄰苯二甲酸酐MeHHPA液體0.050.08甲基納迪克酸酐MNA液體0.138十二烯基琥珀酸酐DDSA液體0.5氯菌酸酐HET粉末235239兩官能團(tuán)型均苯四甲酸酐PMDA粉末286苯酮四酸二酐BTDA粉末227乙二醇雙偏苯三酸酐TMFG固體7080（軟化點(diǎn)）甲基環(huán)已烯基四酸二酐MCTC粉末167游離酸酸酐偏苯三甲酸酐TMA粉末168聚壬二酸酐PAPA固體0.2(100C)表1-23與BA樹脂配合的酸酐

23、固化劑的固化條件、特性和用途類別名稱酸酐當(dāng)量適用期標(biāo)準(zhǔn)固化條件HDT/C特點(diǎn)用途優(yōu)點(diǎn)缺點(diǎn)成層澆浸涂型壓鑄漬料單官能團(tuán)酸酹PA15814h(100C)150CX6h100152價(jià)廉，放熱低，耐藥品性優(yōu)良（堿除外）升華，混合工藝性劣OOTHPA152除不升華外與PA近似著色，混合工藝性劣與其他酸酐混合HHPA15.424h(加促進(jìn)劑/250C)85CX2h+150CX1224h110130低粘度，適用期長(zhǎng)，優(yōu)良耐電痕跡性，耐侯性吸濕性O(shè)OMeTHPA16634min(加促進(jìn)劑/100C)100CX2h+150CX5h121123低粘度，優(yōu)良的工藝性價(jià)格貴些OOOMeHHPA16835min(加促進(jìn)

24、劑/100C)100CX2h+150CX5h136色穩(wěn)定，優(yōu)良的電痕跡性，耐侯性價(jià)格貴些OOOOMNA17856天（加促進(jìn)劑/25C）85CX2h+150CX1224h150175優(yōu)良的工藝性，低收縮，耐熱耐堿差OOODDSA26610天（加促進(jìn)劑/25C）85CX2h+150CX1224h6070優(yōu)良工藝性，電性能、韌性耐藥品性差OOHET38830min(120C)100CXlh+200CXlh+200CX2h145190耐熱性、阻燃性，優(yōu)良的電性能操作工藝性差OO兩PMDA109250耐熱、耐工藝性O(shè)OO官能團(tuán)酸酹藥品性差，脆性BTDA161200CX24h280耐熱，耐藥品性耐高溫老化

25、性溶解性不良(與單官能酸酐共用)OOOOTMEG205194耐熱性，耐藥品性價(jià)貴OOOOMCTC132280工藝性好，耐熱價(jià)貴OOO游離酸酸酐TMA192210速固化，電性能，耐熱性耐藥品性工藝性差OOOPAAP174140CXlh+150CX20h(加促進(jìn)劑)39耐熱性差OOO表1-24配方與固化物性能m(E-44)/m(70酸酐)/m(N,N-二甲基芐胺)？抗拉強(qiáng)度/MPa抗彎強(qiáng)度/MPa抗壓強(qiáng)度/MPa抗剪強(qiáng)度/MPa馬丁耐熱/C體積電阻率/Qcm表面電阻/Q介電損耗角正切介電常數(shù)(106Hz)介電強(qiáng)度/kVmm-1100/56/0.567.5104.0133.018.5961009.5

26、X1062.4X1072.9X10-22.923.0表1-25商品甲基四氫苯酐的性能比較牌號(hào)外觀色澤(加德納法)相對(duì)體積質(zhì)量(25C)黏度(25C)/mPas凝固點(diǎn)/C中合當(dāng)量分子質(zhì)量HN2200淺黃色透明液體11.206551583166QH200淺黃色透明液體11.200.053540158185166表1-26商品甲基六氫苯酐的性能比較牌號(hào)外觀色澤(APHA)相對(duì)體積質(zhì)量(25C)黏度(25C)/mPas凝固點(diǎn)/C碘值中和當(dāng)量分子質(zhì)量HN5500無色透明液體201.1656581528485168MH700無色透明液體501.175070152168B650無色透明液體1.1765151

27、85168表1-27不同澆鑄配方固化物的性能及其比較牌坊及固化物性能123456配料比雙酚A環(huán)氧樹脂100100100606060脂環(huán)族環(huán)氧樹脂404040HN-5500(MeHHPA)5075HN-2200(MeTHPA)4065HHPA4065BDMA0.50.50.5微晶填料200200200300300300固化條件：120CX5h+150CX15h固化物性厶匕能熱變形溫度/c123116117166155160抗彎曲強(qiáng)度/MPa(25C)115.72101.01128.4799.05119.6495.12(50C)115.7293.16109.8397.09112.7881.40(75C)105.9183.3698.0789.2496.1190.22彎曲模量/MPa(25C)8924106908041931686309611(50C)8434100027551921882389120(75C)735595126962764972578434拉伸強(qiáng)度/MPa70.60578676.4647.0743.1550.01伸長(zhǎng)率(%)2.33.94.72.72.32.